Cleaning composition and method of using the same

Abstract

This disclosure relates to cleaning compositions that can be used to clean semiconductor substrates. These cleaning compositions can be used to remove defects resulting from previous processing steps on these semiconductor substrates. These cleaning compositions remove defects / contaminants from semiconductor substrates, thereby preparing the substrates for further processing. The cleaning compositions described herein mainly contain at least one organic acid and at least one organosilane compound.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to U.S. Provisional Application No. 63 / 493,533, filed on 31 March 2023, the contents of which are incorporated herein by reference in their entirety. [Background technology]

[0002] The semiconductor industry is constantly driven to improve chip performance through further miniaturization of devices via process and integration innovations. Chemical mechanical polishing / planarization (CMP) is a powerful technology because it enables many complex integration methods at the transistor level, thereby facilitating an increase in chip density.

[0003] CMP (Chemical Polishing) is a process used to flatten / planarize wafer surfaces by removing material using a surface-based chemical reaction and abrasive-based physical process simultaneously. Generally, the CMP process involves applying a CMP slurry (e.g., an aqueous chemical formulation) to the wafer surface while bringing the wafer surface into contact with a polishing pad and moving the polishing pad across the wafer. The slurry typically contains abrasive components and dissolved chemical components, which can vary significantly depending on the material present on the wafer (e.g., metals, metal oxides, metal nitrides, dielectric materials such as silicon oxide and silicon nitride, etc.) that will interact with the slurry and polishing pad during the CMP process.

[0004] After CMP (Chemical Polishing), various contaminants may be present on the surface of the polished wafer. These contaminants may include, for example, abrasive particles from the CMP slurry, organic residues from the pad or slurry components, and substances removed from the wafer during the CMP process. If these contaminants remain on the surface of the polished wafer, they can lead to failures and / or degraded device performance during further wafer processing steps. Figure 1 shows four different defect mode types after CMP polishing: scratches, residual abrasives, organic particles in the blob, and organic particles in the dust.

[0005] Therefore, contaminants must be effectively removed so that the wafer can undergo predictable further processing and / or achieve optimal device performance. The process of removing these post-polishing contaminants or residues from the wafer surface after CMP is called post-CMP cleaning. The formulations used in this post-CMP cleaning process are called post-CMP (P-CMP) cleaning solutions or compositions. These P-CMP cleaning solutions / compositions are intended to solubilize defects remaining on the wafer surface after the CMP process, thereby removing these defects and cleaning the wafer surface for further processing.

[0006] The post-CMP cleaning process can be performed in a brush box (containing brushes for mechanical action) or a megasonic (advanced ultrasonic / sonic treatment for mechanical action) attached as an attachment / module to the CMP polishing tool. To initiate the P-CMP cleaning process, the brush box or megasonic is filled with the P-CMP cleaning composition. Subsequently, after the CMP polishing process is complete, the CMP polished wafer passes through the brush box and / or megasonic within the CMP polishing tool containing the P-CMP cleaning composition. In the best-case scenario, the wafer is subjected to chemical action by the post-CMP cleaning composition and scrubbing mechanical action by brushing and / or ultrasonic treatment, and then dried and cleaned with very few defects. [Overview of the project]

[0007] In semiconductor chip manufacturing, defects on the wafer surface are crucial to wafer yield. A typical wafer goes through approximately 1000 processes before the chip is fabricated and individual dies are cut from the wafer. Defects are monitored before and after each of these processes. CMP (Chemical Polishing) is a critical step in chip manufacturing. However, the CMP process results in many defects after the polishing process (see Figure 1). Therefore, after the CMP polishing process, post-CMP (P-CMP) cleaning compositions are typically applied to the wafer surface to reduce defects.

[0008] This disclosure features novel P-CMP cleaning compositions that not only reduce wafer defects but also provide a variety of other desirable electrochemical attributes important for chip manufacturing. For example, these P-CMP cleaning compositions not only reduce defects (thus increasing yield) but also minimize galvanic corrosion (or other forms of corrosion) when metals, metal oxides, and metal nitrides come into contact with each other on patterned wafers.

[0009] This disclosure relates to cleaning compositions that can be used to clean semiconductor substrates (e.g., wafers). For example, these cleaning compositions can be used to remove defects resulting from previous processing steps on these semiconductor substrates, such as CMP. In particular, these cleaning compositions remove defects / contaminants from semiconductor substrates, thereby preparing the substrates for further processing. The cleaning compositions described herein generally contain an organic acid and at least one organosilane compound and have a pH in the range of 1 to 14.

[0010] In one embodiment, the present disclosure features a cleaning composition comprising at least one first organic acid, at least one organosilane compound, and water, which is substantially free of abrasives.

[0011] In another embodiment, the present disclosure is characterized by a method for cleaning a substrate surface, comprising contacting a substrate having a surface containing SiN, SiC, TiN, W, Ru, Mo, TEOS, Cu, TaN, Co, silicon oxycarbide, or p-Si with a cleaning composition described herein.

[0012] In another embodiment, the present disclosure features a method for cleaning a substrate, comprising contacting the substrate with a cleaning composition described herein.

[0013] This summary is provided to introduce a selection of concepts that will be further explained in the detailed description below. This summary is not intended to identify any significant or essential features of the claimed subject matter, nor is it intended to be used to help limit the scope of the claimed subject matter. [Brief explanation of the drawing]

[0014] [Figure 1] This figure shows examples of various types of defects encountered before and after post-CMP cleaning using a post-CMP cleaner. The four defect modes shown (scratch, residual abrasive, and organic particles (blobs and dust)) primarily contribute to the total total defect count (TDC) observed on the wafer. Defect images were collected using the Applied Materials SEMVision G5 SEM tool. [Modes for carrying out the invention]

[0015] Embodiments disclosed herein generally relate to cleaning compositions and methods for cleaning substrates (e.g., semiconductor substrates such as wafers) using such compositions. In particular, cleaning compositions can be used to clean substrates after a CMP process. However, the cleaning compositions described herein can also be used to remove residues and / or contaminants from the substrate surface after an etching process, an ashing process, or a plating process.

[0016] As defined herein, residues and / or contaminants may include components present in the CMP polishing composition used to polish the substrate to be cleaned (e.g., abrasives, molecular components, polymers, acids, bases, salts, surfactants, etc.), compounds generated during the CMP process as a result of chemical reactions between the substrate and the polishing composition and / or between components of the polishing composition, polishing pad polymer particles, polishing by-products, organic or inorganic residues (derived from the CMP slurry or CMP pad), substrate (or wafer) particles released during the CMP process, and / or any other removable substances known to accumulate on the substrate after the CMP process.

[0017] In one or more embodiments, the cleaning compositions described herein comprise (1) at least one first organic acid, (2) at least one organosilane compound, and (3) a solvent (e.g., water). In one or more embodiments, the cleaning compositions of the present disclosure may comprise about 0.00001% to about 50% by weight (e.g., about 0.01% to about 5%) of at least one first organic acid, about 0.0001% to about 20% by weight (e.g., about 0.001% to about 10%) of at least one organosilane compound, and the remaining percentage (e.g., about 60% to about 99.99%) of a solvent (e.g., deionized water).

[0018] In one or more embodiments, the Disclosure provides a concentrated P-CMP cleaning composition that can be diluted with water to obtain a point-of-use (POU) cleaning composition up to 20 times, or up to 50 times, or up to 100 times, or up to 200 times, or up to 400 times, or up to 800 times, or up to 1000 times. In other embodiments, the Disclosure provides a point-of-use (POU) cleaning composition that can be used directly to clean a substrate surface without dilution.

[0019] In one or more embodiments, the POU cleaning composition may comprise about 0.00001% to about 5% by weight of at least one first organic acid (e.g., a polycarboxylic acid) and about 0.0001% to about 5% by weight of at least one organosilane compound. In another embodiment, the POU cleaning composition may comprise about 0.00001% to about 5% by weight of at least one first organic acid (e.g., a polycarboxylic acid), about 0.00001% to about 5% by weight of at least one corrosion inhibitor different from the first organic acid (e.g., an amino acid), and about 0.001% to about 5% by weight of at least one organosilane compound.

[0020] In one or more embodiments, the concentrated P-CMP cleaning composition may comprise about 0.01% to about 50% by weight of at least one first organic acid (e.g., polycarboxylic acid) and about 0.005% to about 20% by weight of at least one organosilane compound. In another embodiment, the concentrated P-CMP cleaning composition may comprise about 0.01% to about 30% by weight of at least one first organic acid (e.g., polycarboxylic acid), about 0.01% to about 20% by weight of at least one corrosion inhibitor different from the first organic acid (e.g., amino acid), and about 0.005% to about 15% by weight of at least one organosilane compound.

[0021] In one or more embodiments, the cleaning compositions described herein may comprise at least one (e.g., two, three, or four) organic acids. As used herein, the term “acid” includes an acid or a salt thereof (e.g., a potassium salt or a sodium salt thereof). In some embodiments, at least one organic acid may be selected from the group consisting of carboxylic acids (e.g., monocarboxylic acids, polycarboxylic acids, and dienoic acids), amino acids, sulfonic acids, phosphoric acids, acrylic acids, and phosphonic acids, or salts thereof.In some embodiments, at least one organic acid is formic acid, gluconic acid, acetic acid, malonic acid, citric acid, propionic acid, malic acid, adipic acid, succinic acid, lactic acid, oxalic acid, hydroxyethylidenediphosphonic acid, 2-phosphono-1,2,4-butanetricarboxylic acid, aminotrimethylenephosphonic acid, hexamethylenediaminetetra(methylenephosphonic acid), bis(hexamethylene)triaminephosphonic acid, aminoacetic acid, peracetic acid, potassium acetate, phenoxyacetic acid, glycine , bicine, diglycolic acid, glyceric acid, tricine, alanine, histidine, valine, phenylalanine, proline, glutamine, aspartic acid, ascorbic acid, glutamic acid, arginine, lysine, tyrosine, benzoic acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), 2,4-pentadienoic acid, 5-phenylpenta-2,4-dienoic acid, 2-hydroxypenta-2,4-dienoic acid, 2,4-hexadienoic acid (sorbic acid), 4,5-Hexadienoic acid, 4,6-Heptadienoic acid, 2,6-Dimethylhepta-2,5-Dienoic acid, (3E,5E)-Hepta-3,5-Dienoic acid, (2E,5Z)-Hepta-2,5-Dienoic acid, Octa-3,5-Dienoic acid, (Z)-3,7-Dimethyl-2,6-Octadienoic acid, 5,7-Nonadienoic acid, (E,Z)-2,4-Decadienoic acid, 2,5-Decadienoic acid, Undecadienoic acid, Dodecadienoic acid, Tridecadienoic acid, Tetradecadienoic acid, Pentadecadienoic acid, He The acid may be selected from the group consisting of xadecadienoic acid, heptadecadienoic acid, (9Z,12E)-octadeca-9,12-dienoic acid, octadeca-10,12-dienoic acid, (10E,15Z)-9,12,13-trihydroxyoctadeca-10,15-dienoic acid, 13(S)-hydroxyoctadeca-9Z,11E-dienoic acid, nonadecadienoic acid, henicosadienoic acid, docosadienoic acid, eicosa-11,14-dienoic acid, salts thereof, and mixtures thereof, or a salt thereof.

[0022] In one or more embodiments, at least one organic acid is included in the composition in an amount from about 0.00001 wt% to about 50 wt% of the cleaning composition. For example, at least one organic acid can be at least about 0.00001 wt% or more (e.g., about 0.00005 wt% or more, about 0.0001 wt% or more, about 0.0005 wt% or more, about 0.001 wt% or more, about 0.005 wt% or more, about 0.01 wt% or more, about 0.05 wt% or more, about 0.1 wt% or more, about 0.5 wt% or more, or about 1 wt% or more) to about 50 wt% or less (e.g., about 45 wt% or less, about 40 wt% or less, about 35 wt% or less, about 30 wt% or less, about 25 wt% or less, about 20 wt% or less, about 15 wt% or less, about 10 wt% or less, about 5 wt% or less, or about 1 wt% or less) of the cleaning composition described herein.

[0023] In one or more embodiments, the cleaning composition described herein can include at least one first organic acid. In some embodiments, at least one first organic acid can be selected from the group consisting of carboxylic acids (e.g., monocarboxylic acids and polycarboxylic acids (e.g., dicarboxylic acids and tricarboxylic acids)), sulfonic acids, phosphoric acids, acrylic acids, peracids, and phosphonic acids. In some embodiments, at least one first organic acid can be an acid selected from the group consisting of formic acid, gluconic acid, acetic acid, malonic acid, citric acid, propionic acid, malic acid, adipic acid, succinic acid, lactic acid, oxalic acid, hydroxyethylidene diphosphonic acid, 2-phosphono-1,2,4-butanetricarboxylic acid, aminotrimethylene phosphonic acid, hexamethylenediamine tetra(methylenephosphonic acid), bis(hexamethylene)triamine phosphonic acid, peracetic acid, phenoxyacetic acid, benzoic acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), and mixtures thereof. In some embodiments, at least one first organic acid can be a tricarboxylic acid (e.g., citric acid). In some embodiments, at least one first organic acid does not include amino acids or dienoic acids.

[0024] In one or more embodiments, at least one first organic acid can be from about 0.00001 wt% or more (e.g., about 0.00005 wt% or more, about 0.0001 wt% or more, about 0.0005 wt% or more, about 0.001 wt% or more, about 0.005 wt% or more, about 0.01 wt% or more, about 0.05 wt% or more, about 0.1 wt% or more, about 0.5 wt% or more, or about 1 wt% or more) to about 50 wt% or less (e.g., about 45 wt% or less, about 40 wt% or less, about 35 wt% or less, about 30 wt% or less, about 25 wt% or less, about 20 wt% or less, about 15 wt% or less, about 10 wt% or less, about 8 wt% or less, about 6 wt% or less, about 5 wt% or less, about 4 wt% or less, about 2 wt% or less, or about 1 wt% or less) of the cleaning composition described herein.

[0025] In one or more embodiments, the cleaning compositions described herein may optionally include at least one second organic acid distinct from at least one first organic acid. In some embodiments, the at least one second organic acid may be a dienoic acid (i.e., an acid containing a diene). In some embodiments, the dienoic acid may have 5 to 22 carbon atoms (e.g., 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22). In some embodiments, the dienoic acid may have 5 to 12 carbon atoms (e.g., 5, 6, 7, 8, 9, 10, 11, or 12). In some embodiments, dienoic acid is 2,4-pentadienoic acid, 5-phenylpenta-2,4-dienoic acid, 2-hydroxypenta-2,4-dienoic acid, 2,4-hexadienoic acid (sorbic acid), 4,5-hexadienoic acid, 4,6-heptadienoic acid, 2,6-dimethylhepta-2,5-dienoic acid, (3E,5E)-hepta-3,5-dienoic acid, (2E,5Z)-hepta-2,5-dienoic acid, octa-3,5-dienoic acid, (Z)-3,7-dimethyl-2,6-octadienoic acid, 5,7-nonadienoic acid, (E,Z)-2,4-decadienoic acid, 2,5-decadienoic acid, These may be carboxylic acids containing dienes, such as undecadienoic acid, dodecadienoic acid, tridecadienoic acid, tetradecadienoic acid, pentadecadienoic acid, hexadecadienoic acid, heptadecadienoic acid, (9Z,12E)-octadeca-9,12-dienoic acid, octadeca-10,12-dienoic acid, (10E,15Z)-9,12,13-trihydroxyoctadeca-10,15-dienoic acid, 13(S)-hydroxyoctadeca-9Z,11E-dienoic acid, nonadecadienoic acid, henicosadienoic acid, docosadienoic acid, eicosa-11,14-dienoic acid, or mixtures thereof.

[0026] In one or more embodiments, at least one second organic acid may be in an amount of about 0.0001% by weight or more (e.g., about 0.0005% by weight or more, about 0.001% by weight or more, about 0.005% by weight or more, about 0.01% by weight or more, about 0.02% by weight or more, about 0.04% by weight or more, or about 0.05% by weight or more) to about 0.5% by weight or less (e.g., about 0.4% by weight or less, about 0.3% by weight or less, about 0.2% by weight or less, about 0.1% by weight or less, about 0.08% by weight or less, about 0.06% by weight or less, about 0.05% by weight or less, about 0.04% by weight or less, about 0.03% by weight or less, about 0.02% by weight or less, about 0.01% by weight or less, or about 0.005% by weight or less) of the cleaning composition described herein.

[0027] While we do not wish to be bound by theory, it is thought that including a second organic acid (e.g., dienoic acid) in the above-mentioned range can improve the inhibition of corrosion of certain metals and metal-containing films (e.g., W, Cu, TaN, or TiN) on the substrate during the post-CMP cleaning process. Furthermore, electrochemical studies of several cleaning compositions containing dienoic acid (e.g., sorbic acid) have shown better metal (e.g., W) corrosion protection than P-CMP compositions that do not contain dienoic acid.

[0028] In one or more embodiments, the cleaning compositions described herein may optionally include at least one (e.g., two or three) corrosion inhibitors, which are amino acids distinct from at least one first organic acid and a second organic acid. Generally, the at least one corrosion inhibitor may be a naturally occurring amino acid or an amino acid that does not exist naturally. In some embodiments, the at least one corrosion inhibitor may be selected from the group consisting of aminocarboxylic acids (e.g., aminoacetic acid), glycine, bicine, tricine, alanine, histidine, valine, phenylalanine, proline, glutamine, aspartic acid, glutamic acid, arginine, lysine, tyrosine, and mixtures thereof.

[0029] In one or more embodiments, at least one corrosion inhibitor may be in an amount of about 0.001% by weight or more (e.g., about 0.005% by weight or more, about 0.01% by weight or more, about 0.05% by weight or more, about 0.1% by weight or more, about 0.5% by weight or more, or about 1% by weight or more) to about 20% by weight or less (e.g., about 18% by weight or less, about 16% by weight or less, about 15% by weight or less, about 14% by weight or less, about 12% by weight or less, about 10% by weight or less, about 8% by weight or less, about 6% by weight or less, about 5% by weight or less, about 4% by weight or less, about 2% by weight or less, about 1% by weight or less, or about 0.5% by weight or less) of the cleaning composition described herein.

[0030] In one or more embodiments, the cleaning composition described herein comprises (1) citric acid and histidine or (2) two organic acids such as citric acid and glycine. In some embodiments, the cleaning composition comprises (1) citric acid, histidine, and sorbic acid, or (2) three organic acids such as citric acid, histidine, and glycine. In some embodiments, the cleaning composition comprises four organic acids (e.g., citric acid, histidine, sorbic acid, and glycine).

[0031] In one or more embodiments, the cleaning composition may comprise at least two or three organic acids (e.g., carboxylic acids, amino acids, and / or dienoic acid). In some embodiments, the first organic acid (e.g., carboxylic acid) is present in an amount of about 0.0005% to about 10% by weight of the cleaning composition described herein. In some embodiments, the second organic acid (e.g., dienoic acid) is present in an amount of about 0.0005% to about 0.5% by weight of the cleaning composition described herein. In some other embodiments, the third organic acid (e.g., amino acid) is present in an amount of about 0.005% to about 5% by weight of the cleaning composition described herein.

[0032] In one or more embodiments, the cleaning compositions described herein may optionally comprise at least one (e.g., two or three) anionic polymers. In one or more embodiments, the at least one anionic polymer may comprise one or more anionic groups, such as carboxylate groups, sulfate groups, and phosphate groups. In one or more embodiments, the at least one anionic polymer is formed from one or more monomers selected from the group consisting of (meth)acrylic acid, maleic acid, acrylic acid, malic acid, methacrylic acid, vinylphosphonic acid, vinyl phosphoric acid, vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, acrylamidopropyl sulfonic acid, and sodium phosphinite. In more specific embodiments, at least one anionic polymer is poly(4-styrenesulfonic acid) (PSSA), polyacrylic acid (PAA), poly(vinylphosphonic acid) (PVPA), poly(2-acrylamido-2-methyl-1-propanesulfonic acid), poly(N-vinylacetamide) (PNVA), anionic poly(methyl methacrylate) (PMMA), anionic polyacrylamide (PAM), polyaspartic acid (PASA), anionic poly(ethylene succinate) (PES), anionic polybutylene succinate (PBS), 2-methyl The following groups may be selected: 2-propenoic acid copolymers having monosodium 2-((1-oxo-2-propenyl)amino)-1-propanesulfonic acid and sodium phosphinite; 2-propenoic acid copolymers having monosodium 2-methyl-2-((1-oxo-2-propenyl)amino)-1-propanesulfonic acid and sodium bisulfite; 2-acrylamido-2-methyl-1-propanesulfonic acid-acrylic acid copolymers; poly(4-styrenesulfonic acid-co-acrylic acid-co-vinylphosphonic acid) terpolymers; and mixtures thereof. While we do not wish to be bound by theory, it is thought that anionic polymers can solubilize hydrophobic abrasives and / or defects on the substrate surface, facilitating their removal during the post-CMP cleaning process.

[0033] In one or more embodiments, at least one anionic polymer may have a weight-average molecular weight in the range of about 250 g / mol or more (e.g., about 500 g / mol or more, about 1,000 g / mol or more, 2,000 g / mol or more, about 5,000 g / mol or more, about 10,000 g / mol or more, about 50,000 g / mol or more, about 100,000 g / mol or more, about 200,000 g / mol or more, or about 250,000 g / mol or more) to about 500,000 g / mol or less (e.g., about 400,000 g / mol or less, about 300,000 g / mol or less, about 200,000 g / mol or less, about 100,000 g / mol or less, or about 50,000 g / mol or less, or about 10,000 g / mol or less). In some embodiments, at least one anionic polymer may have a weight-average molecular weight in the range of about 1,000 g / mol or more to about 10,000 g / mol or less. In some embodiments, at least one anionic polymer may have a weight-average molecular weight in the range of about 2,000 g / mol or more to about 6,000 g / mol or less. In some further embodiments, at least one anionic polymer may have a weight-average molecular weight of about 5,000 g / mol.

[0034] In some embodiments, the cleaning compositions described herein include one anionic polymer such as poly(vinylphosphonic acid), 2-acrylamido-2-methyl-1-propanesulfonic acid-acrylic acid copolymer, or poly(4-styrenesulfonic acid-co-acrylic acid-co-vinylphosphonic acid) terpolymer. In some embodiments, the cleaning compositions described herein include two anionic polymers such as (1) poly(4-styreneylsulfonic acid) and polyacrylic acid or (2) 2-acrylamido-2-methyl-1-propanesulfonic acid-acrylic acid copolymer and poly(acrylic) acid.

[0035] In one or more embodiments, at least one anionic polymer is included in the cleaning composition in an amount of about 0.00001% to about 50% by weight of the cleaning composition. For example, the at least one anionic polymer may be in an amount of about 0.00001% or more by weight of the cleaning composition described herein (e.g., about 0.00005% or more by weight, about 0.0001% or more by weight, about 0.0005% or more by weight, about 0.001% or more by weight, about 0.005% or more by weight, about 0.01% or more by weight, about 0.05% or more by weight, about 0.1% or more by weight, about 0.5% or more by weight, or about 1% or more) to about 50% or less by weight (e.g., about 45% or less by weight, about 40% or less by weight, about 35% or less by weight, about 30% or less by weight, about 25% or less by weight, about 20% or less by weight, about 15% or less by weight, about 10% or less by weight, about 5% or less by weight, or about 1% or less by weight).

[0036] In some embodiments, the cleaning composition may comprise at least two or three anionic polymers. In some embodiments, the first anionic polymer is present in an amount of about 0.0005% to about 50% by weight of the cleaning composition described herein. In some embodiments, the second anionic polymer is present in an amount of about 0.0005% to about 30% by weight of the cleaning composition described herein. In some other embodiments, the third anionic polymer is present in an amount of about 0.0005% to about 10% by weight of the cleaning composition described herein.

[0037] In one or more embodiments, the cleaning compositions described herein may comprise at least one (e.g., two or three) organosilane compounds. In one or more embodiments, the at least one organosilane compound comprises at least one acidic group or a salt thereof. In one or more embodiments, the organosilane compound may be a tetraalkyl orthosilicate (e.g., an unspecified example of an alkoxysilane). In one or more embodiments, the acidic groups on the organosilane compound are chemically different. In one or more embodiments, the organosilane compound includes a nitrogen-containing group (e.g., an amino group, an ammonium group, an amide group, a diamide group, an imide group, or an imidazolyl group), an oxygen-containing group (e.g., a carboxylic acid group, a carboxylate group, an oxyranyl group, an ethyleneoxy group, a polyethyleneoxy group, an ester group, an acid anhydride group, an amide group, a diamide group, an imide group, or an alkoxy group), a sulfur-containing group (e.g., a sulfonate group or a sulfonic acid group), a phosphorus-containing group (e.g., a phosphonate group, a phosphonic acid group, or a phosphinic acid group), or any combination thereof. In one or more embodiments, the organosilane compound includes a phosphonic acid group or a sulfonic acid group. In some non-limiting embodiments, at least one organosilane compound comprises (1) at least one acidic group, an ester thereof, or a salt thereof (e.g., any of those described herein) and (2) at least one alkoxy group (e.g., -OR (where R is a linear or branched alkyl group which may be substituted or unsubstituted, cyclic or acyclic)), an alkyl group (e.g., -R (where R is a linear or branched alkyl group which may be substituted or unsubstituted, cyclic or acyclic)), a hydroxyl group (e.g., -OH or a salt thereof), hydrogen (e.g., -H), a halo group (e.g., -X (where X is fluoro, chloro, bromo, or iodine)), or any combination thereof.In some non-limiting embodiments, at least one organosilane comprises (1) at least one alkyl group (e.g., -R (where R is a linear or branched alkyl group which may be substituted or unsubstituted, cyclic or acyclic)) and (2) a further group selected from the group consisting of an alkoxy group (e.g., -OR (where R is a linear or branched alkyl group which may be substituted or unsubstituted, cyclic or acyclic)), an alkyl group (e.g., -R (where R is a linear or branched alkyl group which may be substituted or unsubstituted, cyclic or acyclic)), a hydroxyl group (e.g., -OH or a salt thereof), hydrogen (e.g., -H), a halo group (e.g., -X (where X is fluoro, chloro, bromo, or iodine)), or any combination thereof. In some non-limiting embodiments, at least one organosilane comprises (1) at least one amino group (e.g., -NR. N1 R N2 or -NR N1 -(R N1 and R N2Each of these independently comprises (1) a H, or a linear or branched alkyl group which may be substituted or unsubstituted, cyclic or acyclic, and (2) a further group selected from the group consisting of an alkoxy group (e.g., -OR (where R is a linear or branched alkyl group which may be substituted or unsubstituted, cyclic or acyclic), an alkyl group (e.g., -R (where R is a linear or branched alkyl group which may be substituted or unsubstituted, cyclic or acyclic), a hydroxyl group (e.g., -OH or a salt thereof), hydrogen (e.g., -H), a halo group (e.g., -X (where X is fluoro, chloro, bromo, or iodine)), or any combination thereof.In one or more embodiments, at least one organosilane compound is tetramethyl orthosilicate (TMOS), tetraethyl orthosilicate (TEOS), potassium methylsilicate, (3-glycidyloxypropyl)trimethoxysilane, triethoxysilylpropoxy(polyethyleneoxy)dodecanoate, (3-triethoxysilyl)propyl succinic anhydride, N-(2-aminoethyl)-3-aminopropyl-trimethoxysilane, ureidopropyltriethoxysilane, trimethylmethoxysilane, N-trimethoxy Silylpropyl-N,N,N-trimethylammonium chloride, dimethyldimethoxysilane, vinyltrimethoxysilane, N-trimethoxysilylpropyl-N,N,N-trimethylammonium halide, 3-aminopropylmethyldiethoxysilane, N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole, N-(6-aminohexyl)aminomethyltriethoxysilane, N-(2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimeth Xysilane, (N,N-diethylaminomethyl)triethoxysilane, N-methylaminopropyltrimethoxysilane, 3-(trihydroxysilyl)propylmethylphosphonate, 3-(trihydroxysilyl)-1-propanesulfonic acid, carboxyethylsilanetriol, (2-diethylphosphatoethyl)triethoxysilane, aminoethylaminopropylsilsesquioxane, [3-(trihydroxysilyl)propyl](methyl)phosphate, (3-aminopropyl)methyldimethoxysilane, (3-aminopropyl) Selected from the group consisting of methylmethoxysilane, (3-aminopropyl)triethoxysilane, (3-aminopropyl)trimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, [3-(diethylamino)propyl]trimethoxysilane, 3-(2-aminoethylamino)propylmethyldimethoxysilane, 3-(trimethylsilyl)-1-propanesulfonic acid, 3-{[dimethyl(3-trimethoxysilyl)propyl]ammonio}propane-1-sulfonate, salts thereof, or combinations thereof.

[0038] In one or more embodiments, at least one organosilane compound is present in an amount of about 0.0001% to 20% by weight of the cleaning composition. For example, at least one organosilane compound may be present in an amount of about 0.0001% or more by weight (e.g., about 0.0005% or more by weight, about 0.001% or more by weight, about 0.005% or more by weight, about 0.01% or more by weight, about 0.05% or more by weight, about 0.1% or more by weight, about 0.5% or more by weight, about 1% or more by weight, about 2.5% or more by weight, or about 3% or more) to about 20% or less by weight (e.g., about 15% or less by weight, about 12.5% ​​or less by weight, about 10% or less by weight, about 7.5% or less by weight, about 5% or less by weight, about 2.5% or less by weight, or about 1% or less by weight) of the cleaning composition described herein.

[0039] In one or more embodiments, the cleaning composition may optionally include at least one (e.g., two or three) pH adjusters selected from the group consisting of lithium hydroxide, potassium hydroxide, sodium hydroxide, cesium hydroxide, ammonium hydroxide, triethanolamine, diethanolamine, monoethanolamine, methylethanolamine, methyldiethanolamine, tetrabutylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, ethyltrimethylammonium hydroxide, diethyldimethylammonium hydroxide, dimethyldipropylammonium hydroxide, benzyltrimethylammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, tris(hydroxymethyl)aminoethane, choline hydroxide, and mixtures thereof.

[0040] In one or more embodiments, at least one pH adjusting agent is present in an amount of about 0.001% by weight or more (e.g., about 0.005% by weight or more, about 0.01% by weight or more, about 0.05% by weight or more, about 0.1% by weight or more, about 0.5% by weight or more, about 1% by weight or more, about 5% by weight or more) to about 15% by weight or less (e.g., about 12.5% ​​by weight or less, about 10% by weight or less, about 7.5% by weight or less, about 5% by weight or less, about 2.5% by weight or less, about 1% by weight or less, or about 0.5% by weight or less) of the cleaning composition described herein.

[0041] In some embodiments, the pH value of the cleaning composition may be in the range of about 14 or less (e.g., 13.5 or less, about 13 or less, about 12.5 or less, about 12 or less, about 11.5 or less, about 11 or less, about 10.5 or less, about 10 or less, about 9.5 or less, about 9 or less, about 8.5 or less, about 8 or less, about 7.5 or less, about 7 or less, about 6.5 or less, about 6 or less, about 5.5 or less, about 5 or less, about 4.5 or less, about 4 or less, about 3.5 or less, about 3 or less, about 2.5 or less, about 2 or less, or about 1.5 or less) to about 1 or more (e.g., about 1.5 or more, about 2 or more, about 2.5 or more, about 3 or more, about 3.5 or more, about 4 or more, about 4.5, or about 5 or more). In one or more embodiments, the pH value of the cleaning composition may be acidic. In one or more embodiments, the pH value of the cleaning composition may be basic. While we do not wish to be bound by theory, it is believed that when the cleaning composition described herein has an acidic pH, it can provide sufficient protons to solubilize organic residues resulting from CMP polishing of substrates and provide sufficient cleaning action to solubilize polishing byproducts containing inert metals (e.g., W, Cu). While we do not wish to be bound by theory, it is believed that when the cleaning composition described herein has an alkaline pH, it can result in some substrate surfaces with superior wetting properties compared to an acidic pH.

[0042] While we do not wish to be bound by theory, it is believed that the cleaning compositions described herein may contain a single chemical or an entire chemical at a much lower concentration / amount than conventional cleaners currently used in the semiconductor industry (e.g., CLEAN-100), and may achieve even better performance (e.g., better cleaning effect on exposed materials on substrates and / or lower corrosion). For example, the cleaning compositions described herein may contain a chemical or a total amount of chemicals that is only about 5-20% by weight (e.g., about 5-15% by weight) of the total amount of chemicals in the same chemical (e.g., organic acid or anionic polymer) or conventional cleaners (e.g., CLEAN-100). As a result, it is believed that the cleaning compositions described herein are more cost-effective, environmentally friendly, and offer a much better overall cost of ownership at point of use (due to their high dilutibility (e.g., up to 200x)) compared to conventional cleaners (e.g., CLEAN-100).

[0043] In one or more embodiments, the cleaning composition described herein includes an organic solvent, a pH adjuster, a quaternary ammonium compound (e.g., salts such as tetraalkylammonium salts and hydroxides such as tetraalkylammonium hydroxides), an alkali base (e.g., an alkali hydroxide), a fluorine-containing compound (e.g., a fluoride compound or a fluorinated compound (e.g., a fluorinated polymer / surfactant)), an organosilane (e.g., those not specifically mentioned herein), a silane, etc. (e.g., an alkoxysilane including TEOS and TMOS, which may include a compound lacking at least one acidic group, its ester, or its salt (e.g., any of those described herein)), or a compound including a further group selected from the group consisting of (1) at least one alkyl group (e.g., -R (R may be substituted or unsubstituted, and may be a linear alkyl or a branched alkyl, which may be cyclic or acyclic)), and (2) an alkoxy group (e.g., -OR (R may be substituted or unsubstituted, and may be a linear or branched alkyl, which may be cyclic or acyclic)), an alkyl group (e.g., -R (R may be substituted or unsubstituted, and may be a linear or branched alkyl, which may be cyclic or acyclic)), a hydroxyl group (e.g., -OH or its salt), hydrogen (e.g., -H), a halo group (e.g., -X (X is fluorine, chlorine, bromine, or iodine)), or any combination thereof; an alkoxysilane; and an aminosilane including aminopropyltriethoxysilane, which may include a compound lacking at least one acidic group, its ester, or its salt (e.g., any of those described herein), or (1) at least one amino group (e.g., -NR N1 R N2 or -NR N1 -(R N1 and R N2(1) each of the following independently is H, or a linear or branched alkyl group which may be substituted or unsubstituted, and which may be cyclic or acyclic: (2) an alkoxy group (e.g., -OR (where R is a linear or branched alkyl group which may be substituted or unsubstituted, and which may be cyclic or acyclic), an alkyl group (e.g., -R (where R is a linear or branched alkyl group which may be substituted or unsubstituted, and which may be cyclic or acyclic), a hydroxyl group (e.g., -OH or a salt thereof), hydrogen (e.g., -H), a halo group (e.g., -X (where X is fluoro, chloro, bromo, or iodine)), or a further group selected from the group consisting of any combination thereof, a silicon-containing aminosilane, nitrogen-containing compound (e.g., amino acids, amines, imines (e.g., 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) and amidines (such as 1,5-diazabicyclo[4.3.0]nona-5-ene (DBN)), amides, or imides), polyols, salts (e.g., halide salts or metal salts), polymers (e.g., cationic polymers, nonionic polymers, anionic polymers, or water-soluble polymers), inorganic acids (e.g., hydrochloric acid, sulfuric acid, phosphoric acid, or nitric acid), surfactants (e.g., cationic surfactants, anionic surfactants, nonpolymeric surfactants, or nonionic surfactants) The cleaning composition may substantially omit one or more of the following specific components: zwitterionic compounds, plasticizers, oxidizing agents (e.g., H2O2 and / or periodic acid), corrosion inhibitors (e.g., azole corrosion inhibitors or non-azole corrosion inhibitors), electrolytes (e.g., polymer electrolytes), dienoic acid (e.g., sorbic acid), and / or abrasives (e.g., polymer abrasives, silica abrasives, ceria abrasives, nonionic abrasives, surface-modifying abrasives, negatively / positively charged abrasives, or ceramic abrasive composites). Halide salts that may be excluded from the cleaning composition include alkali metal halides (e.g., sodium halide or potassium halide) or ammonium halides (e.g., ammonium chloride), and may be fluorides, chlorides, bromides, or iodides.As used herein, the term "substantially absent" from a cleaning composition refers to a component that is not intentionally added to the cleaning composition. In some embodiments, the cleaning compositions described herein may contain one or more of the substantially absent components in the cleaning composition in an amount of up to about 1000 ppm (e.g., up to about 500 ppm, up to about 250 ppm, up to about 100 ppm, up to about 50 ppm, up to about 10 ppm, or up to about 1 ppm). In some embodiments, the cleaning compositions described herein may not contain one or more of the components at all.

[0044] In one or more embodiments, the cleaning compositions described herein may include a biocide. Exemplary biocides include, but are not limited to, isothiazolinones (e.g., benzoisothiazolinone, methylisothiazolinone, and methylchloroisothiazolinone), 2-bromo-2-nitropropane-1,3-diol, hydrogen peroxide, and combinations thereof. In some embodiments, the biocide may be present in an amount of about 1000 ppm or less (e.g., about 500 ppm or less, about 250 ppm or less, about 100 ppm or less, about 50 ppm or less, or about 10 ppm or less) to about 1 ppm or more of the cleaning composition described herein.

[0045] When applied to post-CMP cleaning operations, the cleaning compositions described herein can be usefully used to remove contaminants present on the substrate surface after the CMP treatment process. In one or more embodiments, the contaminants causing defects may be at least one selected from the group consisting of abrasives, particles, organic residues, polishing by-products, slurry by-products, slurry-induced organic residues, inorganic polished substrate residues, pad debris, and polyurethane residues. In one or more embodiments, the cleaning compositions of the present disclosure can be used to remove organic residues consisting of organic particles that are insoluble in water and therefore remain on the substrate surface after the CMP polishing process. In other embodiments, the cleaning compositions of the present disclosure can be used to remove abrasive residues / particles and / or polishing by-products, thereby reducing scratches that cause defects on the substrate surface after the CMP polishing process.

[0046] While we do not wish to be bound by theory, organic particles are thought to originate from components of the polishing composition that deposit on the substrate surface after polishing, are insoluble, and therefore remain on the substrate surface as contaminants. The presence of these contaminants causes a defect count on the substrate surface. These defect counts, when analyzed with a defect measurement tool (such as KLA Company's AIT-XUV tool), contribute to the total defect count (TDC), which is the sum of all individual defect counts. In one or more embodiments, the cleaning compositions described herein remove about 30% or more (e.g., about 50% or more, about 75% or more, about 80% or more, about 90% or more, about 95% or more, about 98% or more, about 99% or more, about 99.5% or more, or about 99.9% or more) to about 100% of the total defect count (TDC) remaining on the substrate surface after the polishing / CMP process. The removal of TDC from the substrate surface by the post-CMP cleaning composition is referred to as the cleaning effect of the cleaning composition and is expressed as a percentage. The higher the percentage, the better the cleaning effect, and the more effective / stronger / better the cleaning composition.

[0047] While we do not wish to be bound by theory, we believe there are surprising and unexpected synergistic effects with the components of the cleaning compositions described herein. For example, organic acids can reduce scratches and solubilize metal oxide and silica-containing residues (e.g., abrasive residues on wafers) that can cause scratches; amino acids can act as corrosion inhibitors for metals (e.g., tungsten); and anionic polymers are excellent solubilizers for hydrophobic organic residues remaining on the substrate surface after the CMP process. Furthermore, combinations of tricarboxylic acid organic acids (e.g., citric acid) and dienoic acid (e.g., sorbic acid), along with amino acids (e.g., histidine or glycine) and anionic polymers, optionally, show a significant reduction in metal galvanic corrosion, which is considered key to improving the yield of substrates cleaned after the CMP process.

[0048] In some embodiments, the disclosure features a method for cleaning a substrate (e.g., a wafer). The method may include contacting the substrate with a cleaning composition described herein. In post-CMP cleaning applications, the cleaning composition can be applied to the substrate to be cleaned in any suitable manner. For example, the cleaning composition can be used in conjunction with a wide variety of conventional cleaning tools and techniques (e.g., brush scrubbing, spin rinse drying, etc.). In one or more embodiments, after the CMP polishing process, the cleaning composition described herein can be used in the Brush Box 1 or Brush Box 2 of the Megasonic cleaner module or the Applied Materials Reflexion 300mm CMP polishing tool. The Brush Box has brushes for scrubbing action, while the cleaning composition provides a chemical action for removing defects. The cleaning composition can be applied to the substrate surface in the brush box or Megasonic for a time ranging from about 5 seconds to about 10 minutes (e.g., about 15 seconds to 5 minutes) at a temperature ranging from 20°C to 60°C.

[0049] In addition to the brush box and / or megasonic cleaner, the cleaning compositions described herein can be used as abrasive-free buffing chemicals for platen buffing of substrates on a CMP polisher to remove defects by buffing a substrate on a soft pad in the presence of the cleaning composition on the polishing pad. In a more specific embodiment, the cleaning composition can be used in a buffing station to buff on a soft poultic pad in the buffing station module of a 4-platen Applied Materials Reflexion Prime 300mm CMP polishing tool.

[0050] In some embodiments, the substrate to be cleaned may contain at least one substance selected from the group consisting of low-k dielectrics (e.g., porous silicon oxide with k < 3.5), ultra-low-k dielectrics (e.g., superporous silicon oxide with k < 2.5), tungsten, titanium nitride, tantalum nitride, silicon carbide, silicon oxide (e.g., TEOS), silicon nitride, copper, cobalt, molybdenum, ruthenium, Black Diamond (which may include silicon oxycarbide (e.g., SiOC, SiOC(H), or carbon-doped silica)), and polysilicon (p-Si)) on the substrate surface that may be exposed to the cleaning composition during the cleaning process.

[0051] In some embodiments, a method using the cleaning compositions described herein may further include manufacturing a semiconductor device from a substrate treated with the cleaning composition through one or more steps. For example, a semiconductor device can be manufactured from a substrate treated with the cleaning composition described herein using photolithography, ion implantation, dry / wet etching, plasma etching, vapor deposition (e.g., PVD, CVD, ALD, ECD), wafer mounting, die cutting, packaging, and testing.

[0052] Although only a few exemplary embodiments have been described in detail below, those skilled in the art will readily understand that many modifications are possible in subsequent exemplary embodiments without substantially departing from the present invention. Accordingly, all such modifications are intended to be within the scope of this disclosure as defined in the claims. [Examples]

[0053] Examples are provided to further illustrate the capabilities of the CMP post-cleaning compositions and methods of this disclosure. The examples provided are not intended to limit the scope of this disclosure and should not be construed as such. Unless otherwise specified, all percentages listed are by weight (wt%). The examples shown herein are representative and do not encompass the full and broad scope of the disclosure of the present invention.

[0054] Example 1: Demonstration of defect reduction and post-CMP cleaning effect of the CMP post-cleaning composition of the present invention. In this example, a blanket wafer having a TEOS, polysilicon, copper, silicon nitride, or cobalt film was first polished by CMP using a polishing composition for either copper polishing or barrier film polishing. After polishing, the wafer was then subjected to a P-CMP cleaning operation using the post-CMP cleaning composition of the comparative example. The total defect count (TDC) on the wafer at this stage was then measured to obtain an initial baseline value. The polished and cleaned wafer was then subjected to a second polishing by CMP using a polishing composition for either copper polishing or barrier film polishing. The twice-polished wafer was then subjected to a P-CMP cleaning operation using the cleaning composition of the present invention according to the present disclosure. A typical formulation of the cleaning composition of the present invention according to the present disclosure tested in this example is shown in Table 1 below. The post-CMP cleaning composition of the comparative example used the same components as shown in Table 1 below, except that it did not contain any organosilane compounds, in relatively the same amounts. [Table 1]

[0055] The cleaning efficiency value was reached by using the formula: Cleaning efficiency = [(Baseline TDC - Post TDC) / Baseline TDC)], comparing the total number of defects on the wafer at this stage, called the "post" value, with the initial baseline value. The results are summarized in Table 2 below. [Table 2]

[0056] The results in Table 2 show that both cleaning compositions in this disclosure significantly improved the cleaning of blanket wafers with various films compared to the cleaning compositions of the comparative examples. This improvement in cleaning efficiency can lead to improved device yield and reduced waste when manufacturing semiconductor devices.

[0057] While this disclosure describes examples as set forth herein, it is understood that other modifications and variations are possible without departing from the spirit and scope of this disclosure as defined in the appended claims.

Claims

1. A cleaning composition, At least one first organic acid; At least one organosilane compound; and Contains water; Substantially free of abrasives, composition.

2. The at least one first organic acid includes a monocarboxylic acid or a polycarboxylic acid. The composition according to claim 1.

3. The at least one first organic acid is selected from the group consisting of formic acid, acetic acid, malonic acid, citric acid, propionic acid, malic acid, adipic acid, succinic acid, aspartic acid, ascorbic acid, lactic acid, oxalic acid, hydroxyethylidenediphosphonic acid, 2-phosphono-1,2,4-butanetricarboxylic acid, aminotrimethylenephosphonic acid, hexamethylenediaminetetra(methylenephosphonic acid), bis(hexamethylene)triaminephosphonic acid, peracetic acid, phenoxyacetic acid, benzoic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and mixtures thereof. The composition according to claim 1.

4. The at least one first organic acid is selected from the group consisting of acetic acid, malonic acid, citric acid, propionic acid, malic acid, succinic acid, ascorbic acid, lactic acid, oxalic acid, and mixtures thereof. The composition according to claim 1.

5. The at least one first organic acid is present in an amount of about 0.00001% to about 50% by weight of the composition. The composition according to any one of claims 1 to 4.

6. The at least one organosilane compound contains a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, or a phosphorus-containing group. The composition according to any one of claims 1 to 5.

7. The at least one organosilane compound is tetramethyl orthosilicate (TMOS), tetraethyl orthosilicate (TEOS), potassium methylsilicate, (3-glycidyloxypropyl)trimethoxysilane, triethoxysilylpropoxy(polyethyleneoxy)dodecanoate, (3-triethoxysilyl)propyl succinic anhydride, N-(2-aminoethyl)-3-aminopropyl-trimethoxysilane, ureidopropyltriethoxysilane, trimethylmethoxysilane, N-trimethoxysilylpropyl- N,N,N-trimethylammonium chloride, dimethyldimethoxysilane, vinyltrimethoxysilane, N-trimethoxysilylpropyl-N,N,N-trimethylammonium halide, 3-aminopropylmethyldiethoxysilane, N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole, N-(6-aminohexyl)aminomethyltriethoxysilane, N-(2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane Lan, (N,N-diethylaminomethyl)triethoxysilane, N-methylaminopropyltrimethoxysilane, 3-(trihydroxysilyl)propylmethylphosphonate, 3-(trihydroxysilyl)-1-propanesulfonic acid, carboxyethylsilanetriol, (2-diethylphosphatoethyl)triethoxysilane, aminoethylaminopropylsilsesquioxane, [3-(trihydroxysilyl)propyl](methyl)phosphate, (3-aminopropyl)methyldimethoxysilane, (3-aminopropyl Selected from the group consisting of dimethylmethoxysilane, (3-aminopropyl)triethoxysilane, (3-aminopropyl)trimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, [3-(diethylamino)propyl]trimethoxysilane, 3-(2-aminoethylamino)propylmethyldimethoxysilane, 3-(trimethylsilyl)-1-propanesulfonic acid, 3-{[dimethyl(3-trimethoxysilyl)propyl]ammonio}propane-1-sulfonate, and combinations thereof, The composition according to any one of claims 1 to 6.

8. The at least one organosilane compound is present in an amount of about 0.0001% to 20% by weight of the composition. The composition according to any one of claims 1 to 7.

9. It further comprises at least one second organic acid different from the at least one first organic acid, The above-mentioned at least one second organic acid includes a dienoic acid. The composition according to any one of claims 1 to 8.

10. The at least one second organic acid includes a dienoic acid having 5 to 22 carbon atoms. The composition according to claim 9.

11. The at least one second organic acid is 2,4-pentadienoic acid, 5-phenylpenta-2,4-dienoic acid, 2-hydroxypenta-2,4-dienoic acid, 2,4-hexadienoic acid, 4,5-hexadienoic acid, 4,6-heptadienoic acid, 2,6-dimethylhepta-2,5-dienoic acid, (3E,5E)-hepta-3,5-dienoic acid, (2E,5Z)-hepta-2,5-dienoic acid, octa-3,5-dienoic acid, (Z)-3,7-dimethyl-2,6-octadienoic acid, 5,7-nonadienoic acid, (E,Z)-2,4-decadienoic acid, 2,5-decadienoic acid Dienoic acid, undecadienoic acid, dodecadienoic acid, tridecadienoic acid, tetradecadienoic acid, pentadecadienoic acid, hexadecadienoic acid, heptadecadienoic acid, (9Z,12E)-octadeca-9,12-dienoic acid, octadeca-10,12-dienoic acid, (10E,15Z)-9,12,13-trihydroxyoctadeca-10,15-dienoic acid, 13(S)-hydroxyoctadeca-9Z,11E-dienoic acid, nonadecadienoic acid, henicosadienoic acid, docosadienoic acid, eicosa-11,14-dienoic acid, or mixtures thereof. The composition according to claim 10.

12. The at least one second organic acid is present in an amount of about 0.0001% to about 0.5% by weight of the composition. The composition according to any one of claims 9 to 11.

13. It further contains at least one corrosion inhibitor, The at least one corrosion inhibitor is an amino acid that is chemically different from the at least one first organic acid and the at least one second organic acid. The composition according to any one of claims 1 to 12.

14. The at least one corrosion inhibitor comprises an aminocarboxylic acid, glycine, bicine, tricine, alanine, histidine, valine, phenylalanine, proline, glutamine, aspartic acid, glutamic acid, arginine, lysine, tyrosine, or a mixture thereof. The composition according to claim 13.

15. The at least one corrosion inhibitor is present in an amount of about 0.001% to about 20% by weight of the composition. The composition according to claim 13 or 14.

16. Further comprising at least one anionic polymer, The composition according to any one of claims 1 to 15.

17. The at least one anionic polymer is formed from one or more monomers selected from the group consisting of (meth)acrylic acid, maleic acid, acrylic acid, malic acid, methacrylic acid, vinylphosphonic acid, vinyl phosphoric acid, vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, acrylamidopropyl sulfonic acid, phosphonic acid, phosphoric acid, butadiene / maleic acid, caprolactam, etherimide, 2-ethyl-2-oxazoline, N-iso-propylacrylamide, sodium phosphinite and their co-formation products, and their sodium salts, potassium salts and ammonium salts. The composition according to claim 16.

18. The at least one anionic polymer is poly(4-styrenesulfonate) acid (PSSA), polyacrylic acid (PAA), poly(vinylphosphonic acid) (PVPA), poly(2-acrylamido-2-methyl-1-propanesulfonic acid), poly(N-vinylacetamide) (PNVA), anionic poly(methyl methacrylate) (PMMA), anionic polyacrylamide (PAM), polyaspartic acid (PASA), anionic poly(ethylene succinate) (PES), anionic polybutylene succinate (PBS), 2-methyl 2-propenoic acid copolymer having monosodium salt of -2-((1-oxo-2-propenyl)amino)-1-propanesulfonic acid and sodium phosphinite, 2-propenoic acid copolymer having monosodium salt of 2-methyl-2-((1-oxo-2-propenyl)amino)-1-propanesulfonic acid and sodium bisulfite, 2-acrylamido-2-methyl-1-propanesulfonic acid-acrylic acid copolymer, poly(4-styrenesulfonic acid-co-acrylic acid-co-vinylphosphonic acid) terpolymer, or mixtures thereof, The composition according to claim 16.

19. The at least one anionic polymer includes poly(4-styreneyl sulfonate) acid (PSSA), polyacrylic acid (PAA), poly(vinylphosphonic acid) (PVPA), poly(2-acrylamido-2-methyl-1-propanesulfonic acid), poly(N-vinylacetamide) (PNVA), anionic poly(methyl methacrylate) (PMMA), anionic polyacrylamide (PAM), 2-acrylamido-2-methyl-1-propanesulfonic acid-acrylic acid copolymer, poly(4-styrenesulfonic acid-co-acrylic acid-co-vinylphosphonic acid) terpolymer, or a mixture thereof. The composition according to claim 16.

20. The at least one anionic polymer is present in an amount of about 0.00001% to about 50% by weight of the composition. The composition according to any one of claims 16 to 19.

21. The pH of the composition is approximately 1 to approximately 14. The composition according to any one of claims 1 to 20.

22. A method for cleaning the surface of a substrate, The method involves contacting a substrate having a surface containing SiN, SiC, TiN, W, Ru, Mo, TEOS, Cu, TaN, Co, silicon oxycarbide, or p-Si with the cleaning composition described in any one of claims 1 to 21. method.

23. A method for cleaning a circuit board, The process involves bringing a substrate into contact with the cleaning composition described in any one of claims 1 to 21. method.

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