Solution for post-etch residue removal (PERR)

Abstract

The present invention relates to a composition for removing post-etch residues from a substrate comprising a surface of a molybdenum layer, the composition comprising: (a) 10% to 60% by weight of a water-miscible organic solvent; (b) from 4% to 15% by weight of a C1-C12 amine; (c) 0.5% to 4% by weight of a C4 to C16 quaternary ammonium hydroxide; (d) 0.1% to 5% by weight of a C2 to C10 polyol; (e) from 0.01% to 3% by weight of a polyethyleneimine; and (f) water.

Description

[0001] The present invention relates to a composition, its use, and a method for post-etch residue removal (PERR) for a substrate (especially a semiconductor substrate) containing molybdenum. Background Art

[0002] Resists (such as deep UV photoresists or electron beam resists) are used in microlithography for the production of a wide range of electronic devices, such as semiconductor integrated circuits (ICs), liquid crystal panels, organic electroluminescent panels, printed circuit boards, micromachines, DNA chips, and microdevices, especially ICs with LSI (large scale integration) or VLSI (very large scale integration).

[0003] Copper is commonly used as a low-resistance or wiring material in electronic devices (especially in the vias and interconnects included in ICs). The increasing use of copper and the continuously decreasing size of electronic structures, together with the continuously increasing IC functionality requirements, call for the use of low-k materials and ultra-low-k materials in order to avoid problems of wiring resistance and wiring delay caused by high wiring capacitance. These challenging developments have required and still require continuous optimization of manufacturing methods and thus continuous optimization of the materials used.

[0004] Although damascene patterning has to overcome many technical challenges, copper-based interconnects have been applied to many successive technology nodes. As we move towards 20 nm and smaller local BEOL interconnect metal pitches (for N2 and more advanced technology nodes), the resistance of Cu metal lines increases very rapidly at such small sizes due to electron scattering at the surface and at grain boundaries. In addition, Cu metal lines require a liner to prevent Cu diffusion into the dielectric material. Since this liner requires a fixed thickness to prevent diffusion, scaling the Cu interconnect without being able to scale the liner thickness results in a significant relative increase in metal resistance as the critical dimension decreases.

[0005] Two interesting candidates expected to have lower resistance than Cu at very small sizes are ruthenium (Ru) and molybdenum (Mo). Important advantages of Ru and Mo are that both materials can be patterned by direct metal etching, just like the case of Al before the Cu interconnect era. In addition, since both Ru and Mo can be integrated without a barrier, a reduction in resistance can be expected when integrating Ru or Mo at small sizes.

[0006] Molybdenum can have many advantages sought in the art. For example, it can be used as a conductor in back-end-of-line (BEOL) or middle-end-of-line (MEOL) applications, or in buried power rails or work function layers in logic applications, as well as in word lines or bit lines in advanced memory applications.

[0007] For copper, many so-called post-etch residue removal (PERR) processes have been developed and disclosed in the prior art.

[0008] WO 2010 / 127941 A discloses a post-etch residue removal composition that comprises a liquid composition free of N-alkylpyrrolidone and hydroxylamine and hydroxylamine derivatives and comprises at least two polar organic solvents and at least one quaternary ammonium hydroxide, the polar organic solvents being selected from the group consisting of solvents that exhibit a constant removal rate at 50 °C for a 30 nm thick polymer barrier anti-reflection layer comprising a deep UV-absorbing chromophore in the presence of 0.06% to 4% by weight of dissolved tetramethylammonium hydroxide, the weight percentage being based on the total weight of the corresponding test solution.

[0009] Patterning challenges for direct metal etching of ruthenium and molybdenum at metal pitches of 32 nm and below are described, for example, in J. Vac. Sci. Technol. B [Journal of Vacuum Science and Technology B] 40, 032802 (2022). They are expected to have a MoO of about 2 nm on Mo metal lines x sidewalls, which are patterned with a direct metal etching process, and even more so in wider lines, which may be a major obstacle to integrating Mo in future interconnects.

[0010] Accordingly, there is a strong need for cleaning compositions capable of cleaning wafer structures containing molybdenum, which cleaning compositions, in addition to removing all other etch residues (especially dry etch residues), also exhibit:

[0011] (a) A low molybdenum static etch rate that avoids damaging these structures, since molybdenum is not as expensive as copper;

[0012] (b) Good, preferably complete, removal of molybdenum etch residues (especially etch residues including molybdenum oxide).

[0013] Accordingly, an object of the present invention is to provide a composition for post-etch residue removal that allows good PERR efficiency, removal of etch residues (especially molybdenum etch residues, most particularly molybdenum oxide residues), and good compatibility with substrates, especially with molybdenum. A further object of the present invention is to provide a composition that exhibits substantially complete removal of molybdenum etch residues (substantially oxides) while substantially not eroding molybdenum. SUMMARY OF THE INVENTION

[0014] One embodiment of the present invention is a composition for removing post-etch residues from a substrate comprising a surface of a molybdenum layer, the composition comprising:

[0015] (a) 10% to 60% by weight of a water-miscible organic solvent

[0016] (b) 4% to 15% by weight of C1-C 12 amine;

[0017] (c) 0.5% to 4% by weight of C4 to C 16 quaternary ammonium hydroxide;

[0018] (d) 0.1% to 5% by weight of C2 to C 10 polyol;

[0019] (e) 0.01% to 3% by weight of polyethyleneimine; and

[0020] (f) water.

[0021] The composition is also capable of removing substantially all of the etch residues while effectively protecting the molybdenum conductor lines.

[0022] Another embodiment of the present invention is the use of the composition as described herein for removing post-etch residues from a semiconductor substrate including a surface of a molybdenum layer.

[0023] Yet another embodiment of the present invention is a method for removing post-etch residues from a substrate including a surface of a molybdenum layer, the composition comprising:

[0024] (a) providing a surface of a microelectronic device including a surface of a molybdenum layer and post-etch residues thereon;

[0025] (b) providing the composition as described herein;

[0026] (c) contacting the surface with the composition for a period of time at a temperature effective to remove the post-etch residues without damaging the molybdenum layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 Shows the scheme of the substrate used in Example 3;

[0028] Figure 2 Shows the substrate treated with Composition C1.1 of Example 3;

[0029] Figure 3 Shows the substrate treated with Composition 1.4 of Example 3. DETAILED DESCRIPTION

[0030] The composition of the present invention comprises:

[0031] (a) 10% to 60% by weight of a water-miscible organic solvent

[0032] (b) 4% to 15% by weight of C1 - C 12 amine;

[0033] (c) 0.5% to 4% by weight of C4 to C 16 quaternary ammonium hydroxide;

[0034] (d) 0.1% to 5% by weight of C2 to C 10 polyol;

[0035] (e) 0.01% to 3% by weight of polyethyleneimine; and

[0036] (f) water.

[0037] Definitions

[0038] As used herein, "layer" means a portion of a substrate that is disposed separately on the surface of the substrate and has a distinguishable composition relative to an adjacent layer.

[0039] The term "C x " means that the corresponding group contains x number of C atoms. The term "C x to C y alkyl" means an alkyl group having from x to y carbon atoms and includes unsubstituted straight-chain, branched-chain, and cyclic alkyls unless specifically designated otherwise. As used herein, "alkanediyl" refers to a divalent group of a straight-chain, branched-chain, or cyclic alkane or a combination thereof.

[0040] Unless otherwise indicated, all percentages, ppm, or similar values refer to weight relative to the total weight of the corresponding composition. The terms "wt%" and "% by weight" are used synonymously herein.

[0041] "Post-etch residue" refers to the material remaining after a gas-phase plasma etching process (e.g., back-end-of-line ("BEOL") dual-damascene processing or a wet etching process). Post-etch residues can be organic, organometallic, organosilicon, or inorganic in nature, such as silicon-containing materials, carbon-based organic materials, and etching gas residues (such as oxygen and fluorine). When etching a molybdenum layer, molybdenum etch residues (such as molybdenum oxide) may be present and are typically present. Depending on the substrate and the etching method, such molybdenum oxide may also contain other non-oxide compounds.

[0042] All cited documents are incorporated herein by reference.

[0043] Water-miscible organic solvents

[0044] The cleaning composition comprises one or more water-miscible organic solvents. These water-miscible organic solvents help dissolve other components in the composition and improve the efficiency and solubility of removing organic residues from the wafer surface.

[0045] In the context of the present invention, the term "water-miscible organic solvent" preferably means that an organic solvent meeting this requirement is miscible with water at 20 °C and ambient pressure in a ratio of at least 1:1 (w / w).

[0046] Examples of water-miscible organic solvents that can be used are:

[0047] (a) Ethers, such as but not limited to tripropylene glycol methyl ether, propylene glycol propyl ether, diethylene glycol n-butyl ether (BDG), dipropylene glycol methyl ether (DPM);

[0048] (b) Sulfur-containing solvents:

[0049] (i) Sulfones, such as but not limited to sulfolane;

[0050] (ii) Sulfoxides, such as but not limited to dimethyl sulfoxide (DMSO);

[0051] (c) Alcohols, such as but not limited to tetrahydrofurfuryl alcohol or straight-chain or branched C2 to C6 alkanols, such as ethanol, n-propanol or isopropanol;

[0052] (d) 4-Methylmorpholine-4-oxide, trimethylamine-N-oxide, triethylamine-N-oxide, triethanolamine-N-oxide, pyridine-N-oxide, N-formylmorpholine, N-ethylmorpholine-N-oxide, N-ethylpyrrolidine-N-oxide; or

[0053] (e) Mixtures thereof.

[0054] The water-miscible organic solvent can be protic or aprotic. Preferably, the water-miscible organic solvent is aprotic.

[0055] Preferred solvents are dimethyl sulfoxide, diethyl sulfoxide, methyl ethyl sulfoxide, dipropyl sulfoxide, diphenyl sulfoxide, methyl phenyl sulfoxide and 1,1'-dihydroxybenzene sulfoxide, and sulfolane, or mixtures thereof. The most preferred solvents are dimethyl sulfoxide, sulfolane, and mixtures thereof.

[0056] For most applications, the amount of water-miscible organic solvent in the composition can be in the range having a starting point and an ending point selected from the following list of weight percentages: 10, 12, 15, 20, 25, 29, 30, 33, 35, 40, 45, 50, 54, 59.9, and 60. Examples of such ranges of the solvent include from about 10% to about 60% by weight of the composition; or from about 12% to about 50% by weight; or from about 15% to about 45% by weight; or from about 0.5% to about 30% by weight; or from about 1% to about 30% by weight; or from about 12% to about 40% by weight; or from about 20% to about 49.9% by weight; or from about 25% to about 55% by weight; or from about 30% to about 40% by weight.

[0057] In individual cases, the composition according to the invention as defined herein may further comprise, as optional additional components, one or more water-miscible organic solvents, which are preferably selected from the group consisting of: tetrahydrofuran (THF), N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), ethanol, isopropanol, butyl diglycol, butyl glycol, sulfolane (2,3,4,5-tetrahydrothiophene-1,1-dioxide), and mixtures thereof; more preferably selected from the group consisting of: THF, NMP, DMF, DMSO, sulfolane, and mixtures thereof.

[0058] In a preferred embodiment, the total amount of one or more water-miscible organic solvents in the cleaning composition is from about 15% to about 55% by weight, preferably from about 20% to about 50% by weight, more preferably from about 25% to about 45% by weight, and even more preferably from about 30% to about 40% by weight based on the total weight of the composition.

[0059] Amine

[0060] The cleaning composition comprises one or more amines. These amines assist in removing polymer residues from the wafer substrate.

[0061] Preferably, the amine is different from any other component in the composition, particularly the water-miscible organic solvent and the polyol. More preferably, the amine does not contain any other substituents except for the amino group and the hydroxyl group, and in particular does not contain any other substituents except for the amino group and a single hydroxyl group.

[0062] In a preferred embodiment, the amine is selected from C1 to C 10 alkylamines and C2 to C 10 alkanolamines. Most preferably, it is C2 to C 10 alkanolamines.

[0063] An alkylamine is a compound that includes an amine group substituted by at least one alkyl group. The alkylamine can be any alkylamine that is effective as a cleaning compound as described, including primary, secondary, and tertiary amine compounds. Some useful alkylamines are monoalkylamines such as ethylamine, ethylenediamine, diethylenetriamine, triethylenediamine, tetraethylenepentamine (TEPA), triethylenetetramine, ethylenediamine, hexamethylenediamine, triethylamine, trimethylamine, diethanolamine, and morpholine.

[0064] Preferred alkylamines are those that contain one or two primary, secondary, or tertiary amino groups. Even more preferred are alkylamines that:

[0065] (a) contain one primary amino group;

[0066] (b) contain one secondary or tertiary amino group.

[0067] An alkanolamine is a compound that includes an amine group substituted by at least one hydroxyl group, preferably a single hydroxyl group. The alkanolamine can be any alkanolamine that is effective as a cleaning compound as described, including primary, secondary, and tertiary amine compounds. The alkanolamine compound will have at least one alkanol substituent (e.g., methanol, ethanol, etc.) and one, two, or three alkanol, alkyl, or alternative organic substituents. Some useful alkanolamines are primary alkanolamines such as monoethanolamine (MEA), aminoethylethanolamine, N-methylethanolamine, aminoethoxyethanol, aminoethoxyethoxyethanol, butoxypropylamine, methoxypropylamine, butoxyisopropylamine, 2-ethylhexylisopropoxyamine, ethanolpropylamine, ethylethanolamine, N-hydroxyethylmorpholine, aminopropyldiethanolamine, dimethylaminoethoxyethanol, diethanolamine, N-methyldiethanolamine, monoethanolamine, triethanolamine, 1-amino-2-propanol, 3-amino-1-propanol, diisopropylamine, aminomethylpropanediol, N,N-dimethylaminomethylpropanediol, aminoethylpropanediol, N,N-dimethylaminoethylpropanediol, isopropylamine, 2-amino-1-butanol, aminomethylpropanol, aminodimethylpropanol, N,N-dimethylaminomethylpropanol, isobutanolamine, diisopropanolamine, 3-amino,4-hydroxyoctane, 2-aminobutanol, tris(hydroxymethyl)aminomethane (TRIS), N,N-dimethyltris(hydroxymethyl)aminomethane, hydroxypropylamine, hydroxyethylamine, tris(hydroxyethyl)aminomethane, and combinations thereof.

[0068] Preferred alkanolamines are those that contain one or two hydroxyl groups and one or two primary, secondary, or tertiary amino groups. Even more preferred are alkanolamines that:

[0069] (a) contain one or two hydroxyl groups and one secondary or tertiary amino group;

[0070] (b) contain one hydroxyl group and one or two secondary or tertiary amino groups.

[0071] Particularly preferred alkanolamines are 2-(methylamino)ethan-1-ol (N-methylethanolamine).

[0072] One or more amines may be present in an amount of from about 4% to about 15% by weight, preferably from about 5% to about 14% by weight, more preferably from about 6% to about 11.5% by weight, even more preferably from about 7 to about 13% by weight, and most preferably from about 8% to about 12% by weight.

[0073] Quaternary ammonium hydroxide

[0074] The cleaning composition comprises one or more C4 to C 16 Quaternary ammonium hydroxide as a pH regulator to adjust the pH to an alkaline range.

[0075] Quaternary ammonium hydroxide may be present in the composition in an amount of from about 0.5% to about 4% by weight. Preferably, the composition of the present invention comprises from 0.7% to 3.5% by weight, more preferably from 1% to 3% by weight, and most preferably from 1.5% to 2.5% by weight of at least one quaternary ammonium hydroxide.

[0076] Preferably, the quaternary ammonium hydroxide may be selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and (2-hydroxyethyl)triethylammonium hydroxide.

[0077] Preferably, the quaternary ammonium hydroxide may be selected from C4 to C8 alkyl quaternary ammonium hydroxides, particularly selected from tetramethylammonium hydroxide and tetraethylammonium hydroxide.

[0078] Polyol

[0079] The cleaning composition comprises one or more C2 to C 10 Polyols. These polyols help to increase surface wetting and dissolve polymer residues from the wafer surface.

[0080] Preferably, the polyol is different from any other component in the composition, particularly water-miscible organic solvents and amines. More preferably, the polyol does not contain any other substituents other than hydroxyl groups.

[0081] In a preferred embodiment, the C2 to C 10 Polyol is selected from compounds having the formula HOCH2(CHOH) k CH2OH, where k is an integer from 0 or 1 to 8.

[0082] In a preferred embodiment, the C2 to C 10The polyol is selected from ethylene glycol, glycerol, erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, propylene glycol, 1,4-butanediol, diethylene glycol, and combinations thereof.

[0083] Particularly preferred is a combination of a C4 to C8 polyol (preferably sorbitol) and a C2 or C3 polyol (preferably ethylene glycol).

[0084] The polyol may be present in an amount of about 0.1% to about 5% by weight of C2 to C 10 polyol, preferably in an amount of about 0.2% to about 4.5% by weight, more preferably in an amount of about 0.3% to about 4% by weight, even more preferably in an amount of about 0.4% to about 3% by weight, and most preferably in an amount of about 0.5% to about 2.5% by weight.

[0085] In a preferred embodiment, the polyol comprises or consists essentially of about 0.3% to 1% by weight of a C4 to C8 polyol and about 0.5% to 1.5% by weight of a C2 or C3 polyol.

[0086] Polyethyleneimine (PEI)

[0087] The cleaning composition comprises one or more polyethyleneimine-based molybdenum corrosion inhibitors. When removing post-etch residues from the wafer surface, polyethyleneimine significantly reduces the corrosion of molybdenum (especially molybdenum metal lines).

[0088] It has been found that the addition of polyethyleneimine results in a low etch rate on blanket PVD Mo compared to a composition without polyethyleneimine, but still allows good, preferably complete, removal of the etch residues.

[0089] The polyethyleneimine backbone is understood to mean a compound consisting of a saturated hydrocarbon chain with terminal amino functional groups interrupted by secondary and tertiary amino groups. Such a backbone can be straight-chain or branched. Of course, different polyethyleneimine backbones can be used in mixtures with each other.

[0090] The backbone contains primary, secondary, and tertiary amine nitrogen atoms connected by "linking" units. The backbone essentially contains three types of units, and it should be emphasized that these groups can be distributed along the backbone in any order.

[0091] The units constituting the polyalkyleneimine backbone are (a) primary units having the following formula:

[0092] [H2N-C2H4]- and -NH2

[0093] which terminate the main backbone and any branched chains;

[0094] (b) A secondary amine unit having the following formula:

[0095]

[0096] and (c) a tertiary amine unit having the following formula:

[0097]

[0098] They are the branch points of the main backbone and the secondary backbone, and A E1 represents the continuation of the branched chain structure. The continuation of the branched chain structure herein means that A E1 can contain all of the above primary, secondary, and tertiary amine units except for the terminal group -NH2.

[0099] During the formation of the polyamine backbone, cyclization may occur, and thus, a certain amount of cyclic polyamine may be present in the parent polyalkyleneimine backbone mixture. Each primary and secondary amine unit of the cyclic alkyleneimine undergoes modification by adding polyoxyalkylene units in the same manner as the linear and branched polyalkyleneimines.

[0100] The polyalkyleneimine of the present invention can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst (such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.). Specific methods for preparing these polyalkyleneimine backbones are disclosed in U.S. Patent 2,182,306, U.S. Patent 3,033,746, U.S. Patent 2,208,095, U.S. Patent 2,806,839, and U.S. Patent 2,553,696.

[0101] In addition, the polyalkyleneimine backbone can be partially substituted by an alkylating agent. The substituents can be selected from C1 to C 12 alkyl, C2 to C 12 alkenyl, C2 to C 12 alkynyl, C6 to C 20 alkylaryl, C6 to C 20 arylalkyl, C6 to C 20 aryl. Preferred substituents can be selected from C1 to C6 alkyl, C6 to C 12 alkylaryl, C6 to C 12 arylalkyl, and C6 to C 12 aryl. Preferably, the aryl is phenyl or naphthyl. The terminal groups [H2N-X L1 - and -NH2 can also be substituted by the group R L3 .

[0102] Suitable examples of the alkylating agent are organic compounds containing an active halogen atom, such as arylalkyl halides, alkyl halides, alkenyl halides, and alkynyl halides. Additionally, compounds such as alkyl sulfates, alkyl sultones, and epoxides can also be used. Non-limiting examples of the corresponding alkylating agents include benzyl chloride, propane sultone, dimethyl sulfate, (3-chloro-2-hydroxypropyl)trimethylammonium chloride, etc. Preferably, dimethyl sulfate and / or benzyl chloride are used.

[0103] In a preferred embodiment, the polyethyleneimine is unsubstituted. Depending on the pH of the composition, the amino groups in the polyethyleneimine can exist in their protonated form.

[0104] The weight-average molecular weight M of the polyalkyleneimine w can be from about 800 g / mol to about 50,000 g / mol. The weight-average molecular weight M of the polyalkyleneimine backbone w has a lower limit typically of about 800 g / mol, preferably about 1,200 g / mol, more preferably about 1,500 g / mol. The upper limit of the weight-average molecular weight M w is typically about 50,000 g / mol, preferably about 25,000 g / mol, more preferably about 20,000 g / mol, and most preferably about 10,000 g / mol. A particularly preferred range is from 800 to 25,000 g / mol, and most particularly from 1,000 to 4,000 g / mol. The molecular weight can be determined by size exclusion chromatography (such as GPC) using polymethyl methacrylate (PMMA) as a standard and hexafluoroisopropanol + 0.05% potassium trifluoroacetate as an eluent.

[0105] The polyethyleneimine can be present in an amount of about 0.01% to about 3% by weight, preferably about 0.015% to about 2% by weight, more preferably about 0.2% to about 1.5% by weight, even more preferably about 0.2% to about 1% by weight, and most preferably about 0.2% to about 0.5% by weight. It has been found that even a small amount of polyethyleneimine is sufficient to protect molybdenum on the wafer surface. Further increase in the concentration is possible, but it does not significantly improve the corrosion inhibition performance of the polyethyleneimine.

[0106] Water

[0107] The etching composition of the present invention is water-based and thus contains water. Water has several functions, such as dissolving one or more components in the composition, serving as a carrier for the components, acting as an aid for removing residues, acting as a viscosity regulator for the composition, and acting as a diluent. Preferably, the water used in the composition is deionized (DI) water. The range of water described in the next paragraph includes all water from any source in the composition.

[0108] For most applications, the weight percentage of water in the composition will be present in a range having a starting point and an ending point selected from the group of numbers: 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 92, 94, 96. Examples of ranges of water that can be used in the composition include, for example, from about 20% to about 80% by weight, or from about 25% to about 75% by weight, or from about 30% to about 72% by weight, or from about 35% to about 70% by weight, or from about 40% to about 65% by weight, or from about 45% to about 55% by weight of water. Still other preferred embodiments of the present invention may include water in an amount to achieve the desired weight percentage of the other components.

[0109] Dispersant

[0110] The composition may further comprise a dispersant in the form of a polyalkoxylated polyethyleneimine. "Polyalkoxylated polyethyleneimine" means a polyethyleneimine in which the N-hydrogen atoms are replaced by polyoxyalkylene groups containing C2 to C6 oxyalkylene units, preferably C2 to C4 oxyalkylene repeating units, more preferably C2 to C3 oxyalkylene repeating units, and most preferably C2 oxyalkylene repeating units. The polyalkoxylated polyethyleneimine in combination with polyethyleneimine further supports the cleaning of the wafer surface.

[0111] Generally, the polyethyleneimine backbone of the polyalkoxylated polyalkyleneimine can be prepared as described above. Then polyalkoxylation is carried out by reacting the corresponding alkylene oxide with the polyalkyleneimine (especially polyethyleneimine). The synthesis of polyoxyalkylene groups is known to those skilled in the art. For example, comprehensive details are given in "Polyoxyalkylenes" in Ullmann’s Encyclopedia of Industrial Chemistry, 6th Edition, Electronic Release. When two or more different alkylene oxides are used, the polyoxyalkylene groups formed can be random copolymers, gradient copolymers, or block copolymers.

[0112] The modification of N-H units in the polymer backbone with oxyalkylene units is carried out, for example, by first reacting a polymer (preferably polyethyleneimine) with one or more alkylene oxides (preferably ethylene oxide, propylene oxide or a mixture thereof) in the presence of up to 80% by weight of water at a temperature of about 25 °C to about 150 °C in an autoclave equipped with a stirrer. In the first step of this reaction, the alkylene oxide is added in such an amount that almost all of the hydrogen atoms of the N-H units of the polyalkyleneimine are converted to hydroxyalkyl groups to give a monoalkoxylated polyalkyleneimine. Then the water is removed from the autoclave. After adding a basic catalyst, such as sodium methoxide, potassium tert-butoxide, potassium hydroxide, sodium hydroxide, sodium hydride, potassium hydride or a basic ion exchanger, in an amount of 0.1% to 15% by weight relative to the addition product obtained in the first step of the alkoxylation, an additional amount of the alkylene oxide is added to the reaction product of the first step so as to obtain a polyalkoxylated polyalkyleneimine which contains the desired average number of alkylene oxide units per N-H unit of the polymer. The second step can be carried out, for example, at a temperature of about 60 °C to about 150 °C. The second step of the alkoxylation can be carried out in an organic solvent such as xylene or toluene. For the correct metered addition of the alkylene oxide, it is advisable to determine the number of primary and secondary amine groups of the polyalkyleneimine before alkoxylation.

[0113] Alternatively, polyalkoxylation can also be achieved by graft copolymerization of polyethyleneimine.

[0114] The polyalkoxylated polyalkyleneimine can optionally be functionalized with functional groups other than H in a further reaction step. The additional functionalization can be used to modify the properties of the polyalkoxylated polyalkyleneimine. For this purpose, the hydroxyl groups present in the polyoxyalkylated polyalkyleneimine are converted by suitable reagents capable of reacting with the hydroxyl groups.

[0115] The type of functionalization depends on the desired end use. Depending on the functionalizing agent, the chain ends can be hydrophobic or more hydrophilic. Esterification of the hydroxyl group with an acid is a representative reaction.

[0116] In one embodiment, the alkoxylated polyalkyleneimine is used without any further functionalization.

[0117] In another embodiment, the carboxyl-functionalized polyalkoxylated polyethyleneimine can be obtained by Michael addition reaction with a suitable α,β-unsaturated substance (such as acrylic acid, methacrylic acid, etc.). Preferably, the polyalkoxylated polyethyleneimine is functionalized with carboxylic acid groups. Michael addition or Michael 1,4 addition is a reaction between a Michael donor (enolate or other nucleophiles such as amines) and a Michael acceptor (usually an α,β-unsaturated carbonyl / carboxyl group) to produce a Michael adduct by forming a carbon-carbon bond at the β-carbon of the acceptor. Such reactions are also known as aza-Michael additions. Further description thereof is provided in Additions to and substitutions at C-Cπ-Bonds, M. Mauduit, A. Denicourt-Nowicki, Comprehensive Organic Synthesis (Second Edition), 2014.

[0118] In addition, the polyalkoxylated polyethyleneimine can have a high degree of branching. Preferably, the polyalkoxylated polyethyleneimine is hyperbranched. As used herein, the term "hyperbranched" refers to a highly branched polymer that typically exhibits a globular structure. Hyperbranched polymers typically exhibit significant irregularities in the branching pattern and structure, which typically results in a significant variation in molecular weight (often referred to as polydispersity). A useful measure for evaluating the amount of branching present in a polymer is the degree of branching. As used herein, the term "degree of branching" refers to the ratio of (a) the total number of branched-chain repeating units contained in the polymer to (b) the total number of repeating units contained in the polymer. Hyperbranched polymers having any suitable degree of branching can be used in the compositions described herein. In certain embodiments, the hyperbranched polymer exhibits a degree of branching of at least about 4 to 20 monomer units / molecule. Generally, care should be taken when interpreting the degree of branching information of hyperbranched polymers. For example, some hyperbranched polymers can exhibit a degree of branching of less than about 0.2, but include one or more hyperbranched polymer moieties (or subunits) that exhibit a degree of branching greater than about 0.2. This may be the case, for example, when the hyperbranched polymer core is chain-extended with a long chain of linear repeating units. If sufficiently chain-extended, the overall degree of branching of such polymers can be less than about 0.2.

[0119] The weight-average molecular weight M of the polyalkoxylated polyalkyleneimine w can be from about 500 g / mol to about 500,000 g / mol. The number-average molecular weight M of the polyalkoxylated polyalkyleneimine wThe lower limit is typically about 1500 g / mol, preferably about 2500 g / mol, more preferably about 5000 g / mol. The weight-average molecular weight M w The upper limit is typically about 500,000 g / mol, preferably about 150,000 g / mol, more preferably about 50,000 g / mol, and most preferably about 25,000 g / mol. A particularly preferred range is from 800 to 25,000 g / mol, and most particularly from 5000 to 25,000 g / mol. The molecular weight can be determined by size exclusion chromatography (such as GPC) using polymethyl methacrylate (PMMA) as a standard and hexafluoroisopropanol + 0.05% potassium trifluoroacetate as an eluent.

[0120] The average number of oxyalkylene units in the polyoxyalkylene group can be from 1 to about 30 per N-hydrogen atom in the polyalkyleneimine, preferably from 2 to 25, more preferably from 3 to 20, and most preferably from 5 to 15.

[0121] The polyalkoxylated polyalkyleneimine can be present in an amount of about 0.01% to about 1% by weight, preferably about 0.012% to about 0.8% by weight, more preferably about 0.15% to about 0.6% by weight, even more preferably about 0.02% to about 0.5% by weight, and most preferably about 0.02% to about 0.3% by weight. It has been found that an amount of polyalkoxylated polyalkyleneimine below 0.01 wt.% is not sufficient to improve the cleaning performance of the composition. On the other hand, a further increase in concentration above 1 wt.% is possible, but the performance is no longer improved. Additionally, since many components are involved to obtain the composition, a fine balance is typically required to ensure colloidal stability. Here, the presence of a high amount (above 1 wt.%) of (polymeric) components such as polyalkoxylated polyethyleneimine can be detrimental to the long-term stability of the multi-component system, especially in a substantially aqueous medium.

[0122] Chelating agent

[0123] The cleaning composition can optionally contain one or more chelating agents.

[0124] Preferred chelating agents are 1,2-cyclohexylenedinitrilotetraacetic acid, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, acetylacetonates, 2,2'-azanediyl diacetic acid, ethylenediaminetetraacetic acid, etidronic acid, methanesulfonic acid, acetylacetone, 1,1,1-trifluoro-2,4-pentanedione, 1,4-benzoquinone, 8-hydroxyquinoline, salicylideneaniline; tetrachloro-1,4-benzoquinone, 2-(2-hydroxyphenyl)-benzoxazole, 2-(2-hydroxyphenyl)-benzothiazole, hydroxyquinoline sulfonic acid, sulfosalicylic acid, salicylic acid, pyridine, 2-ethylpyridine, 2-methoxypyridine, 3-methoxypyridine, 2-methylpyridine, dimethylpyridine, piperidine, piperazine, ethylamine, methylamine, isobutylamine, tert-butylamine, tributylamine, dipropylamine, dimethylamine, diethanolamine, methyldiethanolamine, pyrrole, isoxazole, bipyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquinoline, indole, 1-methylimidazole, diisopropylamine, diisobutylamine, aniline, pentamethyldiethylenetriamine, acetoacetamide, ammonium carbamate, ammonium pyrrolidinedithiocarbamate, dimethyl malonate, methyl acetoacetate, N-methylacetoacetamide, tetramethylammonium thiobenzoate, 2,2,6,6-tetramethyl-3,5-heptanedione, tetramethylthiuram disulfide, lactic acid, ammonium lactate, formic acid, propionic acid, γ-butyrolactone, and mixtures thereof.

[0125] The chelating agent can be 1,2-cyclohexylenedinitrilotetraacetic acid (CDTA) or can comprise CDTA and one or more of the other chelating agents described above.

[0126] Also preferred are compositions according to the invention as defined herein, wherein the amount of one or more chelating agents present, based on the total weight of the composition, is from about 0.01% to about 4% by weight, preferably from about 0.02% to about 1% by weight, more preferably from about 0.05% to about 0.8% by weight.

[0127] Surfactant

[0128] The composition can further comprise one or more surfactants.

[0129] Preferred surfactants are selected from the group consisting of:

[0130] (i) Anionic surfactants, which are preferably selected from the group consisting of ammonium lauryl sulfate, fluorosurfactants, preferably selected from the group consisting of perfluorinated alkyl sulfonamide salts (preferably perfluorinated, N-substituted alkyl sulfonamide ammonium salts, PNAAS), perfluorooctane sulfonates, perfluorobutane sulfonates, perfluorononanoates, and perfluorooctanoates; alkyl-aryl ether phosphates and alkyl ether phosphates;

[0131] (ii) Zwitterionic surfactants, which are preferably selected from the group consisting of: (3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulfonate) ("CHAPS"), cocamidopropyl hydroxysultaine (CAS RN 68139-30-0), {[3-(dodecanoylamino)propyl](dimethyl)-ammonio}acetate, phosphatidylserine, phosphatidylethanolamine, phosphatidylcholine; and

[0132] (iii) Nonionic surfactants, which are preferably selected from the group consisting of: glucoside alkyl ethers, glycerol alkyl ethers, cocamide ethanolamine, and lauryldimethylamine oxide.

[0133] More preferred surfactants in the compositions according to the invention are or comprise perfluorinated, N-substituted alkylsulfonamide ammonium salts. The preferred surfactant (E) in the compositions according to the invention does not contain metals or metal ions.

[0134] Also preferred are the compositions according to the invention as defined herein, wherein, based on the total weight of the composition, the amount of one or more surfactants present in the surfactants is from about 0.0001% to about 1% by weight, preferably from about 0.0005% to about 0.5% by weight, more preferably from about 0.001% to about 0.01% by weight.

[0135] Specific surfactants for use in the compositions described herein include but are not limited to bis(2-ethylhexyl) phosphate, perfluoroheptanoic acid, perfluorodecanoic acid, trifluoromethanesulfonic acid, phosphonoacetic acid, dodecenylsuccinic acid, dioctadecyl hydrogen phosphate, octadecyl dihydrogen phosphate, dodecylamine, dodecenylsuccinic acid mono-diethanolamide, lauric acid, palmitic acid, oleic acid, juniperic acid, 12-hydroxy stearic acid, and dodecyl phosphate; polyoxyethylene lauryl ether (Emalmin NL-100 (Sanyo), Brij 30, Brij 98, Brij35), dodecenylsuccinic acid mono-diethanolamide (DSDA, Sanyo), ethylenediamine tetra(ethoxylate-block-propoxylate) tetraol (Tetronic 90R4), polyethylene glycol (e.g., PEG400), polypropylene glycol, polyethylene glycol ether or polypropylene glycol ether, block copolymers based on ethylene oxide and propylene oxide (Newpole PE-68 (Sanyo), Pluronic L31, Pluronic 31R1, Pluronic L61, Pluronic F-127) (Dynol 607), polyoxypropylene sucrose ether (SN008S, Sanyo), tert-octylphenoxypolyethoxyethanol (Triton X100), 10-ethoxy-9,9-dimethyldecan-1-amine ( CF-32), branched polyoxyethylene (9) nonylphenyl ether (IGEPAL CO-250), branched polyoxyethylene (40) nonylphenyl ether (IGEPAL CO-890), polyoxyethylene sorbitan hexaoleate, polyoxyethylene sorbitan tetraoleate, polyethylene glycol sorbitan monooleate (Tween80), sorbitan monooleate (Span 80), a combination of Tween 80 and Span 80, alcohol alkoxylates (e.g., Plurafac RA-20), alkyl-polyglucosides, ethyl perfluorobutyrate, 1,1,3,3,5,5-hexamethyl-1,5-bis[2-(5-norbornen-2-yl)ethyl]trisiloxane, monomeric octadecylsilane derivatives such as SIS6952.0 (Siliclad, Gelest), siloxane-modified polysilazanes such as PP1-SG10 Siliclad Glide 10 (Gelest), silicone-polyether copolymers such as Silwet L-77 (Setre Chemical), Silwet ECO spreader (Momentive), and ethoxylated fluorosurfactants ( FSO-100, FSN-100); cetyltrimethylammonium bromide (CTAB), heptadecafluorooctanesulfonic acid, tetraethylammonium, stearyltrimethylammonium chloride (Econol TMS-28, Sanyo), 4-(4-diethylaminophenylazo)-1-(4-nitrobenzyl)pyridinium bromide, cetylpyridinium chloride monohydrate, benzalkonium chloride, benzethonium chloride, benzyldimethyldodecylammonium chloride, benzyldimethylhexadecylammonium chloride, hexadecyltrimethylammonium bromide, dimethyldioctadecylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium p-toluenesulfonate, didodecyldimethylammonium bromide, di(hydrogenated tallow)dimethylammonium chloride, tetraheptylammonium bromide, tetra(decyl)ammonium bromide, 336 and oxyphenonium bromide, guanidine hydrochloride (C(NH2)3Cl) or trifluoromethanesulfonates such as tetrabutylammonium trifluoromethanesulfonate, dimethyldioctadecylammonium chloride, dimethyldihexadecylammonium bromide, and di(hydrogenated tallow)dimethylammonium chloride (e.g., Arquad 2HT-75, Akzo Nobel), bromide-containing surfactants such as 1-hexadecyltrimethylammonium bromide.

[0136] In some embodiments, the compositions of the present invention will be free or substantially free of any or all of the surfactants listed above.

[0137] Compositions

[0138] Other commonly known components such as dyes, chemical modifiers, microbicides, etc. can be included in the cleaning composition in conventional amounts up to an extent that they do not adversely affect the performance of the composition, for example, in amounts up to about 1% or 5% or 10% by weight of the total composition.

[0139] Alternatively, the cleaning composition can be free or substantially free of any or all of dyes, chemical modifiers, microbicides.

[0140] The cleaning composition is typically prepared by mixing the components together in a container at room temperature until all solids have dissolved in the aqueous medium.

[0141] Generally, the pH of the composition can be in the range of 8 to 14. In a preferred embodiment, the pH of the etching composition is from about 9 to about 13, more preferably from about 10 to about 13, and most preferably from about 11 to about 12.5.

[0142] A cleaning composition is particularly preferred, wherein the composition comprises or consists essentially of the following:

[0143] (a) 10% to 60% by weight of a water-miscible aprotic organic solvent, particularly a sulfoxide or sulfone, most particularly dimethyl sulfoxide or sulfolane;

[0144] (b) 4% to 15% by weight of a C1-C 12 amine, particularly an alkanolamine, most particularly 2-(methylamino)ethan-1-ol;

[0145] (c) 0.5% to 4% by weight of a C4 to C 16 quaternary ammonium hydroxide, particularly a C4 to C8 quaternary ammonium hydroxide, most particularly tetramethylammonium hydroxide or tetraethylammonium hydroxide;

[0146] (d) 0.1% to 5% by weight of a C2 to C 10 polyol, particularly a compound having the formula HOCH2(CHOH) k CH2OH (where k is an integer of 0 or 1 to 8), most particularly sorbitol, ethylene glycol or a mixture thereof;

[0147] (e) 0.01% to 3% by weight of a polyethylenimine, particularly an unsubstituted polyethylenimine, most particularly a polyethylenimine having a weight average molecular weight of 600 to 50,000 g / mol;

[0148] (f) water;

[0149] (g) Optionally, 0.01% to 2% by weight of a polyalkoxylated polyethyleneimine, in particular a polyalkoxylated, in particular polyethoxylated, polyethyleneimine having 5 to 15 alkoxy groups per N-H group; and

[0150] Another cleaning composition is particularly preferred, wherein the composition comprises or consists essentially of the following:

[0151] (a) 20% to 50% by weight of a water-miscible aprotic organic solvent;

[0152] (b) 7% to 13% by weight of an amine;

[0153] (c) 1% to 3% by weight of a quaternary ammonium hydroxide;

[0154] (d) 1% to 3% by weight of a C2 to C 10 polyol;

[0155] (e) 0.02% to 3% by weight of a polyethyleneimine;

[0156] (f) water; and

[0157] (g) Optionally, a polyalkoxylated polyethyleneimine.

[0158] Preferably, the amine is different from the water-miscible organic solvent and the polyol, and / or the water-miscible organic solvent is different from the amine and the polyol, and / or the polyol is different from the amine and the water-miscible organic solvent. Particularly preferably, all components of the composition are different compounds.

[0159] In this context, "essentially" means that the content of any other compound in addition to the specifically mentioned compounds is less than 1% by weight, preferably less than 0.1% by weight, even more preferably less than 0.01% by weight, and most preferably below the detection limit.

[0160] Particularly preferred are the compositions according to the invention as defined herein, wherein the composition consists of the compounds as defined herein and to be defined based on the examples. All components in the composition total 100% by weight of the entire composition.

[0161] Use

[0162] On the other hand, a method for removing post-etch residues from a substrate is provided, the substrate comprising a surface of a molybdenum layer, the method comprising:

[0163] (a) Providing a surface of a microelectronic device, the surface of the microelectronic device comprising a surface of a molybdenum layer and post-etch residues thereon;

[0164] (b) Providing a composition as described herein;

[0165] (c) Contact the surface with the composition for a period of time at a temperature effective to remove post-etch residues without damaging the molybdenum layer.

[0166] Without limitation, such layers can be present and are wires of a damascene structure.

[0167] It should be understood that the normal practice is to prepare a concentrated form of the composition to be diluted before use. For example, the composition can be manufactured in a more concentrated form and thereafter diluted with water or other components at the manufacturer, before use, and / or during use.

[0168] In the use of the compositions described herein, the composition is typically contacted with the device structure for a sufficient time at a temperature in the range of about 30 °C to about 90 °C, preferably about 35 °C to about 60 °C, for about 1 minute to about 200 minutes, preferably about 1 minute to about 10 minutes. Such contact times and temperatures are illustrative, and any other suitable time and temperature conditions effective to achieve the desired removal selectivity can be employed.

[0169] After achieving the desired etching behavior, the composition can be easily removed from the microelectronic device on which it has been previously applied, for example by rinsing, washing, or one or more other removal steps that may be desirable and effective in a given end-use application of the composition of the present invention. For example, the device can be rinsed with a rinse solution comprising deionized water, an organic solvent, and / or dried (e.g., spin drying, N2, vapor drying, etc.).

[0170] Preferably, the Mo etching rate of the composition is 7 Å / min or lower.

[0171] Following the contacting step is an optional rinsing step. The rinsing step can be carried out by any suitable means, such as rinsing the substrate with deionized water by immersion or spraying techniques. In a preferred embodiment, the rinsing step can be carried out using a mixture of deionized water and an organic solvent such as isopropyl alcohol.

[0172] Following the contacting step and the optional rinsing step is an optional drying step, which is carried out by any suitable means, such as isopropyl alcohol (IPA) vapor drying, heating, or by centripetal force.

[0173] The etching compositions described herein can be advantageously used in a method of manufacturing a semiconductor device, the method comprising the step of selectively removing post-etch residues from the surface of a microelectronic device comprising a molybdenum layer as described herein.

[0174] The following examples should further illustrate the invention without limiting the scope of the invention.

[0175] Examples

[0176] Etching experiments were conducted on a full wafer sample and a semi-embedded sample including a PVD Mo layer with a thickness of 47.5 nm as follows.

[0177] 100 ml of the etching solution was placed in a 150 ml beaker, and the beaker was placed in a temperature-controlled water bath. Then, a 2.5 cm × 2.5 cm sample of the corresponding substrate was immersed in the test solution at the desired temperature while stirring the solution at a speed of 250 rpm. Both the full wafer sample and the semi-embedded sample were etched for 2 min, followed by rinsing with DIW for 30 s, and then drying the sample with an N2 gun. The full wafer sample etching experiment was carried out at 40 °C and 60 °C, while the semi-embedded etching experiment was carried out at 40 °C.

[0178] The thickness of the full wafer sample was determined by XRF measurement. The semi-embedded sample was characterized by TEM.

[0179] The etching rate was calculated according to the following formula:

[0180]

[0181] Example 1

[0182] A 100 g semi-aqueous solution with a Mo inhibitor was prepared by adding the following components in the specified order:

[0183] 1. 49.5 g DIW

[0184] 2. 34 g DMSO (from BASF)

[0185] 3. 10.3 g 2-methyl ethanolamine (from ACROS)

[0186] 4. 1 g ethylene glycol (from BASF)

[0187] 5. 4 g of 25 wt.% TMAH solution in DIW (from BASF)

[0188] 6. 0.6 g sorbitol (from BASF)

[0189] 7. 0.025 g of acrylic-functionalized polyethoxylated PEI with an average of 10 EO / N-H groups (M w = 25000 g / mol) (from BASF), which is further referred to as "polyethoxylated PEI"

[0190] 8. 0.025 g PEI (M w = 2000 g / mol) (from BASF)

[0191] The solution was stirred at a speed of 100 rpm with a magnetic stir bar during mixing.

[0192] Solutions of PEI with different Mo inhibitor concentrations and different M were prepared in the same order as above, and the amount of DIW was adjusted to achieve the desired Mo inhibitor concentration. w Solutions of PEI with different Mo inhibitor concentrations and different M were prepared in the same order as above, and the amount of DIW was adjusted to achieve the desired Mo inhibitor concentration.

[0193] The Mo etch rate (ER) of solutions of polyethyleneimine (PEI) with different concentrations and a weight-average molar mass M of 2000 g / mol was determined on blanked specimens at 40 °C and 60 °C. The compositions and results are shown in Table 1. w The Mo etch rate (ER) of solutions of polyethyleneimine (PEI) with different concentrations and a weight-average molar mass M of 2000 g / mol was determined on blanked specimens at 40 °C and 60 °C. The compositions and results are shown in Table 1.

[0194] Table 1

[0195]

[0196]

[0197] Comparative example C1.1, which does not contain any Mo inhibitor, produced a higher Mo etch rate than any formulation containing different concentrations of PEI. Compared with comparative example C1.1 without PEI, comparative example C1.3 containing 0.005 wt.% PEI had no Mo etch inhibition effect, indicating that the inhibitor concentration was insufficient to protect the Mo surface. A PEI concentration of 1 wt.% could be used, but showed a slightly lower corrosion inhibition effect.

[0198] Example 2

[0199] The Mo etch rate (ER) of solutions of polyethyleneimine (PEI) with different molecular weights was determined on blanked specimens at 40 °C and 60 °C. The results are shown in Table 2.

[0200] Table 2

[0201] Example C1.1 1.4 2.1 2.2 2.3 DMSO 34 34 34 34 34 2-Methylethanolamine 10.3 10.3 10.3 10.3 10.3 Ethylene glycol 1 1 1 1 1 TMAH 1 1 1 1 1 Sorbitol 0.6 0.6 0.6 0.6 0.6 Polyethoxylated PEI 0.025 0.025 0.025 0.025 0.025 DIW 53.0000 52.9750 52.9950 52.9000 52.7500 <![CDATA[PEI(M w : 2000 g / mol)]]> 0.025 <![CDATA[PEI(M w : 5000 g / mol)]]> 0.025 <![CDATA[PEI(M w : 800 g / mol)]]> 0.025 <![CDATA[PEI M w : 25,000 g / mol)]]> 0.025 Mo ER A / min at 40 °C 7.3 6.12 7.00 6.00 5.75 Mo ER A / min at 60 °C 11.25 5.75 8.33 8.75 8.75

[0202] The results showed that all solutions of PEI with different molecular weights exhibited a reduced etching of Mo.

[0203] Example 3

[0204] As Figure 1 The test structure (from IMEC) of 32 nm metal pitch self-aligned double patterning dry etching schematically depicted in was treated with cleaning compositions C1.1 and 1.4. The residues after etching were on the surface of the corresponding layer.

[0205] The substrate was examined by TEM. As can be seen from Figure 2 and Figure 3 As can be seen from and, compared with composition C1.1 (Figure 2 ) Compared with Figure 3 ) Composition 1.4 results in better removal of post-etch residues, especially at the bottom of the line, without eroding the Mo line itself.

Claims

1. A composition for removing post - etch residues from a substrate, the substrate comprising a surface of a molybdenum layer, the composition comprising: (a) 10% to 60% by weight of a water - miscible organic solvent; (b) 4% to 15% by weight of C1-C 12 amine; (c) 0.5% to 4% by weight of C4 to C 16 quaternary ammonium hydroxide; (d) 0.1% to 5% by weight of C2 to C 10 polyol; (e) 0.01% to 3% by weight of a polyethyleneimine; and (f) water.

2. The composition according to any one of the preceding claims, wherein, The organic solvent is a sulfur - containing aprotic organic solvent, especially from sulfoxides and sulfones.

3. The composition according to claim 2, wherein, The organic solvent is selected from dimethyl sulfoxide, diethyl sulfoxide, methyl ethyl sulfoxide, dipropyl sulfoxide, and sulfolane.

4. The composition according to any one of the preceding claims, wherein, The amine is selected from C1 to C 10 alkylamines and C2 to C 10 alkanolamines.

5. The composition according to claim 4, wherein, The amine is selected from 2 - methylethanolamine.

6. The composition according to any one of the preceding claims, wherein, The quaternary ammonium hydroxide is selected from C4 to C8 alkyl quaternary ammonium hydroxides, especially selected from tetramethylammonium hydroxide and tetraethylammonium hydroxide.

7. The composition according to any one of the preceding claims, wherein, The C2 to C 10 The polyol is selected from compounds having the formula HOCH2(CHOH) k CH2OH, where k is an integer of 0 or 1 to 8.

8. The composition according to any one of claims 1 to 6, wherein, The C2 to C 10 The polyol is selected from ethylene glycol, glycerol, erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, heptitol, propylene glycol, 1,4-butanediol, diethylene glycol, and combinations thereof.

9. The composition according to any one of the preceding claims, wherein, The polyethyleneimine has a weight - average molecular weight of 600 to 50000 g / mol, preferably 800 to 25000 g / mol.

10. The composition according to any one of the preceding claims, wherein, The polyethyleneimine is unsubstituted.

11. The composition according to any one of the preceding claims, further comprising a polyalkoxylated polyethyleneimine.

12. The composition according to any one of the preceding claims, having a pH of 10 to 13, preferably 11 to 12.

5.

13. The composition according to any one of the preceding claims, consisting essentially of: (a) 20% to 50% by weight of a water - miscible organic solvent; (b) 7% to 13% by weight of an amine; (c) 1% to 3% by weight of a quaternary ammonium hydroxide; (d) 1% to 3% by weight of C2 to C 10 polyol; (e) 0.02% to 3% by weight of a polyethyleneimine; (f) water; and (g) optionally a polyalkoxylated polyethyleneimine.

14. Use of the composition according to any one of the preceding claims for removing post - etch residues from a semiconductor substrate, the semiconductor substrate comprising a surface of a molybdenum layer.

15. A method for removing post - etch residues from a substrate, the substrate comprising a surface of a molybdenum layer, the method comprising: (a) providing a surface of a microelectronic device, the surface of the microelectronic device comprising a surface of a molybdenum layer and post - etch residues thereon; (b) providing the composition according to any one of claims 1 to 13; (c) contacting the surface with the composition for a period of time at a temperature effective to remove the post - etch residues without damaging the molybdenum layer.

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