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) 0.1% to 4% by weight of a C4 to C16 quaternary ammonium hydroxide; (d) 0.5% to 5% by weight of a C2 to C10 polyol; (e) from 0.01% to 1% by weight of a polyalkoxylated polyethyleneimine; (f) from 0.001% to 0.17% by weight of benzethonium chloride or benzalkonium chloride; and (g) water.

Description

[0001] The present invention relates to a composition, its use and a method for post-etch residue removal (PERR) of substrates, in particular semiconductor substrates, which contain molybdenum. Background Art

[0002] Resists (such as deep UV photoresists or electron beam resists) are used in microlithography technology to produce 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, in particular 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, particularly in vias and interconnects contained in integrated circuits (ICs). The increasing use of copper and the ever-decreasing size of electronic structures, along with the ever-increasing functionality of ICs, necessitate the use of low-k and ultra-low-k materials to avoid the problems of wiring resistance and wiring delays caused by high wiring capacitance. These challenging developments have and continue to require continued optimization of manufacturing methods and the materials used therein.

[0004] Despite the numerous technical challenges that damascene patterning must overcome, copper-based interconnects have been adopted for many successive technology nodes. As we move toward local BEOL (back-end-of-line) interconnect metal pitches ≤ 20 nm (for N2 and beyond), we have noticed that the resistance of copper metal lines increases very rapidly at such small dimensions due to electron scattering at the surface and also at grain boundaries. Furthermore, copper metal lines require a liner to prevent copper diffusion into the dielectric material. Since this liner requires a fixed thickness to prevent diffusion, scaling copper interconnects without being able to scale the liner thickness results in a significant relative increase in metal resistance as the critical dimension decreases.

[0005] Two promising candidates for lower resistance than copper (Cu) at very small dimensions are ruthenium (Ru) and molybdenum (Mo). A key advantage of Ru and Mo is that both materials can be patterned by direct metal etching, much like aluminum (Al) was used before the era of Cu interconnects. Furthermore, since both Ru and Mo can be integrated without a barrier, a reduction in resistance is expected when Ru or Mo is integrated at small dimensions.

[0006] Molybdenum, in particular, can offer many of the advantages sought in the field. For example, it can be used as a conductor in BEOL or mid-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, a number of so-called fully wet 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 comprising a liquid composition free of N-alkylpyrrolidone and hydroxylamine and hydroxylamine derivatives and comprising at least two polar organic solvents and at least one quaternary ammonium hydroxide, the polar organic solvent being selected from the group consisting of solvents that exhibit a constant removal rate at 50° C. for a 30 nm thick polymeric blocking antireflective layer comprising deep UV absorbing chromophores in the presence of 0.06 to 4% by weight of dissolved tetramethylammonium hydroxide, the weight percentages being based on the total weight of the respective test solution.

[0009] The presence of various metals with similar removal rates on the surface of the wafer (such as copper, molybdenum, tungsten, cobalt, etc.), combined with the multi-component composition required to achieve suitable removal efficiency, makes the development of suitable PERR compositions challenging. In addition, the patterning challenges of direct metal etching of ruthenium and molybdenum at ≤32nm metal spacing are described, for example, in J. Vac. Sci. Technol. B [Journal of Vacuum Science and Technology B] 40, 032802 (2022). It is expected that MoO with about 2nm on the Mo metal line x The sidewalls, which are patterned with direct metal etch processes and even more so in wider lines, may be the main challenge for integrating Mo in future interconnects.

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

[0011] (a) Low molybdenum static etch rate, which avoids damage to these structures because molybdenum is less expensive than copper;

[0012] (b) Good, preferably complete removal of molybdenum etching residues, in particular etching residues comprising molybdenum oxide.

[0013] It is therefore an object of the present invention to provide a composition for post-etch residue removal (PERR) which allows good efficiency for removing etching residues, in particular dry etching residues, in particular molybdenum etching residues, most particularly molybdenum oxide residues, and good compatibility with substrates, in particular with molybdenum. A further object of the present invention is to provide a composition which shows substantially complete removal of molybdenum etching residues, essentially oxides, while substantially not attacking the molybdenum. Summary of the Invention

[0014] One embodiment of the present invention is a composition for removing post-etch residue 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) 0.1% to 4% by weight of C4 to C 16 quaternary ammonium hydroxides;

[0018] (d) 0.5% to 5% by weight of C2 to C 10 polyols;

[0019] (e) 0.01 to 1% by weight of polyalkoxylated polyethyleneimine;

[0020] (f) 0.001% to 0.17% by weight of benzethonium chloride or benzalkonium chloride; and

[0021] (g) Water.

[0022] The composition is also capable of removing substantially all etch residues while effectively protecting the molybdenum conductor lines. Additionally, despite the presence of several components, the composition maintains colloidal stability and is further capable of providing suitable PERR performance while preventing any undesirable etching or interaction with other metals present on the surface of the wafer.

[0023] Another embodiment of the present invention is the use of a composition as described herein for removing post-etch residues from a semiconductor substrate comprising a surface of a molybdenum layer.

[0024] Yet another embodiment of the present invention is a method of removing post-etch residue from a substrate comprising a surface of a molybdenum layer, the composition comprising:

[0025] (a) providing a microelectronic device surface, the microelectronic device surface comprising a surface of a molybdenum layer and post-etching residue thereon;

[0026] (b) providing a composition as described herein;

[0027] (c) contacting the surface with the composition for a period of time and at a temperature effective to remove post-etch residue while not damaging the molybdenum layer. DETAILED DESCRIPTION

[0028] A composition for removing post-etch residue from a substrate comprising a surface of a molybdenum layer, the composition comprising:

[0029] (a) 10 to 60% by weight of a water-miscible organic solvent;

[0030] (b) 4 to 15% by weight of C1-C 12 amine;

[0031] (c) 0.1% to 4% by weight of C4 to C 16 quaternary ammonium hydroxides;

[0032] (d) 0.5% to 5% by weight of C2 to C 10 polyols;

[0033] (e) 0.01 to 1% by weight of a polyalkoxylated polyethyleneimine;

[0034] (f) 0.001% to 0.17% by weight of benzethonium chloride or benzalkonium chloride; and

[0035] (g) Water.

[0036] definition

[0037] As used herein, a "layer" means a portion of a substrate that is individually disposed on a surface of the substrate and has a distinguishable composition relative to adjacent layers.

[0038] The term "C x " means that the corresponding group contains x number of C atoms. For example, the term "C2 to C 10 "Polyol" refers to a hydrocarbon containing 2 to 10 carbon atoms and carrying 2, 3, 4 or more hydroxyl groups. The hydrocarbon can be selected from straight chain or branched alkyl groups. Similarly, the term "C1 to C 12 "Amine" refers to a hydrocarbon containing 1 to 12 carbon atoms and carrying at least one amine functional group. The hydrocarbon can be selected from linear or branched alkyl groups.

[0039] 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.

[0040] "Post-etch residue" refers to the material remaining after a gas phase plasma etching process, such as a back-end of line ("BEOL") dual damascene process or a wet etching process. Post-etch residue can be organic, organometallic, organosilicon, or inorganic in nature, such as silicon-containing materials, carbon-based organic materials, and materials obtained from etching gas residues such as oxygen and fluorine. When etching a molybdenum layer, molybdenum etch residues such as molybdenum oxide may be present. Other non-oxidizing compounds of molybdenum may also be present, depending on the substrate and the etching method. As is well known to those skilled in the art, the presence of such residues will have a deleterious effect on the final electronic properties of the wafer. The purpose of the PERR composition is to effectively remove the etch residues while minimizing damage to the wafer surface.

[0041] All cited documents are incorporated herein by reference.

[0042] Water-miscible organic solvents

[0043] The cleaning composition comprises one or more water-miscible organic solvents. The water-miscible organic solvents help dissolve components of the composition with low water solubility and improve the efficiency and solubility of removing organic residues from the wafer surface.

[0044] 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 least in a 1:1 (w / w) ratio at 20°C and ambient pressure.

[0045] Examples of water-miscible organic solvents that can be used are:

[0046] (a) ethers, such as but not limited to tripropylene glycol methyl ether, propylene glycol propyl ether, diethylene glycol n-butyl ether (BDG), and dipropylene glycol methyl ether (DPM);

[0047] (b) Sulfur-containing solvents:

[0048] (i) Sulfones, such as but not limited to sulfolane;

[0049] (ii) sulfoxides, such as but not limited to dimethyl sulfoxide (DMSO);

[0050] (c) alcohols, such as, but not limited to, tetrahydrofurfuryl alcohol or linear or branched C2 to C6 alkanols, such as ethanol, n-propanol or isopropanol;

[0051] (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

[0052] (e) mixtures thereof.

[0053] The water-miscible organic solvent may be protic or aprotic. Preferably, the water-miscible organic solvent is aprotic.

[0054] Preferred solvents are dimethyl sulfoxide, diethyl sulfoxide, methyl ethyl sulfoxide, dipropyl sulfoxide, diphenyl sulfoxide, methyl phenyl sulfoxide, 1,1'-dihydroxyphenyl sulfoxide, sulfolane, or mixtures thereof. More preferred solvents are dimethyl sulfoxide, diethyl sulfoxide, methyl ethyl sulfoxide, dipropyl sulfoxide, or sulfolane. The most preferred solvent is dimethyl sulfoxide, sulfolane, or mixtures thereof.

[0055] Preferably, the amount of water-miscible organic solvent in the composition can be within a 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 for solvent include from about 10% to about 60% by weight of the composition; or from about 12% to about 58% by weight; or from about 15% to about 55% by weight; or from about 16% to about 53% by weight; or from about 18% to about 52% by weight; or from about 22% to about 50% by weight; or from about 20% to about 49.9% by weight, or from about 22% to about 45% by weight; or from about 25% to about 40% by weight.

[0056] In individual cases, the composition according to the present invention as defined herein may further comprise a second water-miscible organic solvent, 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. In such cases, the first solvent and the second solvent are different.

[0057] amine

[0058] The cleaning composition comprises one or more amines that aid in the removal of polymer residues from wafer substrates.

[0059] In a preferred embodiment, the amine is selected from C1 to C 10 Alkylamines and C2 to C 10 Alkanolamines. Most preferred are C2 to C5 alkanolamines.

[0060] Alkylamines are compounds that include an amine group substituted with at least one alkyl group. The alkylamine can be any alkylamine that will be 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, diglycolamine, and morpholine.

[0061] Preferred alkylamines are those containing one or two primary, secondary or tertiary amino groups. Even more preferred are alkylamines which:

[0062] (a) contains a primary amino group;

[0063] (b) contains a secondary or tertiary amino group.

[0064] Alkanolamines are compounds comprising an amine group substituted with at least one alkanol group. Alkanolamines can be any alkanolamine that will be 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 alkanols, alkyls, or alternative organic substituents. Some useful alkanolamines are primary alkanolamines, such as monoethanolamine (MEA), aminoethylethanolamine, N-methylaminoethanol, 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.

[0065] Preferred alkanolamines are those containing one or two hydroxyl groups and one or two primary, secondary or tertiary amino groups. Even more preferred are alkanolamines which:

[0066] (a) contains one or two hydroxyl groups and one secondary or tertiary amino group;

[0067] (b) contains one hydroxyl group and one or two secondary or tertiary amino groups.

[0068] A particularly preferred alkanolamine is 2-(methylamino)ethan-1-ol (or N-methylaminoethanol).

[0069] The one or more amines may be present in an amount 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.

[0070] Quaternary ammonium hydroxide

[0071] The cleaning composition comprises one or more C4 to C 16 The quaternary ammonium hydroxide serves as a pH adjuster to adjust the pH to the alkaline range.

[0072] The 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.

[0073] 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.

[0074] Preferably, the quaternary ammonium hydroxide may be selected from C4 to C8 alkyl quaternary ammonium hydroxides, in particular from tetramethylammonium hydroxide and tetraethylammonium hydroxide.

[0075] polyols

[0076] The cleaning composition comprises one or more C2 to C 10 Polyols. These polyols help increase surface wetting and dissolve polymer residues from the wafer surface.

[0077] In a preferred embodiment, C2 to C 10 The polyol is selected from the group consisting of: k A compound of CH2OH, wherein k is 0 or an integer from 1 to 8.

[0078] In a preferred embodiment, C2 to C 10The polyol is selected from ethylene glycol, glycerol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, erythritol, pentaerythritol, trimethylolpropane, galactitol, fucitol, iditol, inositol, volemitol, propylene glycol, 1,4-butanediol, diethylene glycol, and combinations thereof, more preferably selected from ethylene glycol, glycerol, erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, propylene glycol, 1,4-butanediol, diethylene glycol, and combinations thereof.

[0079] Particularly preferred are combinations of C4 to C8 polyols, preferably a combination of sorbitol and at least one C2 or C3 polyol, most preferably a combination of sorbitol and ethylene glycol.

[0080] The polyol may be present in an amount of about 0.5% to about 5% by weight of a C2 to C 10 The polyol is preferably present in an amount of about 0.7% to about 4.5% by weight, more preferably about 0.8% to about 4% by weight, even more preferably about 1% to about 3% by weight, and most preferably about 1% to about 2.5% by weight.

[0081] In preferred embodiments, the polyol comprises or consists essentially of about 0.2% 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.

[0082] Polyalkoxylated polyethyleneimine

[0083] The composition for removing post-etch residue from a substrate comprises a polyalkoxylated polyethyleneimine. The polyalkoxylated polyethyleneimine in combination with benzethonium chloride or benzalkonium chloride helps significantly reduce molybdenum corrosion when removing post-etch residue from a wafer surface.

[0084] The polyalkyleneimine of the polyalkyleneimine backbone is understood to mean a compound consisting of a saturated hydrocarbon chain with a terminal amino functional group, which is interrupted by a secondary amino group and a tertiary amino group. Such backbones can be straight or branched. Of course, different polyalkyleneimine backbones can be used in mixtures thereof. Based on the pH of the surrounding environment, some or all of the amido groups on the polyalkyleneimine can also be reversibly converted into quaternary (cationic) ammonium groups. Alternatively, it is also possible that the modification of the polymer backbone makes it possible for the amido groups to be quaternized. In this article, no matter the ambient pH, the polyalkyleneimine of the polyalkyleneimine will carry a cationic charge. Preferably, the polyalkyleneimine of the polyalkyleneimine has a cationic charge.

[0085] The backbone comprises primary, secondary and tertiary amine nitrogen atoms connected by "linker" units. The backbone comprises essentially three types of units and it is emphasized that these groups can be distributed in any order along the backbone.

[0086] The units constituting the polyalkyleneimine backbone are (a) primary units having the formula:

[0087] [H2N-C2H4]- and -NH2

[0088] It terminates the main chain and any branch chains;

[0089] (b) a secondary amine unit having the formula:

[0090]

[0091] and (c) a tertiary amine unit having the formula:

[0092]

[0093] They are the branching points of the main chain and the secondary chain. E1 The continuation of the chain structure through branching means A E1 All primary, secondary and tertiary amine units mentioned above may be present except for the terminal -NH2 groups.

[0094] The polyalkyleneimines 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. Pat. No. 2,182,306, U.S. Pat. No. 3,033,746, U.S. Pat. No. 2,208,095, U.S. Pat. No. 2,806,839, and U.S. Pat. No. 2,553,696.

[0095] In addition, the polyalkyleneimine backbone may be partially substituted by an alkylating agent. The substituents may be selected from C1 to C 12 Alkyl, C2 to C 12 Alkenyl, C2 to C 12 Alkynyl, C6 to C 20 Alkyl aryl, C6 to C 20 Arylalkyl, C6 to C 20 Aryl. Preferred substituents may be selected from C1 to C6 alkyl, C6 to C 12 Alkyl aryl, C6 to C 12 Arylalkyl, and C6 to C 12 Aryl. Preferably, the aryl is phenyl or naphthyl. The terminal group [H2N-X L1 ]- and -NH2 can also be replaced by groups R L3replace.

[0096] Suitable examples of alkylating agents are organic compounds containing active halogen atoms, such as arylalkyl halides, alkyl halides, alkenyl halides and alkynyl halides. In addition, compounds such as alkyl sulfates, alkyl sultones, epoxides and the like can also be used. Non-limiting examples of corresponding alkylating agents include benzyl chloride, propane sultone, dimethyl sulfate, (3-chloro-2-hydroxypropyl) trimethylammonium chloride and the like. It is preferred to use dimethyl sulfate and / or benzyl chloride.

[0097] During the formation of the polyamine backbone, cyclization may occur and, therefore, a certain amount of cyclic polyamines may be present in the parent polyalkyleneimine backbone mixture. Each primary and secondary amine unit of the cyclic alkyleneimines undergoes modification by the addition of polyoxyalkylene units in the same manner as for linear and branched polyalkyleneimines.

[0098] The term "polyalkoxylated polyethyleneimine" means a polyethyleneimine in which the N-hydrogen atom is substituted by a polyoxyalkylene group comprising a C2 to C6 oxyalkylene repeating unit, preferably a C2 to C4 oxyalkylene repeating unit, more preferably a C2 to C3 oxyalkylene repeating unit, and most preferably a C2 oxyalkylene repeating unit.

[0099] Typically, polyalkyleneimines can be prepared as described above. Polyalkoxylation is then carried out by reacting the corresponding alkylene oxide with polyethyleneimine. The synthesis of polyalkylene oxide groups is well known to those skilled in the art. For example, comprehensive details are provided in "Polyoxyalkylenes" in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, Electronic Release. When using two or more different alkylene oxides, the polyoxyalkylene groups formed can be random copolymers, gradient copolymers or block copolymers.

[0100] The modification of the NH 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 an amount such that substantially all of the hydrogen atoms of the NH units of the polyalkyleneimine are converted to hydroxyalkyl groups, giving a monoalkoxylated polyalkyleneimine. The water is then 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 alkoxylation step, further amounts of alkylene oxide are added to the reaction product of the first step, resulting in a polyalkoxylated polyalkyleneimine containing the desired average number of alkylene oxide units per NH 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 alkoxylation step can be carried out in an organic solvent, such as xylene or toluene. For the correct metering of the alkylene oxide, it is advisable to determine the number of primary and secondary amino groups of the polyalkyleneimine before the alkoxylation.

[0101] Alternatively, polyalkoxylation can also be achieved by graft copolymerization of polyethyleneimine.

[0102] The polyalkyleneimines of polyalkoxylation can optionally be functionalized with groups other than H in a further reaction step. The type of functionalization depends on the desired end use. Depending on the functionalizing agent, the chain ends can be hydrophobic or more hydrophilic. Additional functionalization can be used to modify the properties of the polyalkyleneimines of polyalkoxylation. For example, the hydroxyl groups present in the polyalkyleneimines of polyoxyalkylation can be converted by suitable reagents capable of reacting with the hydroxyl groups. The esterification of hydroxyl groups with acids is a representative reaction.

[0103] Alternatively, carboxyl functionalized polyalkoxylated polyethyleneimines can be obtained by Michael addition reaction with suitable α, β-unsaturated substances (such as acrylic acid, methacrylic acid, etc.). Preferably, the polyalkoxylated polyethyleneimines are functionalized with carboxylic acid groups. Michael addition or Michael 1,4 addition is a reaction between a Michael donor (enolate or other nucleophilic reagent such as an amine) and a Michael acceptor (usually an α, β-unsaturated carbonyl / carboxyl group) to produce a Michael adduct by generating a carbon-carbon bond at the β-carbon of the acceptor. This type of reaction is also called an aza-Michael addition. A further description of this is provided in Additions to and substitutions at C-Cπ-Bonds, M. Mauduit, A. Denicourt-Nowicki, Comprehensive Organic Synthesis (Second Edition), 2014.

[0104] 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 spherical structure. Hyperbranched polymers typically exhibit significant irregularities in branching patterns and structures, which typically result in significant changes in molecular weight (often referred to as polydispersity). A useful metric for assessing 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 the total number of branched repeat units included in (a) the polymer to the total number of repeat units included in (b) the polymer. Hyperbranched polymers with 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. Usually, caution should be exercised when interpreting the degree of branching information of a hyperbranched polymer. For example, certain hyperbranched polymers may exhibit a degree of branching of less than about 0.2, but include one or more hyperbranched polymer segments (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 long chains of linear repeating units. If fully chain-extended, the overall degree of branching of such polymers may be less than about 0.2.

[0105] The mass average molecular weight M of the polyalkoxylated polyalkyleneimine w The weight average molecular weight M of the polyalkoxylated polyalkyleneimine may be from about 500 g / mol to about 500,000 g / mol. w The lower limit of the weight average molecular weight M is generally about 1500 g / mol, preferably about 2500 g / mol, more preferably about 5000 g / mol.w The upper limit of the molecular weight is generally 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 800 to 25,000 g / mol, most particularly 5,000 to 25,000 g / mol. The molecular weight can be determined by size exclusion chromatography (e.g., GPC) using polymethyl methacrylate (PMMA) as a standard and hexafluoroisopropanol + 0.05% potassium trifluoroacetate as an eluent.

[0106] The polyalkoxylated polyalkyleneimine may be present in an amount of from about 0.01% to about 1% by weight, preferably from about 0.015% to about 0.8% by weight, more preferably from about 0.02% to about 0.7% by weight, even more preferably from about 0.04% to about 0.5% by weight, and most preferably from about 0.05% to about 0.3% by weight. It has been found that amounts of polyalkoxylated polyalkyleneimine below 0.01 wt.% are insufficient to protect the platinum on the wafer surface. On the other hand, further increases in concentration above 1 wt.% are possible but do not significantly improve the corrosion inhibition properties of the polyethyleneimine. In addition, since many components are involved in obtaining the composition, a delicate balance is typically required to ensure colloidal stability. Here, the presence of high amounts (above 1 wt.%) of (polymer) components such as polyalkoxylated polyethyleneimine may be detrimental to the long-term stability of the multi-component system, especially in a substantially aqueous medium. The presence of 0.01 to 1% by weight of polyalkoxylated polyethyleneimine in the composition results in good PERR properties while ensuring good colloidal stability, even under long-term tests.

[0107] Benzethonium chloride or benzalkonium chloride

[0108] Benzethonium chloride or benzalkonium chloride significantly reduces the corrosion of molybdenum, especially molybdenum metal lines, when removing post-etch residues from the wafer surface. It was found that the addition of benzethonium chloride or benzalkonium chloride resulted in a lower etch rate on blanket PVD Mo compared to compositions without benzethonium chloride or benzalkonium chloride, but still allowed good, preferably complete, removal of etch residues.

[0109] Benzalkonium chloride refers to a compound having the following formula and is known to be a mixture of various chemical substances.

[0110]

[0111] n=8,10,12,14,16,18

[0112] Preferably, the composition comprises benzethonium chloride.

[0113] Therefore, this ensures the possibility of the composition comprising a higher water content (preferably at least 40 wt.%, more preferably at least 45 wt.%, even more preferably at least 50 wt.%, most preferably at least 51 wt.%). Such substantially aqueous compositions not only have economic benefits, but also have a positive environmental impact.

[0114] Benzethonium chloride or benzalkonium chloride is present in an amount of about 0.001% to about 0.17% by weight, preferably about 0.005% to about 0.15% by weight, more preferably about 0.008% to about 0.12% by weight. At concentrations > 0.17% by weight, undesirable colloidal instability is observed in the composition.

[0115] water

[0116] The etching compositions of the present invention are water-based and therefore contain water. Water has several functions, such as dissolving one or more components in the composition, serving as a carrier for the components, serving as an auxiliary agent for removing residues, serving as a viscosity modifier for the composition, and serving as a diluent. Preferably, the water employed in the composition is deionized (DI) water. The scope of water described in the following paragraph includes all water in the composition from any source.

[0117] For most applications, the weight percent of water in the composition will exist within a range having a starting point and an ending point selected from the following 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 water. Still other preferred embodiments of the present invention may include water in an amount to achieve the desired weight percents of the other ingredients.

[0118] Preferably, the composition is substantially water-based.

[0119] Preferably, the composition comprises at least 40 wt.%, more preferably 45 wt.%, even more preferably at least 50 wt.%, most preferably at least 51 wt.% water.

[0120] chelating agents

[0121] The cleaning compositions may optionally contain one or more chelating agents.

[0122] Preferred chelating agents are 1,2-cyclohexylidene dinitrilotetraacetic acid, 1,1,1,5,5,5-hexafluoro-2,4-pentane-dione, acetylacetonate, 2,2'-azanediyldiacetic 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, hydroxyquinolinesulfonic acid, sulfosalicylic acid, salicylic acid, pyridine, 2-ethylpyridine, 2-methoxypyridine, 3-methoxypyridine, 2-methylpyridine, lutidine, piperidine, piperazine, ethylamine, methylamine, isobutylamine, tert-butylamine, tributylamine, dipropylamine, dimethylamine, di Glycolamine, 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, gamma-butyrolactone, and mixtures thereof.

[0123] The chelating agent may be 1,2-cyclohexylidene dinitrilotetraacetic acid (CDTA) or may include CDTA and one or more of the other chelating agents mentioned above.

[0124] Also preferred are compositions according to the present invention as defined herein wherein the one or more chelating agents are present in an amount of 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, based on the total weight of the composition.

[0125] surfactants

[0126] The composition may further comprise one or more surfactants.

[0127] Preferred surfactants are selected from the group consisting of:

[0128] (i) anionic surfactants, preferably selected from the group consisting of ammonium lauryl sulfate, fluorosurfactants, preferably selected from the group consisting of perfluorinated alkylsulfonamide salts (preferably perfluorinated, N-substituted alkylsulfonamide ammonium salts, PNAAS), perfluorooctanesulfonates, perfluorobutanesulfonates, perfluorononanoates and perfluorooctanoates; alkyl-aryl ether phosphates and alkyl ether phosphates;

[0129] (ii) a zwitterionic surfactant, 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

[0130] (iii) a nonionic surfactant, which is preferably selected from the group consisting of glucoside alkyl ethers, glycerol alkyl ethers, cocamide ethanolamine and lauryl dimethylamine oxide.

[0131] More preferred surfactants in the composition according to the invention are or comprise perfluorinated, N-substituted alkylsulfonamide ammonium salts.Preferred surfactants (E) in the composition according to the invention do not comprise metals or metal ions.

[0132] Also preferred are compositions according to the invention as defined herein wherein the one or more surfactants are present in an amount 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, based on the total weight of the composition.

[0133] 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, dioctadecyl dihydrogen phosphate, dodecylamine, dodecenylsuccinic acid monodiethanolamide, lauric acid, palmitic acid, oleic acid, sabinic acid, 12-hydroxystearic acid, and dodecyl phosphate; polyoxyethylene lauryl ether (Emalmin NL-100 (Sanyo, Brij 30, Brij 98, Brij 35), dodecenylsuccinic acid monodiethanolamide (DSDA, Sanyo), ethylenediaminetetra(ethoxylate-block-propoxylate)tetraol (Tetronic 90R4), polyethylene glycol (e.g., PEG400), polypropylene glycol, polyethylene glycol ethers or polypropylene glycol ethers, 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-dimethyldec-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 (Tween 80), 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 (Gales), silicone-polyether copolymers such as Silwet L-77 (Setre Chemical Company), Silwet ECO spreader (Momentive), and ethoxylated fluorosurfactants ( FSO-100, FSN-100); cetyltrimethylammonium bromide (CTAB), heptadecafluorooctanesulfonic acid, tetraethylammonium, stearyltrimethylammonium chloride (EconolTMS-28, Sanyo Co., Ltd.), 4-(4-diethylaminophenylazo)-1-(4-nitrobenzyl)pyridinium bromide, cetylpyridinium chloride monohydrate, 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.

[0134] In some embodiments, the compositions of the present invention will be free or substantially free of any or all of the optional surfactants listed above.

[0135] Other commonly known optional components (such as dyes, pH adjusters, stabilizers, buffers, dispersants, chemical modifiers, biocides, etc.) can be included in the cleaning composition in conventional amounts to the extent that they do not adversely affect the performance of the composition, for example, in an amount up to a total of about 1% or 5% or 10% by weight of the composition. The presence of one or more of the above optional ingredients can benefit the composition, for example, the presence of a dispersant can positively affect the colloidal stability of the composition.

[0136] Alternatively, the cleaning compositions may be free or substantially free of any or all of the optional components listed above.

[0137] Composition

[0138] The preparation method of the composition for removing the residue after etching from substrate is generally known.These methods can be used to prepare the composition of the invention claimed herein.Cleansing composition is typically prepared by mixing the components together in a container at room temperature until all solids have been dissolved in a water-based medium.This can be carried out by dispersing or dissolving the components (b), (c), (d), (e) and (f) described above in a solution of a water-miscible organic solvent (a) and water (g).Optional ingredients (such as pH adjusting agents or surfactants) can be added simultaneously with other ingredients (b)-(f).For this purpose, conventional and standard mixing methods and mixing equipment can be used, such as stirred vessel, high shear impeller, ultrasonic mixer, homogenizer nozzle or countercurrent mixer.

[0139] The solubility of components (b) to (f) in the solution of the water-miscible organic solvent (a) and water (g) is a key criterion, and in this regard, the addition of one or more components is not limited to any particular order. However, in order to ensure long-term storage stability, one or more components (a) to (g) may be added in part or in full before use. For example, all components of the composition may be combined at the manufacturer, before use and / or during use.

[0140] Typically, the pH of the composition may be in the range of 8 to 14. In preferred embodiments, 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.

[0141] Cleaning compositions are particularly preferred wherein the composition comprises or consists essentially of:

[0142] (a) 10 to 60% by weight of a water-miscible aprotic organic solvent, in particular a sulfoxide or sulfone, most in particular dimethyl sulfoxide or sulfolane;

[0143] (b) 4 to 15% by weight of C1-C 12Amines, especially alkanolamines, most especially 2-(methylamino)ethan-1-ol;

[0144] (c) 0.1% to 4% by weight of C4 to C 16 Quaternary ammonium hydroxides, particularly C4 to C8 quaternary ammonium hydroxides, most particularly tetramethylammonium hydroxide or tetraethylammonium hydroxide;

[0145] (d) 0.5% to 5% by weight of C2 to C 10 Polyols, particularly those having the formula HOCH2(CHOH) k Compounds of CH2OH (wherein k is 0 or an integer from 1 to 8), most particularly sorbitol, ethylene glycol or mixtures thereof;

[0146] (e) 0.01 to 1% by weight of polyalkoxylated polyethyleneimine, in particular polyalkoxylated polyethyleneimine functionalized with carboxylic acid groups, most in particular polyalkoxylated polyethyleneimine functionalized with carboxylic acid groups and having a mass average molecular weight of 500 to 500 000 g / mol;

[0147] (f) 0.001% to 0.17% by weight of benzethonium chloride or benzalkonium chloride; and

[0148] (g) water;

[0149] Another cleaning composition is particularly preferred, wherein the composition comprises or consists essentially of:

[0150] (a) 20 to 50% by weight of a water-miscible aprotic organic solvent;

[0151] (b) 7 to 13% by weight of an amine;

[0152] (c) 0.5 to 3% by weight of a quaternary ammonium hydroxide;

[0153] (d) 1% to 3% by weight of C2 to C 10 polyols;

[0154] (e) 0.02% to 0.5% by weight of a polyalkoxylated polyethyleneimine;

[0155] (f) 0.005% to 0.15% by weight of benzethonium chloride or benzalkonium chloride; and

[0156] (g) Water.

[0157] In this context, "substantially" means that the content of any other compounds than the specifically mentioned compounds is below 1% by weight, preferably below 0.1% by weight, even more preferably below 0.01% by weight, most preferably below the detection limit.

[0158] Compositions according to the invention as defined herein are particularly preferred, wherein the composition consists of compounds as defined herein and to be defined on the basis of the examples.

[0159] application

[0160] In another aspect, there is provided a method of removing post-etch residue from a substrate comprising a surface of a molybdenum layer, the method comprising:

[0161] (a) providing a microelectronic device surface, the microelectronic device surface comprising a surface of a molybdenum layer and post-etching residue thereon;

[0162] (b) providing a composition as described herein;

[0163] (c) contacting the surface with the composition for a period of time and at a temperature effective to remove post-etch residue while not damaging the molybdenum layer.

[0164] Without limitation, such layers may be present in conductive lines of a semi-damascene structure.

[0165] It will be appreciated that it is common practice to prepare concentrated forms of the composition that are to be diluted prior to use. For example, the composition may be manufactured in a more concentrated form and thereafter diluted with water and / or other water-miscible solvents at the manufacturer's site, prior to use and / or during use.

[0166] When using the compositions described herein, the composition is typically contacted with the device structure for a sufficient time at a temperature effective to remove post-etch residue while not damaging the molybdenum layer. Preferably, the contact time is from about 1 minute to about 200 minutes, more preferably from about 1 minute to about 10 minutes, at a temperature preferably in the range of about 30° C. to about 90° C., more preferably from about 35° C. to about 60° C. Such contact times and temperatures are illustrative, and any other suitable time and temperature conditions effective to achieve the desired removal selectivity may be employed.

[0167] After achieving the desired etching behavior, the composition can be easily removed from the microelectronic device to which it has been previously applied, for example, by rinsing, washing, or one or more other removal steps as may be desired 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, steam drying, etc.).

[0168] Preferably, the composition has a Mo etch rate of ≤ 14 A / min, more preferably ≤ 12.0 A / min, most preferably ≤ 9.0 A / min, measured at 40°C.

[0169] The contacting step is followed by an optional rinsing step. The rinsing step can be performed 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 performed using a mixture of deionized water and an organic solvent such as isopropyl alcohol. The organic solvent can be the same as or different from the water-miscible organic solvent (a).

[0170] The contacting step and optional rinsing step are followed by an optional drying step, which is performed by any suitable means, such as isopropyl alcohol (IPA) vapor drying, heating, or by centripetal force.

[0171] The compositions described herein may be advantageously used in a method for the manufacture of a semiconductor device comprising the step of selectively removing post-etch residues from the surface of a microelectronic device comprising a molybdenum layer as described herein.

[0172] The following examples shall further illustrate the present invention without limiting the scope of the present invention.

[0173] Examples

[0174] An etching experiment was conducted as follows on a full-surface sample including a PVD Mo layer having a thickness of 47.5 nm.

[0175] Place 100 ml of etching solution in a 150 ml beaker and place the beaker in a temperature-controlled water bath. Then immerse a 2.5 cm x 2.5 cm sample of the corresponding substrate in the test solution at the desired temperature while stirring the solution at 250 rpm. Etch both full-surface samples for 2 minutes, then rinse with deionized water (DIW) for 30 seconds, and then dry the sample with an N2 gun. Full-surface sample etching experiments were performed at 40°C and 60°C.

[0176] The thickness of the entire sample was determined by XRF measurement.

[0177] The etching rate is calculated according to the following formula:

[0178]

[0179] Example 1

[0180] Prepare 100 g of the composition by adding the following components in the order specified:

[0181] 1.52.99g DIW

[0182] 2.34 g DMSO (from BASF)

[0183] 3.10.3 g 2-(Methylamino)ethan-1-ol (from ACROS)

[0184] 4.1g ethylene glycol (from BASF)

[0185] 5.4 g of 25 wt.% TMAH solution in DIW (from BASF)

[0186] 6.0.6g sorbitol (from BASF)

[0187] 7.0.1 g of acrylic acid functionalized polyethoxylated polyethyleneimine copolymer (M) having an average of 10 EO / NH groups w =25 000 g / mol) (from BASF)

[0188] 8. 0.01 g benzethonium chloride or benzalkonium chloride (from Sigma-Aldrich)

[0189] The solution was stirred with a magnetic stir bar at 100 rpm during mixing.

[0190] Compositions with different components and concentrations (see Table 1 below) were prepared in the same order as above, and the amount of DIW was adjusted to make the total weight up to 100.

[0191] The Mo etch rates (ER) of the solutions at 40° C. and 60° C. were determined on blank samples. The compositions and results are shown in Table 1.

[0192] Table 1

[0193]

[0194] All Examples IE through IE4 were found to be colloidally stable (soluble) and also provided improved Mo corrosion inhibition, as evidenced by the low Mo etch rates in Table 1. On the other hand, Comparative Example C1, which did not include benzethonium chloride or benzalkonium chloride, produced a higher Mo etch rate than any of the formulations (Examples IE1 through IE4) that included varying concentrations of benzethonium chloride or benzalkonium chloride. Both the concentration and selection of components are critical to ensuring not only suitable performance but also suitable colloidal stability. Comparative Example C2, which included 0.2 wt.% benzethonium chloride, produced a turbid or cloudy solution and unacceptable Mo inhibition, thus demonstrating colloidal instability at concentrations exceeding the critical concentration range (0.01 to 0.17 wt.% relative to the total weight of the composition). Furthermore, the presence of benzethonium chloride alone (at a suitable concentration) did not provide suitable Mo inhibition, whereas the combination of components listed in Table 1 did. For example, the absence of polyalkoxylated polyethyleneimine in Comparative Example C3 was found to result in poor Mo inhibition.

Claims

1. A composition for removing post-etch residue 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) 4 to 15% by weight of C1-C 12 amine; (c) 0.1% to 4% by weight of C4 to C 16 quaternary ammonium hydroxides; (d) 0.5% to 5% by weight of C2 to C 10 polyols; (e) 0.01 to 1% by weight of polyalkoxylated polyethyleneimine; (f) 0.001% to 0.17% by weight of benzethonium chloride or benzalkonium chloride; and (g) Water.

2. The composition according to claim 1, wherein The organic solvent is an aprotic organic solvent containing sulfur, in particular from the group consisting of sulfoxides or sulfones.

3. A composition according to any one of the preceding claims, wherein The organic solvent is selected from dimethyl sulfoxide, diethyl sulfoxide, methyl ethyl sulfoxide, dipropyl sulfoxide or sulfolane.

4. A composition according to any one of the preceding claims, wherein The amine is selected from C1 to C 10 Alkylamine or C2 to C 10 Alkanolamines.

5. A composition according to any one of the preceding claims, wherein The amine is 2-(methylamino)ethan-1-ol.

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

7. A composition according to any one of the preceding claims, wherein The C2 to C 10 The polyol is selected from the group consisting of: k A compound of CH2OH, wherein k is 0 or an integer from 1 to 8.

8. A composition according to any one of the preceding claims, 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, heptyl alcohol, propylene glycol, 1,4-butanediol, diethylene glycol, or a combination thereof.

9. A composition according to any one of the preceding claims, wherein The polyalkoxylated polyethyleneimine has a mass average molecular weight Mw of 500 to 500 000 g / mol, preferably 5 000 to 25 000 g / mol.

10. A composition according to any one of the preceding claims, wherein The polyalkoxylated polyethyleneimine has ethylene oxide repeating units in the range of 2 to 25, preferably 5 to 15 repeating units.

11. A composition according to any one of the preceding claims, wherein The polyalkoxylated polyethyleneimine is functionalized with carboxylic acid groups.

12. A composition according to any preceding claim having a pH of from 10 to 13, preferably from 11 to 12.

5.

13. A 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) 0.5 to 3% by weight of a quaternary ammonium hydroxide; (d) 1% to 3% by weight of C2 to C 10 polyols; (e) 0.02 to 3% by weight of a polyalkoxylated polyethyleneimine; (f) 0.005% to 0.15% by weight of benzethonium chloride or benzalkonium chloride; and (g) Water.

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

15. A method for removing post-etch residue from a substrate comprising a surface of a molybdenum layer, the composition comprising: (a) providing a microelectronic device surface, the microelectronic device surface comprising the surface of the molybdenum layer and post-etching residue thereon; (b) providing a composition according to any one of claims 1 to 13; (c) contacting the surface with the composition for a period of time and at a temperature effective to remove the post-etch residue while not damaging the molybdenum layer.

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