Compositions and methods for selectively etching hard masks and / or etching stop layers in the presence of low k-value materials, copper, cobalt, and / or tungsten layers.

Abstract

To provide a method of using a cleaning composition for removing post-etch or post-ash residues from a surface of a semiconductor substrate and / or layers that include an aluminum compound from a surface of a semiconductor substrate.SOLUTION: A cleaning compositions include one or more compounds such as 4-methylmorpholine-4-oxide as a dissolving agent, one or more corrosion inhibitors selected from the group consisting of unsubstituted or substituted benzotriazoles and mixtures thereof, one or more polar aprotic organic solvents, water, and one or more alkyl glycol ethers in combination with one or more oxidizing agents.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to the use of a cleaning composition for removing post-etching or post-ashing residues from the surface of a semiconductor substrate and / or for oxidizing etching or partially oxidizing etching of a layer or mask comprising or consisting of a material selected from the group consisting of TiN, Ta, TaN, Al, and HfOx, and / or for removing a layer containing an aluminum compound from the surface of a semiconductor substrate in combination with one or more oxidizing agents. The present invention further relates to a cleaning composition and a method of using the cleaning composition for removing post-etching or post-ashing residues from the surface of a semiconductor substrate. In a further aspect, the present invention also relates to a wet etching composition comprising a cleaning composition and one or more oxidizing agents and a method of using the wet etching composition. The present invention also relates to a method for the manufacture of semiconductor devices from a semiconductor substrate and a kit comprising a cleaning composition and one or more oxidizing agents.

Background Art

[0002] The method for manufacturing a semiconductor device is a plurality of steps in which photolithography and chemical treatment steps are consecutive. During these steps, an electronic circuit is gradually formed on a substrate, typically a wafer (a "semiconductor substrate", specifically a "semiconductor wafer") made of a pure semiconductor material. Preferably, silicon is used as the semiconductor material. A typical semiconductor substrate (wafer) is made of very pure silicon grown into a single crystal cylindrical ingot (boule) with a maximum diameter of 300 mm using the so-called "Czochralski method". These ingots are then sliced into wafers with a thickness of about 0.75 mm and polished to obtain a very regular and flat surface.

[0003] A particular method for manufacturing semiconductor wafers consists of several steps, including, for example, so-called "front-end of line" ("FEOL") and "back-end of line" ("BEOL") processing stages.

[0004] The FEOL (Front-End-of-Layer) processing stage involves directly forming transistors into the semiconductor wafer material (typically silicon). Raw semiconductor wafers are designed by growing ultra-high-purity, virtually defect-free silicon layers via epitaxy. Following the front-end surface design, the process continues with the growth of a gate insulator (e.g., silicon dioxide), patterning of its gate, patterning of the source and drain regions, and subsequent injection or diffusion of dopants into the semiconductor material to achieve the desired complementary electrical properties.

[0005] 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) must be interconnected to form the desired electrical circuits once they are fabricated by FEOL processing. This is done in a series of wafer processing steps collectively known as BEOL. The BEOL processing step involves creating metal interconnect wires on the surface of a semiconductor wafer separated by layers of low dielectric constant materials, such as materials with a dielectric constant κ < 3.9 (also known as "low k-value materials"). Modern composite process manufacturing methods have been developed for forming integrated circuit (IC) interconnects on semiconductor substrates, incorporating copper (Cu) and, more recently, cobalt (Co) as conductive materials instead of aluminum. These methods include various techniques for selectively creating and removing continuous layers of conductive and insulating (dielectric) materials, such as chemical vapor deposition (CVD), electroplating, photolithography, wet etching, or dry etching, chemical mechanical polishing (CMP), and several cleaning steps, for example, removing residues from the aforementioned material removal steps from the surface of the processed semiconductor substrate.

[0006] Such a single composite process manufacturing method is known as a damascene manufacturing method using its variations, such as the TFVL ("Trench First Via Rust") dual damascene process, the VFTL ("Via First Trench Rust") dual damascene process, the self-aligned dual damascene process, or the dual damascene patterning process using a metal-containing hard mask (see, for example, U.S. Patent No. 6,696,222 for the latter).

[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. After patterning, a thin barrier layer (e.g., consisting 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 this barrier layer, a seed layer is often deposited to support better adhesion of copper to the underlying material and to act as a catalytic material during the plating process. Typical materials for these seed layers are Pd, Co, or other materials, such as compounds containing polymers and organic materials. The original deposition process (damascene process) was designed to process each layer independently. Therefore, so-called "longitudinal interconnect access" ("vias") and metallize levels have different process steps, requiring a series of cleaning, material deposition, CMP, and another cleaning step for each layer. Copper techniques that use this series for their metallize levels and their ILDs and intervia dielectrics ("IVDs") are often called "single damascene processes." Typically, in a single damascene process, each level requires its own capping or etching-stopping layer, an individual ILD layer, and at the top, a material that can be polished together with the interconnecting metal copper, such as SiO2. Alternatively, dual damascene processing technology combines several similar process steps into a single process step, thereby reducing the number of process steps, time, and cost required to construct a BEOL laminate. Thus, the dual damascene process produces the IVD and metallized layers in a single step.

[0008] In damascene fabrication processes or variations thereof, a conductive mask (i.e., a “hard mask”) is often used to protect one or more underlying layers, such as low-k-value materials, for example, layers under dielectric materials, during an etching process. Such conductive (“metallic”) masks (i.e., “hard masks”) are typically deposited in the form of layers containing, for example, Ti, TiN, Ta, TaN, Al, or HfOx (i.e., hafnium oxide), and / or in the form of layers containing, for example, tungsten carbide (WCx) or tungsten nitride (WNx). For example, in a dual damascene patterning process using a metal-containing hard mask, the metal layer deposited on the dielectric (low-k-value) material serves as a hard mask for the second etching process.

[0009] As the demand for further minimization of structures on semiconductor substrates, particularly on semiconductor wafers, progresses, manufacturers face new challenges: for example, in integration schemes for even smaller structures on semiconductor wafers, such as integration schemes for manufacturing 10nm or smaller structures on a semiconductor wafer, or 7nm or smaller structures, via formation is preferably done by using a metal-containing hard mask, often a TiN hard mask, and a subsequent dry etching process to remove low-k-value material located directly beneath the metal-containing hard mask (e.g., a Ti-containing hard mask such as a TiN hard mask) and optionally separated from the metal-containing / TiN hard mask by an additional layer, e.g., a metal-free hard mask, or a connecting layer. To protect the underlying copper and / or cobalt and / or tungsten at the bottom of the formed vias, a thin etching stop layer is usually deposited on top of the copper and / or cobalt and / or tungsten (i.e., on the surface of the copper and / or cobalt and / or tungsten metal). This thin etching stop layer often contains or consists of one or more aluminum compounds, and its film thickness can be 30 nm or less, particularly 20 nm or less, more particularly 10 nm or less, or even 5 nm or less. Such an etching stop layer is often referred to as "ESL" ("etching stop layer" for dry etching).

[0010] To proceed with the manufacturing process, the following materials must be removed: 1) a hard mask containing metal (e.g., a TiN hard mask), 2) any polymer residue remaining in the vias, and 3) an etching stop layer. The removal of these three materials can be achieved by either a one-step or two-step process. In both alternatives to the three removal processes, it is important that certain other materials also present on the semiconductor substrate are not etched, damaged, or removed to the minimum possible extent so that they are protected to the highest possible extent. Such other materials protected by the three removal processes include low-k materials, copper, cobalt, and tungsten, and may be present beneath a layer of low-k materials (as described above) and / or beneath an etching stop layer containing or consisting of one or more aluminum compounds.

[0011] In a one-step process, all three removal processes are carried out simultaneously by applying a suitable composition that typically contains one or more oxidizing agents, such as hydrogen peroxide.

[0012] In a two-step process, in the first step, a hard mask containing metal (e.g., a TiN hard mask) is typically removed along with residues from the previous manufacturing step, such as polymer residues, by applying a composition that typically contains an oxidizing agent, such as hydrogen peroxide. The composition should not damage layers of low-k-value material or etching stop layers, specifically etching stop layers containing or composed of aluminum compounds. In the second step, the etching stop layers are removed by applying a suitable composition. Typically, this second step also removes any polymer residues still present in the vias (see above).

[0013] The composition used in the one-step process described above should selectively remove a hard mask containing or consisting of a metal representative of TiN, an etching stop layer, specifically an etching stop layer containing or consisting of one or more aluminum compounds, and any polymer residue still present in the vias, without damaging any existing layers of low k-value material, any existing copper and / or any existing cobalt, and preferably any existing tungsten, or damaging them to the minimum possible extent.

[0014] For this purpose, the composition used in the one-step process needs to have properties that enable highly controlled specific etching of layers containing or consisting of aluminum compounds, and further thin or ultrathin layers containing or consisting of aluminum compounds, without impairing any additional low k-value materials, copper metals, and / or cobalt metal layers that may be present.

[0015] A specific additional requirement arising in the manufacturing process for structures below 7 nm on semiconductor substrates, particularly for 5 nm structures, is that any tungsten metal or tungsten material present should not be etched, damaged, or removed in the three removal processes, even if it is located beneath a layer of low-k material and / or beneath an etching stop layer containing or consisting of one or more aluminum compounds. Even if the tungsten metal or tungsten material is (only) located beneath a layer of low-k material and / or beneath an etching stop layer containing or consisting of one or more aluminum compounds, it has been found that compositions previously used to perform the three removal processes in a one-step process (such as those described above) are not suitable for adequately protecting any tungsten metal or tungsten material in the three removal processes. It is assumed in this context that compositions previously used to perform the three removal processes in a one-step process may penetrate or diffuse through pores or capillaries present in the layer covering the tungsten metal or tungsten material, i.e., the layer of low-k material and (usually further) the etching stop layer containing one or more aluminum compounds.

[0016] As defined herein, the compositions according to the present invention are particularly suitable for application in a one-step (three-removal) process, specifically for manufacturing processes for structures of 10 nm, preferably structures below 10 nm (the term “structures below 10 nm” throughout this text refers to and includes structures less than 10 nm, e.g., 7 nm structures and / or 5 nm structures), more preferably 7 nm structures. As defined herein, preferred compositions according to the present invention are even suitable for application in a one-step (three-removal) process, specifically for manufacturing processes for structures below 7 nm, particularly 5 nm structures, on semiconductor substrates.

[0017] While dielectric films of aluminum oxide can generally be removed by wet etching in acidic and basic media (see, for example, B. Zhou et al., J. Electrochem. Soc. Vol. 143(2) 619-623 (1996), or J. Oh et al., J. Electrochem. Soc. Vol. 156(4) D217-D222 (2011)), it is known that these methods lack the precision and reliability of etching rates required to etch thin or ultrathin etching stop layers containing or composed of aluminum compounds, such as aluminum oxide.

[0018] U.S. Patent Application Publication No. 2018 / 0148669(A1) addresses a cleaning composition for removing post-etching residues.

[0019] U.S. Patent No. 9,546,321(B2) describes compositions and methods for selectively etching titanium nitride.

[0020] International Publication No. 2008 / 080097(A2) discusses liquid cleaning agents for removing post-etching residues.

[0021] International Publication No. 2019 / 110690(A2) (a document published after the earliest filing date of this patent application) deals with compositions and methods for selectively etching layers containing aluminum compounds in the presence of low k-value materials, copper and / or cobalt layers.

[0022] International Publication No. 03 / 035797(A1) relates to an aqueous cleaning composition containing a copper-specific corrosion inhibitor for cleaning inorganic residues on semiconductor substrates.

[0023] International Publication No. 2004 / 030038(A2) concerns a composition substrate for removing etching residue and a method for using the same.

[0024] International Publication No. WO 2009 / 064336 (A1) pamphlet teaches a composition for removing metal-containing hard mask etching residues from a semiconductor substrate.

[0025] International Publication No. WO 2012 / 009639 (A2) pamphlet relates to an aqueous cleaning agent for removing post-etching residues.

[0026] International Publication No. WO 2014 / 197808 (A1) pamphlet describes a composition and method for selectively etching titanium nitride.

[0027] U.S. Patent Application Publication No. 2004 / 061092 relates to wet etching for selective removal of alumina.

[0028] U.S. Patent Application Publication No. 2010 / 0075478 relates to a method for removing pattern resist.

[0029] U.S. Patent Application Publication No. 2012 / 0052686 relates to a cleaning solution and damascene processing using the same.

Prior Art Documents

Patent Documents

[0030]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

[0031] [Non-Patent Document 1] B.Zhou et al.,J.Electrochem.Soc.Vol.143(2)619-623(1996) [Non-Patent Document 2] J.Oh et al.J.Electrochem.Soc.Vol.156(4)D217-D222(2011) [Overview of the project] [Problems that the invention aims to solve]

[0032] Thus, the main object of the present invention is to provide a composition that helps remove post-etching or post-ashing residue from the surface of a semiconductor substrate, and a composition that helps selectively or partially etch a layer or hard mask and / or a layer containing or consisting of one or more aluminum compounds, in the presence of a low-k material and one or more materials selected from the group consisting of copper, cobalt, and tungsten on the surface of the semiconductor substrate. The composition should not simultaneously impair, or significantly impair, the low-k material and the one or more materials selected from the group consisting of copper, cobalt, and tungsten, which are also present. The composition should be particularly suitable for use in manufacturing processes for creating 7 nm structures and / or structures smaller than 7 nm (ideally including 5 nm structures) on a semiconductor substrate.

[0033] Another object of the present invention is to provide a process for manufacturing a semiconductor device in which post-etching or post-ashing residue is removed from the surface of a semiconductor substrate, and / or a layer or hard mask is selectively etched on the surface of a semiconductor substrate, and / or a layer comprising or consisting of one or more aluminum compounds is selectively etched on the surface of a semiconductor substrate in the presence of a low k-value material and one or more materials selected from the group consisting of copper, cobalt, and tungsten.

[0034] Further objects of the present invention are disclosed or become apparent from this specification and the appended claims. [Means for solving the problem]

[0035] It has been found that the primary and other objectives of the present invention can be achieved by using a cleaning composition containing at least the following components (i.e., one or more further substances may be present): (A) One or more compounds of formula I as a solvent:

[0036] [ka]

[0037] [In the formula, R1 is selected from the group consisting of branched or unbranched (preferably unbranched) alkyl groups having 1, 2, 3, or 4 carbon atoms]; (B) One or more corrosion inhibitors selected from the group consisting of unsubstituted or branched or unbranched alkyl groups having 1, 2, 3, or 4 carbon atoms, aminoalkyl groups having 1, 2, 3, or 4 carbon atoms, benzotriazoles independently substituted once or twice with phenyl, thiophenyl, halogen, hydroxy, nitro, and / or thiols, and mixtures thereof; (C) One or more polar aprotic organic solvents, Preferably, one, at least one, or all polar aprotic organic solvents (C) are selected from the group consisting of the following: - Alkyl sulfone compounds of formula IV: [ka] [In the formula, R5 is a branched (structurally possible) or unbranched alkyl group having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms. R6 is a branched (structurally possible) or unbranched alkyl group having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms. or R5 and R6 together constitute a branched (structurally possible) or unbranched alkylene group having 3 to 5 carbon atoms, preferably 3 to 4 carbon atoms, where one or two carbon atoms of the alkylene group can be independently substituted by -O-R7 (i.e., any -O-R7 group is bonded to a carbon atom of the alkylene group in each case, substituting for any otherwise present hydrogen atoms), and R7 is a branched (structurally possible) or unbranched alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms; - Dimethylformamide, - Dimethyl sulfoxide, - Dimethylacetamide, - N-methylpyrrolidone, - Propylene carbonate, - Tetrahydrofuran, - 2-imidazolidinone having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, and substituted once or twice with a branched (structurally possible) or unbranched alkyl group; preferably 1,3-dimethyl-2-imidazolidinone and - These mixtures More preferably, one, or at least one, or all polar aprotic organic solvents (C) are selected from the group consisting of alkyl sulfone compounds of formula IV as defined above; dimethyl sulfoxide; dimethylacetamide; N-methylpyrrolidone; propylene carbonate; 2-imidazolidinone, preferably 1,3-dimethyl-2-imidazolidinone, which is substituted once or twice by a branched or unbranched alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms; and mixtures thereof. More preferably, one, at least one, or all polar aprotic organic solvents (C) are selected from the group consisting of alkyl sulfone compounds of formula IV as defined above; dimethyl sulfoxides; dimethylacetamides; N-methylpyrrolidones; and mixtures thereof. One or more polar aprotic organic solvents and (D) Water combined with one or more oxidizing agents, Preferably, one or more oxidizing agents are selected from the group consisting of hydrogen peroxide, urea peroxide, peroxydisulfate, ammonium persulfate, peroxymonosulfate, pyrosulfate, ozone, and mixtures thereof. - For removing post-etching or post-ashing residue from the surface of a semiconductor substrate. and / or - A material preferably containing or consisting of a layer or mask, preferably a hard bath, and / or a layer or mask, preferably oxidatively etched or partially etched, preferably partially oxidatively etched, of a layer or mask containing or consisting of a material selected from the group consisting of Ti, TiN, Ta, TaN, Al, and HfOx, is TiN. Preferably, water on the surface of the semiconductor substrate.

[0038] The cleaning compositions, combined with one or more oxidizing agents, are suitable for use on semiconductor substrates without affecting or significantly affecting any existing low-k material, any existing copper, and / or any existing cobalt layers. What was particularly remarkable was that they enabled highly controlled specific etching of layers or hard masks containing or consisting of materials selected from the group consisting of Ti, TiN, Ta, TaN, Al, and HfOx, and / or layers or hard masks containing or consisting of materials selected from the group consisting of tungsten carbide (WCx) and tungsten nitride (WNx), as well as highly controlled specific etching of layers containing or consisting of one or more aluminum compounds, and further, thin or ultrathin layers containing or consisting of aluminum compounds.

[0039] Therefore, cleaning compositions combined with one or more oxidizing agents as defined above are particularly suitable for use in manufacturing processes to create 10 nm structures or structures smaller than 10 nm (as defined above), especially 7 nm structures, in a single step on a semiconductor substrate, including the removal of three types of materials: a hard mask, an etching stop layer, and polymer residue (as described above).

[0040] As defined above, the preferred cleaning compositions, in combination with one or more oxidizing agents, are suitable for application in manufacturing processes for structures below 7 nm, and especially for 5 nm structures, including the removal of three types of materials (hard mask, etching stop layer, and polymer residue, as described above) from a semiconductor substrate in a single step. [Modes for carrying out the invention]

[0041] The present invention, as well as preferred embodiments, parameters, properties, and preferred combinations of these elements, are defined in the appended claims. Preferred aspects, details, modifications, and advantages of the present invention are also defined and described in the following description and the examples described below.

[0042] In the context of the present invention, “one or more aluminum compounds” in a layer containing or consisting of one or more aluminum compounds includes one or more compounds selected from the group consisting of aluminum oxide ("AlOx", "AlOxNyFz", where the indices “x”, “y”, and “z” represent numbers indicating the stoichiometric or non-stoichiometric amount of each chemical element), aluminum nitride, aluminum oxynitride ("AlON"), and aluminum carbide nitride ("AlCNO"). Preferably, the aluminum compound also includes fluorine. As defined herein, the exact composition of the aluminum compound, and the exact content or proportion of the elements aluminum, oxygen, nitrogen, carbon, and / or fluorine present in one of the aluminum compounds, may vary, for example, depending on the type of pretreatment of the semiconductor substrate containing the aluminum compound.

[0043] In this text, the term "etching stop layer" is consistent with its usual meaning in this art and refers to a layer of material that is not etched under the conditions applied in a typical etching process for structuring the surface of a semiconductor substrate (e.g., a microelectronic device), particularly a semiconductor wafer, and coats underlying materials that are potentially sensitive to the etching process, such as copper (e.g., in copper interconnects) or other metals, to protect them from undesirable attack by the etchant applied. After the etching process, the etching stop layer can be removed (if necessary) under conditions specific to the etching stop layer material, without further adversely affecting the underlying materials.

[0044] In the context of the present invention, "low k-value material" is preferably a material having a dielectric constant κ < 3.9. and / or (preferably "and") (i) Silicon-containing materials preferably selected from the group consisting of SiO2, silicon oxycarbide (SiOC), tetraethyl orthosilicate (TEOS), boron-doped phosphosilicate glass (BPSG), fluorine-doped silicon dioxide (fluorosilicate glass FSG), carbon-doped silicon dioxide, organosilicate glass (OSG), carbon-doped oxide (CDO), porous silicon dioxide, porous carbon-doped silicon dioxide, and spin-on silicon polymer materials, preferably hydrogen silsesquioxane (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 the group consisting of spin-on organic polymer dielectrics, preferably polyimide (PI); polynorbornene; benzocyclobutene, and polytetrafluoroethylene (PTFE).

[0045] In the cleaning compositions for use according to the present invention as defined above, one or more solvents (A), one or more corrosion inhibitors (B), and one or more polar aprotic organic solvents (C) can generally be used individually (as a single compound) or in combination with other compounds of the same type (where applicable, the solvent, corrosion inhibitor, and polar aprotic organic solvent, respectively).

[0046] In the context of the present invention, preferably, a “non-proton” solvent means a solvent that is not capable of acting as a proton donor with water (at pH 7).

[0047] As defined above, in the cleaning compositions for use according to the present invention, R1 in the compound of chemical formula I in one or more solvents of component (A) specifically includes methyl, ethyl, and branched and unbranched propyl and butyl. Preferably, R1 is methyl. 4-Methylmorpholine-4-oxide (also referred to hereafter as "4-MM-4-O" or "NMMO" and also known as N-methylmorpholine-N-oxide, CAS RN 7529-22-8) is a particularly preferred compound of chemical formula I for use in cleaning compositions as defined above. This definition of the compound of chemical formula I includes hydrates, specifically the monohydrate of 4-methylmorpholine-4-oxide (CAS RN 70187-32-5), and isomers and tautomers of the compound of chemical formula I.

[0048] In a cleaning composition for use according to the present invention as defined above, if component (B) comprises one or more corrosion inhibitors selected from the group consisting of benzotriazoles that are unsubstituted or substituted (as defined above), this definition comprises one such benzotriazole and a plurality of such benzotriazoles that can be independently unsubstituted or substituted as defined above, and a mixture of such benzotriazoles.

[0049] If component (B) comprises a benzotriazole independently substituted once or twice by a branched or unbranched alkyl group having 1, 2, 3, or 4 carbon atoms, this definition specifically includes methyl, ethyl, and branched and unbranched propyl and butyl groups. Methyl is preferred for the purposes of the present invention. Specific benzotriazoles included by this definition are 5-methylbenzotriazole and 6-methylbenzotriazole (see below for applicable nomenclature). If component (B) comprises a benzotriazole substituted by an aminoalkyl group, where the alkyl group is branched or unbranched and has 1, 2, 3, or 4 carbon atoms, 2-(5-aminopentyl) is preferred for the purposes of the present invention.

[0050] If component (B) contains a benzotriazole that is independently substituted once or twice with a halogen, the halogen is selected from fluorine, chlorine, bromine, and iodine, preferably from chlorine and bromine. A benzotriazole that is substituted with chlorine, preferably once substituted with chlorine, is preferred as a benzotriazole that is independently substituted once or twice with a halogen.

[0051] As is known in the art, in benzotriazole, the bond between positions (i.e., ring nitrogen atoms) 1 and 2, and the bond between positions (i.e., ring nitrogen atoms) 2 and 3, have the same bonding properties. A proton bonded to one nitrogen atom in the nitrogen-containing ring of the benzotriazole structure does not firmly bond to any of the three ring nitrogen atoms present, but rather rapidly moves between positions 1 and 3 to form tautomers. Therefore, for the purposes of the present invention, the name "5-methyl-2H-benzotriazole" as used above includes this compound and all of its tautomers, specifically the compound known as "5-methyl-benzotriazole," "6-methyl-benzotriazole" (CAS RN 49636-02-4), "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 this text, the compounds referred to 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" each have the same meaning as the compound "5-methyl-2H-benzotriazole and all its tautomers."

[0052] Accordingly, for the purposes of the present invention, the name "5-chloro-2H-benzotriazole" as used herein includes this compound and all of its tautomers, specifically the compounds known 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 this text, compounds referred to 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" each have the same meaning as the compound "5-chloro-2H-benzotriazole and all its tautomers." This definition applies mutatis mutandis to other benzotriazoles, in particular substituted benzotriazoles, as defined or referred to in this text.

[0053] Benzotriazoles that are unsubstituted, or branched or unbranched alkyl groups having 1, 2, 3, or 4 carbon atoms, preferably independently substituted once or twice, preferably once, with methyl and / or (preferably "or") halogens, or mixtures thereof, are preferred as component (B). In particularly preferred variations of the present invention, component (B) is selected from the group consisting of unsubstituted benzotriazoles (BTA), 5-methyl-2H-benzotriazoles, 5-chloro-2H-benzotriazoles, and mixtures thereof.

[0054] Preferably, the cleaning composition is used in combination with one or more oxidizing agents according to the present invention as defined herein (or preferably, the cleaning composition is used in combination with one or more oxidizing agents according to the present invention as described above or below), and one, at least one, or all of the polar aprotic organic solvents (C) are alkyl sulfone compounds of formula IV (or multiple alkyl sulfone compounds) as defined above.

[0055] In the context of the present invention, the alkyl sulfone compound of formula IV is selected from the group consisting of ethyl methyl sulfone, ethyl isopropyl sulfone, ethyl isobutyl sulfone, isopropyl isobutyl sulfone, sulfolane, 3-methoxysulfolane, and mixtures thereof. More preferably, the alkyl sulfone compound of formula IV is selected from the group consisting of ethyl methyl sulfone, ethyl isopropyl sulfone, sulfolane, and mixtures thereof. In a particularly preferred variation of the present invention, the alkyl sulfone compound of formula IV includes or is sulfolane.

[0056] In the context of the present invention, “alkylene group” preferably means a divalent chain group of carbon atoms. Examples of “alkylene groups” as used herein include “methylene” (Ra-CH2-Rb), “ethylene” (Ra-CH2-CH2-Rb), “trimethylene” (Ra-CH2-CH2-CH2Rb), and “propylene” (H3C-C(Ra)H-CH2-).

[0057] As defined above, a cleaning composition according to the present invention, in particular a cleaning composition in which one or at least one polar aprotic organic solvent (C), or (in a particularly preferred modification of this embodiment of the invention) all of an alkyl sulfone compound of formula IV (or multiple alkyl sulfone compounds) (or preferably an alkyl sulfone compound of formula IV as described herein), when used in combination with one or more oxidizing agents according to the present invention as defined herein (or preferably in combination with one or more oxidizing agents according to the present invention as described above or below), has been found in our experience to exhibit the following beneficial effects: - High selectivity for etching (especially oxidative etching, or partially etching, especially partially oxidative etching) of a layer or mask containing or consisting of a material selected from the group consisting of Ti, TiN, Ta, TaN, Al, and HfOx, and / or a layer or mask containing or consisting of a material selected from the group consisting of tungsten carbide (WCx) and tungsten nitride (WNx), particularly TiN, while at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and low k-value materials is present on the surface of a semiconductor substrate; and - The cleaning composition exhibits high stability to one or more oxidizing agents, particularly to oxidizing agents containing peroxides, and more particularly to hydrogen peroxide. This high stability to one or more oxidizing agents, when used in combination with one or more oxidizing agents (as defined above), results in long-term high (selective) etching activity of layers or masks containing or made of materials selected from the group consisting of Ti, TiN, Ta, TaN, Al, and HfOx, and / or materials selected from the group consisting of tungsten carbide (WCx) and tungsten nitride (WNx), particularly layers or masks containing or made of TiN (as defined above) of the cleaning composition. For example, when used in combination with one or more oxidizing agents (particularly hydrogen peroxide), the cleaning composition can maintain its high, selective etching activity of layers or masks containing or made of TiN for long periods of 24 hours or more.

[0058] In some cases, the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as defined herein (or preferably the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as described above or below) is also preferred, and the cleaning composition may further consist of: (E) Contains one or more alkyl glycol ethers.

[0059] As defined above, our experience has shown that cleaning compositions containing the additive component (E) as defined above in combination with one or more oxidizing agents are suitable not only for use in manufacturing processes for creating 7nm structures on semiconductor substrates, but even for use in manufacturing processes for creating structures smaller than 7nm, preferably 5nm structures, on semiconductor substrates. This particularly beneficial utility of cleaning compositions containing additive component (E) (preferably preferred component (E) as defined herein and / or in the amounts defined herein or preferred amounts) lies in their ability to protect tungsten (preferably tungsten metal and / or tungsten material) that may be present beneath a layer of low-k material, or beneath an etching stop layer containing or comprising a layer of low-k material and one or more aluminum compounds, in combination with one or more oxidizing agents in a three-step removal process (as described above), preferably a one-step process (as described above).

[0060] Our experiments have shown that compositions previously used to carry out a three-step removal process (without component (E) as defined above), particularly in a one-step process (as described above), are unsuitable for adequately protecting any tungsten metal or tungsten material present in the three-step removal process beneath a layer of low-k material, or beneath an etching stop layer containing or comprising a layer of low-k material and one or more aluminum compounds. Furthermore, our experiments have shown that compositions previously used to carry out a three-step removal process and without component (E) may unintentionally damage, or at least partially etch, tungsten (or tungsten metal and / or tungsten material) present to a significant degree beneath a layer of low-k material, or beneath an etching stop layer containing or comprising a layer of low-k material and one or more aluminum compounds during the three-step removal process. Our experience also leads us to the conclusion that this damage or partial etching of tungsten occurs beneath a layer of low-k material, or beneath an etching stop layer comprising or consisting of a layer of low-k material and one or more aluminum compounds, because compositions not containing component (E) as defined above may penetrate or diffuse into a layer of low-k material, or an etching stop layer comprising or consisting of a layer of low-k material and one or more aluminum compounds that coats tungsten (or tungsten metal and / or tungsten material), in an amount sufficient to unintentionally damage or partially etch the underlying tungsten.

[0061] Further findings from our own experiments indicate that by selecting a certain preferred alkyl glycol ether (as defined and described below) as component (E) of a cleaning composition (as defined above), and / or by using the preferred alkyl glycol ether in the cleaning composition in the amounts defined and described below or a preferred amount, the beneficial properties of the cleaning composition used in combination with one or more oxidizing agents according to the present invention as defined above, to protect tungsten (as tungsten metal or as tungsten material) from damage, removal, or partial etching in the processes and / or methods described above, can be optimized.

[0062] Therefore, the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as defined herein (or preferably the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as described above or below) is preferred. - Component (E) is selected from the group consisting of alkyl glycol ethers having a Hansen polarity solubility parameter δp of ≤8 (MPa) 1 / 2, preferably ≤7.6 (MPa) 1 / 2. and / or - The cleaning composition contains one or more alkyl glycol ethers of formula II as component (E).

[0063] [ka] [In the formula, R2 is a branched or unbranched (preferably unbranched) alkylene group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms. R3 is a branched or unbranched (preferably unbranched) alkyl group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms. and n is an integer in the range of 1 to 6, preferably in the range of 2 to 6.

[0064] Our experience has shown that alkyl glycol ethers as defined above and preferred alkyl glycol ethers as defined below, when combined with one or more oxidizing agents, possess properties (e.g., hydrophobicity and / or viscosity) that make them excellently suitable for use in cleaning compositions for use according to the present invention.

[0065] For the purposes of the present invention, the "Hansen polarity solubility parameter δp" for the alkyl glycol ether of component (E) as defined above is preferably the respective parameter determined by Company Dow in the product data sheet for each compound, which can be accessed at the following internet address: https: / / www.dow.com / en-us / product-search / eseriesglycolethers and https: / / www.dow.com / en-us / product-search / pseriesglycolethers.

[0066] For compounds not found at the above address, the Hansen polar solubility parameter δp is preferably determined for the purposes of the present invention by the method defined in C. Hansen, “Hansen Solubility Parameters: A User's Handbook”, 2nd ed. 2007 (ISBN 9780849372483), particularly on pages 15-16.

[0067] Hansen solubility parameters were developed by Charles M. Hansen in his 1967 doctoral dissertation as a method for predicting whether one material will dissolve in another to form a solution. They are based on the idea that like dislike dissolves like, defining another molecule as "similar" if one molecule binds to itself in a similar manner. Specifically, each molecule is given three Hansen parameters, each generally measured at (MPa) 1 / 2: - δd: Energy from intermolecular dispersion forces - δp: Energy from bipolar intermolecular forces between molecules (referred to as the "Hansen polar solubility parameter" in the text) - δh: Energy from intermolecular hydrogen bonds

[0068] These three parameters can be considered as coordinates for a point in a three-dimensional space known as Hansen space. The closer two molecules are in this three-dimensional space, the more easily they dissolve in each other.

[0069] As defined above, in the cleaning compositions for use according to the present invention, one or more alkyl glycol ethers (E) can generally be used alone (as a single compound) or in combination with other alkyl glycol ethers (E) in each case.

[0070] Furthermore, as defined above, cleaning compositions according to the present invention comprising one or more alkyl glycol ethers (E) and one, or at least one, or all, polar aprotic organic solvents (C) including 2-imidazolidinone, particularly 1,3-dimethyl-2-imidazolidinone, which is substituted once or twice with branched or unbranched alkyl groups having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, have been found in our experiments to exhibit particularly good stability when used in combination with one or more oxidizing agents according to the present invention as defined herein (or preferably in combination with one or more oxidizing agents according to the present invention as described above or below). The particularly good stability (against one or more oxidizing agents, especially hydrogen peroxide) of the cleaning composition results in longer-lasting and higher (selective) etching activity of layers or masks containing or made of materials selected from the group consisting of Ti, TiN, Ta, TaN, Al, and HfOx, and / or tungsten carbide (WCx) and tungsten nitride (WNx), in particular TiN (as defined above), compared to the use of similar cleaning compositions containing one or more alkyl glycol ethers (E) but not 2-imidazolidinone (as defined above) as a polar aprotic organic solvent (C).

[0071] Therefore, the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as defined herein (or preferably the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as described above or below, in particular the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as defined below as "one preferred specific variation of the present invention") is preferred, The cleaning composition includes: One or more polar aprotic organic solvents (C), wherein one or at least one or all of the polar aprotic organic solvents (C) are 2-imidazolidinone, preferably 1,3-dimethyl-2-imidazolidinone, which is substituted once or twice by a branched or unbranched alkyl group having 1 to 4 carbon atoms, preferably having 1 to 2 carbon atoms. and (E) One or more alkyl glycol ethers (as defined herein or as preferred herein).

[0072] A cleaning composition for use in combination with one or more oxidizing agents according to the present invention as defined herein (or preferably the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as described above or below), wherein one, or at least one, or all of the polar aprotic organic solvents (C) are alkyl sulfone compounds of formula IV (or multiple alkyl sulfone compounds) (or preferably the alkyl sulfone compounds of formula IV as described herein), and which may or may not contain one or more alkyl glycol ethers as a further component (E). In many cases, a cleaning composition for use in combination with one or more oxidizing agents according to the present invention as defined herein (or preferably the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as described above or below), wherein one, or at least one, or all of the polar aprotic organic solvents (C) are alkyl sulfone compounds of formula IV (or multiple alkyl sulfone compounds) (or preferably the alkyl sulfone compounds of formula IV as described herein), and which does not contain one or more alkyl glycol ethers (as defined above) as a further component (E).

[0073] The use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as defined herein (or preferably the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as described above or below) is also preferred, and the cleaning composition further comprises: (F) A buffering system suitable for buffering the pH of the cleaning composition to a range of 6 to 9, preferably 7 to 8.5; and / or (G) 1,2-Cyclohexylenedinitrilotetraacetic acid; N,N,N,N-Ethylenediaminetetrakis(methylenephosphonic acid); Ethylenediaminetetraacetic acid; 2,2,6,6-Tetramethyl-3,5-Heptanedione; 1,1,1-Trifluoro-2,4-Pentanedione; 1,1,1,5,5,5-Hexafluoro-2,4-Pentanedione; 1,4-Benzoquinone; Tetrachloro-1,4-Benzoquinone; 8-Hydroxyquinoline; Hydroxy Noline sulfonic acid; 2-(2-hydroxyphenyl)-benzoxazole; 2-(2-hydroxyphenyl)-benzothiazole; pyridine; 2-ethylpyridine; 2-methoxypyridine; 3-methoxypyridine; 2-picoline; dimethylpyridine; piperidine; piperazine; pyrrole; isoxazole; bipyridine; pyrimidine; pyrazine; pyridazine; quinoline, isoquinoline; indole; 1-methylimidazole; aniline; salicylidene One or more chelating agents preferably selected from the group consisting of diphosphoric acid; methylamine; dimethylamine; ethylamine; triethylamine; isobutylamine; diisobutylamine, tert-butylamine; tributylamine; dipropylamine; diglycolamine; diisopropylamine; pentamethyldiethylenetriamine; monoethanolamine; triethanolamine; methyldiethanolamine; acetylacetonate; acetylacetone; 2,2'-azandiyldiacetic acid; ammonium carbamate; ammonium pyrrolidinedithiocarbamate; dimethyl malonate; methyl acetoacetate; acetoacetamide; N-methylacetoacetamide; tetramethylammonium thiobenzoate; tetramethylthiuram disulfide; etidronic acid; formic acid; lactic acid; ammonium lactate; methanesulfonic acid; propionic acid; sulfosalicylic acid; salicylic acid; γ-butyrolactone; and mixtures thereof. Preferably, one or more chelating agents are selected from the group consisting of 1,2-cyclohexylenedinitrilotetraacetic acid, N,N,N,N-ethylenediaminetetrakis (methylenephosphonic acid), and mixtures thereof, in an amount of 0.01% to 3% by mass, more preferably 0.1% to 2% by mass, and even more preferably 0.15% to 1.5% by mass, relative to the total mass of the cleaning composition; and / or (H) One or more surfactants (as defined below), preferably comprising one or more fluorosurfactants.

[0074] Therefore, the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as defined herein (or preferably the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as described above or below) is also preferred, and the pH of the cleaning composition is in the range of 6 to 9, preferably 7 to 8.5.

[0075] It is preferable to use a cleaning composition in combination with one or more oxidizing agents according to the present invention, and the buffer system of component (F) is a combination of a weak acid (e.g., phosphoric acid) and a salt of the weak acid, as known in the art. The buffer system may particularly contain 1,2-cyclohexylenedinitrilotetraacetic acid and / or N,N,N,N-ethylenediaminetetrakis (methylenephosphonic acid) as an acidic element (weak acid) compound that is also a chelating agent (G). Preferred salts of the weak acid in the buffer system include ammonium compounds of formula III. [N(R4)4]OH(III) [In the formula, R4 is independently selected from hydrogen and a branched or unbranched alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. For the purposes of the present invention, tetramethylammonium hydroxide and tetramethylammonium hydroxide are preferred compounds of formula III.]

[0076] In the cleaning compositions for use according to the present invention as defined above, one or more chelating agents (G) can generally be used alone (as a single compound) or in combination with other chelating agents (G) in each case.

[0077] The use of a cleaning composition in combination with one or more oxidizing agents according to the present invention is also preferred, and one or more surfactants (H) (if present) of the cleaning composition as defined above are selected from the group consisting of the following: (i) fluorosurfactants preferably selected from the group consisting of sodium lauryl sulfate, perfluorinated alkyl sulfonamide salts (preferably perfluorinated N-substituted alkyl sulfonamide ammonium salts PNAAS), perfluorooctanesulfonates, perfluorobutanesulfonates, perfluorononanoates, and perfluorooctanoates; anionic surfactants preferably selected from the group consisting of alkylaryl ether phosphates and alkyl ether phosphates; (ii) an amphoteric surfactant preferably selected from the group consisting of (3-[(3-coramidopropyl)dimethylammonio]-1-propanesulfonate ("CHAPS"), cocamidopropyl hydroxysultaine (CAS RN 68139-30-0), {[3-(dodecanoylamino)propyl](dimethyl)ammonio}acetate, phosphatidylserine, phosphatidylethanolamine, and phosphatidylcholine, and (iii) A nonionic surfactant preferably selected from the group consisting of glucoside alkyl ethers, glycerin alkyl ethers, cocamide ethanolamine, and lauryldimethylamine oxide.

[0078] A more preferred surfactant (H) in the composition according to the first preferred modification of the present invention is a perfluorinated N-substituted alkylsulfonamide ammonium salt, or contains the same. The preferred surfactant (H) in the composition according to the present invention does not contain metal or metal ions.

[0079] As defined above, in the cleaning compositions for use according to the present invention, one or more surfactants (H) can generally be used alone (as a single compound) or in combination with other surfactants (H) in each case.

[0080] It is also preferable to use a cleaning composition in combination with one or more oxidizing agents according to the present invention, and as defined above, one or more surfactants (H) (if present) of the cleaning composition are present in a total amount of 0.01% to 2% by mass, more preferably 0.02% to 1% by mass, and even more preferably 0.025% to 0.5% by mass, relative to the total mass of the cleaning composition.

[0081] The use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as defined herein (or preferably the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as described above or below) is also preferred, in the cleaning composition, - One or at least one of the solvents (A) is 4-methylmorpholine-4-oxide or contains it. and / or - One or at least one of the corrosion inhibitors (B) is selected from the group consisting of benzotriazoles independently substituted once or twice with branched or unbranched alkyls having 1, 2, 3, or 4 carbon atoms, and / or halogens preferably selected from the group consisting of chlorine and bromine, and mixtures thereof; and / or - One or at least one polar aprotic organic solvent (C) is selected from the group consisting of dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, propylene carbonate, sulfolane (2,3,4,5-tetrahydrothiophene-1,1-dioxide), tetrahydrofuran, and mixtures thereof. Preferably, one or at least one polar aprotic organic solvent (C) is a dimethyl sulfoxide or a sulfolane. and / or - The total amount of etching solution containing fluoride anions is <0.001% by mass relative to the total mass of the cleaning composition, and preferably the cleaning composition does not contain etching solution containing fluoride anions; and / or - Component (E) comprises one or more alkyl glycol ethers of formula II, and in one or more alkyl glycol ethers of formula II, - R2 is a branched or unbranched alkylene group with 3 to 4 carbon atoms; and / or - R3 is a branched or unbranched alkyl group with 1, 2, 3, 5, or 6 carbon atoms; and / or - n is an integer in the range of 2 to 4; and / or - Does not contain butyl diglycol (also known as "diethylene glycol butyl ether"), a specific compound.

[0082] An etching solution containing fluoride anions in a total amount of <0.001% by mass (as defined above) relative to the total mass of the cleaning composition is preferably selected from the group consisting of ammonium fluoride, acidic ammonium fluoride, triethanolammonium fluoride, diglycolammonium fluoride, methyldiethanolammonium fluoride, tetramethylammonium fluoride, triethylamine trihydrofluoride, hydrogen fluoride, fluoroboric acid, tetrafluoroboric acid, ammonium tetrafluoroboric acid, fluoroacetic acid, ammonium fluoroacetic acid, trifluoroacetic acid, fluorosilicic acid, ammonium fluorosilicate, tetrabutylammonium tetrafluoroboric acid, and mixtures thereof.

[0083] The use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as defined herein (or, more preferably, the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as described above or below) is more preferably, in the cleaning composition, - The total amount of one or more solvents (A), preferably 4-methylmorpholine-4-oxide, is in the range of 1% to 15% by mass, preferably 2% to 12% by mass, and more preferably 3% to 10% by mass, relative to the total mass of the cleaning composition; and / or - One, at least one, or all (preferably all of one or more polar aprotic organic solvents (C)) is an alkyl sulfone compound of formula IV (or multiple alkyl sulfone compounds) (or preferably an alkyl sulfone compound of formula IV) as defined above, and the total amount of one or more solvents (A), preferably 4-methylmorpholine-4-oxide, is in the range of 1% to 15% by mass, preferably 5% to 15% by mass, and more preferably 7% to 12% by mass, based on the total mass of the cleaning composition; and / or - The total amount of one or more corrosion inhibitors (B), preferably selected from the group consisting of unsubstituted or independently once or twice substituted with branched or unbranched alkyls having 1, 2, 3, or 4 carbon atoms and / or halogens, and mixtures thereof, is in the range of 0.1% to 6% by mass, preferably 0.2% to 6% by mass, and preferably 0.5% to 5% by mass, relative to the total mass of the cleaning composition; and / or - The total amount of one or more polar aprotic organic solvents (C) preferably selected from the group consisting of dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, propylene carbonate, sulfolane, tetrahydrofuran, and mixtures thereof is in the range of 1% to 50% by mass, preferably 3% to 45% by mass, and more preferably 5% to 40% by mass, relative to the total mass of the cleaning composition; and / or - One, at least one, or all of the polar aprotic organic solvents (C) (preferably all of the one or more polar aprotic organic solvents (C) are alkyl sulfone compounds of formula IV as defined above (or multiple alkyl sulfone compounds) (or preferably alkyl sulfone compounds of formula IV as defined above), and the total amount of the one or more polar aprotic organic solvents (C) is in the range of 10% to 50% by mass, preferably in the range of 15% to 45% by mass, more preferably in the range of >30% to 45% by mass, based on the total mass of the cleaning composition; and / or - The total amount of one or more alkyl glycol ethers (E), preferably one or more alkyl glycol ethers of formula II, is in the range of 5% to 50% by mass, preferably 10% to 40% by mass, and more preferably 15% to 35% by mass, relative to the total mass of the cleaning composition; and / or - The cleaning composition comprises at least components (A), (B), (C), (D), (E), and (F), preferably at least components (A), (B), (C), (D), and (F), and more preferably at least components (A), (B), (C), (D), and (F), and (G), and (H); and / or - Water (D) fills the remaining portion of the cleaning composition to make 100% by mass.

[0084] In a first preferred alternative, the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as defined herein (or, preferably, the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as described above or below) is preferred, and the total amount of one or more polar aprotic organic solvents (C) preferably selected from the group consisting of dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, propylene carbonate, sulfolane, tetrahydrofuran, and mixtures thereof is in the range of 5% to 15% by mass relative to the total mass of the cleaning composition.

[0085] In a second preferred alternative, the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as defined herein (or, preferably, the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as described above or below) is preferred, wherein the total amount of one or more polar aprotic organic solvents (C) preferably selected from the group consisting of dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, propylene carbonate, sulfolane, tetrahydrofuran, and mixtures thereof is in the range of 30% to 40% by mass relative to the total mass of the cleaning composition.

[0086] For the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as defined herein (or preferably the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as described or described below), the oxidizing agent is preferably applied to the wet etching composition according to the present invention (or its variations or preferred variations) in an amount relative to the cleaning composition as described and defined below.

[0087] One preferred specific variation of the present invention relates to the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as defined herein (or, preferably, the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as described above or below), wherein the cleaning composition comprises or consists of the following components: (A) 4-methylmorpholine-4 oxide as a solvent in an amount of 2% to 12% by mass, more preferably 3% to 10% by mass, relative to the total mass of the cleaning composition; (B) One or more corrosion inhibitors selected from the group consisting of unsubstituted or independently one or two-times substituted benzotriazoles with 1, 2, 3, or 4 carbon atoms, and mixtures thereof, in an amount of 0.2% to 6% by mass, preferably 0.5% to 5% by mass, relative to the total mass of the cleaning composition; (C) One or more polar aprotic organic solvents selected from the group consisting of dimethyl sulfoxides, sulfolanes, and mixtures thereof, in an amount of 3% to 45% by mass, preferably 5% to 15% by mass, relative to the total mass of the cleaning composition; (D) Water to fill the remaining cleaning composition to make 100% by mass. (E) One or more alkyl glycol ethers of formula II in an amount ranging from 10% to 40% by mass, preferably 15% to 35% by mass, relative to the total mass of the cleaning composition. [ka] [In the formula, R2 is an unbranched alkylene group with 2 to 4 carbon atoms. R3 is a branched or unbranched alkyl group with 1 to 6 carbon atoms. and n is an integer in the range of 2 to 6. (F) A buffering system suitable for buffering the pH of the cleaning composition to a range of 6 to 9, preferably 7 to 8.5. and (G) One or more chelating agents selected from the group consisting of 1,2-cyclohexylenedinitrilotetraacetic acid; N,N,N,N-ethylenediaminetetrakis (methylenephosphonic acid); and mixtures thereof, in an amount of 0.1% to 2% by mass, preferably 0.15% to 1.5% by mass, relative to the total mass of the cleaning composition.

[0088] Another preferred specific modification of the present invention relates to the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as defined herein (or preferably the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as described above or below), wherein the cleaning composition comprises or consists of the following components: (A) 4-methylmorpholine-4 oxide as a solvent in an amount of 1% to 15% by mass, more preferably 8% to 15% by mass, relative to the total mass of the cleaning composition; (B) One or more corrosion inhibitors selected from the group consisting of unsubstituted or independently one or two-times substituted benzotriazoles with 1, 2, 3, or 4 carbon atoms, and mixtures thereof, in an amount of 0.2% to 6% by mass, preferably 0.5% to 5% by mass, relative to the total mass of the cleaning composition; (C) One or more polar aprotic organic solvents in an amount of 10% to 50% by mass, preferably 15% to 45% by mass, and more preferably >30% to 45% by mass, relative to the total mass of the cleaning composition, wherein all one or more of the polar aprotic organic solvents (C) are alkyl sulfone compounds of formula IV (as defined above). Preferably, the alkyl sulfone compound of formula IV is selected from the group consisting of ethyl methyl sulfone, ethyl isopropyl sulfone, ethyl isobutyl sulfone, isopropyl isobutyl sulfone, sulfolane, 3-methoxysulfolane, and mixtures thereof; more preferably, the alkyl sulfone compound of formula IV is selected from the group consisting of ethyl methyl sulfone, ethyl isopropyl sulfone, sulfolane, and mixtures thereof; and even more preferably, the plurality of alkyl sulfone compounds of formula IV (alkyl sulfone compounds) are sulfolane; (D) Preferably, fill the remaining cleaning composition with water to make 100% by mass. (F) A buffering system suitable for buffering the pH of the cleaning composition to a range of 6 to 9, preferably 7 to 8.5. (G) 1,2-cyclohexylenedinitrilotetraacetic acid in an amount of 0.1% to 2% by mass, preferably 0.15% to 1.5% by mass, relative to the total mass of the cleaning composition; one or more chelating agents preferably selected from the group consisting of ammonium compounds of formula III as defined above (or preferably as defined above), and mixtures thereof. and (H) Preferably one or more surfactants, comprising 0.01% to 2% by mass, preferably 0.02% to 1% by mass, in total amount relative to the total mass of the cleaning composition, if present.

[0089] The use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as defined herein (or, more preferably, the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as described above or below) is also preferred, and the use includes removing post-etching or post-ashing residue from the surface of a semiconductor substrate. - The semiconductor substrate comprises at least one material selected from the group consisting of copper, cobalt, preferably tungsten, more preferably lower tungsten, and materials with a low k value. and / or, - Use includes cleaning a semiconductor substrate containing at least one material selected from the group consisting of copper, cobalt, preferably tungsten, more preferably lower tungsten; and materials with low k values: and / or - Use involves removing post-etching or post-ashing residue from the surface of a semiconductor substrate in the presence of at least one material selected from the group consisting of copper, cobalt, preferably tungsten, more preferably lower tungsten; and materials with low k values. Post-etching or post-ashing residues include one or more residues selected from the group consisting of the following: - One or more organic compounds containing or not containing fluorine, preferably organic polymers, - Metal-organic complexes, and - Metallic material, preferably titanium and / or titanium oxide and / or titanium nitride; and / or - Use involves removing residues and contaminants from the surface of a semiconductor substrate comprising at least one material selected from the group consisting of copper, cobalt, preferably tungsten, more preferably lower tungsten; and materials with low k values. - Preferably, the residue and contaminants consist of or contain organic compounds, with or without fluorine, preferably organic polymers.

[0090] As used herein, the term “underlying tungsten” means, as defined above, that tungsten (as tungsten metal or tungsten material) is located beneath (completely covered by) at least one layer of low-k material, preferably further comprising or consisting of one or more aluminum compounds (if present, typically located between at least one layer of low-k material and tungsten, separating the entire surface of at least one layer of low-k material from the surface of tungsten). Therefore, preferably, the underlying tungsten is not directly exposed to the cleaning composition (in combination with one or more oxidizing agents) or the wet etching composition (both as defined herein) during the process for manufacturing semiconductor devices (preferably as defined herein) when the cleaning composition (in combination with one or more oxidizing agents) or the wet etching composition penetrates or diffuses through at least one layer of low-k material, and further comprising or consisting of one or more aluminum compounds (if applicable), but may come into contact with the cleaning composition (in combination with one or more oxidizing agents) and / or the wet etching composition.

[0091] The use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as defined herein (or preferably the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as described above or below) is also preferred, and the use includes etching, preferably oxidative etching, or partially etching, preferably partially oxidative etching, a layer or mask containing or comprising a material selected from the group consisting of Ti, TiN, Ta, TaN, Al, and HfOx, preferably a hard mask, and / or etching, preferably oxidative etching, or partially etching, preferably partially oxidative etching, of a layer or mask containing or comprising a material selected from the group consisting of tungsten carbide (WCx) and tungsten nitride (WNx), preferably a hard mask, and etching or partially etching, preferably partially oxidative etching, of a layer or mask, preferably a hard mask, includes the following - In the presence of at least one material selected from the group consisting of copper, cobalt, preferably tungsten, more preferably lower tungsten; and materials with a low k value, remove or partially remove a hard mask containing a metal selected from the group consisting of a Ti hard mask, a TiN hard mask, a Ta hard mask, a TaN hard mask, an Al hard mask, and an HfOx hard mask, and / or a tungsten carbide (WCx) hard mask and a tungsten nitride (WNx) hard mask; more preferably a TiN hard mask. and / or - Etching, preferably oxidative etching, or partially etching, preferably partially oxidative etching, while at least one material selected from the group consisting of copper, cobalt, preferably tungsten, more preferably lower tungsten; and materials with a low k value is present on the surface of the semiconductor substrate; and / or - Etching, preferably selectively, a layer containing an aluminum compound in the presence of a layer of low k-value material, and / or preferably tungsten, more preferably a lower layer containing tungsten; and / or a layer containing copper and / or cobalt; and / or - Removing, preferably selectively removing, a layer containing an aluminum compound from a semiconductor substrate while a layer of low-k-value material and / or preferably a layer containing tungsten, more preferably a lower layer containing tungsten and / or copper and / or cobalt is present. and / or - Removing, preferably selectively removing, a layer containing an aluminum compound from the surface of a semiconductor substrate, while a layer of low-k-value material and / or preferably a layer containing tungsten, more preferably a lower layer containing tungsten and / or copper and / or cobalt is present.

[0092] In a particularly preferred modification of the present invention, the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as defined herein (or preferably the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as described above or below) is preferred. - The cleaning composition is used in combination with one or more oxidizing agents in a one-step process to remove the following: (i) A hard mask containing a metal preferably selected from the group consisting of Ti hard masks, TiN hard masks, Ta hard masks, TaN hard masks, Al hard masks, and HfOx hard masks, and / or a hard mask consisting of a metal preferably selected from the group consisting of tungsten carbide (WCx) hard masks and tungsten nitride (WNx) hard masks, more preferably TiN hard masks. and (ii) Preferably, an etching stop layer of an aluminum compound deposited on a copper layer, preferably on a copper layer, and / or on a cobalt layer, preferably on a cobalt layer, in the presence of tungsten that is completely covered by at least one layer of a low-k material (and preferably further by at least one etching stop layer comprising or consisting of one or more aluminum compounds located between the tungsten and at least one layer of the low-k material); and / or - The cleaning composition is used in combination with one or more oxidizing agents in a separate step or simultaneously in the same step, preferably simultaneously in the same step; and / or - One or more oxidizing agents are selected from the group consisting of hydrogen peroxide, urea peroxide, peroxodisulfate, ammonium persulfate, peroxomonosulfate, pyrosulfate, ozone, and mixtures thereof; preferably one of the one or more oxidizing agents is hydrogen peroxide; and / or - One or more oxidizing agents, preferably hydrogen peroxide, are used in a total amount of 2% to 25% by mass, preferably 5% to 20% by mass, more preferably 7.5% to 20% by mass, and even more preferably 10% to 17.5% by mass, relative to the total mass of the cleaning composition; and / or - One or more stabilizers are used in combination with one or more oxidizing agents and / or, preferably, in combination with a cleaning composition selected from the group consisting of amine-N-oxide; citric acid; 1-hydroxyethane-1,1-diphosphonic acid; glycolic acid; lactic acid; hydroxybutyric acid; glyceric acid; malic acid; tartaric acid; malonic acid; succinic acid; glutaric acid; maleic acid and mixtures thereof.

[0093] The present invention also relates to a cleaning composition as defined above (or a cleaning composition as defined above as preferred) in particular in the context of the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as defined above (including all variations and preferred modifications thereof).

[0094] In general, all aspects of the present invention discussed herein in the context of the use of cleaning compositions in combination with one or more oxidizing agents of the present invention shall apply mutatis mutandis to cleaning compositions according to the present invention as defined above and below herein. Similarly, all aspects of cleaning compositions according to the present invention discussed herein shall apply mutatis mutandis to the use of cleaning compositions in combination with one or more oxidizing agents of the present invention (as defined above).

[0095] The cleaning compositions according to the present invention as defined herein (or preferably the cleaning compositions according to the present invention as described above or below) are preferred - The total amount of etching solution containing fluoride anions is <0.001% by mass relative to the total mass of the cleaning composition, and preferably the cleaning composition does not contain etching solution containing fluoride anions; and / or - The cleaning composition is (F) A buffering system suitable for buffering the pH of the cleaning composition to a range of 6 to 9, and / or - The cleaning composition contains one or more alkyl glycol ethers of formula II as component (E), and in the one or more alkyl glycol ethers of formula II, - R2 is a branched or unbranched alkylene group with 3-4 carbon atoms; and / or - R3 is a branched or unbranched alkyl group with 1, 2, 3, 5, or 6 carbon atoms; and / or - n is an integer in the range of 2 to 4; and / or - Does not contain the specific compound butyl diglycol.

[0096] The present invention also relates to the use of a cleaning composition as defined above (or preferably as defined above) for removing post-etching or post-ashing residue from the surface of a semiconductor substrate.

[0097] In general, the use of a cleaning composition in combination with one or more oxidizing agents of the present invention and / or all aspects of the present invention discussed herein in the context of the cleaning composition of the present invention shall apply mutatis mutandis to the use of a cleaning composition according to the present invention for removing post-etching or post-ashing residue from the surface of a semiconductor substrate according to the present invention as defined above and below herein. Similarly, all aspects of the use of a cleaning composition according to the present invention for removing post-etching or post-ashing residue from the surface of a semiconductor substrate according to the present invention as discussed herein shall apply mutatis mutandis to the use of a cleaning composition in combination with one or more oxidizing agents of the present invention and / or the cleaning composition of the present invention (both as defined above).

[0098] As defined above, cleaning compositions according to the present invention, in particular cleaning compositions in which one or at least one polar aprotic organic solvent (C), or (in a particularly preferred modification of this embodiment of the present invention) all of an alkyl sulfone compound of formula IV (or a plurality of alkyl sulfone compounds of formula IV as preferably described herein), have been found in our experience to be particularly suitable for the following: (a) Reduce the number of nanometer-scale particles (e.g., from the environment) that may be present on or fixed to the surface of the semiconductor substrate (or, for example, avoid the introduction or adsorption of such nanometer-scale particles from the environment onto the surface of the semiconductor substrate): Such nanometer-scale particles (e.g., particles of SiOx, SiC, SiOC, or Ti ions) tend to gradually aggregate to a sub-micrometer or micrometer scale and, if introduced or adsorbed onto the surface of the semiconductor substrate (and not removed by the application of the cleaning composition according to the present invention), can cause defects in semiconductor products manufactured from the semiconductor substrate; and / or (b) Remove particles, particularly post-etching or post-ashing residue particles, from the surface of the semiconductor substrate.

[0099] It has also been found that these two effects described above are more pronounced for cleaning compositions according to the present invention that contain only one or more alkyl sulfone compounds of formula IV as one or more polar aprotic organic solvents (C) (but do not contain alkyl glycol ethers (E), e.g., cleaning composition CCI1 or CCI14) than for similar cleaning compositions that contain one or more alkyl glycol ethers (E) but do not contain polar aprotic organic solvents (C) (e.g., contain butyl diglycol, see e.g., cleaning composition CCI13), or (ii) similar cleaning compositions that contain one or more alkyl glycol ethers (E) and one or more polar aprotic organic solvents (C) but do not contain alkyl sulfone compounds of formula IV (e.g., contain butyl diglycol and dimethyl sulfoxide, see e.g., cleaning composition CCI12).

[0100] As defined above, cleaning compositions according to the present invention, in particular, cleaning compositions in which one, or at least one, or (in a particularly preferred modification of this embodiment of the present invention) all of a polar aprotic organic solvent (C) is an alkyl sulfone compound of formula IV (or a plurality of alkyl sulfone compounds of formula IV as preferably described herein), have been found in our experiments to be particularly low in terms of clouding.

[0101] To remove post-etching or post-ashing residue from the surface of the semiconductor substrate, the use of a cleaning composition as defined above (or preferably a cleaning composition as defined above) is preferred. - The semiconductor substrate comprises at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and materials with a low k value. and / or - Use involves cleaning a semiconductor substrate containing at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and materials with a low k value; and / or - Use involves removing post-etching or post-ashing residue from the surface of a semiconductor substrate in the presence of at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and materials with a low k value. Post-etching or post-ashing residues include one or more residues selected from the group consisting of the following: - One or more organic compounds containing or not containing fluorine, preferably organic polymers, - Metal-organic complexes, and - Metallic material, preferably titanium and / or titanium oxide and / or titanium nitride; and / or - Use involves removing residues and contaminants from the surface of a semiconductor substrate containing at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and low k-value materials. Preferably, the residue and contaminants consist of or include organic compounds, with or without fluorine, preferably organic polymers.

[0102] The present invention also relates to a wet etching composition comprising the following: (W1) In particular, in the context of the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as defined above (including all of its variations and preferred variations), the cleaning composition according to the present invention as defined above (or the cleaning composition according to the present invention as preferred). and (W2) One or more oxidizing agents selected from the group consisting of hydrogen peroxide, urea peroxide, peroxodisulfate, ammonium persulfate, peroxomonosulfate, pyrosulfate, and ozone, in an amount of 2% to 25% by mass, preferably 5% to 20% by mass, more preferably 7.5% to 20% by mass, and even more preferably 10% to 17.5% by mass, relative to the total mass of the cleaning composition.

[0103] In general, all aspects of the present invention discussed herein in the context of using a cleaning composition in combination with one or more oxidizing agents of the present invention, the cleaning composition of the present invention, and / or the cleaning composition of the present invention for removing post-etching or post-ashing residues, apply mutatis mutandis to the wet etching composition according to the present invention as defined above and below herein. Similarly, all aspects of the wet etching composition according to the present invention discussed herein apply mutatis mutandis to using a cleaning composition in combination with one or more oxidizing agents of the present invention, the cleaning composition of the present invention, and / or the cleaning composition of the present invention for removing post-etching or post-ashing residues.

[0104] The pH of the wet etching composition according to the present invention (or, preferably, the wet etching composition according to the present invention as described above or below) is preferably in the range of 6 to 9, more preferably in the range of 6.5 to 8.0.

[0105] In the context of using cleaning compositions in combination with one or more oxidizing agents of the present invention, similarly to those described above, a wet etching composition according to the present invention as defined above (particularly, a preferred wet etching composition according to the present invention), in particular, a wet etching composition in which one, or at least one, or (in a particularly preferred modification of this embodiment of the present invention) all of a polar aprotic organic solvent (C) is an alkyl sulfone compound of formula IV (or a plurality of alkyl sulfone compounds of formula IV as preferred) has been found in our experiments to exhibit the following beneficial effects: - High selectivity for etching, in particular oxidative etching, or partial etching, in particular partially oxidative etching, of a layer or mask containing or consisting of a material selected from the group consisting of Ti, TiN, Ta, TaN, Al, and HfOx, and / or a layer or mask containing or consisting of a material selected from the group consisting of tungsten carbide (WCx) and tungsten nitride (WNx), particularly TiN, while at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and low k-value materials is present on the surface of a semiconductor substrate; and - High etching rate stability over long periods. High etching rate stability results from layers or masks containing or consisting of materials selected from the group consisting of Ti, TiN, Ta, TaN, Al, and HfOx, and / or materials selected from the group consisting of tungsten carbide (WCx) and tungsten nitride (WNx); in particular, it results in high (selective) etching rates over long periods for layers or masks containing or consisting of materials containing or consisting of TiN (as defined above). For example, a wet etching composition can protect high selective etching rates for layers or masks containing or consisting of TiN over long periods of 24 hours or more (see also the Examples section).

[0106] Furthermore, the present invention also relates to the use of wet etching compositions as defined above (or preferably to the use of wet etching compositions as defined above) for the following purposes. - Preferably, a hard mask containing a metal selected from the group consisting of copper, cobalt, preferably tungsten, more preferably lower-k-value tungsten; and materials with a low k-value, in the presence of at least one material selected from the group consisting of Ti hard mask, TiN hard mask, Ta hard mask, TaN hard mask, Al hard mask, and HfOx hard mask, and / or a hard mask containing a metal selected from the group consisting of tungsten carbide (WCx) hard mask and tungsten nitride (WNx) hard mask; more preferably, a TiN hard mask is removed or partially removed. and / or - Preferably, on the surface of a semiconductor substrate, at least one material selected from the group consisting of copper, cobalt, preferably tungsten, more preferably lower tungsten; and low k-value materials is present, and a layer or mask containing or consisting of a material selected from the group consisting of Ti, TiN, Ta, TaN, Al, and HfOx, and / or a layer or mask containing or consisting of a material selected from the group consisting of tungsten carbide (WCx) and tungsten nitride (WNx); preferably TiN, is etched, preferably oxidatively etched, or partially etched, preferably partially oxidatively etched; and / or - Etching, preferably selectively etching, a layer containing an aluminum compound in the presence of a layer of low k-value material, and / or a layer containing copper and / or cobalt, and / or preferably a layer containing tungsten, more preferably a lower layer containing tungsten; and / or - Removing, preferably selectively removing, a layer containing an aluminum compound from a semiconductor substrate while a layer of low-k-value material and / or a layer containing copper and / or cobalt and / or preferably tungsten, more preferably a lower layer containing tungsten is present; and / or - Remove, preferably selectively remove, a layer containing an aluminum compound from the surface of a semiconductor substrate while a layer of low-k-value material and / or a layer containing copper and / or cobalt and / or preferably tungsten, more preferably a lower layer containing tungsten is present; and / or - Preferably, post-etching or post-ashing residue is removed from the surface of the semiconductor substrate in the presence of at least one material selected from the group consisting of copper, cobalt, preferably tungsten, more preferably lower-grade tungsten, and materials with a low k value. Post-etching or post-ashing residues preferably include one or more residues selected from the group consisting of: - One or more organic compounds containing or not containing fluorine, preferably organic polymers, - Metal-organic complexes, and - Metallic material, preferably titanium and / or titanium oxide and / or titanium nitride.

[0107] In general, all aspects of the present invention considered herein in the context of the use of cleaning compositions in combination with one or more oxidizing agents of the present invention, the cleaning compositions of the present invention, the use of cleaning compositions for removing post-etching or post-ashing residues of the present invention, and / or wet etching compositions of the present invention, apply mutatis mutandis to the use of wet etching compositions according to the present invention as defined above and below herein. Similarly, all aspects of wet etching compositions according to the present invention considered herein apply mutatis mutandis to the use of cleaning compositions in combination with one or more oxidizing agents of the present invention, the cleaning compositions of the present invention, the use of cleaning compositions for removing post-etching or post-ashing residues of the present invention, and / or wet etching compositions of the present invention.

[0108] In a further embodiment, the present invention also relates to a process for manufacturing a semiconductor device from a semiconductor substrate, comprising the following steps. P1) A wet etching composition is prepared by mixing a cleaning composition according to the present invention as defined above (or a cleaning composition according to the present invention as preferred above), wherein one or more oxidizing agents are preferably selected from the group consisting of hydrogen peroxide, urea peroxide, peroxodisulfate, ammonium persulfate, peroxomonosulfate, pyrosulfate, ozone, and mixtures thereof. or The wet etching composition according to the present invention (or preferably the wet etching composition according to the present invention as defined above) brings about as defined above. and P2) Preferably, in the presence of at least one material selected from the group consisting of copper, cobalt, preferably tungsten, more preferably lower tungsten, and materials with a low k value, the wet etching composition received or provided in step P1) is brought into contact with the following at least once: - A layer or mask on the surface of a semiconductor substrate, preferably selected from the group consisting of a Ti layer or mask, a TiN layer or mask, a Ta layer or mask, a TaN layer or mask, an Al layer or mask, and an HfOx layer or mask, and / or a layer or mask selected from the group consisting of a tungsten nitride (WNx) layer or mask and a tungsten carbide (WCx) layer or mask; more preferably a TiN layer or mask. and / or - An etching stop layer comprising or consisting of one or more aluminum compounds deposited on the surface of a semiconductor substrate, preferably on a copper layer and / or on a cobalt layer, preferably on a cobalt layer, Preferably, as follows: - Etch the layer or mask, preferably selectively oxidatively etched, or partially etch, preferably selectively partially oxidatively etched. and / or - Remove, preferably selectively remove, an etching stop layer containing an aluminum compound from the surface of a semiconductor substrate. and / or - Preferably, a one-step process to remove post-etching or post-ashing residue from the surface of the semiconductor substrate.

[0109] In general, all aspects of the present invention considered herein in the context of the use of cleaning compositions in combination with one or more oxidizing agents of the present invention, the cleaning compositions of the present invention, the cleaning compositions of the present invention for removing post-etching or post-ashing residues, the wet etching compositions of the present invention, and / or the wet etching compositions of the present invention, apply mutatis mutandis to the processes for manufacturing semiconductor devices according to the present invention as defined above and below herein. Similarly, all aspects of the processes for manufacturing semiconductor devices according to the present invention, as considered herein, apply mutatis mutandis to the use of cleaning compositions in combination with one or more oxidizing agents of the present invention, the cleaning compositions of the present invention, the cleaning compositions of the present invention for removing post-etching or post-ashing residues, the wet etching compositions of the present invention, and / or the wet etching compositions of the present invention.

[0110] In further embodiments, the present invention also relates to a kit for etching, preferably oxidative etching, or partially etching, preferably partially oxidative etching, and / or etching, a layer or mask containing or comprising a material selected from the group consisting of Ti, TiN, Ta, TaN, Al, and HfOx, and / or a layer or mask containing or comprising a material selected from the group consisting of tungsten carbide (WCx) and tungsten nitride (WNx), preferably TiN, for the removal of post-etching or post-ashing residue from the surface of a semiconductor substrate, and / or As individual ingredients: (K1) A cleaning composition according to the present invention as defined above (or preferably a cleaning composition according to the present invention as defined above) and (K2) One or more oxidizing agents preferably selected from the group consisting of hydrogen peroxide, urea peroxide, peroxodisulfate, ammonium persulfate, peroxomonosulfate, pyrosulfate, ozone, and mixtures thereof; more preferably one of the one or more oxidizing agents is hydrogen peroxide; And as individual components, optionally include or combine component (K1) and / or component (K2): (K3) Preferably comprising one or more stabilizers selected from the group consisting of amine-N-oxide; citric acid; 1-hydroxyethane-1,1-diphosphonic acid; glycolic acid; lactic acid; hydroxybutyric acid; glyceric acid; malic acid; tartaric acid; malonic acid; succinic acid; glutaric acid; maleic acid and mixtures thereof.

[0111] In general, all aspects of the present invention considered herein in the context of the use of cleaning compositions in combination with one or more oxidizing agents of the present invention, the cleaning compositions of the present invention, the cleaning compositions of the present invention for removing post-etching or post-ashing residues, the wet etching compositions of the present invention, the use of the wet etching compositions of the present invention, and / or the processes of the present invention for the manufacture of semiconductor devices, apply mutatis mutandis to the kits according to the present invention as defined above and below herein. Similarly, all aspects of the kits according to the present invention considered herein apply mutatis mutandis to the use of cleaning compositions in combination with one or more oxidizing agents of the present invention, the cleaning compositions of the present invention, the cleaning compositions of the present invention for removing post-etching or post-ashing residues, the wet etching compositions of the present invention, the use of the wet etching compositions, and / or the processes of the present invention for the manufacture of semiconductor devices.

[0112] The cleaning compositions according to the present invention (including all of its variations and preferred variations as defined herein), the wet etching compositions according to the present invention (including all of its variations and preferred variations as defined herein), and / or the kits according to the present invention (including all of its variations and preferred variations as defined herein) are designed and intended for use or application in the process of manufacturing semiconductor devices (including all of this process variations and preferred variations as defined herein).

[0113] The present invention, and its variations thereof, are defined in the following embodiments A1 to A15:

[0114] A1. Use of a cleaning composition containing at least the following ingredients: (A) One or more compounds of formula I as a solvent:

[0115] [ka] [In the formula, R1 is selected from the group consisting of branched or unbranched alkyl groups having 1, 2, 3, or 4 carbon atoms; (B) One or more corrosion inhibitors selected from the group consisting of unsubstituted or branched or unbranched alkyl groups having 1, 2, 3, or 4 carbon atoms, aminoalkyl groups having branched or unbranched alkyl groups with 1, 2, 3, or 4 carbon atoms, benzotriazoles independently substituted once or twice with phenyl, thiophenyl, halogen, hydroxy, nitro, and / or thiols, and mixtures thereof; (C) One or more polar aprotic organic solvents; and (D) Water in combination with one or more oxidizing agents, - For removing post-etching or post-ashing residue from the surface of a semiconductor substrate. and / or - Water for use in a cleaning composition for etching or partially etching a layer or mask containing or consisting of a material selected from the group consisting of Ti, TiN, Ta, TaN, Al, and HfOx.

[0116] A2. The cleaning composition may further include the following: (E) Use according to embodiment A1, comprising one or more alkyl glycol ethers:

[0117] A3. Component (E) is selected from the group consisting of alkyl glycol ethers with a Hansen polarity solubility parameter δp of ≤8 (MPa) 1 / 2. and / or - The cleaning composition contains one or more alkyl glycol ethers of formula II as component (E), as used in embodiment A2: [ka] [In the formula, R2 is a branched or unbranched alkylene group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms. R3 is a branched or unbranched alkyl group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms. and n is an integer in the range of 1 to 6, preferably in the range of 2 to 6.

[0118] A4. Cleaning compositions, and further: (F) A buffering system suitable for buffering the pH of the cleaning composition to a range of 6 to 9, preferably 7 to 8.5; and / or (G) One or more chelating agents in an amount preferably in the range of 0.01% to 3% by mass, more preferably in the range of 0.1% to 2% by mass, and even more preferably in the range of 0.15% to 1.5% by mass, relative to the total mass of the cleaning composition; and / or (H) Use according to any one of embodiments A1 to A3, preferably comprising one or more surfactants including one or more fluorosurfactants.

[0119] A5. In a cleaning composition, - One or at least one of the solvents (A) is 4-methylmorpholine-4-oxide, or contains the same. and / or - One or at least one of the corrosion inhibitors (B) is selected from the group consisting of unsubstituted or independently one or two substituted benzotriazoles selected from the group consisting of branched or unbranched alkyls having 1, 2, 3, or 4 carbon atoms and / or halogens selected from the group consisting of chlorine or bromine, and mixtures thereof; and / or - One or at least one polar aprotic organic solvent (C) is selected from the group consisting of dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, propylene carbonate, sulfolane, tetrahydrofuran, and mixtures thereof. Preferably, one or at least one polar aprotic organic solvent (C) is dimethyl sulfoxide. and / or - The total amount of etching solution containing fluoride anions is <0.001% by mass relative to the total mass of the cleaning composition, and preferably the cleaning composition does not contain etching solution containing fluoride anions; and / or - In one or more alkyl glycol ethers of formula II, - R2 is a branched or unbranched alkylene group with 3 to 4 carbon atoms; and / or - R3 is a branched or unbranched alkyl group with 1, 2, 3, 5, or 6 carbon atoms; and / or - n is an integer in the range of 2 to 4; and / or - Use as described in any one of embodiments A1 to A4, which does not include the specific compound butyl diglycol.

[0120] A6. In cleaning compositions - The total amount of one or more solvents (A), preferably 4-methylmorpholine-4-oxide, is in the range of 1% to 15% by mass, preferably 2% to 12% by mass, and more preferably 3% to 10% by mass, relative to the total mass of the cleaning composition. and / or - The total amount of one or more corrosion inhibitors (B), preferably selected from the group consisting of unsubstituted or independently once or twice substituted with branched or unbranched alkyls having 1, 2, 3, or 4 carbon atoms and / or halogens, and mixtures thereof, is in the range of 0.1% to 6% by mass, preferably 0.2% to 6% by mass, and more preferably 0.5% to 5% by mass, relative to the total mass of the cleaning composition; and / or - The total amount of one or more polar aprotic organic solvents (C) preferably selected from the group consisting of dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, propylene carbonate, sulfolane, tetrahydrofuran, and mixtures thereof is in the range of 1% to 50% by mass, preferably 3% to 45% by mass, and more preferably 5% to 40% by mass, relative to the total mass of the cleaning composition; and / or - The total amount of one or more alkyl glycol ethers (E), preferably one or more alkyl glycol ethers of formula II, is in the range of 5% to 50% by mass, preferably 10% to 40% by mass, and more preferably 15% to 35% by mass, relative to the total mass of the cleaning composition; and / or - The cleaning composition comprises at least components (A), (B), (C), (D), (E), and (F); and / or - Water (D) fills the remainder of the cleaning composition to make 100% by mass, as described in any one of embodiments A1 to A5.

[0121] A7. Use includes removing post-etching or post-ashing residue from the surface of a semiconductor substrate. - The semiconductor substrate comprises at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and materials with a low k value. and / or - Use involves cleaning a semiconductor substrate containing at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and materials with a low k value; and / or - Use involves removing post-etching or post-ashing residue from the surface of a semiconductor substrate in the presence of at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and low k-value materials. Post-etching or post-ashing residues include one or more residues selected from the group consisting of the following: - One or more organic compounds containing or not containing fluorine, preferably organic polymers, - Metal-organic complexes, and - Metallic material, preferably titanium and / or titanium oxide and / or titanium nitride; and / or - Use involves removing residues and contaminants from the surface of a semiconductor substrate comprising at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and materials with a low k value. - Preferably, the residue and contaminants consist of or include organic compounds containing or not containing fluorine, preferably organic polymers, as described in any one of embodiments A1 to A6.

[0122] A8. Use includes etching, preferably oxidative etching or partial etching, preferably partially oxidative etching, of a layer or mask, preferably a hard mask, which contains or consists of a material selected from the group consisting of Ti, TiN, Ta, TaN, Al, and HfOx, and etching or partial etching of a layer or mask, preferably a hard mask, includes the following: - Preferably, remove, preferably partially remove, a hard mask containing a metal preferably selected from the group consisting of a Ti hard mask, a TiN hard mask, a Ta hard mask, a TaN hard mask, an Al hard mask, and an HfOx hard mask, while at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and materials with a low k value is present. and / or - Etching, preferably oxidative etching, or partially etching, preferably partially oxidative etching, is performed on the surface of a semiconductor substrate in the presence of at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and materials with a low k value; and / or - Etching, preferably selectively, a layer containing an aluminum compound in the presence of a layer of low k-value material, and / or preferably a layer containing tungsten, and / or a layer containing copper and / or cobalt; and / or - In the presence of a layer of low-k-value material, and / or preferably a layer containing tungsten, and / or a layer containing copper and / or cobalt, remove, preferably selectively remove, a layer containing an aluminum compound from a semiconductor substrate. and / or - Use according to any one of embodiments A1 to A7, wherein a layer containing an aluminum compound is removed, preferably selectively, from the surface of a semiconductor substrate in the presence of a layer of low k-value material and / or preferably a layer containing tungsten and / or a layer containing copper and / or cobalt.

[0123] A9. - The cleaning composition is used in combination with one or more oxidizing agents in a one-step process to remove the following: (i) A hard mask containing a metal preferably selected from the group consisting of Ti hard mask, TiN hard mask, Ta hard mask, TaN hard mask, Al hard mask, and HfOx hard mask, more preferably a TiN hard mask. and (ii) an etching stop layer of an aluminum compound deposited on a copper layer, preferably on the copper layer, and / or a cobalt layer, preferably on the cobalt layer, in the presence of tungsten which is completely covered by at least one layer of a material with a low k value; and / or - The cleaning composition is used in combination with one or more oxidizing agents in a separate step or simultaneously in the same step, preferably simultaneously in the same step; and / or - One or more oxidizing agents are selected from the group consisting of hydrogen peroxide, urea peroxide, peroxodisulfate, ammonium persulfate, peroxomonosulfate, pyrosulfate, ozone, and mixtures thereof, preferably one of the one or more oxidizing agents being hydrogen peroxide; and / or - One or more oxidizing agents, preferably hydrogen peroxide, are used in a total amount of 2% to 25% by mass, preferably 5% to 20% by mass, more preferably 7.5% to 20% by mass, and even more preferably 10% to 17.5% by mass, relative to the total mass of the cleaning composition; and / or - One or more stabilizers are used in combination with one or more oxidizing agents and / or in combination with a cleaning composition, preferably selected from the group consisting of amine-N-oxide; citric acid; 1-hydroxyethane-1,1-diphosphonic acid; glycolic acid; lactic acid; hydroxybutyric acid; glyceric acid; malic acid; tartaric acid; malonic acid; succinic acid; glutaric acid; maleic acid and mixtures thereof, as described in any one of embodiments A1 to A8.

[0124] A10. A cleaning composition defined in any one of embodiments 1 to 6.

[0125] A11. Use of the cleaning composition according to Embodiment 10 for removing post-etching or post-ashing residue from the surface of a semiconductor substrate, preferably as defined in Embodiments 1 and / or 7.

[0126] A12. (W1) A cleaning composition defined in any one of embodiments 1 to 6, preferably defined in any one of embodiments 2 to 6. and (W2) A wet etching composition preferably comprising one or more oxidizing agents preferably selected from the group consisting of hydrogen peroxide, urea peroxide, peroxodisulfate, ammonium persulfate, peroxomonosulfate, pyrosulfate, and ozone, in an amount of 2% to 25% by mass, preferably 5% to 20% by mass, more preferably 7.5% to 20% by mass, and even more preferably 10% to 17.5% by mass, relative to the total mass of the cleaning composition.

[0127] A13. A method using the wet etching composition described in Embodiment 12 for the following purposes. - Preferably, remove, preferably partially remove, a hard mask containing a metal preferably selected from the group consisting of a Ti hard mask, a TiN hard mask, a Ta hard mask, a TaN hard mask, an Al hard mask, and a HfOx hard mask, more preferably a TiN hard mask, while at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and materials with a low k value is present. and / or - Preferably, on the surface of a semiconductor substrate, at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and low k-value materials is present, and a layer or mask containing or consisting of a material selected from the group consisting of Ti, TiN, Ta, TaN, Al, and HfOx, preferably containing or consisting of TiN, is etched, preferably oxidatively etched, or partially etched, preferably partially oxidatively etched; and / or - Etching, preferably selectively, a layer containing an aluminum compound in the presence of a layer of low k-value material, and / or a layer containing copper and / or cobalt, and / or preferably a layer containing tungsten; and / or - Removing, preferably selectively removing, layers containing aluminum compounds from a semiconductor substrate while layers of low-k-value material and / or layers containing copper and / or cobalt and / or preferably layers containing tungsten are present; and / or - Removing, preferably selectively removing, a layer containing an aluminum compound from the surface of a semiconductor substrate while a layer of low-k-value material and / or a layer containing copper and / or cobalt and / or preferably a layer containing tungsten are present; and / or - Preferably, post-etching or post-ashing residue is removed from the surface of a semiconductor substrate in the presence of at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and materials with a low k value. Post-etching or post-ashing residues preferably include one or more residues selected from the group consisting of: - One or more organic compounds containing or not containing fluorine, preferably organic polymers, - Metal-organic complexes, and - Metallic material, preferably titanium and / or titanium oxide and / or titanium nitride.

[0128] A14. A method for manufacturing a semiconductor device from a semiconductor substrate, comprising the following steps: P1) A wet etching composition is prepared by mixing a cleaning composition described in any one of embodiments 1 to 6, preferably one of embodiments 2 to 6, with one or more oxidizing agents preferably selected from the group consisting of hydrogen peroxide, urea peroxide, peroxodisulfate, ammonium persulfate, peroxomonosulfate, pyrosulfate, ozone, and mixtures thereof. or The wet etching composition described in embodiment 12 yields and P2) Preferably, the wet etching composition received or provided in step P1) is brought into contact with the following at least once, in the presence of at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and materials with a low k value: - On the surface of a semiconductor substrate, a layer or hard mask preferably selected from the group consisting of a Ti layer or mask, a TiN layer or mask, a Ta layer or mask, a TaN layer or mask, an Al layer or mask, and an HfOx layer or mask, more preferably a TiN layer or mask, and / or - An etching stop layer comprising or consisting of one or more aluminum compounds deposited on the surface of a semiconductor substrate, a layer containing copper, preferably on the copper layer, and / or a layer containing cobalt, preferably on the cobalt layer. Preferably, as follows: - Etch the layer or mask, preferably selectively oxidatively etched, or partially etch, preferably selectively partially oxidatively etched. and / or - Remove, preferably selectively remove, an etching stop layer containing or consisting of one or more aluminum compounds from the surface of a semiconductor substrate. and / or - A method for removing post-etching or post-ashing residue from the surface of a semiconductor substrate, preferably in a one-step process.

[0129] A15. A kit for etching, preferably oxidatively etching, or partially etching, preferably partially oxidatively etching, and / or etching, on the surface of a semiconductor substrate, preferably for the removal of post-etching or post-ashing residue from the surface of the semiconductor substrate, and / or for etching a layer or mask containing or made of TiN, preferably for post-etching or post-ashing residue from the surface of the semiconductor substrate, and / or for etching a layer containing or made of one or more aluminum compounds, preferably selectively etching, in the presence of a layer of low k-value material and / or preferably a layer containing tungsten, more preferably an underlying layer containing tungsten and / or copper and / or cobalt. As individual ingredients: (K1) Cleaning composition according to any one of embodiments 1 to 6; and (K2) One or more oxidizing agents preferably selected from the group consisting of hydrogen peroxide, urea peroxide, peroxodisulfate, ammonium persulfate, peroxomonosulfate, pyrosulfate, ozone, and mixtures thereof; more preferably one of the one or more oxidizing agents is hydrogen peroxide; And as individual components, optionally include or combine component (K1) and / or component (K2): (K3) A kit comprising one or more stabilizers preferably selected from the group consisting of amine-N-oxide; citric acid; 1-hydroxyethane-1,1-diphosphonic acid; glycolic acid; lactic acid; hydroxybutyric acid; glyceric acid; malic acid; tartaric acid; malonic acid; succinic acid; glutaric acid; maleic acid and mixtures thereof. [Examples]

[0130] The following embodiments are intended to further describe and illustrate the present invention without limiting its scope.

[0131] The following abbreviations will be used in the Examples section: *: Also acts as a weak acid component in the buffer system (F). 5-Me-BTA: 5-methylbenzotriazole (as defined above) b: Remaining (up to 100% by mass) BTA: Benzotriazole (unsubstituted) BDG: Butyl diglycol BTG: Butyl triglycol CDTA: 1,2-Cyclohexylene dinitrilotetraacetic acid DGMHE: Diethylene glycol monohexyl ether DGMME: Diethylene glycol monomethyl ether DIA: 1,3-dimethyl-2-imidazolidinone DiAHP: Diammonium hydrogen phosphate DMSO: Dimethyl sulfoxide EDTMP: N,N,N,N-ethylenediaminetetrakis(methylenephosphonic acid) EGMBE: Ethylene glycol monobutyl ether EIS: Ethyl isopropyl sulfone NMMO: 4-Methylmorpholine-4-oxide ST: Surface tension (mN / m) TEAH: Tetraethylammonium hydroxide TMAH: Tetramethylammonium hydroxide na: No data available

[0132] [Example 1] Production of the cleaning composition according to the present invention The following cleaning compositions according to the present invention (CCI1-CCI7 and CCI8-CCI5) were prepared by mixing (as appropriate) components (A)-(H) in each case. Details are shown below in Tables 1a and 1b. The notation of components (A)-(H) corresponds to the notation of components as defined above.

[0133] [Table 1]

[0134] [Table 2]

[0135] [Example 2] Production of the wet etching composition according to the present invention The following wet etching compositions according to the present invention (WEI1-WEI7, WEI8-WEI11, and WEI15) are prepared by mixing the respective cleaning compositions of the present invention CCI1-CCI7, CCI8-CCI11, or CCI15 (see Example 1) in each case in which a sufficient amount of hydrogen peroxide (H2O2, 31% in water) is obtained as the final concentration or mass ratio, as shown in Tables 2a and 2b below, where "mass %H2O2" in each case is given relative to the total mass of the respective cleaning compositions (CCI1-CCI7, CCI8-CCI11, and CCI15) used to produce a certain wet etching composition, and "mass %H2O2" in each case represents the amount or concentration of pure (undiluted) hydrogen peroxide present in the respective wet etching composition.

[0136] [Table 3]

[0137] [Table 4]

[0138] [Example 3] Measurement of etching loss for TiN The etching loss for the TiN layer caused by the wet etching composition of the present invention in Example 2 was determined according to the method described in International Publication No. 2015 / 173730(A1), or similarly. The wet etching compositions were prepared by mixing each cleaning composition with a specific amount of hydrogen peroxide immediately before conducting the etching rate experiment.

[0139] Si test wafers with TiN layers (the thickness of the TiN layers was in the range of 200-300 nm as physically deposited TiN "PVD TiN") were selected from a suitable commercial source and divided into smaller specimens. The layer thickness and etching rate were then measured by X-ray fluorescence analysis (XRF) using methods known to themselves. XRF is suitable for non-contact and non-destructive measurement of the thickness of thin layers and determination of their chemical composition. For this type of measurement, the X-ray source and detector are positioned on the same side of the sample. When X-rays are applied to a layer on a substrate, if the layer is thin enough to some extent, the radiation will penetrate the layer according to its thickness, and in turn, induce characteristic fluorescence radiation in the substrate material beneath. This fluorescence radiation will be absorbed and attenuated by the layer on its way to the detector. The thickness of the layer can be determined based on the intensity attenuation of the fluorescence radiation from the substrate material.

[0140] To determine the initial film or layer thickness of the applicable material, XRF recipes were created for the initial wafers based on the layer thickness reported by the supplier and verified by transmission electron microscopy (TEM) cross-section.

[0141] Next, the wet etching composition was heated to the test temperature (59°C for this Example 3 experiment) and mechanically stirred. The wafer specimen was fixed to a mechanical holder and brought into contact with the wet etching composition in a beaker for the reaction time (1 minute for this Example 3 experiment). Subsequently, the specimen was removed from the wet etching composition and washed with ultrapure water, isopropyl alcohol, or a mixture of ultrapure water and isopropyl alcohol for about 1 minute. After that, the specimen was dried with nitrogen gas. The residual thickness of the TiN layer after etching was measured again in the same manner as described above, and the etching loss was calculated by subtracting the thickness of the layer after contact with the wet etching composition from the thickness of the same layer before contact with the test composition. The results of this test (etching loss of the TiN layer) are shown in Table 3 below. Unless otherwise specified, all etching loss values ​​measured in Examples 3 to 5 are shown in Å.

[0142] [Example 4] Measurement of etching losses for aluminum oxide (AlOx), cobalt, and copper. Si wafers or wafer pieces (collectively referred to below as "test wafers") with appropriate types of outer layers (the thickness of the Co layer was in the range of 25–200 nm; the thickness of the AlOx layer was approximately 20 nm; all outer layers suitable for conducting etching loss experiments were sufficiently thick to allow meaningful measurement results after etching) were obtained from commercially available sources. The test wafers were pre-treated as applicable: Cu and Co were each immersed in an oxalic acid solution for 20–30 seconds, then rinsed with water and dried. The AlOx coated surface was not pre-treated.

[0143] The aluminum oxide (AlOx) coated surface was used as a representative model for layers containing or consisting of one or more aluminum compounds (as defined above).

[0144] A wet etching composition (see Example 2 and Table 2 above) was prepared, and a test wafer (see above) was brought into contact with the wet etching composition in a glass beaker at a temperature of 59°C for 10 minutes in the case of an AlOx surface or a Cu surface, and for a reaction time of 5 minutes in the case of a cobalt surface. The wafer was then removed from the wet etching composition, rinsed with water or isopropanol, and dried with nitrogen gas.

[0145] The thicknesses of the copper, cobalt, and aluminum oxide layers on the test wafer were determined before and after contact with the test composition by X-ray fluorescence analysis (as described in Example 3 above). To ensure reproducibility, the experiment was performed at least three times.

[0146] The difference between the measurement value of the copper, cobalt, or AlOx layer before contact with the wet etching composition and the measurement value of the same copper, cobalt, or AlOx layer after contact with the wet etching composition was determined in each case as the etching loss obtained for each layer (as described in Example 3 above). The results of this test (etching loss of the Cu, Co, or AlOx layer) are shown in Table 3 below (each given value in Table 3 represents the average of at least three experiments).

[0147] [Example 5] Measurement of etching loss for the underlying tungsten layer A Si test wafer was manufactured comprising a series of layers: (i) a low k-value material layer (top layer, layer thickness: 75 Å), (ii) an etching stop layer consisting of one or more aluminum compounds (AlOx layer as the first lower layer below the top layer, layer thickness: 50 Å), and (iii) a tungsten ("lower W") layer (a layer containing tungsten metal as the second lower layer below the first lower layer, layer thickness: 1500 Å, located on the surface of the Si test wafer). Manufactured in this manner, the Si test wafer stack, comprising (in a given order) (i) a low k-value material layer, (ii) an etching stop layer, (iii) a tungsten layer, and (iv) the surface of the Si test wafer, was sealed on all sides such that the wet etching composition applied to the top layer (i) of the stack could only come into contact with the tungsten layer (iii) by passing through (permeating or diffusing) (i) the top layer and (ii) the etching stop layer (the first layer below) (as done in this experiment).

[0148] The Si test wafer stack is then etched by contacting it with the wet etching composition manufactured according to Example 2 in an etching process equivalent to the etching process described in Example 3 above (applicable test temperature in this Example 5: 59°C, applicable reaction time in this Example 5: 1 minute). The thickness of the tungsten layer before and after etching is then determined according to the method described in Example 3 above, and the etching loss of each tungsten layer is calculated as described in Example 3. The results of this test are shown in Table 3 below.

[0149]

Table 5

[0150] From the results shown in Table 3 above, it can be seen that at least the wet etching compositions WEI1, WEI4, and WEI5 are excellent in etching rate selectivity for TiN (for selectively etching a hard mask containing or consisting of TiN), AlOx (for selectively removing an etching stop layer containing or consisting of one or more aluminum compounds), Cu (for protecting any copper present in the etching process to the highest possible extent), and Co (for protecting any copper present in the etching process to the highest possible extent). Therefore, it can be concluded that all the wet etching compositions WEI1 to WEI7 are suitable for application in the manufacturing process for a structure of 10 nm or less than 10 nm, for example, a structure of 7 nm, on a semiconductor substrate, including the removal process consisting of three types in one step of the process as described above.

[0151] From the results shown in Table 3 above, it can be further seen that the wet etching compositions WEI4, WEI5, WEI6, and WEI7 according to the present invention (all showing beneficial etching loss for W layers below <10 nm under the test conditions of Example 5) are excellently suited for application in manufacturing processes for 7 nm structures or structures below 7 nm, such as 5 nm structures, on semiconductor substrates, including the three types of removal steps in a single process as described above.

[0152] [Example 6] Measurement of etching loss for TiN as a function of time in wet etching compositions Similar to Example 3 above, the etching loss of TiN caused by the wet etching compositions WEI8-WEI11 and WEI15 of the present invention in Example 2 (see Table 2b) was determined in accordance with or similar to the method described in International Publication No. 2015 / 173730(A1).

[0153] In this Example 6, a Si test wafer (12 inches) with a TiN layer (TiN layer thickness: approximately 300 nm as PVD TiN) was filled with 100 mL of wet etching composition as specified in Table 4 below, and then held at a temperature of 60°C in each case at time intervals as specified in Table 4 below. After each time interval, the residual thickness of the TiN layer on the test wafer was determined as described in Example 3 above and compared with the thickness of the TiN layer on the same test wafer at the start of the experiment. The residual activity of the wet etching composition tested in this experiment after the predetermined time intervals was then given in the form of an etching rate in angstroms / min (Å / min), as is commonly done in this art. The results of this experiment are shown in Table 4 below (the figures shown in Table 4 are within the measurement accuracy of the applied method).

[0154] [Table 6]

[0155] The results shown in Table 4 above indicate that the wet etching compositions according to the present invention provide a stable etching rate to the TiN layer over a long period of time, particularly when they contain only the alkyl sulfone compound of formula IV as the polar aprotic organic solvent (C), and more particularly when they contain sulfolane or ethyl isopropyl sulfone as the polar aprotic organic solvent (C) (but without alkyl glycol ether (E)). In this experiment, the etching rates of such wet etching compositions according to the present invention performed on the TiN layer (see, for example, WEI8 and WEI9) were stable and did not decrease for at least 24 hours (within the measurement accuracy of the test method).

[0156] The results shown in Table 4 above indicate that a wet etching composition containing one or more alkyl glycol ethers (E) as defined herein (but without a polar aprotic organic solvent (C)) provided a stable etching rate to the TiN layer over a slightly shorter time.

[0157] The results shown in Table 4 above further demonstrate that the wet etching composition, which includes one or more alkyl glycol ethers (E) and a polar aprotic organic solvent (C) as defined herein, but does not include the alkyl sulfone compound of formula IV as defined above, provided a stable etching rate to the TiN layer over a slightly shorter time.

[0158] Furthermore, the results shown in Table 4 above show that the etching rate of a wet etching composition containing one or more alkyl glycol ethers (E) as defined herein and 1,3-dimethyl-2-imidazolidinone as a polar aprotic organic solvent (C) as defined herein (but not containing an alkyl sulfone compound of formula IV as defined herein; see, for example, WEI15) was at a level approximately equivalent to that of a wet etching composition containing an alkyl sulfone compound of formula IV as the polar aprotic organic solvent (C), and showed an etching rate for the TiN layer for at least 24 hours.

[0159] [Example 7] Measurement of particle count in the nanometer to micrometer range in cleaning compositions As described in Example 1 above, washing compositions CCI12, CCI13, and CCI14 (200 mL each) were prepared and filtered. After filtration, the amounts of liquid particles with particle sizes of 0.15 μm, 0.2 μm, 0.3 μm, and 0.5 μm were determined using a liquid particle counter (Rion KS 40 A or Rion KS 19F, Rion, Inc., Japan).

[0160] In this experiment, it was found that cleaning composition CCI14 contained the lowest amount of particles in all particle size categories (see above), followed by cleaning composition CCI13, and then cleaning composition CCI12. From these results, it can be concluded that cleaning composition CCI14 (containing an alkyl sulfone compound of formula IV (sulfolane) as the polar aprotic organic solvent (C)) had the most beneficial inhibitory effect on particle aggregation of the tested cleaning compositions.

[0161] [Example 8] Measurement of particle counts in the nanometer to micrometer range on the surface of a semiconductor substrate. A cleaning composition according to the present invention was prepared (see Example 1 above) and applied to the surface (SiO surface) of a 300 mm non-patterned wafer. The wafer was then thoroughly processed, including rinsing and drying. Subsequently, the surface of the processed wafer was inspected for the number of particles on its surface using an industrial non-patterned wafer surface inspection system (KLA Tencor (USA): Surfscan® SP3, SP5, or SP7, respectively).

[0162] In this experiment, wafers treated with the cleaning composition CCI1 showed a particularly low number of particles on their surface after treatment.

[0163] [Example 9] Measurement of etching loss for aluminum oxide (AlOx) layers as a function of pH value of wet etching compositions Similar to Example 4 above, a test wafer with three different types of AlOx outer layers was obtained.

[0164] A wet etching composition (see Example 2 above and Table 2) was prepared, and the etching rate of the wet etching composition was determined as described in Example 4 above or in a manner similar to that described in Example 4 above at a temperature of 60 °C.

[0165] The etching rate of the wet etching composition according to the present invention was determined on two different sets of wafer surfaces as described in Example 3 or Example 4 above or in a manner similar to these methods: on one set of wafer surfaces supporting three different types of AlOx outer layers that had not been subjected to plasma etching (control), and on another set of wafer surfaces supporting three different types of AlOx outer layers that had been subjected to plasma etching. The results of this experiment are shown in Table 5 below.

[0166]

Table 7

[0167] The wet etching compositions WEI1 and WEI8 were prepared as described above (see Examples 1 and 2). The wet etching composition WEI16 was prepared in the same manner as WEI1 of a cleaning composition identical to CCI1, except that the content of tetramethylammonium hydroxide (TEAH) was lower in the cleaning composition used for the production of the wet etching composition WEI16 and was in the range of 0.1 to 0.4% by mass based on the total mass of the cleaning composition. The pH of the wet etching composition WEI16 was 6.5.

[0168] From the results in Table 5 above, the wet etching compositions according to the present invention with a pH value in the range of 6 to 9, preferably 6.5 to 8.0, exhibit etching rates for different types of layers containing aluminum compounds (different types of AlOx outer layers), indicating that the wet etching compositions are well-suited for highly controlled specific etching of layers containing or consisting of one or more aluminum compounds.

Claims

1. A method using a cleaning composition comprising at least the following components: (A) One or more compounds of formula I as a solvent: 【Chemistry 1】 [In the formula, R １ [These are selected from the group consisting of branched or unbranched alkyl groups with 1, 2, 3, or 4 carbon atoms.] a solvent in an amount of 1% to 15% by mass relative to the total mass of the cleaning composition; (B) One or more corrosion inhibitors selected from the group consisting of unsubstituted or branched or unbranched alkyl groups having 1, 2, 3, or 4 carbon atoms, aminoalkyl groups having branched or unbranched alkyl groups with 1, 2, 3, or 4 carbon atoms, benzotriazoles independently substituted once or twice with phenyl, thiophenyl, halogen, hydroxy, nitro, and / or thiols, and mixtures thereof. a corrosion inhibitor in an amount ranging from 0.1% to 6% by mass relative to the total mass of the cleaning composition; (C) One or more polar aprotic organic solvents, One, or at least one, or all of the polar aprotic organic solvents (C) are: - Dimethylformamide, - Dimethyl sulfoxide, - Dimethylacetamide, - N-methylpyrrolidone, - Propylene carbonate, - Tetrahydrofuran, - 2-imidazolidinones that are substituted once or twice with branched or unbranched alkyl groups having 1 to 4 carbon atoms. and - These mixtures A polar aprotic organic solvent selected from the group consisting of the following: and comprising a polar aprotic organic solvent in an amount of 1% to 11% by mass relative to the total mass of the cleaning composition; (D) Water; and (E) One or more alkyl glycol ethers combined with one or more oxidizing agents, in an amount of 15% to 35% by mass relative to the total mass of the cleaning composition. One or more oxidizing agents are selected from the group consisting of hydrogen peroxide, urea peroxide, peroxydisulfate, ammonium persulfate, peroxymonosulfate, pyrosulfate, ozone, and mixtures thereof. - For removing post-etching or post-ashing residue from the surface of a semiconductor substrate. and / or - Ti, TiN, Ta, TaN, Al, and HfO ｘ Alkyl glycol ether for etching or partially etching a layer or mask containing or comprising a material selected from the group consisting of and / or a layer or mask containing or comprising a material selected from the group consisting of tungsten carbide and tungsten nitride. A method using a cleaning composition containing [the specified ingredient].

2. - Component (E) has a Hansen polarity solubility parameter δ ｐ ≤ 8 (MPa) １／２ Selected from the group consisting of alkyl glycol ethers, and / or - The cleaning composition has as component (E) formula II: 【Chemistry 2】 [In the formula, R ２ This is a branched or unbranched alkylene group having 1 to 6 carbon atoms. R ３ This is a branched or unbranched alkyl group having 1 to 8 carbon atoms. and n is an integer in the range of 1 to 6. Containing one or more alkyl glycol ethers, The method according to claim 1.

3. In the aforementioned cleaning composition, one or more alkyl glycol ethers of formula II(E) are present. -R ２ This is a branched or unbranched alkylene group with 3 to 4 carbon atoms. and / or -R ３ This is a branched or unbranched alkyl group having 1, 2, 3, 5, or 6 carbon atoms. and / or -n is an integer in the range of 2 to 4. and / or - Does not contain butyl diglycol. The method according to claim 2.

4. The cleaning composition is: (F) A buffering system suitable for buffering the pH of the cleaning composition to a range of 6 to 9; and / or (G) One or more chelating agents in an amount ranging from 0.01% to 3% by mass relative to the total mass of the cleaning composition; and / or (H) One or more surfactants The method according to claim 1 or 2, further comprising:

5. In a cleaning composition, - One or at least one of the solvents (A) is 4-methylmorpholine-4-oxide, or contains the same. and / or - One or at least one of the corrosion inhibitors (B) is selected from the group consisting of benzotriazoles and mixtures thereof, which are unsubstituted or independently substituted once or twice with branched or unbranched alkyls having 1, 2, 3, or 4 carbon atoms, and / or halogens selected from the group consisting of chlorine and bromine; and / or - One or at least one polar aprotic organic solvent (C) is selected from the group consisting of dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, propylene carbonate, sulfolane, tetrahydrofuran, and mixtures thereof. and / or - The total amount of etching solution containing fluoride anions is <0.001% by mass relative to the total mass of the cleaning composition. The method according to any one of claims 1 to 3.

6. In cleaning compositions - The total amount of one or more solvents (A) is in the range of 2% to 12% by mass relative to the total mass of the cleaning composition. and / or - The total amount of one or more corrosion inhibitors (B) is in the range of 0.2% to 6% by mass relative to the total mass of the cleaning composition. and / or - The cleaning composition comprises at least components (A), (B), (C), (D), (E), and (F); and / or - Water (D) fills the remaining portion of the cleaning composition to make 100% by mass. The method according to any one of claims 1 to 5.

7. The method includes removing post-etching or post-ashing residue from the surface of a semiconductor substrate. - The semiconductor substrate comprises at least one material selected from the group consisting of copper, cobalt, tungsten, and materials with a low k value. and / or - The method includes cleaning a semiconductor substrate containing at least one material selected from the group consisting of copper, cobalt, tungsten, and materials with a low k value; and / or - The method includes removing post-etching or post-ashing residue from the surface of a semiconductor substrate in the presence of at least one material selected from the group consisting of copper, cobalt, tungsten, and low k-value materials. Post-etching or post-ashing residues are - One or more organic polymers, with or without fluorine, - Metal-organic complexes, and - Metallic materials containing titanium and / or titanium oxides and / or titanium nitrides, It includes one or more residues selected from the group that includes or consists of; and / or - The method includes removing residues and contaminants from the surface of a semiconductor substrate containing at least one material selected from the group consisting of copper, cobalt, tungsten, and low k-value materials. The method according to any one of claims 1 to 6.

8. The method includes or consists of etching or partially etching a layer or mask comprising or consisting of a material selected from the group consisting of Ti, TiN, Ta, TaN, Al, and HfO ｘ and / or a layer or mask selected from materials comprising or consisting of a material selected from the group consisting of tungsten carbide (WC ｘ ) and tungsten nitride (WN ｘ ), wherein etching or partially etching the layer or mask comprises - In the presence of at least one material selected from the group consisting of copper, cobalt, and materials with a low k value, a Ti hard mask, a TiN hard mask, a Ta hard mask, a TaN hard mask, an Al hard mask, and HfO ｘ Removing or partially removing a hard mask containing a metal selected from the group consisting of hard masks and / or tungsten carbide hard masks and tungsten nitride hard masks, and / or - Etching or partially etching a semiconductor substrate while at least one material selected from the group consisting of copper, cobalt, tungsten, and low k-value materials is present on its surface; and / or - Etching an aluminum compound layer in the presence of a low k-value material layer and / or a tungsten-containing layer and / or a copper and / or cobalt-containing layer; and / or - Removing a layer containing an aluminum compound from a semiconductor substrate while a layer of low-k-value material and / or a layer containing tungsten and / or a layer containing copper and / or cobalt are present. and / or - Removing a layer containing an aluminum compound from the surface of a semiconductor substrate while a layer of low-k value material and / or a layer containing tungsten and / or a layer containing copper and / or cobalt are present. The method according to any one of claims 1 to 6, including

9. - The cleaning composition is used in combination with one or more oxidizing agents in a one-step process to remove the following: (i) Ti hard mask, TiN hard mask, Ta hard mask, TaN hard mask, Al hard mask, and HfO ｘ A hard mask comprising a metal selected from the group consisting of hard masks and / or from the group consisting of tungsten carbide hard masks and tungsten nitride hard masks, and (ii) Etching stop layers of aluminum compounds deposited on a copper-containing layer and / or on a cobalt-containing layer, in the presence of tungsten completely covered by at least one layer of a low k-value material; and / or - The cleaning composition is used in combination with one or more oxidizing agents in a separate or simultaneous process; and / or - One or more oxidizing agents are used in an amount ranging from 2% to 25% by mass relative to the total mass of the cleaning composition; and / or - The oxidizing agent is hydrogen peroxide, and is used in an amount ranging from 7.5% to 20% by mass relative to the total mass of the cleaning composition. and / or - One or more stabilizers are used in combination with one or more oxidizing agents and / or in combination with the cleaning composition, including amine-N-oxide; citric acid; 1-hydroxyethane-1,1-diphosphonic acid; glycolic acid; lactic acid; hydroxybutyric acid; Glyceric acid; Malic acid; tartaric acid; Malonic acid; Selected from the group consisting of succinic acid; glutaric acid; maleic acid and mixtures thereof, The method according to any one of claims 1 to 8.

10. The cleaning composition according to any one of claims 1 to 6.

11. The cleaning composition is (F) A buffering system suitable for buffering the pH of the cleaning composition to a range of 6 to 9 A cleaning composition according to claim 10, comprising:

12. The cleaning composition according to claim 11, wherein the total amount of etching solution containing fluoride anions is <0.001% by mass relative to the total mass of the cleaning composition.

13. A method for removing post-etching or post-ashing residue from the surface of a semiconductor substrate, using the cleaning composition according to any one of claims 10 to 12, as described in claim 1 and / or 7.

14. (W1) Cleaning composition according to any one of claims 1 to 6 and (W2) One or more oxidizing agents selected from the group consisting of hydrogen peroxide, urea peroxide, peroxodisulfate, ammonium persulfate, peroxomonosulfate, pyrosulfate, and ozone; A wet etching composition containing the following:

15. The wet etching composition according to claim 14, comprising one or more oxidizing agents of component (W2) in a total amount ranging from 2% to 25% by mass relative to the total mass of the cleaning composition.

16. - In the presence of at least one material selected from the group consisting of copper, cobalt, tungsten, and materials with a low k value, a Ti hard mask, TiN hard mask, Ta hard mask, TaN hard mask, Al hard mask, and HfO ｘ Remove or partially remove a hard mask containing a metal selected from the group consisting of hard masks and / or tungsten carbide hard masks and tungsten nitride. and / or - On the surface of a semiconductor substrate, at least one material selected from the group consisting of copper, cobalt, tungsten, and materials with a low k value is present, and Ti, TiN, Ta, TaN, Al, and HfO ｘ A layer or mask comprising or consisting of a material selected from the group consisting of, and / or tungsten carbide (WC ｘ ) and tungsten nitride (WN ｘ Etching or partially etching a layer or mask containing or consisting of a material selected from the group consisting of ); and / or - Etching an aluminum compound layer in the presence of a low k-value material layer, and / or a layer containing copper and / or cobalt, and / or a layer containing tungsten; and / or - Remove the aluminum compound-containing layer from the semiconductor substrate while a layer of low-k-value material and / or a layer containing copper and / or cobalt and / or a layer containing tungsten are present; and / or - Remove the layer containing an aluminum compound from the surface of a semiconductor substrate while a layer of low-k material and / or a layer containing copper and / or cobalt and / or tungsten are present; and / or - A method of using the wet etching composition according to claim 14 or 15 to remove post-etching or post-ashing residue from the surface of a semiconductor substrate in the presence of at least one material selected from the group consisting of copper, cobalt, tungsten, and low k-value materials, Post-etching or post-ashing residues are - One or more organic polymers, with or without fluorine, - Metal-organic complexes, and - Metallic materials containing titanium and / or titanium oxides and / or titanium nitrides A method comprising one or more residues selected from the group including or consisting of.

17. The following steps: P1) A wet etching composition is prepared by mixing the cleaning composition according to any one of claims 1 to 6 with one or more oxidizing agents selected from the group consisting of hydrogen peroxide, urea peroxide, peroxodisulfate, ammonium persulfate, peroxomonosulfate, pyrosulfate, ozone, and mixtures thereof. or A step of preparing the wet etching composition according to claim 13 or 14, and P2) The wet etching composition received or prepared in step P1), - To etch a layer or mask, or to partially etch it. and / or - To remove an etching stop layer containing or consisting of one or more aluminum compounds from the surface of a semiconductor substrate, and / or - To remove post-etching or post-ashing residue from the surface of the semiconductor substrate, - Ti layer or mask, TiN layer or mask, Ta layer or mask, TaN layer or mask, Al layer or mask, and HfO on the surface of a semiconductor substrate ｘ A layer or hard mask selected from the group consisting of layers or masks, and / or a layer or hard mask selected from the group consisting of tungsten carbide hard masks and tungsten nitride hard masks, and / or - A step of bringing at least one etching stop layer, which contains or consists of one or more aluminum compounds deposited on a copper-containing layer and / or a cobalt-containing layer on the surface of a semiconductor substrate, into contact with the substrate at least once. A method for manufacturing semiconductor devices from a semiconductor substrate, including [specific components / features].

18. A kit for etching a layer containing or consisting of one or more aluminum compounds, in the presence of a layer of low-k-value material, and / or a layer containing tungsten, and / or a layer containing copper and / or cobalt on the surface of a semiconductor substrate, As individual ingredients: (K1) The cleaning composition according to any one of claims 1 to 6; and (K2) One or more oxidizing agents selected from the group consisting of hydrogen peroxide, urea peroxide, peroxodisulfate, ammonium persulfate, peroxomonosulfate, pyrosulfate, ozone, and mixtures thereof; A kit that includes the following:

19. As individual components, they may also include, or be combined with, component (K1) and / or component (K2): (K3) amine-N-oxide; citric acid; 1-hydroxyethane-1,1-diphosphonic acid; glycolic acid; lactic acid; hydroxybutyric acid; Glyceric acid; Malic acid; tartaric acid; Malonic acid; The kit according to claim 18, comprising one or more stabilizers selected from the group consisting of succinic acid; glutaric acid; maleic acid and mixtures thereof.

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