Use of a composition for cleaning the surface of a semiconductor substrate comprising nickel and aluminium, respective composition and process

Abstract

Described herein is the use of a composition comprising one or more organic nitrogen compounds for cleaning the surface of a semiconductor substrate, wherein said surface comprises a binary metallic material comprising nickel and aluminium, and a respective composition. Moreover, described is herein a process for the manufacture of a semiconductor device involving said composition comprising one or more organic nitrogen compounds.

Description

[0001] Use of a composition for cleaning the surface of a semiconductor substrate comprising nickel and aluminium, respective composition and process

[0002] The present invention relates to the use of a composition comprising one or more organic nitrogen compounds for cleaning the surface of a semiconductor substrate, wherein said surface comprises a binary metallic material comprising nickel and aluminium, and to a respective composition. Moreover, the present invention relates to a process for the man- ufacture of a semiconductor device involving said composition comprising one or more organic nitrogen compounds.

[0003] Resists such as deep UV photo resists or electron beam resists are used in the microlitho- graphic technique for producing a wide range of electrical devices, e.g. semiconductor integrated circuits (ICs), liquid crystal panels, organic electroluminescent panels, printed cir- cuit boards, micro machines, DNA chips and micro plants, in particular ICs with LSI (large- scale integration) or VLSI (very-large-scale integration).

[0004] Copper is customarily used as the low electrical resistance or wiring material in the electrical devices, in particular in the “vertical interconnect accesses” (“vias”) and interconnects contained in the ICs. The increasing use of copper and the ever decreasing dimensions of the electrical structures together with the ever increasing functionalities of the ICs require the use of low-k and ultra low-k materials in order to avoid problems with wiring resistance and wiring delay caused by high wiring capacities. These challenging developments have demanded and still demand the continuing optimization of the methods of manufacture and of the materials utilized therefore.

[0005] Although damascene patterning had to overcome many technical challenges, copperbased interconnects have been used for many consecutive technology nodes. As technology is progressing toward local “back end of line” (“BEOL”) interconnect metal pitches of 20 nm and smaller (for technology nodes beyond “N2”), the resistance of copper metal lines increases very fast at such small dimensions due to electron scattering at surfaces and at grain boundaries. Moreover, copper metal lines require a liner to prevent copper diffusion in the dielectric material. As this liner needs 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 a function of reducing critical dimension.

[0006] For the reasons outlined here above, different materials are currently reviewed in the technological field for their potential to replace copper in its function as interconnect material, where such candidate materials should retain all desired properties of copper, but avoid its shortcomings. A potential candidate for replacing copper in the interconnect application is a binary metallic compound comprising nickel and aluminium, preferably a Ni / AI-alloy, as is e.g. discussed by L. Chen et al. in Applied Physics Letters 113(18):183503, Oct. 2018 (lhtps: / / doi.org / 10.1063 / 1 .5049620). In industrial production processes involving wet cleaning of surfaces comprising such binary metallic compounds comprising nickel and aluminium, in particular wet cleaning of respective surfaces of semiconductor substrates, the lowest possible material loss and etching rates are demanded.

[0007] Document CN 105 552 117 A relates to a semiconductor device with a metal gate electrode and a manufacturing method thereof.

[0008] Document US 2009 / 01 18153 A1 deals with a liquid removal composition and process for removing photoresist and / or sacrificial anti-reflective coating (SARC) material from a microelectronic device having same thereon.

[0009] In the light of the prior art, there is still a need for a composition for effectively cleaning the surface of a semiconductor substrate comprising a binary metallic compound comprising nickel and aluminium (NiAl or Ni / AI binary alloy), where such composition also shows a low etching rate of aluminium and nickel which are present in said binary metallic compound comprising nickel and aluminium, on the surface of the semiconductor substrate. In this regard, it has been found that it is of high importance that the cleaning process does not | BASF SE | 231203 alter the composition of the binary metallic compound comprising nickel and aluminium on the surface of the semiconductor substrate, since the desired performance of the binary metallic compound comprising nickel and aluminium (the binary Ni / AI alloy) depends strongly on the preservation of the correct ratio of nickel and aluminium of said binary metallic compound.

[0010] Correspondingly, it was a primary object of the present invention to provide a composition which is suited for cleaning the surface of a semiconductor substrate, wherein said surface comprises a binary metallic material comprising nickel and aluminium and which composition shows a low etching rate of aluminium, nickel and of a binary metallic compound comprising nickel and aluminium, on the surface of the semiconductor substrate. It was a further object of the present invention to provide a composition for the purpose explained above, which in addition shows a favourable EHS-profile (environment, health and safety-profile), i.e. which composition comprises components, in particular organic nitrogen compounds, which exhibit a comparatively low risk to human health and / or to the safety of the workplace and the environment.

[0011] It has now been found that the primary object and other objects of the present invention can be accomplished by the use of a composition comprising as components

[0012] A) one or more organic nitrogen compounds, selected from the group consisting of:

[0013] A1) a compound of formula I wherein

[0014] R1and R2are, independently of each other, hydrogen or alkyl having 1 to 3 carbon atoms, which may optionally be substituted once by hydroxy;

[0015] R3and R4are, independently of each other, hydrogen or alkyl having 1 to 2 carbon atoms, which may optionally be substituted once by hydroxy; SE | 231203

[0016] R5is hydrogen or alkyl having 1 to 2 carbon atoms, which may optionally be substituted once by hydroxy;

[0017] R20is hydrogen or alkyl having 1 to 2 carbon atoms; and n is 1 or 2;

[0018] A2) a compound of formula II wherein

[0019] R6is hydrogen, -NH2 or -N(H)-CH3;

[0020] R7is hydrogen or alkyl having 1 to 2 carbon atoms;

[0021] R8is hydrogen, alkyl having 1 to 2 carbon atoms or phenyl; with the proviso that R7and R8are not both hydrogen when R6is hydrogen; or R7and R8, together with the nitrogen atom to which they are bonded, form a 5- or 6-membered carbocyclic ring, wherein one ring carbon atom may optionally be replaced by oxygen;

[0022] A3) a compound of formula III wherein

[0023] R9and R10are, independently of each other, alkyl having 1 to 3 carbon atoms, which may optionally be substituted once by hydroxy;

[0024] R11is hydrogen, alkyl having 1 to 3 carbon atoms, which may optionally be substituted once by hydroxy, and

[0025] R12is hydrogen or alkyl having 1 to 2 carbon atoms; and

[0026] A4) a compound of formula IV and

[0027] R14and R15, together with the nitrogen atom to which they are bonded, form a 5- or 6-membered carbocyclic ring, wherein one ring carbon atom may optionally be replaced by -N(H)- or by oxygen and wherein one ring carbon atom may optionally be part of a carbonyl group;

[0028] B) one or more water-miscible, dipolar-aprotic organic solvents,

[0029] C) one or more quaternary alkyl ammonium hydroxides having 4 to 16 carbon atoms;

[0030] D) one or more organic polyol compounds having 2 to 10 carbon atoms, and

[0031] F) water for cleaning the surface of a semiconductor substrate, wherein said surface comprises a binary metallic material comprising nickel and aluminium.

[0032] The invention as well as preferred variants and preferred combinations of parameters, properties and elements thereof are defined in the appended claims. Preferred aspects, details, modifications and advantages of the present invention are also defined and explained in the following description and in the examples stated below.

[0033] It has now be found that a composition as disclosed herein is particularly suited for the use of cleaning the surface of a semiconductor substrate, wherein said surface comprises a binary metallic material comprising nickel and aluminium and which composition shows a low etching rate of aluminium, nickel and of a binary metallic compound comprising nickel and aluminium, on the surface of the semiconductor substrate.

[0034] It has further been found that said composition disclosed herein, in particular preferred variants of said composition, in addition shows (or show, respectively) a favourable EHS- profile (environment, health and safety-profile), i.e. such composition comprises components, in particular organic nitrogen compounds, which exhibit a comparatively low risk to human health and / or to the safety of the workplace and the environment. Preferred variants of said composition disclosed herein e.g. comprise organic nitrogen compounds of component A) which do not carry one, two, three or which do not carry any of the four labels selected from the group consisting of “GHS02”, “GHS05”, “GHS07” or“GHS08”, according to the “Globally harmonized system of classification and labelling of chemicals”.

[0035] Without wishing to be bound by theory, the present inventors currently believe that the role of component A) in the composition for use according to the present invention as described herein lies mainly in the beneficial removal of polymer residues, e.g. post-etch and / or postash residues.

[0036] Preferred is a use according to the present invention as defined herein (or a use according to the present invention as described herein as being preferred), comprising as component

[0037] A) one or more organic nitrogen compounds, selected from the group consisting of:

[0038] A1) a compound of formula la wherein

[0039] R1aand R2aare, independently of each other, hydrogen or alkyl having 1 to 2 carbon atoms;

[0040] R3aand R4aare, independently of each other, hydrogen, alkyl having 1 to 2 carbon atoms, or -CH2-OH;

[0041] R5ais hydrogen or -(CH2)2-OH; and n is 1 or 2;

[0042] A2) a compound of formula Ila wherein

[0043] R6is hydrogen, -NH2 or -N(H)-CH3;

[0044] R7ais hydrogen;

[0045] R8ais hydrogen, -CH3 or phenyl, with the proviso that R7aand R8aare not both hydrogen when R6is hydrogen, or R7aand R8a, together with the nitrogen atom to which they are bonded, form a 5- or 6-membered carbocyclic ring, wherein one ring carbon atom may optionally be replaced by oxygen; and

[0046] A3) a compound of formula Illa | BASF SE | 231203 wherein

[0047] R9aand R10aare, independently of each other, alkyl having 1 to 2 carbon atoms, or - CH2-C(H)(CH3)-OH;

[0048] R11ais hydrogen, alkyl having 1 to 2 carbon atoms or -CH2-C(H)(CH3)-OH, and

[0049] R12ais hydrogen or -CH3; preferably in a total amount in the range of from 5 to 25 wt.-%, based on the total weight of the composition.

[0050] It has been found in own experiments, that the use of a composition as defined in the preferred variant of the present invention as described here above results in particularly beneficially low etching rates of nickel and / or aluminium which are present in a binary metallic compound comprising nickel and aluminium (in particular a Ni / AI-alloy), and is associated with a comparatively low risk to human health and / or to the safety of the workplace and the environment (as explained above).

[0051] Also preferred is a use according to the present invention as defined herein (or a use according to the present invention as described herein as being preferred), wherein the one or more organic nitrogen compounds of component A) is selected from the group consisting of tris(hydroxymethyl)amino-ethane, 2-(2-aminoethoxy)ethanol, 2- [2-(dimethylamino)eth- oxy]ethanol), 2-amino-2-methyl-1 -propanol, 3-amino-1 -propanol, monoethanolamine; N- formylmorpholine, urea, 1 ,3-dimethylurea, formanilide; 2-[2-(dimethylaminoethyl)-methyla- mino]-ethanol and N,N,N’,N’-tetrakis(2-hydroxypropyl)ethylenediamine, preferably is selected from the group consisting of tris(hydroxymethyl)amino-ethane, 2-(2- aminoethoxy)ethanol, 2- [2-(dimethylamino)ethoxy]ethanol), 2-amino-2-methyl-1 -propanol, N-formylmorpholine, urea, 1 ,3-dimethylurea, formanilide; 2-[2-(dimethylaminoethyl)-me- thylamino]-ethanol and N,N,N’,N’-tetrakis(2-hydroxypropyl)ethylenediamine, and more preferably is selected from the group consisting of urea, 1 ,3-dimethylurea, formanilide; 2-[2-(dimethylaminoethyl)-methylamino]-ethanol and N,N,N’,N’-tetrakis(2-hy- droxypropyl)ethylenediamine.

[0052] It has been found in own experiments, that the use of a composition as defined in the preferred variant of the present invention as described here above results in most cases in even more beneficially low etching rates of nickel and / or aluminium aluminium which are present in a binary metallic compound comprising nickel and aluminium (in particular a Ni / AI-alloy), and is associated in most cases with a particularly comparatively low risk to human health and / or to the safety of the workplace and the environment (as explained above).

[0053] Preferred is then a use according to the present invention as defined herein (or a use according to the present invention as described herein as being preferred), wherein the composition

[0054] - comprises as further component:

[0055] E) one or more polyalkoxylated polyethyleneimines, preferably in a total amount in the range of from 0.01 to 2 wt.-%, more preferably of from 0.05 to 1 wt.-%, based on the total weight of the composition; and / or

[0056] - has a pH value in the range of from 11 to 14, preferably of from 13 to 14.

[0057] Without wishing to be bound by theory, the present inventors currently believe that the role of (optional) component E) in the composition for use according to the present invention as described herein lies mainly in supporting the beneficial removal of polymer residues from the surface of a semiconductor substrate, e.g. post-etch and / or post-ash residues.

[0058] As used herein, the term “polyalkoxylated polyethyleneimine(s)” means polyethylene- imine(s) whose N-hydrogen atoms are at least partially substituted by polyoxyalkylene groups comprising oxyalkylene repeat units, wherein the oxyalkylene repeat units comprise 2 to 6, preferably 2 to 4, more preferably 2 carbon atoms. Generally, the polyalkyleneimines of said polyalkoxylated polyethyleneimine(s) can be prepared as described here below.

[0059] The polyalkoxylation of the polyethyleneimine(s) is then performed by reacting the respective alkylene oxides with the polyethyleneimines, as is outlined in more detail here below.

[0060] The one or more polyalkoxylated polyethyleneimines of component E) in the composition for use according to the present invention are therefore polyalkoxylated polyethyleneimines having polyethyleneimine backbones, the latter of which are to be understood as meaning compounds which consist of a saturated hydrocarbon chain with terminal amino functions which is interrupted by secondary and tertiary amino group. Such backbones may be linear or branched. Different polyethyleneimine backbones can be used in a mixture with one another. Based on the pH of the ambient environment, some or all the amine groups of a polyalkoxylated polyethyleneimine may also be reversibly converted to quaternary (cationic) ammonium groups. Alternatively, modification of the polymer backbone such that the amine groups are quaternized is also possible. As used herein, the polyalkoxylated poly- ethyeleneimine will usually bear a cationic charge irrespective of ambient pH. Preferably, the polyalkoxylated polyethyleneimine has a cationic charge.

[0061] Said polyethyleneimine backbones comprise primary, secondary and tertiary amine nitrogen atoms connected by "linking" units. The backbone comprises essentially three types of units, and these groups may be distributed along the backbone in any order. The units which may make up the polyalkyleneimine backbones comprise:

[0062] (a) primary units selected from the group consisting of a unit of formula “[H2N-C2H4]-“ and a unit of formula “-NH2”, which primary units terminate the main backbone and any branching chains;

[0063] (b) secondary amine units having the formula V: and

[0064] (c) tertiary amine units having the formula VI: which are the branching points of the main and secondary backbone chains, AE1representing a continuation of the chain structure by branching. Continuation of the chain structure by branching here means that AE1may contain all primary, secondary and tertiary amine units described above except termination group -NH2.

[0065] 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, sulphuric 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

[0066] In addition, the polyalkyleneimine backbones may be partly substituted by alkylating agents.

[0067] The substituents may be selected from alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkynyl having 2 to 12 carbon atoms, alkylaryl having 6 to 20 carbon atoms, arylalkyl having 6 to 20 carbon atoms and aryl having 6 to 20 carbon atoms. Preferred substituents may be selected from alkyl having 1 to 6 carbon atoms, alkylaryl having 6 to 12 carbon atoms, arylalkyl having 6 to 12 carbon atoms, and aryl having 6 to 12 carbon atoms. It is preferred that any aryl group is phenyl or naphthyl.

[0068] Suitable examples for alkylating agents are organic compounds which contain active halogen atoms, such as arylalkyl halides, alkyl, alkenyl and alkynyl halides, and the like. Additionally, compounds such as alkyl sulfates, alkyl sultones, epoxides, and the like may also be used. Non-limiting examples of corresponding alkylating agents comprise benzyl chloride, propane sultone, dimethyl sulfate, (3-chloro-2-hydroxypropyl) trimethyl ammonium chloride, or the like. Preference is given to using dimethyl sulfate and / or benzyl chloride.

[0069] During the formation of the polyamine backbones, cyclization may occur. Therefore, an amount of cyclic polyamine may be present in the parent polyalkyleneimine backbone mixture. Most of or each primary and secondary amine unit of the cyclic alkyleneimines undergoes modification by the addition of polyoxyalkylene units in the same manner as linear and branched polyalkyleneimines.

[0070] The synthesis of polyalkylene oxide groups is known to those skilled in the art. Comprehensive details are given, for example, in “Polyoxyalkylenes” in Ullmann’s Encyclopedia of Industrial Chemistry, 6thEdition, Electronic Release. When two or more different alkylene oxides are used, the polyoxyalkylene groups formed may be random copolymers, gradient copolymers or block copolymers.

[0071] The modification of the N-H units in the polymer backbone with oxyalkylene units is carried out, for instance, by first reacting the polymer, preferably polyethyleneimine, with one or more alkylene oxides, preferably ethylene oxide, propylene oxide, or mixtures thereof, in the presence of up to 80 % by weight of water at a temperature of from about 25 to about 150 °C, preferably in an autoclave fitted with a stirrer. In the first step of the reaction alkylene oxide is added in such an amount that at least nearly all hydrogen atoms of the N- H-units of the polyalkyleneimine are converted into hydroxyalkyl groups to give monoalkox- ylated polyalkyleneimines. The water is then removed from the autoclave. Afterthe addition of a basic catalyst, for example sodium methylate, potassium tertiary butylate, potassium hydroxide, sodium hydroxide, sodium hydride, potassium hydride or an alkaline ion exchanger, in an amount of 0.1 to 15 % by weight with reference to the addition product obtained in the first step of the alkoxylation, further amounts of alkylene oxide are added to the reaction product of the first step so that a polyalkoxylated polyalkyleneimine is obtained which contains the intended average number of alkylene oxide units per N-H unit of the polymer. A second step may be carried out for instance at temperatures of from about 60 to about 150 °C. The second step of the alkoxylation may be carried out in an organic solvent such as xylene or toluene. For the correct metered addition of the alkylene oxides, it is advisable, before the alkoxylation, to determine the number of primary and secondary amine groups of the polyalkyleneimine.

[0072] Alternatively, the polyalkoxylation may also be achieved by graft-copolymerization of polyethyleneimine.

[0073] The polyalkoxylated polyalkyleneimines may optionally be functionalized with groups different from hydrogen in a further reaction step. The type of functionalization depends on the desired end use. According to the functionalizing agent, the chain end can be hydro- phobized or more strongly hydrophilized. An additional functionalization can serve to modify the properties of the polyalkoxylated polyalkyleneimines. For instance, the hydroxy groups present in the polyoxyalkylated polyalkyleneimines are converted by means of suitable agents, which are capable of reaction with hydroxy groups. Esterification of the hydroxy groups with acids is one representative reaction.

[0074] Alternatively, the carboxylic functionalized polyalkoxylated polyethyleneimines may be obtained by Michael addition reaction with suitable a, p-unsaturated species, such as acrylic acid, methacrylic acid, among others. Preferably, the polyalkoxylated polyethyleneimine is functionalized with carboxylic acid groups. The Michael addition or Michael 1 ,4 addition is a reaction between a Michael donor (an enolate or other nucleophile such as amines) and a Michael acceptor (usually an a, p-unsaturated carbonyl / carboxyl) to produce a Michael adduct by creating a carbon-carbon bond at the acceptor's p-carbon. Such reactions are also called aza-michael additions. Further description of the same is provided in “Comprehensive Organic Synthesis” 4 (2nded. 2014) 189-341 , Elsevier Ltd. (ISBN 978-0-08- 097743-0), see chapter “Additions to and substitutions at C-C u-Bonds” by M. Mauduit et al.

[0075] Furthermore, the polyalkoxylated polyethyleneimine may have a high degree of branching, preferably the polyalkoxylated polyethyleneimine is hyperbranched. As used herein, the term “hyperbranched” refers to highly branched polymers that typically exhibit a globular structure. Hyperbranched polymers typically exhibit substantial irregularity in terms of branching pattern and structure, which typically results in substantial variation in molecular weight (often referred to as polydispersity). One useful measure 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 (a) the total number of branch repeat units included in a polymer to (b) the total number of repeat units included in the polymer. Hyperbranched polymers having any suitable degree of branching may be employed in compositions described herein. In certain embodiments, the hyperbranched polymers exhibit a degree of branching of at least about 4 to 20 monomer units per molecule. Care should generally be exercised in interpreting degree of branching information for hyperbranched polymers. For example, certain hyperbranched polymers may exhibit a degree of branching of less than about 0.2 yet include one or more hyperbranched polymer portions (or subunits) that exhibit a degree of branching of greater than about 0.2. This may be the case, for example, when a hyperbranched polymer core is chain extended using long chains of linear repeat units. If sufficiently chain extended, the overall degree of branching for such a polymer may be less than about 0.2.

[0076] The mass average molecular mass Mw of the polyalkoxylated polyalkyleneimine as used in component E) of the composition for use according to the present invention may be of from about 500 g / mol to about 500 000 g / mol. The lower limit of the weight average molecular mass Mw of the polyalkoxylated polyalkyleneimine is generally about 1 500 g / mol, preferably about 2 500 g / mol, more preferably about 5 000 g / mol. The upper limit of the weight average molecular mass Mw is generally about 500 000 g / mol, preferably about 150 000 g / mol, more preferably about 50 000 g / mol, most preferably about 25 000 g / mol. A particularly preferred range is of from 800 to 25 000 g / mol, most particularly 5 000 to 25 000 g / mol. The molecular mass can preferably be determined by size exclusion chromatography, in particular by gel permeation chromatography (GPC) using polymethylmethacrylate (PMMA) as standard and hexafluorisopropanol + 0.05% potassium trifluoracetate as eluent.

[0077] Preferred is then also a use according to the present invention as defined herein (or a use according to the present invention as described herein as being preferred), wherein in the composition

[0078] - the one or more water-miscible, dipolar-aprotic organic solvents of component B) of the composition is selected from the group consisting of tetra hydrofuran, N-methylpyr- rolidone, dimethyl sulfoxide, sulfolane, diethylsulfoxide, methylethyl-sulfoxide, dipropyl sulfoxide, diphenylsulfoxide, methylphenylsulfoxide and 1 ,1 ’-dihydroxyphenyl sulfoxide; preferably is selected from the group consisting of tetrahydrofuran, N-methylpyrroli- done, dimethyl sulfoxide and sulfolane; and / or

[0079] - the quaternary alkyl ammonium hydroxide (also known as tetraalkyl ammonium hydroxide) having 4 to 16 carbon atoms of component C) of the composition is selected from the group consisting of tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium and (2-hydroxyethyl)triethylammonium hydroxide; and / or

[0080] - the one or more organic polyol compounds having 2 to 10 carbon atoms of component D) of the composition is selected from the group consisting of ethylene glycol, glycerol, erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, propylene glycol, 1 ,4-butanediol and diethylene glycol; preferably is selected from the group consisting of ethylene glycol, glycerol, xylitol, mannitol, sorbitol, propylene glycol and diethylene glycol.

[0081] Preferably, the one or more water-miscible, dipolar-aprotic organic solvents of component B) of the composition described above serve for dissolving other components in the composition and for improving the efficiency and solubility of organic residue removal from the surface of the semiconductor substrate to be cleaned. The composition for use according to the present invention may comprise only one water-miscible, dipolar-aprotic organic solvent of component B) or it may comprise a mixture of two or more of such water-miscible, dipolar-aprotic organic solvents. In one preferred variant of the present invention, the composition for use according to the present invention comprises only one water-miscible, dipolar-aprotic organic solvent, preferably dimethylsulfoxide.

[0082] Preferably, the one or more quaternary alkyl ammonium hydroxides having 4 to 16 carbon atoms of component C) of the composition described above serve to adjust the pH of the respective composition to an alkaline pH range.

[0083] Preferably, the one or more organic polyol compounds having 2 to 10 carbon atoms of component D) of the composition described above serve to increase the wetting of the surface of the semiconductor substrate to be cleaned, and (where applicable) to dissolve any polymer residues from said surface. Preferably the one or more organic polyol compound is different from any other components in the composition, in particular from the one or more water-miscible dipolar-aprotic organic solvent(s) of component B) and from the one or more organic nitrogen compounds of component A). The composition for use according to the present invention may comprise only one organic polyol compound having 2 to 10 carbon atoms of component D) or it may comprise a mixture of two or more such organic polyol compounds. A mixture of two organic polyol compounds is preferred forthe purposes of the present invention. In one preferred variant of the present invention, the composition for use according to the present invention comprises a mixture of ethylene glycol and sorbitol as component D).

[0084] Moreover, there is preferred a use according to the present invention as defined herein (or a use according to the present invention as described herein as being preferred), wherein

[0085] - the total amount of the one or more nitrogen compounds of component A) of the composition (or of the preferred nitrogen compounds of component A) of the composition which are selected from the preferred or more preferred groups as defined above, including from groups A1), A2) and A3)) is in the range of from 5 to 25 wt.-%, preferably of from 5 to 20 wt.-%, more preferably of from 7 to 18 wt.-%, based on the total weight of the composition; and / or

[0086] - the total amount of the one or more water-miscible, dipolar-aprotic organic solvents of component B) of the composition (or of the preferred one or more water-miscible, dipolar-aprotic organic solvents of component B) of the composition which are selected from the preferred or more preferred groups as defined above) is in the range of from 20 to 60 wt.-%, preferably of from 12 to 50 wt.-%, more preferably of from 15 to 45 wt.- %, yet more preferably in the range of from 20 to 40 wt.-%, based on the total weight of the composition; and / or

[0087] - the total amount of the one or more quaternary ammonium hydroxide having 4 to 16 carbon atoms of component C) of the composition (or of the preferred one or more quaternary ammonium hydroxide(s) having 4 to 16 carbon atoms of component C) of the composition which are selected from the preferred or more preferred groups as defined above) is in the range of from 0.5 to 4 wt.-%, preferably of from 0.6 to 3.5 wt.- %, more preferably of from 0.7 to 2.5 wt.-%, based on the total weight of the composition; and / or

[0088] - the total amount of the one or more organic polyol compounds having 2 to 10 carbon atoms of component D) of the composition (or of the preferred one or more organic polyol compounds having 2 to 10 carbon atoms of component D) of the composition which are selected from the preferred or more preferred groups as defined above) is in the range of from 0.3 to 4 wt.-%, preferably of from 0.4 to 3 wt.-%, more preferably of from 0.5 to 2.5 wt.-%, based on the total weight of the composition; and / or

[0089] - the composition comprises one or more unsubstituted polyethyleneimines in a total amount of at most < 0.01 wt.-%, preferably of at most < 0.009 wt.-%, based on the total weight of the composition, more preferably wherein the composition does not comprise unsubstituted polyethyleneimines.

[0090] It has been found in own experiments that a composition comprising at least the components A), B) C) and D) in the total amounts or preferred total amounts as defined here above is excellently suited for the purpose of cleaning the surface of a semiconductor substrate, wherein said surface comprises a binary metallic material comprising nickel and aluminium. Preferred total amounts of the component A) as provided here above, when combined with preferred total amounts of components B) C) and / or D) as provided here above, result in particularly preferred compositions for the purpose of cleaning the surface of a semiconductor substrate, wherein said surface comprises a binary metallic material comprising nickel and aluminium (preferably a Ni / AI-alloy), according to the present invention.

[0091] A particularly preferred variant of the present invention therefore relates to the use of a composition according to the present invention as defined herein (or a use according to the present invention as described herein as being preferred), wherein

[0092] - the total amount of the one or more nitrogen compounds of component A) of the composition (or of the preferred nitrogen compounds of component A) of the composition which are selected from the preferred or more preferred groups as defined above, including from groups A1), A2) and A3)) is in the range of from 7 to 18 wt.-%, based on the total weight of the composition; and / or (preferably and)

[0093] - the total amount of the one or more water-miscible, dipolar-aprotic organic solvents of component B) of the composition (or of the preferred one or more water-miscible, dipolar-aprotic organic solvents of component B) of the composition which are selected from the preferred or more preferred groups as defined above) is in the range of from 20 to 40 wt.-%, based on the total weight of the composition; and / or (preferably and)

[0094] - the total amount of the one or more quaternary ammonium hydroxide(s) having 4 to 16 carbon atoms of component C) of the composition (or of the preferred one or more quaternary ammonium hydroxide having 4 to 16 carbon atoms of component C) of the composition which are selected from the preferred or more preferred groups as defined above) is in the range of from 0.7 to 2.5 wt.-%, based on the total weight of the composition; and / or (preferably and)

[0095] - the total amount of the one or more organic polyol compounds having 2 to 10 carbon atoms of component D) of the composition (or of the preferred one or more organic polyol compounds having 2 to 10 carbon atoms of component D) of the composition which are selected from the preferred or more preferred groups as defined above) is in the range of 0.5 to 2.5 wt.-%, based on the total weight of the composition.

[0096] In a certain variant of the present invention is preferred the use of a composition according to the present invention as defined herein (or a use according to the present invention as described herein as being preferred) wherein the composition comprises one or more unsubstituted polyethyleneimines in a total amount of at most < 0.01 wt.-%, preferably of at most < 0.009 wt.-%, based on the total weight of the composition, more preferably wherein the composition does not comprise unsubstituted polyethyleneimines.

[0097] As used herein, the term “unsubstituted polyethyleneimines” means polyethyleneimines which are not “polyalkoxylated polyethyleneimine(s)” as defined above as forming optional component E) of the compositions described here above in the context of the use according to the present invention, i.e. such “unsubstituted polyethyleneimines” are polyethylene- imine(s) whose N-hydrogen atoms are not substituted by polyoxyalkylene groups comprising oxyalkylene repeat units. Any “unsubstituted polyethyleneimines” as discussed herein are therefore different from the “polyalkoxylated polyethyleneimine(s)” which may optionally be present as component E) of the composition described here above in the context of the use according to the present invention.

[0098] Generally, said “unsubstituted polyalkyleneimines” can be prepared as described here above in the context of the preparation of the “polyalkoxylated polyethyleneimine(s)”, however, with the difference that the “unsubstituted polyalkyleneimines” are not polyalkoxylated by reacting any alkylene oxides with the unsubstituted polyethyleneimines.

[0099] As is known in the relevant field of technology, concentrated forms of the composition to be used according to the present invention and described here above may be used perse, or / where applicable) may be diluted prior to use. For example, said composition may be manufactured in a more concentrated form and may thereafter be diluted with water and / or with other components at the manufacturer site, before use and / or during use.

[0100] In certain variants, a use of a composition according to the present invention as defined herein (or a use according to the present invention as described herein as being preferred) may therefore also be preferred, wherein the composition described here above is used in diluted form, preferably as 1 :1 (w / w) dilution with deionized water, as 1 :10 (w / w) dilution with deionized water, or as 1 :100 (w / w) dilution with deionized water.

[0101] Accordingly, a use of a composition according to the present invention as defined herein may be preferred in certain cases (or a use according to the present invention as described herein as being preferred), wherein

[0102] - the total amount of the one or more nitrogen compounds of component A) of the composition (or of the preferred nitrogen compounds of component A) of the composition which are selected from the preferred or more preferred groups as defined above, including from groups A1), A2) and A3)) is in the range of from 2.5 to 12.5 wt.-%, or from 0.5 to 2.5 wt.-%, or from 0.05 to 0.25 wt.-%, based on the total weight of the composition; and / or

[0103] - the total amount of the one or more water-miscible, dipolar-aprotic organic solvents of component B) of the composition (or of the preferred one or more water-miscible, dipolar-aprotic organic solvents of component B) of the composition which are selected from the preferred or more preferred groups as defined above) is in the range of from 10 to 30 wt.-%, or from 2 to 6 wt.-%, or from 0.2 to 0.6 wt.-%, based on the total weight of the composition; and / or

[0104] - the total amount of the one or more quaternary ammonium hydroxide(s) having 4 to 16 carbon atoms of component C) of the composition (or of the preferred one or more quaternary ammonium hydroxide having 4 to 16 carbon atoms of component C) of the composition which are selected from the preferred or more preferred groups as defined above) is in the range of from 0.25 to 2 wt.-%, or from 0.05 to 0.4 wt.-%, or from 0.005 to 0.04 wt.-%, based on the total weight of the composition; and / or

[0105] - the total amount of the one or more organic polyol compounds having 2 to 10 carbon atoms of component D) of the composition (or of the preferred one or more quaternary ammonium hydroxide having 4 to 16 carbon atoms of component C) of the composition which are selected from the preferred or more preferred groups as defined above) is in the range of from 0.15 to 2 wt.-%, or from 0.03 to 0.4 wt.-%, or from 0.003 to 0.04 wt.- %, based on the total weight of the composition.

[0106] A use of a composition according to the present invention as defined herein is furthermore preferred (or a use according to the present invention as described herein as being preferred), wherein the cleaning of the semiconductor substrate’s surface comprises:

[0107] - removing post-etch and / or post ash residue from the surface of the semiconductor substrate, wherein said surface comprises a binary metallic material comprising nickel and aluminium (preferably a Ni / AI-alloy) and the composition is in contact with said binary metallic material; and / or

[0108] - removing residues and / or contaminants from the surface of the semiconductor substrate, wherein said surface comprises a binary metallic material comprising nickel and aluminium (preferably a Ni / AI-alloy) and the composition is in contact with said binary metallic material.

[0109] The present invention also pertains to a composition comprising at least components A), B), C), D) and F) as defined here above with regard to the use of said composition (or to a respective composition as defined here above as being preferred), preferably for cleaning a semiconductor substrate comprising a surface which comprises a binary metallic material comprising nickel and aluminium (preferably a Ni / AI-alloy).

[0110] Generally, all aspects of the present invention discussed herein in the context of the use of the composition for cleaning the surface of a semiconductor substrate according to the present invention as defined herein, apply mutatis mutandis to the composition comprising at least components A), B), C), D) and F) according to the present invention as defined herein, and vice versa.

[0111] More specifically, a composition according to the present invention as defined herein is preferred (or a composition according to the present invention as described herein as being preferred), wherein the one or more organic nitrogen compounds of component A) are selected from the group consisting of urea, 1 ,3-dimethylurea, formanilide; 2-[2-(dimethylami- noethyl)-methylamino]-ethanol and N,N,N’,N’-tetrakis(2-hydroxypropyl)ethylenediamine.

[0112] Likewise preferred is a composition according to the present invention as defined herein (or a composition according to the present invention as described herein as being preferred), wherein the composition comprises unsubstituted polyethyleneimines in a total amount of at most < 0.01 wt.-%, preferably of at most < 0.009 wt.-%, based on the total weight of the composition, more preferably wherein the composition does not comprise unsubstituted polyethyleneimines.

[0113] Under a further aspect, the present invention also relates to a method of making a semiconductor device from a semiconductor substrate, comprising the steps:

[0114] P1) providing or preparing a semiconductor substrate comprising a surface, wherein said surface comprises a binary metallic material comprising nickel and aluminium,

[0115] P2) providing or preparing a composition comprising at least components A), B), C), D) and F) as defined here above in the context of the use of said composition for cleaning the surface of a semiconductor substrate according to the present invention (or to a respective composition as defined here above as being preferred)

[0116] P3) contacting the semiconductor substrate’s surface, including the binary metallic material, at least once with the composition provided or prepared in step P2).

[0117] Generally, all aspects of the present invention discussed herein in the context of the use of the composition for cleaning the surface of a semiconductor substrate according to the present invention as defined herein and / or of the composition comprising at least components A), B), C), D) and F) according to the present invention as defined herein, apply mutatis mutandis to the method of making a semiconductor device from a semiconductor substrate according to the present invention as described herein, and vice versa.

[0118] In the method of making according to the present invention as described herein, the composition may typically be contacted with the semiconductor substrate’s surface, including the binary metallic material, for a sufficient time and at an appropriate temperature for effecting cleaning the surface of the semiconductor substrate, wherein said surface comprises a binary metallic material comprising nickel and aluminium (preferably a Ni / AI-alloy).

[0119] A sufficient time for effecting cleaning the surface of the semiconductor substrate is preferably in the range of from 1 minute to 200 minutes, more preferably from 1 minute to 10 minutes. An appropriate temperature for effecting cleaning the surface of the semiconductor substrate is preferably in the range of from 30 °C to 90 °C, more preferably from 35 °C to 60 °C.

[0120] Following the achievement of the desired cleaning action, the said composition may preferably be removed from the semiconductor substrate’s surface to which it has previously been applied, e.g., by rinsing, washing, or other removal step(s), as may be desired and efficacious in a given application of the composition. For example, the semiconductor substrate’s surface may be rinsed with a rinse solution including deionized water and / or an organic solvent (e.g. isopropanol) and / or may be dried (e.g., spin-dried, dried with a N2- gun, vapor-dried etc.) for removing the said composition from the semiconductor substrate’s surface.

[0121] Preferred is a method according to the present invention as defined herein (or a method according to the present invention as described herein as being preferred), wherein the binary metallic material comprising nickel and aluminium is or comprises a Ni / AI-alloy.

[0122] Moreover is preferred a method according to the present invention as defined herein (or a method according to the present invention as described herein as being preferred), wherein the semiconductor substrate provided or prepared in step P1) has post-etch and / or post ash residues on its said surface and the process comprises as additional step:

[0123] P4a) removing the post-etch and / or post ash residues from the surface of the semiconductor substrate, preferably together with the composition which was contacted before with the semiconductor substrate’s surface in step P3).

[0124] In a further variant of the present invention is preferred a method according to the present invention as defined herein (or a method according to the present invention as described herein as being preferred), wherein the semiconductor substrate provided or prepared in step P1) has residues and / or contaminants on its said surface and the method comprises as additional step:

[0125] P4b) removing residues and / or contaminants from the surface of the semiconductor substrate, preferably together with the composition which was contacted before with the semiconductor substrate’s surface in step P3). I BASF SE 1 231203

[0126] Examples:

[0127] The following examples are meant to further explain and describe the invention without limiting its scope.

[0128] Example 1 : Preparation of compositions for cleaning the surface of a semiconductor sub- strate

[0129] The following compositions C01 to C023 (see tables 1 and 2 for details) for cleaning the surface of a semiconductor substrate, wherein said surface comprises a binary metallic material comprising nickel and aluminium (preferably a Ni / AI-alloy), were prepared by mixing the components (A) to (F) as shown in table 1 below. For mixing, the solutions were stirred with a magnetic stirring bar at a speed of 500 rpm.

[0130] Table 1 : Components of compositions for cleaning the surface of a semiconductor substrate

[0131] Table 2: Components A) (A1) to A4)) of compositions for cleaning the surface of a semi-conductor substrate BASFSE | 231203

[0132] Example 2: Measurement of etch rates of compositions on Ni and Al substrates

[0133] The etch rates of compositions C01 to C23 from Example 1 were determined on Ni and Al substrates, respectively.

[0134] Blank 300 mm nickel test substrates (common test wafers with diameter 300 mm) having thicknesses of 30 nm, or blank aluminium substrates having thicknesses of 30 nm, were obtained from commercial sources and broken into smaller coupons. Then, the initial thicknesses of the nickel or aluminium substrates were measured by wavelength dispersive X- ray fluorescence (“WD-XRF”) analysis in a manner known per se (cf. e.g. N. Ekinci et al. in “X-Ray Fluorescence in Biological Sciences: Principles, Instrumentation and Applications”, 1sted., John Wiley & Sons Ltd., 2022, or H. Takahara in Rigaku Journal, 33(2), 2017).

[0135] For the etching experiments, 100 g of each etching solution C01 to C23 was prepared and placed into a 150 ml beaker. The beaker was placed in a temperature-controlled (40 °C) water bath and two coupons of the kind to be measured (Ni or Al, respectively) were dipped for 2 min. each into the etching solution, while the etching solution was stirred at 300 rpm speed.

[0136] Thereafter, the coupons were withdrawn from the etching solution, rinsed with deionized water and dried with a nitrogen gun. Subsequently, the final thicknesses of the nickel or aluminium substrates so treated were determined by X-ray fluorescence (“XRF”) analysis in a manner known per se. The etching rates observed in these experiments were calculated as follows and are shown (in units of [A / min.]) in table 3 below (cf. 4thand 5throws): [Thickness after etching (A)] — [Thickness before etching (A)]

[0137] Etching rate Etching time (min. )

[0138] In table 3 below, the entry “Etch rate Ni on Ni / AI-alloy substrate” means the determination of the Ni / AI-alloy etch rate by determination of the Ni XRF-intensity. Similarly, the entry “Etch rate Al on Ni / AI-alloy substrate” means the determination of the Ni / AI-alloy etch rate by determination of the Al XRF-intensity. | BASF SE 231203

[0139] Table 3: Etch rates of compositions on Ni substrates, Al substrates and Ni / AI substrates

[0140] Example 3: Measurement of etch rates of compositions on Ni / AI substrates

[0141] The etch rates of compositions C01 to C23 from Example 1 were also determined on substrates comprising a binary metallic material comprising nickel and aluminium (i.e. a Ni / AI- alloy), as explained here below:

[0142] Blank Ni / AI-alloy test substrates (2 x 2 cm) having thicknesses of 33 nm were obtained from Interuniversity Microelectronics Centre, Leuven, Belgium (IMEC). Then, the initial thicknesses of the Ni / AI-alloy substrates were measured by Rigaku AZX400 WD-XRF analysis in a manner known per se (cf. e.g. N. Ekinci et al., see above): The individual elements (nickel or aluminium, respectively) and their intensities were converted for this purpose into the respective thickness values, as is further explained here below:

[0143] A protocol was set up in advance in the XRF computer, using a coupon of NiAI-alloy as standard, with a given thickness of about 33 nm. The initial thickness of the standard was determined by transmission electron microscopy (“TEM”) analysis. In the protocol, the measured Ni and Al intensities from the standard sample were set individually corresponding to 30 nm thickness, and linear calibration relations between intensity and thickness were made for Ni and Al individually. Once measuring an experimental sample using this protocol, the measured intensity of Ni and Al in the sample were automatically converted into equivalent thicknesses by the protocol.

[0144] The etching experiments were performed analogously to the etching experiments discussed in Example 2 above. The etching rates observed in the experiments of this Example 3 were calculated as discussed below and are shown (in units of [A / min.]) in table 3 above (see 2ndand 3rdrows):

[0145] In an experiment, before and after the cleaning process, the samples were measured by XRF, and equivalent thicknesses of Ni and Al intensities were recorded, and the equivalent thickness losses were converted into the etch rates by dividing the thickness loss by the respective process time. An example of this experimental procedure is provided here below:

[0146] Before the cleaning process, a NiAI-coupon was measured by XRF using 1) Al intensity giving an equivalent thickness of 304.179 A (AI-KA intensity of 34.7258 kcps); and 2) Ni intensity giving an equivalent thickness of 244.367 A (Ni-KA intensity of 11.1929 kcps).

[0147] Afterthe cleaning process, a NiAl coupon was measured by XRF using 1) Al intensity giving an equivalent thickness of 294.935 A (AI-KA intensity of 33.7142 kcps); and 2) Ni intensity giving an equivalent thickness of 242.874 A (Ni-KA intensity of 11 .1247 kcps).

[0148] The loss of equivalent thickness determined by the differences of the Al signals before and after the cleaning process (9.244 A) was then divided by the process time (2 minutes) to give the cleaning process etch rate of 4.622 A / min; and the loss of equivalent thickness determined by the differences of the Ni signals before and afterthe cleaning process (1 .493 A) was then divided by the process time (2 minutes) to give the respective etch rate of 0.7465 A / min.

[0149] These etch rates (for Al and Ni) were averaged with the respective results of another coupon to give the reported value.

[0150] Compositions for use according to the present invention which showed etch rates on Ni / AI- alloy substrates of aluminium of < 10 A / min. and of nickel of < 3 A / min. in table 3 above are generally regarded herein as suited for the use of cleaning the surface of a semiconductor substrate, wherein said surface comprises a binary metallic material comprising nickel and aluminium.

[0151] Compositions for use according to the present invention which showed etch rates on Ni / AI- alloy substrates of aluminium of < 9 A / min. and of nickel of < 2 A / min. in table 3 above are regarded herein as preferably suited for the use of cleaning the surface of a semiconductor substrate, wherein said surface comprises a binary metallic material comprising nickel and aluminium.

[0152] Compositions for use according to the present invention which showed etch rates on Ni / AI- alloy substrates of aluminium of < 8 A / min. and of nickel of < 1 A / min. in table 3 above are regarded herein as particularly preferably suited for the use of cleaning the surface of a semiconductor substrate, wherein said surface comprises a binary metallic material comprising nickel and aluminium.

[0153] It can therefore be seen from the results shown in table 3 above that the compositions C01 , C02, C03, C06, C07, C12, C15, C16 are preferably suited for the use of cleaning the surface of a semiconductor substrate, wherein said surface comprises a binary metallic material comprising nickel and aluminium (Ni / AI-alloy). I BASF SE 1 231203 | 231203WQ01 ~~~

[0154] The compositions C01 , C02, C03, C04, C05, C06, C07, C09, C10, C1 1 and C16 also show a particularly good EHS-profile.

[0155] Example 4: Measurement of etch rates of diluted compositions on Ni / AI substrates

[0156] Dilution experiments were conducted by adding 9 or 99 portions of deionized water (“DIW”) into 1 portion of an undiluted composition (as is shown in table 4 below) and the etch rates of the so diluted compositions were then determined on relevant substrates, as is also shown in table 4 below:

[0157] Etching experiments with the diluted compositions were performed analogously to the etching experiments discussed in Examples 2 and 3 above. The etching rates observed in the experiments of this Example 4 were calculated analogously as discussed in Examples 2 and 3 above and are shown (in units of [A / min.]) in table 4 below.

[0158] Table 4: Etch rates of diluted compositions on Ni substrates, Al substrates and Ni / AI substrates

Claims

| BASF SE231203Claims:1 . Use of a composition comprising as componentsA) one or more organic nitrogen compounds, selected from the group consisting of:A1) a compound of formula IwhereinR1and R2are, independently of each other, hydrogen, or alkyl having 1 to 3 carbon atoms, which may optionally be substituted once by hydroxy; R3and R4are, independently of each other, hydrogen or alkyl having 1 to 2 carbon atoms, which may optionally be substituted once by hydroxy;R5is hydrogen or alkyl having 1 to 2 carbon atoms, which may optionally be substituted once by hydroxy;R20is hydrogen or alkyl having 1 to 2 carbon atoms; and n is 1 or 2;A2) a compound of formula IIwherein1 231203 | 231203WQ01 ~~R6is hydrogen, -NH2 or -N(H)-CH3;R7is hydrogen or alkyl having 1 to 2 carbon atoms;R8is hydrogen, alkyl having 1 to 2 carbon atoms or phenyl; with the proviso that R7and R8are not both hydrogen when R6is hydrogen; or R7and R8, together with the nitrogen atom to which they are bonded, form a 5- or 6-membered carbocyclic ring, wherein one ring carbon atom may optionally be replaced by oxygen;A3) a compound of formula IIIwhereinR9and R10are, independently of each other, alkyl having 1 to 3 carbon atoms, which may optionally be substituted once by hydroxy;R11is hydrogen, alkyl having 1 to 3 carbon atoms, which may optionally be substituted once by hydroxy, and R12is hydrogen or alkyl having 1 to 2 carbon atoms; andA4) a compound of formula IVwherein| BASF SE231203R13is hydroxy or -NH2; andR14and R15, together with the nitrogen atom to which they are bonded, form a 5- or 6-membered carbocyclic ring, wherein one ring carbon atom may optionally be replaced by -N(H)- or by oxygen and wherein one ring carbon atom may optionally be part of a carbonyl group;B) one or more water-miscible, dipolar-aprotic organic solvents,C) one or more quaternary alkyl ammonium hydroxides having 4 to 16 carbon atoms,D) one or more organic polyol compounds having 2 to 10 carbon atoms, andF) water for cleaning the surface of a semiconductor substrate, wherein said surface comprises a binary metallic material comprising nickel and aluminium.

2. Use of a composition according to claim 1 , comprising as componentA) one or more organic nitrogen compounds, selected from the group consisting of:A1) a compound of formula laR1aand R2aare, independently of each other, hydrogen or alkyl having 1 to 2 carbon atoms;R3aand R4aare, independently of each other, hydrogen, alkyl having 1 to 2 carbon atoms or -CH2-OH;R5ais hydrogen or -(CH2)2-OH; and n is 1 or 2;A2) a compound of formula IlawhereinR6is hydrogen, -NH2 or -N(H)-CH3;R7ais hydrogen; R8ais hydrogen, -CH3 or phenyl, with the proviso that R7aand R8aare not both hydrogen when R6is hydrogen, or R7aand R8a, together with the nitrogen atom to which they are bonded, form a 5- or 6-membered carbocyclic ring, wherein one ring carbon atom may optionally be replaced by oxygen; andA3) a compound of formula IllawhereinR9aand R10aare, independently of each other, alkyl having 1 to 2 carbon atoms, or -CH2-C(H)(CH3)-OH;R11ais hydrogen, alkyl having 1 to 2 carbon atoms or -CH2-C(H)(CH3)-OH, andR12ais hydrogen or -CH3.

3. Use according to any of claims 1 or 2, wherein the one or more organic nitrogen compounds of component A) is selected from the group consisting of tris(hydroxymethyl)amino-ethane, 2-(2-aminoethoxy)ethanol, 2-[2-(dimethylamino) ethoxyjethanol), 2-amino-2-methyl-1 -propanol, 3-amino-1 -propanol, monoethanolamine; N-formylmorpholine, urea, 1 ,3-dimethylurea, formanilide; 2-[2-(dimethylami- noethyl)-methylamino]-ethanol and N,N,N’,N’-tetrakis(2-hydroxypropyl)ethylenedia- mine, preferably is selected from the group consisting of tris(hydroxymethyl)amino-ethane, 2-(2-aminoethoxy)ethanol, 2- [2-(dimethylamino)ethoxy]ethanol), 2-amino-2-methyl- 1-propanol, N-formylmorpholine, urea, 1 ,3-dimethylurea, formanilide; 2-[2-(dimethyl- aminoethyl)-methylamino]-ethanol and N,N,N’,N’-tetrakis(2-hydroxypropyl)ethylene- diamine, and more preferably is selected from the group consisting of urea, 1 ,3-dimethylurea, formanilide; 2-[2-(dimethylaminoethyl)-methylamino]-ethanol and N,N,N’,N’-tetra- kis(2-hydroxypropyl)ethylenediamine.

4. Use according to any of the preceding claims, wherein the composition comprises as further component:E) one or more polyalkoxylated polyethyleneimines, preferably in a total amount in the range of from 0.01 to 2 wt.-%, more preferably of from 0.05 to 1 wt.-%, based on the total weight of the composition.

5. Use according to any of the preceding claims, wherein the composition has a pH value in the range of from 11 to 14, preferably of from 13 to 14.

6. Use according to any of the preceding claims, wherein in the composition- the one or more water-miscible, dipolar-aprotic organic solvents of component B) of the composition is selected from the group consisting of tetrahydrofuran, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, diethylsulfoxide, methylethylsulfoxide, dipropyl sulfoxide, diphenylsulfoxide, methylphenylsulfoxide and 1 ,1 ’-dihydroxyphenyl sulfoxide; preferably is selected selected from the group consisting of tetrahydrofuran, N- methylpyrrolidone, dimethyl sulfoxide and sulfolane; and / or- the quaternary alkyl ammonium hydroxide having 4 to 16 carbon atoms of component C) of the composition is selected from the group consisting of tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium and (2-hydroxyethyl)triethylammonium hydroxide; and / or- the one or more organic polyol compounds having 2 to 10 carbon atoms of component D) of the composition is selected from the group consisting of ethylene glycol, glycerol, erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, propylene glycol, 1 ,4-butanediol and diethylene glycol; preferably is selected from the group consisting of ethylene glycol, glycerol, xylitol, mannitol, sorbitol, propylene glycol and diethylene glycol.

7. Use according to any of the preceding claims, wherein- the total amount of the one or more nitrogen compounds of component A) of the composition is in the range of from 5 to 25 wt.-%, preferably of from 5 to 20 wt.- %, more preferably of from 7 to 18 wt.-%, based on the total weight of the composition; and / or- the total amount of the one or more water-miscible, dipolar-aprotic organic solvents of component B) of the composition is in the range of from 20 to 60 wt.-%, preferably of from 12 to 50 wt.-%, more preferably of from 15 to 45 wt.-%, yet more preferably in the range of from 20 to 40 wt.-%, based on the total weight of the composition; and / or- the total amount of the one or more quaternary ammonium hydroxide having 4 to 16 carbon atoms of component C) of the composition is in the range of from 0.5 to 4 wt.-%, preferably of from 0.6 to 3.5 wt.-%, more preferably of from 0.7 to 2.5 wt.-%, based on the total weight of the composition; and / or- the total amount of the one or more organic polyol compounds having 2 to 10 carbon atoms of component D) of the composition is in the range of from 0.3 to 4 wt.-%, preferably of from 0.4 to 3 wt.-%, more preferably of from 0.5 to 2.5 wt.- %, based on the total weight of the composition; and / or- the composition comprises one or more unsubstituted polyethyleneimines in a total amount of at most < 0.01 wt.-%, preferably of at most < 0.009 wt.-%, based on the total weight of the composition, more preferably wherein the composition does not comprise unsubstituted polyethyleneimines.

8. Use according to any of the preceding claims, wherein the cleaning of the semiconductor substrate’s surface comprises- removing post-etch and / or post ash residue from the surface of the semiconductorsubstrate, wherein said surface comprises a binary metallic material comprising nickel and aluminium and the composition is in contact with said binary metallic material; and / or- removing residues and / or contaminants from the surface of the semiconductor substrate, wherein said surface comprises a binary metallic material comprising nickel and aluminium and the composition is in contact with said binary metallic material.

9. Composition as defined in any of claims 1 to 7, for cleaning a semiconductor substrate comprising a surface which comprises a binary metallic material comprising nickel and aluminium.

10. Composition according to claim 9, wherein the one or more organic nitrogen compounds of component A) are selected from the group consisting of urea, 1 ,3-dime- thylurea, formanilide; 2-[2-(dimethylaminoethyl)-methylamino]-ethanol and N,N,N’,N’-tetrakis(2-hydroxypropyl)ethylenediamine.11 . Composition according to any of claims 9 to 10, wherein the composition comprises unsubstituted polyethyleneimines in a total amount of at most < 0.01 wt.-%, preferably of at most < 0.009 wt.-%, based on the total weight of the composition, more preferably wherein the composition does not comprise unsubstituted polyethyleneimines.

12. Method of making a semiconductor device from a semiconductor substrate, comprising the steps:P1) providing or preparing a semiconductor substrate comprising a surface, wherein said surface comprises a binary metallic material comprising nickel and aluminium,P2) providing or preparing a composition as defined in any of claims 1 to 7, andP3) contacting the semiconductor substrate’s surface, including the binary metallic material, at least once with the composition provided or prepared in step P2).

13. Method according to claim 12, wherein the binary metallic material comprising nickel and aluminium is or comprises a NiAl alloy.BASF SE1 23120314. Method according to any of claims 12 or 13, wherein the semiconductor substrate provided or prepared in step P1) has post-etch and / or post ash residues on its said surface and the process comprises as additional stepP4a) removing the post-etch and / or post ash residues from the surface of the sem- iconductor substrate, preferably together with the composition which was contacted before with the semiconductor substrate’s surface in step P3).

15. Method according to any of claims 12 or 13, wherein the semiconductor substrate provided or prepared in step P1) has residues and / or contaminants on its said surface and the method comprises as additional step P4b) removing residues and / or contaminants from the surface of the semiconductor substrate, preferably together with the composition which was contacted before with the semiconductor substrate’s surface in step P3).

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