Cleaning compositions and methods of use thereof

Abstract

The present disclosure relates to cleaning compositions used for cleaning semiconductor substrates. These cleaning compositions can remove defects / contaminants on semiconductor substrates resulting from previous processing, thereby making the substrate suitable for further processing. The cleaning compositions described herein primarily contain at least one pH adjuster and at least one biosurfactant.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Application No. 63 / 071,730, filed August 28, 2020, 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 device miniaturization through process and integration innovations. Chemical-mechanical polishing / planarization (CMP) is a powerful technology because it enables many complex integration schemes at the transistor level, thereby facilitating increased chip density.

[0003] CMP is a process used to planarize or flatten a wafer surface by removing material using an abrasive-based physical process in conjunction with a surface-based chemical reaction. Generally, the CMP process involves applying a CMP slurry (aqueous chemical formulation) to the wafer surface, contacting the wafer surface with a polishing pad, and moving the polishing pad relative to the wafer. The slurry typically contains abrasive and dissolving chemical components that can vary significantly depending on the materials present on the wafer (e.g., metals, metal oxides, metal nitrides, dielectric materials such as silicon oxides, silicon nitrides, etc.) that interact with the slurry and polishing pad during the CMP process.

[0004] After CMP processing, various contaminants may be present on the polished wafer surface. Examples of contaminants include particulate abrasives from the CMP slurry, organic residues from the pad or slurry components, and materials removed from the wafer during the CMP process. If these contaminants are left on the polished wafer surface, they can lead to failures and / or reduced device performance during further wafer processing steps. Therefore, contaminants must be effectively removed so that the wafer can predictably undergo further processing and / or achieve optimal device performance. The process of removing these post-polishing contaminants or residues on 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. These P-CMP cleaning solutions / formulations solubilize or otherwise loosen defects remaining on the wafer surface after the CMP step, thereby removing these defects and leaving the wafer surface clean. This cleaning process ensures that device performance and chip yield are optimized when the wafer undergoes further processing. Summary of the Invention [Problem to be solved by the invention]

[0005] In semiconductor chip manufacturing, wafer surface defectivity is key to wafer yield, which determines the top and bottom lines of chip companies worldwide. A typical wafer undergoes approximately 1,000 processes before chips are fabricated and individual dies are cut from the wafer. During each of these processes, defectivity is monitored before and after the process. CMP (chemical mechanical polishing) is a critical step in chip manufacturing. However, the CMP step introduces a significant amount of defects after the polishing step. Therefore, after the CMP polishing step, a post-CMP (P-CMP) cleaning composition is typically applied to the wafer surface to reduce defects. This disclosure discusses a novel P-CMP cleaning composition that can effectively reduce wafer contaminants and defects without corroding wafer components, while significantly reducing the environmental footprint. [Means for solving the problem]

[0006] The present disclosure relates to cleaning compositions used to clean semiconductor substrates. These cleaning compositions remove defects / contaminants on the semiconductor substrate resulting from previous processing, thereby making the substrate suitable for further processing.

[0007] In one aspect, the disclosure features a cleaning composition that includes at least one pH adjuster and at least one biosurfactant selected from the group consisting of glycolipids, lipopeptides, and mixtures thereof, where the composition has a pH of about 1 to about 14.

[0008] In another aspect, the disclosure features a method for cleaning a substrate, the method includes polishing a substrate (e.g., a wafer) using a CMP composition to form a polished substrate, and contacting the polished substrate with a cleaning composition described herein to clean the polished substrate.

[0009] This Summary is provided to introduce a selection of concepts that are further described below in the Detailed Description. This Summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to be used as an aid in limiting the scope of the claimed subject matter. DETAILED DESCRIPTION OF THE INVENTION

[0010]

[0001] Embodiments disclosed herein generally relate to compositions and methods of using the compositions to clean substrates. In particular, the 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 substrate surfaces after an etching process, an ashing process, or a plating process.

[0011] Residues and / or contaminants as defined herein may include components (e.g., abrasives, molecular components, polymers, acids, bases, salts, surfactants, etc.) present in the CMP polishing composition used to polish the substrate being cleaned, compounds produced 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 (from the CMP slurry or CMP pad), substrate (or wafer) particles liberated during the CMP process, and / or any other removable material known to deposit on a substrate after the CMP process.

[0012] In one or more embodiments, the present disclosure relates to cleaning compositions comprising at least one biosurfactant. As used herein, the term "biosurfactant" is intended to refer to amphiphilic organic molecules, such as those produced by living organisms (e.g., microorganisms) and containing both hydrophobic groups (e.g., alkyl chains) and hydrophilic groups (e.g., carboxylic acid groups). Surfactants commonly used in the semiconductor industry are manufactured using petroleum-based precursors and / or energy-intensive chemical reactions. In contrast, biosurfactants can have favorable environmental and energy profiles (e.g., biodegradability and / or production by less energy-intensive processes) while providing the performance characteristics necessary to perform advanced semiconductor operations. Furthermore, due to their unique chemical structure, biosurfactants, when used alone or in combination with non-biosurfactant surfactants, can also provide improved performance during semiconductor operations (e.g., increased removal of defects on wafers and / or reduced removal rates of certain dielectric and / or metal films). Therefore, the use of biosurfactants within the semiconductor industry offers an opportunity for improved or sustained performance combined with a significantly reduced environmental footprint.

[0013] In one or more embodiments, the cleaning compositions described herein include at least one pH adjuster (e.g., an acid, such as an organic acid) and at least one biosurfactant. In one or more embodiments, the cleaning compositions of the present disclosure may include from about 0.00001% to about 50% by weight (e.g., from about 0.01% to about 5% by weight) of the at least one pH adjuster, from about 0.00001% to about 50% by weight (e.g., from about 0.005% to about 10% by weight) of the at least one biosurfactant, and the remaining weight percent (e.g., from about 60% to about 99.99% by weight) of a solvent (e.g., deionized water).

[0014] In one or more embodiments, the present disclosure provides concentrated P-CMP cleaning compositions that can be diluted with water 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 to obtain a point-of-use (POU) cleaning composition. In other embodiments, the present disclosure provides point-of-use (POU) cleaning compositions that can be used directly to clean a substrate surface.

[0015] In one or more embodiments, the POU cleaning composition can include from about 0.00001% to about 5% by weight of at least one pH adjuster (e.g., at least one amino acid or at least one carboxylic acid) and from about 0.00001% to about 5% by weight of at least one biosurfactant. In another embodiment, the POU cleaning composition can include from about 0.00001% to about 5% by weight of at least one amino acid, from about 0.00001% to about 5% by weight of at least one biosurfactant, and from about 0.00001% to about 5% by weight of at least one carboxylic acid.

[0016] In one or more embodiments, the concentrated P-CMP cleaning composition can include from about 0.01% to about 30% by weight (e.g., from about 0.05% to about 20% by weight) of at least one pH adjuster (e.g., at least one amino acid or at least one carboxylic acid) and from about 0.005% to about 15% by weight of at least one biosurfactant. In another embodiment, the concentrated P-CMP cleaning composition can include from about 0.005% to about 20% by weight of at least one amino acid, from about 0.005% to about 15% by weight of at least one biosurfactant, and from about 0.005% to about 20% by weight of at least one carboxylic acid.

[0017] In one or more embodiments, the cleaning compositions described herein may include at least one (e.g., two or three) pH adjuster. In some embodiments, the pH adjuster may be an acid (e.g., an organic or inorganic acid) or a base (e.g., an organic or inorganic base). In some embodiments, the pH adjuster may be an organic acid or a salt thereof. In such embodiments, the at least one pH adjuster may be selected from the group consisting of a carboxylic acid (e.g., a polycarboxylic acid or an acrylic acid), an amino acid, a sulfonic acid, a phosphoric acid, a phosphonic acid, or a salt thereof. In some embodiments, the at least one organic acid or salt thereof may be 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, 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, glutamic acid, arginine, lysine, tyrosine, benzoic acid, salts thereof, and mixtures thereof. In one or more embodiments, the cleaning composition includes at least two organic acids (e.g., a first organic acid and a second organic acid) as pH adjusters.

[0018] In one or more embodiments, the pH adjuster can be a base. For example, the at least one pH adjuster can be selected from the group consisting of hydroxides (e.g., ammonium hydroxide, potassium hydroxide, cesium hydroxide, or choline hydroxide), alkanolamines (e.g., monoethanolamine, diethanolamine, triethanolamine, methylethanolamine, methyldiethanolamine), tetraalkylammonium hydroxides (e.g., tetrabutylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, ethyltrimethylammonium hydroxide, diethyldimethylammonium hydroxide, dimethyldipropylammonium hydroxide, benzyltrimethylammonium hydroxide, or tris(2-hydroxyethyl)methylammonium hydroxide), and any combination thereof. In some embodiments, the pH adjuster can be free of any metal ions.

[0019] In one or more embodiments, the amount of the at least one pH adjuster is about 0.00001% to about 50% by weight of the cleaning composition. For example, the amount of the at least one pH adjuster (e.g., an organic acid or a salt thereof) can be about 0.00001% or more (e.g., about 0.00005% or more, about 0.0001% or more, about 0.0005% or more, about 0.001% or more, about 0.005% or more, about 0.01% or more, about 0.02% or more, about 0.05% or more, about 0.1% or more, about 0.5% or more, or about 1% or more) to about 50% or less (e.g., about 45% or less, about 40% or less, about 35% or less, about 30% or less, about 25% or less, about 20% or less, about 15% or less, about 10% or less, about 5% or less, or about 1% or less) by weight of the cleaning composition described herein.

[0020] In one or more embodiments, the cleaning compositions described herein can be either acidic or basic. In some embodiments, the polishing composition can have a pH in the range of about 1 or more to about 14 or less. If the cleaning composition is acidic, the pH can range from 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 more, or about 5 or more) to about 7 or less (e.g., about 6.5 or less, about 6 or less, about 5.5 or less, about 5 or less, about 4.5 or less, or about 4 or less). When the cleaning composition is basic, the pH can range from about 7 or more (e.g., about 7.5 or more, about 8 or more, about 8.5 or more, about 9 or more, about 9.5 or more, about 10 or more, about 10.5 or more, about 11 or more, about 11.5 or more, or about 12 or more) to about 14 or less (e.g., about 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 more, or about 10 or less).

[0021] In one or more embodiments, the cleaning compositions described herein may include at least two or three organic acids (e.g., amino acids or carboxylic acids). In some embodiments, the first organic acid is present in an amount of from about 0.0005% to about 50% by weight of the cleaning composition. In some embodiments, the second organic acid is present in an amount of from about 0.0005% to about 30% by weight of the cleaning composition. In yet some other embodiments, the third organic acid is present in an amount of from about 0.0005% to about 10% by weight of the cleaning composition.

[0022] In one or more embodiments, the cleaning compositions described herein may include at least one (e.g., two or three) biosurfactant. In one or more embodiments, the at least one biosurfactant may be a microbial growth by-product, such as a microbial metabolic product (i.e., the biosurfactant may be produced by a microorganism). The microbial growth by-product (i.e., the biosurfactant) may be recovered from the cultured yeast or fungal strain (i.e., the microorganism) through a purification process that removes the microorganisms responsible for producing the microbial growth by-product.

[0023] In one or more embodiments, the biosurfactant can be selected from the group consisting of glycolipids, lipopeptides, and mixtures thereof. In one or more embodiments, the biosurfactant comprises a glycolipid selected from the group consisting of rhamnolipids, sophorolipids, trehalose lipids, mannosylerythritol lipids, and mixtures thereof. In one or more embodiments, the biosurfactant comprises a lipopeptide selected from the group consisting of surfactin, iturin, fengicin, lichenicin, and mixtures thereof.

[0024] In one or more embodiments, the glycolipid is a rhamnolipid biosurfactant selected from monorhamnolipids, dirhamnolipids, and mixtures thereof. Rhamnolipid biosurfactants are surface-active compounds released by microorganisms. They are biodegradable, non-toxic, and environmentally friendly materials. Their production depends on fermentation conditions, environmental factors, and nutrient availability. In some embodiments, rhamnolipids comprise a glycosyl head group (i.e., a rhamnose moiety) and a fatty acid tail (e.g., one or more (e.g., two or three) C 10 ~C 14 Depending on the details of the fermentation, the fatty acid tail of the rhamnolipid can be 10-28 (e.g., 20-28 or 24-28) carbons in length. In some embodiments, the fatty acid tail can include a 3-(hydroxyalkanoyloxy)alkanoic acid (HAA) group. For example, the fatty acid tail can include a group of formula (A): -R1-C(O)O-R2-COOH, where R1 and R2 are each independently C 10 ~C 14 It is a straight-chain or branched alkylene group.

[0025] Formula I shows a typical monorhamnolipid, RLL or R1 (α-L-rhamnopyranosyl-β-hydroxydecanoyl-β-hydroxydecanoic acid, C 26 H 48 The structure of O9 (504 g / mol) is shown.

[0026] [ka]

[0027] Formula II shows another exemplary dirhamnolipid, RRLL or R2 (2-O-α-L-rhamnopyranosyl-α-L-rhamnopyranosyl-β-hydroxydecanoyl-β-hydroxydecanoate, C 32 H 58 O 13 (650 g / mol)) is shown below.

[0028] [ka]

[0029] As mentioned above, there are two main groups of rhamnolipids: monorhamnolipids and dirhamnolipids. Monorhamnolipids have a single rhamnose sugar ring. The common name for the monorhamnolipid RLL (most often produced by P. aeruginosa) is L-rhamnosyl-β-hydroxydecanoyl-β-hydroxydecanoic acid (often called Rha-C10-C10), and it is C 26 H 48 It has the formula O9. Its IUPAC name is 3-[3-[(2R,3R,4R,5R,6S)-3,4,5-trihydroxy-6-methyloxan-2-yl]oxydecanoyloxy]decanoic acid.

[0030] Dirhamnolipids have two rhamnose sugar rings. The common name for dirhamnolipid RRLL is L-rhamnosyl-L-rhamnosyl-β-hydroxydecanoyl-β-hydroxydecanoate (often called Rha-Rha-C10-C10), and C 32 H 58 O 13It has the formula: The IUPAC name is 3-[3-[4,5-dihydroxy-6-methyl-3-(3,4,5-trihydroxy-6-methyloxan-2-yl)oxyoxan-2-yl]oxydecanoyloxy]decanoic acid. Some other more common forms or names of dirhamnolipids include L-rhamnopyranosyl-L-rhamnopyranosyl-β-hydroxydecanoyl-β-hydroxydecanoate (often referred to as Rha-Rha-C10-C10), L-rhamnopyranosyl-L-rhamnopyranosyl-β-hydroxydecanoyl-β-hydroxydodecanoate (often referred to as Rha-Rha-C10-C12), and L-rhamnopyranosyl-L-rhamnopyranosyl-β-hydroxytetradecanoyl-β-hydroxytetradecanoate (often referred to as Rha-Rha-C14-C14).

[0031] Rhamnolipid preparations for use as biosurfactants in the cleaning compositions described herein can be crude or highly purified rhamnolipids. Crude rhamnolipid preparations contain rhamnolipids with many impurities, which can include both external impurities (e.g., resulting from biological production processes) and / or various rhamnolipid mixtures, causing reduced effects on the formulation. Highly purified rhamnolipid preparations contain rhamnolipids from which external impurities have been removed and / or mixtures of rhamnolipids (e.g., dirhamnolipids, monorhamnolipids, or mixtures thereof) that have been purified to meet specific parameters to cause increased effects on the formulation. In one or more embodiments, the weight percent ratio of monorhamnolipids to dirhamnolipids in the cleaning composition ranges from about 0.1:99.9 to 99.9:0.1, respectively. For example, the weight percent ratio of monorhamnolipid to dirhamnolipid in the polishing composition is about 0.1:99.9 or more (e.g., about 0.1:99.5 or more, about 1:99 or more, about 5:95 or more, about 10:90 or more, about 15:85 or more, about 20:80 or more, about 25:75 or more, about 30:70 or more, about 35:65 or more, about 40:60 or more, about 45:55 or more, or at least about 50:50 or more) to about 99.9:0.1 or less (e.g., about 99.5:0.5 or less, about 99:1 or less, about 95:5 or less, about 90:10 or less, about 85:15 or less, about 80:20 or less, about 75:25 or less, about 70:30 or less, about 65:35 or less, about 60:40 or less, about 55:45 or less, or about 50:50 or less).

[0032] In one or more embodiments, the rhamnolipid preparation is prepared by removing undesirable impurities from the initial mixture obtained from the microorganisms, then determining the percentage and type of rhamnolipids to be present in the final cleaning composition, and simply diluting the rhamnolipid preparation with the solvent used in the cleaning composition. Crude rhamnolipid preparations and highly purified rhamnolipid preparations can be prepared by methods well known to those skilled in the art. In some embodiments, a rhamnolipid preparation for use as a biosurfactant in the polishing compositions described herein may contain about 50% by weight or more (e.g., about 55% by weight or more, about 65% by weight or more, about 70% by weight or more, about 75% by weight or more, about 80% by weight or more, about 85% by weight or more, about 90% by weight or more, about 95% by weight or more, about 98% by weight or more, about 99% by weight or more, about 99.5% by weight or more, or about 99.9% by weight or more).

[0033] In one or more embodiments, the glycolipid is a sophorolipid biosurfactant. Sophorolipids (also known as sophorose lipids or SLs) are a group of biosurfactants consisting of a dimeric sugar (sophorose) and a hydroxyl fatty acid linked by a β-glycosidic bond. There are two types of SLs: acidic (non-lactonic) SLs and lactonic SLs. The hydroxyl fatty acid moiety of acidic SLs has a free carboxylic acid functional group, while the hydroxyl fatty acid moiety of lactonic SLs forms a macrocyclic lactone ring with the 4"-hydroxyl group of sophorose by intramolecular esterification. Sophorose lipids are generally classified into two forms: (1) the lactone form represented by formula (III) below, and (2) the acid form represented by formula (IV) below.

[0034] [ka]

[0035] In the formula, R1 and R2 each represent H or COCH3; R3 represents H or CH3; when R3 represents H, R4 represents a saturated or unsaturated C12 to C16 hydrocarbon group (for example, a C12 to C16 alkylene group optionally containing one or more (for example, 2, 3, 4, or 5) double bonds), and when R3 represents CH3, R4 represents a saturated or unsaturated C11 to C15 hydrocarbon group (for example, a C11 to C15 alkylene group optionally containing one or more (for example, 2, 3, 4, or 5) double bonds).

[0036] [ka]

[0037] wherein R1-R4 are as defined above. A commercial example of a sophorolipid biosurfactant is REWOFERM SL ONE available from Evonik (Essen, Germany), which contains a mixture of sophorolipids (i.e., lactone and acid forms) produced by fermenting glucose, fatty acids, and C18 unsaturated esters with glycerol in the presence of the yeast Candida bombicola, and contains about 30-50% sophorolipids by weight.

[0038] As is clear from the above, sophorose lipids have many derivatives characterized by the position and number of acetyl groups, the presence or absence of double bonds in the fatty acid side chain, the carbon chain length of the fatty acid side chain, the position of the glycosidic ether bond in the fatty acid side chain, the position of the hydroxyl group on the sophorose moiety that is part of the lactone ring, and other structural parameters. Sophorose lipids generally occur as a mixture of these compounds. Sophorose lipids are generally produced in the form of a highly viscous oil that is difficult to handle. However, sophorose lipids in the diacetyllactone form, which are relatively hydrophobic, can be produced in a solid form. In one or more embodiments, the glycolipid is a sophorolipid that contains about 5% by weight or more (e.g., about 10% by weight or more, about 15% by weight or more, about 20% by weight or more, about 25% by weight or more, about 30% by weight or more, about 35% by weight or more, about 40% by weight or more, about 45% by weight or more, or about 50% by weight or more) to about 95% by weight or less (e.g., about 90% by weight or less, about 85% by weight or less, about 80% by weight or less, about 75% by weight or less, about 70% by weight or less, about 65% by weight or less, about 60% by weight or less, about 55% by weight or less, about 50% by weight or less).

[0039] In one or more embodiments, the amount of biosurfactant is about 0.00001% or more (e.g., about 0.00005% or more, about 0.0001% or more, about 0.0005% or more, about 0.001% or more, about 0.002% or more, about 0.004% or more, about 0.005% or more, about 0.006% or more, about 0.008% or more, about 0.01% or more, about 0.02% or more, about 0.03% or more, about 0.04% or more, about 0.05% or more, about 0.1% or more, about 0.5% or more, or about 1% or more) to about 50% or less (e.g., about 45% by weight or less, about 40% by weight or less, about 35% by weight or less, about 30% by weight or less, about 25% by weight or less, about 20% by weight or less, about 15% by weight or less, about 10% by weight or less, about 5% by weight or less, about 1% by weight or less, about 0.5% by weight or less, about 0.1% by weight or less, or about 0.05% by weight or less).

[0040] In one or more embodiments, one or more (e.g., two or three) biosurfactants are the only surfactants in the cleaning compositions described herein. However, in some embodiments, the cleaning compositions may contain one or more (e.g., two or three) additional surfactants different from the biosurfactants selected from the group consisting of anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic surfactants, and mixtures thereof.

[0041] Examples of suitable cationic surfactants include, but are not limited to, fatty amine salts and fatty ammonium salts.

[0042] Examples of suitable nonionic surfactants include, but are not limited to, ether surfactants, ether ester surfactants, ester surfactants, and acetylene surfactants. Ether surfactants include polyethylene glycol mono-4-nonylphenyl ether, polyethylene glycol monooleyl ether, and triethylene glycol monododecyl ether. An example of an ether ester surfactant is polyoxyethylene ether of glycerin ester. Ester surfactants include, for example, polyethylene glycol fatty acid esters, glycerin esters, and sorbitan esters. Acetylenic surfactants include, for example, ethylene oxide adducts of acetylene alcohols, ethylene oxide adducts of acetylene glycols, and ethylene oxide adducts of acetylene diols.

[0043] Examples of suitable amphoteric surfactants include, but are not limited to, betaine surfactants.

[0044] Suitable anionic surfactants include, but are not limited to, carboxylates, sulfonates, sulfates, and phosphates. Carboxylate salts include, for example, fatty acid salts (e.g., soaps) and alkyl ether carboxylates. Sulfonates include, for example, alkyl benzene sulfonates, alkyl naphthalene sulfonates, and α-olefin sulfonates. Sulfates include, for example, higher alcohol sulfates and alkyl sulfates. Phosphates include, for example, alkyl phosphates and alkyl phosphate esters.

[0045] When the cleaning compositions described herein include a second surfactant as described above, the amount of the second surfactant can range from about 0.001 wt. % or more (e.g., about 0.002 wt. % or more, about 0.0003 wt. % or more, about 0.0005 wt. % or more, about 0.01 wt. % or more, about 0.05 wt. % or more, or about 0.1 wt. % or more) to about 1 wt. % or less (e.g., about 0.8 wt. % or less, about 0.6 wt. % or less, about 0.5 wt. % or less, about 0.4 wt. % or less, about 0.2 wt. % or less, or about 0.1 wt. % or less) of the total weight of the cleaning composition.

[0046] In one or more embodiments, the cleaning compositions described herein may include at least one (e.g., two or three) anionic polymers. In one or more embodiments, the at least one anionic polymer may include one or more anionic groups, such as carboxylate, sulfate, 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, vinylphosphonic acid, vinylphosphoric acid, vinylsulfonic acid, allylsulfonic acid, styrenesulfonic acid, acrylamide, acrylamidopropylsulfonic acid, and sodium phosphinate. In more specific embodiments, the at least one anionic polymer is selected from the group consisting of poly(4-styrenesulfonic acid (PSSA), polyacrylic acid) (PAA), poly(vinylphosphonic acid) (PVPA), poly(2-acrylamido-2-methyl-1-propanesulfonic acid), poly(N-vinylacetamide (PNVA), polyethyleneimine (PEI), anionic poly(methyl methacrylate) (PMMA), anionic polyacrylamide (PAM), polyaspartic acid (PASA), anionic poly(ethylene succinate) (PES), anionic polybutylene succinate (PBS), poly(vinyl alcohol) (PVA), 2-methyl-2-((1-oxo-2-propenyl)amino)-1-propanesulfonic acid monosodium salt, and sodium phosphinite (sodium 2-propenoic acid copolymer with 2-methyl-2-((1-oxo-2-propenyl)amino)-1-propanesulfonic acid monosodium salt and sodium hydrogen sulfite sodium salt, 2-acrylamido-2-methyl-1-propanesulfonic acid-acrylic acid copolymer, poly(4-styrenesulfonic acid-co-acrylic acid-co-vinylphosphonic acid) terpolymer, and mixtures thereof.Without wishing to be bound by theory, it is believed that the anionic polymer can solubilize hydrophobic abrasive materials and / or defects on the wafer surface, facilitating their removal during the post-CMP cleaning process.

[0047] In one or more embodiments, the at least one anionic polymer can have a weight average molecular weight ranging from about 250 g / mol or greater (e.g., about 500 g / mol or greater, about 1000 g / mol or greater, about 2,000 g / mol or greater, about 5,000 g / mol or greater, about 10,000 g / mol or greater, about 50,000 g / mol or greater, about 100,000 g / mol or greater, about 200,000 g / mol or greater, or about 250,000 g / mol or greater) 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, the at least one anionic polymer can have a weight average molecular weight ranging from about 1000 g / mol to about 10,000 g / mol. In some embodiments, the at least one anionic polymer can have a weight average molecular weight ranging from about 2000 g / mol to about 6,000 g / mol. In further embodiments, the at least one anionic polymer can have a weight average molecular weight of about 5,000 g / mol.

[0048] 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-styrenesulfonic acid) and poly(acrylic) acid or (2) 2-acrylamido-2-methyl-1-propanesulfonic acid-acrylic acid copolymer and poly(acrylic) acid.

[0049] In one or more embodiments, the at least one anionic polymer is present in an amount of about 0.00001% to about 50% by weight of the cleaning compositions described herein. For example, the at least one anionic polymer may be present in an amount of about 0.00001% by weight or more (e.g., about 0.00005% by weight or more, about 0.0001% by weight or more, 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 0.05% 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 50% by weight or less (e.g., about 45% by weight or less, about 40% by weight or less, about 35% by weight or less, about 30% by weight or less, about 25% by weight or less, about 20% by weight or less, about 15% by weight or less, about 10% by weight or less, about 5% by weight or less, or about 1% by weight or less).

[0050] In some embodiments, the cleaning compositions may include 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 compositions 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 compositions described herein. In yet some other embodiments, the third anionic polymer is present in an amount of about 0.0005% to about 10% by weight of the cleaning compositions described herein.

[0051] In one or more embodiments, the cleaning compositions described herein may further comprise at least one (e.g., two, three, or four) optional additives selected from the group consisting of an azole compound, a dienoic acid, a corrosion inhibitor, a chelating agent, and a water-soluble polymer.

[0052] The azole compound is not particularly limited, but specific examples include substituted or unsubstituted triazoles (e.g., benzotriazoles), substituted or unsubstituted tetrazoles, substituted or unsubstituted diazoles (e.g., imidazoles, benzimidazoles, thiadiazoles, and pyrazoles), and substituted or unsubstituted benzothiazoles. In this specification, substituted diazoles, triazoles, or tetrazoles refer to diazoles, triazoles, or tetrazoles in which one or more hydrogen atoms have been substituted with, for example, a carboxyl group, an alkyl group (e.g., methyl, ethyl, propyl, butyl, pentyl, or hexyl group), a halogen group (e.g., F, Cl, Br, or I), an amino group, or a hydroxyl group.In one or more embodiments, the azole compound is tetrazole, benzotriazole, tolyltriazole, methylbenzotriazole (e.g., 1-methylbenzotriazole, 4-methylbenzotriazole, 5-methylbenzotriazole), ethylbenzotriazole (e.g., 1-ethylbenzotriazole), propylbenzotriazole (e.g., 1-propylbenzotriazole), butylbenzotriazole (e.g., 1-butylbenzotriazole, 5-butylbenzotriazole), pentylbenzotriazole (e.g., 1-pentylbenzotriazole), hexylbenzotriazole (e.g., 1-hexylbenzotriazole, 5-hexylbenzotriazole), dimethylbenzotriazole (e.g., 5,6-dimethylbenzotriazole), chlorobenzotriazole (e.g., 5-chlorobenzotriazole), ), dichlorobenzotriazole (e.g., 5,6-dichlorobenzotriazole), chloromethylbenzotriazole (e.g., 1-(chloromethyl)-1-H-benzotriazole), chloroethylbenzotriazole, phenylbenzotriazole, benzylbenzotriazole, aminotriazole, aminobenzimidazole, pyrazole, imidazole, aminotetrazole, adenine, benzimidazole, thiabendazole, 1,2,3-triazole, 1,2,4-triazole, 1-hydroxybenzotriazole, 2-methylbenzothiazole, 2-aminobenzimidazole, 2-amino-5-ethyl-1,3,4-thiadiazole, 3,5-diamino-1,2,4-triazole, 3-amino-5-methylpyrazole, 4-amino-4H-1,2,4-triazole, and combinations thereof. Without wishing to be bound by theory, it is believed that azole compounds can be used as corrosion inhibitors in the cleaning compositions described herein to reduce the removal of certain materials (e.g., metal or dielectric materials) during the cleaning process.

[0053] In some embodiments, the azole compound can be about 0.001% or more (e.g., about 0.002% or more, about 0.004% or more, about 0.005% or more, about 0.006% or more, about 0.008% or more, about 0.01% or more, about 0.02% or more, about 0.04% or more, about 0.05% or more, about 0.06% or more, about 0.08% or more, or about 0.1% or more) to about 0.2% or less (e.g., about 0.18% or less, about 0.16% or less, about 0.15% or less, about 0.14% or less, about 0.12% or less, about 0.1% or less, about 0.08% or less, about 0.06% or less, about 0.05% or less, about 0.04% or less, about 0.03% or less, about 0.02% or less, or about 0.01% or less) by weight of the cleaning composition.

[0054] In one or more embodiments, the cleaning compositions described herein may optionally include a dienoic acid (i.e., a diene-containing acid). In some embodiments, the dienoic acid can have 5 to 22 (e.g., 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22) carbons. In some embodiments, the dienoic acid can have 5 to 12 (e.g., 5, 6, 7, 8, 9, 10, 11, or 12) carbons. In some embodiments, the 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-nonadecadienoic acid, (E,Z)-2,4-decadienoic acid, 2,5-decadienoic acid, 5,7-nonadecadienoic acid, (E,Z)-2,4-decadienoic acid, 5,7-decadienoic acid, 5,7-hex ... The organic acid may be a diene-containing carboxylic acid, such as 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, and eicosa-11,14-dienoic acid. In some embodiments, the at least one organic acid may comprise a mixture (e.g., two or three) of the dienoic acids described herein. Without wishing to be bound by theory, it is believed that the inclusion of a dienoic acid can improve corrosion inhibition of certain metal and metal-containing films (e.g., W, Cu, TaN, or TiN) on a substrate during a post-CMP cleaning process.

[0055] In one or more embodiments, dienoic acid can be from about 0.0001% or more (e.g., about 0.0005% or more, about 0.001% or more, about 0.005% or more, about 0.01% or more, about 0.02% or more, about 0.04% or more, or about 0.05% or more) to about 0.5% or less (e.g., about 0.4% or less, about 0.3% or less, about 0.2% or less, about 0.1% or less, about 0.08% or less, about 0.06% or less, about 0.05% or less, about 0.04% or less, about 0.03% or less, about 0.02% or less, about 0.01% or less, or about 0.005% or less) by weight of the cleaning compositions described herein.

[0056] In some embodiments, the cleaning compositions described herein may optionally include a non-azole corrosion inhibitor. Examples of non-azole corrosion inhibitors include dienoic acids, alkylamines (e.g., ethylamine, propylamine, or butylamine), and organic phosphonic acids (e.g., ethylphosphonic acid).

[0057] In some embodiments, the non-azole corrosion inhibitor comprises about 0.001% or more (e.g., about 0.002% or more, about 0.004% or more, about 0.005% or more, about 0.006% or more, about 0.008% or more, about 0.01% or more, about 0.02% or more, about 0.04% or more, about 0.05% or more, about 0.06% or more, about 0.08% or more, or about 0.1% or more) to about 0.2% or less (e.g., about 0.18% or less, about 0.16% or less, about 0.15% or less, about 0.14% or less, about 0.12% or less, about 0.1% or less, about 0.08% or less, about 0.06% or less, about 0.05% or less by weight, about 0.04% or less, about 0.03% or less, about 0.02% or less, or about 0.01% or less by weight).

[0058] In one or more embodiments, the chelating agent is selected from the group consisting of gluconic acid, lactic acid, citric acid, tartaric acid, malic acid, glycolic acid, malonic acid, formic acid, oxalic acid, acetic acid, propionic acid, peracetic acid, succinic acid, lactic acid, aminoacetic acid, phenoxyacetic acid, bicine, diglycolic acid, glyceric acid, tricine, alanine, histidine, valine, phenylalanine, proline, glutamine, aspartic acid, glutamic acid, arginine, lysine, tyrosine, benzoic acid, ammonia, 1,2- The chelating agent may be selected from the group consisting of ethanedisulfonic acid, 4-amino-3-hydroxy-1-naphthalenesulfonic acid, 8-hydroxyquinoline-5-sulfonic acid, aminomethanesulfonic acid, benzenesulfonic acid, hydroxylamine O-sulfonic acid, methanesulfonic acid, m-xylene-4-sulfonic acid, poly(4-styrenesulfonic acid), polyanetholesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, salts thereof, and mixtures thereof. Without wishing to be bound by theory, it is believed that the chelating agent may serve as a removal rate enhancer to facilitate the removal of certain materials on the substrate.

[0059] In some embodiments, the chelating agent can be from about 0.1 wt. % or more (e.g., about 0.2 wt. % or more, about 0.3 wt. % or more, about 0.4 wt. % or more, about 0.5 wt. % or more, about 0.6 wt. % or more, about 0.7 wt. % or more, about 0.8 wt. % or more, about 0.9 wt. % or more, or about 1 wt. % or more) to about 10 wt. % or less (e.g., 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, about 1 wt. % or less, about 0.8 wt. % or less, about 0.6 wt. % or less, or about 0.5 wt. % or less) of the cleaning compositions described herein.

[0060] Specific examples of water-soluble polymers include, but are not limited to, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, and hydroxyethyl cellulose. Without wishing to be bound by theory, it is believed that the water-soluble polymer may act as a removal rate inhibitor to reduce the removal rate of uncertain exposed materials on the substrate that are not intended to be removed or that should be removed at a slower rate during the cleaning process.

[0061] In some embodiments, the water-soluble polymer can be from about 0.01 wt. % or more (e.g., about 0.02 wt. % or more, about 0.03 wt. % or more, about 0.04 wt. % or more, about 0.05 wt. % or more, about 0.06 wt. % or more, about 0.07 wt. % or more, about 0.08 wt. % or more, about 0.09 wt. % or more, or about 0.1 wt. % or more) to about 1 wt. % or less (e.g., about 0.8 wt. % or less, about 0.6 wt. % or less, about 0.5 wt. % or less, about 0.4 wt. % or less, about 0.2 wt. % or less, about 0.1 wt. % or less, about 0.08 wt. % or less, about 0.06 wt. % or less, or about 0.05 wt. % or less).

[0062] In one or more embodiments, the cleaning compositions described herein may contain certain ingredients, such as organic solvents, pH adjusters (e.g., acids or bases), quaternary ammonium compounds (e.g., salts or hydroxides), amines, alkali bases (e.g., alkali hydroxides), fluorine-containing compounds (e.g., fluoride compounds or fluorinated polymers / surfactants), silicon-containing compounds such as silanes (e.g., alkoxysilanes), nitrogen-containing compounds (e.g., amino acids, amines, or imines (e.g., amidines, such as 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN))), salts (e.g., halogenated The cleaning composition may be substantially free of: inorganic salts or metal salts, polymers such as polyols (e.g., nonionic polymers, cationic polymers, or anionic polymers), inorganic acids (e.g., hydrochloric acid, sulfuric acid, phosphoric acid, or nitric acid), surfactants (e.g., cationic surfactants, anionic surfactants, nonionic surfactants, or other than the biosurfactants described herein), plasticizers, oxidizers (e.g., HO), corrosion inhibitors (e.g., azole corrosion inhibitors or non-azole corrosion inhibitors), electrolytes (e.g., polyelectrolytes), and / or abrasives (e.g., silica / ceria abrasives, nonionic abrasives, surface-modified abrasives, or negatively / positively charged abrasives). Halide salts that can be excluded from the cleaning composition include alkali metal halides (e.g., sodium or potassium halides) or ammonium halides (e.g., ammonium chloride), and may be fluorides, chlorides, bromides, or iodides. As used herein, a component that is "substantially free" 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 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, about 10 ppm or less, or about 1 ppm or less) of one or more of the components that are substantially free from the cleaning composition. In some embodiments, the cleaning compositions described herein may be completely free of one or more of the components.

[0063] When applied to post-CMP cleaning operations, the cleaning compositions described herein are useful for cleaning contaminants present on a substrate surface after the CMP processing step. In one or more embodiments, the contaminants can 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 polishing substrate residues, and the like. In one or more embodiments, the cleaning compositions of the present disclosure can be used to remove organic residues composed of organic particles that are insoluble in water and therefore remain on the substrate surface after the CMP polishing step. Without being bound by theory, it is believed that the organic particles are generated from polishing composition components that deposit on the substrate surface after polishing and are insoluble, thereby adhering to the wafer surface as contaminants. The presence of these contaminants causes defect counts on the wafer surface. These defect counts, when analyzed with a defect measurement tool such as KLA Tencor Company's AIT-XUV tool, can be used to measure the number of individual defects. In one or more embodiments, the cleaning compositions described herein provide a total defect count (TDC) of about 30% of the total defect count (TDC) remaining on the substrate surface after the polishing / CMP process. % or more , or about 50 % or more , or about 75 % or more , or about 80 % or more , or about 90 % or more , or about 95 % or more , or about 98 % or more , or about 99 % or more , or approximately 99.5 % or more or removes more than 99.9% of the contaminants.

[0064] In one or more embodiments, the present disclosure features a method for cleaning a substrate (e.g., a wafer). The method can include polishing a substrate with a CMP composition to form a polished substrate and contacting the polished substrate with a cleaning composition described herein to clean the polished substrate. In some embodiments, the CMP composition can include a solvent (e.g., water), a pH adjuster (e.g., an acid or base), and abrasive particles. In some embodiments, polishing the substrate can be performed by applying a polishing composition to the surface of the substrate, contacting a pad with the surface of the substrate, and moving the pad relative to the substrate.

[0065] 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 with a wide variety of conventional cleaning tools and techniques (e.g., on-platen buffing / cleaning, brush cleaning, spin rinse dry, etc.). In some embodiments, the substrate may comprise at least one of silicon oxide (e.g., tetraethylorthosilicate (TEOS), high density plasma oxide (HDP), high aspect ratio process oxide (HARP), or borophosphosilicate glass (BPSG)), spin-on film (e.g., inorganic particle-based film or crosslinked carbon polymer-based film), silicon nitride, silicon carbide, high-K dielectric (e.g., hafnium metal oxide, aluminum metal oxide, or zirconium metal oxide), silicon (e.g., polysilicon (p-Si), single crystal silicon, or amorphous silicon), carbon, metal (e.g., tungsten, copper, cobalt, ruthenium, molybdenum, titanium, tantalum, or aluminum), metal nitride (e.g., titanium nitride or tantalum nitride), and mixtures or combinations thereof.

[0066] In one or more embodiments, the cleaning methods described herein include the steps of: (A) providing a substrate containing post-CMP residue; (B) contacting the substrate with a cleaning composition described herein; (C) rinsing the substrate with a suitable rinse solvent; and (D) optionally removing the rinse solvent and drying the substrate by any suitable means that does not compromise the integrity of the substrate.

[0067] The 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 substrate in the cleaning composition, spraying the cleaning composition onto the substrate, flowing the cleaning composition onto the substrate, or any combination thereof.

[0068] Cleaning compositions of the present disclosure can be effectively used at temperatures up to about 90°C (eg, from about 25°C to about 80°C, from about 30°C to about 60°C, or from about 40°C to about 60°C).

[0069] Similarly, cleaning times can vary over a wide range depending on the particular cleaning method and temperature used. For cleaning by an immersion batch process, a suitable time range is, for example, about 60 minutes or less (e.g., about 1 minute to about 60 minutes, about 3 minutes to about 20 minutes, or about 4 minutes to about 15 minutes). Cleaning times for single-wafer processes can range from about 10 seconds to about 5 minutes (e.g., about 15 seconds to about 4 minutes, about 15 seconds to about 3 minutes, or about 20 seconds to about 2 minutes).

[0070] To further enhance the cleaning ability of the cleaning agent of the present disclosure, mechanical agitation means can be used. Suitable agitation means include, for example, circulation of the cleaning composition over the substrate, flow or spray of the cleaning composition over the substrate, and ultrasonic or megasonic agitation during the cleaning process. The orientation of the semiconductor substrate with respect to the ground can be at any angle. Horizontal or vertical orientation is preferred.

[0071] Following cleaning, the substrate can be rinsed with a suitable rinsing solvent for about 5 seconds to about 5 minutes, with or without agitation. Examples of suitable rinsing solvents include, but are not limited to, deionized (DI) water, methanol, ethanol, isopropyl alcohol, N-methylpyrrolidinone, γ-butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate. Alternatively, an aqueous rinse (such as a dilute aqueous ammonium hydroxide solution) with a pH > 8 can be used. Preferred examples of rinsing solvents include, but are not limited to, a dilute aqueous ammonium hydroxide solution, DI water, methanol, ethanol, and isopropyl alcohol. The solvent can be applied using a method similar to that used to apply the cleaning agents described herein. The cleaning composition can be removed from the substrate before the rinsing step begins, or can still be in contact with the substrate at the start of the rinsing step. Preferably, the temperature used in the rinsing step is between 16°C and 27°C.

[0072] Optionally, the semiconductor substrate is dried after the rinsing step. Any suitable drying means known in the art can be used. Suitable drying means include, for example, spin drying, flowing a dry gas through the semiconductor substrate, or heating the semiconductor substrate with a heating means such as a hot plate or infrared lamp, Marangoni drying, Rotagon drying, IPA drying, or any combination thereof. Drying times depend on the specific method used, but are typically on the order of 30 seconds to several minutes.

[0073] In one or more embodiments, the method of using the cleaning compositions described herein can further include fabricating a semiconductor device (e.g., an integrated circuit device such as a semiconductor chip) from a substrate treated with the cleaning composition through one or more steps. For example, photolithography, ion implantation, dry / wet etching, plasma etching, deposition (e.g., PVD, CVD, ALD, ECD), wafer attachment, die cutting, packaging, and testing can be used to fabricate a semiconductor device from a substrate treated with the cleaning compositions described herein. [Example]

[0074] In the following examples, 200 mm silicon nitride wafers were first polished using an abrasive slurry and a hard pad. A post-CMP clean was then performed on the wafer using an on-platen buff / clean using an AMAT Mirra tool and a soft pad in conjunction with the cleaning composition described in this example. After the post-CMP clean was completed, the wafer was rinsed with deionized water and dried using a Sematech SRD (spin rinse dry) tool. The total defect count on the wafer was then measured using an AIT-XUV tool from KLA Tencor Company.

[0075] Example 1 In this example, the ability of biosurfactants to improve the cleaning performance of commercial post-CMP cleaners was tested. The following post-CMP cleaning compositions were tested in this example: (1) water only (Comparative Example 1); (2) a commercial post-CMP cleaner (Comparative Example 2); and (3) the same commercial post-CMP cleaner with two loading levels of biosurfactant (Comparative Example 3 and Comparative Example 4). Table 1 summarizes the test results.

[0076] [Table 1]

[0077] The above results indicate that the addition of biosurfactant to a commercial p-CMP cleaning agent reduced both the total defect count and the SiN removal rate when compared to a commercial p-CMP cleaning agent without biosurfactant. In particular, the addition of approximately 160 ppm biosurfactant in Composition 4 reduced TDC by approximately 63% and SiN removal rate by approximately 14% compared to the values ​​obtained for the commercial p-CMP cleaner without biosurfactant (i.e., Composition 2). This result is significant because minimizing TDC and material removal rate during p-CMP cleaning is crucial to achieving a high yield of usable substrates for further processing.

[0078] While only a few exemplary embodiments have been described in detail above, those skilled in the art will readily appreciate that many modifications are possible in the exemplary embodiments without substantially departing from the invention, and all such modifications are intended to be included within the scope of the present disclosure as defined in the following claims. Exemplary embodiments of the present invention are described below. <1> at least one pH adjuster; and At least one biosurfactant selected from the group consisting of glycolipids, lipopeptides, and mixtures thereof. A cleaning composition comprising: The composition has a pH of about 1 to about 14. <2> the at least one pH adjuster comprises a carboxylic acid, an amino acid, a sulfonic acid, a phosphoric acid, or a phosphonic acid; <1> The composition described in <3> the at least one pH adjuster comprises at least one carboxylic acid; <1> The composition described in <4> the at least one pH adjuster is selected from the group consisting of formic 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, 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, glutamic acid, arginine, lysine, tyrosine, benzoic acid, and mixtures thereof; <1> The composition described in <5> the amount of the at least one pH adjuster is from about 0.00001% to about 50% by weight of the composition; <1> The composition described in <6> The composition comprises at least two pH adjusters. <1> The composition described in <7> The at least one biosurfactant comprises a glycolipid selected from the group consisting of rhamnolipids, sophorolipids, trehalose lipids, mannosylerythritol lipids, and mixtures thereof; <1> The composition described in <8> The glycolipid is a rhamnolipid selected from the group consisting of monorhamnolipids, dirhamnolipids, and mixtures thereof; <7> The composition described in <9> The at least one biosurfactant comprises a sophorolipid of formula (III), <7> The composition according to claim 1,

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Claims

1. at least one pH adjuster; and At least one biosurfactant comprising a glycolipid selected from the group consisting of rhamnolipids, sophorolipids, trehalose lipids, mannosylerythritol lipids, and mixtures thereof. A post-chemical mechanical polishing / planarization (CMP) cleaning composition comprising: having a pH of 1 to 14; The composition has a removal rate that removes 30% or more of the total defect count (TDC) remaining on the substrate surface after the polishing / CMP process.

2. The composition of claim 1 , wherein the at least one pH adjuster comprises a carboxylic acid, an amino acid, a sulfonic acid, a phosphoric acid, or a phosphonic acid.

3. The composition of claim 1 , wherein the at least one pH adjuster comprises at least one carboxylic acid.

4. 2. The composition of claim 1, wherein the at least one pH adjuster is selected from the group consisting of formic 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, 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, glutamic acid, arginine, lysine, tyrosine, benzoic acid, and mixtures thereof.

5. 10. The composition of claim 1, wherein the amount of the at least one pH adjuster is from 0.00001% to 50% by weight of the composition.

6. The composition of claim 1 , wherein the composition comprises at least two pH adjusters.

7. 2. The composition of claim 1, wherein the glycolipid is a rhamnolipid selected from the group consisting of monorhamnolipids, dirhamnolipids, and mixtures thereof.

8. 2. The composition of claim 1, wherein the at least one biosurfactant comprises a sophorolipid of formula (III): 【Chemical 1】 In the formula, R １ and R ２ are H or COCH ３ represents; R ３ is H or CH ３ represents; R ３ When represents H, R ４ represents a saturated or unsaturated C12 to C16 hydrocarbon group, R ３ is CH ３ When R ４ represents a saturated or unsaturated C11 to C15 hydrocarbon group.

9. 2. The composition of claim 1, wherein the at least one biosurfactant comprises a sophorolipid of formula (IV): 【Chemistry 2】 In the formula, R １ and R ２ are H or COCH ３ represents; R ３ is H or CH ３ represents; R ３ When represents H, R ４ represents a saturated or unsaturated C12 to C16 hydrocarbon group, R ３ is CH ３ When R ４ represents a saturated or unsaturated C11 to C15 hydrocarbon group.

10. The composition according to claim 1, wherein the glycolipid comprises 5% by weight or more and 95% by weight or less of an acidic sophorolipid.

11. 10. The composition of claim 1, wherein the at least one biosurfactant further comprises a lipopeptide selected from the group consisting of surfactin, iturin, fengicin, lichenicin, and mixtures thereof.

12. 10. The composition of claim 1, wherein the amount of said at least one biosurfactant is from 0.00001% to 50% by weight of said composition.

13. The composition of claim 1 , wherein the at least one biosurfactant is the only surfactant in the composition.

14. a second surfactant different from the at least one biosurfactant, the second surfactant being selected from the group consisting of anionic surfactants, nonionic surfactants, and cationic surfactants. The composition of claim 1 further comprising:

15. The composition of claim 1 further comprising at least one anionic polymer.

16. 10. The composition of claim 1, further comprising at least one dienoic acid.

17. polishing a substrate with the CMP composition to form a polished substrate; and contacting the polished substrate with the composition of claim 1 to clean the polished substrate. A method for cleaning a substrate, comprising:

18. 18. The method of claim 17, wherein the substrate is a wafer having a surface comprising SiN, SiC, TiN, TaN, W, silicon oxide, Cu, Co, Ru, Mo, Ti, Ta, Al, carbon, silicon, hafnium oxide, aluminum oxide, zirconium oxide, p-Si, or a combination thereof.

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