Alkaline composition for cleaning substrate comprising cobalt and copper, use and method thereof

Abstract

The invention claimed herein relates to an alkaline composition for cleaning a substrate comprising: i) copper or a copper alloy and ii) cobalt or a cobalt alloy, the composition comprising: a) at least one pH adjusting agent selected from compounds of formula (I) wherein Ra, Rb, Rd and Rf are independently from each other selected from unsubstituted linear or branched C1-C12 alkyl groups, re is selected from an unsubstituted straight chain or branched chain C4-C9 alkyl group; ra, Rb, Re and Rf may be bonded such that the dashed bond between Re and N is a single bond or a double bond, and when the dashed bond is a double bond, Rd is absent, and Ra, Rb, Re and Rf may be bonded to form one or more 6-or 7-membered rings; a) at least one complexing agent selected from C2 to C12 hydrocarbons having at least two sulfonic acid groups or carboxylic acid groups, b) at least one polymeric dispersant having a weight average molecular weight > = 1000 g / mol; and c) a solvent comprising water. (I).

Description

Technical Field

[0001] The invention claimed herein relates to an alkaline composition for cleaning a substrate, its use, and a method thereof, the substrate comprising copper or a copper alloy and cobalt or a cobalt alloy. Background Technology

[0002] Manufacturing electrical devices, particularly semiconductor integrated circuits (ICs); liquid crystal panels; organic electroluminescent panels; printed circuit boards; micromachines; DNA chips; microdevices and magnetic heads; ICs preferably having LSI (large-scale integrated circuits) or VLSI (very large-scale integrated circuits); and optical devices, particularly optical glasses such as photomasks, lenses, and prisms; inorganic conductive films such as indium tin oxide (ITO); optical integrated circuits; optical switching elements; optical waveguides; optical single crystals such as the end faces of optical fibers and scintillators; solid-state laser single crystals; sapphire substrates for blue laser LEDs; semiconductor single crystals; and glass substrates for magnetic disks; requires high-precision methods, which in particular include surface preparation using high-purity cleaning compositions, pre-weaving cleaning, post-etching cleaning, and / or post-chemical polishing cleaning steps.

[0003] Special care must be taken when manufacturing ICs with LSI or VLSI. The semiconductor wafers used for this purpose consist of a semiconductor substrate (such as silicon) on which regions are patterned for depositing different materials with electrically insulating, conductive, or semiconductor properties. To achieve proper patterning, excess material used to form different layers on the substrate must be removed. Furthermore, a flat or planar semiconductor wafer surface is crucial for manufacturing practical and reliable ICs. Therefore, during IC manufacturing, it is necessary to clean, remove, and / or polish certain surfaces of the semiconductor wafer before proceeding to the next process step.

[0004] Most processing operations involving wafer substrate surface preparation, deposition, electroplating, etching, and chemical mechanical planarization (CMP) require cleaning operations in various ways to ensure that ICs are free of contaminants, which could otherwise harmfully affect IC functionality or even prevent them from performing their intended functions.

[0005] For example, one such problem arises from residues left on the substrate after CMP processing. During, for example, Cu-CMP, the copper ion concentration may exceed the maximum solubility of copper-inhibitor complexes. Therefore, copper-inhibitor complexes may precipitate from the solution and may solidify as residues on the surface. Furthermore, these residues may adhere to the surface of the polishing pad and accumulate, eventually filling the grooves in the polishing pad. Additionally, abrasive particles and chemicals contained in the CMP slurry, as well as reaction byproducts, can cause severe damage when left on the wafer surface. Moreover, polishing copper damascene structures containing low-k or ultra-low-k dielectric materials (such as carbon-doped oxides or organic films) can produce carbon-rich particles that settle onto the wafer surface. Worse still, these low-k or ultra-low-k dielectric materials, along with silicon carbide, silicon nitride, or silicon oxynitride CMP stop layers, are highly hydrophobic and therefore difficult to clean with water-based cleaning solutions.

[0006] Another process commonly used in IC manufacturing that generates residues involves vapor phase plasma etching (VPE), which transfers the pattern of a developed photoresist coating (used to form vias and trenches) to underlying layers, which may consist of a hard mask, interlayer dielectric, and etch stop layer. Residues from VPE (which may contain chemical elements present on and within the substrate and in the plasma gas) typically deposit on back-to-offline (BEOL) structures and, if not removed, can interfere with subsequent siliconization and contact formation.

[0007] Recent advancements in wafer fabrication and manufacturing have led to the use of new materials, particularly metals and metal alloys, in the fabrication of microelectronic devices. For example, conventional barrier layer materials have been replaced in integrated circuits by cobalt (Co) and cobalt alloys to reduce layer thickness and IC size. Another approach is the use of cobalt as a novel plug material in integrated circuits. With the introduction of these new cobalt-containing or cobalt alloy layers and plugs, there is an industrial need for post-CMP removal / cleaning compositions capable of removing post-CMP residues and contaminants (including corrosion inhibitors of the deposits) without harmfully affecting the new cobalt layer material.

[0008] Additionally, if the substrate comprises metal sputtering based on, for example, cobalt and copper (e.g., cobalt-lined integration as described in US 2012 / 0161320), and these surfaces are in contact with the cleaning solution, care must be taken to ensure the cleaning solution is compatible with both metals. This is especially true for Cu-PCC and PERR solutions. For PERR, the metal structure is only open at the bottom of the vias, etched into the dielectric layer. However, for post-Cu CMP, the upper surface of the metal sputtering is fully exposed to the PCC solution. Galvanic corrosion may also need to be considered because the metal or material exhibiting metallic conductivity is in galvanic contact (cobalt-lined integration) and immersed in the PERR or PCC cleaning solution. Examples of metals involved can be Ru, Pt, Co, Ir, Pd, Re, Rh, Ti, Ta, Mn, Ni, Al, Cr, V, Mo, Zr, Nb, W, Zr, Cu, their alloys, and conductive materials (like TiN and TaN). Additionally, Cu can be a filler material.

[0009] US 2018 / 0371371 A1 and US 2019 / 002802 A1 disclose an aqueous CMP post-cleaning composition comprising polyethylene glycol, anionic polymer poly(acrylic acid), acrylic acid-maleic acid copolymer, polyaspartic acid, polyglutamic acid, polyvinylphosphonic acid, polyvinylsulfonic acid, poly(styrene sulfonic acid), polycarboxylic acid ether, polyphosphorous acid, and copolymers thereof. On the other hand, US 10351809 B2 discloses a cleaning composition and method for cleaning post-chemical mechanical polishing (CMP) residues and contaminants from microelectronic devices. This cleaning mixture comprises at least one organic amine, at least one solvent, at least one quaternary base, at least one complexing agent, at least one reducing agent, optionally at least one additional etchant, and optionally at least one cleaning additive, wherein the cleaning composition is substantially free of alkali metal hydroxides, alkaline earth metal hydroxides, and tetramethylammonium hydroxide. The aforementioned compositions are intended for cleaning substrates, particularly those containing cobalt. However, despite these advances, formulating suitable compositions is often challenging. An additional hurdle often encountered is the incompatibility or low solubility of the various components, which makes the compositions unsuitable for manufacture in concentrated form. This reduces their processability and economic viability. Therefore, there remains a need to provide improved, cleaner compositions. Summary of the Invention

[0010] Surprisingly, the composition of the invention claimed herein, as described below, was found to provide not only high processability but also surprisingly low cobalt and copper etching rates.

[0011] Therefore, in one aspect, the invention claimed herein relates to an alkaline composition for cleaning a substrate comprising i) copper or a copper alloy and ii) cobalt or a cobalt alloy, the composition comprising:

[0012] a) At least one pH adjuster selected from compounds having formula I.

[0013]

[0014] Formula I

[0015] in

[0016] Ra, Rb, Rd, and Rf are independently selected from unsubstituted straight or branched C1-C chains. 12 alkyl,

[0017] Re is selected from unsubstituted straight-chain or branched C4-C9 alkyl groups; such that the dashed bond between Re and N is a single or double bond, and Rd does not exist when the dashed bond is a double bond.

[0018] Ra, Rb, Re, and Rf can bond together to form one or more 6- or 7-membered rings;

[0019] b) At least one complexing agent selected from C2 to C3 groups having at least two sulfonic acid groups or carboxylic acid groups. 12 hydrocarbon,

[0020] c) at least one polymer dispersant having a weight-average molecular weight ≥ 1000 g / mol; and

[0021] d) Solvents containing water.

[0022] On the other hand, the invention claimed herein relates to a concentrate for preparing a composition as described herein, the concentrate comprising:

[0023] a) At least one pH adjuster, ≥ 4.0 to ≤ 40.0 wt.%;

[0024] b) At least one complexing agent, ≥ 0.1 to ≤ 3.0 wt.%

[0025] c) at least one polymer dispersant of ≥ 0.01 to ≤ 3.0 wt.%; and

[0026] d) The remaining solvent containing water.

[0027] On the other hand, the invention claimed herein relates to the use of the composition as described herein for removing the following from a substrate:

[0028] (a) Post-etching residue (PERR) or post-ashing residue (PARR), or

[0029] (b) Chemical-mechanical planarization (CMP) residues,

[0030] The substrate includes (i) a cobalt or cobalt alloy surface and (ii) a copper or copper alloy surface.

[0031] On the other hand, this method fabricates microelectronic devices, the method comprising:

[0032] (a) Providing a microelectronic substrate comprising (i) a cobalt or cobalt alloy surface and (ii) a copper or copper alloy surface having etch residues, ashing residues, or chemical mechanical planarization (CMP) residues.

[0033] (b) to provide the composition as described herein; and

[0034] (c) Contact (i) the cobalt or cobalt alloy surface and (ii) the copper or copper alloy surface with the composition at a certain temperature for a certain time to effectively remove, at least partially and preferably completely, etch residues, ashing residues or chemical mechanical planarization (CMP) residues from the substrate.

[0035] On the other hand, the invention claimed herein relates to a method for manufacturing a semiconductor device, the method comprising the processing described herein.

[0036] The invention claimed herein is associated with at least one of the following objectives:

[0037] (1) A composition capable of substantially and effectively removing post-CMP residues and contaminants, particularly from substrates containing or composed of cobalt or cobalt alloys (e.g., cobalt as part of a layer or as an insert) without adversely affecting electrical materials and devices, especially without adversely affecting semiconductor integrated circuits and providing a high-quality surface finish.

[0038] (2) The compositions and methods of the invention claimed herein are intended to provide improved performance in inhibiting etching for both copper and cobalt.

[0039] (3) The compositions of the invention claimed herein are intended to provide stable formulations without precipitation or phase separation, especially under alkaline conditions.

[0040] (4) The compositions of the invention claimed herein are intended to provide easy-to-use, environmentally friendly compositions that allow for easy processability and improved economic viability. Detailed Implementation

[0041] The following detailed descriptions are merely exemplary in nature and are not intended to limit the invention claimed herein or its application and uses. Furthermore, they are not intended to be bound by any theories presented in the foregoing technical field, background art, summary of the invention, or the following detailed descriptions.

[0042] As used herein, the terms “comprising” and “comprised of” are synonymous with “including” or “containing” and are inclusive or open-ended, and do not exclude additional unlisted members, elements, or method steps. It should be understood that, as used herein, the terms “comprising” and “comprised of” include the terms “consisting of” and “consists of”.

[0043] Furthermore, the terms “(a)”, “(b)”, “(c)”, “(d)”, etc., in the specification and claims are used to distinguish similar elements and are not necessarily used to describe a sequential or chronological order. It should be understood that such terms are interchangeable where appropriate, and embodiments of the invention claimed herein can be operated in any order other than those described or shown herein. Where the terms “(A)”, “(B)”, and “(C)”, or “(a)”, “(b)”, “(c)”, “(d)”, “(i)”, “(ii)”, etc., relate to steps of a method, use, or measurement, there is no temporal or time interval continuity between these steps; that is, these steps may be performed simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months, or even years between them, unless otherwise indicated in the application above or below.

[0044] The different aspects of the invention claimed herein are defined in more detail in the following paragraphs. Each aspect so defined may be combined with any one or more other aspects unless expressly indicated otherwise. In particular, any feature indicated as preferred or advantageous may be combined with any one or more other features indicated as preferred or advantageous.

[0045] Throughout this specification, references to "an embodiment," "an embodiment," or "a preferred embodiment" mean that a particular feature, structure, or property described in connection with that embodiment is included in at least one embodiment of the invention claimed herein. Therefore, the phrases "in one embodiment," "in an embodiment," or "in a preferred embodiment" appearing in different places throughout this specification do not necessarily all refer to the same embodiment, but may refer to the same embodiment. Furthermore, in one or more embodiments, features, structures, or properties may be combined in any suitable manner, as will be apparent to those skilled in the art from this disclosure. Moreover, although some embodiments described herein include some but not others of features included in other embodiments, combinations of features from different embodiments are intended to be within the scope of this subject matter and form different embodiments, as will be understood by those skilled in the art. For example, in the appended claims, any of the claimed embodiments may be used in any combination.

[0046] Furthermore, the scope defined throughout this specification also includes end values; that is, the range of 1 to 10 means that both 1 and 10 are included in this range. For the avoidance of doubt, the applicant is entitled to obtain any equivalent means in accordance with applicable law.

[0047] For the purposes of the invention claimed herein, '% by weight' or 'wt.%' as used herein refers to the total weight of the coating composition. Additionally, as described below, the sum of the wt.% of all compounds in each component is 100 wt.%.

[0048] For the purposes of the invention claimed herein, a substrate is defined as a semiconductor wafer made of silicon or a similar half-metal for use in the manufacture of microelectronic devices.

[0049] For the purposes of the invention claimed herein, polishing or cleaning refers to the process following chemical-mechanical planarization (CMP), where an alkaline composition as described herein can be used to remove debris and residues remaining on the semiconductor surface after the CMP step. It is well known that CMP aims to remove specific layers from a semiconductor substrate, involving a combination of chemical and mechanical actions. The mechanical action is typically performed using a polishing pad, which is typically pressed against the surface to be polished and mounted on a moving stage. In a typical CMP process step, a rotating wafer holder brings the wafer to be polished into contact with the polishing pad. The CMP composition is typically applied between the wafer to be polished and the polishing pad. On the other hand, abrasive particles (such as silica particles) in the CMP composition are essential for achieving “chemical” polishing. Additionally, the presence of specific chemicals (such as oxidants, like peroxides) in the CMP composition is important to ensure high removal rates of specific target layers / metals (such as copper and / or cobalt). However, the alkaline composition described herein is substantially free of any abrasive particles (especially silica particles) or oxidants (especially peroxides).

[0050] For the purposes of this invention, "substantially free" means that the composition does not contain any concentration of the components that could affect the cleaning function of the composition. Preferably, the particle content is less than 10 ppm, more preferably less than 1 ppm, and most preferably below the detection limit. In a preferred embodiment, the composition is filtered prior to use to ensure that the particle concentration is below the desired value. For example, preferably, the composition is substantially free of abrasive particles and / or oxidants, and preferably, the concentration of abrasive particles and / or oxidants in the composition is less than 10 ppm. However, any trace amounts of such particles / components that may remain on the semiconductor surface as part of the residue after the CMP step will not impair the cleaning application involving the alkaline composition described herein.

[0051] For the purposes of the invention claimed herein, corrosion inhibitors are defined as compounds that form a protective molecular layer on a metal surface.

[0052] For the purposes of the invention claimed herein, the term "aqueous" means that the composition of the invention contains water. The water content of different compositions may vary considerably. As described herein, the alkaline composition is an aqueous composition and contains at least 50.0 wt.%, preferably at least 60 wt.%, more preferably at least 80 wt.%, even more preferably at least 90.0 wt%, and still more preferably at least 90.0 wt% water.

[0053] For the purposes of the invention claimed herein, the term "alkaline" means that the compositions of the present invention have a pH in the range of 7.5 to 14.0, preferably 8.5 to 13.0, and more preferably 8.5 to 12.5, even more preferably 9.0 to 12.0, and most preferably 10.5 to 11.9.

[0054] For the purposes of the invention claimed herein, the term "copper inhibitor" refers to a compound that inhibits the static removal of copper from a substrate by etching. "Cobalt inhibitor" refers to a compound that inhibits the static removal of cobalt from a substrate by etching.

[0055] All cited references are incorporated into this paper by way of citation.

[0056] For the purposes of the invention claimed herein, the measurement techniques disclosed are well known to those skilled in the art.

[0057] In one aspect of the invention claimed herein, an alkaline composition for cleaning a substrate comprising i) copper or a copper alloy and ii) cobalt or a cobalt alloy, the composition comprising:

[0058] a) At least one pH adjuster selected from compounds having formula I.

[0059]

[0060] Formula I

[0061] in

[0062] Ra, Rb, Rd, and Rf are independently selected from unsubstituted straight or branched C1-C chains. 12 alkyl,

[0063] Re is selected from unsubstituted straight-chain or branched C4-C9 alkyl groups; such that the dashed bond between Re and N is a single or double bond, and Rd does not exist when the dashed bond is a double bond.

[0064] Ra, Rb, Re, and Rf can bond together to form one or more 6- or 7-membered rings;

[0065] b) At least one complexing agent selected from C2 to C3 groups having at least two sulfonic acid groups or carboxylic acid groups. 12 hydrocarbon,

[0066] c) at least one polymer dispersant having a weight-average molecular weight ≥ 1000 g / mol; and

[0067] d) Solvents containing water.

[0068] The alkaline composition of the present invention comprises components (a), (b), (c), and (d) as described below, and optionally additional components.

[0069] (a) pH adjuster

[0070] According to the invention claimed herein, the composition comprises at least one pH adjuster selected from compounds having formula I.

[0071]

[0072] Formula I

[0073] in

[0074] Ra, Rb, Rd, and Rf are independently selected from unsubstituted straight or branched C1-C chains. 12 alkyl,

[0075] Re is selected from unsubstituted straight-chain or branched C4-C9 alkyl groups; such that the dashed bond between Re and N is a single or double bond, and Rd does not exist when the dashed bond is a double bond.

[0076] Ra, Rb, Re, and Rf can bond together to form one or more 6- or 7-membered rings.

[0077] For the purposes of the invention claimed herein, a pH adjuster is defined as a compound added to a composition to adjust its pH to a desired value. As demonstrated below in the Examples section, specific tertiary amine compounds having formula I or Ia ensure an alkaline pH while maintaining low static etching rates (SER) for both copper and cobalt. For the purposes of the invention claimed herein, the pH adjuster is selected from tertiary amines and may not be selected from primary ammonium, secondary ammonium, or quaternary ammonium groups.

[0078] In the context of the invention claimed herein, as used herein, the term "alkyl" refers to a non-cyclic saturated unsubstituted aliphatic group, including straight-chain or branched alkyl saturated hydrocarbon groups, defined by the general formula C1. n H 2n+1 It is represented as n, where n is the number of carbon atoms, such as 1, 2, 3, 4, etc.

[0079] Unsubstituted linear C1-C 12 The alkyl group is preferably selected from the group consisting of: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl; more preferably selected from the group consisting of: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl.

[0080] Unreplaced branch C1-C 12The alkyl group is preferably selected from the group consisting of: isopropyl, isobutyl, neopentyl, 2-ethylhexyl, 2-propyl-heptyl, 2-butyl-octyl, 2-pentyl-nonyl, 2-hexyl-decyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl and isododecyl, more preferably selected from the group consisting of: isopropyl, isobutyl, neopentyl, 2-ethylhexyl, 2-propyl-heptyl, 2-butyl-octyl, 2-pentyl-nonyl, 2-hexyl-decyl, isohexyl, isoheptyl, isooctyl and isononyl.

[0081] Preferably, the composition comprises at least one pH adjuster selected from compounds having Formula I.

[0082]

[0083] Formula I

[0084] in

[0085] Ra, Rb, Rd, and Rf are independently selected from unsubstituted straight-chain C1-C9 alkyl groups.

[0086] Re is selected from unsubstituted straight-chain or branched C4-C9 alkyl groups; such that the dashed bond between Re and N is a single or double bond, and Rd does not exist when the dashed bond is a double bond.

[0087] Ra, Rb, Re, and Rf can bond together to form one or more 6- or 7-membered rings.

[0088] Preferably, Ra, Rb, Rd, and Rf are independently selected from unsubstituted straight-chain or branched C1-C. 10 Alkyl groups, more preferably selected from unsubstituted straight-chain or branched C1-C9 alkyl groups, and even more preferably selected from unsubstituted straight-chain or branched C1-C6 alkyl groups.

[0089] More preferably, Ra, Rb, Rd, and Rf are independently selected from unsubstituted linear C1-C molecules. 12 Alkyl groups, more preferably selected from unsubstituted straight-chain C1-C9 alkyl groups, and most preferably selected from unsubstituted straight-chain C1-C6 alkyl groups.

[0090] Preferably, Ra, Rb, Re, and Rf can be bonded to form one, two, or three hexagonal or septagonal rings, more preferably they can be bonded to form one or two hexagonal or septagonal rings.

[0091] Those skilled in the art should understand that, in cases where Ra, Rb, Re, and Rf are bonded to form one or more ring structures, one or more H atoms from the alkyl group will be replaced by C-C bonds to form a fused ring structure, and the carbon group attached to the N atom will be an alkylene group or a -C(H2)- group.

[0092] Preferably, the dashed bond between Re and N is a single bond.

[0093] While diamines are well known for their ability to chelate metals (by forming five- or six-membered rings with the metal ions to be complexed), it should be noted, without being bound by theory, that such cyclic diamines lead to undesirable high copper and / or cobalt etching rates (as demonstrated by the high SER values ​​in the Examples section below). For the purposes of this invention, it is considered that the carbon chain length of Re in compounds having Formula I must be carefully tuned to avoid cyclization or chelation. Preferably, Re is ≥ C4 alkyl, more preferably, Re is ≥ C5 alkyl. On the other hand, the composition needs to have suitable high water solubility, especially when manufactured as a concentrate, where increased solubility of the pH adjuster is important. In this regard, it should be noted that having Re ≥ C 10 Alkyl compounds of formula I cause undesirable turbidity, making them unsuitable for commercial applications (see Examples section below). Preferably, Re is ≤ C9 alkyl, more preferably, Re is ≤ C8 alkyl.

[0094] Preferably, Re is selected from unsubstituted straight-chain or branched C4-C8 alkyl groups, and more preferably from unsubstituted straight-chain or branched C5-C8 alkyl groups.

[0095] More preferably, Re is selected from unsubstituted straight-chain C4-C9 alkyl, even more preferably from unsubstituted straight-chain C4-C8 alkyl, and most preferably from unsubstituted straight-chain C5-C8 alkyl.

[0096] Preferably, the pH adjuster is selected from those having

[0097] Compounds of formula Ia,

[0098]

[0099] Formula Ia

[0100] In formula Ia, Ra and Rc are bonded to form a 6- or 7-membered ring (A), more preferably a 7-membered ring (A), and Ra is selected from unsubstituted straight-chain or branched C1-C. 12 Alkyl groups, and Rc is selected from unsubstituted straight-chain C1-C9 alkyl groups.

[0101] More preferably, Rc is selected from unsubstituted straight-chain C1-C6 alkyl groups, even more preferably from unsubstituted straight-chain or branched C1-C5 alkyl groups, and even more preferably from unsubstituted straight-chain C1-C4 alkyl groups.

[0102] Preferably, the alkaline composition comprises at least one pH adjuster selected from compounds having formula I or formula Ia.

[0103]

[0104] Formula I or Formula Ia

[0105] in

[0106] Ra, Rb, Rd, and Rf are independently selected from unsubstituted straight or branched C1-C chains. 12 The alkyl group, more preferably at least one of Ra, Rb, Rd and Rf in formula I is methyl, and even more preferably at least two of Ra, Rb, Rd and Rf in formula I are methyl.

[0107] Re is selected from unsubstituted straight-chain or branched C4-C9 alkyl groups; such that the dashed bond between Re and N is a single bond.

[0108] Rc is selected from unsubstituted straight-chain C1-C9 alkyl groups, and

[0109] In formula Ia, Ra and Rc are bonded to form a 6- or 7-membered ring (A).

[0110] More preferably, Ra, Rb, Rd and Rf in formula I or Ia are independently selected from unsubstituted straight-chain or branched C1-C6 alkyl groups, and Rc is selected from unsubstituted straight-chain C1-C4 alkyl groups.

[0111] Preferably, Ra, Rb, Rc, Re, and Rf do not contain any additional substituents, particularly groups selected from -COOH and its derivatives, -SO3H and its derivatives, -OH, -OR, or halogens.

[0112] Preferably, the pH adjuster, i.e., the compound having formula I or Ia, has a solubility in water (at 25°C) of at least 70 g / L, more preferably at least 150 g / L, even more preferably at least 200 g / L, more preferably at least 400 g / L, and even more preferably the pH adjuster is completely miscible with water at 25°C (soluble at any concentration).

[0113] The pH adjuster can be gaseous, liquid, or solid, preferably solid or liquid, and most preferably liquid (at 20°C). Liquid amines are easier to process than gaseous amines and are not bound by theory. It should be noted that gaseous amines (such as N,N,N-trimethylamine) can cause an undesirable increase in etching rate, especially if the substrate is exposed to the vapor of the composition and the pH adjuster exhibits a high vapor pressure. Preferably, the pH adjuster has a boiling point of at least 5°C, more preferably at least 20°C, and even more preferably at least 35°C (at 1 atm or 10¹³ mbar).

[0114] For the purposes of this invention, pKa refers to the most acidic proton associated with the N-atom of a pH adjuster (i.e., a compound having formula I or Ia). As mentioned above, pH adjusters play a crucial role in ensuring an alkaline pH, but at the same time, the pKa of the pH adjuster preferably needs to meet environmental regulations and processing challenges. For example, substances labeled as highly corrosive pose additional processing and transportation challenges to their manufacture.

[0115] Preferably, the pH adjuster has a pKa ≤ 13.5, more preferably pKa ≤ 13.0, and even more preferably pKa ≤ 12.5. Preferably, the pH adjuster has a pKa ≥ 9.0, more preferably pKa ≥ 9.2, and even more preferably pKa of 9.5 to 13.5, and even more preferably pKa of 9.9 to 12.1.

[0116] More preferably, the pH adjuster is selected from N,N,N,N-tetramethyl-1,6-hexanediamine, N,N,N,N-tetramethyl-1,5-pentanediamine, N,N,N,N-tetramethyl-1,4-butanediamine, N,N,N,N-tetramethyl-1,7-heptanediamine, N,N,N,N-tetramethyl-1,8-octanediamine, 1,5-diazabicyclo[4.4.0]dec-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene, and 1,9-diazabicyclo[6.4.0]dodec-8-ene.

[0117] Preferably, the concentration of pH adjuster (a) is in the range of ≥ 0.02 wt.% to ≤ 40.0 wt.% based on the total weight of the composition.

[0118] Based on the total weight of the composition, the concentration of the pH adjuster (a) is preferably no more than 40.0 wt.%, more preferably no more than 39.0 wt.%, even more preferably no more than 38.0 wt.%, particularly no more than 36.5 wt.%, even more preferably no more than 35.0 wt.%, and most preferably no more than 32.0 wt.%. Concentrations exceeding 40.0 wt.% have been observed to cause colloidal instability and / or phase separation in the composition, especially in the presence of one or more water-miscible organic solvents. Based on the total weight of the composition, the concentration of the pH adjuster (a) is preferably at least 0.02 wt.%, more preferably at least 0.05 wt.%, even more preferably at least 0.06 wt.%, particularly at least 0.07 wt.%, even more preferably at least 0.08 wt.%, still more preferably at least 0.085 wt.%, more preferably at least 0.09 wt.%, and most preferably at least 0.1 wt.%. Based on the total weight of the composition, the concentration of pH adjuster (a) is more preferably in the range of ≥ 0.05 wt.% to ≤ 38.0 wt.%, and most preferably in the range of ≥ 0.1 wt.% to ≤ 32.0 wt.%.

[0119] (b) Complexing agents

[0120] According to the invention claimed herein, the alkaline composition for cleaning a substrate comprises at least one complexing agent selected from C2 to C3 groups having at least two sulfonic acid groups or carboxylic acid groups. 12 hydrocarbon.

[0121] Typically, complexing agents in liquid media can dissolve metal salts or prevent metal ions from forming insoluble precipitates and promote debris removal by forming readily soluble complexes with dissolved metal ions.

[0122] Preferably, the complexing agent is selected from C2 to C3 groups having at least two sulfonic acid groups or carboxylic acid groups. 10 Hydrocarbons, even more preferably selected from those having at least two sulfonic acid groups or carboxylic acid groups (C3 to C4). 10 Hydrocarbons. The complexing agent may further contain one or more nitrogen donors (such as amine or pyridine-type nitrogen), or a phenolic OH group for complexing metal ions. The complexing agent may contain additional functional groups, such as hydroxyl or chlorine.

[0123] More preferably, the complexing agent is selected from C2 to C3 groups having at least two carboxylic acid groups and optionally one or more chlorine and / or hydroxyl functional groups. 12 hydrocarbon.

[0124] Even more preferably, the complexing agent is selected from alendronic acid, phthalic acid, citric acid, tartaric acid, hydroxymalonic acid, adipic acid, oxalic acid, malonic acid, aspartic acid, succinic acid, glutaric acid, glutamic acid, pimelic acid, sebacic acid, octanoic acid, azelaic acid, sebacic acid, oxalic acid, malic acid, maleic acid, gluconic acid, pimelic acid, mucoconic acid, ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, N,N-bis(carboxymethyl)alanine, hypozoxytriacetic acid, diethylenetriaminepentaacetic acid, bis(salicylyl)ethylenediamine, aminotris(methylenephosphonic acid), diethylenetriaminepenta(methylphosphonic acid), ethylenediaminetetra(methylenephosphonic acid), or mixtures thereof.

[0125] More preferably, the complexing agent is selected from phthalic acid, citric acid, tartaric acid, hydroxymalonic acid, adipic acid, oxalic acid, malonic acid, aspartic acid, succinic acid, glutaric acid, oxalic acid, maleic acid, gluconic acid, ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, N,N-bis(carboxymethyl)alanine, hypozoxytriacetic acid, diethylenetriaminepentaacetic acid, bis(salicylyl)ethylenediamine, aminotris(methylenephosphonic acid), diethylenetriaminepenta(methylphosphonic acid), ethylenediaminetetra(methylenephosphonic acid), or mixtures thereof.

[0126] Even more preferably, the complexing agent is selected from citric acid, tartaric acid, hydroxymalonic acid, malonic acid, succinic acid, glutaric acid, malic acid, or mixtures thereof.

[0127] Most preferably, the complexing agent is citric acid.

[0128] Preferably, the complexing agent (b) is present in an amount ranging from ≥ 0.005 wt.% to ≤ 3.0 wt.% based on the total weight of the composition.

[0129] More preferably, based on the total weight of the composition, the complexing agent (b) is present in an amount not greater than 3.0 wt.%, more preferably not greater than 2.0 wt.%, and most preferably not greater than 1.0 wt.%. Based on the total weight of the composition, the amount of (b) is preferably at least 0.005 wt.%, more preferably at least 0.008 wt.%, and most preferably at least 0.01 wt.%. Based on the total weight of the composition, the concentration of the complexing agent (b) is more preferably in the range of ≥ 0.05 wt.% to ≤ 4.0 wt.%, and most preferably in the range of ≥ 0.008 wt.% to ≤ 1.0 wt.%.

[0130] (c) Polymer dispersants

[0131] According to the invention claimed herein, the composition comprises at least one polymeric dispersant (c) having a weight-average molecular weight ≥ 1000 g / mol.

[0132] Unbound by theory, polymer dispersants help disperse silica particles left as residue after CMP cleaning. A portion of the dispersant, for example, adsorbs onto the surface of the particles to be dispersed. Another portion of the dispersant, for example, reaches the solution from the particles. Literature on adsorbed polymer structures is well-known in the art and can be found, for example, in Lipatov and Sergeeva, Adsorption of Polymers, 1974. A portion of the dispersant in the solvent supports the rinsing of the particles from the surface of the substrate to be cleaned. Improved interaction with the solvent also increases the barrier between the two particles or between the particles and the substrate surface, ensuring that agglomeration or redeposition does not occur.

[0133] The chemical properties of the solvated portion and the portion adsorbed onto the particle surface can be the same or different. Simulated dispersion mechanisms and dispersants are well known in the art and described, for example, in TFTadros, Applied Surfactants - Principles and Applications, 1st Edition, 2005, Chapter 7.

[0134] As can be observed from Table 1 below, polymer dispersant (C) containing at least one polymer dispersant (c) with a weight average molecular weight ≥ 1000 g / mol prevents unwanted precipitation or agglomeration while ensuring low cobalt and copper SER.

[0135] Preferably, the polymer dispersant (c) with a weight-average molecular weight ≥ 1000 g / mol is selected from anionic, amphoteric, nonionic, or cationic polymers. Among these, anionic and nonionic polymers are preferred. These polymers can be homopolymers or copolymers derived from anionic or nonionic monomers.

[0136] The monomers may be ethylene oxide, propylene oxide, styrene, vinylpyrrolidone, acrylamide, amino acids, carbohydrates, vinyl alcohol, maleic acid, vinyl sulfonic acid, vinyl phosphonic acid, formaldehyde, phenol sulfonic acid, naphthalene sulfonic acid, phenol, or mixtures thereof.

[0137] More preferably, the dispersant is an anionic homopolymer or copolymer containing monomer units selected from sulfuric acid or phosphonic acid groups, or a nonionic polymer containing monomer units selected from ethylene oxide or vinylpyrrolidone.

[0138] Preferably, the polymeric dispersant (c) with a weight-average molecular weight ≥ 1000 g / mol is not selected from polymers or copolymers of acrylic acid. Unbound by theory, the presence of polymers or copolymers of acrylic acid leads to an undesirable increase in the cobalt etching rate (SER).

[0139] Preferred polymers are polyvinylpyrrolidone, polyethylene oxide, ethylene oxide-propylene oxide copolymers, naphthalenesulfonic acid-formaldehyde condensates, phenolsulfonic acid-formaldehyde condensates, or mixed naphthalenesulfonic acid-phenolsulfonic acid-formaldehyde condensates. Polymers obtained by the condensation of aromatic compounds and aldehyde compounds may also contain phenolic, cresol, or xylenol units.

[0140] According to the present invention, the weight-average molecular weight (M) of the polymer dispersant w ≥ 1000 g / mol. Preferably, the weight-average molecular weight (M) of the polymer dispersant is ≥ 1000 g / mol. w ≥ 1100 g / mol, more preferably ≥ 1500 g / mol, and most preferably ≥ 1800 g / mol. Note that M w Polymers with a concentration < 1000 g / mol are inactive or have low surface activity in terms of dispersibility. Preferably, the weight-average molecular weight (M) of the polymer dispersant is... w ≤ 100,000 g / mol, more preferably ≤ 80,000 g / mol, even more preferably ≤ 50,000 g / mol, and most preferably ≤ 20,000 g / mol. M w Polymers with a mass concentration > 100,000 g / mol exhibit undesirable high viscosity and low water solubility, making processing difficult. Weight-average molecular weight was determined by gel permeation chromatography.

[0141] Preferably, the polymer dispersant (c) is not selected from cationic polymers or copolymers. Without being bound by theory, the use of cationic copolymers in the composition is expected to result in insufficient cleaning, particularly in silica removal. Additionally, cationic polymers can negatively interact with carboxylic hydrocarbons (if present in the composition) and form unwanted emulsions. Preferably, the amount of cationic polymer or copolymer (such as, for example, polyethyleneimine (PEI) or cationic polyacrylamide) in the composition is < 0.01 wt% based on the total weight of the composition.

[0142] Preferably, the polymeric dispersant (c) is present in an amount ranging from ≥ 0.001 wt.% to ≤ 3.0 wt.% based on the total weight of the composition.

[0143] More preferably, based on the total weight of the composition, the polymeric dispersant (c) is present in an amount not greater than 2.5 wt.%, even more preferably not greater than 2.0 wt.%, most preferably not greater than 1.5 wt.%, and most preferably not greater than 1.0 wt.%. Based on the total weight of the composition, the amount of (C) is preferably at least 0.005 wt.%, more preferably at least 0.008 wt.%, and most preferably at least 0.01 wt.%. Based on the total weight of the composition, the concentration of the polymeric dispersant (c) is more preferably in the range of ≥ 0.005 wt.% to ≤ 2.5 wt.%, even more preferably in the range of ≥ 0.008 wt.% to ≤ 1.5 wt.%, and most preferably in the range of ≥ 0.01 wt.% to ≤ 1.0 wt.%.

[0144] (d) Solvents containing water

[0145] According to the invention claimed herein, the composition comprises a solvent containing water (d).

[0146] For the compositions of the invention claimed herein, water is a particularly preferred medium. Preferably, the solvent (d) consists essentially of water.

[0147] The presence of a water-miscible organic solvent in combination with water does not adversely affect performance. Preferably, solvent (d) can be a combination of water and one or more water-miscible organic solvents. In the context of this invention, the term "water-miscible organic solvent" preferably means an organic solvent that is miscible with water at a ratio of at least 1:1 (w / w) at 20°C and ambient pressure. Preferably, the water-miscible organic solvent is selected from C1 to C4 alcohols such as isopropanol, dimethyl sulfoxide (DMSO), γ-butyrolactone, sulfolane, alkylene glycols, and alkylene glycol derivatives such as ethylene glycol or propylene glycol. In particular, the preferred compositions of this invention do not contain one or more water-miscible organic solvents.

[0148] For the purposes of the invention claimed herein, if the total amount of the components other than (d) is y wt.% based on the total weight of the composition, then the amount of (d) is (100-y) wt.% of the composition.

[0149] Based on the total weight of the composition, the amount of solvent (d) in the composition is preferably not greater than 99.99 wt.%, more preferably not greater than 99.9 wt.%, most preferably not greater than 99.8 wt.%, particularly preferably not greater than 99.5 wt.%, especially not greater than 97.0 wt.%, for example not greater than 95.0 wt.%. Based on the total weight of the composition, the amount of solvent (d) in the composition is preferably at least 30.0 wt.%, more preferably at least 50.0 wt.%, most preferably at least 55.5 wt.%, particularly preferably at least 62.5 wt.%, particularly at least 75.0 wt.%, for example at least 80.0 wt.%.

[0150] The composition further comprises optional additives selected from reducing agents, oxygen scavengers, wetting agents, biocides, or mixtures thereof. Preferably, the composition is substantially free of one or more optional additives. More preferably, the composition may be substantially free of wetting agents and / or reducing agents.

[0151] reducing agent

[0152] Residues of oxidants such as peroxides, persulfates, or periodates from previous process steps (e.g., CMP or etching steps) may be present, and these can cause corrosion of small metallic features on the wafer during subsequent cleaning steps. To prevent this, a reducing agent can optionally be added to the composition to neutralize the remaining oxidants. Preferably, the reducing agent is selected from organic compounds containing at least one primary or secondary hydroxyl group. A preferred type of reducing agent is a saturated organic compound containing at least four hydroxyl groups.

[0153] A more preferred type of reducing agent is a saturated organic compound containing at least four hydroxyl groups, one of which is a primary hydroxyl group. Preferred reducing agents include pentaerythritol, tetrahydroxybutane, pentahydroxypentane, hexahydroxyhexane, 1,4-dehydrated sorbitol, etc. This compound can, for example, form an acetal with carbohydrates (like isomaltitol), or it can be a free molecule (like mannitol). A more preferred type of reducing agent is a sugar alcohol containing at least four hydroxyl groups. Examples of such sugar alcohols are sorbitol, arabinitol, isomaltitol, mannitol, threitol, erythritol, xylitol, or lactitol. This compound can, for example, form an acetal with carbohydrates (like isomaltitol), or it can be a free molecule (like mannitol). Particularly preferred reducing agents are sorbitol or xylitol.

[0154] Preferably, the reducing agent is present in an amount ranging from ≥ 0.01 wt.% to ≤ 7.0 wt.% based on the total weight of the composition.

[0155] More preferably, based on the total weight of the composition, the reducing agent is present in an amount of not more than 7.0 wt.%, more preferably not more than 5.0 wt.%, and most preferably not more than 3.0 wt.%. Based on the total weight of the composition, the amount of reducing agent is preferably at least 0.01 wt.%, more preferably at least 0.03 wt.%, and most preferably at least 0.05 wt.%. Based on the total weight of the composition, the concentration of the reducing agent is more preferably in the range of ≥ 0.05 wt.% to ≤ 5.0 wt.%, and most preferably in the range of ≥ 0.06 wt.% to ≤ 3.0 wt.%.

[0156] Oxygen scavenger

[0157] Ambient oxygen dissolved in the solvent may have already damaged small metal patterns on the substrate. To prevent this, an oxygen scavenger can be added.

[0158] Oxygen scavengers are typically unsaturated organic compounds containing at least one C-C double bond. This double bond can be a single bond or part of a conjugated or aromatic system. Preferred types of oxygen scavengers are furanones and their derivatives, such as 2-furanone, 3-methyl-2-furanone, 4-hydroxy-2,5-dimethyl-3-furanone, 5-hydroxymethyl-2-furanone, 5-ethyl-3-hydroxy-4-methyl-2-furanone, ascorbic acid, or isoascorbic acid. More preferred are furanone derivatives containing at least two OH- groups on the furanone ring, such as ascorbic acid or isoascorbic acid. Ascorbic acid is particularly preferred.

[0159] Another preferred type of oxygen scavenger is phenolic derivatives. Examples include tyrosine, dihydroxybenzene, its isomers hydroquinone, catechol and resorcinol and derivatives such as 4-methoxyphenol (MeHQ), trihydroxybenzene, its isomers such as pyrogallol and phlorogallol and derivatives such as gallic acid or tannic acid type compounds, tetrahydroxybenzene, its isomers and derivatives.

[0160] Most preferably, the oxygen scavenger is selected from ascorbic acid, 4-methoxyphenol, or gallic acid.

[0161] Preferably, the composition is substantially free of oxygen scavengers. When present in the composition, the amount of oxygen scavenger in the composition, based on the total weight of the composition, is preferably no more than 10.0 wt.%, more preferably no more than 8.0 wt.%, and most preferably no more than 5.0 wt.%. Based on the total weight of the composition, the amount of oxygen scavenger in the composition is preferably at least 0.01 wt.%, more preferably at least 0.03 wt.%, most preferably at least 0.05 wt.%, particularly preferably at least 0.08 wt.%, and especially at least 0.1 wt.%.

[0162] wetting agent

[0163] The compositions of the present invention may optionally contain a wetting agent. Suitable wetting agents are well known in the art and are typically any molecule consisting of at least one hydrophobic portion and at least one hydrophilic portion, such as a surfactant.

[0164] Preferably, the wetting agent can be selected from anionic, nonionic, or cationic surfactants, more preferably from nonionic surfactants. Even more preferably, the wetting agent is selected from...

[0165] -Alkoxylated fatty alcohols-Preferably, the alkoxylated fatty alcohols are ethylene oxide, propylene oxide, or higher epoxides and C8-C62 ... 10 Adducts of fatty alcohols – particularly preferred wetting agents are the Plurafac LF series from BASF.

[0166] -Alkyl polyglucoside-preferably derived from C8-C 20 Alkyl polyglucosides – particularly preferred are the Glucopon series wetting agents from BASF.

[0167] -C 12 To C 24 Alkyl carboxylic acid or sarcosine - preferably C 12 To C 20 Alkylsarcosines – particularly preferred are N-oleoylsarcosine, N-cocoylsarcosine, N-lauroylsarcosine, or 4-butyl-benzoyl-sarcosine.

[0168] Preferably, the cloud point of the wetting agent, measured in water according to DIN 53917, is ≥ 30°C, more preferably ≥ 35°C. Even more preferably, the cloud point, measured in water according to DIN 53917, is ≥ 30°C to ≤ 50°C, and most preferably ≥ 35°C to ≤ 45°C.

[0169] Preferably, the composition is substantially free of wetting agents. When present in the composition, the amount of wetting agent in the composition, based on the total weight of the composition, is preferably no more than 10.0 wt.%, more preferably no more than 8.0 wt.%, and most preferably no more than 5.0 wt.%. Based on the total weight of the composition, the amount of wetting agent in the composition is preferably at least 0.005 wt.%, more preferably at least 0.008 wt.%, most preferably at least 0.01 wt.%, particularly preferably at least 0.015 wt.%, and especially at least 0.018 wt.%.

[0170] Composition

[0171] The properties of the composition may depend on the pH of the corresponding composition. According to the invention claimed herein, the pH of the alkaline composition is in the range of ≥ 7.5 to ≤ 14.0. Preferably, the pH of the composition is ≥ 8.5, more preferably ≥ 9.0, most preferably ≥ 9.5, particularly preferably ≥ 10.0, and particularly preferably ≥ 10.5. The pH of the composition is preferably ≤ 14.0, more preferably ≤ 13.5, most preferably ≤ 13.0, particularly preferably ≤ 12.5, and particularly preferably ≤ 11.5. The pH of the composition is preferably in the range of ≥ 8.5 to ≤ 13.0, preferably ≥ 8.7 to ≤ 12.5, and more preferably ≥ 9.0 to ≤ 11.5. For comparative purposes, the pH values ​​mentioned herein and in the Examples section refer to diluted compositions. When comparing the pH of concentrated forms, those skilled in the art will expect small variations in the values ​​mentioned herein. In this regard, pH variations can be expected in the range of ±1.5, more preferably ±1.3.

[0172] Preferably, the composition is substantially free of any particles, particularly silica particles. "Substantially free" means that the composition does not contain any amount of particles that affect its cleaning function. Preferably, the particle content is less than 10 ppm, more preferably less than 1 ppm, and most preferably below the detection limit. In a preferred embodiment, the composition is filtered before use.

[0173] Preferably, the composition is substantially free of any oxidizing agents, particularly any peroxides. "Substantially free" here means that the composition does not contain any amount of added oxidizing agents that increase the corrosion of copper or cobalt, but specifically excludes ambient oxygen (O2) dissolved in the composition. Preferably, the oxidizing agent content (other than O2) in the cleaning composition is less than 10 ppm, more preferably less than 1 ppm. Most preferably, the content of any oxidizing agent (other than O2) is below the detection limit.

[0174] Preferably, the composition is substantially free of any metal ions, such as sodium or calcium. While no such metal ions are actively added to the composition, the presence of trace amounts of such metals (preferably below 10 ppm, more preferably below 1 ppm) will not adversely affect the performance or cleaning function of the composition. Although the absence of sodium or similar metal ions is preferred, their presence (e.g., as part of a salt in one or more components) will not introduce any adverse effects on the performance of the composition.

[0175] Preferably, the composition is substantially free of any film-forming agents, particularly triazoles, benzotriazoles, substituted triazoles, or their derivatives. Although no reagents are actively added to the composition, the presence of trace amounts of such reagents (preferably less than 10 ppm, more preferably less than 1 ppm) will not adversely affect the performance or cleaning function of the composition.

[0176] Preferred embodiments of the invention claimed herein relate to an alkaline composition comprising

[0177] a) pH adjuster ≥ 0.02 to ≤ 40.0 wt.%;

[0178] b) A complexing agent ≥ 0.005 to ≤ 3.0 wt.%, wherein the complexing agent is selected from C2 to C3 groups having at least two sulfonic acid groups or carboxylic acid groups. 12 hydrocarbon,

[0179] c) ≥ 0.001 to ≤ 3.0 wt.% of a polymer dispersant having a weight-average molecular weight ≥ 1000 g / mol; and

[0180] d) The remaining solvent containing water,

[0181] The above is as defined herein and will be defined based on examples; all are based on the total weight of the composition, wherein the pH of the composition is from about 7.5 to about 13.0, preferably from about 9 to about 11.0, and wherein in each case, the amount % of the components adds up to 100% by weight. The concentrations of components (a) to (d) may vary within the above preferred ranges.

[0182] Another preferred embodiment of the invention claimed herein relates to an alkaline composition for cleaning a substrate comprising i) copper or a copper alloy and ii) cobalt or a cobalt alloy, the composition comprising:

[0183] a) pH adjuster ≥ 0.02 to ≤ 40.0 wt.%;

[0184] b) A complexing agent ≥ 0.005 to ≤ 3.0 wt.%, wherein the complexing agent is selected from C2 to C3 groups having at least two sulfonic acid groups or carboxylic acid groups. 12 hydrocarbon,

[0185] c) ≥ 0.001 to ≤ 3.0 wt.% of a polymer dispersant having a weight-average molecular weight ≥ 1000 g / mol; and

[0186] d) The remaining solvent containing water,

[0187] The above is as defined herein and will be defined based on examples; all are based on the total weight of the composition, wherein the pH of the composition is from about 7.5 to about 13.0, preferably from about 9 to about 11.0, and wherein in each case, the amount % of the components adds up to 100% by weight. The concentrations of components (a) to (d) may vary within the above preferred ranges.

[0188] Another preferred embodiment of the invention claimed herein relates to an alkaline composition for cleaning a substrate comprising i) copper or a copper alloy and ii) cobalt or a cobalt alloy, the composition comprising:

[0189] a) pH adjuster ≥ 0.02 to ≤ 40.0 wt.%;

[0190] b) At least one complexing agent, ≥ 0.005 to ≤ 3.0 wt.%, selected from citric acid, tartaric acid, hydroxymalonic acid, malonic acid, succinic acid, glutaric acid, malic acid, or mixtures thereof.

[0191] c) At least one polymeric dispersant, ≥ 0.001 to ≤ 3.0 wt.%, having a weight-average molecular weight ≥ 1000 g / mol, wherein the polymeric dispersant is selected from polyvinylpyrrolidone, polyethylene oxide, ethylene oxide-propylene oxide copolymer, naphthalenesulfonic acid formaldehyde condensate, phenolsulfonic acid formaldehyde condensate, or a mixed naphthalenesulfonic acid-phenolsulfonic acid formaldehyde condensate; and

[0192] d) The remaining solvent containing water,

[0193] The above is as defined herein and will be defined based on examples; all are based on the total weight of the composition, wherein the pH of the composition is from about 7.5 to about 13.0, preferably from about 9 to about 11.0, and wherein in each case, the amount % of the components adds up to 100% by weight. The concentrations of components (a) to (d) may vary within the above preferred ranges.

[0194] The compositions of the present invention can be prepared by conventional and standard mixing methods, and mixing instruments (such as stirring vessels, in-line dissolvers, high-shear impellers, ultrasonic mixers, homogenizer nozzles, or countercurrent mixers) can be used to mix the components of the composition in the desired amounts.

[0195] It should be understood that the common practice is to prepare a concentrated form of the composition to be diluted before use. For example, the composition may be manufactured in a more concentrated form and subsequently diluted at the manufacturer's premises, before and / or during use, with water and optionally a water-miscible solvent (collectively referred to as a diluent), or other components. The dilution ratio may range from about 1.0 parts diluent to 0.01 parts composition concentrate to about 200 parts diluent to 1 part composition concentrate, preferably in the range of 150:1 to 10:1, more preferably 120:1 to 20:1.

[0196] This composition can be specifically prepared by diluting a concentrate with water, a water-miscible organic solvent, or a combination thereof, the concentrate comprising:

[0197] a) at least one pH adjuster, ≥ 4.0 to ≤ 40.0 wt.%, preferably ≥ 5.0 to ≤ 38.0 wt.%, more preferably ≥ 7.0 to ≤ 32.0 wt.%;

[0198] b) At least one complexing agent, ≥ 0.1 to ≤ 3.0 wt.%, preferably ≥ 0.8 to ≤ 3.0 wt.%, more preferably ≥ 0.85 to ≤ 2.0 wt.%.

[0199] c) at least one polymer dispersant in an amount of ≥ 0.005 to ≤ 3.0 wt.%, preferably ≥ 0.008 to ≤ 3.0 wt.%, more preferably ≥ 0.01 to ≤ 2.5 wt.%; and

[0200] d) The remaining solvent containing water.

[0201] The preferred dilution factor (by weight) is about 30 and greater. More preferably, it is 50 and greater. Even more preferably, it is 75 and greater. Even more preferably, it is 100 and greater.

[0202] application

[0203] The compositions of the present invention are well suited to the methods of the present invention.

[0204] However, the primary objective of the method of the present invention is to process substrates that can be used to manufacture electrical devices, particularly semiconductor integrated circuits (ICs), liquid crystal panels; organic electroluminescent panels; printed circuit boards; micromachines; DNA chips; microdevices and magnetic heads; more preferably ICs having LSI (large-scale integrated circuits) or VLSI (very large-scale integrated circuits); and optical devices, particularly optical glasses such as photomasks, lenses, and prisms; inorganic conductive films such as indium tin oxide (ITO); optical integrated circuits; optical switching elements; optical waveguides; optical single crystals such as the end faces of optical fibers and scintillators; solid-state laser single crystals; sapphire substrates for blue laser LEDs; semiconductor single crystals; and glass substrates for magnetic disks.

[0205] Preferably, the method of the present invention includes surface preparation, pre-electroplated cleaning, post-etching cleaning or post-CMP cleaning steps, especially the post-etching or post-CMP cleaning step.

[0206] The cleaning composition is particularly useful for removing from substrates

[0207] (a) Post-etching residue (PERR) or post-ashing residue (PARR), or

[0208] (b) Chemical-mechanical planarization (CMP) residues,

[0209] The substrate includes (i) a cobalt or cobalt alloy surface and (ii) a copper or copper alloy surface.

[0210] The method of the present invention is particularly well suited for processing substrates that can be used to manufacture ICs with LSI or VLSI, especially for back-to-the-line (BEOL) processing.

[0211] The method of the present invention is most particularly well suited for cleaning semiconductor wafers after CMP, especially by copper damascene or dual damascene processes, in the manufacture of ICs having LSI or VLSI.

[0212] Therefore, one embodiment relates to a kit containing one or more components suitable for forming the compositions described herein in one or more containers. Preferably, one container contains at least one pH adjuster and at least one complexing agent; and a second container contains the remaining components, such as at least one complexing agent, at least one polymer dispersant, a solvent comprising water, and optionally other components described herein, for combination at a manufacturing facility or point of use.

[0213] In the use of the compositions described herein, the compositions are typically contacted with the device structure for a sufficient period of about 25 seconds to about 200 minutes, preferably about 5 minutes to about 60 minutes, at a temperature typically in the range of about 10°C to about 80°C, preferably about 20°C to about 60°C. Such contact times and temperatures are illustrative, and any other suitable time and temperature conditions can be used to effectively achieve the desired removal selectivity.

[0214] After achieving the desired cleaning effect, the composition can be readily removed from the microelectronic device previously applied thereto, for example by rinsing, washing, or one or more other removal steps as desired and effective in the application of the composition to a given end use of the invention. For example, the device can be rinsed with a rinsing solution comprising deionized water, an organic solvent, and / or dried (e.g., rotary drying, N2, steam drying, etc.).

[0215] The cleaning compositions described herein can be advantageously used for post-etching or post-ashing residue removal (PERR, PARR), post-CMP cleaning, surface preparation, and pre-plating cleaning of substrates, particularly those comprising both cobalt or cobalt alloy surfaces and copper or copper alloy surfaces.

[0216] The cleaning composition described herein can be advantageously used in a method for manufacturing a semiconductor device, the method comprising the following steps:

[0217] (a) Providing a microelectronic substrate comprising (i) a cobalt or cobalt alloy surface and (ii) a copper or copper alloy surface having etch residues, ashing residues, or chemical mechanical planarization (CMP) residues.

[0218] (b) Provide the compositions as described herein;

[0219] (c) Contact (i) the cobalt or cobalt alloy surface and (ii) the copper or copper alloy surface with the composition at a certain temperature for a certain time to effectively remove, at least partially, etch residues, ashing residues or chemical mechanical planarization (CMP) residues from the substrate.

[0220] Preferably, the etching residue, ashing residue, or chemical mechanical planarization (CMP) residue is completely removed from the substrate.

[0221] Preferably, the static etching rate (SER) of copper is < 4.0 Å / min, more preferably < 3.5 Å / min, even more preferably < 3.3 Å / min, and most preferably < 3.0 Å / min.

[0222] Preferably, the static etching rate (SER) of cobalt is < 5.0 Å / min, more preferably < 4.0 Å / min, even more preferably < 3.0 Å / min, and most preferably < 2.5 Å / min.

[0223] The static etching rate was measured using a standard method as described in the Examples section of this paper.

[0224] The composition according to the invention claimed herein has at least one of the following advantages:

[0225] (1) Appropriately improved performance in suppressing the etching of both copper and cobalt (as demonstrated by low SER values).

[0226] (2) The compositions of the invention claimed herein provide stable formulations or dispersions in which no phase separation, agglomeration or precipitation occurs, especially under alkaline conditions.

[0227] (3) The composition of the invention claimed herein allows for easy processability, such as compatibility with industrially relevant steps such as microfiltration.

[0228] (4) The method of the invention claimed herein is easy to apply and requires as few steps as possible.

[0229] (5) The compositions and methods of the invention claimed herein are formulated with moderately or lowly corrosive components, thereby improving economic feasibility, processability, packaging and transport, etc.

[0230] (6) The composition of the invention claimed herein is designed to provide an appropriately low etching rate while preventing undesirable surface defects and ensuring high surface quality. Example

[0231] The following list of embodiments is provided to further illustrate this disclosure, but is not intended to limit this disclosure to the specific embodiments listed below.

[0232] 1. An alkaline composition for cleaning a substrate, the substrate comprising i) copper or a copper alloy and ii) cobalt or a cobalt alloy, the composition comprising:

[0233] a) At least one pH adjuster selected from compounds having formula I.

[0234]

[0235] Formula I

[0236] in

[0237] Ra, Rb, Rd, and Rf are independently selected from unsubstituted straight or branched C1-C chains. 12alkyl,

[0238] Re is selected from unsubstituted straight-chain or branched C4-C9 alkyl groups; such that the dashed bond between Re and N is a single or double bond, and Rd does not exist when the dashed bond is a double bond.

[0239] Ra, Rb, Re, and Rf can bond together to form one or more 6- or 7-membered rings;

[0240] b) At least one complexing agent selected from C2 to C3 groups having at least two sulfonic acid groups or carboxylic acid groups. 12 hydrocarbon,

[0241] c) at least one polymer dispersant having a weight-average molecular weight ≥ 1000 g / mol; and

[0242] d) Solvents containing water.

[0243] 2. The composition according to Example 1, wherein Ra, Rb, Re and Rf can be bonded to form a compound having formula Ia,

[0244]

[0245] Formula Ia,

[0246] Ra and Rc are bonded to form a 6-membered or 7-membered ring (A), more preferably a 7-membered ring (A) having formula Ia.

[0247] 3. The composition according to any one of Examples 1 to 2, wherein Ra, Rb, Rd and Rf are independently selected from unsubstituted straight-chain or branched C1-C6 alkyl groups, and Rc is selected from unsubstituted straight-chain C1-C4 alkyl groups.

[0248] 4. The composition according to any one of Examples 1 to 3, wherein the pKa of the pH adjuster is ≥ 9.0, preferably 9.0 to 12.0.

[0249] 5. The composition according to any one of Examples 1 to 4, wherein the dispersant is selected from polyvinylpyrrolidone, polyethylene oxide, ethylene oxide-propylene oxide copolymer, naphthalene sulfonic acid formaldehyde condensate, phenol sulfonic acid formaldehyde condensate, or a mixed naphthalene sulfonic acid-phenol sulfonic acid formaldehyde condensate.

[0250] 6. The composition according to any one of Examples 1 to 5, wherein the complexing agent is selected from citric acid, tartaric acid, hydroxymalonic acid, malonic acid, succinic acid, glutaric acid, malic acid, or mixtures thereof.

[0251] 7. The composition according to any one of Examples 1 to 6 further comprises a reducing agent selected from sugar alcohols, particularly sorbitol, preferably in an amount of 0.01 to 7.0 wt.%, more preferably 0.07 to 5.0 wt.%.

[0252] 8. The composition according to any one of Examples 1 to 7 is substantially free of triazoles, quaternary ammonium salts, alkanolamines, or derivatives thereof.

[0253] 9. The composition according to any one of Examples 1 to 8 further comprises an oxygen scavenger selected from ascorbic acid, 4-methoxyphenol or gallic acid.

[0254] 10. The composition according to any one of Examples 1 to 9, wherein the solvent is substantially composed of water.

[0255] 11. The composition according to any one of Examples 1 to 10, further comprising a water-miscible organic solvent, preferably in an amount of 0.1 to 20 wt.%.

[0256] 12. The composition according to any one of the foregoing embodiments has a pH of 7.5 to 14.0, preferably 9.0 to 12.5.

[0257] 13. The composition according to any one of the foregoing embodiments, comprising:

[0258] a) pH adjuster ≥ 0.02 to ≤ 40.0 wt.%;

[0259] b) Complexing agent ≥ 0.005 to ≤ 3.0 wt.%,

[0260] c) ≥ 0.001 to ≤ 3.0 wt.% of polymer dispersant; and

[0261] d) The remaining solvent containing water.

[0262] 14. A concentrate for preparing the composition according to any one of the foregoing embodiments, the concentrate comprising:

[0263] a) A pH adjuster of ≥ 4.0 to ≤ 40.0 wt.%, preferably ≥ 7.0 to ≤ 38.0 wt.%;

[0264] b) A complexing agent of ≥ 0.1 to ≤ 3.0 wt.%, preferably ≥ 0.3 to ≤ 3.0 wt.%,

[0265] c) ≥ 0.01 to ≤ 3.0 wt.%, preferably ≥ 0.1 to ≤ 3.0 wt.% of a polymer dispersant; and

[0266] d) The remaining solvent containing water.

[0267] 15. Use of the composition according to any one of claims 1 to 13 for removing the following from a substrate:

[0268] (a) Post-etching residue (PERR) or post-ashing residue (PARR), or

[0269] (b) Chemical-mechanical planarization (CMP) residues,

[0270] The substrate includes (i) a cobalt or cobalt alloy surface and (ii) a copper or copper alloy surface.

[0271] 16. A method for fabricating a microelectronic device, the method comprising:

[0272] (a) Providing a microelectronic substrate comprising (i) a cobalt or cobalt alloy surface and (ii) a copper or copper alloy surface having etch residues, ashing residues, or chemical mechanical planarization (CMP) residues.

[0273] (b) providing the composition according to any one of Examples 1 to 13; and

[0274] (c) Contact (i) the cobalt or cobalt alloy surface and (ii) the copper or copper alloy surface with the composition at a certain temperature for a certain time to effectively remove, at least partially and preferably completely, etch residues, ashing residues or chemical mechanical planarization (CMP) residues from the substrate.

[0275] 17. A method for manufacturing a semiconductor device, the method comprising the processing described in Example 16.

[0276] Although the invention claimed herein has been described with respect to specific embodiments thereof, certain modifications and equivalents will be apparent to those skilled in the art and are intended to be included within the scope of the invention claimed herein. Example

[0277] The following materials are used to electronic grade purity. All amounts given for compounds in the composition are absolute amounts of the entire mixture, excluding any water.

[0278] pH adjuster:

[0279] A-1N,N,N',N'-Tetramethyl-1,6-hexanediamine

[0280] A-21,8-diazabicyclo[5.4.0]undec-7-ene

[0281] A-3 Tri-N-ethylamine (comparative)

[0282] A-4 Tri-N-propylamine (Comparative)

[0283] A-5N,N,N',N'-Tetramethyl-1,10-decanediamine (comparative)

[0284] A-6N-methylethanolamine (comparative)

[0285] A-7N,N,N',N'-Tetramethyl-1,3-propanediamine (comparative)

[0286] A-82-(dimethylamino)-2-methylprop-1-ol (comparative)

[0287] A-92-Amino-2-methylprop-1-ol (comparative)

[0288] A-10 Choline Hydroxide (Comparison)

[0289] A-111,4-diazabicyclo[2.2.2]octane (comparative)

[0290] A-121,3,5-Triazine (Comparative)

[0291] A-13N-ethylpyrrolidine (comparative)

[0292] A-141,5-diazabicyclo[4.3.0]non-5-ene (comparative)

[0293] A-151,1,3,3-Tetramethylguanidine (comparative)

[0294] Complexing agents:

[0295] B-1 citric acid

[0296] β-2-malonic acid

[0297] β-3-hydroxymalonic acid

[0298] B-4 adipic acid

[0299] B-5 malic acid

[0300] β-6-glutaric acid

[0301] B-7 Tartaric Acid

[0302] B-8 succinic acid

[0303] B-9 glycine (comparison)

[0304] B-10 etidronic acid (comparison)

[0305] B-11 histidine (comparison)

[0306] Dispersant:

[0307] C-1 vinylpyrrolidone homopolymer (Luviskol K17 from BASF; Mw-10000 g / mol)

[0308] The condensate of C-2 phenolsulfonic acid with formaldehyde, phenol, and urea, sodium salt (Tamol DN).

[0309] C-3 polyethylene glycol (Pluriol E1500 E, M) w 1500 g / mol)

[0310] C-4 acrylic resin (Joncryl 682; M w - 1700 g / mol; (comparison)

[0311] Solvent:

[0312] D-1 Water

[0313] D-2 Ethylene Glycol

[0314] D-31,2-Propanediol

[0315] D-4 dimethyl sulfoxide (DMSO)

[0316] additive

[0317] reducing agent:

[0318] E-1D-sorbitol

[0319] E-2 Xylitol

[0320] Wetting agent:

[0321] F-1 is an alkoxylated main unbranched fatty alcohol and contains higher alkyl oxidants as well as ethylene oxide (Plurafac LF401; viscosity at 25°C measured by Brookfield at 60 rpm is approximately 135 mPa·s).

[0322] F-2C8-C 10 Alkyl polyglucoside of fatty alcohol (Glucopon 225DK; viscosity at 23°C approximately 4000 mPa·s using Brookfield LVT according to EN 12092)

[0323] F-3N-Oleylsarcosine (from BASF's Sarkosyl O)

[0324] Composition

[0325] The components in the composition are thoroughly mixed, and all mixing procedures are carried out under stirring. The concentrate typically contains the following components: approximately 10 wt% pH adjuster, 0.5 wt% complexing agent, and 0.6 wt% polymer dispersant, and optionally 3.5 wt.% reducing agent, 3.0 wt.% wetting agent, and 15.0 wt.% water-miscible solvent. The composition is brought to 100 wt.% using ultrapure water (UPW). For etching experiments, the diluted composition is typically used by diluting the concentrate composition approximately 50 times. Further details of the test compositions are provided in Tables 1 and 2 below.

[0326] Static Etching Rate (SER) Experiment

[0327] Two cobalt and two copper blank wafer samples (each 2 × 2 cm) were pre-etched in 1 wt.% oxalic acid at room temperature for 1 min each. The samples were then rinsed with ultrapure water and air-dried. The cobalt and copper level thicknesses on the samples were determined by XRF. A ready-to-use PCC formulation was heated to 60°C, and the two cobalt blank wafer samples (2 × 2 cm) were immersed in a tempering solution for 3 min. The samples were then rinsed with ultrapure water and air-dried. The same procedure was repeated with the two copper blank wafer samples. The wafer sample thicknesses were determined by XRF. The static etching rate (SER) was determined by calculating the difference in cobalt / copper level thickness before and after PCC solution treatment and dividing by the 3 min etching time.

[0328] Turbidity measurement (turbidity determination method)

[0329] The turbidity of both the concentrate and a 50-fold diluted composition was measured using a Hach Lange TL2350 instrument (Hach Lange GmbH). Scattered light from the sample was measured at a 90-degree angle to the incident beam. Measurements were performed using white light (tungsten; l = 340–850 nm). The turbidity meter was calibrated using a formazine standard. All samples showing a turbidity < 1.3 NTU (NTU = turbidity unit in turbidity determination) were considered non-turbid.

[0330] For further evaluation, the diluted compositions in Tables 1 and 2 were prepared by appropriate dilution of the concentrate compositions. In this document, the final concentrations of these components are as follows: 0.012 wt.% polymer dispersant, and optionally 0.07 wt.% reducing agent, 0.06 wt.% wetting agent, and 0.3 wt.% water-miscible solvent. Additionally, all compositions contain pH adjusters at the concentrations mentioned below, and molar concentrations are also considered to ensure comparability of results from the various compositions. Similarly, since the complexing agents mentioned herein have different degrees of engagement, they are added at the concentrations mentioned below to ensure comparability of results. The compositions were brought to 100 wt.% using ultrapure water (UPW).

[0331]

[0332]

[0333]

[0334] Table 2 - For the comparative examples - Continued

[0335]

[0336] result

[0337] Preferably, the SER value of copper should be < 4.0 and the SER value of cobalt should be < 5.0. Examples 1-19 in Table 1 show surprisingly low static etching rates for cobalt and copper. Furthermore, the concentrated compositions mentioned above are commercially important for ease of transport. However, at higher concentrations, the overall compatibility and miscibility of the various essential components are low. Examples 1-19 in Table 1 are readily processed in solvents (water or water together with water-miscible solvents such as ethylene glycol) without visible turbidity. Similar results were obtained even when the compositions were formulated as concentrates, for example, compositions containing approximately 10 wt% pH adjuster and correspondingly adjusted other components compared to the examples in Table 1. Similar results were also noted when alternative water-miscible solvents such as propylene glycol (D-3) or DMSO (D-4) were used (see Examples 15-16 in Table 1). Optional ingredients such as wetting agents were also tested, and acceptable results were obtained (Examples 17-19 in Table 1 containing dispersants F-1 to F-3). It should be noted that while reducing agents are optional (see Example 1), their presence also provides acceptable results. Additionally, xylitol (E-2), the reducing agent, was tested by substituting sorbitol (E-1) in Example 2 of Table 1, and acceptable results were observed regarding both SER and turbidity.

[0338] Replacing one or more essential components with components no longer according to the invention results in undesirable effects. For example, Comparative Examples 1-3 and 11, which contain compounds A-3 to A-5 and A-13 in Table 2 instead of the pH adjuster according to the invention, result in undesirable turbidity / precipitation. Similar undesirable turbidity is also noted in Comparative Example 17, which contains an acrylic resin (C-4; dispersant) in Table 2. Careful selection of various key components (such as complexing agents and polymeric dispersants) is crucial to ensuring low SER. Therefore, it is noteworthy that using increased concentrations of complexing agents in Examples 4-11 (see Table 1) also produces acceptable low SER.

[0339] When the composition is not according to the invention, undesirable high SER values ​​for copper and / or cobalt are also noted. For example, Comparative Examples 4 to 10, 12 and 13, which contain pH adjusters (A-6 to A-12, A14 and A15) not according to the invention, show high SER values. Similar undesirable results are also noted when complexing agents not according to the invention are used in the composition (Comparative Examples 14-16, which contain B-9 to B11 in Table 2).

Claims

1. An alkaline composition for cleaning a substrate, the substrate comprising i) copper or a copper alloy and ii) cobalt or a cobalt alloy, the composition comprising: a) At least one pH adjuster selected from compounds having formula I. Formula I in Ra, Rb, Rd, and Rf are independently selected from unsubstituted straight or branched C1-C chains. 12 alkyl, Re is selected from unsubstituted straight-chain or branched C4-C9 alkyl groups; such that the dashed bond between Re and N is a single or double bond, and Rd does not exist when the dashed bond is a double bond. Ra, Rb, Re, and Rf can bond together to form one or more 6- or 7-membered rings; b) At least one complexing agent selected from C2 to C3 groups having at least two sulfonic acid groups or carboxylic acid groups. 12 hydrocarbon, c) at least one polymer dispersant having a weight-average molecular weight ≥ 1000 g / mol; and d) Solvents containing water.

2. The composition according to claim 1, wherein, Rc is selected from unsubstituted straight or branched C2-C chains. 12 alkyl.

3. The composition according to any one of claims 1 to 2, wherein, Ra, Rb, Rd, and Rf are independently selected from unsubstituted straight-chain or branched C1-C6 alkyl groups.

4. The composition according to any one of claims 1 to 3, wherein, The pH adjuster has a pKa ≥ 9.

0.

5. The composition according to any one of claims 1 to 4, wherein, The dispersant is selected from polyvinylpyrrolidone, polyethylene oxide, ethylene oxide-propylene oxide copolymer, naphthalene sulfonic acid formaldehyde condensate, phenol sulfonic acid formaldehyde condensate, or a mixed naphthalene sulfonic acid-phenol sulfonic acid formaldehyde condensate.

6. The composition according to any one of claims 1 to 5, wherein, The complexing agent is selected from citric acid, tartaric acid, hydroxymalonic acid, malonic acid, succinic acid, glutaric acid, malic acid, or mixtures thereof.

7. The composition according to any one of claims 1 to 6, wherein it is substantially free of triazoles, quaternary ammonium salts, alkanolamines, or derivatives thereof.

8. The composition according to any one of claims 1 to 7, wherein, The solvent (d) is essentially composed of water.

9. The composition according to any one of the preceding claims, wherein the pH is from 7.5 to 14.

0.

10. The composition according to any one of the preceding claims, comprising: a) 0.02 to 40.0 wt.% of this pH adjuster; b) 0.005 to 3.0 wt.% of the complexing agent, c) 0.001 to 3.0 wt.% of the polymer dispersant; and d) The remaining solvent containing water.

11. A concentrate for preparing a composition according to any one of the preceding claims, the concentrate comprising: a) 4.0 to 40.0 wt.% of this pH adjuster; b) 0.1 to 3.0 wt.% of the complexing agent, c) 0.01 to 3.0 wt.% of the polymer dispersant; and d) The remaining solvent containing water.

12. Use of the composition according to any one of claims 1 to 10 for removing the following from a substrate: (a) Post-etching residue (PERR) or post-ashing residue (PARR), or (b) Chemical-mechanical planarization (CMP) residues, The substrate includes (i) a cobalt or cobalt alloy surface and (ii) a copper or copper alloy surface.

13. A method for fabricating a microelectronic device, the method comprising: (a) Providing a microelectronic substrate comprising (i) a cobalt or cobalt alloy surface and (ii) a copper or copper alloy surface having etch residues, ashing residues, or chemical mechanical planarization (CMP) residues. (b) Providing the composition according to any one of claims 1 to 10; as well as (c) Contact (i) the cobalt or cobalt alloy surface and (ii) the copper or copper alloy surface with the composition at a certain temperature for a certain time to effectively remove, at least partially and preferably completely, etch residues, ashing residues or chemical mechanical planarization (CMP) residues from the substrate.

14. A method for manufacturing a semiconductor device, the method comprising the processing according to claim 13.

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