Cleaning Composition

Abstract

The present disclosure relates to cleaning compositions containing 1) at least one redox agent, 2) at least one chelating agent which is a polyaminopolycarboxylic acid, 3) at least one corrosion inhibitor which is a substituted or unsubstituted benzotriazole, 4) at least one sulfonic acid, and 5) water.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63 / 152,486, filed February 23, 2021, and U.S. Provisional Patent Application No. 63 / 070,886, filed August 27, 2020, the contents of which are incorporated herein by reference in their entireties.

[0002] The present disclosure relates to cleaning compositions for semiconductor substrates and methods for cleaning semiconductor substrates. More particularly, the present disclosure relates to cleaning compositions for use on semiconductor substrates after etching of a metal layer or a dielectric material layer deposited on the substrate, as well as the removal of residue remaining on the substrate after bulk resist removal. [Background technology]

[0003] In the fabrication of integrated circuit devices, photoresist is used as an intermediate mask to transfer the original mask pattern of a reticle onto a wafer substrate through a series of photolithography and etching (e.g., plasma etching) steps. One of the key steps in the fabrication process of integrated circuit devices is the removal of the patterned photoresist film from the wafer substrate. Generally, this step can be performed in one of two ways.

[0004] One method involves a wet stripping process in which a photoresist-coated substrate is contacted with a photoresist stripper solution consisting primarily of an organic solvent and an amine. However, such stripper solutions generally cannot completely and reliably remove photoresist films, especially if the photoresist film has been subjected to UV irradiation and plasma treatment during fabrication. Some photoresist films become highly crosslinked by such treatments, making them more difficult to dissolve in the stripper solution. Furthermore, the chemicals used in these conventional wet stripping methods may not be effective at removing inorganic or organometallic residual materials formed during plasma etching of metal or oxide layers with halogen-containing gases.

[0005] Another method of photoresist film removal involves exposing the photoresist-coated wafer to an oxygen-based plasma to burn the resist film from the substrate in a process known as plasma ashing. However, plasma ashing is also not fully effective at removing the plasma etching by-products mentioned above. Instead, removal of the plasma etching by-products is typically achieved by subsequently exposing the treated metal and dielectric thin films to specific cleaning solutions.

[0006] Metal-containing substrates are generally susceptible to corrosion. For example, substrates containing materials such as aluminum, copper, aluminum-copper alloys, tungsten nitride, tungsten, cobalt, titanium oxide, other metals, and metal nitrides are susceptible to corrosion. Furthermore, dielectrics (e.g., interlayer dielectrics or ultra-low-k dielectrics) in integrated circuit devices can be etched using conventional cleaning chemistries. Furthermore, as device dimensions shrink, the amount of corrosion that integrated circuit device manufacturers are willing to tolerate tends to shrink.

[0007] At the same time, because residue removal is becoming more difficult and corrosion must be controlled to lower levels than before, cleaning solutions must be safe to use and environmentally friendly.

[0008] Therefore, the cleaning solution must be effective in removing etching and / or ashing residues and also be non-corrosive to all exposed substrate materials. Summary of the Invention

[0009] The present disclosure is directed to non-corrosive cleaning compositions useful for removing residues (e.g., plasma etching residues and / or plasma ashing residues) and other materials (e.g., metal oxides) from semiconductor substrates as an intermediate step in a multi-step manufacturing process. Such residues include various relatively insoluble mixtures of organic compounds, such as residual photoresist; organometallic compounds; metal oxides, such as aluminum oxide (AlOx), silicon oxide (SiOx), titanium oxide (TiOx), zirconium oxide (ZrOx), tantalum oxide (TaOx), and hafnium oxide (HfOx), which may form as reaction by-products from exposed metal; metals, such as aluminum (Al), aluminum / copper alloys, copper (Cu), titanium (Ti), tantalum (Ta), tungsten (W), and cobalt (Co); doped metals, such as boron-doped tungsten (WBx); metal nitrides, such as aluminum nitride (AlN), aluminum oxynitride (AlOxNy), silicon nitride (SiN), titanium nitride (TiN), tantalum nitride (TaN), and tungsten nitride (WN); alloys thereof; and others. An advantage of the cleaning compositions described herein is that they are capable of cleaning a wide range of residues encountered and are generally non-corrosive to exposed substrate materials (e.g., exposed metal oxides (such as AlOx), metals (e.g., aluminum, aluminum / copper alloys, copper, titanium, tantalum, tungsten, and cobalt), metal nitrides (e.g., silicon nitride, titanium nitride, tantalum nitride, and tungsten nitride), and alloys thereof).

[0010] In one aspect, the disclosure features a cleaning composition including (e.g., consisting of, or consisting essentially of): 1) at least one redox agent; 2) at least one chelating agent that is a polyaminopolycarboxylic acid; 3) at least one corrosion inhibitor that is a substituted or unsubstituted benzotriazole; 4) at least one sulfonic acid; and 5) water.

[0011] In another aspect, the disclosure features a method for cleaning residue from a semiconductor substrate. The method includes contacting a semiconductor substrate containing post-etch and / or post-ash residue with a cleaning composition described herein. For example, the method can include the following steps: (a) providing a semiconductor substrate containing post-etch and / or post-ash residue, (b) contacting the semiconductor substrate with a cleaning composition described herein, (c) rinsing the semiconductor substrate with a suitable rinse solvent, and (d) optionally drying the semiconductor substrate by any means that removes the rinse solvent and does not compromise the integrity of the semiconductor substrate.

[0012] In yet another aspect, the disclosure features a method for cleaning a semiconductor substrate having a metal layer thereon, the method including: (1) oxidizing the metal layer to form a metal oxide layer, and (2) removing the metal oxide layer from the semiconductor substrate by contacting the metal oxide layer with a cleaning composition described herein.

[0013] The details of one or more embodiments of the invention are set forth in the description below. Other features, objects, and advantages of the invention will be apparent from the description and from the claims. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 shows the surface roughness after digital etching of blanket Co substrates with formulations FE-8 to FE-12 described in Example 2. DETAILED DESCRIPTION OF THE INVENTION

[0015] For purposes of definition herein, unless otherwise specified, all percentages expressed should be understood to be percentages by weight based on the total weight of the cleaning composition. Unless otherwise specified, ambient temperature is defined as between about 16°C and about 27°C, e.g., 25°C.

[0016] In the definitions herein, the terms "layer" and "film" are used interchangeably.

[0017] As defined herein, a "water-soluble" substance (e.g., a water-soluble alcohol, a water-soluble ketone, a water-soluble ester, or a water-soluble ether) refers to a substance that has a solubility of at least 5% by weight in water at 25°C.

[0018] In general, the present disclosure relates to cleaning compositions (e.g., non-corrosive cleaning compositions) that include: 1) at least one redox agent; 2) at least one chelating agent that is a polyaminopolycarboxylic acid; 3) at least one corrosion inhibitor that is a substituted or unsubstituted benzotriazole; 4) at least one sulfonic acid; and 5) water.

[0019] In some embodiments, the compositions of the present disclosure contain at least one (e.g., two, three, or four) redox agents, which are believed to facilitate dissolution of residues on semiconductor surfaces, such as photoresist residues, metal residues, and metal oxide residues. As defined herein, the term "redox agent" refers to a compound that can induce oxidation and / or reduction in the semiconductor cleaning process. One example of a suitable redox agent is hydroxylamine. In some embodiments, the redox agents or cleaning compositions described herein do not contain peroxides (e.g., hydrogen peroxide).

[0020] In some embodiments, the at least one redox agent can be present in an amount of at least about 0.1 wt. % (e.g., at least about 0.2 wt. %, at least about 0.3 wt. %, at least about 0.4 wt. %, at least about 0.5 wt. %, at least about 0.6 wt. %, at least about 0.7 wt. %, at least about 0.8 wt. %, at least about 0.9 wt. %, or at least about 1 wt. %) and / or at most about 5 wt. % (e.g., at most about 4.5 wt. %, at most about 4 wt. %, at most about 3.5 wt. %, at most about 3 wt. %, at most about 2.5 wt. %, at most about 2 wt. %, at most about 1.5 wt. %, or at most about 1 wt. %) of the cleaning compositions of the present disclosure.

[0021] In some embodiments, the compositions of the present disclosure contain at least one (e.g., two, three, or four) chelating agent, which may be a polyaminopolycarboxylic acid. For purposes of this disclosure, polyaminopolycarboxylic acid refers to a compound having multiple (e.g., two, three, or four) amino groups and multiple (e.g., two, three, or four) carboxylic acid groups. Suitable classes of polyaminopolycarboxylic acid chelating agents include, but are not limited to, mono- or polyalkylenepolyaminepolycarboxylic acids, polyaminoalkanepolycarboxylic acids, polyaminoalkanolpolycarboxylic acids, and hydroxyalkyletherpolyaminepolycarboxylic acids.

[0022] Suitable polyaminopolycarboxylic acid chelating agents include, but are not limited to, butylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetrapropionic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid, propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid (EDTA), trans-1,2-diaminocyclohexanetetraacetic acid, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, 1,6-hexamethylenediamine-N,N,N',N'-tetraacetic acid, N,N-bis(2-hydroxybenzyl)ethylenediamine-N,N-diacetic acid, diaminopropanetetraacetic acid, 1,4,7,10-tetraazacyclododecanetetraacetic acid, diaminopropanoltetraacetic acid, and (hydroxyethyl)ethylenediaminetriacetic acid.

[0023] In some embodiments, the compositions of the present disclosure comprise at least about 0.01 wt.% (e.g., at least about 0.02 wt.%, at least about 0.04 wt.%, at least about 0.05 wt.%, at least about 0.06 wt.%, at least about 0.08 wt.%, at least about 0.1 wt.%, at least about 0.12 wt.%, at least about 0.14 wt.%, at least about 0.15 wt.%, at least about 0.16 wt.%, at least about 0.18 wt.%, or at least about 0.2 wt.%) and / or at most about 0.5 wt.% (e.g., at most about 0.45 wt.%, at most about 0.4 wt.%, at most about 0.35 wt.%, at most about 0.3 wt.%, at most about 0.25 wt.%, or at most about 0.2 wt.%) of a polyaminopolycarboxylic acid chelating agent.

[0024] In some embodiments, the cleaning compositions of the present disclosure contain at least one (e.g., two, three, or four) corrosion inhibitor. In some embodiments, the corrosion inhibitor can be selected from substituted or unsubstituted benzotriazoles. Without wishing to be bound by theory, it is believed that such cleaning compositions can exhibit significantly improved compatibility with materials that may be present in semiconductor substrates and that should not be removed by the cleaning composition (e.g., Co, boron-doped tungsten (WBx), tungsten, TiN, SiOx, AlOx, or SiN) compared to cleaning compositions that do not contain a corrosion inhibitor.

[0025] Suitable classes of substituted benzotriazoles include, but are not limited to, benzotriazoles substituted with at least one substituent selected from the group consisting of alkyl, aryl, halogen, amino, nitro, alkoxy, and hydroxy groups. Substituted benzotriazoles further include those fused with one or more aryl (e.g., phenyl) or heteroaryl groups.

[0026] Benzotriazoles suitable for use as corrosion inhibitors include, but are not limited to, benzotriazole (BTA), 1-hydroxybenzotriazole, 5-phenylthiolbenzotriazole, 5-chlorobenzotriazole, 4-chlorobenzotriazole, 5-bromobenzotriazole, 4-bromobenzotriazole, 5-fluorobenzotriazole, 4-fluorobenzotriazole, naphthotriazole, tolyltriazole, 5-phenylbenzotriazole, 5-nitrobenzotriazole, 4-nitrobenzotriazole, 2-(5-aminopentyl)-benzotriazole, 1-aminobenzotriazole, 5-methyl-1H-benzotriazole (also known as 5-methylbenzotriazole or 5MBTA), benzotriazole-5-carboxylic acid, 4-methylbenzotriazole, 4-ethylbenzotriazole, 5-ethylbenzotriazole, 4-propylbenzotriazole, Examples of benzotriazole include benzotriazole, 5-propylbenzotriazole, 4-isopropylbenzotriazole, 5-isopropylbenzotriazole, 4-n-butylbenzotriazole, 5-n-butylbenzotriazole, 4-isobutylbenzotriazole, 5-isobutylbenzotriazole, 4-pentylbenzotriazole, 5-pentylbenzotriazole, 4-hexylbenzotriazole, 5-hexylbenzotriazole, 5-methoxybenzotriazole, 5-hydroxybenzotriazole, dihydroxypropylbenzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]-benzotriazole, 5-t-butylbenzotriazole, 5-(1',1'-dimethylpropyl)-benzotriazole, 5-(1',1',3'-trimethylbutyl)benzotriazole, 5-n-octylbenzotriazole, and 5-(1',1',3',3'-tetramethylbutyl)benzotriazole.

[0027] In some embodiments, the at least one corrosion inhibitor can be present in the cleaning compositions of the present disclosure in an amount of at least about 0.05 wt.% (e.g., at least about 0.1 wt.%, at least about 0.15 wt.%, at least about 0.2 wt.%, at least about 0.25 wt.%, at least about 0.3 wt.%, at least about 0.35 wt.%, at least about 0.4 wt.%, at least about 0.45 wt.%, or at least about 0.5 wt.%) and / or at most about 1 wt.% (e.g., at most about 0.9 wt.%, at most about 0.8 wt.%, at most about 0.7 wt.%, at most about 0.6 wt.%, at most about 0.5 wt.%, at most about 0.4 wt.%, at most about 0.3 wt.%, at most about 0.2 wt.%, or at most about 0.1 wt.%).

[0028] In some embodiments, the cleaning compositions of the present disclosure comprise at least one (e.g., two, three, or four) sulfonic acid. In some embodiments, the at least one sulfonic acid comprises a sulfonic acid of formula (I): R-SO3H (I) where R is C1-C 12 Alkyl groups, C1-C 12 a cycloalkyl group or an aryl group, wherein the alkyl group, the cycloalkyl group or the aryl group is selected from the group consisting of halogen, OH, NH2, NO2, COOH, C1-C 12 Cycloalkyl groups, C1-C optionally substituted with halogen 12 It may be substituted with at least one substituent selected from the group consisting of an alkoxy group and an aryl group optionally substituted with OH. In some embodiments, R is a C1-C4 alkyl group, such as a methyl group, an ethyl group, a propyl group, or a butyl group. As used herein, the term "alkyl group" refers to a saturated hydrocarbon group that may be linear or branched. As used herein, the term "cycloalkyl group" refers to a saturated cyclic hydrocarbon group. As used herein, the term "aryl group" refers to a hydrocarbon group having one or more aromatic rings (e.g., two or more fused aromatic rings). In some embodiments, the aryl group may have 6 to 10 ring carbons.

[0029] Examples of suitable sulfonic acids include, but are not limited to, methanesulfonic acid, trifluoromethanesulfonic acid, ethanesulfonic acid, trifluoroethanesulfonic acid, perfluoroethylsulfonic acid, perfluoro(ethoxyethane)sulfonic acid, perfluoro(methoxyethane)sulfonic acid, dodecylsulfonic acid, perfluorododecylsulfonic acid, butanesulfonic acid, perfluorobutanesulfonic acid, propanesulfonic acid, perfluoropropanesulfonic acid, octyl sulfonic acid, perfluorooctane sulfonic acid, 2-methylpropanesulfonic acid, cyclohexylsulfonic acid, perfluorohexanesulfonic acid, benzylsulfonic acid, hydroxybenzoates ... Examples of suitable sulfonic acids include hydroxyphenylmethanesulfonic acid, naphthylmethanesulfonic acid, norbornanesulfonic acid, benzenesulfonic acid, chlorobenzenesulfonic acid, bromobenzenesulfonic acid, fluorobenzenesulfonic acid, hydroxybenzenesulfonic acid, nitrobenzenesulfonic acid, 2-hydroxy-5-sulfobenzoic acid, toluenesulfonic acid (e.g., paratoluenesulfonic acid), methylchlorobenzenesulfonic acid, dodecylbenzenesulfonic acid, butylbenzenesulfonic acid, cyclohexylbenzenesulfonic acid, picryl sulfonic acid, dichlorobenzenesulfonic acid, dibromobenzenesulfonic acid, and 2,4,5-trichlorobenzenesulfonic acid.

[0030] In some embodiments, the at least one sulfonic acid can be present in the cleaning compositions of the present disclosure in an amount of at least about 1 wt. % (e.g., at least about 1.2 wt. %, at least about 1.4 wt. %, at least about 1.5 wt. %, at least about 1.6 wt. %, at least about 1.8 wt. %, at least about 2 wt. %, at least about 2.2 wt. %, at least about 2.4 wt. %, at least about 2.5 wt. %, at least about 2.6 wt. %, at least about 2.8 wt. %, or at least about 3 wt. %) and / or 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. %, at most about 5 wt. %, at most about 4 wt. %, at most about 3 wt. %, or at most about 2 wt. %).

[0031] Without wishing to be bound by any particular theory, it is believed that cleaning compositions including sulfonic acids can minimize the surface roughness of semiconductor substrates treated with the cleaning compositions.

[0032] In some embodiments, cleaning compositions of the present disclosure can optionally contain at least one (e.g., two, three, or four) pH adjusters (e.g., acids or bases) to control the pH between about 4 and about 7. In some embodiments, cleaning compositions of the present disclosure can have a pH of at least about 4 (e.g., at least about 4.2, at least about 4.4, at least about 4.5, at least about 4.6, at least about 4.8, or at least about 5) to at most about 7 (e.g., at most about 6.8, at most about 6.6, at most about 6.5, at most about 6.4, at most about 6.2, at most about 6, at most about 5.8, at most about 5.6, or at most about 5.5). Without wishing to be bound by theory, cleaning compositions with a pH below 4 are believed to increase the etch rate of certain metals (e.g., Co, W, or WBx) or dielectric materials to undesirable levels. Furthermore, without wishing to be bound by any particular theory, it is believed that cleaning compositions with a pH greater than 7 have a reduced ability to clean etch or ashing residues, resulting in incomplete cleaning. The effective pH may vary depending on the types and amounts of ingredients used in the cleaning compositions described herein.

[0033] If a pH adjuster is required, the required amount of pH adjuster will vary with varying concentrations of other ingredients (e.g., hydroxylamine, sulfonic acid, and corrosion inhibitor) in different formulations and may also vary as a function of the molecular weight of the particular pH adjuster used. In some embodiments, the pH adjuster can be at least about 0.1 wt. % (e.g., at least about 0.2 wt. %, at least about 0.4 wt. %, at least about 0.5 wt. %, at least about 0.6 wt. %, at least about 0.8 wt. %, at least about 1 wt. %, at least about 1.2 wt. %, at least about 1.4 wt. %, or at least about 1.5 wt. %) and / or at most about 3 wt. % (e.g., at most about 2.8 wt. %, at most about 2.6 wt. %, at most about 2.5 wt. %, at most about 2.4 wt. %, at most about 2.2 wt. %, at most about 2 wt. %, or at most about 1.8 wt. %) of the cleaning compositions of the present disclosure. In some embodiments, pH adjusters may be excluded from the cleaning compositions described herein.

[0034] In some embodiments, the pH adjuster does not contain any metal ions (except for trace metal ion impurities). Suitable metal ion-free pH adjusters include acids and bases. Suitable acids that can be used as pH adjusters include carboxylic acids. Exemplary carboxylic acids include, but are not limited to, monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, monocarboxylic alpha-hydroxy acids and beta-hydroxy acids, dicarboxylic alpha-hydroxy acids or beta-hydroxy acids, or tricarboxylic alpha-hydroxy acids and beta-hydroxy acids. Examples of suitable carboxylic acids include citric acid, maleic acid, fumaric acid, lactic acid, glycolic acid, oxalic acid, tartaric acid, succinic acid, or benzoic acid.

[0035] Suitable bases that can be used as pH adjusters include ammonium hydroxide, quaternary ammonium hydroxides, monoamines (including alkanolamines), and cyclic amines. Examples of suitable 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. Examples of suitable monoamines include, but are not limited to, triethylamine, tributylamine, tripentylamine, diethylamine, butylamine, dibutylamine, and benzylamine. Examples of suitable alkanolamines include, but are not limited to, monoethanolamine, diethanolamine, triethanolamine, and aminopropyldiethanolamine.

[0036] In some embodiments, the pH adjuster may comprise a cyclic amine. In some embodiments, the cyclic amine comprises a cyclic amine of formula (I):

[0037] [ka]

[0038] In the formula, n is 1, 2, or 3; m is 1, 2, or 3; R1 to R 10 are each independently H, C1-C6 alkyl, or aryl; L is -O-, -S-, -N(R a )- or -C(R a R b )- and R a and R b are each independently H, C1-C6 alkyl, or aryl; R 11 is either H or R a Along with L and R11 forms a second bond with the C atom to which it is bonded.

[0039] In some embodiments, L in Formula (I) is —N(R a )-. In such embodiments, n can be 2; m can be 1 or 3; R1 to R 10 can be H; R 11 is R a Along with L and R 11 A second bond can be formed between the carbon atom to which the amine is attached. Examples of such amines include 1,8-diazabicyclo[5.4.0]-7-undecene (DBU;

[0040] [ka]

[0041] ) and 1,5-diazabicyclo[4.3.0]-5-nonene (DBN;

[0042] [ka]

[0043] ) are listed.

[0044] In some embodiments, L in Formula (I) is —C(R a R b )-. In such embodiments, n can be 2; m can be 2, and R1-R 11 can each be H. An example of such an amine is octahydro-2H-quinolizine (

[0045] [ka]

[0046] )

[0047] Without wishing to be bound by any particular theory, it is believed that the cyclic amines or alkanolamines described herein reduce the corrosive effect of the cleaning compositions by adjusting the pH of the cleaning compositions, reducing the surface roughness of semiconductor substrates treated with the cleaning compositions, and slowing the etch rate of such cleaning compositions against exposed substrate materials that are not intended to be removed during the cleaning process (e.g., exposed metal or dielectric materials such as Co or WBx).

[0048] In some embodiments, cleaning compositions of the present disclosure may include water. Preferably, the water is deionized, ultra-pure, and free of organic contaminants, and has a minimum resistance of about 4 to about 17 MΩ. More preferably, the water has a resistance of at least 17 MΩ.

[0049] In some embodiments, water can comprise at least about 55% by weight (e.g., at least about 60% by weight, at least about 65% by weight, at least about 70% by weight, at least about 72% by weight, at least about 75% by weight, at least about 76% by weight, at least about 78% by weight, at least about 80% by weight, at least about 82% by weight, at least about 84% by weight, at least about 85% by weight, at least about 86% by weight, at least about 88% by weight, or at least about 90% by weight) of the cleaning compositions of the present disclosure and / or at most about 98% by weight (e.g., at most about 97% by weight, at most about 96% by weight, at most about 95% by weight, at most about 94% by weight, at most about 93% by weight, at most about 92% by weight, at most about 91% by weight, or at most about 90% by weight).

[0050] In some embodiments, the cleaning compositions of the present disclosure may optionally contain at least one (e.g., two, three, four, or more) water-soluble organic solvent selected from the group consisting of water-soluble alcohols, water-soluble ketones, water-soluble esters, and water-soluble ethers (e.g., glycol diethers).

[0051] Classes of water-soluble alcohols include, but are not limited to, alkanediols (including, but not limited to, alkylene glycols), glycols, alkoxyalcohols (including, but not limited to, glycol monoethers), saturated aliphatic monohydric alcohols, unsaturated non-aromatic monohydric alcohols, and low molecular weight alcohols with cyclic structures. Examples of water-soluble alkanediols 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. Examples of water-soluble alkylene glycols include, but are not limited to, ethylene glycol, propylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, and tetraethylene glycol.

[0052] Examples of water-soluble alkoxy alcohols include, but are not limited to, 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 1-methoxy-2-butanol, and water-soluble glycol ethers such as glycol monoethers. Examples of water-soluble glycol monoethers include, but are not limited to, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-normal propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-normal butyl ether (also referred to as ethylene glycol butyl ether or EGBE), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-normal propyl ether, diethylene glycol mono-normal butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol mono-normal butyl ether, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol, 2-ethoxy-1-propanol, propylene glycol mono-normal propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-normal propyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobenzyl ether, and diethylene glycol monobenzyl ether.

[0053] Examples of water-soluble saturated aliphatic monohydric alcohols include, but are not limited to, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 2-pentanol, t-pentyl alcohol, and 1-hexanol.

[0054] Examples of water-soluble unsaturated non-aromatic monohydric alcohols include, but are not limited to, allyl alcohol, propargyl alcohol, 2-butenyl alcohol, 3-butenyl alcohol, and 4-penten-2-ol.

[0055] Examples of water-soluble low molecular weight alcohols having a cyclic structure include, but are not limited to, tetrahydrofurfuryl alcohol, furfuryl alcohol, and 1,3-cyclopentanediol.

[0056] Examples of water-soluble ketones include, but are not limited to, acetone, cyclobutanone, cyclopentanone, diacetone alcohol, 2-butanone, 2,5-hexanedione, 1,4-cyclohexanedione, 3-hydroxyacetophenone, 1,3-cyclohexanedione, and cyclohexanone.

[0057] Examples of water-soluble esters include, but are not limited to, ethyl acetate; glycol monoesters such as ethylene glycol monoacetate and 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.

[0058] In some embodiments, the at least one organic solvent can be present in the cleaning compositions of the present disclosure in an amount of at least about 0.1 wt.% (e.g., at least about 0.2 wt.%, at least about 0.4 wt.%, at least about 0.5 wt.%, at least about 0.6 wt.%, at least about 0.8 wt.%, at least about 1 wt.%, at least about 1.5 wt.%, at least about 2 wt.%, at least about 2.5 wt.%, at least about 3 wt.%, at least about 5 wt.%, or at least about 10 wt.%) and / or at most about 40 wt.% (e.g., at most about 38 wt.%, at most about 35 wt.%, at most about 30 wt.%, at most about 25 wt.%, at most about 20 wt.%, at most about 15 wt.%, at most about 10 wt.%, at most about 9 wt.%, at most about 8 wt.%, at most about 6 wt.%, at most about 5 wt.%, at most about 4 wt.%, or at most about 3.5 wt.%).

[0059] Without wishing to be bound by any particular theory, it has been unexpectedly discovered that the inclusion of a relatively high amount (e.g., from about 6% to about 36% by weight) of a water-soluble glycol monoether (e.g., ethylene glycol mono-n-butyl ether) in the cleaning compositions described herein can significantly reduce the surface roughness of semiconductor substrates treated with the cleaning compositions.

[0060] In some embodiments, cleaning compositions of the present disclosure may include hydroxylamine, diethylenetriaminepentaacetic acid, 5-methyl-1H-benzotriazole, 1,8-diazabicyclo[5.4.0]undec-7-ene or monoethanolamine, methanesulfonic acid, and water. In some embodiments, such cleaning compositions may further include ethylene glycol butyl ether.

[0061] In some embodiments, the cleaning composition of the present disclosure comprises: (1) hydroxylamine in an amount of about 0.1% to about 5% (e.g., about 0.5% to about 2%) by weight of the composition; (2) diethylenetriaminepentaacetic acid in an amount of about 0.01% to about 0.5% (e.g., about 0.1% to about 0.5%) by weight of the composition; (3) 5-methyl-1H-benzotriazole in an amount of about 0.05% to about 1% (e.g., about 0.1% to about 0.5%) by weight of the composition; and (4) a hydroxylamine derivative in an amount of about 0.01% to about 0.5% (e.g., about 0.1% to about 0.5%) by weight of the composition. (4) methanesulfonic acid in an amount of about 1% to about 10% by weight (e.g., about 2% to about 5% by weight) of the composition; (5) 1,8-diazabicyclo[5.4.0]undec-7-ene or monoethanolamine in an amount of about 0.1% to about 3% by weight (e.g., about 0.5% to about 2% by weight) of the composition; and (6) water in an amount of about 75% to about 98% by weight (e.g., about 85% to about 95% by weight) of the composition, wherein the pH of the composition is about 4 to about 7 (e.g., about 4.5 to about 6). In some embodiments, such cleaning compositions may further comprise ethylene glycol butyl ether in an amount of about 0.5% to about 10% by weight (e.g., about 1% to about 5% by weight) of the composition.

[0062] In some embodiments, the cleaning compositions of the present disclosure may include hydroxylamine, diethylenetriaminepentaacetic acid, 5-methyl-1H-benzotriazole, ethylene glycol butyl ether, methanesulfonic acid, and water. In some embodiments, such cleaning compositions do not include a pH adjuster.

[0063] In some embodiments, the cleaning composition of the present disclosure comprises (1) hydroxylamine in an amount from about 0.1% to about 5% by weight (e.g., from about 0.5% to about 2% by weight) of the composition; (2) diethylenetriaminepentaacetic acid in an amount from about 0.01% to about 0.5% by weight (e.g., from about 0.1% to about 0.5% by weight) of the composition; and (3) 5-methyl-1H-benzotriazole in an amount from about 0.05% to about 1% by weight (e.g., from about 0.1% to about 0.5% by weight) of the composition. (4) methanesulfonic acid in an amount of about 1% by weight to about 10% by weight (e.g., about 1% by weight to about 5% by weight) of the composition; (5) ethylene glycol butyl ether in an amount of about 1% by weight to about 40% by weight (e.g., about 3% by weight to about 40% by weight) of the composition; and (6) water in an amount of about 55% by weight to about 98% by weight (e.g., about 55% by weight to about 95% by weight) of the composition, and the pH of the composition is about 4 to about 7 (e.g., about 4.5 to about 6.5).

[0064] Additionally, in some embodiments, the cleaning compositions of the present disclosure may contain optional additives such as additional pH adjusters, additional corrosion inhibitors, additional organic solvents, surfactants, biocides, and antifoam agents. Examples of suitable antifoam agents include polysiloxane antifoam agents (e.g., polydimethylsiloxane), polyethylene glycol methyl ether polymers, ethylene oxide / propylene oxide copolymers, and glycidyl ether-capped acetylene diol ethoxylates (such as those described in U.S. Patent No. 6,717,019, which is incorporated herein by reference).

[0065] In some embodiments, the cleaning compositions of the present disclosure may specifically exclude one or more additive components (in any combination of two or more). Such components may include polymers, oxygen scavengers, quaternary ammonium compounds (e.g., salts or hydroxides), amines, alkali bases (e.g., NaOH, KOH, LiOH, Mg(OH)2, and Ca(OH)2), surfactants, antifoaming agents, fluoride-containing compounds, silicon-containing compounds (e.g., silicates or silanes (e.g., alkoxysilanes)), 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 chlorate, tetramethylammonium iodate, tetramethylammonium perborate, ammonium persulfate, tetramethyl ... the corrosion inhibitor is selected from the group consisting of: ammonium, tetramethylammonium perchlorate, tetramethylammonium periodate, tetramethylammonium persulfate, urea hydrogen peroxide, and peracetic acid), abrasives, hydroxycarboxylic acids, carboxylic acids and polycarboxylic acids (e.g., those lacking an amino group), cyclic compounds (e.g., cyclic compounds having at least two rings such as substituted or unsubstituted naphthalene or substituted or unsubstituted biphenyl ether), chelating agents, corrosion inhibitors (azole or non-azole corrosion inhibitors), buffers, guanidine, guanidine salts, acids such as organic and inorganic acids (e.g., sulfuric acid, sulfurous acid, nitrous acid, nitric acid, phosphorous acid, phosphoric acid, etc.), pyrrolidone, polyvinylpyrrolidone, metal salts (e.g., metal halides), and catalysts (e.g., metal-containing catalysts).

[0066] The cleaning compositions described herein can be prepared by simply mixing the components together, or by blending two compositions of the kit.

[0067] In some embodiments, the cleaning compositions of the present disclosure are not specifically designed to remove bulk photoresist films from semiconductor substrates. Rather, the cleaning compositions of the present disclosure can be designed to remove all residues after bulk resist removal by dry or wet stripping methods. Thus, in some embodiments, the cleaning methods of the present disclosure are preferably employed after a dry or wet photoresist stripping process. This photoresist stripping process is typically performed after a pattern transfer process, such as an etching or implant process, or to correct mask errors before pattern transfer. The chemical makeup of the residue depends on the process preceding the cleaning step.

[0068] Any suitable dry stripping process can be used to remove bulk resist from a semiconductor substrate. Examples of suitable dry stripping processes include oxygen-based plasma ashing, such as fluorine / oxygen plasma or N2 / H2 plasma; ozone gas phase treatment; fluorine plasma treatment, high-temperature H2 gas treatment (e.g., as described in U.S. Pat. No. 5,691,117, the entire contents of which are incorporated herein by reference). In addition, any conventional organic wet stripping solution known to those skilled in the art can be used to remove bulk resist from a semiconductor substrate.

[0069] A preferred stripping process used in combination with the cleaning method of the present disclosure is a dry stripping process. Preferably, this dry stripping process is an oxygen-based plasma ashing process. This process removes most of the photoresist from a semiconductor substrate by applying an active oxygen atmosphere at high temperature (typically 250°C) under vacuum conditions (i.e., 1 Torr). Organic materials are oxidized by this process and removed with the process gas. However, this process generally does not remove all inorganic or organometallic contaminants from the semiconductor substrate. Subsequent cleaning of the semiconductor substrate with the cleaning composition of the present disclosure is typically required to remove these residues.

[0070] In some embodiments, the present disclosure features a method for cleaning residue from a semiconductor substrate. Such a method can be performed, for example, by contacting a semiconductor substrate containing post-etch and / or post-ash residue with a cleaning composition described herein. The method may further include rinsing the semiconductor substrate with a rinse solvent after the contacting step and / or drying the semiconductor substrate after the rinsing step. In some embodiments, the semiconductor substrate may further include at least one material (e.g., exposed material) or at least one layer of material, wherein the material is selected from the group consisting of Cu, Co, W, boron (B)-doped W, AlOx, AlN, AlOxNy, Ti, TiN, Ta, TaN, TiOx, ZrOx, HfOx, and TaOx.

[0071] In some embodiments, the cleaning method comprises the steps of: (a) providing a semiconductor substrate containing post-etch and / or post-ash residues; (b) contacting the semiconductor substrate with a cleaning composition described herein; (c) rinsing the semiconductor substrate with a suitable rinse solvent; and (d) optionally drying the semiconductor substrate by any suitable means that removes the rinse solvent and does not compromise the integrity of the semiconductor substrate. In some embodiments, the cleaning method further comprises forming a semiconductor device (e.g., an integrated circuit device such as a semiconductor chip) from the semiconductor substrate obtained by the method.

[0072] In some embodiments, the cleaning method does not substantially remove certain exposed materials on the semiconductor substrate, such as metals (e.g., Co, Cu, W, or B-doped W (WBx)), oxides (e.g., aluminum oxide (AlOx or Al2O3), silicon oxide (SiOx), zirconium oxide (ZrOx)), nitrides (e.g., TiN or SiN), and polysilicon. For example, in some embodiments, the method removes about 5% or less by weight (e.g., about 3% or less by weight, about 1% or less by weight, about 0.5% or less by weight, or about 0.1% or less by weight) of any of the above materials in the semiconductor substrate.

[0073] Semiconductor substrates cleaned by this method may contain various metal oxides that must be removed in addition to organic and metalorganic residues. Semiconductor substrates are typically composed of silicon; silicon germanium; III-V compounds such as GaAs; or any combination thereof. The semiconductor substrate may also contain exposed integrated circuit structures, such as interconnect features (e.g., metal lines and dielectric materials). Metals and metal alloys used in interconnect features include, but are not limited to, aluminum; aluminum alloyed with copper; copper, titanium, tantalum, cobalt, and silicon; titanium nitride, tantalum nitride, tungsten, and alloys thereof. The semiconductor substrate may also contain layers of interlayer dielectrics, silicon oxide, silicon nitride, silicon carbide, titanium oxide, and carbon-doped silicon oxide.

[0074] The semiconductor substrate can be contacted 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.

[0075] The cleaning composition of the present disclosure can be effectively used at temperatures up to about 90°C (eg, about 25°C to about 80°C, about 30°C to about 60°C, or about 40°C to about 60°C).

[0076] Similarly, cleaning times can vary over a wide range depending on the particular cleaning method and temperature used. When cleaning by an immersion batch process, 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).

[0077] Suitable cleaning times for single wafer processes can range from about 10 seconds to about 5 minutes (eg, 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).

[0078] To further improve the cleaning ability of the cleaning composition of the present disclosure, mechanical agitation means can be employed. Examples of suitable agitation means include circulating the cleaning composition over the substrate; flowing or spraying the cleaning composition over the substrate; and ultrasonic or megasonic agitation during the cleaning process. The orientation of the semiconductor substrate relative to the floor can be at any angle. Horizontal or vertical orientation is preferred.

[0079] The cleaning compositions of the present disclosure can be used in conventional cleaning tools known to those skilled in the art. An important advantage of the cleaning compositions of the present disclosure is that they contain, in whole or in part, relatively non-toxic, non-corrosive, and non-reactive components, making the cleaning compositions stable over a wide range of temperatures and processing times. The cleaning compositions of the present disclosure are chemically compatible with virtually all materials used to construct existing and proposed semiconductor wafer cleaning process tools for batch and single wafer cleaning.

[0080] Following cleaning, the semiconductor substrate may be rinsed with a suitable rinse solvent for about 5 seconds to about 5 minutes, with or without agitation. Examples of suitable rinse solvents include, but are not limited to, deionized (DI) water, methanol, ethanol, isopropyl alcohol, N-methylpyrrolidinone, gamma-butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate. Alternatively, an aqueous rinse with a pH greater than 8 (such as a dilute aqueous ammonium hydroxide solution) can be employed. Preferred examples of rinse solvents include, but are not limited to, a dilute aqueous ammonium hydroxide solution, deionized water, methanol, ethanol, and isopropyl alcohol. The solvent may be applied using a method similar to that used to apply the cleaning compositions described herein. The cleaning composition may be removed from the semiconductor substrate before the rinsing step begins, or may still be in contact with the semiconductor substrate at the start of the rinsing step. Preferably, the temperature used in the rinsing step is between 16°C and 27°C.

[0081] Optionally, the semiconductor substrate is dried after the rinsing step. Any suitable drying means known in the art can be used. Examples of suitable drying means include spin drying, flowing a drying gas over the semiconductor substrate or heating the semiconductor substrate with a heating means such as a hot plate or infrared lamp, Marangoni drying, Rotagoni drying, IPA drying, or any combination thereof. The drying time depends on the particular method used, but is typically between 30 seconds and several minutes.

[0082] In some embodiments, the cleaning compositions described herein can be used to remove metal oxide layers from semiconductor substrates. In some embodiments, the disclosure features a method for treating a semiconductor substrate having a metal layer thereon, the method including: (1) oxidizing the metal layer to form a metal oxide layer; and (2) contacting the metal oxide layer with a cleaning composition described herein to remove the metal oxide layer from the semiconductor substrate. This method is also known as a "metal recess process." In some embodiments, the semiconductor substrate may contain metal-based materials other than a metal layer or a metal oxide layer, and some or all of such metal-based materials may be removed by the oxidation and removal steps described above.

[0083] In some embodiments, the metal layer comprises a single metal or a mixture of metals (e.g., an alloy), hi some embodiments, the metal layer comprises cobalt, ruthenium, molybdenum, copper, tungsten, titanium, aluminum, or alloys thereof.

[0084] In some embodiments, the metal oxide layer comprises an oxide of a single metal or an oxide of a metal alloy. In some embodiments, the metal oxide layer comprises cobalt oxide, ruthenium oxide, molybdenum oxide, copper oxide, tungsten oxide, titanium oxide, or aluminum oxide. In some embodiments, the metal oxide layer may cover at least a portion of the surface of the metal layer, or may cover the entire surface of the metal layer.

[0085] In some embodiments, the metal oxide layer can range from a monolayer to 10 atomic layers. The thickness of a monoatomic metal or metal oxide layer is generally at most about 1 nm (e.g., about 0.3 nm to about 0.4 nm). In some embodiments, the metal oxide layer can have a thickness of at most about 10 nm (e.g., about 3 to about 4 nm).

[0086] In general, the method for performing the oxidation step is not particularly limited and can include liquid treatment and / or gas treatment. In some embodiments, the liquid treatment can include contacting a chemical solution (e.g., an oxidizing chemical solution) with the metal layer on the semiconductor substrate. In some embodiments, the gas treatment can include contacting an oxidizing gas (e.g., ozone or an ozone-containing gas) with the metal layer on the semiconductor substrate, heating the metal layer on the semiconductor substrate in an oxidizing atmosphere (e.g., in oxygen, an oxygen-containing gas, etc.), or performing a plasma treatment on the metal layer on the semiconductor substrate using an oxidizing gas (e.g., an oxygen-containing gas). In some embodiments, two or more of the above-mentioned oxidation methods can be used in combination.

[0087] In some embodiments, the oxidation step includes contacting the metal layer on the semiconductor substrate with a chemical solution capable of oxidizing the metal. In some embodiments, the chemical solution is different from the cleaning compositions described herein. In some embodiments, the chemical solution is selected from the group consisting of water, an aqueous hydrogen peroxide solution, an aqueous ammonia and hydrogen peroxide solution, an aqueous hydrofluoric acid and hydrogen peroxide solution, an aqueous sulfuric acid and hydrogen peroxide solution, an aqueous hydrochloric acid and hydrogen peroxide solution, oxygen-dissolved water, ozone-dissolved water, an aqueous perchloric acid solution, and an aqueous sulfuric acid solution.

[0088] In some embodiments, the aqueous hydrogen peroxide solution comprises hydrogen peroxide in an amount of about 0.5% to about 31% by weight (eg, about 3% to about 15% by weight) of the total weight of the solution.

[0089] In some embodiments, the aqueous solution of ammonia and hydrogen peroxide can be formed by combining an aqueous solution of ammonia, an aqueous solution of hydrogen peroxide, and water in a weight ratio of about 1:1:1 to about 1:3:4.5, where the aqueous solution of ammonia includes 28% ammonia by weight and the aqueous solution of hydrogen peroxide includes 30% hydrogen peroxide by weight.

[0090] In some embodiments, the aqueous solution of hydrofluoric acid and hydrogen peroxide can be formed by mixing aqueous hydrofluoric acid, aqueous hydrogen peroxide, and water in a weight ratio of about 1:1:1 to about 1:3:200, wherein the aqueous hydrofluoric acid solution comprises 49% hydrofluoric acid by weight and the aqueous hydrogen peroxide solution comprises 30% hydrogen peroxide by weight.

[0091] In some embodiments, the aqueous solution of sulfuric acid and hydrogen peroxide can be formed by mixing aqueous sulfuric acid, aqueous hydrogen peroxide, and water in a weight ratio of about 3:1:0 to about 1:1:10, where the aqueous sulfuric acid solution comprises 98% sulfuric acid by weight and the aqueous hydrogen peroxide solution comprises 30% hydrogen peroxide by weight.

[0092] In some embodiments, the aqueous solution of hydrochloric acid and hydrogen peroxide can be formed by combining aqueous hydrochloric acid, aqueous hydrogen peroxide, and water in a weight ratio of about 1:1:1 to about 1:1:30, where the aqueous hydrochloric acid comprises 37% hydrochloric acid by weight and the aqueous hydrogen peroxide comprises 30% hydrogen peroxide by weight.

[0093] In this specification, the description "A:B:C=x:y:z" to "A:B:C=X:Y:Z" satisfies at least one (e.g., two or three) of the ranges "A:B=x:y" to "A:B=X:Y", "B:C=y:z" to "B:C=Y:Z", and "A:C=x:z" to "A:C=X:Z".

[0094] In some embodiments, the oxygen-dissolved water contains oxygen in an amount of about 20 to about 500 ppm by weight based on the total weight of the water.

[0095] In some embodiments, the ozone-dissolved water contains ozone in an amount of about 1 to about 60 ppm by weight based on the total weight of the water.

[0096] In some embodiments, the aqueous perchloric acid solution comprises perchloric acid in an amount of about 0.001% to 60% by weight of the total weight of the solution.

[0097] In some embodiments, the aqueous sulfuric acid solution comprises sulfuric acid in an amount of about 0.001% to 60% by weight of the total weight of the solution.

[0098] In some embodiments, the method of contacting the semiconductor substrate with the chemical solution described herein is not particularly limited and may include immersing the semiconductor substrate in the chemical solution in a tank, spraying the chemical solution onto the semiconductor substrate, flowing the chemical solution over the semiconductor substrate, and combinations thereof.

[0099] In some embodiments, the contact time between the semiconductor substrate and the chemical solution in the oxidation step is about 0.25 minutes to about 10 minutes (e.g., about 0.5 minutes to about 5 minutes), and the temperature of the chemical solution in the oxidation step is about 20°C to about 75°C (e.g., about 20°C to about 60°C).

[0100] In embodiments where gas processing is used, the oxidizing gas (or atmosphere) in contact with the semiconductor substrate to be processed includes an oxygen-containing gas (e.g., dry air or oxygen), an ozone-containing gas (e.g., ozone), and mixtures thereof. In some embodiments, the oxidizing gas may include one or more gases other than those listed above. In some embodiments, the semiconductor substrate to be processed is contacted with an oxygen atmosphere, an ozone atmosphere, or a mixed atmosphere including oxygen and ozone.

[0101] In embodiments in which gas processing is used, the semiconductor substrate may be heated (e.g., from about 40° C. to about 200° C.) in an oxidizing atmosphere (e.g., in the presence of oxygen or ozone) or while the semiconductor substrate is in contact with an oxidizing gas (e.g., oxygen, ozone, or a mixture thereof).

[0102] In some embodiments, the method for contacting the semiconductor substrate with the cleaning composition described herein in the removal step is not particularly limited and may include the same method as the method for contacting the semiconductor substrate with the chemical solution in the oxidation step. In some embodiments, the contact time between the semiconductor substrate and the cleaning composition in the removal step is about 0.25 minutes to about 10 minutes (e.g., about 0.5 minutes to about 5 minutes). In some embodiments, the temperature of the cleaning composition in the removal step is about 20°C to about 75°C (e.g., about 20°C to about 60°C).

[0103] In some embodiments, the metal oxide layer may be partially or completely removed in the removal step. In some embodiments, some or all of the metal layer below the metal oxide layer (e.g., the metal layer exposed to the cleaning composition after the metal oxide layer is removed) may be intentionally or inevitably removed in the removal step. In embodiments in which the processed semiconductor substrate contains metal-based materials other than the metal oxide layer and the metal layer, some or all of the metal-based materials may be intentionally or unavoidably removed. When the metal layer and / or metal-based materials other than the metal layer are not intentionally removed, it is preferable that the amount of the metal layer and / or metal-based materials other than the metal layer that are inevitably removed is small.

[0104] Without wishing to be bound by any particular theory, it is believed that a metal oxide layer has a higher solubility in the cleaning compositions described herein than a metal layer. Also, without wishing to be bound by any particular theory, it is believed that by oxidizing the surface of the metal layer to form a thin metal oxide layer and then using the cleaning compositions described herein to remove the metal oxide layer (thereby removing a portion of the metal layer below the metal oxide layer), only a thin surface of the metal layer contained in the processed semiconductor substrate can be removed (or dissolved).

[0105] In some embodiments, the cleaning composition used in the removal step may be degassed in advance to reduce the amount of dissolved oxygen. Without wishing to be bound by any particular theory, it is believed that the exposed metal layer after removing the metal oxide layer with the cleaning composition may be oxidized by the dissolved oxygen in the cleaning composition to form a new metal oxide layer, and thus this newly formed metal oxide layer can be further removed by the cleaning composition. Therefore, without wishing to be bound by any particular theory, it is believed that reducing the amount of dissolved oxygen in the cleaning composition can suppress the removal of an excessive amount of the metal layer.

[0106] Furthermore, without wishing to be bound by any particular theory, it is believed that the amount of etching of the metal layer can be controlled with high precision by alternately repeating the oxidation step and the removal step. In some embodiments, the oxidation step and the removal step can be alternately performed for at least 1 cycle (e.g., at least 3 cycles or at least 5 cycles) to at most 20 cycles (e.g., at most 15 cycles or at most 10 cycles), where a combination of the oxidation step and the removal step is defined as one cycle.

[0107] In some embodiments, a method for manufacturing an integrated device using the cleaning compositions described herein may include the following steps: First, a layer of photoresist is applied to a semiconductor substrate. The resulting semiconductor substrate may be subjected to a pattern transfer process, such as an etching or implant process, to form an integrated circuit. The photoresist may then be largely removed by a dry or wet stripping method (e.g., an oxygen-based plasma ashing process). Any residue remaining on the semiconductor substrate may then be removed using the cleaning compositions described herein in the above manner. The semiconductor substrate may then be processed to form one or more additional circuits on the substrate, or may be processed to be formed into a semiconductor chip, for example, by assembling (e.g., dicing and bonding) and packaging (e.g., chip encapsulation).

[0108] The contents of all publications (eg, patents, patent application publications, and articles) cited herein are hereby incorporated by reference in their entirety. [Example]

[0109] The present disclosure will be described in more detail with reference to the following examples, which are for illustrative purposes only and should not be construed as limiting the scope of the present disclosure. The percentages given are by weight (wt%) unless otherwise specified. Controlled stirring during testing was performed at 300 rpm with a 1-inch stir bar unless otherwise specified.

[0110] General Procedure 1 Blend of ingredients Samples of the cleaning composition were prepared by adding the remaining ingredients of the formula to the calculated amount of organic solvent with stirring. After a homogeneous solution was obtained, optional additives (if used) were added.

[0111] General Procedure 2 Cleaning evaluation by beaker test Cleaning of PER (post-etch residue) from substrates was performed with the described cleaning compositions using multilayer semiconductor substrates of photoresist / TiOx / SiN / Co / ILD (ILD = interlayer dielectric) or photoresist / TiOx / SiN / W / WBx / ILD, which had been lithographically patterned and etched in a plasma metal etcher, followed by oxygen plasma ashing to completely remove the top layer of photoresist.

[0112] The test coupons were held in 4-inch long plastic locking tweezers, allowing them to be suspended in a 500 ml beaker containing approximately 200 milliliters of the cleaning composition of the present disclosure. Prior to immersion, the cleaning composition was preheated to the desired test temperature (typically 40°C or 70°C) with controlled agitation. The coupons, still held in the plastic tweezers, were then placed in the heated cleaning composition with the PER layer-containing side facing the stir bar to conduct the cleaning test. The coupons were allowed to rest in the cleaning composition for a period of time (typically 2-5 minutes) while the cleaning composition was maintained at the test temperature with controlled agitation. After the desired cleaning time, the coupons were quickly removed from the cleaning composition and placed in a 500 ml plastic beaker filled with approximately 400 ml of deionized water at ambient temperature (17°C or below) and gently agitated. The coupons were then left in the beaker of deionized water for approximately 15 seconds, quickly removed, and rinsed with isopropanol for approximately 30 seconds. The coupons were immediately exposed to a stream of nitrogen gas from a handheld nitrogen blow gun, which blew any liquid droplets off the coupons and further dried the coupon device surfaces completely. Following this final nitrogen drying step, the coupons were removed from the plastic tweezers holder and placed device-side up in a lidded plastic carrier for short-term storage. Scanning electron microscope (SEM) images were then collected for key features of the cleaned test coupon device surfaces.

[0113] General Procedure 3a Beaker test for material compatibility evaluation Blanket Co on silicon substrates, W on silicon substrates, B-doped W (WBx) on silicon substrates, SiO2 on silicon substrates, SiN on silicon substrates, AlOx on silicon substrates, and TiN on silicon substrates were diced into approximately 1-inch by 1-inch square test coupons for material compatibility testing. The test coupons were first measured for thickness or sheet resistance using a CDE Resmap 273 four-point probe for metal films (Co, W, and WBx) or by ellipsometry using a Woollam M-2000X for dielectric films (SiO2, AlOx, SiN, and TiN). The test coupons were then mounted in 4-inch long plastic locking tweezers and treated for 10 minutes with the side of the coupon containing the Co, W, WBx, SiO2, AlOx, SiN, or TiN layer facing the stir bar, as described in General Procedure 2 for the cleaning procedure.

[0114] After a final nitrogen drying step, the coupons were removed from the plastic tweezers holder and placed in a plastic carrier with a lid. The post thickness or sheet resistance of the post-processed test coupon surface was then collected by a CDE Resmap 273 four-point probe for metal films (Co, W, and WBx) or by ellipsometry using a Woollam M-2000X for dielectric films (SiO2, AlOx, SiN, and TiN).

[0115] General procedure 3b Digital Etching Process Using the Beaker Test The blanket Co on the silicon substrate was diced to produce approximately 1-inch by 1-inch square test coupons for the digital etching process. The test coupons were first measured for thickness or sheet resistance using a CDE Resmap 273 four-point probe. The test coupons were then attached to 4-inch long plastic locking tweezers and treated similarly to the cleaning procedure described in General Procedure 2, except that the test coupons were subjected to five cycles of the following: (1) 40°C deionized water for 30 seconds, (2) 25°C cleaning composition for 30 or 60 seconds, and (3) deionized water rinse. After completing the five cycles, the coupons were immediately exposed to a stream of nitrogen gas from a handheld nitrogen blow gun to thoroughly dry the coupon device surface.

[0116] After the nitrogen drying step, the coupons were removed from the plastic tweezers holder and placed in a plastic carrier with a lid. The post thickness or sheet resistance of the post-processed test coupon surface was then collected for Co films using a CDE Resmap 273, a four-point probe.

[0117] [Example 1]

[0118] Formulation Examples 1 to 7 (FE-1 to FE-7) were prepared according to General Procedure 1 and evaluated according to General Procedures 2 and 3a. The formulations are summarized in Table 1, and the cleaning results and etch rates (ER) (Å / min) for Co, W, B-doped W (WBx), TiN, SiO2, AlOx, and SiN are summarized in Table 2. The results in Table 2 were obtained within cleaning times of 10 to 30 minutes at a cleaning temperature of 21°C.

[0119] [Table 1]

[0120] HA = hydroxylamine; EGBE = ethylene glycol butyl ether; DTPA = diethylenetriaminepentaacetic acid; 5MBTA = 5-methyl-1H-benzothiazole; BTA = benzothiazole; MEA = monoethanolamine; DBU = 1,8-diazabicyclo[5.4.0]-7-undecene; MSA = methanesulfonic acid.

[0121] [Table 2]

[0122] ER = etch rate; N / A = not applicable.

[0123] As shown in Tables 1 and 2, formulations FE-1 to FE-6 (containing monoethanolamine or DBU as a pH adjuster) exhibited excellent compatibility (i.e., relatively low etch rates) with at least both Co and WBx to which they may be exposed in the cleaning process, while formulation FE-7 (not containing monoethanolamine or DBU) exhibited a relatively high etch rate with WBx.

[0124] [Example 2]

[0125] Formulation Examples 8 to 12 (FE-8 to FE-12) were prepared according to General Procedure 1. "Co ER" and "WBx ER" were evaluated according to General Procedure 3a. Digital etch loss for Co was evaluated according to General Procedure 3b.

[0126] The formulations and etching results for Co and WBx are summarized in Table 3 and shown in Figure 1. Results were obtained at a cleaning temperature of 25°C.

[0127] [Table 3]

[0128] As shown in Table 3, formulations FE-8 to FE-12 exhibited somewhat higher Co etching rates as the amount of EGBE increased from 3 wt% to 36 wt%. Also, as shown in Figure 1, formulations FE-8 to FE-12 exhibited significantly reduced surface roughness as the amount of EGBE increased from 3 wt% to 36 wt%.

[0129] Other embodiments are within the scope of the following claims. The present application also includes the following aspects. [Section 1] 1) at least one redox agent; 2) at least one chelating agent which is a polyaminopolycarboxylic acid; and 3) at least one corrosion inhibitor which is a substituted or unsubstituted benzotriazole; and 4) at least one sulfonic acid; 5) Water, 1. A cleaning composition comprising: [Section 2] Item 1, wherein the at least one redox agent comprises hydroxylamine. [Section 3] Item 2. The composition according to Item 1, wherein the at least one redox agent is present in an amount of about 0.1% by weight to about 5% by weight of the composition. [Section 4] Item 2. The composition according to item 1, wherein the polyaminopolycarboxylic acid is selected from the group consisting of mono- or polyalkylenepolyaminepolycarboxylic acids, polyaminoalkanepolycarboxylic acids, polyaminoalkanolpolycarboxylic acids, and hydroxyalkyletherpolyaminepolycarboxylic acids. [Section 5] Item 5. The composition according to item 4, wherein the polyaminopolycarboxylic acid is diethylenetriaminepentaacetic acid. [Section 6] Item 2. The composition according to Item 1, wherein the polyaminopolycarboxylic acid is present in an amount of about 0.01% by weight to about 0.5% by weight of the composition. [Section 7] Item 1, wherein the at least one corrosion inhibitor comprises a benzotriazole optionally substituted with at least one substituent selected from the group consisting of an alkyl group, an aryl group, a halogen group, an amino group, a nitro group, an alkoxy group, and a hydroxy group. [Section 8] Item 8. The composition of item 7, wherein the at least one corrosion inhibitor comprises 5-methyl-1H-benzotriazole. [Section 9] Item 2. The composition according to item 1, wherein the at least one corrosion inhibitor is present in an amount of about 0.05% to about 1% by weight of the composition. [Section 10] Item 2. The composition according to item 1, wherein the at least one sulfonic acid comprises a sulfonic acid represented by formula (I): R-SO 3 H (I) (Wherein R is C 1 -C 12 Alkyl group, C 1 -C12 is a cycloalkyl group or an aryl group, 1 -C 12 Alkyl group, C 1 -C 12 The cycloalkyl group or aryl group may contain halogen, OH, NH 2 , NO 2 , COOH, C 1 -C 12 Cycloalkyl group, optionally substituted with halogen 1 -C 12 It may be substituted with at least one substituent selected from the group consisting of an alkoxy group and an aryl group optionally substituted with OH. [Section 11] Item 11. The composition of item 10, wherein the at least one sulfonic acid comprises methanesulfonic acid. [Section 12] Item 2. The composition according to item 1, wherein the at least one sulfonic acid is about 1% by weight to about 10% by weight of the composition. [Section 13] Item 1. The composition according to item 1, further comprising at least one pH adjuster, wherein the pH adjuster is a base that does not contain metal ions. [Section 14] Item 14. The composition according to item 13, wherein the at least one pH adjuster comprises a cyclic amine or an alkanolamine. [Section 15] Item 14. The composition of item 13, wherein the at least one pH adjuster comprises 1,8-diazabicyclo[5.4.0]undec-7-ene or monoethanolamine. [Section 16] Item 14. The composition according to Item 13, wherein the at least one pH adjuster is present in an amount of about 0.1% to about 3% by weight of the composition. [Section 17] Item 2. The composition according to item 1, wherein the water accounts for about 55% to about 98% by weight of the composition. [Section 18] Item 1. The composition according to item 1, further comprising at least one organic solvent selected from the group consisting of water-soluble alcohols, water-soluble ketones, water-soluble esters, and water-soluble ethers. [Section 19] Item 19. The composition of item 18, wherein the at least one organic solvent comprises ethylene glycol butyl ether. [Section 20] Item 19. The composition according to item 18, wherein the at least one organic solvent is about 0.1% by weight to about 40% by weight of the composition. [Section 21] Item 1. The composition according to item 1, having a pH of about 4 to about 7. [Section 22] Item 1. The composition according to item 1, comprising hydroxylamine, diethylenetriaminepentaacetic acid, 5-methyl-1H-benzotriazole, 1,8-diazabicyclo[5.4.0]undec-7-ene, methanesulfonic acid, and water. [Section 23] hydroxylamine in an amount of about 0.1% to about 5% by weight of the composition; diethylenetriaminepentaacetic acid in an amount of about 0.01% to about 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of about 0.05% to about 1% by weight of the composition; methanesulfonic acid in an amount of about 1% to about 10% by weight of the composition; 1,8-diazabicyclo[5.4.0]undec-7-ene in an amount of about 0.1% to about 3% by weight of the composition; and water in an amount of about 75% to about 98% by weight of the composition; pH is about 4 to about 7; Item 23. The composition according to item 22. [Section 24] hydroxylamine in an amount of about 0.5% to about 2% by weight of the composition; diethylenetriaminepentaacetic acid in an amount of about 0.1% to about 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of about 0.1% to about 0.5% by weight of the composition; methanesulfonic acid in an amount of about 2% to about 5% by weight of the composition; 1,8-diazabicyclo[5.4.0]undec-7-ene in an amount of about 0.5% to about 2% by weight of the composition; and water in an amount of about 85% to about 95% by weight of the composition; pH is about 4.5 to about 6. Item 24. The composition according to item 23. [Section 25] Item 23. The composition according to item 22, further comprising ethylene glycol butyl ether. [Section 26] hydroxylamine in an amount of about 0.1% to about 5% by weight of the composition; diethylenetriaminepentaacetic acid in an amount of about 0.01% to about 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of about 0.05% to about 1% by weight of the composition; methanesulfonic acid in an amount of about 1% to about 10% by weight of the composition; 1,8-diazabicyclo[5.4.0]undec-7-ene in an amount of about 0.1% to about 3% by weight of the composition; ethylene glycol butyl ether in an amount of about 0.5% to about 10% by weight of the composition; and water in an amount of about 75% to about 98% by weight of the composition; pH is about 4 to about 7; Item 26. The composition according to item 25. [Section 27] hydroxylamine in an amount of about 0.5% to about 2% by weight of the composition; diethylenetriaminepentaacetic acid in an amount of about 0.1% to about 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of about 0.1% to about 0.5% by weight of the composition; methanesulfonic acid in an amount of about 2% to about 5% by weight of the composition; 1,8-diazabicyclo[5.4.0]undec-7-ene in an amount of about 0.5% to about 2% by weight of the composition; ethylene glycol butyl ether in an amount of about 1% to about 5% by weight of the composition; and water in an amount of about 85% to about 95% by weight of the composition; pH is about 4.5 to about 6. Item 27. The composition according to item 26. [Section 28] Item 1. The composition according to item 1, comprising hydroxylamine, diethylenetriaminepentaacetic acid, 5-methyl-1H-benzotriazole, monoethanolamine, methanesulfonic acid, and water. [Section 29] hydroxylamine in an amount of about 0.1% to about 5% by weight of the composition; diethylenetriaminepentaacetic acid in an amount of about 0.01% to about 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of about 0.05% to about 1% by weight of the composition; methanesulfonic acid in an amount of about 1% to about 10% by weight of the composition; monoethanolamine in an amount of about 0.1% to about 3% by weight of the composition; and water in an amount of about 75% to about 98% by weight of the composition; pH is about 4 to about 7; Item 29. The composition according to item 28. [Section 30] hydroxylamine in an amount of about 0.5% to about 2% by weight of the composition; diethylenetriaminepentaacetic acid in an amount of about 0.1% to about 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of about 0.1% to about 0.5% by weight of the composition; methanesulfonic acid in an amount of about 2% to about 5% by weight of the composition; monoethanolamine in an amount of about 0.5% to about 2% by weight of the composition; and water in an amount of about 85% to about 95% by weight of the composition; pH is about 4.5 to about 6. Item 30. The composition according to item 29. [Section 31] Item 29. The composition according to item 28, further comprising ethylene glycol butyl ether. [Section 32] hydroxylamine in an amount of about 0.1% to about 5% by weight of the composition; diethylenetriaminepentaacetic acid in an amount of about 0.01% to about 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of about 0.05% to about 1% by weight of the composition; methanesulfonic acid in an amount of about 1% to about 10% by weight of the composition; monoethanolamine in an amount of about 0.1% to about 3% by weight of the composition; ethylene glycol butyl ether in an amount of about 0.5% to about 10% by weight of the composition; and water in an amount of about 75% to about 98% by weight of the composition; pH is about 4 to about 7; Item 32. The composition according to item 31. [Section 33] hydroxylamine in an amount of about 0.5% to about 2% by weight of the composition; diethylenetriaminepentaacetic acid in an amount of about 0.1% to about 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of about 0.1% to about 0.5% by weight of the composition; methanesulfonic acid in an amount of about 2% to about 5% by weight of the composition; monoethanolamine in an amount of about 0.5% to about 2% by weight of the composition; ethylene glycol butyl ether in an amount of about 1% to about 5% by weight of the composition; and water in an amount of about 85% to about 95% by weight of the composition; pH is about 4.5 to about 6. Item 33. The composition according to item 32. [Section 34] Item 1. The composition according to item 1, comprising hydroxylamine, diethylenetriaminepentaacetic acid, 5-methyl-1H-benzotriazole, ethylene glycol butyl ether, methanesulfonic acid, and water. [Section 35] hydroxylamine in an amount of about 0.1% to about 5% by weight of the composition; diethylenetriaminepentaacetic acid in an amount of about 0.01% to about 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of about 0.05% to about 1% by weight of the composition; methanesulfonic acid in an amount of about 1% to about 10% by weight of the composition; ethylene glycol butyl ether in an amount of about 1% to about 40% by weight of the composition; and water in an amount of about 55% to about 98% by weight of the composition; pH is about 4 to about 7; Item 35. The composition according to item 34. [Section 36] hydroxylamine in an amount of about 0.5% to about 2% by weight of the composition; diethylenetriaminepentaacetic acid in an amount of about 0.1% to about 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of about 0.1% to about 0.5% by weight of the composition; methanesulfonic acid in an amount of about 1% to about 5% by weight of the composition; ethylene glycol butyl ether in an amount of about 3% to about 40% by weight of the composition; and water in an amount of about 55% to about 95% by weight of the composition; pH is about 4.5 to about 6.5, Item 36. The composition according to item 35. [Section 37] A method for cleaning a semiconductor substrate having post-etching residues and / or post-ashing residues, comprising contacting the semiconductor substrate with the cleaning composition according to any one of items 1 to 36. A method for cleaning residue from a semiconductor substrate. [Section 38] A method for treating a semiconductor substrate having a metal layer on a surface thereof, comprising: oxidizing the metal layer to form a metal oxide layer; A step of removing the metal oxide layer from the semiconductor substrate by contacting the cleaning composition according to any one of items 1 to 36 with the metal oxide layer; A method for processing a semiconductor substrate, comprising: [Section 39] Item 39. The method of item 38, wherein the metal layer comprises cobalt, ruthenium, molybdenum, copper, tungsten, titanium, aluminum, or an alloy thereof. [Section 40] Item 39. The method according to Item 38, wherein the oxidizing step includes contacting the metal layer on the semiconductor substrate with a chemical solution, and the chemical solution is selected from the group consisting of water, an aqueous hydrogen peroxide solution, an aqueous ammonia and hydrogen peroxide solution, an aqueous hydrofluoric acid and hydrogen peroxide solution, an aqueous sulfuric acid and hydrogen peroxide solution, an aqueous hydrochloric acid and hydrogen peroxide solution, oxygen-dissolved water, ozone-dissolved water, a perchloric acid solution, and a sulfuric acid solution. [Section 41] Item 39. The method according to Item 38, wherein the oxidizing step includes contacting an oxidizing gas with the metal layer, heating the metal layer in an oxidizing atmosphere, or subjecting the metal layer to a plasma treatment using an oxidizing gas.

Claims

1. 1) at least one redox agent; 2) at least one chelating agent which is a polyaminopolycarboxylic acid; and 3) at least one corrosion inhibitor which is a substituted or unsubstituted benzotriazole; and 4) at least one sulfonic acid; 5) Water, Including, A cleaning composition having a pH of 4 to 7.

2. The composition of claim 1 , wherein the at least one redox agent comprises a hydroxylamine.

3. 10. The composition of claim 1, wherein the at least one redox agent is from 0.1% to 5% by weight of the composition.

4. 2. The composition of claim 1, wherein the polyaminopolycarboxylic acid is selected from the group consisting of mono- or polyalkylenepolyaminepolycarboxylic acids, polyaminoalkanepolycarboxylic acids, polyaminoalkanolpolycarboxylic acids, and hydroxyalkyletherpolyaminepolycarboxylic acids.

5. The composition of claim 4 wherein the polyaminopolycarboxylic acid is diethylenetriaminepentaacetic acid.

6. The composition of claim 1, wherein the polyaminopolycarboxylic acid is 0.01% to 0.5% by weight of the composition.

7. 10. The composition of claim 1, wherein the at least one corrosion inhibitor comprises a benzotriazole optionally substituted with at least one substituent selected from the group consisting of alkyl groups, aryl groups, halogen groups, amino groups, nitro groups, alkoxy groups, and hydroxy groups.

8. The composition of claim 7, wherein the at least one corrosion inhibitor comprises 5-methyl-1H-benzotriazole.

9. 10. The composition of claim 1, wherein the at least one corrosion inhibitor is 0.05% to 1% by weight of the composition.

10. The composition of claim 1 , wherein the at least one sulfonic acid comprises a sulfonic acid represented by formula (I): R-SO ３ H (I) (Wherein R is C １ -C １２ Alkyl group, C １ -C １２ is a cycloalkyl group or an aryl group, １ -C １２ Alkyl group, C １ -C １２ The cycloalkyl group or the aryl group may be selected from halogen, OH, NH ２ , NO ２ , COOH, C １ -C １２ cycloalkyl group, optionally substituted with halogen; １ -C １２ It may be substituted with at least one substituent selected from the group consisting of an alkoxy group and an aryl group optionally substituted with OH.

11. The composition of claim 10, wherein the at least one sulfonic acid comprises methanesulfonic acid.

12. The composition of claim 1, wherein the at least one sulfonic acid is from 1% to 10% by weight of the composition.

13. 10. The composition of claim 1, further comprising at least one pH adjuster, said pH adjuster being a metal ion-free base.

14. 14. The composition of claim 13, wherein the at least one pH adjuster comprises a cyclic amine or an alkanolamine.

15. 14. The composition of claim 13, wherein the at least one pH adjuster comprises 1,8-diazabicyclo[5.4.0]undec-7-ene or monoethanolamine.

16. The composition of claim 13, wherein the at least one pH adjuster is from 0.1% to 3% by weight of the composition.

17. The composition of claim 1, wherein the water is from 55% to 98% by weight of the composition.

18. The composition of claim 1 , further comprising at least one organic solvent selected from the group consisting of water-soluble alcohols, water-soluble ketones, water-soluble esters, and water-soluble ethers.

19. 20. The composition of claim 18, wherein the at least one organic solvent comprises ethylene glycol butyl ether.

20. 19. The composition of claim 18, wherein the at least one organic solvent is from 0.1% to 40% by weight of the composition.

21. 10. The composition of claim 1 comprising hydroxylamine, diethylenetriaminepentaacetic acid, 5-methyl-1H-benzotriazole, 1,8-diazabicyclo[5.4.0]undec-7-ene, methanesulfonic acid, and water.

22. hydroxylamine in an amount of 0.1% to 5% by weight of the composition; diethylenetriaminepentaacetic acid in an amount of 0.01% to 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of 0.05% to 1% by weight of the composition; methanesulfonic acid in an amount of 1% to 10% by weight of the composition; 1,8-diazabicyclo[5.4.0]undec-7-ene in an amount of 0.1% to 3% by weight of the composition; and water in an amount of 75% to 98% by weight of the composition.

22. The composition of claim 21.

23. hydroxylamine in an amount of 0.5% to 2% by weight of the composition; Diethylenetriaminepentaacetic acid in an amount of 0.1% to 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of 0.1% to 0.5% by weight of the composition; methanesulfonic acid in an amount of 2% to 5% by weight of the composition; 1,8-diazabicyclo[5.4.0]undec-7-ene in an amount of 0.5% to 2% by weight of the composition; and water in an amount of 85% to 95% by weight of the composition; pH is 4.5 to 6; 23. The composition of claim 22.

24. 22. The composition of claim 21, further comprising ethylene glycol butyl ether.

25. hydroxylamine in an amount of 0.1% to 5% by weight of the composition; diethylenetriaminepentaacetic acid in an amount of 0.01% to 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of 0.05% to 1% by weight of the composition; methanesulfonic acid in an amount of 1% to 10% by weight of the composition; 1,8-diazabicyclo[5.4.0]undec-7-ene in an amount of 0.1% to 3% by weight of the composition; ethylene glycol butyl ether in an amount of 0.5% to 10% by weight of the composition; and water in an amount of 75% to 98% by weight of the composition.

25. The composition of claim 24.

26. hydroxylamine in an amount of 0.5% to 2% by weight of the composition; Diethylenetriaminepentaacetic acid in an amount of 0.1% to 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of 0.1% to 0.5% by weight of the composition; methanesulfonic acid in an amount of 2% to 5% by weight of the composition; 1,8-diazabicyclo[5.4.0]undec-7-ene in an amount of 0.5% to 2% by weight of the composition; ethylene glycol butyl ether in an amount of 1% to 5% by weight of the composition; and water in an amount of 85% to 95% by weight of the composition; pH is 4.5 to 6; 26. The composition of claim 25.

27. 10. The composition of claim 1 comprising hydroxylamine, diethylenetriaminepentaacetic acid, 5-methyl-1H-benzotriazole, monoethanolamine, methanesulfonic acid, and water.

28. hydroxylamine in an amount of 0.1% to 5% by weight of the composition; diethylenetriaminepentaacetic acid in an amount of 0.01% to 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of 0.05% to 1% by weight of the composition; methanesulfonic acid in an amount of 1% to 10% by weight of the composition; Monoethanolamine in an amount of 0.1% to 3% by weight of the composition; and water in an amount of 75% to 98% by weight of the composition.

28. The composition of claim 27.

29. hydroxylamine in an amount of 0.5% to 2% by weight of the composition; Diethylenetriaminepentaacetic acid in an amount of 0.1% to 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of 0.1% to 0.5% by weight of the composition; methanesulfonic acid in an amount of 2% to 5% by weight of the composition; Monoethanolamine in an amount of 0.5% to 2% by weight of the composition; and water in an amount of 85% to 95% by weight of the composition; pH is 4.5 to 6; 29. The composition of claim 28.

30. 28. The composition of claim 27, further comprising ethylene glycol butyl ether.

31. hydroxylamine in an amount of 0.1% to 5% by weight of the composition; diethylenetriaminepentaacetic acid in an amount of 0.01% to 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of 0.05% to 1% by weight of the composition; methanesulfonic acid in an amount of 1% to 10% by weight of the composition; Monoethanolamine in an amount of 0.1% to 3% by weight of the composition; ethylene glycol butyl ether in an amount of 0.5% to 10% by weight of the composition; and water in an amount of 75% to 98% by weight of the composition.

31. The composition of claim 30.

32. hydroxylamine in an amount of 0.5% to 2% by weight of the composition; Diethylenetriaminepentaacetic acid in an amount of 0.1% to 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of 0.1% to 0.5% by weight of the composition; methanesulfonic acid in an amount of 2% to 5% by weight of the composition; Monoethanolamine in an amount of 0.5% to 2% by weight of the composition; ethylene glycol butyl ether in an amount of 1% to 5% by weight of the composition; and water in an amount of 85% to 95% by weight of the composition; pH is 4.5 to 6; 32. The composition of claim 31.

33. 10. The composition of claim 1 comprising hydroxylamine, diethylenetriaminepentaacetic acid, 5-methyl-1H-benzotriazole, ethylene glycol butyl ether, methanesulfonic acid, and water.

34. hydroxylamine in an amount of 0.1% to 5% by weight of the composition; diethylenetriaminepentaacetic acid in an amount of 0.01% to 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of 0.05% to 1% by weight of the composition; methanesulfonic acid in an amount of 1% to 10% by weight of the composition; ethylene glycol butyl ether in an amount of 1% to 40% by weight of the composition; and water in an amount of 55% to 98% by weight of the composition.

34. The composition of claim 33.

35. hydroxylamine in an amount of 0.5% to 2% by weight of the composition; Diethylenetriaminepentaacetic acid in an amount of 0.1% to 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of 0.1% to 0.5% by weight of the composition; methanesulfonic acid in an amount of 1% to 5% by weight of the composition; ethylene glycol butyl ether in an amount of 3% to 40% by weight of the composition; and water in an amount of 55% to 95% by weight of the composition; pH is 4.5 to 6.5; 35. The composition of claim 34.

36. contacting a semiconductor substrate having post-etch and / or post-ash residues with the cleaning composition of any one of claims 1 to 35, A method for cleaning residue from a semiconductor substrate.

37. A method for treating a semiconductor substrate having a metal layer on a surface thereof, comprising: oxidizing the metal layer to form a metal oxide layer; removing the metal oxide layer from the semiconductor substrate by contacting the metal oxide layer with the cleaning composition of any one of claims 1 to 35; A method for processing a semiconductor substrate, comprising:

38. 38. The method of claim 37, wherein the metal layer comprises cobalt, ruthenium, molybdenum, copper, tungsten, titanium, aluminum, or alloys thereof.

39. 38. The method of claim 37, wherein the oxidizing step includes contacting the metal layer on the semiconductor substrate with a chemical solution, the chemical solution being selected from the group consisting of water, an aqueous hydrogen peroxide solution, an aqueous ammonia and hydrogen peroxide solution, an aqueous hydrofluoric acid and hydrogen peroxide solution, an aqueous sulfuric acid and hydrogen peroxide solution, an aqueous hydrochloric acid and hydrogen peroxide solution, oxygen-dissolved water, ozone-dissolved water, a perchloric acid solution, and a sulfuric acid solution.

40. 38. The method of claim 37, wherein the oxidizing step comprises contacting the metal layer with an oxidizing gas, heating the metal layer in an oxidizing atmosphere, or subjecting the metal layer to a plasma treatment using an oxidizing gas.

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