Compositions and methods for selectively etching aluminum compound-containing layers in the presence of low-K materials, copper, and / or cobalt layers.

Abstract

This invention describes a composition for selectively etching an aluminum compound-containing layer in the presence of a low-k material layer and / or a layer containing copper and / or cobalt, and the corresponding use of the composition. It further describes a method for manufacturing a semiconductor device, comprising the step of selectively etching at least one aluminum compound-containing layer by contacting the composition in the presence of a low-k material layer and / or a layer containing copper and / or cobalt.

Description

[0001] This invention relates to a composition for selectively etching an aluminum compound-containing layer in the presence of a low-k material layer and / or a layer containing copper and / or cobalt, and the corresponding use of the composition. The invention further relates to a method for manufacturing a semiconductor device, comprising the step of selectively etching the at least one aluminum compound-containing layer by contacting the composition in the presence of a low-k material layer and / or a layer containing copper and / or cobalt.

[0002] The method for manufacturing semiconductor devices involves a multi-step sequence of photolithography and chemical processing steps, during which electronic circuitry is gradually generated on a wafer made of pure semiconducting material (“semiconductor wafer”). Silicon is preferably used as the semiconductor material. Typical semiconductor wafers are made from extremely pure silicon grown in single-wafer column ingots (synthetic corundum) with a diameter of up to 300 mm using the so-called “Czochralski process.” These ingots are then diced into wafers approximately 0.75 mm thick and polished to obtain a very conventional and flat surface.

[0003] The specific methods used to manufacture semiconductor wafers are structured in several stages, which include processing stages such as the so-called "front-end-of-line" ("FEOL") and "back-end-of-line" ("BEOL") stages.

[0004] The FEOL (Front-End Surface Engineering) stage refers to the direct formation of transistors within the material of a semiconductor wafer (typically silicon). The raw semiconductor wafer is engineered by growing an ultrapure, virtually defect-free silicon layer via epitaxy. Following front-end surface engineering, the growth of the gate dielectric (e.g., silicon dioxide), gate patterning, source and drain patterning, and subsequent implantation or diffusion of dopants into the semiconducting material are performed to obtain the desired complementary electrical characteristics.

[0005] Once various devices (e.g., Dynamic Random Access Memory, DRAM; Static Random Access Memory, SRAM; Electrically Programmable Read-Only Memory, EPROM; or Complementary Metal-on-Silicon, CMOS) have been produced in the FEOL process, they must be interconnected to form the desired circuitry. This occurs in a series of wafer processing steps collectively known as BEOL. The BEOL processing stage involves creating metal interconnects on the surface of a semiconductor wafer through layers separated by materials with low dielectric constants (e.g., materials with a dielectric constant κ < 3.9) (also known as “low-k materials”). With the introduction of copper (Cu) instead of aluminum as the conductive material, complex multi-step manufacturing processes have been developed for forming integrated circuit (IC) interconnects on semiconductor substrates. These processes include various methods for selectively producing and removing successive layers of conductive and insulating (dielectric) materials, such as using chemical vapor deposition (CVD), electroplating, photolithography, wet or dry etching techniques, chemical mechanical polishing (CMP), and several cleaning steps, such as removing residues from the surface of the processed semiconductor substrate from previous material removal steps. In recent years, cobalt metal has also attracted much attention in the semiconductor industry, for example, for use in barrier layers or seed layers and / or for encapsulating copper interconnects to improve the methods of manufacturing semiconductor devices.

[0006] One such multi-step manufacturing method is called a damascene manufacturing method, which can be varied as bimetallic damascene methods, including TFVL ("grooving before via") bimetallic damascene method, VFTL ("via before groove") bimetallic damascene method, self-aligned bimetallic damascene method, or bimetallic damascene patterning method with metal hard shielding (for the latter see, for example, US6,696,222).

[0007] In damascene processing, the desired IC interconnect structure is patterned by etching the shape of the structure into the underlying interlayer dielectric (“ILD”) material. Following patterning, a thin barrier layer (e.g., made of Ta / TaN, TiN, CoWP, NiMoP, or NiMoB) is typically deposited on top of the etched structure as a copper diffusion barrier. On top of the barrier layer, a seed layer is typically deposited to support better adhesion of the copper to the underlying material; this seed layer also acts as a catalyst during the electroplating process. Typical materials used for these seed layers include compounds of Pd and Co, or other compounds such as polymers and organic materials. The original deposition method (metal damascene process) is designed to process each layer itself. Therefore, the so-called “vertical interconnect channels” (“vias”) and metallization layers have different processing steps and require a series of cleaning, material deposition, CMP, and another cleaning step for each layer. The copper technique used for its metallization layer and for its ILD and inter-via dielectric (“IVD”) is often referred to as a “single damascene process.” Typically, in a single damascene process, each layer requires its own capping layer or etch-stop layer, a separate ILD layer, and a top layer of material (e.g., SiO2) that can be polished together with the interconnect copper metal. Alternatively, a bimetallic damascene process combines certain similar processing steps with a single processing step, thus reducing the number of processing steps, time, and cost required to construct a BEOL stack. Therefore, the bimetallic damascene process fabricates both the IVD and the metallization layer in a single step.

[0008] In this damascene fabrication method or variations thereof, a conductive shield (or "hard shield") is typically used to protect one or more underlying layers, such as the layer beneath a low-k dielectric material during certain etching steps. Such conductive ("metallic") shields (or "hard shields") are typically composed of, for example, Ti, TiN, Ta, TaN, Al, or HfO. x Deposited in the form of layers of (i.e., hafnium oxide) or AlCu. For example, in a bimetallic damascene patterning method with a metal hard shield, the metal layer deposited on the dielectric (low-k) material acts as a hard shield for the second etching step.

[0009] The ever-increasing need to further minimize structures on semiconductor wafers presents manufacturers with new challenges. For example, in integration schemes aimed at further minimizing structures on semiconductor wafers, such as those for fabricating 20nm or smaller structures or 10nm or smaller structures, via generation is preferably achieved by using a metallic hard shield, typically a TiN hard shield, and a subsequent dry etching step to remove the low-k material beneath the metallic (e.g., TiN) hard shield (optionally separated from the metallic / TiN hard shield by an additional layer, such as a non-metallic hard shield or bonding layer). To protect the underlying copper and / or cobalt at the bottom of the via to be generated, a thin etch-stop layer is typically deposited on the copper and / or cobalt (i.e., the copper and / or cobalt metal surface). This thin etch-stop layer typically comprises or is composed of an aluminum compound and can have a maximum thickness of 30nm or less, particularly 20nm or less, more particularly 10nm or less, or even 5nm or less.

[0010] To continue the manufacturing process, the following materials must be removed: 1) a metallic (e.g., TiN) hard shield; 2) any polymer residue remaining in the vias; and 3) an etched termination layer. Simultaneously, materials such as low-k materials, copper, and / or cobalt should not be etched. This triple removal of materials (while preserving layers of low-k materials, copper, and / or cobalt to the greatest extent possible) can be achieved through a one-step or two-step process.

[0011] In this one-step method, all three removal steps are carried out simultaneously by coating a suitable composition that typically contains an oxidant such as hydrogen peroxide.

[0012] In this two-step method, in the first step, the metal (e.g., TiN) hard shield is typically removed along with residues from previous generation steps (e.g., polymerization residues) by coating a composition typically containing an oxidizing agent such as hydrogen peroxide. This composition should not damage the low-k material layer or the etch-stop layer, particularly etch-stop layers containing or composed of aluminum compounds. In the second step, the etch-stop layer is removed by coating a suitable composition. Typically, in this second step, polymerization residues still remaining in the vias are also removed (see above).

[0013] The composition to be used in this second step should remove only the thin etch-stop layer, particularly etch-stop layers containing or composed of aluminum compounds, without (or only minimally) damaging layers of low-k materials, copper, and / or cobalt. For this purpose, the composition to be used in this second step needs to have the property of allowing highly controlled and specific etching of layers containing or composed of aluminum compounds, even thin or ultrathin layers containing or composed of aluminum compounds, without damaging layers of low-k materials, copper, and / or cobalt that may also be present. Therefore, in this second step of the two-step method, the use of the composition according to the invention as defined herein is preferred.

[0014] It is known that dielectric films of alumina can generally be removed by wet etching in acidic and alkaline media (see, for example, B. Zhou et al., J. Electrochem. Soc. 143(2) 619-623 (1996) or J. Oh et al., J. Electrochem. Soc. 156(4) D217-D222 (2011)), but they do not have the etching rate precision and reliability required for etching thin or ultrathin etch-stopping layers containing aluminum compounds (e.g., alumina) or composed of aluminum compounds (e.g., alumina).

[0015] Document WO 03 / 035797 relates to an aqueous cleaning composition containing a copper-specific corrosion inhibitor for cleaning inorganic residues on semiconductor substrates.

[0016] Document WO 2012 / 009639 A2 relates to an aqueous cleaning agent for removing residues after etching.

[0017] Document US 2004 / 061092 relates to wet etching for selective removal of alumina.

[0018] Document US 2010 / 0075478 relates to a method for removing resist patterns.

[0019] Document WO 2009 / 064336 teaches a composition for removing metal hard shielding etching residues from a semiconductor substrate.

[0020] Document WO 2004 / 030038 A2 relates to a composition matrix for removing etching residues and its use.

[0021] Document US 2012 / 0052686 relates to a cleaning solution and a method for metal mounting using the same.

[0022] Therefore, the main objective of this invention is to provide a composition for selectively etching a layer of aluminum compound in the presence of a low-k material layer and / or a layer containing copper and / or cobalt, which has the characteristic of allowing highly controlled and specific etching, even etching of thin or ultrathin layers of aluminum compound, while not damaging or significantly damaging the low-k material layer and / or the layer containing copper and / or cobalt metal that is also present.

[0023] Another specific object of the present invention is to provide a method for manufacturing a semiconductor device, wherein a layer of aluminum compound is selectively etched in the presence of a low-k material, copper metal, and / or cobalt metal. Other objects of the invention are disclosed in or will become apparent from this specification and the appended claims.

[0024] The main and other objectives of the present invention have been found to be achieved by a composition for selectively etching a layer containing an aluminum compound, preferably a layer containing aluminum oxide, in the presence of a low-k material layer and / or a layer containing copper and / or cobalt, the composition comprising (i.e., one or more other substances may be present):

[0025] (A) One or more solubilizers selected from:

[0026] Compound of Formula I:

[0027]

[0028] Where R 1 Selected from:

[0029] - Hydrogen and

[0030] --C(O)-R 2 , where R 2 Selected from hydrogen and alkyl groups having 1, 2, 3 or 4 carbon atoms;

[0031] Compound of Formula II:

[0032]

[0033] Where R 3 It is an alkyl group having 1, 2, 3 or 4 carbon atoms;

[0034] -Trimethylamine-N-oxide,

[0035] -Triethylamine-N-oxide,

[0036] -Triethanolamine-N-oxide,

[0037] -Pyridine-N-oxide,

[0038] -N-ethylpyrrolidine-N-oxide and

[0039] - its mixture;

[0040] (B) One or more etchants containing fluorine anions; preferably selected from: ammonium fluoride, ammonium difluoride, triethanolamine fluoride, diethylene glycol ammonium fluoride, methyl diethanolamine fluoride, tetramethylammonium fluoride, triethylamine trihydrofluoride, hydrogen fluoride, fluoroboric acid, tetrafluoroboric acid, ammonium tetrafluoroborate, fluoroacetic acid, ammonium fluoroacetate, trifluoroacetic acid, fluorosilicic acid, ammonium fluorosilicate, tetrabutylammonium tetrafluoroborate, and mixtures thereof;

[0041] (C) One or more corrosion inhibitors, selected from:

[0042] Benztriazoles that are unsubstituted or independently substituted once or twice with the following: C 1-4 Alkyl, amino-C 1-4 Alkyl, phenyl, phenylthio, halogen, hydroxyl, nitro and / or thiol groups;

[0043] Ethylene urea, ethylene thiourea, 1,2,4-triazole, 5-aminotetrazole, 5-amino-1,3,4-thiadiazole-2-thiol, 3-amino-1H-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, tolyltriazole, 3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, naphthiatriazole, 1H-tetrazole-5-acetic acid, 1-phenyl-2-tetrazolin-5-thione, 4-methyl-2-phenylimidazolium, 2-mercaptothiazoline, 2,4-diamino-6 1,3,5-Triazine, Thiazole, Imidazole, Benzimidazole, Triazine, Methyltetrazole, 1,3-Dimethyl-2-imidazolinone, 1,5-Pentamethylenetetrazole, 1-Phenylacetetrazol, 2H-Imidazol-2-thione, 4-Methyl-4H-1,2,4-Triazol-3-thiol, 5-Amino-1,3,4-Thiadiazole-2-thiol, Benzothiazole, Trimethylbenzene Phosphate, Indazole, Adenine, Cytosine, Guanine, Thymine, 2,2'-azanediyl diacetic acid, Propanthiol, Citric Acid, Ascorbic Acid, Thiourea, 1,1,3,3-Tetramethylurea, Urea, Uric Acid, Glycine, Dodecylphosphonic Acid, Oxalic Acid, Malonic Acid, Succinic Acid, Triazine

[0044] and its mixtures;

[0045] (D) One or more chelating agents selected from: histidine, preferably L-histidine; 1,2-cyclohexanediaminetetraacetic acid, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, acetylacetonate, 2,2'-azaalkyldiacetic acid, ethylenediaminetetraacetic acid, atetzonic acid, methanesulfonic acid, acetylacetone, 1,1,1-trifluoro-2,4-pentanedione, 1,4-benzoquinone, 8-hydroxyquinoline, salinomyline; tetrachloro-1,4-benzoquinone, 2-(2-hydroxyphenyl)-benzo[a] azole, 2-(2-hydroxyphenyl)-benzothiazole, hydroxyquinoline sulfonic acid, sulfosalicylic acid, salicylic acid, pyridine, 2-ethylpyridine, 2-methoxypyridine, 3-methoxypyridine, 2-methylpyridine, dimethylpyridine, piperidine, piperazine, triethylamine, triethanolamine, ethylamine, methylamine, isobutylamine, tert-butylamine, tributylamine, dipropylamine, dimethylamine, diethylene glycolamine, monoethanolamine, methyldiethanolamine, pyrrole, isobutylamine Azole, bipyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquinoline, indole, 1-methylimidazolium, diisopropylamine, diisobutylamine, aniline, pentamethyldiethylenetriamine, acetylacetamide, ammonium carbamate, pyrrolidine dithiocarbamate, dimethyl malonate, methyl acetoacetate, N-methylacetylacetamide, tetramethylammonium thiobenzoate, 2,2,6,6-tetramethyl-3,5-heptadecyl, tetramethylthiuramdisulfide, lactic acid, ammonium lactate, formic acid, propionic acid, γ-butyrolactone, and mixtures thereof;

[0046] and

[0047] (G) Water.

[0048] Of particular surprise, the compositions according to the invention are suitable for allowing highly controlled and specific etching of layers containing or composed of aluminum compounds, even thin or ultrathin layers containing or composed of aluminum compounds, without damaging or significantly damaging layers of low-k materials, copper metals and / or cobalt metals that are also present.

[0049] The present invention, along with preferred embodiments and preferred combinations of parameters, characteristics, and elements thereof, are defined within the scope of the appended claims. Preferred aspects, details, modifications, and advantages of the invention are also defined and explained in the following description and in the embodiments set forth below.

[0050] In the context of this invention, "aluminum compound" includes one or more compounds selected from aluminum oxide ("AlO"). xAluminum compounds include aluminum nitride, aluminum oxynitride (“AlON”), and aluminum carbonitride (“AlCNO”). Preferably, the aluminum compound also contains fluorine. The precise composition of the aluminum compound and the precise content or ratio of the elements aluminum, oxygen, nitrogen, carbon, and / or fluorine present in the aluminum compound as defined herein may vary, for example, depending on the type of pretreatment of the semiconductor device containing the aluminum compound.

[0051] In the context of this invention, "a layer comprising an aluminum compound or composed of an aluminum compound" preferably means an etch stop layer, more preferably an etch stop layer deposited on a copper layer and / or a cobalt layer, and more preferably an etch stop layer on a copper layer or a cobalt layer.

[0052] As mentioned herein, an etch-stop layer (consistent with its common meaning in the art) is a material layer that is not etched under conditions common etching methods used for the surface of structured microelectronic devices, particularly semiconductor wafers, and covers and thus protects the underlying material, such as copper or other metals like copper interconnects, which may be sensitive to the etching method, from the attack of undesirable etchants. After the etching process, the etch-stop layer can be removed under conditions specific to the material of the etch-stop layer, without adversely affecting the underlying material.

[0053] In the context of this invention, "low-k material" is preferably a material having a dielectric constant κ < 3.9.

[0054] And / or (preferably "and")

[0055] The materials are selected from: (i) silicon-containing materials, preferably selected from: SiO2, silicon oxycarbide (SiOC), tetraethyl orthosilicate (TEOS), boron-doped phosphorus silicate glass (BPSG), fluorine-doped silica (fluorosilicate glass, FSG), carbon-doped silica, organosilicon glass (OSG), carbon oxide (CDO), porous silica, porous carbon-doped silica and spin-coated silicon polymer materials, preferably silane (HSQ) and methylsilsesquioxane (MSQ; preferably organosiloxane (i.e., siloxane containing carbon-silicon bonds); and preferably organosilane (i.e. silane containing carbon-silicon bonds); and (ii) polymer materials, preferably selected from: spin-coated organic polymer dielectrics, preferably containing polyimide (PI); polynorbornene; benzocyclobutene and polytetrafluoroethylene (PTFE).

[0056] In the context of this invention, the term "selective etching" (or "selective etching rate") preferably means that when the composition according to the invention is applied to a layer containing an aluminum compound or composed of an aluminum compound in the presence of a low-k material layer and / or a layer containing copper and / or cobalt, preferably a layer containing copper, the etching rate of the composition for etching the layer containing an aluminum compound, preferably alumina, or composed of an aluminum compound, preferably alumina, is at least 10 times, preferably at least 100 times, the etching rate of the composition for the low-k material and / or for the layer containing copper and / or cobalt, preferably for the layer containing copper.

[0057] In the context of this invention, the term "selective etching in the presence of a cobalt layer" (or "selective etching rate in the presence of a cobalt layer" or equivalent expression) preferably means that when the composition according to the invention is coated on a layer containing an aluminum compound or composed of an aluminum compound in the presence of a low-k material layer and / or a cobalt-containing layer, the etching rate of the composition for etching the aluminum compound, preferably alumina, or the layer composed of an aluminum compound, preferably alumina, is at least twice, preferably at least three times, the etching rate of the composition for the low-k material and / or for the cobalt-containing layer. As is known in the art, cobalt or cobalt-containing layers are generally more sensitive to etching methods of the type described or mentioned herein than copper or copper-containing layers.

[0058] In the compositions (variations) according to the invention as defined above, the one or more solubilizers (A), the one or more etchants containing fluorine anions (B), the one or more corrosion inhibitors (C) and the one or more chelating agents (D) can generally be used alone (as a single compound) or in combination with other compounds of the same type (solvents, etchants, corrosion inhibitors or chelating agents, respectively, as specifically optionally).

[0059] In component (A), in the case where one or more solubilizers of the composition according to the invention comprise compound of formula I, R 1 Preferably, the group -C(O)-R 2 , where R 2 Selected from: hydrogen and alkyl groups having 1, 2, 3, or 4 carbon atoms. In R 2 When the alkyl group has 1, 2, 3, or 4 carbon atoms, this group includes methyl, ethyl, and branched and unbranched propyl and butyl groups. Preferably, R 2 Hydrogen is present. N-Formylmorpholine (CAS RN 4394-85-8, also referred to herein as "NFM") is a particularly preferred compound of formula I for use in compositions according to the invention.

[0060] In component (A), in the case where one or more solubilizers of the composition according to the invention comprise a compound of formula II, R3 It includes methyl, ethyl, and branched and unbranched propyl and butyl groups. Preferably, R 3 The methyl group is 4-methylmorpholine-4-oxide (also referred to herein as "4-MM-4-O", and also as N-methylmorpholine-N-oxide, CAS RN 7529-22-8) is a particularly preferred compound of formula II for use in compositions according to the invention. The inventive definition of formula II includes hydrates of 4-methylmorpholine-4-oxide (CAS RN 70187-32-5), isomers of formula II, and tautomers, particularly monohydrates.

[0061] In component (B) (in all variations) of the composition according to the invention, one or more etchants containing fluoride anions may contain one or more fluoride anions or provide one or more fluoride anions upon contact with water. The composition according to the invention as defined herein (or the preferred composition according to the invention as described above or below) is therefore preferred in that the component (B) or at least one component is selected from: ammonium fluoride, ammonium difluoride, triethanolamine fluoride, diethylene glycol ammonium fluoride, methyl diethanolamine fluoride, tetramethylammonium fluoride, triethylamine trihydrofluoride, hydrogen fluoride, fluoroboric acid, tetrafluoroboric acid, ammonium tetrafluoroborate, fluoroacetic acid, ammonium fluoroacetate, trifluoroacetic acid, fluorosilicic acid, ammonium fluorosilicate, tetrabutylammonium tetrafluoroborate, and mixtures thereof; and preferably the component (B) is ammonium fluoride (CAS RN 12125-01-8), and more preferably component (B) is ammonium fluoride.

[0062] Compositions according to the invention containing ammonium fluoride as component (B) have demonstrated stable and reproducible controlled (selective) etching rates for etching layers containing aluminum compounds, especially alumina, or composed of aluminum compounds, especially alumina, in the presence of low-k material layers and / or layers containing copper and / or cobalt.

[0063] In the case where component (C) contains an unsubstituted or substituted benzotriazole (as defined above), this definition includes one or more such benzotriazoles that can be independently unsubstituted or substituted as defined above, including mixtures of such benzotriazoles.

[0064] In component (C), there is an independent C 1-4 Alkyl or amino-C 1-4 In the case of benzotriazole with alkyl substitution once or twice, "C 1-4 "Alkyl" means an alkyl group having 1, 2, 3, or 4 carbon atoms and includes methyl, ethyl, branched and unbranched propyl and butyl groups. In component (C), it includes C... 1-4In the case of alkyl-substituted benzotriazoles, methyl is preferred. The specific compounds included in this invention are defined as 5-methylbenzotriazole and 6-methylbenzotriazole (applicable to the nomenclature seen below). When component (C) contains an amino-C... 1-4 In the case of alkyl-substituted benzotriazoles, 2-(5-amino-pentyl) is preferred.

[0065] In the case where component (C) contains a benzotriazole that is independently substituted once or twice with a halogen, the halogen is selected from fluorine, chlorine, bromine, and iodine. Chlorination substitution, preferably once, is preferred for the benzotriazole. In the case where component (C) contains a halogen-substituted benzotriazole (preferably as defined above), this substance is also referred to herein as "halobenzotriazole".

[0066] In component (C) there are unsubstituted or independently C 1-4 Alkyl, amino-C 1-4 In cases where benzotriazoles are substituted once or twice with alkyl, phenyl, phenylthio, halogen, hydroxy, nitro, and / or thiol groups, this definition specifically includes the compounds benzotriazole, 6-methyl-benzotriazole (6-Me-BTA), 5-methyl-benzotriazole (5-Me-BTA), 1-hydroxybenzotriazole, 5-phenyl-benzotriazole, 5-nitro-benzotriazole, 2-(5-amino-pentyl)-benzotriazole, 5-phenylthiol-benzotriazole, halobenzotriazole (wherein the halogen group is selected from F, Cl, Br, and I), and 2-mercaptobenzothiazole.

[0067] As is known in the art, in benzotriazole, it has been demonstrated that the bonds between positions 1 and 2 (i.e., the ring nitrogen atoms) and between positions 2 and 3 (i.e., the ring nitrogen atoms) have the same bond properties. The proton attached to one nitrogen atom in the nitrogen-containing ring of the benzotriazole structure does not bind tightly to any of the three ring nitrogen atoms, but rather migrates rapidly between positions 1 and 3, thus producing tautomers.

[0068] For the purposes of this invention, the name “5-methyl-2H-benzotriazole” as used above therefore includes this compound and all its tautomers, particularly compounds called “5-methyl-benzotriazole”, “6-methyl-benzotriazole” (CAS RN49636-02-4), “6-methyl-1H-benzo[d][1.2.3]triazole”, “5-methyl-1H-benzo[d][1.2.3]triazole” and “5-methyl-2H-benzo[d][1.2.3]triazole”. Conversely, in each instance, the compounds referred to herein as “5-methyl-2H-benzotriazole,” “5-methyl-benzotriazole,” “6-methyl-benzotriazole,” “6-methyl-1H-benzo[d][1.2.3]triazole,” “5-methyl-1H-benzo[d][1.2.3]triazole,” “5-methyl-2H-benzo[d][1.2.3]triazole,” “5-Me-BTA,” or “6-Me-BTA” have the same meaning as the compound “5-methyl-2H-benzotriazole and all its tautomers.”

[0069] Accordingly, for the purposes of this invention, the name “5-chloro-2H-benzotriazole” as used in this text includes this compound and all its tautomers, particularly compounds referred to as “5-chloro-benzotriazole” (CAS RN 94-97-3), “6-chloro-benzotriazole”, “6-chloro-1H-benzo[d][1.2.3]triazole”, “5-chloro-1H-benzo[d][1.2.3]triazole” and “5-chloro-2H-benzo[d][1.2.3]triazole”. Conversely, in each instance, compounds referred to herein as “5-chloro-2H-benzotriazole,” “5-chloro-benzotriazole,” “6-chloro-benzotriazole,” “6-chloro-1H-benzo[d][1.2.3]triazole,” “5-chloro-1H-benzo[d][1.2.3]triazole,” “5-chloro-2H-benzo[d][1.2.3]triazole,” “5-Cl-BTA,” or “6-Cl-BTA” have the same meaning as the compound “5-chloro-2H-benzotriazole and all its tautomers.” This definition applies to other benzotriazoles as defined or mentioned herein, especially substituted benzotriazoles.

[0070] Without substitution or independent of C 1-4 Alkyl (preferably methyl) and / or (preferably "or") halogen substitution once or twice, preferably once, is preferred for benzotriazole. In a particularly preferred variation of the invention, component (C) is selected from: unsubstituted benzotriazole (BTA), 5-methyl-2H-benzotriazole, 5-chloro-2H-benzotriazole and mixtures thereof.

[0071] Preferably, the compositions according to the invention as defined herein (or as described above or below, preferred compositions according to the invention) conform to the following criteria.

[0072] -The or at least one component (A) is selected from:

[0073] - Compounds of Formula I as defined above (or preferred Formula I compounds as defined above),

[0074] and

[0075] - Compounds of Formula II as defined above (or preferred Formula II compounds as defined above),

[0076] and / or

[0077] - Component (B) is selected from: ammonium fluoride, ammonium difluoride, triethanolamine fluoride, diethylene glycol ammonium fluoride, methyl diethanolamine fluoride, tetramethylammonium fluoride, triethylamine trihydrofluoride, hydrogen fluoride, fluoroboric acid, tetrafluoroboric acid, ammonium tetrafluoroborate, fluoroacetic acid, ammonium fluoroacetate, trifluoroacetic acid, fluorosilicic acid, ammonium fluorosilicate, tetrabutylammonium tetrafluoroborate, and mixtures thereof;

[0078] Preferably, or at least one component (B) is ammonium fluoride, more preferably, component (B) is ammonium fluoride.

[0079] and / or

[0080] -The or at least one component (C) is selected from:

[0081] - benzotriazoles that are unsubstituted or independently substituted once or twice, preferably once: C 1-4 Alkyl, amino-C 1-4 Alkyl, phenyl, phenylthio, halogen, hydroxyl, nitro and / or (preferably "or") thiol groups;

[0082] Preferably, it is an unsubstituted or independently substituted benzotriazole once or twice, preferably once: C 1-4 Alkyl groups and / or (preferably "or") halogens,

[0083] -Succinic acid

[0084] and

[0085] - Its mixture.

[0086] Preferably, the composition according to the invention conforms to the following as defined herein (or as described above or below as a preferred composition according to the invention).

[0087] - The component (D) or at least one component is selected from: histidine, preferably L-histidine; 1,2-cyclohexanediaminetetraacetic acid and mixtures thereof.

[0088] and / or

[0089] -The composition contains the following as another component:

[0090] (E) One or more surfactants.

[0091] In the compositions according to the invention as defined above, one or more surfactants (E) may generally (if present) be used alone (as a single compound) or in combination with other compounds of the same type in each instance.

[0092] More preferably, compositions according to the invention as defined herein (or compositions according to the invention as described above or below) are preferred.

[0093] - The pH of the composition is in the range of 3.5 to 8.

[0094] and / or

[0095] -The composition contains the following as another component:

[0096] (F) Buffer system suitable for buffering the pH of the composition in the range of 3.5 to 8.

[0097] Preferably, the composition according to the invention as defined herein (or as described above or below as a preferred composition according to the invention) comprises (i.e., one or more other substances may be present):

[0098] (A) One or more solubilizers selected from:

[0099] - Compounds of Formula I as defined above (or preferred Formula I compounds as defined above),

[0100] and

[0101] - Compounds of Formula II as defined above (or preferred Formula II compounds as defined above),

[0102] (B) One or more etchants selected from: ammonium fluoride, ammonium difluoride, triethanolamine fluoride, diethylene glycol ammonium fluoride, methyl diethanolamine fluoride, tetramethylammonium fluoride, triethylamine trihydrofluoride, hydrogen fluoride, fluoroboric acid, tetrafluoroboric acid, ammonium tetrafluoroborate, fluoroacetic acid, ammonium fluoroacetate, trifluoroacetic acid, fluorosilicic acid, ammonium fluorosilicate, tetrabutylammonium tetrafluoroborate, and mixtures thereof;

[0103] Preferably, the etchant component (B) is ammonium fluoride, and more preferably, the etchant component (B) is ammonium fluoride;

[0104] (C) One or more corrosion inhibitors, selected from:

[0105] - benzotriazoles that are unsubstituted or independently substituted once or twice, preferably once: C 1-4 Alkyl, amino-C 1-4 Alkyl, phenyl, phenylthio, halogen, hydroxyl, nitro and / or (preferably "or") thiol groups;

[0106] Preferably, it is an unsubstituted or independently substituted benzotriazole once or twice, preferably once: C 1-4 Alkyl groups and / or (preferably "or") halogens,

[0107] -Succinic acid

[0108] and

[0109] -its mixture,

[0110] (D) One or more chelating agents selected from histidine, 1,2-cyclohexanediaminetetraacetic acid, and mixtures thereof.

[0111] and

[0112] (G) Water,

[0113] The pH of the composition is in the range of 3.5 to 8.

[0114] In a first preferred variation, the composition according to the invention relates to a composition for selectively etching a layer containing an aluminum compound, preferably a layer containing aluminum oxide, in the presence of a low-k material layer and / or a layer containing copper and / or cobalt, preferably in the presence of a low-k material and / or a copper layer, wherein the composition contains (i.e., one or more other substances may be present) or consists of (i.e., no other substances are present except for components (A) to (G) as defined below).

[0115] (A) One or more solubilizers selected from: 4-methylmofolin-4-oxide, trimethylamine-N-oxide, triethylamine-N-oxide, triethanolamine-N-oxide, pyridine-N-oxide, N-ethylmofolin-N-oxide, N-ethylpyrrolidine-N-oxide, and mixtures thereof;

[0116] (B) One or more etchants containing fluorine anions, preferably selected from: ammonium fluoride, ammonium difluoride, triethanolamine fluoride, diethylene glycol ammonium fluoride, methyl diethanolamine fluoride, tetramethylammonium fluoride, triethylamine trihydrofluoride, hydrogen fluoride, fluoroboric acid, tetrafluoroboric acid, ammonium tetrafluoroborate, fluoroacetic acid, ammonium fluoroacetate, trifluoroacetic acid, fluorosilicic acid, ammonium fluorosilicate, tetrabutylammonium tetrafluoroborate, and mixtures thereof;

[0117] (C) One or more corrosion inhibitors selected from: benzotriazole, (6-methyl-benzotriazole (6-Me-BTA)), 5-methyl-benzotriazole, ethylidene urea, ethylidene thiourea, 1,2,4-triazole, 5-aminotetrazole, 1-hydroxybenzotriazole, 5-amino-1,3,4-thiadiazole-2-thiol, 3-amino-1H-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, tolyltriazole, 5-phenyl-benzotriazole Triazoles, 5-nitro-benzotriazoles, 3-amino-5-mercapto-1,2,4-triazoles, 1-amino-1,2,4-triazoles, 2-(5-amino-pentyl)-benzotriazoles, 1-amino-1,2,3-triazoles, 1-amino-5-methyl-1,2,3-triazoles, 3-mercapto-1,2,4-triazoles, 3-isopropyl-1,2,4-triazoles, 5-benzylthio-benzotriazoles, halogenated benzotriazoles (where the halogen is selected from: F, Cl, Br and...) I) Naphthyltriazole, 1H-tetrazole-5-acetic acid, 2-mercaptobenzothiazole, 1-phenyl-2-tetrazoleline-5-thione, 2-mercaptobenzimidazole, 4-methyl-2-phenylimidazolium, 2-mercaptothiazoline, 2,4-diamino-6-methyl-1,3,5-triazine, thiazole, imidazole, benzimidazole, triazine, methyltetrazole, 1,3-dimethyl-2-imidazolinone, 1,5-pentamethylenetetraazole, 1-phenyl-5-mercaptotetrazole, 2H-imidazolium-2- Thione, 4-methyl-4H-1,2,4-triazol-3-thiol, 5-amino-1,3,4-thiadiazol-2-thiol, benzothiazole, tricresyl phosphate, indazole, adenine, cytosine, guanine, thymine, 2,2'-azaalkyldiacetic acid, propanethiol, citric acid, ascorbic acid, thiourea, 1,1,3,3-tetramethylurea, urea, uric acid, glycine, dodecylphosphonic acid, oxalic acid, malonic acid, succinic acid, hypozoxytriacetic acid and mixtures thereof;

[0118] (D) One or more chelating agents selected from: 1,2-cyclohexanediaminetetraacetic acid, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, acetylacetonate, 2,2'-azaalkyldiacetic acid, ethylenediaminetetraacetic acid, ethionine, methanesulfonic acid, acetylacetone, 1,1,1-trifluoro-2,4-pentanedione, 1,4-benzoquinone, 8-hydroxyquinoline, salinomyline; tetrachloro-1,4-benzoquinone, 2-(2-hydroxyphenyl)-benzo[a] azole, 2-(2-hydroxyphenyl)-benzothiazole, hydroxyquinoline sulfonic acid, sulfosalicylic acid, salicylic acid, pyridine, 2-ethylpyridine, 2-methoxypyridine, 3-methoxypyridine, 2-methylpyridine, dimethylpyridine, piperidine, piperazine, triethylamine, triethanolamine, ethylamine, methylamine, isobutylamine, tert-butylamine, tributylamine, dipropylamine, dimethylamine, diethylene glycolamine, monoethanolamine, methyldiethanolamine, pyrrole, isobutylamine Azole, bipyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquinoline, indole, 1-methylimidazolium, diisopropylamine, diisobutylamine, aniline, pentamethyldiethylenetriamine, acetylacetamide, ammonium carbamate, pyrrolidine dithiocarbamate, dimethyl malonate, methyl acetoacetate, N-methylacetylacetamide, tetramethylammonium thiobenzoate, 2,2,6,6-tetramethyl-3,5-heptadecane, tetramethylthiuram disulfide, lactic acid, ammonium lactate, formic acid, propionic acid, γ-butyrolactone and mixtures thereof;

[0119] (E) One or more surfactants;

[0120] (F) A buffering system suitable for buffering the pH of the composition in the range of 6 to 8, preferably in the range of 6.4 to 7.5, and

[0121] (G) Water,

[0122] The pH of the composition is in the range of 6 to 8, preferably in the range of 6.4 to 7.5.

[0123] In the compositions according to the invention as defined above, particularly in the compositions according to the first preferred variation, the one or more solubilizers (A), the one or more etchants containing fluorine anions (B), the one or more corrosion inhibitors (C), the one or more chelating agents (D), and the one or more surfactants (E) can generally be used alone (as a single compound) or in combination with other compounds of the same type (respectively, solubilizers, etchants, corrosion inhibitors, chelating agents, or surfactants, as specifically optionally).

[0124] Preferably, the composition is a first preferred variation of the invention as defined herein, wherein

[0125] The buffer system (F) is selected from: phosphate buffers containing NaH2PO4 and Na2HPO4, HEPES buffers containing 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid, TRIS buffers containing tris(hydroxymethyl)-aminomethane, ammonium acetate buffers, and mixtures thereof.

[0126] The buffer system is more preferably an ammonium acetate buffer, and most preferably an ammonium acetate buffer.

[0127] and / or

[0128] The pH of the composition is in the range of 6.4 to 7.5, preferably in the range of 6.8 to 7.5, and more preferably in the range of 7.0 to 7.4.

[0129] In the preferred compositions of the first preferred variation of the invention as defined above, the use of a single buffer system (e.g., ammonium acetate buffer alone or HEPES buffer alone) is preferred over the use of a mixture of buffer systems. All buffers as defined above are known in the art, and those skilled in the art will appreciate the ways in which such buffers are applied and adjusted in the context of the invention. Compositions according to the invention with a pH in the range of 6.4 to 7.5, preferably 6.8 to 7.5, and more preferably 7.0 to 7.4, have demonstrated particularly stable and reproducible controlled (selective) etching rates for etching layers containing aluminum compounds, especially alumina, or composed of aluminum compounds, especially alumina, in the presence of a low-k material layer and / or a layer containing copper and / or cobalt, preferably in the presence of a low-k material and / or a copper layer. Furthermore, the aforementioned compositions according to the invention have demonstrated particular stability over periods exceeding 6 months, e.g., storage stability.

[0130] The composition of the first preferred variation of the invention as defined herein (or the composition of the first preferred variation of the invention as described above or below) is preferred in that: the or at least one component (A) is 4-methylmorpholine-4-oxide (CAS RN 7529-22-8), wherein the preferred component (A) is 4-methylmorpholine-4-oxide.

[0131] Compositions according to a first preferred variation of the invention, containing 4-methylmorpholine-4-oxide as component (A), have demonstrated stable and reproducible selective etching rates for etching layers containing aluminum compounds, particularly aluminum oxide, or composed of aluminum compounds, particularly aluminum oxide, in the presence of low-k material layers and / or layers containing copper and / or cobalt, especially in the presence of low-k material layers and / or copper layers.

[0132] Compositions according to a first preferred variation of the invention, containing ammonium fluoride as component (B), have demonstrated stable and reproducible controlled (selective) etching rates for etching layers containing aluminum compounds, particularly alumina, or composed of aluminum compounds, particularly alumina, in the presence of low-k material layers and / or layers containing copper and / or cobalt, especially in the presence of low-k material layers and / or copper layers.

[0133] The composition of the first preferred variation of the invention as defined herein (or the composition of the first preferred variation of the invention as described above or below) is also preferred in that the component (C) is selected from: benzotriazole (CAS RN 95-14-7), 6-methyl-benzotriazole (CAS RN 136-85-6), and combinations (i.e., mixtures) of benzotriazole and 6-methyl-benzotriazole, preferably a combination of benzotriazole and 6-methyl-benzotriazole. Compositions of the first preferred variation of the invention containing benzotriazole, 6-methyl-benzotriazole, and combinations of benzotriazole and 6-methyl-benzotriazole as component (C), preferably containing a combination of benzotriazole and 6-methyl-benzotriazole as component (C), have been shown to correlate with preferred, particularly low, copper etching rates. See also the above for the nomenclature of unsubstituted and substituted benzotriazoles.

[0134] The composition of the first preferred variation of the invention as defined herein (or the composition of the first preferred variation of the invention as described above or below) is also preferred in that: component (D) is 1,2-cyclohexanediaminetetraacetic acid (CDTA; CAS RN 13291-61-7) or contains CDTA and one or more of the other chelating agents mentioned above. The composition of the first preferred variation of the invention containing CDTA as component (D) has demonstrated stable and reproducible controlled (selective) etching rates for etching layers containing aluminum compounds, especially alumina, or composed of aluminum compounds, especially alumina, in the presence of low-k material layers and / or layers containing copper and / or cobalt, particularly in the presence of low-k material layers and / or copper layers: this etching rate on the semiconductor wafer is found to be uniform on a single wafer and between different wafers, with minimal or no center-edge effect.

[0135] Compositions according to the invention as defined herein (or compositions according to the invention as described above or below that are preferred), especially compositions of the first preferred variant of the invention as defined herein, are also preferred in that one or more surfactants (E) (if present) are selected from:

[0136] (i) Anionic surfactants, preferably selected from: ammonium dodecyl sulfate; fluorinated surfactants, preferably selected from: perfluorinated alkyl sulfonamide salts (preferably perfluorinated N-substituted alkyl sulfonamide ammonium salts, PNAAS), perfluorooctanoate, perfluorobutane sulfonate, perfluorononanoate and perfluorooctanoate; alkyl-aryl ether phosphates and alkyl ether phosphates.

[0137] (ii) an amphoteric surfactant, preferably selected from: (3-[(3-cholanopropyl)dimethylammonium]-1-propanesulfonate) (“CHAPS”), cocamidopropylhydroxysulfonate (CAS RN68139-30-0), {[3-(dodecanoylamino)propyl](dimethyl)ammonium}acetate, phosphatidylserine, phosphatidylethanolamine, phosphatidylcholine, and

[0138] (iii) A nonionic surfactant, preferably selected from: glucoside alkyl ether, glycerol alkyl ether, cocamidoethanolamine and dodecyl dimethyl amino oxide.

[0139] The more preferred surfactant (E) in the composition of the first preferred variation according to the invention is or contains a perfluorinated N-substituted alkyl sulfonamide ammonium salt.

[0140] The preferred surfactant (E) in the composition according to the invention does not contain metal or metal ions.

[0141] In individual cases, a composition according to the first preferred variation of the invention as defined herein (or a composition according to the first preferred variation of the invention as described above or below) may further comprise the following other components as optionally selected:

[0142] (H) One or more water-miscible organic solvents, preferably selected from: tetrahydrofuran (THF), N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), ethanol, isopropanol, diethylene glycol butyl ether, ethylene glycol monobutyl ether, sulfolane (2,3,4,5-tetrahydrothiophene-1,1-dioxide) and mixtures thereof; more preferably selected from: THF, NMP, DMF, DMSO, sulfolane and mixtures thereof.

[0143] In the context of this invention, the term "water-miscible organic solvent" preferably means that an organic solvent satisfying this requirement is miscible with water at a ratio of at least 1:1 (w / w) at 20°C and ambient (atmospheric) pressure. This or at least one water-miscible organic solvent (H) is preferably sulfolane. More preferably, the composition according to a first preferred variation of the invention does not contain one or more water-miscible organic solvents (H).

[0144] The composition of the first preferred variation of the invention as defined herein is particularly preferred in the following cases: wherein one or more of the preferred components (A), (B), (C), (D), (E) and (F) as defined above are combined to produce the final (alternative) composition of the first preferred variation of the invention (containing all components (A) to (G), or, in the less preferred case where component (H) is present, containing all components (A) to (H)).

[0145] In a second preferred variation, the composition according to the invention relates to a composition for selectively etching a layer containing an aluminum compound, preferably a layer containing aluminum oxide, in the presence of a low-k material layer and / or a layer containing copper and / or cobalt, preferably in the presence of a low-k material and / or cobalt layer, the composition comprising (i.e., one or more other substances may be present) or consisting of (i.e., no other substances are present except for components (A) to (D) and (G) as defined below):

[0146] (A) One or more solubilizers selected from:

[0147] Compounds of formula I (having substituents R as defined above) 1 and R 2 (the preferred meaning)

[0148]

[0149] Where R 1 Selected from:

[0150] - Hydrogen and

[0151] --C(O)-R 2 , where R 2 Selected from hydrogen and alkyl groups having 1, 2, 3 or 4 carbon atoms;

[0152] Compounds of formula II (having substituents R as defined above) 3 (the preferred meaning)

[0153]

[0154] Where R 3 It is an alkyl group having 1, 2, 3 or 4 carbon atoms;

[0155] -Trimethylamine-N-oxide

[0156] -Triethylamine-N-oxide,

[0157] -Triethanolamine-N-oxide,

[0158] -Pyridine-N-oxide,

[0159] -N-ethylpyrrolidine-N-oxide and

[0160] - its mixture;

[0161] (B) One or more etchants containing fluorine anions, preferably selected from: ammonium fluoride, ammonium difluoride, triethanolamine fluoride, diethylene glycol ammonium fluoride, methyl diethanolamine fluoride, tetramethylammonium fluoride, triethylamine trihydrofluoride, hydrogen fluoride, fluoroboric acid, tetrafluoroboric acid, ammonium tetrafluoroborate, fluoroacetic acid, ammonium fluoroacetate, trifluoroacetic acid, fluorosilicic acid, ammonium fluorosilicate, tetrabutylammonium tetrafluoroborate, and mixtures thereof;

[0162] (C) One or more corrosion inhibitors, selected from:

[0163] Benztriazoles that are unsubstituted or independently substituted once or twice with the following: C 1-4 Alkyl, amino-C 1-4 Alkyl, phenyl, phenylthio, halogen, hydroxyl, nitro and / or thiol groups;

[0164] Ethylene urea, ethylene thiourea, 1,2,4-triazole, 5-aminotetrazole, 5-amino-1,3,4-thiadiazole-2-thiol, 3-amino-1H-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, tolyltriazole, 3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole, 2-(5-amino-pentyl)-benzotriazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, naphthiatriazole, 1H-tetrazole-5-acetic acid, 1-phenyl-2-tetrazolin-5-thione, 4-methyl-2-phenylimidazolium, 2-mercapto-5-thiophene Thiazolinone, 2,4-diamino-6-methyl-1,3,5-triazine, thiazole, imidazole, benzimidazole, triazine, methyltetrazole, 1,3-dimethyl-2-imidazolinone, 1,5-pentamethylenetetrazolium, 1-phenyl-5-mercaptotetrazole, 2H-imidazol-2-thione, 4-methyl-4H-1,2,4-triazol-3-thiol, 5-amino-1,3,4-thiadiazol-2-thiol, benzothiazole, tricresyl phosphate, indazole, adenine, cytosine, guanine, thymine, 2,2'-azaalkyldiacetic acid, propanethiol, citric acid, ascorbic acid, thiourea, 1,1,3,3-tetramethylurea, urea, uric acid, glycine, dodecylphosphonic acid, oxalic acid, malonic acid, succinic acid, hypozoxytriacetic acid

[0165] and its mixtures;

[0166] (D) One or more chelating agents selected from: histidine, preferably L-histidine; 1,2-cyclohexanediaminetetraacetic acid, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, acetylacetonate, 2,2'-azaalkyldiacetic acid, ethylenediaminetetraacetic acid, atetzonic acid, methanesulfonic acid, acetylacetone, 1,1,1-trifluoro-2,4-pentanedione, 1,4-benzoquinone, 8-hydroxyquinoline, salinomyline; tetrachloro-1,4-benzoquinone, 2-(2-hydroxyphenyl)-benzo[a] azole, 2-(2-hydroxyphenyl)-benzothiazole, hydroxyquinoline sulfonic acid, sulfosalicylic acid, salicylic acid, pyridine, 2-ethylpyridine, 2-methoxypyridine, 3-methoxypyridine, 2-methylpyridine, dimethylpyridine, piperidine, piperazine, triethylamine, triethanolamine, ethylamine, methylamine, isobutylamine, tert-butylamine, tributylamine, dipropylamine, dimethylamine, diethylene glycolamine, monoethanolamine, methyldiethanolamine, pyrrole, isobutylamine Azole, bipyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquinoline, indole, 1-methylimidazolium, diisopropylamine, diisobutylamine, aniline, pentamethyldiethylenetriamine, acetylacetamide, ammonium carbamate, pyrrolidine dithiocarbamate, dimethyl malonate, methyl acetoacetate, N-methylacetylacetamide, tetramethylammonium thiobenzoate, 2,2,6,6-tetramethyl-3,5-heptadecane, tetramethylthiuram disulfide, lactic acid, ammonium lactate, formic acid, propionic acid, γ-butyrolactone and mixtures thereof;

[0167] and

[0168] (G) Water,

[0169] The pH of the composition is preferably in the range of 3.5 to 6, and more preferably in the range of 4.0 to 5.5.

[0170] In the compositions according to the invention as defined above, particularly in the compositions of the second preferred variation according to the invention, the one or more solubilizers (A), the one or more etchants (B) containing fluorine anions, the one or more corrosion inhibitors (C) and the one or more chelating agents (D) can generally be used alone (as a single compound) or in combination with other compounds of the same type (respectively, solubilizers, etchants, corrosion inhibitors or chelating agents, as specifically optionally).

[0171] The composition according to the invention as defined herein (or the composition according to the invention as described above or below, including compositions of the first preferred variation and the second preferred variation) is also preferred in that the total amount of one or more solubilizers (i.e., solubilizing components, preferably preferred solubilizing components as defined above) of component (A) present on a total basis of the composition is in the range of 0.01 to 20% by weight, preferably in the range of 2 to 15% by weight, more preferably in the range of 2 to 12% by weight; and in some cases, preferably in the range of 2 to 6% by weight.

[0172] The compositions according to the invention as defined herein (or the compositions according to the invention as described above or below, including compositions of the first preferred variation and the second preferred variation) are also preferred in that the total amount of one or more etchants (containing fluorine anions, i.e., etchant components, preferably preferred etchants of component (B) as defined above) present in the composition by weight is in the range of 0.001 to 1% by weight, preferably in the range of 0.01 to 0.1% by weight, more preferably in the range of 0.02 to 0.08% by weight. Compositions according to the invention containing the preferred total amount of etchant component (B) as defined herein have shown an excellent balance between acceptable etching rates (especially for etching layers containing aluminum compounds, preferably alumina or composed of aluminum compounds, preferably alumina) and etching rate selectivity (especially in the presence of low-k material layers and / or layers containing copper and / or cobalt, more particularly copper layers (in the case of compositions relating to the first preferred variation according to the invention) and more particularly cobalt layers (in the case of compositions relating to the second preferred variation according to the invention).

[0173] The compositions according to the invention as defined herein (or the compositions according to the invention as described above or below, including compositions of the first preferred variation and the second preferred variation) are also preferred in that the total amount of one or more corrosion inhibitors (C) (i.e., corrosion inhibitor components, preferably the preferred corrosion inhibitor components as defined above) present, based on the total weight of the composition, is in the range of 0.01 to 4% by weight, preferably in the range of 0.1 to 2% by weight, more preferably in the range of 0.2 to 1.5% by weight. Compositions according to the invention containing the preferred total amount of corrosion inhibitor components (C) as defined herein have shown an excellent balance between acceptable etching rates (especially for etching layers comprising aluminum compounds, preferably alumina, or composed of aluminum compounds, preferably alumina) and etching rate selectivity (especially in the presence of low-k material layers and / or layers comprising copper and / or cobalt, more particularly copper layers (in the case of compositions relating to the first preferred variation according to the invention) and more particularly cobalt layers (i.e., selective etching rates in the presence of cobalt layers) (in the case of compositions relating to the second preferred variation according to the invention).

[0174] The composition according to the invention as defined herein (or the composition according to the invention as described above or below, including compositions of the first preferred variation and the second preferred variation) is also preferred in that the total amount of one or more chelating agents (i.e. chelating agent components, preferably preferred chelating agent components as defined above) of the component (D) is in the range of 0.01 to 4% by weight, preferably in the range of 0.02 to 1% by weight, and more preferably in the range of 0.05 to 0.8% by weight, based on the total weight of the composition.

[0175] The composition according to the invention as defined herein, preferably according to a first preferred variation (or as described above or below, according to the invention, preferably according to a first preferred variation), is also preferred in that the total amount of one or more surfactants (i.e., surfactant components, preferably preferred surfactant components as defined above) of component (E) present in the composition, based on the total weight of the composition, is in the range of 0.0001 to 1% by weight, preferably in the range of 0.001 to 0.5% by weight, more preferably in the range of 0.002 to 0.1% by weight.

[0176] The composition according to the invention as defined herein, preferably the first preferred variation of the composition (or the composition according to the invention as described above or below, preferably the first preferred variation of the composition), is also preferred in that the total amount of the buffer system (i.e. the buffer component) of the component (F) present on a total basis of the composition is in the range of 0.1 to 10% by weight, preferably in the range of 0.2 to 5% by weight, more preferably in the range of 0.3 to 3% by weight.

[0177] In individual cases, a composition according to the first preferred variation of the invention as defined herein (or a composition according to the first preferred variation of the invention as described above or below) is preferred in that the total amount of one or more water-miscible organic solvents (H) (i.e., solvent components) present in the composition is in the range of 0 to 30% by weight, preferably in the range of 0 to 10% by weight, more preferably in the range of 0 to 7.5% by weight, and even more preferably in the range of 0 to 6% by weight.

[0178] The compositions according to the invention as defined herein are also preferred in the following ways: (or the compositions according to the invention as described above or below are preferred, including compositions of the first preferred variation and the second preferred variation), wherein components (A), (B), (C), (D), (E) (if present), (F) (if present), (G) and (H) (if present) total 100% by weight (i.e., total weight) of the composition, wherein water is preferably in the balance to 100% by weight (i.e., total weight) of the total composition.

[0179] The composition of the first preferred variation of the invention as defined herein is particularly preferred in the following cases: wherein the total amount or preferred total amount of components (A), (B), (C), (D), (E), (F) and (optionally present) (H) as defined above is combined with preferred or more preferred components (A), (B), (C), (D), (E), (F) and / or (optionally present) (H) as defined above.

[0180] The composition of the first preferred variation of the invention as defined herein (or the composition of the first preferred variation of the invention as described above or below) is particularly preferred in that the composition consists of (i.e., no other substances are present except for components (A) to (H) as defined below):

[0181] (A) One or more solubilizers selected from: 4-methylmorpholine-4-oxide, trimethylamine-N-oxide, triethylamine-N-oxide, triethanolamine-N-oxide, pyridine-N-oxide, N-ethylmorpholine-N-oxide, N-ethylpyrrolidine-N-oxide, and mixtures thereof, wherein the one or more solubilizers preferably contain or include 4-methylmorpholine-4-oxide.

[0182] The total weight of the composition is in the range of 0.01 to 20% by weight, preferably in the range of 2 to 12% by weight, more preferably in the range of 2 to 6% by weight, and preferably 4-methylmorpholine-4-oxide;

[0183] (B) One or more etchants containing fluoride anions, selected from: ammonium fluoride, ammonium difluoride, triethanolamine fluoride, diethylene glycol ammonium fluoride, methyl diethanolamine fluoride, tetramethylammonium fluoride, triethylamine trihydrofluoride, hydrogen fluoride, fluoroboric acid, tetrafluoroboric acid, ammonium tetrafluoroborate, fluoroacetic acid, ammonium fluoroacetate, trifluoroacetic acid, fluorosilicic acid, ammonium fluorosilicate, tetrabutylammonium tetrafluoroborate, and mixtures thereof, preferably containing ammonium fluoride.

[0184] The total amount is in the range of 0.01 to 0.1% by weight, more preferably in the range of 0.02 to 0.08% by weight, and preferably ammonium fluoride, based on the total weight of the composition.

[0185] (C) One or more corrosion inhibitors selected from: benzotriazole, 6-methylbenzotriazole, 5-methylbenzotriazole, ethylidene urea, ethylidene thiourea, 1,2,4-triazole, 5-aminotetrazole, 1-hydroxybenzotriazole, 5-amino-1,3,4-thiadiazole-2-thiol, 3-amino-1H-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, tolyltriazole, 5-phenylbenzotriazole, 5-nitrobenzotriazole, 3-amino 5-Mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole, 2-(5-amino-pentyl)-benzotriazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, 5-benzylthiol-benzotriazole, halogenated benzotriazole (where the halogen is selected from: F, Cl, Br and I), naphthiazole, 1H-tetrazole-5-acetic acid, 2 1-Mercaptobenzothiazole, 1-Pheny-2-tetrazoline-5-thione, 2-Mercaptobenzimidazole, 4-Methyl-2-phenylimidazolium, 2-Mercaptothiazoline, 2,4-Diamino-6-methyl-1,3,5-triazine, thiazole, imidazole, benzimidazole, triazine, methyltetrazole, 1,3-dimethyl-2-imidazolineone, 1,5-pentamethylenetetrazolium, 1-phenyl-5-mercaptotetrazole, 2H-imidazolium-2-thione, 4-methyl-4H-1,2,4-triazolium-3- Thiols, 5-amino-1,3,4-thiadiazole-2-thiol, benzothiazole, tricresyl phosphate, indazole, adenine, cytosine, guanine, thymine, 2,2'-azaalkyldiacetic acid, propanethiol, citric acid, ascorbic acid, thiourea, 1,1,3,3-tetramethylurea, urea, uric acid, glycine, dodecylphosphonic acid, oxalic acid, malonic acid, succinic acid, hypozoxytriacetic acid, and mixtures thereof, preferably selected from: benzotriazole, 6-methyl-benzotriazole, and mixtures thereof.

[0186] The total amount is in the range of 0.01 to 4% by weight, preferably in the range of 0.1 to 2% by weight, more preferably in the range of 0.2 to 1.5% by weight, and preferably selected from the group consisting of benzotriazole, 6-methyl-benzotriazole and mixtures thereof.

[0187] (D) One or more chelating agents selected from: 1,2-cyclohexanediaminetetraacetic acid, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, acetylacetonate, 2,2'-azaalkyldiacetic acid, ethylenediaminetetraacetic acid, ethionine, methanesulfonic acid, acetylacetone, 1,1,1-trifluoro-2,4-pentanedione, 1,4-benzoquinone, 8-hydroxyquinoline, salinomyline; tetrachloro-1,4-benzoquinone, 2-(2-hydroxyphenyl)-benzo[a] azole, 2-(2-hydroxyphenyl)-benzothiazole, hydroxyquinoline sulfonic acid, sulfosalicylic acid, salicylic acid, pyridine, 2-ethylpyridine, 2-methoxypyridine, 3-methoxypyridine, 2-methylpyridine, dimethylpyridine, piperidine, piperazine, triethylamine, triethanolamine, ethylamine, methylamine, isobutylamine, tert-butylamine, tributylamine, dipropylamine, dimethylamine, diethylene glycolamine, monoethanolamine, methyldiethanolamine, pyrrole, isobutylamine The following compounds are permitted: azoles, bipyridines, pyrimidines, pyrazines, pyridazines, quinolines, isoquinolines, indole, 1-methylimidazolium, diisopropylamine, diisobutylamine, aniline, pentamethyldiethylenetriamine, acetoacetamide, ammonium carbamate, pyrrolidine dithiocarbamate, dimethyl malonate, methyl acetoacetate, N-methylacetoacetamide, tetramethylammonium thiobenzoate, 2,2,6,6-tetramethyl-3,5-heptadecane, tetramethylthiuram disulfide, lactic acid, ammonium lactate, formic acid, propionic acid, γ-butyrolactone, and mixtures thereof, preferably containing or including 1,2-cyclohexanediaminetetraacetic acid.

[0188] The total amount is in the range of 0.01 to 4% by weight, preferably in the range of 0.02 to 1% by weight, more preferably in the range of 0.05 to 0.8% by weight, and preferably 1,2-cyclohexanediaminetetraacetic acid.

[0189] (E) One or more surfactants selected from: (i) anionic surfactants, preferably selected from: ammonium dodecyl sulfate; fluorosurfactants, preferably selected from: perfluorinated alkyl sulfonamide salts (preferably perfluorinated N-substituted alkyl sulfonamide ammonium salts), perfluorooctyl sulfonate, perfluorobutane sulfonate, perfluorononanoate and perfluorooctyl sulfonate; alkyl-aryl ether phosphates and alkyl ether phosphates; (ii) zwitterionic surfactants, preferably selected from: (3-[(3-cholanopropyl)dimethylammonium]-1-propanesulfonate), cocamidopropylhydroxysulfonate, {[3-(dodecylamino)propyl](dimethyl)ammonium}acetate, phosphatidylserine, phosphatidylethanolamine, phosphatidylcholine; (iii) nonionic surfactants, preferably selected from: glucoside alkyl ethers, glycerol alkyl ethers, cocamidoethanolamine and dodecyl dimethylamino oxide; and the one or more surfactants are preferably or contain perfluorinated N-substituted alkyl sulfonamide ammonium salts.

[0190] The total amount is in the range of 0.0001 to 1% by weight, preferably in the range of 0.001 to 0.5% by weight, more preferably in the range of 0.002 to 0.1% by weight, and preferably selected from the group consisting of perfluorinated N-substituted alkyl sulfonamide ammonium salts.

[0191] (F) A buffer system suitable for buffering the pH of the composition in the range of 6.4 to 7.5, preferably in the range of 6.8 to 7.5, more preferably in the range of 7.0 to 7.4, preferably selected from: phosphate buffers containing NaH2PO4 and Na2HPO4, HEPES buffers containing 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid, TRIS buffers containing tris(hydroxymethyl)-aminomethane, and ammonium acetate buffers, more preferably containing or being a buffer containing ammonium acetate.

[0192] The total amount is in the range of 0.1 to 10% by weight, preferably in the range of 0.2 to 5% by weight, and more preferably in the range of 0.3 to 3% by weight, based on the total weight of the composition.

[0193] (G) Water, present in the remainder of the composition in each example, reaching a total of 100% by weight.

[0194] and

[0195] (H) One or more water-miscible organic solvents, preferably selected from: tetrahydrofuran (THF), N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and sulfolane (2,3,4,5-tetrahydrothiophene-1,1-dioxide) and mixtures thereof.

[0196] The total amount, based on the total weight of the composition, is in the range of 0 to 30% by weight, preferably in the range of 0 to 10% by weight, more preferably in the range of 0 to 7.5% by weight, and even more preferably in the range of 0 to 6% by weight.

[0197] The pH of the composition is in the range of 6.4 to 7.5, preferably in the range of 6.8 to 7.5, and more preferably in the range of 7.0 to 7.4.

[0198] and

[0199] In each example, the total weight percentage of components (A), (B), (C), (D), (E), (F), (G) and (if present) (H) is 100% by weight.

[0200] In the particularly preferred composition of the first preferred variation of the invention as defined above, preferred or more preferred components (A), (B), (C), (D), (E), (F) and / or (optionally present) (H) and / or components (A), (B), (C), (D), (E), (F) and / or (optionally present) (H) as defined above may be combined to produce even more preferred compositions of the first preferred variation of the invention.

[0201] The composition of the first preferred variation of the invention as defined herein (or the composition of the first preferred variation of the invention as described above) is particularly preferred in the following cases: wherein the composition comprises the following:

[0202] (A) 4-Methylmorpholine-4-oxide as a solubilizer

[0203] The total weight of the composition is preferably in the range of 0.01 to 20% by weight, more preferably in the range of 2 to 12% by weight, and even more preferably in the range of 2 to 6% by weight.

[0204] (B) Ammonium fluoride as an etchant

[0205] The total amount is preferably in the range of 0.01 to 0.1% by weight, more preferably in the range of 0.02 to 0.08% by weight, based on the total weight of the composition.

[0206] (C) One or more corrosion inhibitors selected from: benzotriazole, 6-methyl-benzotriazole, and mixtures thereof.

[0207] The total amount is preferably in the range of 0.01 to 4% by weight, more preferably in the range of 0.1 to 2% by weight, and even more preferably in the range of 0.2 to 1.5% by weight, based on the total weight of the composition.

[0208] (D) 1,2-Cyclohexanediaminetetraacetic acid as a chelating agent

[0209] The total amount is preferably in the range of 0.01 to 4% by weight, more preferably in the range of 0.02 to 1% by weight, and even more preferably in the range of 0.05 to 0.8% by weight, based on the total weight of the composition.

[0210] (E) One or more surfactants, wherein the one or more surfactants, or at least one of them, is a perfluorinated N-substituted alkylsulfonamide ammonium salt.

[0211] The total amount of the composition is preferably in the range of 0.0001 to 1% by weight, more preferably in the range of 0.001 to 0.5% by weight, and even more preferably in the range of 0.002 to 0.1% by weight.

[0212] (F) A buffer system suitable for buffering the pH of the composition in the range of 6.4 to 7.5, preferably in the range of 6.8 to 7.5, more preferably in the range of 7.0 to 7.4, preferably an ammonium acetate buffer.

[0213] The total amount is preferably in the range of 0.1 to 10% by weight, more preferably in the range of 0.2 to 5% by weight, and even more preferably in the range of 0.3 to 3% by weight, based on the total weight of the composition.

[0214] and

[0215] (G) Water, present in the remainder of the composition in each example, reaching a total of 100% by weight.

[0216] The pH of the composition is in the range of 6.4 to 7.5, preferably in the range of 6.8 to 7.5, and more preferably in the range of 7.0 to 7.4.

[0217] and

[0218] In each example, the total weight percentage of components (A), (B), (C), (D), (E), (F) and (G) is preferably added together to 100% by weight.

[0219] The composition of the second preferred variation of the invention as defined herein (or the composition of the second preferred variation of the invention as described above or below) is preferred in the following cases: wherein:

[0220] (A) The component (A) is a compound of formula I as defined above (or a preferred compound of formula I as defined above), and preferably the component (A) is N-formylmorpholine.

[0221] The preferred component (A) is present in a total amount in the range of 0.01 to 20% by weight, more preferably in the range of 2 to 15% by weight, even more preferably in the range of 2 to 12% by weight, and even more preferably in the range of 5 to 12% by weight, based on the total weight of the composition.

[0222] The composition of the second preferred variation of the invention as defined herein (or the composition of the second preferred variation of the invention as described above or below) is also preferred in the following cases: wherein:

[0223] (B) Component (B) is selected from: ammonium fluoride, ammonium difluoride, triethanolamine fluoride, diethylene glycol ammonium fluoride, methyl diethanolamine fluoride, tetramethylammonium fluoride, triethylamine trihydrofluoride, hydrogen fluoride, fluoroboric acid, tetrafluoroboric acid, ammonium tetrafluoroborate, fluoroacetic acid, ammonium fluoroacetate, trifluoroacetic acid, fluorosilicic acid, ammonium fluorosilicate, tetrabutylammonium tetrafluoroborate, and mixtures thereof;

[0224] Preferably, or at least one component (B) is ammonium fluoride, and more preferably, component (B) is ammonium fluoride.

[0225] Preferably, component (B) is present in a total amount in the range of 0.01 to 0.1% by weight based on the total weight of the composition, more preferably in a total amount in the range of 0.02 to 0.08% by weight.

[0226] The composition of the second preferred variation of the invention as defined herein (or the composition of the second preferred variation of the invention as described above or below) is also preferred in the following cases: wherein:

[0227] (C) The component (C) is selected from:

[0228] - benzotriazoles that are unsubstituted or independently substituted once or twice, preferably once: C 1-4 Alkyl groups and / or (preferably "or") halogens;

[0229] -Succinic acid

[0230] and

[0231] - its mixture;

[0232] The preferred component (C) is present in a total amount in the range of 0.01 to 4% by weight based on the total weight of the composition, more preferably in the range of 0.1 to 2% by weight, and even more preferably in the range of 0.2 to 1.5% by weight.

[0233] The composition of the second preferred variation of the invention as defined herein (or the composition of the second preferred variation of the invention as described above or below) is also preferred in the following: wherein:

[0234] (D) The component (D) is histidine, preferably L-histidine;

[0235] The preferred component (D) is present in a total amount in the range of 0.01 to 4% by weight based on the total weight of the composition, more preferably in the range of 0.02 to 1% by weight, and even more preferably in the range of 0.05 to 0.8% by weight.

[0236] The composition of the second preferred variation of the invention as defined herein (or the composition of the second preferred variation of the invention as described above or below) is particularly preferred in the following cases: wherein:

[0237] (A) The component (A) is a compound of formula I as defined above (or a preferred compound of formula I as defined above), and preferably the component (A) is N-formylmorpholine.

[0238] It is preferably present in a total amount in the range of 0.01 to 20% by weight, more preferably in the range of 2 to 15% by weight, even more preferably in the range of 2 to 12% by weight, and even more preferably in the range of 5 to 12% by weight, based on the total weight of the composition.

[0239] (B) Component (B) is selected from: ammonium fluoride, ammonium difluoride, triethanolamine fluoride, diethylene glycol ammonium fluoride, methyl diethanolamine fluoride, tetramethylammonium fluoride, triethylamine trihydrofluoride, hydrogen fluoride, fluoroboric acid, tetrafluoroboric acid, ammonium tetrafluoroborate, fluoroacetic acid, ammonium fluoroacetate, trifluoroacetic acid, fluorosilicic acid, ammonium fluorosilicate, tetrabutylammonium tetrafluoroborate, and mixtures thereof;

[0240] Preferably, or at least one component (B) is ammonium fluoride, and more preferably, component (B) is ammonium fluoride.

[0241] It is preferably present in a total amount in the range of 0.01 to 0.1% by weight based on the total weight of the composition, and more preferably in a total amount in the range of 0.02 to 0.08% by weight.

[0242] (C) The component (C) is selected from:

[0243] - benzotriazoles that are unsubstituted or independently substituted once or twice, preferably once: C 1-4 Alkyl groups and / or (preferably "or") halogens;

[0244] -Succinic acid

[0245] and

[0246] - its mixture;

[0247] It is preferably present in a total amount in the range of 0.01 to 4% by weight based on the total weight of the composition, more preferably in the range of 0.1 to 2% by weight, and even more preferably in the range of 0.2 to 1.5% by weight.

[0248] (D) The component (D) is histidine, preferably L-histidine;

[0249] It is preferably present in a total amount in the range of 0.01 to 4% by weight based on the total weight of the composition, more preferably in the range of 0.02 to 1% by weight, and even more preferably in the range of 0.05 to 0.8% by weight.

[0250] and

[0251] Component (G) is water, preferably present in the remainder in each example to reach a total of 100% by weight of the composition.

[0252] The pH of the composition is in the range of 3.5 to 6, preferably in the range of 4.0 to 5.5.

[0253] and

[0254] In each example, the total weight percentage of components (A), (B), (C), (D) and (G) is preferably added together to 100% by weight.

[0255] The composition of the second preferred variation of the invention as defined herein (or the composition of the second preferred variation of the invention as described above or below) is also preferred in the following cases: wherein:

[0256] (A) Component (A) is a compound of formula I as defined above (or a preferred compound of formula I as defined above), wherein the preferred component (A) is N-formylmorpholine.

[0257] It is present in a total amount in the range of 0.01 to 20% by weight, preferably in the range of 2 to 15% by weight, more preferably in the range of 2 to 12% by weight, and even more preferably in the range of 5 to 12% by weight, based on the total weight of the composition.

[0258] (B) Component (B) is selected from: ammonium fluoride, ammonium difluoride, triethanolamine fluoride, diethylene glycol ammonium fluoride, methyl diethanolamine fluoride, tetramethylammonium fluoride, triethylamine trihydrofluoride, hydrogen fluoride, fluoroboric acid, tetrafluoroboric acid, ammonium tetrafluoroborate, fluoroacetic acid, ammonium fluoroacetate, trifluoroacetic acid, fluorosilicic acid, ammonium fluorosilicate, tetrabutylammonium tetrafluoroborate, and mixtures thereof;

[0259] Preferably, or at least one component (B) is ammonium fluoride, and more preferably, component (B) is ammonium fluoride.

[0260] And it is present in a total amount in the range of 0.01 to 0.1% by weight based on the total weight of the composition, preferably in the range of 0.02 to 0.08% by weight;

[0261] (C) Component (C) is selected from:

[0262] - benzotriazoles that are unsubstituted or independently substituted once or twice, preferably once: C 1-4 Alkyl groups and / or (preferably "or") halogens;

[0263] -Succinic acid

[0264] and

[0265] - its mixture;

[0266] The total amount is in the range of 0.01 to 4% by weight, preferably in the range of 0.1 to 2% by weight, and more preferably in the range of 0.2 to 1.5% by weight, based on the total weight of the composition.

[0267] (D) Component (D) is histidine, preferably L-histidine;

[0268] It is present in a total amount in the range of 0.01 to 4% by weight, preferably in the range of 0.02 to 1% by weight, and more preferably in the range of 0.05 to 0.8% by weight, based on the total weight of the composition.

[0269] and

[0270] Component (G) is water, present in the remainder in each example to reach a total of 100% by weight of the composition.

[0271] The pH of the composition is in the range of 3.5 to 6, preferably in the range of 4.0 to 5.5.

[0272] and

[0273] In each example, the total weight percentage of components (A), (B), (C), (D), and (G) adds up to 100% by weight.

[0274] In its own experiments, it has been found that compositions containing histidine, preferably L-histidine, as the or at least one component (D), especially as the component (D), according to the second preferred variation, exhibit a more selective etching rate in the presence of a cobalt layer compared to compositions not containing histidine as the or at least one component (D), especially as the component (D), according to the second preferred variation.

[0275] The composition of the second preferred variation of the invention as defined herein (or the composition of the second preferred variation of the invention as described above or below) is also preferred in that: the or at least one component (A) is N-formylmorpholine (CAS RN4394-85-8), wherein the preferred component (A) is N-formylmorpholine.

[0276] Compositions according to a second preferred variation of the invention, containing N-formylmorpholine as a solubilizing component (A) (especially in the preferred amount specified above), have demonstrated excellent stability against precipitation and enhanced solubility, even at temperatures below room temperature.

[0277] Component (C) is selected from:

[0278] -unreplaced or independently transmitted via C 1-4 Alkyl alkyl (preferably "or") halogen substitution once or twice, preferably once benzotriazole; preferably 5-methyl-2H-benzotriazole and 5-chloro-2H-benzotriazole;

[0279] -Succinic acid

[0280] and

[0281] -The mixture thereof, the composition of the second preferred variation according to the invention has demonstrated stable and reproducible selective etching rates for etching layers containing aluminum compounds, especially aluminum oxide or composed of aluminum compounds, especially aluminum oxide (i.e. selective etching rates in the presence of cobalt layers) in the presence of low-k material layers and / or layers containing copper and / or cobalt, especially in the presence of low-k material layers and / or copper layers.

[0282] Particularly preferred are compositions according to the second preferred variation of the invention as defined herein (or compositions according to the second preferred variation of the invention as described above or below), which comprise or consist of the following:

[0283] (A) N-formylmorpholine as a solubilizer

[0284] The composition is preferably present in a total amount in the range of 0.01 to 20% by weight, more preferably in the range of 2 to 15% by weight, even more preferably in the range of 2 to 12% by weight, and even more preferably in the range of 5 to 12% by weight, based on the total weight of the composition.

[0285] (B) Ammonium fluoride as an etchant;

[0286] The total amount is preferably in the range of 0.01 to 0.1% by weight, more preferably in the range of 0.02 to 0.08% by weight, based on the total weight of the composition.

[0287] (C) Corrosion inhibitors, selected from:

[0288] 5-Methyl-2H-benzotriazole,

[0289] -5-Chloro-2H-benzotriazole,

[0290] -Succinic acid

[0291] and

[0292] - its mixture;

[0293] The total amount is preferably in the range of 0.01 to 4% by weight, more preferably in the range of 0.1 to 2% by weight, and even more preferably in the range of 0.2 to 1.5% by weight, based on the total weight of the composition.

[0294] (D) Histidine as a chelating agent, preferably L-histidine;

[0295] The total amount is preferably in the range of 0.01 to 4% by weight, more preferably in the range of 0.02 to 1% by weight, and even more preferably in the range of 0.05 to 0.8% by weight, based on the total weight of the composition.

[0296] and

[0297] (G) Water, preferably present in the remainder of the composition in each example, reaching a total of 100% by weight.

[0298] The pH of the composition is in the range of 3.5 to 6, preferably in the range of 4.0 to 5.5.

[0299] and

[0300] In each example, the total weight percentage of components (A), (B), (C), (D) and (G) is preferably added together to 100% by weight.

[0301] The invention also relates to the use of compositions according to the invention as defined herein (including the use of compositions of the first preferred variant and compositions of the second preferred variant) (or the preferred uses according to the invention as described herein).

[0302] -It is used for selective etching of layers containing aluminum compounds, preferably aluminum oxide, in the presence of low-k material layers and / or layers containing copper and / or cobalt;

[0303] When using the composition of the first preferred variation of the invention, it is preferably achieved in the presence of a low-k material layer and / or a copper-containing layer, preferably in the presence of a copper layer;

[0304] And / or when using the composition of the second preferred variation of the invention, it is preferably achieved in the presence of a low-k material layer and / or a layer containing cobalt, preferably in the presence of a cobalt layer;

[0305] and / or

[0306] -It is used to selectively remove layers containing aluminum compounds, preferably aluminum oxide, from a substrate in the presence of low-k material layers and / or layers containing copper and / or cobalt;

[0307] When using the composition of the first preferred variation of the invention, it is preferably achieved in the presence of a low-k material layer and / or a copper-containing layer, preferably in the presence of a copper layer;

[0308] And / or when using the composition of the second preferred variation of the invention, it is preferably achieved in the presence of a low-k material layer and / or a layer containing cobalt, preferably in the presence of a cobalt layer;

[0309] and / or

[0310] -It is used to selectively remove layers containing aluminum compounds, preferably aluminum oxide, from the surface of a semiconductor substrate in the presence of low-k material layers and / or layers containing copper and / or cobalt;

[0311] When using the composition of the first preferred variation of the invention, it is preferably achieved in the presence of a low-k material layer and / or a copper-containing layer;

[0312] And / or when using the composition of the second preferred variation of the invention, it is preferably implemented in the presence of a low-k material layer and / or a layer containing cobalt, preferably in the presence of a cobalt layer.

[0313] Generally, all aspects of the invention discussed in the context of the compositions of the invention (including the first preferred variations and the second preferred variations) are applicable to the use of the compositions of the invention as defined above and below (including the use of the first preferred variations and the use of the second preferred variations). Similarly, all aspects of the use of the compositions of the invention discussed herein are applicable to the compositions of the invention.

[0314] The uses of the invention as defined above (including uses of compositions of the first preferred variation and compositions of the second preferred variation) (or uses of the invention as described herein as preferred in particular) are especially preferred in the following cases: wherein the use is for removing the following two-step process:

[0315] (i) Metallic hard shielding, preferably selected from: Ti hard shielding, TiN hard shielding, Ta hard shielding, TaN hard shielding, Al hard shielding, HfO x Hafnium oxide hard shielding and AlCu (i.e., AlCu alloy) hard shielding, more preferably TiN hard shielding.

[0316] and

[0317] (ii) An etch-stop layer of an aluminum compound deposited on a copper-containing layer, preferably a copper layer, and / or a cobalt-containing layer, preferably a cobalt layer.

[0318] Preferably, this use is applied in the second step (ii);

[0319] Furthermore, the use of the composition of the first preferred variation of the present invention is preferred in the two-step method in which an etch-stopping layer of an aluminum compound is deposited on a copper-containing layer, preferably a copper layer;

[0320] And / or preferably, the use of the composition of the second preferred variation of the invention in the two-step method in which an etch-stopping layer of an aluminum compound is deposited on a layer containing cobalt, preferably a cobalt layer.

[0321] In a preferred application of the two-step method according to the invention as defined above, the method step (i) of removing the metal hard shield is preferably the first method step and the method step (ii) of removing the etch stop layer is the second method step. The second method step may be performed directly after the first method step, or one or more other method steps may be performed between the first method step and the second method step.

[0322] The uses of the invention as defined above (including the uses of compositions of the first preferred variation and compositions of the second preferred variation) (or the uses of the invention as described herein as preferred) are also preferred in the following cases: wherein the etch-stopping layer of the aluminum compound, preferably alumina, has a maximum thickness of 30 nm or less, preferably 20 nm or less, more preferably 10 nm or less, and even more preferably 5 nm or less before etching.

[0323] The use of the invention as defined above (or the preferred use of the invention as described herein) is also preferred in the following cases: wherein the two-step method is part of a metal damascene process for manufacturing interconnects of integrated circuits.

[0324] The present invention also relates to a method for manufacturing a semiconductor device, comprising the steps of: selectively etching the at least one aluminum compound layer by contacting at least one layer comprising an aluminum compound, preferably alumina, or composed of an aluminum compound, preferably alumina, with a composition according to the invention as defined herein (including compositions of a first preferred variation and compositions of a second preferred variation) (or compositions according to the invention as described herein) at least once, in the presence of a low-k material layer and / or a layer comprising copper and / or cobalt.

[0325] In cases where the method includes the step of selectively etching at least one layer comprising an aluminum compound, preferably alumina, or composed of an aluminum compound, preferably alumina, in the presence of a low-k material layer and / or a copper-containing layer, preferably a copper layer, it is preferable to contact the at least one aluminum compound layer with a composition of the invention according to a first preferred variation as defined herein (or a composition of the invention according to a first preferred variation as described herein) at least once.

[0326] In cases where the method includes the step of selectively etching at least one layer comprising an aluminum compound, preferably alumina, or composed of an aluminum compound, preferably alumina, in the presence of a low-k material layer and / or a cobalt-containing layer, preferably a cobalt layer, it is preferable to contact the at least one aluminum compound layer with a composition of the second preferred variation of the invention as defined herein (or a composition of the second preferred variation of the invention as described herein) at least once.

[0327] Generally, in the context of the compositions of the present invention and / or the use of the compositions of the present invention, all aspects of the invention discussed herein are applicable to the methods of the present invention for manufacturing semiconductor devices as defined above and below. Similarly, all aspects of the methods of the present invention for manufacturing semiconductor devices are applicable to the compositions of the present invention and / or the use of the compositions of the present invention.

[0328] The method of the present invention as defined above is preferably performed in the presence of a low-k material layer and a layer comprising copper and / or cobalt, preferably in the presence of a low-k material layer and a layer comprising copper, preferably in the presence of a copper layer, wherein a composition of the first preferred variation of the invention as defined herein (or a composition of the first preferred variation of the invention as described herein) is used; and preferably in the presence of a low-k material layer and a layer comprising cobalt, preferably in the presence of a cobalt layer, wherein a composition of the second preferred variation of the invention as defined herein (or a composition of the second preferred variation of the invention as described herein) is used.

[0329] The method of the present invention as defined above (or the method of the present invention as described herein) is also preferred in the following ways: wherein the at least one layer comprising an aluminum compound or composed of an aluminum compound is a top layer, a layer comprising copper and / or cobalt is a bottom layer covered by the top layer, and there is or does not have at least one additional layer present between the top layer and the bottom layer, preferably no at least one (i.e., no) additional layer present between the top layer and the bottom layer.

[0330] The method of the present invention as defined above (or the method of the present invention as described herein) is also preferred in the following cases: wherein the method for manufacturing a semiconductor device is a metal damascene method for manufacturing interconnects of an integrated circuit.

[0331] The method of the present invention as defined above (or the method of the present invention as described herein as preferred) is also preferred in the following cases: wherein the method comprises a two-step cleaning method, preferably a cleaning method for a semiconductor device, comprising the following steps:

[0332] - In the first step, the metallic hard shield is removed, preferably selected from: Ti hard shield, TiN hard shield, Ta hard shield, TaN hard shield, Al hard shield, HfO. x Hafnium oxide hard shielding and AlCu hard shielding; more preferably TiN hard shielding.

[0333] - Subsequently, in a separate second step, at least one layer containing an aluminum compound, preferably alumina, or composed of an aluminum compound, preferably alumina, is selectively etched.

[0334] Preferably, the metal hard shielding in the preferred method of the present invention as defined above is selected from: Ti hard shielding, TiN hard shielding, Ta hard shielding, TaN hard shielding, Al hard shielding, HfO. x Hafnium oxide hard shielding and AlCu (AlCu alloy) hard shielding. More preferably, the metal hard shielding is TiN hard shielding.

[0335] In the preferred two-step method according to the invention as defined above, the separate second method step may be performed directly after the first method step, or one or more other method steps may be performed between the first method step and the separate second method step.

[0336] The method of the invention as defined above (or the method of the invention as described herein) is also preferred in that at least one layer comprising an aluminum compound, preferably alumina, or composed of an aluminum compound, preferably alumina, has a maximum thickness of 30 nm or less, preferably 20 nm or less, more preferably 10 nm or less, and even more preferably 5 nm or less prior to etching. In some cases, the method of the invention as defined above (or the method of the invention as described herein) is preferred in that at least one layer comprising an aluminum compound, preferably alumina, or composed of an aluminum compound, preferably alumina, has a maximum thickness of 2 nm or less, preferably 1 nm or less, more preferably 0.5 nm or less. Example:

[0337] The following examples are intended to further illustrate the invention without limiting its scope.

[0338] Example 1: Preparation of the composition according to the invention (first preferred variation) and a comparative composition (not according to the invention).

[0339] The preferred compositions of the first preferred variation of the invention (denoted as "I", i.e., compositions I1 to I8) are prepared by mixing components (A) to (G) or (A) to (H) (specifically optional). Details are given below in Table 1a. Other compositions according to the invention (denoted as "I", i.e., compositions I9 to I13) are prepared by mixing components (A) to (G) or (A) to (H) (specifically optional). Details are given below in Table 1b. In addition, comparative compositions (not according to the invention, denoted as "C", i.e., compositions C1 to C2) are also prepared in a similar manner, as shown in more detail below in Table 1c. To adjust the pH of different compositions, the total amount of the acidic buffer component (acetic acid in a 96 wt% solution in water, with acetate buffer used in the water) is added to the composition, followed by the addition of a suitable amount of the corresponding alkaline (basic) buffer component (ammonia in a 29 wt% solution in water, with acetate buffer used in the water) until the desired pH of the composition is reached.

[0340] Table 1a: Preferred test compositions according to the present invention (first preferred variation)

[0341]

[0342] Table 1b: Other test compositions according to the invention (first preferred variation)

[0343]

[0344] Table 1c: Comparative Test Compositions

[0345]

[0346] BDG: Butyl diethylene glycol (diethylene glycol butyl ether)

[0347] All weight percent of the components in Tables 1a, 1b and 1c are calculated based on pure, undiluted compounds.

[0348] Example 2: Determination of alumina (AlOx) and copper etching results of the test composition (first preferred variant)

[0349] Si wafers or wafers with appropriate outer layers (hereinafter collectively referred to as "test wafers") are obtained from commercial sources. The test wafers undergo pretreatment, optionally: Cu is immersed in oxalic acid solution for 20-30 seconds, followed by rinsing with water and drying. This is not performed on AlO₂ wafers. x The coated surface undergoes pretreatment. In each example, copper and AlO₂ on the test wafer are examined. x The layer has The thickness.

[0350] Alumina (AlO) x The coated surface serves as a representative model of a layer (as defined above) containing or composed of an aluminum compound.

[0351] Prepare the test composition (as defined in Tables 1a, 1b and 1c) and in a glass beaker at 60°C and in AlO2. x For the surface case, a reaction period of 1 minute is maintained, and for the Cu surface case, a reaction period of 5 to 10 minutes is maintained, to bring the test wafer (see above) into contact with the test composition. The wafer is then removed from the test composition, rinsed with water or isopropanol, and dried with nitrogen.

[0352] The thicknesses of the copper and aluminum oxide layers on the test wafer were determined by X-ray fluorescence analysis before and after contact with the test composition. The experiment was repeated at least three times to ensure reproducibility.

[0353] In each example, copper or AlO x The total etch loss is determined by subtracting the measured thickness of the same copper or aluminum oxide layer after contact with the test composition from the measured thickness of the layer before contact with the test composition. The etch rate is obtained by dividing the total etch loss by the program time. The result is calculated based on the etch rate of the layer after contact with the test composition. The values ​​are shown in Table 2 below (each given value in Table 2 represents the average of at least three experiments).

[0354] Table 2: Alumina and copper etching results of the test composition (first preferred variant)

[0355]

[0356] AlO on Si wafers in Table 2 x An etch rate value ">100" for the layer indicates that the entire AlO2 layer is removed within a one-minute application reaction period or before the end of that one-minute application reaction period. x The meaning of the layer is that the precise etch rate cannot be measured in these instances (hereinafter, such instances are also referred to as "over-etched" instances).

[0357] Based on the test results obtained, the following observations can be made:

[0358] The preferred test compositions (I1, I2, I3, I4, I5, I6 and I7) of the first preferred variation of the invention listed in Table 1a all exhibit AlO x High etch rate selectivity relative to Cu layer etching (see results in Table 2). In compositions with a pH of 6.4 (or higher; see compositions I6 and I7), AlO xThe appearance of “over-etching” of the layer (i.e., a value >100% etch) disappears first (during the applied period). Therefore, compositions having a pH value of 6.4 (or higher, up to 7.5) are considered preferred test compositions according to the invention.

[0359] Over-etching results indicate that deviations from the optimal pH value or composition can lead to an unfavorable increase in the etching rate, thus resulting in a loss of etching rate selectivity. Simply reducing the etching time to achieve the optimal etching result is not preferred, as this may lead to even less accurate etching times due to practical limitations. For example, the etching time selected in the embodiments of the present invention for etching AlO2... x The 1-minute etching time for the layer is an industrially relevant timeframe. For practical reasons, the etching rate achieved using a particular composition is also relevant, in addition to the total etching loss.

[0360] In the practically preferred pH range (pH 6.8 to 7.5), compositions containing organic solvents according to the first preferred variation of the invention more strongly tend to exhibit incomplete etching results, with a sharp drop between pH 7.1 and 7.3 (see compositions I4 and I5). Conversely, composition I1, which does not contain organic solvents, exhibits a high but controlled etching rate (but no over-etching) and high etching rate selectivity for the Cu layer in the preferred pH range. Compositions not containing organic solvents according to the first preferred variation of the invention (see, for example, compositions I1 and I2) are therefore preferred.

[0361] The test compositions of the first preferred variation according to the invention listed in Table 1b demonstrate AlO x The etching rate selectivity relative to the Cu layer is good (see compositions I9, I10 without organic solvents or containing preferred organic solvents) or satisfactory (see compositions I11, I12 and I13, all containing butyl diethylene glycol as a less preferred organic solvent). All test compositions listed in Table 1b showed etching under the applied reaction conditions.

[0362] The comparative compositions (C1, C2) listed in Table 1c do not exhibit AlO x The etching rate selectivity relative to the Cu layer is satisfactory, i.e., the significantly unfavorable etching of the Cu layer is observed in each example (see Table 2 above).

[0363] Example 3: Preparation of the composition according to the invention (second preferred variation) and a comparative composition (not according to the invention)

[0364] The compositions (compositions I20, I21, and I22) of the second preferred variation according to the invention are prepared by mixing components (A) to (D) and (G). Details are given below in Table 3. Furthermore, comparative compositions (compositions C20 and C21, not according to the invention) are also prepared in a similar manner, as shown in more detail in Table 4 below.

[0365] Table 3: Test compositions according to the present invention (second preferred variation)

[0366]

[0367] Table 4: Comparative Test Compositions

[0368]

[0369] DMSO: Dimethyl sulfoxide

[0370] All weight percent of the components in Tables 3 and 4 are calculated based on pure, undiluted compounds.

[0371] Example 4: Determination of alumina (AlOx) and cobalt etching results of the test composition (second preferred variant)

[0372] Having an outer layer of appropriate type (Co; AlO) x The Si wafers or wafers (collectively referred to below as "test wafers") of tetraethyl orthosilicate ("TEOS") deposited by plasma deposition were obtained from commercial sources. The test wafers were pretreated, optionally by immersing Co in oxalic acid solution for 20-30 seconds, followed by rinsing with water and drying. This was not performed on AlO₂-coated Si wafers. x The coated surface is pretreated.

[0373] Alumina (AlO) x The coated surface serves as a representative model of a layer (as defined above) containing or composed of an aluminum compound.

[0374] The test composition was prepared (as defined in Tables 3 and 4) and the test wafer (see above) was brought into contact with the test composition in a glass beaker at 40°C for 1 minute on a cobalt-coated surface, at 35°C for 15 seconds on an alumina-coated surface, and at 35°C for 10 minutes on a TEOS surface. The test wafer was then removed from the test composition, rinsed with water or isopropanol, and dried under nitrogen.

[0375] The thicknesses of the cobalt, TEOS, and alumina layers on the test wafer were determined by X-ray fluorescence analysis before and after contact with the test composition. The experiment was repeated at least three times to ensure reproducibility.

[0376] In each example, the difference between the measured thickness of the cobalt, TEOS, or AlOx layer before contact with the test composition and the measured thickness of the same cobalt, TEOS, or AlOx layer after contact with the test composition was determined as the total etching loss. The etching rate was obtained by dividing the total etching loss by the program time. The results were calculated using the etching rate of the layer after contact with the test composition. The values ​​are shown in Table 5 below (each given value in Table 5 represents the average of at least three experiments).

[0377] Table 5: Etching results of the test compositions for cobalt, TEOS, and alumina (second preferred variation)

[0378]

[0379] From the test results shown in Table 5, the following observations can be made:

[0380] Composition I20 according to the present invention exhibits AlO x Satisfactory etch rate selectivity compared to the etching of Co and TEOS layers.

[0381] The compositions I22 and C20 according to the present invention (not comparative compositions according to the present invention) regarding AlO x The etch rate selectivity relative to the etching of the Co layer showed similarly satisfactory results (but see the results of Example 5 below).

[0382] Example 5: Testing the stability of the composition (second preferred variant) against precipitation.

[0383] The test composition I20 and the comparative test composition C20 according to the present invention were cooled to 5°C for 72 hours. Immediately after the cooling period, the solution stability (i.e., the precipitated substances) of the two compositions was visually inspected.

[0384] It was found that composition I20 according to the invention remained transparent after the cooling period, indicating that it still had solution stability even at lower temperatures, while the comparative composition C20 showed precipitation of the substance, indicating that the solution was not stable enough at temperatures below room temperature.

[0385] These observations suggest that compositions containing the solubilizer according to the invention (in composition I20: N-formylmorpholine) exhibit enhanced solution stability against precipitation compared to compositions that do not contain the solubilizer according to the invention or contain a solubilizer other than the solubilizer according to the invention (in comparative composition C20: DMSO).

[0386] As is known in the art, compositions of materials used for etching one or more materials for manufacturing semiconductor devices must remain stable under manufacturing conditions, for example, without forming precipitates that could interfere with or damage the manufacturing process or its products. Therefore, compositions of materials used for etching one or more materials for manufacturing semiconductor devices that form precipitates under the conditions of such manufacturing processes are unacceptable for industrial use.

Claims

1. A composition for selectively etching a layer comprising an aluminum compound in the presence of a low-k material layer and / or a layer comprising copper and / or cobalt, said composition comprising: (A) One or more solubilizers selected from 4-methylmorphofolin-4-oxide, N-ethylmorphofolin-N-oxide, and mixtures thereof; (B) One or more etchants containing fluorine anions; (C) One or more corrosion inhibitors, The component (C) is a combination of benzotriazole and 6-methylbenzotriazole; (D) One or more chelating agents selected from: 1,2-cyclohexanediaminetetraacetic acid, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, acetylacetonate, 2,2'-azaalkyldiacetic acid, ethylenediaminetetraacetic acid, ethionine, methanesulfonic acid, acetylacetone, 1,1,1-trifluoro-2,4-pentanedione, 1,4-benzoquinone, 8-hydroxyquinoline, salinomyline; tetrachloro-1,4-benzoquinone, 2-(2-hydroxyphenyl)-benzo[a] azole, 2-(2-hydroxyphenyl)-benzothiazole, hydroxyquinoline sulfonic acid, sulfosalicylic acid, salicylic acid, pyridine, 2-ethylpyridine, 2-methoxypyridine, 3-methoxypyridine, 2-methylpyridine, dimethylpyridine, piperidine, piperazine, triethylamine, triethanolamine, ethylamine, methylamine, isobutylamine, tert-butylamine, tributylamine, dipropylamine, dimethylamine, diethylene glycolamine, monoethanolamine, methyldiethanolamine, pyrrole, isobutylamine Azole, bipyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquinoline, indole, 1-methylimidazolium, diisopropylamine, diisobutylamine, aniline, pentamethyldiethylenetriamine, acetylacetamide, ammonium carbamate, pyrrolidine dithiocarbamate, dimethyl malonate, methyl acetoacetate, N-methylacetylacetamide, tetramethylammonium thiobenzoate, 2,2,6,6-tetramethyl-3,5-heptadecane, tetramethylthiuram disulfide, lactic acid, ammonium lactate, formic acid, propionic acid, γ-butyrolactone, and mixtures thereof; (E) One or more surfactants; (F) A buffer system suitable for buffering the pH of the composition in the range of 6 to 8, and (G) Water, The pH of the composition is in the range of 6 to 8.

2. The composition according to claim 1, wherein the pH of the composition is in the range of 6.4 to 7.

5.

3. The composition according to claim 1, wherein the one or more etchants (B) containing fluorine anions are selected from: ammonium fluoride, ammonium difluoride, triethanolamine fluoride, diethylene glycol ammonium fluoride, methyl diethanolamine fluoride, tetramethylammonium fluoride, triethylamine trihydrofluoride, hydrogen fluoride, fluoroboric acid, tetrafluoroboric acid, ammonium tetrafluoroborate, fluoroacetic acid, ammonium fluoroacetate, trifluoroacetic acid, fluorosilicic acid, ammonium fluorosilicate, tetrabutylammonium tetrafluoroborate, and mixtures thereof.

4. The composition according to claim 2, wherein the one or more etchants (B) containing fluorine anions are selected from: ammonium fluoride, ammonium difluoride, triethanolamine fluoride, diethylene glycol ammonium fluoride, methyl diethanolamine fluoride, tetramethylammonium fluoride, triethylamine trihydrofluoride, hydrogen fluoride, fluoroboric acid, tetrafluoroboric acid, ammonium tetrafluoroborate, fluoroacetic acid, ammonium fluoroacetate, trifluoroacetic acid, fluorosilicic acid, ammonium fluorosilicate, tetrabutylammonium tetrafluoroborate, and mixtures thereof.

5. The composition according to any one of claims 1-4, wherein - The component (D) is 1,2-cyclohexanediaminetetraacetic acid. and / or - The component (B) is ammonium fluoride.

6. The composition according to any one of claims 1-4, wherein the total amount of the one or more solubilizers of component (A) present on a total weight basis of the composition is in the range of 2 to 15% by weight.

7. The composition according to claim 5, wherein the total amount of the one or more solubilizers of component (A) present on a total weight basis of the composition is in the range of 2 to 15% by weight.

8. The composition according to any one of claims 1-4, wherein the total amount of the one or more etchants of component (B) present on a total weight basis of the composition is in the range of 0.001 to 1% by weight.

9. The composition according to claim 7, wherein the total amount of the one or more etchants of component (B) present on a total weight basis of the composition is in the range of 0.001 to 1% by weight.

10. The composition according to any one of claims 1-4, wherein the total amount of the one or more corrosion inhibitors of component (C) present on a total weight basis of the composition is in the range of 0.01 to 4% by weight.

11. The composition according to claim 9, wherein the total amount of the one or more corrosion inhibitors of component (C) present on a total weight basis of the composition is in the range of 0.01 to 4% by weight.

12. Use of the composition according to any one of claims 1-11, It is used for selective etching of layers containing aluminum compounds in the presence of low-k material layers and / or layers containing copper and / or cobalt; and / or It is used to selectively remove layers containing aluminum compounds from a substrate in the presence of low-k material layers and / or layers containing copper and / or cobalt; and / or It is used to selectively remove aluminum compound-containing layers from the surface of a semiconductor substrate in the presence of low-k material layers and / or layers containing copper and / or cobalt.

13. The use according to claim 12, wherein it is used to remove the following two-step method: (i) Metallic hard shielding, selected from: Ti hard shielding, TiN hard shielding, Ta hard shielding, TaN hard shielding, Al hard shielding, HfO x Hard shielding and AlCu hard shielding and (ii) An etch-stop layer of aluminum compound deposited on a copper-containing layer and / or a cobalt-containing layer. The aforementioned use is for the second step (ii).

14. A method for manufacturing a semiconductor device, comprising the following steps In the presence of a low-k material layer and / or a layer containing copper and / or cobalt, the at least one aluminum compound layer is selectively etched by contacting at least one layer containing an aluminum compound or composed of an aluminum compound with the composition as described in any one of claims 1-11 at least once. and The etching is performed in the presence of a low-k material layer and a layer containing copper and / or cobalt.

15. The method of claim 14, wherein the at least one layer comprising an aluminum compound or composed of an aluminum compound is a top layer, a layer comprising copper and / or cobalt is a bottom layer covered by the top layer, and there is or is not at least one additional layer present between the top and bottom layers.

16. The method according to claim 14 or 15, wherein the method comprises a two-step cleaning method, which includes the following steps: In the first step, the metallic hard shield is removed, and it is selected from: Ti hard shield, TiN hard shield, Ta hard shield, TaN hard shield, Al hard shield, and HfO. x Hard shielding and AlCu hard shielding Subsequently, in a separate second step, the at least one layer containing or composed of an aluminum compound is selectively etched.

17. The method of claim 14 or 15, wherein the at least one layer comprising an aluminum compound or composed of an aluminum compound has a maximum thickness of 20 nm or less prior to etching.

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