Cleaning composition

Abstract

To provide a polishing composition for simultaneously removing particles from a polished surface using a CMP slurry containing a polishing rate enhancer and removing pad stain from a polishing pad contacted with the CMP slurry containing a polish rate enhancer.SOLUTION: A cleaning composition for post-CMP cleaning of semiconductor surfaces includes one or more of a reducing agent, a particle remover, a surfactant and a base. When the reducing agent(s) has a standard reduction potential of less than 1.224 V, the cleaning composition according to the present disclosure removes MnO2 pad stain from a polishing pad and reduces post-polishing surface defects (by removing particles).SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The following description of the background technology of this technology is provided solely as an aid to understanding this technology and does not constitute a description or composition of prior art relating to this technology.

[0002] This disclosure relates to the field of cleaning compositions and cleaning methods for post-CMP (chemical mechanical polishing / planarization) semiconductor surfaces. [Background technology]

[0003] Many CMP slurries and methods include metal-based inorganic oxidizers (e.g., KMnO4, Fenton reagents (e.g., iron nitrate or a combination of iron nitrate and hydrogen peroxide)) to improve thin film removal rates. However, metal-based oxidizers typically precipitate metal oxide species on the polished surface, which leads to undesirable pad staining, a high defect count, and metal contamination.

[0004] Oxide abrasives (e.g., ZrO2, CeO2, etc.) contained in the slurry can cause adsorption of the oxide abrasive onto the semiconductor surface (post-CMP particle defects) due to the high attractive force between the oxide abrasive particles and the semiconductor surface. Post-CMP particle defects are difficult to remove, and ammonia-containing cleaning solutions are typically used in the post-CMP cleaning process. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] W. Al-Soufi et al., A Model for Monomer and Micellar Concentrations in Surfactant Solutions: Application to Conductivity, NMR, Diffusion, and Surface Tension Data, 370 J. COLLOID&INTERFACE SCI. pp. 102-10 (2012) [Non-Patent Document 2] Concentration-model for Surfactants Near the CMC, UNIV. SANTIAGO DE COMPOSTELA (Spain), https: / / www.usc.gal / fotofqm / en / units / single-molecule-fluorescence / concentration-model-surfactants-near-cmc [Non-Patent Document 3] JTDavis, PROC.INT'L CONGR.SURFACE ACTIVITY, 426 pages (2nd edition. 1957) [Non-Patent Document 4] Hydrophilic-Lipophilic Balance, WIKIPEDIA (January 19, 2020), https: / / en.wikipedia.org / wiki / Hydrophilic-lipophilic_balance [Overview of the project]

[0006] Given this technological background, it is desirable to develop a novel cleaning compound for rinsing the surface of polishing plates and for use in brush boxes to remove pad stains / metal inclusions originating from metal-based inorganic oxidizers (such as KMnO4).

[0007] In one embodiment, which can be combined with any other aspect or embodiment, the present disclosure relates to a composition for post-CMP cleaning of semiconductor surfaces comprising one or more reducing agents, particle removers, bases, and surfactants.

[0008] In some embodiments, one or more reducing agents result in a standard reduction potential (E°) of less than 1.224 V. In some embodiments, one or more reducing agents include at least one selected from sulfites, dithionates, thiosulfates, iodides, phosphites, hypophosphites, formic acid, phosphorous acid, ascorbic acid, hydrogen peroxide, hydroxylamines, oxalic acid, sodium sulfite, and their alkali salts. In some embodiments, the reducing agent includes ascorbic acid. In some embodiments, one or more reducing agents are present at a concentration of 0.01 to 10% by weight of the total weight of the composition. In some embodiments, one or more reducing agents are present at a concentration of 0.1 to 1% by weight of the total weight of the composition.

[0009] In some embodiments, the particle remover is citric acid, an amino acid, or an aminophosphonic acid. Examples of amino acids include glycine, alanine, arginine, and histidine. Examples of aminophosphonic acids include N-(phosphonomethyl)iminodiacetic acid hydrate, hydroxyphosphonoacetic acid, hydroxyethane-1,1-diphosphonic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid, ethylenediaminetetramethylphosphonic acid (EDTMP), or 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP). In some embodiments, the particle remover contains an aminophosphonic acid. In some embodiments, the particle remover contains 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP). In some embodiments, the particle remover is present at a concentration of 0.05 to 5% by weight of the total weight of the composition. In some embodiments, the particle remover is present at a concentration of 0.5 to 1% by weight of the total weight of the composition.

[0010] In some embodiments, the base includes alkylated amines. In some embodiments, the base includes 2-(diethylamino)ethanethiol, captamine, diethylethanolamine, methylcysteamine, 2-(tert-butylamino)ethanethiol, 2,2'-dimethoxy-1,1-dimethyldimethylamine, 3-amino-4-octanol, 3-butoxypropylamine, N-acetylcysteamine, homocysteamine, N,N-dimethylhydroxylamine, 2-(isopropylamino)ethanol, 2-(methylthioethyl)amine, 1-aminopropane-2-thiol, leucinol, cysteamine and / or N,O-dimethylhydroxylamine. In some embodiments, the base includes 3-amino-4-octanol. In some embodiments, the base is present at a concentration of 0.05 to 5% by weight of the total weight of the composition. In some embodiments, the base is present at a concentration of 0.5 to 1% by weight of the total weight of the composition.

[0011] In some embodiments, the surfactant includes a carboxylic acid surfactant. In some embodiments, the surfactant is represented by the following formula (I): C m H 2m+1 -(OCH2CH2) n -L-COOH (I) (In the formula, 6 ≤ m ≤ 20, n ≥ 5, and L is bond, -O-, -S-, -R) 1 -, -SR 1 - or - OR 1 - and R 1 (The surfactant is a C1-4 alkylene). In some embodiments, the surfactant contains capryleth-9-carboxylic acid. In some embodiments, the surfactant is present at a concentration of 0.01 to 10% by weight of the total weight of the composition. In some embodiments, the surfactant is present at a concentration of 0.1 to 1% by weight of the total weight of the composition.

[0012] In some embodiments, the composition has a pH of 2 to 6, preferably 2 to 5, and more preferably 2 to 4. In some embodiments, the pH is approximately 3.

[0013] In another embodiment, the present disclosure relates to a method for simultaneously removing pad stain from a polishing pad and particles from a semiconductor surface after polishing, comprising the steps of supplying a composition for post-CMP cleaning of the semiconductor surface to the semiconductor surface, and bringing a polishing pad into contact with the semiconductor surface in the presence of the composition for post-CMP cleaning to produce a post-polished semiconductor surface with a reduced number of defects. In some embodiments, the pad stain includes MnO2.

[0014] In some embodiments, the number of defects after post-CMP cleaning (number of defects on a 300mm wafer after polishing) (especially the number of SP1 defects) is 100 or less. In some embodiments, the number of defects is 70 or less. In some embodiments, the number of defects is 50 or less. In some embodiments, the number of defects is 20 or less. In some embodiments, the semiconductor surface after polishing has a number of defects of 2 or less after cleaning. In some embodiments, the semiconductor surface after polishing has a number of defects of 0 after cleaning.

[0015] In some embodiments, the composition for post-CMP cleaning of semiconductor surfaces comprises one or more reducing agents; particle removers; bases; and surfactants.

[0016] In some embodiments, one or more reducing agents result in a standard reduction potential (E°) of less than 1.224 V. In some embodiments, one or more reducing agents include ascorbic acid, hydrogen peroxide, hydroxylamine, oxalic acid, sodium sulfite, their alkali salts, or any combination thereof. In some embodiments, the reducing agent includes ascorbic acid. In some embodiments, one or more reducing agents are present at a concentration of 0.01 to 10% by weight of the total weight of the composition. In some embodiments, one or more reducing agents are present at a concentration of 0.1 to 1% by weight of the total weight of the composition.

[0017] In some embodiments, the particle remover comprises glycine, N-(phosphonomethyl)iminodiacetic acid hydrate, hydroxyphosphonoacetic acid, citric acid, hydroxyethane-1,1-diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, or 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP). In some embodiments, the particle remover comprises 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP). In some embodiments, the particle remover is present at a concentration of 0.05 to 5% by weight based on the total weight of the composition. In some embodiments, the particle remover is present at a concentration of 0.5 to 1% by weight based on the total weight of the composition.

[0018] In some embodiments, the base comprises an alkylated amine. In some embodiments, the base comprises 2-(diethylamino)ethanethiol, captamine, diethylethanolamine, methylcysteamine, 2-(tert-butylamino)ethanethiol, 2,2'-dimethoxy-1,1-dimethyl-dimethylamine, 3-amino-4-octanol, 3-butoxypropylamine, N-acetylcysteamine, homocysteamine, N,N-dimethylhydroxylamine, 2-(isopropylamino)ethanol, 2-(methylthioethyl)amine, 1-aminopropan-2-thiol, leucinol, cysteamine, and / or N,O-dimethylhydroxylamine. In some embodiments, the base comprises 3-amino-4-octanol. In some embodiments, the base is present at a concentration of 0.05 to 5% by weight based on the total weight of the composition. In some embodiments, the base is present at a concentration of 0.5 to 1% by weight based on the total weight of the composition.

[0019] In some embodiments, the surfactant comprises a carboxylic acid surfactant. In some embodiments, the surfactant is represented by the following formula (I): C m H 2m+1 -(OCH2CH2) n -L-COOH (I) (where 6 ≦ m ≦ 20, n ≧ 5, and L is a bond, -O-, -S-, -R 1 -, -S-R 1- or - OR 1 - and R 1 (The surfactant is a C1-4 alkylene). In some embodiments, the surfactant contains capryleth-9-carboxylic acid. In some embodiments, the surfactant is present at a concentration of 0.01 to 10% by weight of the total weight of the composition. In some embodiments, the surfactant is present at a concentration of 0.1 to 1% by weight of the total weight of the composition.

[0020] In some embodiments, the composition has a pH of 2 to 6. In some embodiments, the pH is approximately 3.

[0021] In another embodiment, the present disclosure relates to a method for polishing a semiconductor surface by any of the methods described above, comprising the steps of polishing the semiconductor surface with a polishing composition comprising a removal rate enhancer, and simultaneously removing pad stain from a polishing pad and removing particles from the semiconductor surface. In some embodiments, the removal rate enhancer comprises KMnO4. In some embodiments, the pad stain comprises MnO2.

[0022] Additional aspects and / or embodiments of the present invention are presented non-limitingly in the detailed description of the present art described below. The following detailed description is illustrative and explanatory, but not intended to limit it.

[0023] The various purposes, aspects, characteristics, and benefits of this disclosure will become clearer and better understood by referring to the detailed description in conjunction with the attached figures. [Brief explanation of the drawing]

[0024] [Figure 1] Figure 1A shows the formation of pad stain on the surface of an IC1010™ polishing pad (Dupont) after polishing with a KMnO4-containing slurry for 60 minutes. Figure 1B shows that the pad stain was almost completely removed after rinsing the polishing platen surface for 30 seconds using composition A (ascorbic acid as a reducing agent). [Figure 2] Figure 2A shows an SP1 defect map from a PCVD carbon wafer polished with a KMnO4-containing slurry and then rinsed with ammonia, without using the cleaning composition according to this disclosure. Figure 2B shows an SP1 defect map from a PCVD carbon wafer polished with a KMnO4-containing slurry using composition A, followed by a pad cleaning process and rinsing of the polishing platen surface (mapping defects on a TEOS (tetraethyl orthosilicate-derived silicon dioxide) 300 mm wafer). [Modes for carrying out the invention]

[0025] In this specification, "X~Y" indicating a range means "X or greater and Y or less". When multiple "X~Y" ranges are listed, for example, "X1~Y1, or X2~Y2", the disclosure of each value as an upper limit, the disclosure of each value as a lower limit, and all combinations of these upper and lower limits are disclosed (i.e., the legal basis for corrections). Specifically, corrections with respect to X1 or greater, corrections with respect to Y2 or less, corrections with respect to X1 or less, corrections with respect to Y2 or greater, corrections with respect to X1~X2, corrections with respect to X1~Y2, etc., must all be considered legal. In addition, unless otherwise specified, operations and measurements of physical properties, etc., shall be performed under conditions of room temperature (20~25℃) / relative humidity 40~50%RH.

[0026] The cleaning compositions disclosed herein utilize the reduction-oxidation behavior of reducing agents, enabling the removal of MnO2-based pad stains and a reduction in the number of defects as measured by SP1. The compositions of the present invention are subject to the general constraint E o (還元剤) <E o (金属酸化物ステイン) As long as you follow the instructions, additional reducing agents and MO x It can be applied to the creation of a base pad stain.

[0027] Reducing agent In some embodiments, the cleaning compositions according to this disclosure include a reducing agent. For example, a reducing agent added to a cleaning chemical, including a particle remover, results in the removal of pad stain formation and metal contamination caused by a KMnO4-based slurry, and a significant reduction in post-CMP defects. Preferably, complete removal is achieved. In some embodiments, the reducing agent according to this disclosure is an agent that can act as a reducing agent in the acidic, neutral, or basic range. Thus, for example, an acidic cleaning composition may be prepared by including an agent that can act as a reducing agent in the basic range (reducing agent). In some embodiments, the acidic range may be pH 1 or higher and less than pH 7, pH 2 to 6, or pH 2.5 to 5. The pH may be the pH described in "pH of Composition" below. In some embodiments, the neutral range may be about pH 7 (particularly pH 7). In some embodiments, the basic range may be greater than pH 7 and less than or equal to pH 14, pH 8 to 12, or pH 9 to 11. pH can be determined using a pH meter (for example, LAQUA® manufactured by Horiba, Ltd., or any other suitable pH meter).

[0028] Due to the action of the oxidizing agent, unintended products accumulate on the surface of the pad on the polishing platen in the polishing apparatus, appearing as stains. This phenomenon is called pad stain formation. These stains can cause scratches or clog the pad, which can hinder the polishing process. Pad stain formation appears as surface discoloration. Examples of "defects" include abrasive grains used in the previous process, fragments torn from the polishing pad, or water-insoluble substances in the polishing process. Some typical examples of metal contamination include, for example, the presence of MnO2 as a residue on the surface of a carbon film after polishing it with a composition containing ZrO2 and KMnO4, or the presence of metal oxides such as Fe3O4 as a residue on the surface of tungsten after polishing it with a composition containing SiO2, iron nitrate, and KMnO4. Such water-insoluble substances, such as MnO2 derived from KMnO4 and Fe3O4 derived from iron nitrate, can be removed by the composition of this application. In particular, when the composition of this application contains hydrogen peroxide, bubbles may be generated through interaction with MnO2, and these bubbles are expected to further enhance the cleaning effect. Furthermore, hydrogen peroxide is particularly preferable from the viewpoint of not impairing the stability of the composition.

[0029] Thus, the number of defects containing Group 7 elements (e.g., MnO2) or Group 8 elements (e.g., Fe3O4) can be removed or reduced by performing a cleaning process using the cleaning composition according to this disclosure.

[0030] The use of KMnO4 as a removal rate enhancer in CMP slurry results in the formation of manganese oxide (e.g., MnO4) as a pad stain by-product (Equation 1). 2(s) ) will result. MnO4 - ( aq) +4H + +3e - ⇔MnO 2(s) +2H2O(E°=1.7V) (1) As long as the E° of the reducing agent is less than the E° of MnO2 (1.224V), the removal of MnO2 pad stains can be achieved by using a reducing agent in an acidic medium (Equation 2). MnO 2(s) +4H + +2e - ⇔Mn 2+ (aq) +2H2O(E°=1.224V) (2) Therefore, the compositions according to this disclosure may contain any reducing agent having a standard reduction potential E° < 1.224 V, thereby enabling the removal of pad stains. Furthermore, when used in combination with a particulate remover, a surfactant and / or a base, such a reducing agent-containing composition can result in a surface having post-CMP cleaning defects < 100. In some embodiments, one or more reducing agents are agents that provide a standard reduction potential (E°) of less than 1.224 V in the acidic, neutral, or basic range. Thus, for example, an acidic cleaning composition may be prepared by containing an agent (reducing agent) that provides a standard reduction potential (E°) of less than 1.224 V in the basic range.

[0031] In some embodiments, one or more reducing agents include, substantially consist of, or comprise sulfites, dithionates, thiosulfates, iodides, phosphites, hypophosphites, formic acid, phosphorous acid, ascorbic acid, hydrogen peroxide, hydroxylamines, oxalic acid, sodium sulfite, alkali salts thereof, or any combination thereof. In some embodiments, one or more reducing agents include, substantially consist of, or comprise ascorbic acid. In some embodiments, the reducing agent has an organic acid having a lactone structure with hydroxyl groups. In some embodiments, the reducing agent has an organic acid having a lactone structure with multiple (two or more, three or more, four or more, seven or fewer, six or fewer, five or fewer) hydroxyl groups. The lactone structure may be any of β-lactone, γ-lactone, δ-lactone, or ε-lactone. In some embodiments, one or more reducing agents include, substantially consist of, or comprise as an organic acid having a lactone structure with hydroxyl groups.

[0032] In some embodiments, one or more reducing agents are present in the composition at concentrations of at least about 0.001% by weight, at least about 0.002% by weight, at least about 0.003% by weight, at least about 0.004% by weight, at least about 0.005% by weight, at least about 0.006% by weight, at least about 0.007% by weight, at least about 0.008% by weight, at least about 0.009% by weight, at least about 0.01% by weight, at least about 0.02% by weight, at least about 0.03% by weight, at least about 0.04% by weight, at least about 0.05% by weight, at least about 0.06% by weight, at least about 0.07% by weight, at least about 0.08% by weight, at least about 0.09% by weight, at least about 0.1% by weight, at least about 0.2% by weight, at least about 0.3% by weight, at least about 0.4% by weight, at least about 0.5% by weight, or any range or value in between, based on the total weight of the composition. In some embodiments, one or more reducing agents are present in the composition at a concentration of at least about 0.6% by weight, at least about 0.7% by weight, at least about 0.8% by weight, or any range or value between these, relative to the total weight of the composition. In some embodiments, one or more reducing agents are present in the composition at a concentration of at least about 1% by weight, at least about 1.5% by weight, at least about 2% by weight, at least about 2.5% by weight, or any range or value between these, relative to the total weight of the composition. In the case of "multiple," this refers to the total amount. The meaning of "multiple" in this specification may be interpreted in this way. The absence of the term "multiple" in this specification does not limit the presence of "multiple" reducing agents.

[0033] In some embodiments, hydrogen peroxide is present in the composition at a concentration of at least about 0.001% by weight, at least about 0.002% by weight, at least about 0.003% by weight, at least about 0.004% by weight, at least about 0.005% by weight, at least about 0.006% by weight, at least about 0.007% by weight, at least about 0.008% by weight, at least about 0.009% by weight, at least about 0.01% by weight, at least about 0.02% by weight, at least about 0.03% by weight, at least about 0.04% by weight, at least about 0.05% by weight, at least about 0.06% by weight, at least about 0.07% by weight, at least about 0.08% by weight, at least about 0.09% by weight, at least about 0.1% by weight, at least about 0.2% by weight, at least about 0.3% by weight, at least about 0.4% by weight, at least about 0.5% by weight, or any range or value in between, based on the total weight of the composition. In some embodiments, hydrogen peroxide is present in the composition at a concentration of at least about 0.6% by weight, at least about 0.7% by weight, at least about 0.8% by weight, or any range or value in between, based on the total weight of the composition. In some embodiments, hydrogen peroxide is present in the composition at a concentration of at least about 1% by weight, at least about 1.5% by weight, at least about 2% by weight, at least about 2.5% by weight, or any range or value in between, based on the total weight of the composition.

[0034] In some embodiments, one or more reducing agents are present in the composition at a concentration of about 20% by weight or less, about 19% by weight or less, about 18% by weight or less, about 17% by weight or less, about 16% by weight or less, about 15% by weight or less, about 14% by weight or less, about 13% by weight or less, about 12% by weight or less, about 11% by weight or less, about 10% by weight or less, about 9% by weight or less, about 8% by weight or less, about 7% by weight or less, about 6% by weight or less, about 5% by weight or less, about 4% by weight or less, about 3% by weight or less, about 2% by weight or less, about 1% by weight or less, or any range or value in between, based on the total weight of the composition.

[0035] In some embodiments, hydrogen peroxide is present in the composition at a concentration of about 20% by weight or less, about 19% by weight or less, about 18% by weight or less, about 17% by weight or less, about 16% by weight or less, about 15% by weight or less, about 14% by weight or less, about 13% by weight or less, about 12% by weight or less, about 11% by weight or less, about 10% by weight or less, about 9% by weight or less, about 8% by weight or less, about 7% by weight or less, about 6% by weight or less, about 5% by weight or less, about 4% by weight or less, about 3% by weight or less, about 2% by weight or less, about 1% by weight or less, or any range or value in between, based on the total weight of the composition.

[0036] For the purposes of this disclosure, “standard reduction potential” (E°) is a measure of the tendency of a chemical species to gain or lose electrons from an electrode, thereby undergoing reduction or oxidation, respectively. Standard reduction potential can be measured in volts (V) or millivolts (mV). Each chemical species has its own intrinsic standard reduction potential. Generally, the higher the positive reduction potential, the greater the affinity for electrons and the greater the tendency to be reduced. Standard reduction potential can be measured under standard temperature and pressure (25°C, 1 atm) with reference to a standard hydrogen electrode (SHE).

[0037] In some embodiments, one or more reducing agents are used in the following voltage ranges: less than 1.224V, less than 1.220V, less than 1.210V, less than 1.200V, less than 1.190V, less than 1.180V, less than 1.170V, less than 1.160V, less than 1.150V, less than 1.140V, less than 1.130V, less than 1.120V, less than 1.110V, less than 1.100V, less than 1.09V, less than 1.08V, less than 1.07V, 1 Less than 0.06V, less than 1.05V, less than 1.04V, less than 1.03V, less than 1.02V, less than 1.01V, less than 1.00V, less than 0.95V, less than 0.90V, less than 0.85V, less than 0.80V, less than 0.75V, less than 0.70V, less than 0.65V, less than 0.60V, less than 0.55V, less than 0.50V, less than 0.45V, less than 0.40V, less than 0.35V, less than 0.30V, less than 0.25V, Less than 0.20V, less than 0.15V, less than 0.10V, less than 0.05V, less than 0V, less than -0.05V, less than -0.10V, less than -0.20V, less than -0.30V, less than -0.40V, less than -0.50V, less than -0.60V, less than -0.70V, less than -0.80V, less than -0.90V, less than -1.00V, less than -1.10V, less than -1.20V, less than -1.30V, less than -1.40V, -1. It has a standard reduction potential (E°) of less than 50V, less than -1.60V, less than -1.70V, less than -1.80V, less than -1.90V, less than -2.00V, less than -2.10V, less than -2.20V, less than -2.30V, less than -2.40V, less than -2.50V, less than -2.60V, less than -2.70V, less than -2.80V, less than -2.90V, less than -3.00V, or any range or value in between. Having such an upper limit (especially -3.04V, for example) can increase stability in water and suppress unexpected reactions with other additives. In some embodiments, one or more reducing agents have a standard reduction potential (E°) of -3.0V or higher, -2.0V or higher, -1.0V or higher, greater than 0V, 0.1V or higher, 0.2V or higher, 0.21V or higher, 0.25V or higher, 0.3V or higher, 0.32V or higher, 0.34V or higher, 0.35V or higher, 0.4V or higher, 0.5V or higher, 0.6V or higher, or 0.65V or higher, or any range or value in between. Having such a lower limit allows for the ionization of zirconia and Mn.

[0038] Particle removal agent In some embodiments, the cleaning composition according to the Disclosure comprises a particle remover. The particle remover can be any agent suitable for removing residual fine particles from the surface of an abrasive object polished using a chemical mechanical polishing slurry (e.g., a CMP slurry containing cerium oxide particles or zirconia particles). The particle remover may be one or more.

[0039] In one embodiment of the present invention, the CMP slurry may contain abrasive grains (particles) and a removal rate enhancer (polishing speed accelerator). Examples of abrasive grains (particles) include inorganic particles and organic particles. Specific examples of inorganic particles include metal oxide particles such as silica, alumina, ceria, titania, and zirconia, silicon nitride particles, silicon carbide particles, and boron nitride particles. Specific examples of organic particles include polymethyl methacrylate (PMMA) particles.

[0040] In one embodiment of the present invention, the particle removal agent has one or more, two or more, three or more, four or more, five or more, seven or more, or eight or more phosphonic acid groups (-P(=O)(OH)2) or salts thereof groups, or an alkyl group substituted with one or more, two or more, three or more, four or more, five or more, seven or more, or eight or more phosphonic acid groups or salts thereof groups. In one embodiment of the present invention, the particle removal agent has eight or fewer, seven or fewer, six or fewer, five or fewer, four or fewer, three or fewer, or two or fewer phosphonic acid groups or salts thereof groups, or an alkyl group substituted with eight or fewer, seven or fewer, six or fewer, five or fewer, four or fewer, three or fewer, or two or fewer phosphonic acid groups or salts thereof groups.

[0041] In one embodiment of the present invention, the particle removal agent is N(R 1 )(R 2 )(R 3 A compound represented by ) or a salt thereof, or C(R 1 )(R 2 )(R 3 )(R 4It contains compounds represented by ) or salts thereof.

[0042] R 1 ~R 3 , R 1 ~R 4 Each of these independently represents a hydrogen atom, a carboxyl group, a hydroxyl group, a phosphonic acid group or a salt thereof, or a substituted or unsubstituted linear or branched alkyl group having 1 to 5 carbon atoms, in which case R 1 ~R 3 Of these, one or more are phosphonic acid groups or groups of a salt thereof, or alkyl groups substituted with phosphonic acid groups or groups of a salt thereof, R 1 ~R 4 One or more of these groups are phosphonic acid groups or groups of a salt thereof, or alkyl groups substituted with phosphonic acid groups or groups of a salt thereof.

[0043] R 1 ~R 3 , R 1 ~R 4 There are no particular restrictions on the substituted or unsubstituted linear or branched alkyl group having 1 to 5 carbon atoms, and examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl groups.

[0044] Here, "substituted or unsubstituted" for an alkyl group means that one or more hydrogen atoms of the alkyl group may or may not be substituted by other substituents. The substituents that can be substituted are not particularly limited. Examples of substituents include fluorine atoms (F), chlorine atoms (Cl), bromine atoms (Br), iodine atoms (I), phosphonic acid groups (-PO3H2), phosphate groups (-OPO3H2), thiol groups (-SH), cyano groups (-CN), nitro groups (-NO2), hydroxyl groups (-OH), linear or branched alkoxy groups with 1 to 10 carbon atoms (e.g., methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, octyloxy group, dodecyloxy group, etc.), aryl groups with 6 to 30 carbon atoms (e.g., phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group), and cycloalkyl groups with 3 to 20 carbon atoms (e.g., cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group).

[0045] Here, the alkyl group substituted with a phosphonic acid group or a salt thereof is a linear or branched alkyl group having 1 to 5 carbon atoms substituted with one or more phosphonic acid groups or salts thereof, and examples include (mono)phosphonomethyl group, (mono)phosphonoethyl group, (mono)phosphono-n-propyl group, (mono)phosphonoisopropyl group, (mono)phosphono-n-butyl group, (mono)phosphonoisobutyl group, (mono)phosphono-s-butyl group, (mono)phosphono-t-butyl group, diphosphonomethyl group, diphosphonoethyl group, diphosphono-n-propyl group, diphosphonoisopropyl group, diphosphono-n-butyl group, diphosphonoisobutyl group, diphosphono-s-butyl group, diphosphono-t-butyl group, or groups of their salts.

[0046] In one embodiment of the present invention, examples of salts include alkali metal salts such as sodium salts and potassium salts, salts of group 2 elements such as calcium salts and magnesium salts, amine salts, ammonium salts, and the like.

[0047] In some embodiments, the particle remover comprises, substantially comprises, or may comprise, a protic organic acid molecule. In some embodiments, the protic organic acid molecule may, in non-limiting examples, include glycine, N-(phosphonomethyl)iminodiacetic acid hydrate, hydroxyphosphonoacetic acid, citric acid, hydroxyethane-1,1-diphosphonic acid, or 2-phosphonobutane-1,2,4-tricarboxylic acid. In some embodiments, the particle remover comprises hydroxyethane-1,1-diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, or a combination thereof. In some embodiments, the particle remover comprises, substantially comprises, or comprises hydroxyethane-1,1-diphosphonic acid (HEDP). In some embodiments, the protic organic acid molecule substantially does not contain small amounts of trace metals. A single particle remover may be used, or two or more particle removers may be used in combination.

[0048] In some embodiments, the particle remover is present in the composition at a concentration of at least about 0.001% by weight, at least about 0.002% by weight, at least about 0.003% by weight, at least about 0.004% by weight, at least about 0.005% by weight, at least about 0.006% by weight, at least about 0.007% by weight, at least about 0.008% by weight, at least about 0.009% by weight, at least about 0.01% by weight, at least about 0.02% by weight, at least about 0.03% by weight, at least about 0.04% by weight, at least about 0.05% by weight, at least about 0.06% by weight, at least about 0.07% by weight, at least about 0.08% by weight, at least about 0.09% by weight, at least about 0.1% by weight, at least about 0.2% by weight, at least about 0.3% by weight, at least about 0.4% by weight, at least about 0.5% by weight, or any range or value in between, based on the total weight of the composition.

[0049] In some embodiments, the particle remover is present in the composition at a concentration of about 20% by weight or less, about 19% by weight or less, about 18% by weight or less, about 17% by weight or less, about 16% by weight or less, about 15% by weight or less, about 14% by weight or less, about 13% by weight or less, about 12% by weight or less, about 11% by weight or less, about 10% by weight or less, about 9% by weight or less, about 8% by weight or less, about 7% by weight or less, about 6% by weight or less, about 5% by weight or less, about 4% by weight or less, about 3% by weight or less, about 2% by weight or less, about 1% by weight or less, about 0.9% by weight or less, about 0.8% by weight or less, about 0.7% by weight or less, about 0.6% by weight or less, or any range or value in between, based on the total weight of the composition.

[0050] In some embodiments, the particle remover (e.g., a protic organic acid) has at least one, at least two, at least three, at least four, at least five, at least six, at least seven, at least eight, or more dissociated complex-forming functional groups. In some embodiments, the particle remover (e.g., a protic organic acid) has 10 or fewer, 9 or fewer, 8 or fewer, 7 or fewer, 6 or fewer, 5 or fewer, 4 or fewer, or 3 or fewer complex-forming functional groups. In this disclosure, “dissociated complex-forming functional group” refers to a proton-donating group having a lone pair of electrons. Examples of dissociated complex-forming functional groups include phosphate groups, phosphonate groups, carboxyl groups (or carboxylic acid groups), and sulfo groups. Of these, phosphate groups are preferred from the viewpoint of adsorption to particles (e.g., including cerium oxide or zirconia). In other words, the particle removal agent preferably contains at least one phosphate group (-OP(=O)(OH)2) or phosphonate group (-P(=O)(OH)2). One or more of these groups may be present in a single molecule in various combinations of types (e.g., phosphate, carboxyl, and / or sulfo). The phosphonate group is also called a phosphonic acid group.

[0051] surfactants In some embodiments, the compositions according to the Disclosure comprise one or more surfactants. In some embodiments, the surfactant comprises, substantially comprises, or comprises cationic surfactants, anionic surfactants, nonionic surfactants, or any combination thereof. In some embodiments, one or more surfactants comprise anionic surfactants.

[0052] In some embodiments, the surfactant may include one or more compounds represented by the following formula (I): C m H 2m+1 -(OCH2CH2) n -LR (I) (In the formula, 6 ≤ m ≤ 20, n ≥ 5, and L is -O-, -S-, -R) 1 -, -SR 1 - or - OR 1 -Join (R 1 C 1~4 R represents an alkylene, and R represents an anionic group. In some embodiments, the anionic group can be a sulfonic acid group (or sulfonate), a carboxylic acid group (or carboxylate), a phosphonic acid group (or phosphonate), or any other suitable anionic group. In some embodiments, R is a carboxylic acid group (-COOH).

[0053] In formula (I), m represents the number of carbon atoms in the terminal alkyl group and is an integer between 6 and 20. In some embodiments, m is 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20. In some embodiments, m can be between 7 and 10. In some embodiments, m is 8. m less than 6 is undesirable because it can lead to increased hydrophilicity and insufficient particle removal performance. m greater than 20 is undesirable because it can lead to increased hydrophobicity and insufficient particle removal performance.

[0054] In some embodiments, in formula (I), n (the number of moles of ethylene oxide added) is an integer greater than or equal to 5 (e.g., 5, 6, 7, 8, 9, 10, 11, or 12). In some embodiments, n is 5 or greater and 12 or less, 6 or greater and 12 or less, 7 or greater and 12 or less, 8 or greater and 12 or less, 6 or greater and 11 or less, 7 or greater and 11 or less, 8 or greater and 11 or less, 7 or greater and 10 or less, or 8 or greater and 10 or less, or any range or value in these. In some embodiments, n is 8. In some embodiments, n less than 5 is undesirable because it can lead to increased hydrophobicity and insufficient particle removal performance. The upper limit of n is not particularly limited, but an upper limit of n greater than 12 is undesirable because it can lead to increased hydrophilicity and insufficient particle removal performance.

[0055] In some embodiments, in formula (I), L represents a divalent group, -O-, -S-, -R 1 -, -SR 1 - or - OR 1 - is. L is -R 1 -, -SR 1 - or - OR 1 -If R 1 This represents an alkylene group (such as a methylene group, ethylene group, trimethylene group, propylene group, or tetramethylene group) having 1 to 4 carbon atoms.

[0056] In some embodiments, in formula (I), R represents an anionic group. From the viewpoint of the adsorption capacity of the anionic group, R is preferably at least one selected from the group consisting of carboxyl groups, sulfonate groups, phosphate groups, phosphonate groups, and salts thereof. In some embodiments, R is at least one selected from the group consisting of carboxyl groups and salts thereof.

[0057] In some embodiments, the surfactant represented by formula (I) is a polyoxyethylene alkylene ether carboxylic acid, or a salt thereof, represented by the following formula (II): C m H 2m+1-(OCH2CH2) n -O-CH2-COOH (II) (In the formula, m and n have the same definitions as discussed above with respect to formula (I)). Preferred embodiments of m and n in formula (II) are the same as those disclosed with respect to formula (I), and therefore their detailed description is omitted here.

[0058] The surfactant represented by formula (II) is not particularly limited, but non-limiting examples include capryleth-6 carboxylic acid (m=8, n=5 in formula (II)) or its salts; capryleth-9 carboxylic acid (m=8, n=8 in formula (II)) or its salts. In some embodiments, the surfactant of formula (II) is capryleth-9 carboxylic acid or its salts. In some embodiments, capryleth-9 carboxylic acid is preferred from the viewpoint of particle removal performance. Only one of these compounds may be used alone, or two or more may be used in combination.

[0059] In some embodiments, the surfactant is present in the composition at a concentration of at least about 0.001% by weight, at least about 0.002% by weight, at least about 0.003% by weight, at least about 0.004% by weight, at least about 0.005% by weight, at least about 0.006% by weight, at least about 0.007% by weight, at least about 0.008% by weight, at least about 0.009% by weight, at least about 0.01% by weight, at least about 0.02% by weight, at least about 0.03% by weight, at least about 0.04% by weight, at least about 0.05% by weight, at least about 0.06% by weight, at least about 0.07% by weight, at least about 0.08% by weight, at least about 0.09% by weight, at least about 0.1% by weight, or any range or value in between, based on the total weight of the composition.

[0060] In some embodiments, the surfactant is present in the composition at a concentration of about 20% by weight or less, about 19% by weight or less, about 18% by weight or less, about 17% by weight or less, about 16% by weight or less, about 15% by weight or less, about 14% by weight or less, about 13% by weight or less, about 12% by weight or less, about 11% by weight or less, about 10% by weight or less, about 9% by weight or less, about 8% by weight or less, about 7% by weight or less, about 6% by weight or less, about 5% by weight or less, about 4% by weight or less, about 3% by weight or less, about 2% by weight or less, about 1% by weight or less, about 0.9% by weight or less, about 0.8% by weight or less, about 0.7% by weight or less, about 0.6% by weight or less, about 0.5% by weight or less, about 0.4% by weight or less, about 0.3% by weight or less, or any range or value in between, based on the total weight of the composition.

[0061] In some embodiments (for example, the surfactant is polyoxyethylene alkyl ether carboxylic acid), the surfactant has a hydrophilic-lipophilic balance (HLB) value that, when determined by the Davies method, is 2 or higher, 3 or higher, 4 or higher, 5 or higher, 6 or higher, 7 or higher, 7.2 or higher, 7.5 or higher, 7.8 or higher, 8 or higher, 8.2 or higher, 8.5 or higher, 8.8 or higher, 9 or higher, 9.2 or higher, 9.5 or higher, 9.8 or higher, 10 or higher, 10.5 or higher, 11 or higher, 11.5 or higher, 12 or higher, 12.5 or higher, 13 or higher, 13.5 or higher, 14 or higher, 14.5 or higher, 15 or higher, or any range or value in between. In some embodiments, the surfactant (for example, polyoxyethylene alkyl ether carboxylic acid) has an HLB value of 7 or higher, 7.2 or higher, 7.5 or higher, 7.8 or higher, or 8 or higher. In some embodiments, the surfactant (e.g., polyoxyethylene alkyl ether carboxylic acid) has an HLB value of 20 or less, 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, 13 or less, 12 or less, 11 or less, 10 or less, 9 or less, 8 or less, or any range or value in between. In this specification, the hydrophilic-lipophilic balance (HLB) value by the Davies method is determined by the following relationship (Equation 5): 1 HLB = 7 + Total number of hydrophilic groups - Total number of lipophilic groups (5) See JTDavis, PROC. INT'L CONGR. SURFACE ACTIVITY, p. 426 (2nd edition, 1957).

[0062] 1 Equation (5) is a simplified version of the following equation relating to HLB, which can also be used in some embodiments:

number

[0063] base In some embodiments, the compositions according to this disclosure include a base. In some embodiments, the base may include an organic amine compound. In some embodiments, the organic amine compound is a non-aromatic amine compound (i.e., does not contain an aromatic ring). In some embodiments, the organic amine compound may include a hydroxyl group, an alkoxy group, a thiol group, or any combination thereof. In some embodiments, the base may be one or more.

[0064] In some embodiments, the base comprises an alkylated amine. In some embodiments, the base comprises an alkylated amine containing a hydroxyl group. In some embodiments, the number of carbon atoms in the alkyl group of the alkylated amine (alkylated amine containing a hydroxyl group) is 3-15, 4-14, 5-13, 6-12, 7-11, or 8-10.

[0065] The organic amine compounds are not particularly limited, but examples include 2-(diethylamino)ethanethiol, captamine, diethylethanolamine, methylcysteamine, 2-(tert-butylamino)ethanethiol, 2,2'-dimethoxy-1,1-dimethyldimethylamine, 3-amino-4-octanol, 3-butoxypropylamine, N-acetylcysteamine, homocysteamine, N,N-dimethylhydroxylamine, 2-(isopropylamino)ethanol, 2-(methylthioethyl)amine, 1-aminopropane-2-thiol, leucinol, cysteamine, and N,O-dimethylhydroxylamine. In some embodiments, the base is at least one selected from the group consisting of 2-(diethylamino)ethanethiol, captamine, 3-amino-4-octanol, cysteamine, N,N-dimethylhydroxylamine, and N,O-dimethylhydroxylamine. In some embodiments, the base is at least one selected from the group consisting of 2-(diethylamino)ethanethiol, captamine, and 3-amino-4-octanol. In some embodiments, the base is 3-amino-4-octanol. A single base may be used in the cleaning composition, or a combination of two or more bases may be used.

[0066] In some embodiments, the base is present in the composition at a concentration of at least about 0.001% by weight, at least about 0.002% by weight, at least about 0.003% by weight, at least about 0.004% by weight, at least about 0.005% by weight, at least about 0.006% by weight, at least about 0.007% by weight, at least about 0.008% by weight, at least about 0.009% by weight, at least about 0.01% by weight, at least about 0.02% by weight, at least about 0.03% by weight, at least about 0.04% by weight, at least about 0.05% by weight, at least about 0.06% by weight, at least about 0.07% by weight, at least about 0.08% by weight, at least about 0.09% by weight, at least about 0.1% by weight, at least about 0.2% by weight, at least about 0.3% by weight, at least about 0.4% by weight, at least about 0.5% by weight, or any range or value in between, based on the total weight of the composition.

[0067] In some embodiments, the base is present in the composition at a concentration of about 20% by weight or less, about 19% by weight or less, about 18% by weight or less, about 17% by weight or less, about 16% by weight or less, about 15% by weight or less, about 14% by weight or less, about 13% by weight or less, about 12% by weight or less, about 11% by weight or less, about 10% by weight or less, about 9% by weight or less, about 8% by weight or less, about 7% by weight or less, about 6% by weight or less, about 5% by weight or less, about 4% by weight or less, about 3% by weight or less, about 2% by weight or less, about 1% by weight or less, about 0.9% by weight or less, about 0.8% by weight or less, about 0.7% by weight or less, about 0.6% by weight or less, or any range or value in between, based on the total weight of the composition.

[0068] pH of the composition In some embodiments, the pH of the composition is acidic (e.g., less than 7). In some embodiments, the pH of the composition is less than 7, 6.9 or less, 6.8 or less, 6.7 or less, 6.6 or less, 6.5 or less, 6.4 or less, 6.3 or less, 6.2 or less, 6.1 or less, 6.0 or less, 5.9 or less, 5.8 or less, 5.7 or less, 5.6 or less, 5.5 or less, 5.4 or less, 5.3 or less, 5.2 or less, 5.1 or less, 5.0 or less, 4.9 or less, 4.8 or less, 4.7 or less, 4.6 or less, 4.5 or less, 4.4 or less, 4.3 or less, 4.2 or less, 4.1 or less, 4.0 or less, 3.9 or less, 3.8 or less, 3.7 or less, 3.6 or less, 3.5 or less, 3.4 or less, 3.3 or less, 3.2 or less, 3.1 or less, 3.0 or less, 2.9 or less, 2.8 or less, 2.7 or less, 2.6 or less, 2.5 or less, 2.4 or less, 2.3 or less, 2.2 or less, 2.1 or less, 2.0 or less, or any range or value in between.

[0069] In some embodiments, the pH of the composition is 1.0 or higher, 1.1 or higher, 1.2 or higher, 1.3 or higher, 1.4 or higher, 1.5 or higher, 1.6 or higher, 1.7 or higher, 1.8 or higher, 1.9 or higher, 2.0 or higher, 2.1 or higher, 2.2 or higher, 2.3 or higher, 2.4 or higher, 2.5 or higher, 2.6 or higher, 2.7 or higher, 2.8 or higher, 2.9 or higher, 3.0 or higher, 3.1 or higher, 3.2 or higher, 3.3 or higher, 3.4 or higher, 3.5 or higher. Above, 3.6 or higher, 3.7 or higher, 3.8 or higher, 3.9 or higher, 4.0 or higher, 4.1 or higher, 4.2 or higher, 4.3 or higher, 4.4 or higher, 4.5 or higher, 4.6 or higher, 4.7 or higher, 4.8 or higher, 4.9 or higher, 5.0 or higher, 5.1 or higher, 5.2 or higher, 5.3 or higher, 5.4 or higher, 5.5 or higher, 5.6 or higher, 5.7 or higher, 5.8 or higher, 5.9 or higher, 6.0 or higher, or any range or value in between.

[0070] In some embodiments, the pH of the composition is 2-6, 2-5, 2-4, 2-3, 3-6, 3-5, 3-4, 4-6, 4-5, or 5-6. In some embodiments, the pH of the composition is approximately 3.

[0071] The pH values ​​used herein shall be determined using a pH meter (for example, LAQUA® manufactured by Horiba, Ltd., or any other suitable pH meter).

[0072] pH adjuster In some embodiments, the compositions according to the present disclosure may further include one or more pH adjusters for adjusting the pH to a desired pH value. In some embodiments, the above-mentioned “surfactants,” “particle removers,” “bases” (e.g., “organic amine compounds”) and “reducing agents” are not considered pH adjusters.

[0073] The pH adjuster is not particularly limited, and as discussed above, any suitable pH adjuster may be used to bring the pH of the composition to any desired range. In some embodiments, one or more pH adjusters may include, substantially consist of, inorganic compounds, organic compounds, or combinations thereof. In some embodiments, one or more pH adjusters may include inorganic acids (e.g., hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, boric acid, carbonic acid, hypophosphorous acid, phosphorous acid, and phosphoric acid); organic acids (e.g., carboxylic acids such as formic acid, acetic acid, propionic acid, benzoic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, maleic acid, phthalic acid, malic acid, tartaric acid, and lactic acid); and / or organic sulfonic acids (e.g., methanesulfonic acid, ethanesulfonic acid, isethionic acid, etc.). In some embodiments, one or more pH adjusting agents may include divalent or higher acids from among the above acids (e.g., sulfuric acid, carbonic acid, phosphoric acid, oxalic acid, etc.), which contain one or more protons (H + ) can be released and may be in the form of a base (e.g., ammonium bicarbonate or ammonium hydrogen phosphate), but any counterion can be used (e.g., weak basic cations such as ammonium or triethanolamine).

[0074] In some embodiments, one or more pH adjusters may include one or more alkali metal hydroxides (e.g., NaOH, KOH) or salts thereof (e.g., carbonates, bicarbonates, sulfates, acetates, etc.); quaternary ammonium compounds (e.g., tetramethylammonium, tetraethylammonium, tetrabutylammonium, etc.); quaternary ammonium hydroxides (e.g., tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide) or salts thereof; ammonia; amines; or any other suitable pH adjusters.

[0075] As discussed above, pH adjusters can be present in any amount suitable for achieving the desired pH value.

[0076] Other additives In some embodiments, the composition may contain other additives at any concentration. However, it is undesirable to add unnecessary components that may cause defects or pad stains. Therefore, any other additives, if present, are preferably present at relatively low concentrations. Examples of other additives include wetting agents, preservatives, dissolved gases, and oxidizing agents.

[0077] In some embodiments, the composition does not contain polymer particles. In some embodiments, the composition does not contain sulfate surfactants. In some embodiments, the composition is substantially free of polymer particles. In some embodiments, the composition is substantially free of sulfate surfactants.

[0078] dispersion medium In some embodiments, the composition comprises a dispersion medium or solvent. The dispersion medium can serve to disperse or dissolve the individual components. In some embodiments, the dispersion medium comprises, substantially comprises, or comprises water. In some embodiments, the dispersion medium may be a mixed solvent (e.g., water and an organic solvent) to facilitate the dispersion or dissolution of the individual components. In some embodiments, the organic solvent comprises, substantially comprises, or comprises acetone, acetonitrile, ethanol, methanol, isopropanol, glycerin, ethylene glycol, propylene glycol, or any other suitable organic solvent. In some embodiments, the organic solvent is miscible with water. In some embodiments, one or more organic solvents may be used without mixing with water (e.g., individual components may be dispersed or dissolved in one or more organic solvents). In some embodiments, a dispersion or solution of such components in one or more organic solvents may then be mixed with water. One or more organic solvents may be used alone or in combination of two or more.

[0079] In some embodiments, the water is preferably impurity-free water, or water containing as few impurities as possible. Limiting the impurity content can prevent contamination of the surface treatment or cleaning target and / or promote the further effective action of other components in the composition. For example, water with a total transition metal ion content of 100 ppb or less is preferred. In some embodiments, the total concentration of transition metal ions is 500 ppm or less, 400 ppm or less, 300 ppm or less, 200 ppm or less, 100 ppm or less, 900 ppb or less, 800 ppb or less, 700 ppb or less, 600 ppb or less, 500 ppb or less, 400 ppb or less, 300 ppb or less, 200 ppb or less, 100 ppb or less, 900 ppt or less, 800 ppt or less, 700 ppt or less, 600 ppt or less, 500 ppt or less, 400 ppt or less, 300 ppt or less, 200 ppt or less, or 100 ppt or less, or any range or value in between. Here, the purity of the water can be improved, for example, by removing impurity ions using one or more ion exchange resins, by using one or more filters, distillation and / or other operations, or by removing foreign substances. In some embodiments, the water may be deionized water (e.g., ion-exchanged water), distilled water, pure water, or ultrapure water.

[0080] A method for simultaneously removing pad stain from a polishing pad and removing particles from the polished surface. In another embodiment, the present disclosure relates to a method for simultaneously removing pad stain from a polishing pad and removing particles from a post-polished surface, comprising the steps of supplying a cleaning composition for post-CMP cleaning of the surface to the post-polished surface, and contacting the polishing pad with the post-polished surface in the presence of the cleaning composition for post-CMP cleaning to produce a post-polished surface with a reduced number of defects.

[0081] In some embodiments, the polished surface is a semiconductor surface (e.g., carbon (e.g., PCVD (plasma-enhanced chemical vapor deposition) carbon), Si, doped Si, TiO2, GaAs, etc.). In some embodiments, the semiconductor surface is patterned with metal wiring such as copper or tungsten. In some embodiments, the polished surface is polished using a CMP composition containing polishing particles (e.g., silica, alumina, cerium oxide, zirconia, titania, etc.). In some embodiments, the polished surface is polished using a CMP composition containing a polishing rate accelerator (e.g., KMnO4).

[0082] In some embodiments, the step of applying the cleaning composition of the present disclosure to a polished surface results in a surface with a reduced defect count. In some embodiments, the reduced defect count is less than 500, less than 450, less than 400, less than 350, less than 300, less than 250, less than 220, less than 200, less than 190, less than 180, less than 170, less than 160, less than 150, less than 140, less than 130, less than 120, less than 110, less than 100, less than 90, less than 80, less than 70, less than 60, less than 50, less than 40, less than 30, less than 20, less than 10, less than 9, less than 8, less than 7, less than 6, less than 5, less than 4, less than 3, less than 2, less than 1, or 0, or any range or value in between.

[0083] In some embodiments, when a polishing pad is brought into contact with the polished surface in the presence of a cleaning composition, residual pad stains are removed by bringing a CMP composition containing a polishing rate accelerator (e.g., KMnO4) into contact with the polishing pad. In some embodiments, the pad stains include manganese oxide (e.g., MnO2). In some embodiments, when a polishing pad is brought into contact with the polished surface, the pad stains are removed, preferably completely.

[0084] In some embodiments, contact is made for at least 1 second, at least 2 seconds, at least 3 seconds, at least 4 seconds, at least 5 seconds, at least 6 seconds, at least 7 seconds, at least 8 seconds, at least 9 seconds, at least 10 seconds, at least 15 seconds, at least 20 seconds, at least 25 seconds, at least 30 seconds, at least 35 seconds, at least 40 seconds, at least 45 seconds, at least 50 seconds, at least 55 seconds, at least 60 seconds, at least 75 seconds, at least 90 seconds, at least 100 seconds, at least 120 seconds, at least 150 seconds, at least 180 seconds, at least 5 minutes, at least 10 minutes, at least 15 minutes, at least 20 minutes, at least 25 minutes, at least 30 minutes, at least 35 minutes, at least 40 minutes, at least 45 minutes, at least 50 minutes, at least 55 minutes, at least 60 minutes, or any range or value in between.

[0085] In some embodiments, the cleaning composition is substantially free of abrasive particles. Examples of such abrasive particles include those described above. In this specification, "substantially free" means that the composition may contain the relevant component in amounts of 100 ppm by weight or less, 50 ppm by weight or less, or 10 ppm by weight or less. Examples of abrasive particles include inorganic particles and organic particles, as described above. Specific examples of inorganic particles include metal oxide particles such as silica, alumina, ceria, titania, and zirconia, silicon nitride particles, silicon carbide particles, and boron nitride particles. Specific examples of organic particles include polymethyl methacrylate (PMMA) particles.

[0086] The terms described above are expected to be readily understood by those skilled in the art, but the following definitions are provided to facilitate the explanation of the subject matter currently disclosed.

[0087] The terms "a" or "an" can refer to one or more of its entities, i.e., to multiple referents. Thus, the terms "a" or "an," "one or more," and "at least one" are used interchangeably herein. Furthermore, when we refer to "an element" with the indefinite article "a" or "an," we do not rule out the possibility that there may be more than one element unless the context explicitly requires that there be only one or one of those elements.

[0088] Throughout this specification, when we refer to “one embodiment,” “an embodiment,” “aspect,” or “aspect,” we mean that any particular characteristic, structure, or feature described in relation to this embodiment is included in at least one embodiment of this disclosure. Therefore, every occurrence of the phrase “in one embodiment” or “in an embodiment” in various places throughout this specification does not necessarily refer to the same embodiment. Furthermore, any specific characteristic, structure, or feature can be combined with any preferred method in one or more embodiments.

[0089] As used herein, the terms “about” or “approximately” when preceding a number indicate a value within a range of plus or minus 10% of that number.

[0090] As will be understood by those skilled in the art, for all purposes, and in particular with respect to presenting the descriptions provided, all scopes disclosed herein also encompass all possible sub-scopes and combinations thereof. Any scope enumerated can be readily recognized as well described and as being able to be divided into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each scope discussed herein can readily be divided into the bottom third, the middle third, the top third, etc. As will also be understood by those skilled in the art, all terms such as “at most,” “at least,” “greater than,” and “less than” include the numbers enumerated and refer to scopes that can later be divided into the sub-scopes discussed above. Finally, as will be understood by those skilled in the art, a scope includes each of its individual members. Thus, for example, a group having 1 to 3 cells means a group having 1, 2, or 3 cells. Similarly, a group having 1 to 5 cells means a group having 1, 2, 3, 4, or 5 cells, etc.

[0091] Unless otherwise specified, all terms used herein (including technical and scientific terms) have the same meaning as those generally understood by those skilled in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the context of this application and related art, and should not be interpreted in an ideal or overly formal sense unless expressly defined herein. Such terms, not expressly defined below, should be interpreted according to their general meanings.

[0092] Furthermore, if any feature or aspect of this disclosure is described in relation to the Markush group, a person skilled in the art will recognize that this disclosure is also described in relation to any individual member or subgroup of members of the Markush group.

[0093] Unless otherwise specified in the context, the various features of the present invention described herein are specifically intended to be used in any combination. Furthermore, this disclosure is also intended to show that in some embodiments, any feature or combination of features described herein may be excluded or omitted. For illustrative purposes, where this specification states that a composite comprises components A, B, and C, it is specifically intended that any one of A, B, or C, or any combination thereof, may be omitted or denied, either individually or in any combination.

[0094] Unless otherwise explicitly stated, all specified embodiments, features, and terms are intended to include any of the listed embodiments, features, or terms, and their equivalents.

[0095] All patents, patent applications, provisional applications, and publications mentioned or enumerated herein are incorporated by reference, including all figures and tables, in their entirety, to the extent that they do not contradict the express teachings herein.

[0096] Hereafter, some specific embodiments contemplated by this disclosure will be described in detail. While various embodiments are described herein, it should be understood that this technology is not intended to be limited to the embodiments described herein. Rather, it is intended to cover alternatives, variations, and equivalents that may fall within the spirit and scope of the technology as defined by the appended claims.

[0097] Example 1 Removal of MnO2 pad stains using a cleaning compound containing reducing agents and particle removers. Preparation of cleaning composition To test the effectiveness of the cleaning composition according to this disclosure in removing MnO2 pad stains, the following cleaning composition was prepared by adding the listed components to deionized water. In this composition ("Composition A"), the reducing agent was ascorbic acid, the particle remover was HEDP, the surfactant was capryleth-9-carboxylic acid, and the base was 3-amino-4-octanol. This cleaning composition is shown in Table 1 below.

[0098] [Table 1]

[0099] Pad stain removal Metal-based oxidizing agents (e.g., KMnO4) can enable higher removal rates than conventional non-metallic oxidizing agents (e.g., H2O2). However, the use of KMnO4 is limited because it forms MnO2 by-products that generate stains on the polishing pad, significantly increasing the number of post-CMP defects. Figure 1A shows an IC1010 pad after polishing for approximately 60 minutes using a KMnO4-containing slurry (colloidal zirconia (average secondary particle size 70 nm): 0.5 wt%, KMnO4: 0.3 wt%, pH: 3.0). The polishing conditions (polishing parameters), except for the polishing time, are as shown in Table 4. To confirm the chemical composition of the pad stain, X-ray photoelectron spectroscopy (XPS) was performed on sections of the stained pad. As shown in Table 2, Mn2p 3 / 2 Peak fitting analysis of the peaks indicates the presence of manganese oxide. This table shows the characteristic peak components of MnO-containing species at binding energies of 640.7 eV, 642.1 eV, and 644.0 eV. (These peaks originate from the Mn metal, Mn 2p 3 / 2This is observed at higher binding energies, which have a characteristic binding energy of approximately 638.5 eV. The average secondary particle diameter can be measured by dynamic light scattering methods, such as laser diffraction scattering. Specifically, the average secondary particle diameter of the abrasive grains corresponds to the particle diameter D50 in the particle size distribution of the abrasive grains determined by laser diffraction scattering, where the cumulative particle mass from the fine particles reaches 50% of the total particle mass.

[0100] [Table 2]

[0101] As shown in Figure 1B, this MnO x The contained pad stain can be removed by rinsing the polishing platen surface for 30 seconds using composition A. The cleaning conditions (polishing parameters) are as shown in Table 4, except for the polishing time. Although we do not wish to be bound by any particular theory, soluble Mn, which can be washed away from the pad if a reducing agent is present, can be removed. 2+ It can generate ions.

[0102] Removal of SP1 defect Furthermore, the ability of the cleaning composition according to this disclosure to remove defects from polished PCVD (plasma-enhanced chemical deposition) carbon wafers polished using the above-mentioned KMnO4-containing slurry was screened. The carbon wafer used was a 300 mm PCVD carbon BTW (blanket test wafer). The polishing conditions (polishing parameters) are shown in Table 4.

[0103] An SP1 defect map was generated using the KLA-Tencor SP1 surface analysis system ("SP1") after polishing the wafer surface with the above-mentioned KMnO4-containing slurry. The name (model number) of SP1 is Surfscan SP1. As shown in Figure 2A, it was found that the wafer cleaned with ammonia rinse, which is a comparative example of the present invention, had a very large number of defects. The composition of the ammonia rinse is listed in Table 5.

[0104] In contrast, referring to Figure 2B, it was found that wafers cleaned by rinsing the polishing platen surface with composition A, and then by subsequent wafer rinsing, had fewer defects than those cleaned with ammonia. This is also shown in Table 5. Looking at composition B, if an appropriate reducing agent is used in this cleaning composition (even in the absence of particle removers, etc.), pad stains can be removed to some extent, and defects can be reduced compared to cleaning with ammonia rinsing, which cannot remove pad stains.

[0105] Example 2 Compositions B to G were prepared by replacing the ascorbic acid in composition A of Example 1 with other reducing agents, and evaluated in the same manner as in Example 1. The names of several candidate reducing agents, their standard reduction potential (E°) values, and their predicted pad stain removal abilities are summarized in Table 3 below.

[0106] [Table 3]

[0107] To reduce the number of defects to a more desirable level, for example, less than 100, the reducing agent MnO shown in Table 3 is used. x The ability to remove pad stains was screened in combination with additional cleaning components. The defect count referred to here is the number of SP1 defects.

[0108] The SP1 defect count is the value indicated by the SP1 output, while the total particle defect count is calculated by reviewing 200 defects selected using a Review SEM (Hitachi High-Tech Corporation; RS-4000) for defect measurement after the SP1 measurement, and multiplying the SP1 defect count by the proportion of particles among those defects.

[0109] The test conditions are shown in Table 4. The tested formulations are shown in Table 5. All cleaning compositions were formulated at a pH of 3.0 ± 0.5 in PoU. (A certain degree of pH variation was tolerated as no additional pH adjusters were added to the formulations.) Equal amounts of reducing agents (except H2O2) were used in all tested compositions, based on weight percentage. In the case of H2O2, 3% by weight was added in PoU. The hydrogen peroxide (H2O2) was in the form of an aqueous solution, with a concentration of 30% by volume.

[0110] [Table 4]

[0111] Using platen 2, the surface of the PCVD carbon BTW (blanket test wafer) was polished with the above abrasive and polishing parameters. Then, the wafer was moved to platen 3 and rinsed (cleaned) with composition A and polishing parameters. After that, the wafer was moved to cleaning machine 1 (brush box 1) and cleaned with composition A while rubbing the wafer surface with a roller-type PVA sponge and cleaning parameters. After that, the wafer was moved to cleaning machine 2 (brush box 2) and cleaned with composition A while rubbing the wafer surface with a roller-type PVA sponge and cleaning parameters.

[0112] After polishing the wafer, it is acceptable to rinse it on the platen, but in a particularly preferred embodiment, it is then further cleaned in a brush box (cleaning machine). This cleaning in the brush box (cleaning machine) may be performed multiple times as described above.

[0113] Under the polishing and cleaning conditions described in Table 4, the number of surface defects on a 300 mm PCVD carbon (carbon film deposited by plasma CVD) BTW (blanket test wafer) was measured using the compositions shown in Table 5.

[0114] [Table 5]

[0115] As demonstrated in Table 5, all screened reducing agents were able to remove MnO2 pad stains compared to ammonia. Furthermore, as demonstrated by the results for compositions A-G, all reducing agents were able to reduce the total number of SP1 defects compared to the number of defects observed with ammonia. The effectiveness of the particle remover is highlighted by comparing the results for composition B (ascorbic acid only; no particle remover) with composition A (ascorbic acid + particle remover). Composition B was able to reduce the total number of SP1 defects and the total number of defects to 681 and 136, respectively, while composition A, containing the particle remover, was able to further reduce the total number of SP1 defects and the total number of defects to 17 and 0, respectively. Therefore, in the presence of ascorbic acid and the particle remover, the total number of defects is virtually eliminated.

[0116] While certain embodiments are described as examples, it should be understood that modifications and alterations can be made herein by those skilled in the art without departing from the broader aspects of the art, as set forth in the following claims.

[0117] The compositions and methods described herein as exemplary may be suitably carried out without any one or more elements or limitations not specifically disclosed herein. Therefore, terms such as “comprising,” “including,” and “containing” should be interpreted broadly and non-restrictively. Furthermore, the terms and expressions used herein are for illustrative purposes only, not limitation, and are not intended to exclude any equivalent of any of the features or parts thereof. It should be recognized that various modifications are possible within the scope of the claimed disclosure. Therefore, while this disclosure is specifically disclosed by preferred embodiments and optional features, it should be understood that modifications and variations of the disclosure embodied herein may be subject to legal action by those skilled in the art, and such modifications and variations shall be deemed to fall within the scope of this disclosure.

[0118] This disclosure is described broadly and generally herein. Each of the narrower and sub-species groupings that fall within the general disclosure also forms part of the Method. This includes general descriptions of the Method by conditional or negative limitation, removing any subject matter from its genus, whether or not the removed substance is specifically enumerated herein. The Art should not be limited to the specific embodiments described herein, which are intended as single examples of individual aspects of the Art. As will be obvious to those skilled in the art, numerous modifications and variations of the Art can be made without departing from its spirit and scope. In addition to those enumerated herein, functionally equivalent methods and apparatus within the scope of the Art will be obvious to those skilled in the art from the foregoing description. Such modifications and variations are intended to fall within the scope of the Art. It should be understood that the Art is not limited to specific methods, reagents, compound compositions or biological systems, and can naturally vary. It should also be understood that the terminology used herein is intended only to describe specific embodiments and is not intended to limit them.

[0119] Those skilled in the art will readily understand that this disclosure is well suited to achieving its purpose and obtaining the objectives and benefits expressed therein, as well as those specific thereto. Modifications and other uses therein will occur to those skilled in the art. These modifications are included within the spirit of this disclosure and are defined by the claims describing non-limiting embodiments of this disclosure.

[0120] Furthermore, if any characteristics or aspects of the present disclosure are described in relation to the Markush group, a person skilled in the art will recognize that the present disclosure is also described in relation to any individual member or subgroup of members of the Markush group.

[0121] All references, articles, publications, patents, patent publications, and patent applications cited herein are incorporated in their entirety for all purposes. However, wherever any reference, article, publication, patent, patent publication, or patent application cited herein is mentioned, it should not be taken as any form of acknowledgment or suggestion that they constitute valid prior art or form a common part of general knowledge in any country worldwide.

[0122] Other embodiments are described in the following claims.

[0123] This application is based on U.S. Provisional Application No. 63 / 248,067, filed on September 24, 2021, the disclosures thereof being incorporated herein by reference in their entirety.

[0124] Furthermore, the present invention encompasses the following embodiments and forms.

[0125] 1. A cleaning composition for post-CMP cleaning of semiconductor surfaces, comprising one or more reducing agents, particle removers, surfactants, and bases.

[0126] 2. The cleaning composition according to 1, wherein one or more reducing agents yield a standard reduction potential (E°) of less than 1.224V.

[0127] 3. The cleaning composition according to 1. or 2., wherein the one or more reducing agents comprises at least one selected from sulfites, dithionates, thiosulfates, iodides, phosphates, hypophosphates, formic acid, phosphorous acid, ascorbic acid, hydrogen peroxide, hydroxylamines, oxalic acid, sodium sulfite, alkali salts thereof, or any combination thereof.

[0128] 4. The cleaning composition according to any one of 1 to 3, wherein the reducing agent comprises at least one of ascorbic acid and hydrogen peroxide.

[0129] 5. The cleaning composition according to any one of 1. to 4., wherein the one or more reducing agents are present at a concentration of 0.01 to 10% by weight based on the total weight of the composition.

[0130] 6. The cleaning composition according to any one of 1. to 5., wherein the one or more reducing agents are present at a concentration of 0.1 to 1% by weight based on the total weight of the composition.

[0131] 7. The cleaning composition according to any one of 1. to 6., wherein the particle remover contains glycine, N-(phosphonomethyl)iminodiacetic acid hydrate, hydroxyphosphonoacetic acid, citric acid, hydroxyethane-1,1-diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, or 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP).

[0132] 8. The particle remover contains a compound represented by N(R 1 )(R 2 )(R 3 ) or a salt thereof, or a compound represented by C(R 1 )(R 2 )(R 3 )(R 4 ) or a salt thereof, wherein R 1 to R 3 and R 1 to R 4 each independently represent a hydrogen atom, a carboxyl group, a hydroxyl group, a phosphonic acid group or a salt thereof, or a linear or branched alkyl group having 1 to 5 carbon atoms which may be substituted or unsubstituted. At this time, one or more of R 1 to R 3 are a phosphonic acid group or a salt thereof, or an alkyl group substituted with a phosphonic acid group or a salt thereof, and one or more of R 1 to R​​​

[0133] 9. The cleaning composition according to any one of 1 to 8, wherein the particle removal agent comprises 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP).

[0134] 10. The cleaning composition according to any one of 1 to 9, wherein the particle removal agent is present at a concentration of 0.05 to 5% by weight relative to the total weight of the composition.

[0135] 11. The cleaning composition according to any one of 1 to 10, wherein the particle removal agent is present at a concentration of 0.5 to 1% by weight relative to the total weight of the composition.

[0136] 12. A cleaning composition according to any one of 1 to 11, wherein the base comprises 2-(diethylamino)ethanethiol, captamine, diethylethanolamine, methylcysteamine, 2-(tert-butylamino)ethanethiol, 2,2'-dimethoxy-1,1-dimethyldimethylamine, 3-amino-4-octanol, 3-butoxypropylamine, N-acetylcysteamine, homocysteamine, N,N-dimethylhydroxylamine, 2-(isopropylamino)ethanol, 2-(methylthioethyl)amine, 1-aminopropane-2-thiol, leucinol, cysteamine and / or N,O-dimethylhydroxylamine.

[0137] 13. A cleaning composition according to any one of 1 to 12, wherein the base comprises an alkylated amine.

[0138] 14. A cleaning composition according to any one of 1 to 13, wherein the base comprises 3-amino-4-octanol.

[0139] 15. The cleaning composition according to any one of 1 to 14, wherein the base is present at a concentration of 0.05 to 5% by weight relative to the total weight of the composition.

[0140] 16. The cleaning composition according to any one of 1. to 15., wherein the base is present at a concentration of 0.5 to 1% by weight based on the total weight of the composition.

[0141] 17. The cleaning composition according to any one of 1. to 16., wherein the surfactant contains a carboxylic acid surfactant.

[0142] 18. The surfactant is of the formula (I): C m H 2m+1 -(OCH2CH2) n -L-COOH (I) (where 6 ≦ m ≦ 20, n ≧ 5, L is a bond, -O-, -S-, -R 1 -, -S-R 1 - or -O-R 1 -, and R 1 is C 1~4 alkylene) The cleaning composition according to any one of 1. to 17., which is represented by

[0143] 19. The cleaning composition according to any one of 1. to 18., wherein the surfactant contains capryles-9-carboxylic acid.

[0144] 20. The cleaning composition according to any one of 1. to 19., wherein the surfactant is present at a concentration of 0.01 to 10% by weight based on the total weight of the composition.

[0145] 21. The cleaning composition according to any one of 1. to 20., wherein the surfactant is present at a concentration of 0.1 to 1% by weight based on the total weight of the composition.

[0146] 22. The reducing agent provides a standard reduction potential (E°) of less than 1.224 V, or contains at least hydrogen peroxide, and the particle remover is a compound represented by N(R 1 )(R 2 )(R 3 ) or a salt thereof, or C(R1 )(R 2 )(R 3 )(R 4 The compound represented by ) or a salt thereof, where R 1 ~R 3 and R 1 ~R 4 Each of these independently represents a hydrogen atom, a carboxyl group, a hydroxyl group, a phosphonic acid group or a salt thereof, or a substituted or unsubstituted linear or branched alkyl group having 1 to 5 carbon atoms, in which case R 1 ~R 3 One or more of these are groups of a phosphonic acid group or a salt thereof, or alkyl groups substituted with groups of a phosphonic acid group or a salt thereof, and R 1 ~R 4 One or more of these are groups of a phosphonic acid group or a salt thereof, or alkyl groups substituted with groups of a phosphonic acid group or a salt thereof, and the surfactant is of formula (I): C m H 2m+1 -(OCH2CH2) n -L-COOH (I) (In the formula, 6 ≤ m ≤ 20, n ≥ 5, and L is bond, -O-, -S-, -R) 1 -, -SR 1 - or - OR 1 - and R 1 C 1~4 A cleaning composition according to any one of 1 to 21, wherein the base is represented by (an alkylene), and the base comprises an alkylated amine containing a hydroxyl group.

[0147] 23. A cleaning composition for post-CMP cleaning of semiconductor surfaces, comprising hydrogen peroxide, a particle remover, a surfactant, and a base.

[0148] 24. The cleaning composition according to 23, comprising hydrogen peroxide, hydroxyethane-1,1-diphosphonic acid, capryleth-9-carboxylic acid, and 3-amino-4-octanol.

[0149] 25. The cleaning composition according to any one of 1 to 24, wherein the composition has a pH of 2 to 6.

[0150] 26. The cleaning composition according to 25, wherein the pH is approximately 3.

[0151] 27. A method for simultaneously removing pad stain from a polishing pad and removing particles from a semiconductor surface after polishing, comprising the steps of: supplying a cleaning composition described in any one of 1. to 26. to the semiconductor surface; and bringing the polishing pad into contact with the semiconductor surface in the presence of the cleaning composition to produce a post-polished semiconductor surface with a reduced number of defects.

[0152] 28. The method according to 27, wherein the pad stain contains MnO2.

[0153] 29. The method according to 27. or 28., wherein the reduced number of defects is 100 or less.

[0154] 30. The method according to any one of 27. to 29., wherein the number of defects reduced is 70 or less.

[0155] 31. The method according to any one of 27. to 30., wherein the number of defects reduced is 50 or less.

[0156] 32. The method according to any one of 27. to 31., wherein the number of defects reduced is 20 or less.

[0157] 33. The method according to any one of 27. to 32., wherein the polished semiconductor surface has a total number of particle defects of 2 or less after contact.

[0158] 34. The method according to any one of 27. to 33., wherein the polished semiconductor surface has a total number of particle defects that becomes 0 after contact.

[0159] 35. A method for polishing a semiconductor surface, comprising the steps of: polishing the semiconductor surface with a polishing composition containing a removal rate improving agent; and simultaneously removing pad stain from a polishing pad and removing particles from the semiconductor surface by any one of the methods described in 27. to 34.

[0160] 36. A method for producing a polished semiconductor surface, comprising the steps of: polishing the semiconductor surface with a polishing composition containing a removal rate improving agent; and simultaneously removing pad stain from a polishing pad and removing particles from the semiconductor surface by any one of the methods described in 27. to 34.

[0161] 37. The method according to 35. or 36., wherein the removal rate improving agent contains KMnO4 and the pad stain contains MnO2.

Claims

1. A cleaning composition for post-CMP cleaning of semiconductor surfaces, Reducing agent, Particle removal agent, Surfactants, and base Includes, The reducing agent comprises at least one selected from sulfites, dithionates, thiosulfates, iodides, phosphites, hypophosphites, formic acid, phosphorous acid, ascorbic acid, hydrogen peroxide, hydroxylamines, oxalic acid, sodium sulfite, alkali salts thereof, or any combination thereof. The reducing agent is present in the cleaning composition at a concentration of at least 0.55% by weight. A cleaning composition wherein the base comprises one or more of the following: 2-(diethylamino)ethanethiol, captamine, diethylethanolamine, methylcysteamine, 2-(tert-butylamino)ethanethiol, 2,2'-dimethoxy-1,1-dimethyldimethylamine, 3-amino-4-octanol, 3-butoxypropylamine, N-acetylcysteamine, homocysteamine, N,N-dimethylhydroxylamine, 2-(isopropylamino)ethanol, 2-(methylthioethyl)amine, 1-aminopropane-2-thiol, leucinol, cysteamine, and N,O-dimethylhydroxylamine.

2. The cleaning composition according to claim 1, wherein the reducing agent comprises at least one of ascorbic acid and hydrogen peroxide.

3. The cleaning composition according to claim 1, wherein the particle removal agent comprises glycine, N-(phosphonomethyl)iminodiacetic acid hydrate, hydroxyphosphonoacetic acid, citric acid, hydroxyethane-1,1-diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, or 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP).

4. The particle remover is a compound represented by N(R １ )(R ２ )(R ３ ), or a salt thereof, or a compound represented by C(R １ )(R ２ )(R ３ )(R ４ ), or a salt thereof, where R １ to R ３ and R １ to R ４ each independently represent a hydrogen atom, a carboxyl group, a hydroxyl group, a phosphonic acid group or a salt thereof, or a linear or branched alkyl group having 1 to 5 carbon atoms which may or may not be substituted. At this time, one or more of R １ to R ３ is a phosphonic acid group or a salt thereof, or an alkyl group substituted with a phosphonic acid group or a salt thereof, and one or more of R １ to R ４ contain a phosphonic acid group or a salt thereof, or an alkyl group substituted with a phosphonic acid group or a salt thereof. The cleaning composition according to claim 1.

5. The cleaning composition according to claim 1, wherein the particle removal agent comprises 1-hydroxyethylidene-1,1-diphosphonic acid.

6. The cleaning composition according to claim 1, wherein the base comprises 3-amino-4-octanol.

7. The surfactant is of formula (I): C ｍ H ２ｍ＋１ -(OCH ２ CH ２ ) ｎ -L-COOOH (I) (In the formula, 6 ≤ m ≤ 20, n ≥ 5, L represents bonding, -O-, -S-, -R １ -, -S-R １ - or - OR - R １ - and R １ C １～４ (It is alkylene.) The cleaning composition according to claim 1, as represented by [the specified figure].

8. The cleaning composition according to claim 1, wherein the surfactant comprises capryleth-9-carboxylic acid.

9. The reducing agent is hydrogen peroxide, The particle removal agent is hydroxyethane-1,1-diphosphonic acid, The surfactant is capryleth-9-carboxylic acid, The cleaning composition according to claim 1, wherein the base is 3-amino-4-octanol.

10. A method for simultaneously removing pad stains from the polishing pad and particles from the semiconductor surface after polishing, A step of supplying the cleaning composition according to any one of claims 1 to 9 to the semiconductor surface, The step of bringing the polishing pad into contact with the semiconductor surface in the presence of the cleaning composition to produce a polished semiconductor surface with a reduced number of defects. Methods that include...

11. The aforementioned pad stain is MnO ２ The method according to claim 10, including the method described in claim 10.

12. A method for manufacturing a polished semiconductor surface, The steps include polishing a semiconductor surface with a polishing composition containing a removal rate improving agent, and The method according to claim 10, comprising the steps of simultaneously removing pad stain from a polishing pad and removing particles from the semiconductor surface, Methods that include...

13. The removal rate improving agent is KMnO ４ The method according to claim 12, including the method described in claim 12.

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