Cleaning composition and method of using the same

Abstract

The present invention provides a cleaning composition that can be used to clean semiconductor substrates. [Solution] The cleaning composition described herein mainly comprises at least one organic acid and at least one anionic polymer.

Description

Technical Field

[0001] The present invention relates to a cleaning composition and a method of using the same.

Background Art

[0002] The present invention claims priority from U.S. Provisional Application No. 62 / 991,612, filed on March 19, 2020, the content of which is incorporated herein by reference in its entirety.

[0003] The semiconductor industry is continuously driven to improve chip performance through further miniaturization of devices through process innovation and integration innovation. Chemical mechanical polishing / planarization (CMP) is a powerful technique because it enables many complex integration schemes at the transistor level, thereby facilitating improved chip density.

[0004] CMP is a process used to planarize / flatten the wafer surface by removing material using a polishing-based physical process in parallel with a surface-based chemical reaction. Generally, the CMP process involves contacting the wafer surface with a polishing pad and moving the polishing pad relative to the wafer while applying a CMP slurry (e.g., an aqueous chemical formulation) to the wafer surface. The slurry typically contains a polishing component and dissolved chemical components. These can vary widely depending on the materials (e.g., metals, metal oxides, metal nitrides, dielectric materials such as silicon oxides, silicon nitrides, etc.) present on the wafer that will interact with the slurry and the polishing pad during the CMP process.

[0005] After CMP processing, various contaminants may be present on the surface of the polished wafer. These contaminants may include, for example, 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 left on the surface of the polished wafer, these contaminants may lead to defects during further wafer processing steps and / or reduced device performance. Figure 1 shows four different types of defects after CMP polishing: scratches, residual abrasives, blob-like organic particles, and dust-like organic particles.

[0006] Therefore, the contaminants must be efficiently removed so that the wafer can proceed with further processing in a predictable manner 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 post-CMP (P-CMP) cleaning compositions. These P-CMP cleaning solutions / formulations are intended to solubilize defects remaining on the wafer surface after the CMP step, thereby removing these defects and cleaning the wafer surface. This ensures that the device performance and chip yield are satisfactory after the wafer undergoes further processing.

[0007] The post-CMP cleaning process can be carried out using a brush box (containing brushes for mechanical action) or a megasonic (advanced ultrasonic / sonic treatment for mechanical action) as an attachment / module on the CMP polishing tool. To begin the P-CMP cleaning process, the brush box or megasonic is flooded with the P-CMP cleaning composition. Then, after the CMP polishing process is complete, the CMP-polished wafer is passed through the brush box and / or megasonic containing the P-CMP cleaning composition on the CMP polishing tool. In the best-case scenario, the wafer will have a very low defect state and be dry and clean after being subjected to chemical action with the post-CMP cleaning composition and scrubbing mechanical action with brushes and / or ultrasonic treatment. [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] In semiconductor chip manufacturing, the defect status on the wafer surface is key to wafer yield. A typical wafer goes through approximately 1000 processes before the chip is fabricated and individual dies are cut from the wafer. In each of these processes, the defect status is monitored before and after the process. CMP is a critical step in chip manufacturing. However, the CMP step introduces many defects after the polishing step (see pre-images in Figures 1 and 2). Therefore, after the CMP polishing step, a post-CMP (P-CMP) cleaning composition is typically applied to the wafer surface to reduce defects (see post-treatment image in Figure 2). This disclosure features a novel P-CMP cleaning composition that not only reduces wafer defects but also provides various other desirable electrochemical properties that are crucial for chip manufacturing. For example, these P-CMP cleaning compositions not only reduce the defect status (thus increasing yield) but also ensure that there is no galvanic corrosion (or other forms of corrosion) when metals and metal oxides and metal nitrides come into contact with each other on the patterned wafer. [Means for solving the problem]

[0009] This disclosure relates to cleaning compositions that can be used to clean semiconductor substrates. For example, these cleaning compositions can be used to remove defects that have occurred in previous processing steps on these semiconductor substrates, such as CMP. In particular, these cleaning compositions can remove defects / impurities from semiconductor substrates, thereby making the substrates suitable for further processing. The cleaning compositions described herein generally comprise an organic acid and an anionic polymer and have a pH in the range of 0.1 to 7.

[0010] In one embodiment, the present disclosure features a cleaning composition comprising at least one first organic acid; at least one second organic acid different from the at least one first organic acid, the second organic acid comprising dienoic acid; at least one anionic polymer; and water, the composition having a pH of about 0.1 to about 7.

[0011] In another embodiment, the present disclosure features a cleaning composition comprising at least one organic acid; an anionic polymer including poly(4-styrenesulfonic acid) (PSSA), polyacrylic acid (PAA), poly(vinylphosphonic acid) (PVPA), poly(2-acrylamido-2-methyl-1-propanesulfonic acid), poly(N-vinylacetamide) (PNVA), 2-acrylamido-2-methyl-1-propanesulfonic acid-acrylic acid copolymer, and poly(4-styrenesulfonic acid-co-acrylic acid-co-vinylphosphonic acid) ternary polymer; and water, wherein the composition has a pH of about 0.1 to about 7.

[0012] In another embodiment, the Disclosure features a method for cleaning a wafer surface, comprising contacting a wafer having a surface containing SiN, SiC, TiN, W, Ru, Mo, TEOS, Cu, TaN, Co, or p-Si with a cleaning composition described in the Disclosure.

[0013] In another embodiment, the present disclosure features a method for cleaning a substrate, which includes bringing the substrate into contact with a cleaning composition described herein.

[0014] This summary is provided to introduce selected concepts from those further described in the detailed description below. This summary is not intended to identify key or essential features of the subject matter described in the claims, nor is it intended to be used to help limit the scope of the subject matter described in the claims. [Brief explanation of the drawing]

[0015] [Figure 1] Figure 1: Examples of various types of defect states encountered before and after cleaning with post-CMP cleaning agents. These four defect states (scratch, residual polishing, 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 scanning electron microscope tool. [Figure 2] Total Defect Count (TDC) on silicon nitride wafers, collected with KLA's AIT XUV tool. The first and second rows show the TDC on two wafers (i.e., wafer 1 and wafer 2) after CMP and before treatment with the P-CMP cleaning composition (also referred to as pre-images). The third and fourth rows show the TDC on these two wafers after treatment with the P-CMP cleaning composition (also referred to as post-images). The TDC count is shown next to each wafer. The comparative example (first column) was the industry standard Fujifilm Wako Pure Chemical Industries P-CMP cleaner CLEAN-100. The second, third, and fourth columns show cleaners A, B, and C, which are P-CMP cleaning compositions from this disclosure. As seen in the wafer map, the comparative example gave only about a 40% improvement in defect status, while cleaners A-C of the present invention gave about 90%-98% defect reduction. [Figure 3]Total defect count (TDC) on tungsten (W) wafers and titanium nitride (TiN) wafers before and after cleaning with cleaner C (PRE TDC) using KLA's AIT XUV tool. [Figure 4] Total defect count (TDC) on various nonmetallic / silicon dielectric films collected with KLA's AIT XUV tool. TDCs are shown before cleaning after CMP with cleaner C (PRE TDC) and after cleaning after CMP (PST TDC). The films shown are (from left to right): i) TEOS (a form of silicon oxide), ii) LK (Low k dielectric), iii) ULK (Ultra low k dielectric), iv) HARP (another form of silicon oxide), v) SiN (silicon nitride), and vi) SiC (silicon carbide). [Figure 5] Total defect count (TDC) on patterned wafers containing multiple metallic and non-metallic films, collected using KLA's AIT XUV tool. The TDC shown is after post-CMP cleaning with cleaner C (PST TDC). Patterned wafers containing multiple chips have approximately 150 PST-TDC for defects larger than 180 nm. [Modes for carrying out the invention]

[0016] Embodiments disclosed herein generally relate to cleaning compositions and methods for using such compositions to clean substrates (e.g., semiconductor substrates such as wafers). In particular, the cleaning compositions can be used to clean substrates after a CMP process. However, the cleaning compositions described herein may also be used to remove residues and / or impurities from the substrate surface after an etching process, an ashing process, or a plating process.

[0017] In the definitions of this disclosure, residues and / or impurities 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 chemical reactions 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 released during the CMP process, and / or any other removable materials known to deposit on the substrate after the CMP process.

[0018] In one or more embodiments, the cleaning composition described herein comprises (1) at least one first organic acid, (2) at least one second organic acid different from the at least one first organic acid, the second organic acid comprising a dienoic acid, and (3) at least one anionic polymer. In one or more embodiments, the cleaning composition of the present disclosure may comprise about 0.00001% to about 50% by weight (e.g., about 0.01% to about 5%) of the at least one first organic acid, about 0.0001% to about 0.5% by weight (e.g., about 0.01% to about 0.1%) of the at least one second organic acid, about 0.00001% to about 50% by weight (e.g., about 0.005% to about 10%) of the at least one anionic polymer, and a solvent (e.g., deionized water) comprising the remaining weight % (e.g., about 60% to about 99.99%).

[0019] In one or more embodiments, the Disclosure provides a concentrated P-CMP cleaning composition that can be diluted with water up to 20, 50, 100, 200, 400, 800, or 1000 times to obtain a point-of-use (POU) cleaning composition. In a preferred embodiment, the POU cleaning composition is diluted 200 times. In other embodiments, the Disclosure provides a point-of-use (POU) cleaning composition that can be used directly to clean a substrate surface.

[0020] 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., polycarboxylic acid), about 0.0001% to about 0.1% by weight of at least one second organic acid (e.g., dienoic acid), and about 0.00001% to about 5% by weight of at least one anionic polymer. 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., polycarboxylic acid), about 0.0001% to about 0.1% by weight of at least one second organic acid (e.g., dienoic acid), about 0.00001% to about 5% by weight of at least one third organic acid (e.g., amino acid) different from the first and second organic acids, and about 0.00001% to about 5% by weight of at least one anionic polymer.

[0021] In one or more embodiments, 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 0.5% by weight of at least one second organic acid (e.g., dienoic acid), and about 0.005% to about 15% by weight of at least one anionic polymer. 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 0.5% by weight of at least one second organic acid (e.g., dienoic acid), about 0.01% to about 5% by weight of at least one third organic acid (e.g., amino acid) different from the first and second organic acids, and about 0.005% to about 15% by weight of at least one anionic polymer.

[0022] In one or more embodiments, the cleaning compositions described herein may comprise at least one (e.g., two, three, or four) organic acids. In this disclosure, the term “acid” encompasses acids and their salts (e.g., potassium or sodium salts thereof). In some embodiments, the 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, the at least one organic acid may be an acid or a salt thereof 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(methylene phosphonic acid), bis(hexamethylene)triamine phosphonic 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, 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, 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 a mixture thereof, salts thereof, and mixtures of these salts.

[0023] In one or more embodiments, the at least one organic acid is included in the composition in an amount of from about 0.00001% to about 50% by weight based on the cleaning composition. For example, the at least one organic acid may be present in the cleaning composition described in the present disclosure 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).

[0024] In one or more embodiments, the cleaning composition described in the present disclosure may include at least one first organic acid. In some embodiments, the at least one first organic acid may 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, the at least one first organic acid may 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(methylene phosphonic acid), bis(hexamethylene)triamine phosphonic acid, peracetic acid, phenoxyacetic acid, benzoic acid, and mixtures thereof. In some embodiments, the at least one first organic acid may be a tricarboxylic acid (e.g., citric acid). In some embodiments, the at least one first organic acid does not include amino acids or dienoic acids.

[0025] In one or more embodiments, the at least one first organic acid 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 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, or about 1% by weight or less) relative to the cleaning composition described herein.

[0026] In one or more embodiments, the cleaning composition described herein may include at least one second organic acid, which is different from the 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, the dienoic acid is a carboxylic acid containing a diene, for example, 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-deca Dienoic acid, 2,5-decadienoic 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.

[0027] In one or more embodiments, the 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) relative to the cleaning composition described herein.

[0028] While we do not wish to be bound by theory, it is believed that including a second organic acid (e.g., dienoic acid) in the aforementioned quantity range can improve corrosion protection of certain metals and metal-containing films (e.g., W, Cu, TaN, or TiN) on the substrate during the post-CMP cleaning process. As shown in the examples below, electrochemical tests of several embodiments containing dienoic acid (e.g., sorbic acid) showed better metal (e.g., W) corrosion protection than P-CMP compositions without dienoic acid.

[0029] In one or more embodiments, the cleaning composition described herein may contain at least one third organic acid, which is different from the at least one first organic acid and the second organic acid. In some embodiments, the at least one third organic acid may be an amino acid (e.g., a natural amino acid or a non-natural amino acid). In some embodiments, the at least one third organic acid 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.

[0030] In one or more embodiments, the at least one third organic acid may be 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, 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) relative to the cleaning composition described herein.

[0031] In one or more embodiments, the cleaning composition described herein comprises two organic acids, for example, (1) citric acid and histidine, or (2) citric acid and glycine. In some embodiments, the cleaning composition comprises three organic acids, for example, (1) citric acid, histidine, and sorbic acid, or (2) citric acid, histidine, and glycine. In some embodiments, the cleaning composition comprises four organic acids (for example, citric acid, histidine, sorbic acid, and glycine).

[0032] In one or more embodiments, the cleaning composition may contain at least two or at least 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 relative to 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 relative to the cleaning composition described herein. In several other embodiments, the third organic acid (e.g., amino acid) is present in an amount of about 0.005% to about 5% by weight relative to the cleaning composition described herein.

[0033] In one or more embodiments, the cleaning composition described herein may comprise at least one (e.g., two or three) anionic polymer. In one or more embodiments, the at least one anionic polymer may comprise one or more anionic groups, examples of which include 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, vinylphosphonic acid, vinyl phosphoric acid, vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, acrylamide, acrylamidopropyl sulfonic acid, and sodium phosphinite. In a specific embodiment, the 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), polyethyleneimine (PEI), anionic poly(methyl methacrylate) (PMMA), anionic polyacrylamide (PAM), polyaspartic acid (PASA), anionic poly(ethylene succinate) (PES), anionic polybutylene succinate (PBS), poly(vinyl The following may be selected from the group consisting of (PVA) alcohol, 2-propenoic acid copolymer with 2-methyl-2-((1-oxo-2-propenyl)amino)-1-propanesulfonic acid monosodium salt and sodium phosphinite, 2-propenoic acid copolymer with 2-methyl-2-((1-oxo-2-propenyl)amino)-1-propanesulfonic acid monosodium salt and sodium bisulfite sodium salt, 2-acrylamido-2-methyl-1-propanesulfonic acid-acrylic acid copolymer, poly(4-styrenesulfonic acid-co-acrylic acid-co-vinylphosphonic acid) ternary polymer, and mixtures thereof.While we do not wish to be bound by theory, it is believed that the anionic polymer can solubilize hydrophobic polishing materials and defects on the wafer surface, thereby facilitating their removal during the post-CMP cleaning process.

[0034] In one or more embodiments, the 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, about 2,000 g / mol or more, about 5,000 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, the 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, the 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, the at least one anionic polymer may have a weight-average molecular weight of about 5,000 g / mol.

[0035] In some embodiments, the cleaning composition described herein comprises 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) ternary polymer. In some embodiments, the cleaning composition described herein comprises two anionic polymers such as (1) poly(4-styreneylsulfonic acid) and poly(acrylic acid), or (2) 2-acrylamido-2-methyl-1-propanesulfonic acid-acrylic acid copolymer and poly(acrylic acid).

[0036] In one or more embodiments, the at least one anionic polymer is included in the composition in an amount of about 0.00001% to about 50% by weight relative to the cleaning composition. For example, the amount of the at least one anionic polymer relative to the cleaning composition described in this disclosure may be 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).

[0037] In some embodiments, the cleaning composition may contain two or more or three or more anionic polymers. In some embodiments, the first anionic polymer is present in an amount of about 0.0005% to about 50% by weight relative to 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 relative to the cleaning composition described herein. In several other embodiments, the third anionic polymer is present in an amount of about 0.0005% to about 10% by weight relative to the cleaning composition described herein.

[0038] In some embodiments, the pH value of the cleaning composition may be in the range of 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, about 4 or less, about 3.5 or less, about 3 or less, about 2.5 or less, or about 2 or less) to about 0.1 or more (e.g., about 0.2 or more, about 0.5 or more, about 1 or more, about 2 or more, about 2.5 or more, about 3 or more, or about 3.5 or more). While we do not wish to be bound by theory, it is believed that if the cleaning composition described herein has an acidic pH in the above range, the cleaning composition can supply enough protons to solubilize organic residues generated from CMP polishing of substrates and can provide sufficient cleaning action to solubilize polishing by-products including inert metals (e.g., W, Cu).

[0039] While we do not wish to be bound by theory, it is believed that the cleaning compositions described herein can still achieve better performance (e.g., better cleaning efficiency and / or lower corrosion of exposed materials on the substrate) while containing far lower concentrations / amounts of a single chemical material or a group of chemical materials as a whole compared to conventional cleaners currently used in the semiconductor industry (e.g., CLEAN-100). For example, the cleaning compositions described herein may contain only about 5-20% by weight (e.g., about 5-15% by weight) of a chemical material, or the total amount of a group of chemical materials, compared to the same chemical material (e.g., organic acid or anionic polymer) in conventional cleaners (e.g., CLEAN-100), or the total amount of a group of chemical materials. As a result, the cleaning compositions described herein are believed to be more cost-effective, environmentally friendly, and offer a much better overall cost of ownership in the field of use compared to conventional cleaners (e.g., CLEAN-100) (because the cleaning compositions are highly dilutable (e.g., up to 200x)).

[0040] In one or more embodiments, the cleaning composition described herein includes an organic solvent, a pH adjuster, a quaternary ammonium compound (e.g., a salt or hydroxide), an alkaline base (e.g., an alkaline hydroxide), a fluorine-containing compound, a silane (e.g., an alkoxysilane), a nitrogen-containing compound (e.g., an amino acid, an amine, or an imine, such as an amidine such as 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) and 1,5-diazabicyclo[4.3.0]nona-5-ene (DBN)), a polyol, a salt (e.g., a halide salt or a metal salt), a polymer (e.g., a cationic poly The cleaning composition may be substantially free of one or more specific components, such as polymers, nonionic 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), plasticizers, oxidizing agents (e.g., H2O2), corrosion inhibitors (e.g., azole or non-azole corrosion inhibitors), electrolytes (e.g., polymer electrolytes), and / or abrasives (e.g., silica / ceria abrasives, nonionic abrasives, surface-modifying abrasives, or negatively / positively charged abrasives). Examples of 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), which may be chlorides, bromides, or iodides. In this disclosure, "substantially free" components in the cleaning composition refer to components that are not intentionally added to the cleaning composition. In some embodiments, the cleaning compositions described herein may contain one or more of the above components that are substantially absent from the cleaning composition in an amount of about 1000 ppm or less (for example, 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). In some embodiments, the cleaning compositions described herein may be completely absent from one or more of the above components.

[0041] In one or more embodiments, the cleaning compositions described herein may include a biocide. Examples of 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 relative to the cleaning composition described herein.

[0042] When applied to post-CMP cleaning operations, the cleaning compositions described herein can typically be used to remove contaminants present on the substrate surface after the CMP treatment step. In one or more embodiments, the contaminants causing defect conditions may be 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, etc. In one or more embodiments, the cleaning compositions of the herein may be used to remove organic residues consisting of organic particles that are not needed in water and therefore remain on the wafer surface after the CMP polishing step. In another embodiment, the cleaning compositions of the herein may be used to remove abrasive residues / particles and / or polishing by-products to reduce scratches that cause defect conditions on the wafer surface after the CMP polishing step.

[0043] While we do not wish to be bound by theory, it is thought that organic particles are formed from polishing composition components that deposit on the substrate surface after polishing and remain on the wafer surface as impurities because they are insoluble. The presence of these impurities results in a defect count on the wafer surface. When these defect counts are analyzed by a defect measurement tool (e.g., the AIT-XUV tool available from KLA), they give a total defect count (TDC), which is the sum of all individual defect counts (see Figure 2). 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 wafer surface by the post-CMP cleaning composition is called the cleaning efficiency of the cleaning composition and is expressed as a percentage. The higher the percentage, the better the cleaning efficiency, and the more powerful / stronger / effective the cleaning composition.

[0044] While we do not wish to be bound by theory, we believe that the components of the cleaning compositions of this disclosure exhibit surprising and unpredictable synergistic effects. For example, the organic acids reduce scratches and solubilize metal oxide and silica-containing residues (e.g., abrasive residues on wafers) that can cause scratch formation; the amino acids act as corrosion inhibitors for metals (e.g., tungsten); and the anionic polymers are excellent solubilizers for hydrophobic organic residues left on the substrate surface after the CMP process. Furthermore, the combination of organic tricarboxylic acids (e.g., citric acid) and dienoic acids (e.g., sorbic acid), along with optionally amino acids (e.g., histidine or glycine) and anionic polymers, is thought to exhibit a significant reduction in metal galvanic corrosion, which is key to improving the yield of substrates cleaned after CMP.

[0045] In some embodiments, the Disclosure features a method for cleaning a substrate (e.g., a wafer). This method may include contacting the substrate with the cleaning composition of the Disclosure. 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 range of conventional cleaning tools and techniques (e.g., brush scrubbing, spin rinse drying, etc.). In one or more embodiments, after the CMP polishing step, the cleaning composition described in the Disclosure may be used in the megasonic cleaner module or brush box 1 or brush box 2 of the Applied Materials Reflexion 300mm CMP polishing tool. The brush box has brushes for scrubbing, while the cleaning composition provides a chemical action to remove defects. The cleaning composition may be applied to the wafer surface in the brush box or the megasonic at a temperature in the range of 20°C to 60°C for a time in the range of about 5 seconds to about 10 minutes (e.g., about 15 seconds to 5 minutes).

[0046] In addition to the brush box and / or megasonic cleaner, the cleaning composition described herein may be used as an abrasive-free buffing chemical material for buffing wafers on platens in a Reflexion polishing machine to remove defects by buffing wafers on a soft pad with the cleaning composition present on the polishing pad. In other embodiments, the cleaning composition may be used in a buffing station to buff on soft plomeric pads in a buffing station module of a 4-platen Applied Materials Reflexion Prime 300 mmCMP polishing tool.

[0047] In some embodiments, the substrate to be cleaned may contain at least one material selected from the group consisting of low-k dielectrics (e.g., porous silicon oxide with k<3.5), ultralow-k dielectrics (e.g., ultraporous silicon oxide with k<2.5), tungsten, titanium nitride, tantalum nitride, silicon carbide, silicon oxide (e.g., TEOS), silicon nitride, copper, cobalt, molybdenum, ruthenium, and polysilicon) on the wafer surface that may be exposed to the cleaning composition during the cleaning process.

[0048] In some embodiments, the method using the cleaning composition described herein may further include manufacturing a semiconductor device from a substrate treated with the cleaning composition in one or more steps. To manufacture a semiconductor device from a substrate treated with the cleaning composition of the herein, for example, photolithography, ion implantation, dry / wet etching, plasma etching, deposition (e.g., PVD, CVD, ALD, ECD), wafer mounting, die cutting, packaging, and testing may be used.

[0049] Only a few exemplary embodiments are described below, but those skilled in the art will readily understand that many modifications are possible in the subsequent exemplary embodiments without departing essentially from the present invention. Accordingly, all such modifications are intended to fall within the scope of the present disclosure as defined in the claims. [Examples]

[0050] Examples are given to further illustrate the capabilities of the CMP post-cleaning compositions and methods of this disclosure. The given examples are not intended, nor should they be construed, as limiting the scope of this disclosure. Percentages listed are by weight (wt%) unless otherwise noted. The anionic polymers described in the examples were obtained from various suppliers and in some cases have minor differences in carbon chain length and molecular weight. The examples shown in this disclosure are representative and do not encompass the full scope of the disclosure of the present invention.

[0051] Example 1: Demonstration of defect reduction on silicon nitride wafers and post-CMP cleaning efficiency of post-CMP cleaning composition. In this embodiment, the control / comparative CMP post-cleaning composition was Fujifilm Wako Pure Chemical Industries CLEAN-100, a leading industrial product that has been used as the standard industrial CMP post-cleaning composition for cleaning copper interconnects for over a decade. Wako Pure Chemical Industries CLEAN-100 is generally known to contain citric acid, a nonpolymeric surfactant, and water. As shown in Figure 2 and Table 1, four representative examples of p-CMP cleaners from this disclosure (i.e., cleaners A, B, C, and D) were compared to CLEAN-100. Cleaner A contained one anionic polymer (i.e., poly(vinylphosphonic acid)) and two organic acids (i.e., citric acid and glycine). Cleaner B contained two anionic polymers (i.e., poly(4-styrenesulfonic acid) and poly(acrylic acid)) and three organic acids (i.e., citric acid, sorbic acid, and histidine). Cleaner C contained one type of anionic polymer (i.e., 2-acrylamido-2-methyl-1-propanesulfonic acid-acrylic acid copolymer) and three types of organic acids (i.e., citric acid, sorbic acid, and histidine). Cleaner D contained one type of anionic polymer (i.e., poly(4-styrenesulfonic acid-co-acrylic acid-co-vinylphosphonic acid) ternary polymer) and one type of organic acid (i.e., citric acid).

[0052] In the comparative example, CLEAN-100 was diluted 100-fold to obtain a point-of-use (POU) cleaning composition. On the other hand, the examples of this disclosure, namely Cleaners A to D, were each diluted 200-fold to obtain POU post-CMP cleaning compositions.

[0053] For post-CMP cleaning performance testing, the generated defect state (pre-cleaning TDC) on a 12-inch SiN wafer was measured. The 12-inch SiN wafer was then polished using an Applied Materials Reflexion polishing machine. The brush box of the polishing machine (including the PVA brush) was filled with a P-CMP cleaning composition (CLEAN-100 or Cleaners A-D; in separate, independent CMP polishing runs on different SiN blanket wafers). After CMP polishing, the SiN wafer was moved through the brush box containing the P-CMP cleaning composition. After cleaning by a combination of chemical and mechanical actions, the SiN wafer was discharged in a dry state (dry-in and dry-out tools), and the post-cleaning defect state (post-cleaning TDC) was measured using an AIT tool from KLA. The pre-cleaning and post-cleaning TDCs are summarized in Table 1 below and shown in Figure 2. Specifically, Figure 2 shows the total defect count (TDC) wafer maps before (pre-) and after (post-) cleaning with CLEAN-100 and cleaners A-C on a silicon nitride (SiN) wafer. Table 1 summarizes and quantifies the results for CLEAN-100 and cleaners A-D.

[0054] As shown in Table 1, the comparative example CLEAN-100 showed a cleaning efficiency of 40% on the SiN blanket film. In other words, the TDC on the SiN wafer decreased by 40% after using CLEAN-100 as the post-CMP cleaning composition. Typically, for a good post-CMP cleaning composition, the cleaning efficiency should be >60%. Surprisingly, the P-CMP cleaning compositions of this disclosure were particularly effective in cleaning the SiN wafer surface. As shown in Table 1, the cleaning efficiencies of cleaners A to D were 89%, 97%, 98%, and 92%, respectively. The cleaning efficiency was calculated using the following formula. Washing efficiency = [(TDC before washing - TDC after washing) / TDC before washing] × 100

[0055] Table 1. Defect status of SiN blank wafers and total defect count (TDC) before and after cleaning. [Table 1]

[0056] Since Cleaner C was the most effective post-CMP cleaning composition, Cleaner C was further tested in other examples on other films such as Cu&TaN (Example 2), W&TiN (Example 3), and nonmetals such as silicon oxide (TEOS&HARP), silicon nitride, and silicon carbide (Example 4). Cleaner C contained a 2-acrylamide-2-methyl-1-propanesulfonic acid-acrylic acid copolymer (anionic polymer), citric acid (first organic acid), sorbic acid (second organic acid, dienoic acid), and histidine (third organic acid, amino acid). The anionic polymer is a copolymer of 2-acrylamide-2-methyl-1-propanesulfonic acid and acrylic acid, referred to in this disclosure as "2-acrylamide-2-methyl-1-propanesulfonic acid-acrylic acid copolymer" and has CAS number 40623-75-4.

[0057] The performance of cleaner C on a patterned wafer (containing multiple metallic and non-metallic films) in the post-CMP cleaning process is described in Example 5. For Examples 2, 3, 4, and 5, cleaner C was diluted 200-fold to obtain a POU post-CMP cleaning composition.

[0058] Since Cu and W are the two most important metals in semiconductor processing, the wafer maps of these metal combinations using Cleaner C were examined not only for defect states but also for their electrochemical properties. Cleaner C was also investigated for its cleaning efficiency after TDC and CMP on non-metallic / silicon dielectric films (see Example 4).

[0059] Example 2: Post-CMP cleaning performance and electrochemical properties of cleaner C on a Cu&TaN assembly. In this embodiment, the cleaner C, a composition according to the present invention, was investigated on blanket copper (Cu) wafers and blanket tantalum nitride (TaN) wafers for its defect state performance / TDC reduction and electrochemical properties / galvanic corrosion properties. Cu is typically found in back-end interconnect structures and is responsible for the wiring of transistors. Cu exists in a multi-level metallization state with TaN, which prevents electron leakage as it moves through the Cu wiring. Therefore, it is typical to see Cu metal surrounded by a TaN barrier metal nitride. For this reason, both Cu wafers and TaN wafers were tested in this embodiment.

[0060] The average TDC on Cu blanket wafers and TaN blanket wafers before and after cleaning was measured using KLA's AIT XUV tool, and the results are summarized in Table 2. As shown in Table 2, cleaner C surprisingly showed high cleaning efficiency (i.e., 89%) on TaN blanket wafers.

[0061] Table 2. Defect reduction performance of cleaner C on Cu blanket wafers and TaN blanket wafers. [Table 2]

[0062] Table 3 summarizes the electrochemical properties of Cleaner C, Cleaner C without dienoic acid, and comparative CLEAN-100 on Cu blanket wafers and TaN blanket wafers. As shown in Table 3, Cleaner C exhibited a very low static etching rate (SER), namely 9.2 A / min on the Cu film and 0.2 A / min on the TaN film, compared to Cleaner C without dienoic acid and CLEAN-100 (which contains neither anionic polymers, amino acids, nor dienoic acid). In addition, Cleaner C showed a smaller galvanic corrosion coupling current (ΔEcorr.) of approximately 735 mV compared to Cleaner C without dienoic acid and CLEAN-100. These results suggest that Cleaner C showed significantly reduced corrosion of Cu and TaN after post-CMP cleaning compared to Cleaner C without dienoic acid and CLEAN-100. In other words, compared to Cleaner C and CLEAN-100 without dienoic acid, Cleaner C after CMP showed better electrochemical properties. While we do not wish to be bound by theory, it is thought that the synergistic effect of the amino acid (histidine) and dienoic acid (sorbic acid) in Cleaner C (which together act synergistically as a dual corrosion inhibitor for surface protection and passivation of Cu and TaN) compared to Cleaner C and CLEAN-100 without dienoic acid gave Cleaner C a much lower SER and corrosion potential.

[0063] Table 3. Static etching rate (SER) and electrochemical properties / corrosion characteristics of the present invention's formulation (Cleaner C) and comparative formulation (CLEAN-100) of back-end obline (BEOL) metals such as copper (Cu) and liners such as tantalum nitride (TaN). [Table 3]

[0064] Example 3: Post-CMP cleaning performance and electrochemical properties of a W and TiN combination using cleaner C. In this embodiment, cleaner C, a composition according to the present invention, was investigated on tungsten (W) blanket wafers and titanium nitride (TiN) blanket wafers for its defect state performance / TDC reduction and electrochemical properties / galvanic corrosion properties. W is typically present in the front-end metal gate region, and in contacts, vias, and plugs. Apart from Cu, W is the most widely found metal in semiconductors. W typically occurs in tandem with a TiN barrier that prevents electron leakage as it moves through W metal gates, plugs, contacts, or wiring. Therefore, it is typical to see W metal surrounded by a TiN barrier metal nitride. For this reason, both W and TiN were tested in this embodiment.

[0065] Table 4: Defect reduction performance of cleaner C on W blanket wafers and TiN blanket wafers. [Table 4]

[0066] Table 4 summarizes the average TDC on W blanket wafers and TiN blanket wafers before and after cleaning, and is shown in Figure 3. As shown in Table 4, the post-CMP cleaning performance of cleaner C on the W film was high at 93%, indicating that cleaner C was remarkably effective in cleaning W wafers.

[0067] Table 5 summarizes the electrochemical properties of Cleaner C, Cleaner C without dienoic acid (sorbic acid), and comparative CLEAN-100 on W blanket wafers and TiN blanket wafers. Table 5 also includes two other compositions, Cleaner E and F, which are identical to Cleaner C except that the histidine used in Cleaner C is replaced with equal amounts of glycine and aspartic acid, respectively. As can be seen in Table 5, among the tested cleaning compositions, Cleaner C showed a relatively low static etching rate (SER), namely 1.48 A / min on the W film and 0.068 A / min on the TiN film. In addition, Cleaner C exhibited the lowest galvanic corrosion coupling current voltage (ΔEcorr.) of approximately 119 mV, and a lower SER compared to CLEAN-100 (which does not contain anionic polymers, amino acids, or dienoic acid) or Cleaner C without dienoic acid. This indicates that substantially less corrosion of W and TiN is present after post-CMP cleaning with Cleaner C compared to CLEAN-100 or Cleaner C without dienoic acid. While we do not wish to be bound by theory, it is thought that the synergistic combination of the first organic acid (carboxylic acid), second organic acid (dienoic acid), and third organic acid (amino acid) present in Cleaner C can significantly reduce SER and improve metal corrosion protection. In conclusion, since Cleaner C had lower galvanic corrosion and a much lower SER, post-CMP Cleaner C (containing dienoic acid) showed the best electrochemical properties compared to CLEAN-100.

[0068] Table 5. Static etching rate (SER) and electrochemical properties / corrosion characteristics of the front-end (FEOL) metal such as tungsten (W) and the liner such as titanium nitride (TiN) for the formulation and comparative formulation (CLEAN-100) according to the present invention.

[0069] [Table 5]

[0070] Example 4. Post-CMP cleaning performance on non-metallic / silicon dielectrics using Cleaner C. On a typical patterned wafer / device wafer, metals such as Cu and W exist together with nonmetals / insulators such as silicon oxide, silicon nitride, and silicon carbide. The metals / wirings conduct electricity / electrons, while the nonmetals / insulators surround the metals, preventing electron leakage. The most important metals are generally Cu and W, while the most important insulators / dielectrics are generally silicon oxide and silicon nitride. Therefore, it is desirable that the cleaning composition has effective cleaning performance on these insulators / nonmetals, because these insulators / nonmetals are mixed with metals on any semiconductor chip.

[0071] In this embodiment, Cleaner C, a composition according to the present invention, was tested on various nonmetals commonly found as silicon-based dielectric films. Specifically, the silicon-based dielectric films tested were i) TEOS (a form of silicon oxide), ii) LK (low k dielectric; e.g., porous silicon oxide with k < 3.5), ULK (ultra-low k dielectric; e.g., ultraporous silicon oxide with k < 2.5), iv) HARP (another form of silicon oxide), v) SiN (silicon nitride), and vi) SiC (silicon carbide). The average TDC on the dielectric bracket wafer before and after cleaning with Cleaner C, and the cleaning efficiency of Cleaner C on these six films are summarized in Table 6.

[0072] The main silicon-based dielectrics attracting attention as insulators for Cu and W conductors in semiconductor devices are silicon oxides (TEOS and HARP) and silicon nitrides (SiN). As shown in Table 6, cleaner C surprisingly demonstrated outstanding cleaning efficiency on both silicon oxides (99% for TEOS and 99.8% for HARP) and on silicon nitrides (91%).

[0073] Table 6. Defect reduction performance of cleaner C on non-metallic / silicon blanket wafers [Table 6]

[0074] Example 5. Post-CMP cleaning performance on a patterned device wafer using Cleaner C. Examples 1-4 demonstrated the performance of Cleaner C on a blanket film containing only one type of material exposed to the post-CMP cleaning composition. However, actual chips / devices typically contain many metallic and non-metallic film types on a single chip. These multi-film wafers are called patterned wafers, and once all fabrication / processing is performed on the patterned wafer, they are cut into dies / individual chips.

[0075] In Example 5, the performance of Cleaner C was tested on a patterned wafer polished by the CMP process. After cleaning with Cleaner C, the total defect count (TDC) was analyzed using KLA's AIT-XUV defect state measurement tool. Figure 5 shows the TDC map of the patterned wafer after cleaning with Cleaner C diluted 200 times as a put-to-use (POU) dilution. As can be seen from Figure 5, the patterned wafer was very clean and had a very low defect state. The TDC for the patterned wafer was low, with approximately 150 defects with a size greater than 180 nm. This further confirms the high defect state cleaning efficiency of the cleaning composition of this disclosure on patterned wafers / device wafers.

[0076] While this disclosure has been described in relation to the embodiments described herein, it is understood that other modifications and variations are possible without departing from the spirit and scope of this disclosure as set forth in the attached claims. The embodiments relating to this disclosure also include the following embodiments: <1> At least one first organic acid; At least one second organic acid different from the at least one first organic acid, wherein the at least one second organic acid includes a dienoic acid; At least one anionic polymer; and water; Includes, A cleaning composition having a pH of approximately 0.1 to 7. <2> The above-mentioned at least one first organic acid includes a monocarboxylic acid or a polycarboxylic acid. <1> The composition described above. <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, potassium acetate, phenoxyacetic acid, benzoic acid, and mixtures thereof. <1> The composition described above. <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. <1> The cleaning composition described above. <5> The at least one first organic acid is present in the composition in an amount of about 0.00001% to about 50% by weight. <1> The composition described above. <6> The above-mentioned at least one second organic acid includes a dienoic acid having 5 to 22 carbon atoms. <1> The composition described above. <7> The above-mentioned 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-de Includes cadienoic 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. <6> The composition described above. <8> The aforementioned at least one second organic acid is present in an amount of about 0.0001% to about 0.5% by weight relative to the cleaning composition. <1> The composition described above. <9> A third organic acid, different from the aforementioned first and second acids, further comprising a third organic acid containing an amino acid. <1> The composition described above. <10> The above-mentioned at least one third organic acid includes aminocarboxylic acid, glycine, bicine, tricine, alanine, histidine, valine, phenylalanine, proline, glutamine, aspartic acid, glutamic acid, arginine, lysine, tyrosine, or a mixture thereof. <9> The composition described above. <11> The aforementioned at least one third organic acid includes glycine, histidine, alanine, proline, arginine, lysine, aspartic acid, or a mixture thereof. <9> The composition described above. <12> The aforementioned at least one third organic acid is present in the composition in an amount of about 0.001% to about 20% by weight. <9> The composition described above. <13> 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, acrylamide, malic acid, methacrylic acid, vinylphosphonic acid, vinylsulfonic acid, allylsulfonic acid, styrenesulfonic acid, acrylamide, acrylamidopropylsulfonic acid, phosphonic acid, phosphoric acid, vinyl phosphoric acid, butadiene / maleic acid, caprolactam, etherimide, 2-ethyl-2-oxazoline, N-isopropylacrylamide, sodium phosphinite, and co-formed products thereof, as well as their sodium salts, potassium salts, and ammonium salts. <1> The composition described above. <14> The aforementioned 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), poly(vinyl alcohol) (PVA), 2-propenoic acid and monosodium 2-methyl-2-((1-oxo-2-propenyl)amino)-1-propanesulfonic acid and sodium phosphinite (sodium This includes copolymers with phosphinite, copolymers of 2-propenoic acid and monosodium 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) ternary polymer, or mixtures thereof. <1> The composition described above. <15> The at least one anionic polymer includes poly(4-styrenesulfonic acid) (PSSA), polyacrylic acid (PAA), poly(vinylphosphonic acid) (PVPA), poly(2-acrylamide-2-methyl-1-propanesulfonic acid), poly(N-vinylacetamide) (PNVA), anionic poly(methyl methacrylate) (PMMA), anionic polyacrylamide (PAM), 2-acrylamide-2-methyl-1-propanesulfonic acid-acrylic acid copolymer, poly(4-styrenesulfonic acid-co-acrylic acid-co-vinylphosphonic acid) ternary polymer, or a mixture thereof. <1> The composition described above. <16> The at least one anionic polymer is present in an amount of about 0.00001% to about 50% by weight relative to the cleaning composition. <1> The composition described above. <17> The pH of the above composition is approximately 1 to approximately 6.5. <1> The composition described above. <18> The pH of the aforementioned composition is approximately 2 to approximately 5. <1> The composition described above. <19> At least one organic acid; At least one anionic polymer comprising poly(4-styrenesulfonic acid) (PSSA), polyacrylic acid (PAA), poly(vinylphosphonic acid) (PVPA), poly(2-acrylamide-2-methyl-1-propanesulfonic acid), poly(N-vinylacetamide) (PNVA), 2-acrylamide-2-methyl-1-propanesulfonic acid-acrylic acid copolymer, poly(4-styrenesulfonic acid-co-acrylic acid-co-vinylphosphonic acid) ternary polymer, or mixtures thereof; and water; A cleaning composition comprising, A cleaning composition having a pH of approximately 0.1 to 7. <20> The at least one anionic polymer includes poly(vinylphosphonic acid) (PVPA), poly(2-acrylamide-2-methyl-1-propanesulfonic acid), poly(N-vinylacetamide) (PNVA), 2-acrylamide-2-methyl-1-propanesulfonic acid-acrylic acid copolymer, or poly(4-styrenesulfonic acid-co-acrylic acid-co-vinylphosphonic acid) ternary polymer, or a mixture thereof. <19> The composition described above. <21> A wafer having a surface containing SiN, SiC, TiN, W, Ru, Mo, TEOS, Cu, TaN, Co, or p-Si, <1> A method for cleaning a wafer surface, comprising contacting it with the cleaning composition described in [the relevant document]. <22> circuit board <1> A method for cleaning a substrate, comprising contacting it with the cleaning composition described in [the relevant document].

Claims

1. At least one first organic acid; At least one second organic acid different from the at least one first organic acid, wherein the at least one second organic acid includes a dienoic acid; At least one anionic polymer; and water; Includes, A cleaning composition having a pH of approximately 0.1 to approximately 7.

2. The composition according to claim 1, wherein the at least one first organic acid comprises a monocarboxylic acid or a polycarboxylic acid.

3. The composition according to claim 1, wherein 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, potassium acetate, phenoxyacetic acid, benzoic acid, and mixtures thereof.

4. The cleaning composition according to claim 1, wherein 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.

5. The composition according to claim 1, wherein the at least one first organic acid is present in an amount of about 0.00001% to about 50% by weight relative to the composition.

6. The composition according to claim 1, wherein the at least one second organic acid comprises a dienoic acid having 5 to 22 carbon atoms.

7. The above-mentioned 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, The composition according to claim 6, comprising 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 a mixture thereof.

8. The composition according to claim 1, wherein the at least one second organic acid is present in an amount of about 0.0001% to about 0.5% by weight relative to the cleaning composition.

9. The composition according to claim 1, further comprising at least one third organic acid different from the at least one first acid and the second acid, the third organic acid containing an amino acid.

10. The composition according to claim 9, wherein the at least one third organic acid comprises an aminocarboxylic acid, glycine, bicine, tricine, alanine, histidine, valine, phenylalanine, proline, glutamine, aspartic acid, glutamic acid, arginine, lysine, tyrosine, or a mixture thereof.

11. The composition according to claim 9, wherein the at least one third organic acid comprises glycine, histidine, alanine, proline, arginine, lysine, aspartic acid, or a mixture thereof.

12. The composition according to claim 9, wherein the at least one third organic acid is present in an amount of about 0.001% to about 20% by weight relative to the composition.

13. The composition according to claim 1, wherein 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, acrylamide, malic acid, methacrylic acid, vinylphosphonic acid, vinylsulfonic acid, allylsulfonic acid, styrenesulfonic acid, acrylamide, acrylamidopropylsulfonic acid, phosphonic acid, phosphoric acid, vinyl phosphoric acid, butadiene / maleic acid, caprolactam, etherimide, 2-ethyl-2-oxazoline, N-isopropylacrylamide, sodium phosphinite, and co-formed products thereof, as well as their sodium salts, potassium salts, and ammonium salts.

14. The at least one anionic polymer is poly(4-styrenylsulfonate) (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), poly(vinyl alcohol) (PVA), 2-propenoic acid and 2-methyl-2-((1-oxo-2-propenyl)amino)-1-propanesulfonic acid monosodium salt and sodium phosphinite (sodium The composition according to claim 1, comprising a copolymer of phosphinite, a copolymer of 2-propenoic acid and monosodium 2-methyl-2-((1-oxo-2-propenyl)amino)-1-propanesulfonic acid and sodium bisulfite, a 2-acrylamido-2-methyl-1-propanesulfonic acid-acrylic acid copolymer, a poly(4-styrenesulfonic acid-co-acrylic acid-co-vinylphosphonic acid) ternary polymer, or a mixture thereof.

15. The composition according to claim 1, wherein the at least one anionic polymer comprises poly(4-styrenesulfonic acid) (PSSA), polyacrylic acid (PAA), poly(vinylphosphonic acid) (PVPA), poly(2-acrylamide-2-methyl-1-propanesulfonic acid), poly(N-vinylacetamide) (PNVA), anionic poly(methyl methacrylate) (PMMA), anionic polyacrylamide (PAM), 2-acrylamide-2-methyl-1-propanesulfonic acid-acrylic acid copolymer, poly(4-styrenesulfonic acid-co-acrylic acid-co-vinylphosphonic acid) ternary polymer, or a mixture thereof.

16. The composition according to claim 1, wherein the at least one anionic polymer is present in an amount of about 0.00001% to about 50% by weight relative to the cleaning composition.

17. The composition according to claim 1, wherein the pH of the composition is about 1 to about 6.

5.

18. The composition according to claim 1, wherein the pH of the composition is about 2 to about 5.

19. At least one type of organic acid; At least one anionic polymer comprising poly(4-styrene sulfonate) acid (PSSA), polyacrylic acid (PAA), poly(vinylphosphonic acid) (PVPA), poly(2-acrylamide-2-methyl-1-propanesulfonic acid), poly(N-vinylacetamide) (PNVA), 2-acrylamide-2-methyl-1-propanesulfonic acid-acrylic acid copolymer, poly(4-styrenesulfonic acid-co-acrylic acid-co-vinylphosphonic acid) ternary polymer, or mixtures thereof; and water; A cleaning composition comprising, A cleaning composition having a pH of approximately 0.1 to approximately 7.

20. The composition according to claim 19, wherein the at least one anionic polymer comprises poly(vinylphosphonic acid) (PVPA), poly(2-acrylamide-2-methyl-1-propanesulfonic acid), poly(N-vinylacetamide) (PNVA), 2-acrylamide-2-methyl-1-propanesulfonic acid-acrylic acid copolymer, or poly(4-styrenesulfonic acid-co-acrylic acid-co-vinylphosphonic acid) ternary polymer, or a mixture thereof.

21. A method for cleaning the surface of a wafer, comprising contacting a wafer having a surface containing SiN, SiC, TiN, W, Ru, Mo, TEOS, Cu, TaN, Co, or p-Si with the cleaning composition described in claim 1.

22. A method for cleaning a substrate, comprising contacting the substrate with the cleaning composition described in claim 1.

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