Compositions and methods for selectively etching hardmasks and / or etch stop layers in the presence of layers of low-k materials, copper, cobalt, and / or tungsten - Patents.com

Abstract

for removing post-etch or post-ash residues from the surface of a semiconductor substrate, and / or TiN, Ta, TaN, Al, and HfO x a layer or mask comprising or consisting of a material selected from the group consisting of: x ) and tungsten nitride (WN x Methods of using cleaning compositions in combination with one or more oxidizing agents are described for oxidatively etching or partially oxidatively etching a layer or mask comprising or consisting of a material selected from the group consisting of: aluminum compounds, and / or for removing a layer comprising an aluminum compound from the surface of a semiconductor substrate. Additionally, cleaning compositions and methods of using the cleaning compositions for removing post-etch or post-ash residues from the surface of a semiconductor substrate are described. Under further aspects, wet etching compositions comprising the cleaning composition and one or more oxidizing agents, and methods of using the wet etching compositions are described. Methods of producing semiconductor devices from semiconductor substrates, and kits comprising the cleaning composition and one or more oxidizing agents are also described.

Description

[Technical field]

[0001] The present invention relates to a method for removing post-etch or post-ash residues from a surface of a semiconductor substrate and / or a method for removing post-etch or post-ash residues from a surface of a semiconductor substrate, comprising the steps of: x and / or a layer or mask comprising or consisting of a material selected from the group consisting of tungsten carbide (WC x ) and tungsten nitride (WN x The present invention relates to the use of the cleaning composition in combination with one or more oxidizing agents for oxidative etching or partial oxidative etching of a layer or mask comprising or consisting of a material selected from the group consisting of: ), and / or for removing a layer comprising an aluminum compound from the surface of a semiconductor substrate. The present invention further relates to the cleaning composition and a method of using the cleaning composition for removing post-etch or post-ash residues from the surface of a semiconductor substrate. Under a further aspect, the present invention also relates to a wet etching composition comprising the 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 a semiconductor device from a semiconductor substrate, and to a kit comprising the cleaning composition and one or more oxidizing agents. [Background technology]

[0002] The method for manufacturing semiconductor devices is a multi-step process of successive photolithographic and chemical processing steps during which electronic circuits are gradually created on a substrate, typically a wafer made of pure semiconductor material ("semiconductor substrate", specifically "semiconductor wafer"). Preferably, silicon is used as the semiconductor material. Typical semiconductor substrates (wafers) are made of very pure silicon that is grown using the so-called "Czochralski process" into single-crystal cylindrical ingots (boules) with a diameter of up to 300 mm. 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] Certain methods for manufacturing semiconductor wafers consist of several stages, including, for example, so-called "front-end of the line" ("FEOL") and "back-end of the line" ("BEOL") processing stages.

[0004] The FEOL processing stage refers to the formation of transistors directly in the material of a semiconductor wafer (usually silicon). The raw semiconductor wafer is engineered by the growth of an ultra-pure and virtually defect-free silicon layer by epitaxy. The front-end surface engineering is followed by the growth of a gate insulator (e.g. silicon dioxide), the patterning of that gate, the patterning of source and drain regions, and the subsequent implantation or diffusion of dopants into the semiconductor material to obtain the desired complementary electrical properties.

[0005] Once the various devices (e.g., dynamic random access memory DRAM; static random access memory SRAM; electrically programmable read-only memory EPROM; or complementary metal-on-silicon CMOS) have been created in FEOL processing, they must be interconnected to form the desired electrical circuits. This is done in a series of wafer processing steps collectively referred to as BEOL. BEOL processing stages involve creating metal interconnect wires on the surface of the semiconductor wafer separated by layers of low dielectric constant material, e.g., material with a dielectric constant κ<3.9 (also known as "low-k material"). With the introduction of copper (Cu) and more recently also cobalt (Co) as conductive materials instead of aluminum, advanced multi-step manufacturing methods for forming integrated circuit (IC) interconnects on semiconductor substrates have been developed, including various methods for selectively creating and removing successive layers of conductive and insulating (dielectric) materials using, for example, chemical vapor deposition (CVD), electroplating, photolithography, wet or dry etching techniques, chemical mechanical polishing (CMP), and several cleaning steps to, for example, remove residues of previous material removal steps from the surface of the processed semiconductor substrate.

[0006] One such multi-step manufacturing method is known as a damascene manufacturing method using a dual damascene process such as a TFVL ("trench first via last") dual damascene process, a VFTL ("via first trench last") dual damascene process, a self-aligned dual damascene process, or variations thereof such as a dual damascene process using a metal-containing hard mask (see, for example, U.S. Pat. No. 6,696,222 for the latter).

[0007] In damascene processing techniques, the desired IC interconnect structure is patterned by etching the shape of the structure into the underlying interlayer dielectric ("ILD") material. After patterning, typically a thin barrier layer (e.g., made of Ta / TaN, TiN, CoWP, NiMoP, or NiMoB) is deposited on top of the etched structure as a copper diffusion barrier. On top of that barrier layer, a seed layer is often deposited that supports better adhesion of copper onto the underlying material and also acts as a catalytic material during the plating process. Typical materials for these seed layers are Pd, Co, or other materials, such as compounds including polymers and organic materials. The original deposition process (the damascene process) was designed to process each layer independently. Thus, the so-called "vertical interconnect accesses" ("vias") and metallization levels have different process steps, requiring a series of cleaning, material deposition, CMP, and another cleaning step for each layer. Copper technologies that use this series for its metallization level and its ILD as well as for the intervia dielectric ("IVD") are often referred to as "single damascene processes." Typically, in a single damascene process, each level requires its own cap or etch stop layer, a separate ILD layer, and on top, a need for a material that can be polished together with the interconnect copper metal, e.g., SiO2. Alternatively, dual damascene fabrication techniques combine certain similar process steps into one single process step, thereby reducing the number of process steps and time, as well as the cost, required to build a BEOL stack. Thus, a dual damascene process fabricates the IVD and metallization layers at once.

[0008] In a damascene manufacturing process 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 materials, e.g., an underlying layer of a dielectric material, during an etching step. Such conductive ("metal") masks (i.e., "hard masks") are typically made of, for example, Ti, TiN, Ta, TaN, Al, or HfO. x(i.e. hafnium oxide) and / or tungsten carbide (WC x ) or tungsten nitride (WN x For example, in a dual damascene patterning process using a metal-containing hardmask, a metal layer deposited on a dielectric (low-k) material serves as a hardmask for the second etching step.

[0009] With the ongoing demand for further miniaturization of structures on semiconductor substrates, especially semiconductor wafers, manufacturers are faced with new challenges: for example, in integration schemes for further miniaturized structures on semiconductor wafers, such as integration schemes for fabricating 10 nm or smaller structures on semiconductor wafers, or for fabricating 7 nm or smaller structures on semiconductor wafers, via formation is preferably done by using a metal-containing hardmask, often a TiN hardmask, followed by a dry etching step to remove low-k material located beneath the metal-containing hardmask (e.g., a Ti-containing hardmask such as a TiN hardmask) and optionally separated from the metal-containing / TiN hardmask by an additional layer, e.g., a non-metal-containing hardmask, or by a connecting layer. To protect the underlying copper and / or cobalt and / or tungsten at the bottom of the via to be formed, a thin etch stop layer is usually deposited on 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 etch stop layer often comprises or consists of one or more aluminum compounds and may have a thickness of 30 nm or less, particularly 20 nm or less, more particularly 10 nm or less or even 5 nm or less. Such an etch stop layer is often referred to as an "ESL" ("etch stop layer" for dry etching processes).

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

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

[0012] In a two-step process, in a first step, the metal-containing hard mask (e.g., TiN hard mask) is usually removed together with the residues of the previous manufacturing step, e.g., polymer residues, by applying a composition that usually contains an oxidizing agent such as hydrogen peroxide. The composition should not damage the layer of low-k material or the etch stop layer, in particular the etch stop layer that contains or consists of an aluminum compound. In a second step, the etch stop layer is removed by applying a suitable composition. Typically, in this second step, the polymer residues still present in the vias are also removed (see above).

[0013] The composition used in the one-step process as described above should selectively remove the hard mask, including a metal typically comprising or consisting of TiN, the etch stop layer, specifically an etch stop layer comprising or consisting of one or more aluminum compounds, and any polymeric residue still present in the via, while leaving undamaged or to the minimum possible extent any present layer of low-k material, any present copper and / or any present cobalt, and preferably any present tungsten.

[0014] For this purpose, the compositions used in the one-step process must have properties that allow very controlled and specific etching of, inter alia, layers comprising or consisting of aluminum compounds, as well as thin or ultrathin layers comprising or consisting of aluminum compounds, without damaging further layers of low-k material, copper metal, and / or cobalt metal that may be present.

[0015] A particular further requirement arising in the manufacturing process for structures below 7 nm, especially for structures of 5 nm, on semiconductor substrates is that any tungsten metal or tungsten material present, even if present under a layer of low-k material and / or under an etch stop layer containing or consisting of one or more aluminum compounds, should not be etched, damaged or removed in the three removal processes. It has been found that compositions previously used to carry out the three removal processes in a one-step process, especially as described above, are not suitable to adequately protect any tungsten metal or tungsten material in the three removal processes, even if (only) present under a layer of low-k material and / or under an etch stop layer containing or consisting of one or more aluminum compounds. It is assumed in this context that compositions previously used to carry out 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 etch stop layer containing one or more aluminum compounds.

[0016] The compositions according to the invention as defined herein are particularly suitable for application in one-step (three removal) processes, in particular in manufacturing processes for 10 nm structures, preferably sub-10 nm structures (the term "sub-10 nm structures" as used herein refers throughout the text to and includes structures smaller than 10 nm, e.g. 7 nm structures and / or 5 nm structures), more preferably 7 nm structures. The preferred compositions according to the invention as defined herein are even suitable for application in one-step (three removal) processes, in particular in manufacturing processes for sub-7 nm structures, especially 5 nm structures, on semiconductor substrates.

[0017] Aluminum oxide dielectric films 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)), but are known not to have the etch rate precision and reliability required to etch thin or ultra-thin etch stop layers comprising or consisting of aluminum compounds, e.g., aluminum oxide.

[0018] US 2018 / 0148669 A1 addresses cleaning compositions for removing post-etch residues.

[0019] US Pat. No. 9,546,321 B2 describes compositions and methods for selectively etching titanium nitride.

[0020] WO 2008 / 080097 A2 discusses liquid cleaning agents for the removal of post-etch residues.

[0021] WO 2019 / 110690 A2 (a document published after the earliest filing date of this patent application) addresses compositions and methods for selectively etching a layer comprising an aluminum compound in the presence of a layer of low-k material, copper and / or cobalt.

[0022] WO 03 / 035797 A1 relates to an aqueous cleaning composition containing a copper-specific corrosion inhibitor for cleaning inorganic residues on semiconductor substrates.

[0023] WO 2004 / 030038 A2 relates to a composition substrate for removing etching residues and a method of using the same.

[0024] WO 2009 / 064336 A1 teaches compositions for the removal of metal-containing hardmask etch residues from semiconductor substrates.

[0025] WO 2012 / 009639 A2 relates to aqueous cleaning agents for the removal of post-etch residues.

[0026] WO 2014 / 197808 A1 describes compositions and methods for selectively etching titanium nitride.

[0027] US 2004 / 061092 relates to wet etching for selective removal of alumina.

[0028] US Patent Application Publication No. 2010 / 0075478 relates to a method for patterned resist removal.

[0029] US Patent Application Publication No. 2012 / 0052686 relates to cleaning fluids and damascene processes using same. [Prior art documents] [Patent documents]

[0030] [Patent Document 1] U.S. Patent No. 6,696,222 [Patent Document 2] US Patent Application Publication No. 2018 / 0148669(A1) [Patent Document 3] U.S. Patent No. 9,546,321(B2) [Patent Document 4] International Publication No. 2008 / 080097(A2) Brochure [Patent Document 5] International Publication No. 2019 / 110690(A2) Brochure [Patent Document 6] International Publication No. 03 / 035797(A1) Brochure [Patent Document 7] International Publication No. 2004 / 030038(A2) Brochure [Patent Document 8] International Publication No. 2009 / 064336(A1) Brochure [Patent Document 9] International Publication No. 2012 / 009639(A2) Brochure [Patent Document 10] International Publication No. 2014 / 197808(A1) Brochure [Patent Document 11] US Patent Application Publication No. 2004 / 061092 [Patent Document 12] US Patent Application Publication No. 2010 / 0075478 [Patent Document 13] US Patent Application Publication No. 2012 / 0052686 [Non-patent literature]

[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) Summary of the Invention [Problem to be solved by the invention]

[0032] Thus, the main object of the present invention is to provide a composition useful for removing post-etch or post-ash residues from the surface of a semiconductor substrate, and for selectively etching or partially etching a layer or hard mask and / or a layer comprising 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 damage or significantly damage the low-k material and one or more materials selected from the group consisting of copper, cobalt, and tungsten that are also present. The composition should be particularly suitable for use in manufacturing processes for making 7 nm and / or sub-7 nm structures (ideally including 5 nm structures) on semiconductor substrates.

[0033] Another object of the present invention is to provide a process for manufacturing a semiconductor device, wherein post-etch or post-ash residues are removed from a 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 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 in or will be apparent from this specification and the appended claims. [Means for solving the problem]

[0035] It has now been found that the main and other objects of the present invention are achieved by the use of a cleaning composition comprising at least the following components (i.e. one or more additional substances may also be present): (A) One or more compounds of formula I as solubilizing agents:

[0036] [ka]

[0037] [In the formula, R 1 is selected from the group consisting of branched or unbranched (preferably unbranched) alkyl having 1, 2, 3, or 4 carbon atoms; (B) one or more corrosion inhibitors selected from the group consisting of benzotriazoles, which are unsubstituted or substituted once or twice independently with branched or unbranched alkyl having 1, 2, 3, or 4 carbon atoms, aminoalkyl having 1, 2, 3, or 4 carbon atoms, phenyl, thiophenyl, halogen, hydroxy, nitro, and / or thiol, and mixtures thereof; (C) one or more polar aprotic organic solvents, Preferably, one, or at least one, or all of the polar aprotic organic solvents (C) are selected from the group consisting of: - an alkyl sulfone compound of formula IV: [ka] [In the formula, R 5 is a branched (structurally possible) or unbranched alkyl group having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms; R 6 is a branched (structurally possible) or unbranched alkyl group having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms; or R 5 and R 6 and together form a branched (if structurally possible) or unbranched alkylene group having 3 to 5 carbon atoms, preferably 3 to 4 carbon atoms, and one or two carbon atoms of the alkylene group are represented by -OR 7 (i.e. any -OR 7 groups are independently substituted by R 7is a branched (if 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 substituted once or twice with a branched (where structurally possible) or unbranched alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms; preferably 1,3-dimethyl-2-imidazolidinone and - A mixture of these More preferably, one, or at least one, or all of the polar aprotic organic solvents (C) are selected from the group consisting of alkylsulfone compounds of formula IV as defined above; dimethylsulfoxide; dimethylacetamide; N-methylpyrrolidone, propylene carbonate; 2-imidazolidinones substituted once or twice with branched or unbranched alkyl groups having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, preferably 1,3-dimethyl-2-imidazolidinones; and mixtures thereof; Even more preferably, one, or at least one, or all of the polar aprotic organic solvents (C) are selected from the group consisting of alkylsulfone compounds of formula IV as defined above; dimethylsulfoxide; dimethylacetamide; N-methylpyrrolidone; and mixtures thereof. One or more polar aprotic organic solvents and (D) water in combination with one or more oxidizing agents, Preferably, the one or more oxidizing agents are selected from the group consisting of hydrogen peroxide, urea peroxide, peroxydisulfuric acid, ammonium persulfate, peroxymonosulfuric acid, pyrosulfuric acid, ozone, and mixtures thereof; - for removing post-etch or post-ash residues from a surface of a semiconductor substrate and / or - Ti, TiN, Ta, TaN, Al, and HfO x A layer or mask comprising or consisting of a material selected from the group consisting of, preferably hard mask, and / or tungsten carbide (WC x ) and tungsten nitride (WN x For etching, preferably oxidatively etching or partially etching, preferably partially oxidatively etching, a layer or mask comprising or consisting of a material selected from the group consisting of: Water, preferably on the surface of the semiconductor substrate.

[0038] The cleaning compositions in combination with one or more oxidizing agents are suitable for use on semiconductor substrates and ... x and / or a layer or hard mask comprising or consisting of a material selected from the group consisting of tungsten carbide (WC x ) and tungsten nitride (WN x It has been particularly surprising that the present invention enables highly controlled and specific etching of layers or hard masks comprising or consisting of a material selected from the group consisting of:

[0039] The cleaning compositions in combination with one or more oxidizing agents as defined above are therefore particularly suitable for use in manufacturing processes for making 10 nm or sub-10 nm structures (as defined above), in particular 7 nm structures, including the triple removal of hard masks, etch stop layers and polymeric residues (as explained above) in one step on semiconductor substrates.

[0040] As defined above, the present preferred cleaning compositions in combination with one or more oxidizing agents are suitable for application even in manufacturing processes for sub-7 nm structures, especially 5 nm structures, including triple removal of hard masks, etch stop layers and polymeric residues (as explained above) in one step on semiconductor substrates. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

[0042] In the context of the present invention, the "one or more aluminum compounds" of the layer comprising or consisting of one or more aluminum compounds is defined as aluminum oxide ("AlO x ", "AlO x N y F z ", where the indices "x", "y", and "z" represent numbers indicating the stoichiometric or non-stoichiometric amounts of the respective chemical elements), aluminum nitride, aluminum oxynitride ("AlON"), and aluminum oxide carbonitride ("AlCNO"). Preferably, the aluminum compound further comprises fluorine. As defined herein, the exact composition of the aluminum compound and the exact content or percentage of the elements aluminum, oxygen, nitrogen, carbon, and / or fluorine present in one of the one or more aluminum compounds may vary depending on, for example, the type of pretreatment of the semiconductor substrate with the aluminum compound.

[0043] An "etch stop layer" as referred to herein is consistent with its usual meaning in the art and is a layer of material that is not etched under conditions applied in conventional etching processes for structuring the surface of a semiconductor substrate (e.g., a microelectronic device), in particular a semiconductor wafer, and that covers underlying materials potentially sensitive to the etching process, such as copper (e.g., in copper interconnects) or other metals, to protect them from undesired attack by the applied etchants. After the etching process, the etch stop layer can be removed (if necessary) under conditions specific to the material of the etch stop layer that also do not adversely affect the underlying materials.

[0044] In the context of the present invention, a "low k material" is preferably a material with 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), tetraethylorthosilicate (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 polymeric materials, preferably hydrogen silsesquioxane (HSQ) and methyl silsesquioxane (MSQ); preferably organosiloxane (i.e., siloxane containing carbon-silicon bonds); and preferably organosilanes (i.e., silanes containing carbon-silicon bonds); and (ii) polymeric materials, preferably selected from the group consisting of spin-on organic polymeric dielectrics, preferably including polyimides (PI); polynorbornenes; benzocyclobutenes, and polytetrafluoroethylene (PTFE).

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

[0046] In the context of the present invention, preferably, an "aprotic" solvent means a solvent which is preferably unable to act as a proton donor towards water (at pH 7).

[0047] In the cleaning composition for use according to the invention as defined above, R in the compound of formula I in one or more dissolving agents of component (A) 1 Specifically, R includes methyl, ethyl, and branched and unbranched propyl and butyl. 1 is methyl. 4-Methylmorpholine-4-oxide (also referred to herein 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 formula I for use in cleaning compositions as defined above. This definition of the compound of 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 formula I.

[0048] In cleaning compositions for use according to the invention as defined above, when component (B) comprises one or more corrosion inhibitors selected from the group consisting of benzotriazoles which are unsubstituted or substituted (as defined above), this definition includes one such benzotriazole, and multiple such benzotriazoles which may be independently unsubstituted or substituted as defined above, including mixtures of such benzotriazoles.

[0049] When component (B) comprises benzotriazoles substituted once or twice independently with branched or unbranched alkyls having 1, 2, 3, or 4 carbon atoms, this definition specifically includes methyl, ethyl, and branched and unbranched propyl and butyl. Methyl is preferred for the purposes of the present invention. Specific benzotriazoles encompassed by this definition are 5-methylbenzotriazole and 6-methylbenzotriazole (see below for applicable nomenclature). When component (B) comprises benzotriazoles substituted with aminoalkyls, the alkyls being branched or unbranched and having 1, 2, 3, or 4 carbon atoms, 2-(5-amino-pentyl) is preferred for the purposes of the present invention.

[0050] When component (B) comprises a benzotriazole substituted independently once or twice by a halogen, the halogen is selected from fluorine, chlorine, bromine and iodine, preferably from chlorine and bromine. Benzotriazole substituted, preferably substituted once by chlorine, is preferred as benzotriazole substituted independently once or twice by a halogen.

[0051] As 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 been found to have the same bonding properties. The proton attached to one nitrogen atom in the nitrogen-containing ring of the benzotriazole structure is not tightly bound to any of the three ring nitrogen atoms present, but rather moves rapidly between positions 1 and 3 to produce a tautomer. Thus, for 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 context, the compound 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" has the same meaning in each instance as the compound "5-methyl-2H-benzotriazole and all of 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, in particular the compound 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 also "5-chloro-2H-benzo[d][1.2.3]triazole". Conversely, the compound referred to in the present text 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" has in each case the same meaning as the compound "5-chloro-2H-benzotriazole and all of its tautomers". This definition applies mutatis mutandis to other benzotriazoles, in particular substituted benzotriazoles, as defined or mentioned in the present text.

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

[0054] The use of a cleaning composition in combination with one or more oxidizing agents according to the invention as defined herein (or preferably in combination with one or more oxidizing agents according to the invention as described above or below) is preferred, wherein one, or at least one, or all of the polar aprotic organic solvents (C) is an alkylsulfone compound(s) of formula IV as defined above.

[0055] In the context of the present invention, the alkylsulfone 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 alkylsulfone 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 variant of the present invention, the alkylsulfone compound of formula IV comprises or is sulfolane.

[0056] In the context of the present invention, an "alkylene group" preferably means a divalent chain group of carbon atoms. Examples of "alkylene groups" as used herein include "methylene" (R a -CH2-R b ), "Ethylene" (R a -CH2-CH2-R b ), "Trimethylene" (R a -CH2-CH2-CH2R b ), and "propylene" (H3C-C(R a )H-CH2-).

[0057] It has been found in own experience that cleaning compositions according to the invention as defined above, in particular cleaning compositions in which one, or at least one, or (in a particularly preferred variant of this aspect of the invention) all of the polar aprotic organic solvents (C) are alkylsulfone compound(s) of formula IV (or alkylsulfone compounds of formula IV as described herein as preferred), when used in combination with one or more oxidizing agents according to the invention as defined herein (or in combination with one or more oxidizing agents according to the invention as described above or below as preferred), exhibit the following beneficial effects: - on the surface of the semiconductor substrate, in particular Ti, TiN, Ta, TaN, Al and HfO, in the presence of at least one material selected from the group consisting of copper, cobalt, preferably tungsten and low-k materials; x and / or a layer or mask comprising or consisting of a material selected from the group consisting of tungsten carbide (WC x ) and tungsten nitride (WN x ), in particular a high selectivity for etching (in particular oxidative etching or partial etching, in particular partial oxidative etching) of layers or masks comprising or consisting of a material selected from the group consisting of: and - exhibits high stability of the cleaning composition against one or more oxidizing agents, in particular against oxidizing agents including peroxides, more particularly against hydrogen peroxide. High stability against one or more oxidizing agents is achieved by the cleaning composition against one or more oxidizing agents, in particular against Ti, TiN, Ta, TaN, Al, and HfO, when used in combination with one or more oxidizing agents (as defined above). x and / or a layer or mask comprising or consisting of a material selected from the group consisting of tungsten carbide (WC x ) and tungsten nitride (WN xIn particular, the cleaning composition, comprising or consisting of a material selected from the group consisting of TiN (as defined above), provides a high (selective) activity for etching a layer or mask comprising or consisting of TiN (as defined above) over a long period of time. For example, the cleaning composition, when used in combination with one or more oxidizing agents (particularly with hydrogen peroxide), can maintain its high, selective activity for etching a layer or mask comprising or consisting of TiN for an extended period of time 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 invention as defined herein (or as preferred above or below with one or more oxidizing agents according to the invention) is also preferred, the cleaning composition comprising, as further components: (E) one or more alkyl glycol ethers.

[0059] It has been found by own experience that the cleaning composition comprising the additive component (E) as defined above in combination with one or more oxidizing agents as defined above is not only suitable for use in a manufacturing process for making 7 nm structures on a semiconductor substrate, but even suitable for use in a manufacturing process for making structures below 7 nm, preferably 5 nm structures on a semiconductor substrate. This particularly beneficial utility of the cleaning composition comprising the additive component (E) (preferably the preferred component (E) as defined herein and / or in an amount or preferred amount as defined herein) is due to its ability to protect tungsten (preferably tungsten metal and / or tungsten material) that may be present under a layer of low-k material or under a layer of low-k material and an etch stop layer comprising or consisting of one or more aluminum compounds in a triple removal process (as described above), preferably carried out as a one-step process (as described above), in combination with one or more oxidizing agents.

[0060] It has been found by experiment that compositions previously used to perform a ternary removal process (not including component (E) as defined above), particularly in a one-step process (as described above), are not suitable to adequately protect any tungsten metal or tungsten material present under the layer of low-k material, or under the layer of low-k material and an etch stop layer that includes or consists of one or more aluminum compounds, during the ternary removal process. Moreover, it has been found by experiment that compositions previously used to perform a ternary removal process that do not include component (E) may unintentionally damage or at least partially etch tungsten (or tungsten metal and / or tungsten material) that is present to a significant extent under the layer of low-k material, or under the layer of low-k material and an etch stop layer that includes or consists of one or more aluminum compounds, during the ternary removal process. Own experiments have also led to the conclusion that this damage or partial etching of tungsten beneath the layer of low-k material, or beneath the layer of low-k material and an etch stop layer comprising or consisting of one or more aluminum compounds, occurs because compositions that do not include component (E), as defined above, can penetrate or diffuse through the layer of low-k material, or the layer of low-k material and an etch stop layer comprising or consisting of one or more aluminum compounds that coats the tungsten (or tungsten metal and / or tungsten material), in an amount sufficient to inadvertently damage or partially etch the underlying tungsten.

[0061] Further findings from own experiments indicate that by selecting certain preferred alkyl glycol ethers (as defined and explained below) as component (E) of the cleaning composition (as defined above) and / or by using preferred alkyl glycol ethers in the cleaning composition in amounts or preferred amounts as defined and explained below, 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 being damaged, removed or partially etched in the processes and / or methods described above can be optimized.

[0062] Thus, the use of a cleaning composition in combination with one or more oxidizing agents according to the invention as defined herein (or preferably in combination with one or more oxidizing agents according to the invention as described above or below) is preferred: - Component (E) has a Hansen polar solubility parameter δ p is ≦8(MPa) 1 / 2 , preferably ≦7.6 (MPa) 1 / 2 and n is an integer from 1 to 3. The alkyl glycol ethers are selected from the group consisting of and / or The cleaning composition comprises as component (E) one or more alkyl glycol ethers of formula II.

[0063] [ka] [In the formula, R 2 is a branched or unbranched (preferably unbranched) alkylene group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms; R 3 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 ranging from 1 to 6, preferably from 2 to 6.

[0064] It has been found in own experience that the alkyl glycol ethers as defined above and the preferred alkyl glycol ethers as defined below have properties (e.g. hydrophobicity and / or viscosity) which make them eminently suitable for use in cleaning compositions for use according to the invention in combination with one or more oxidizing agents.

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

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

[0067] Hansen solubility parameters were developed by Charles M. Hansen in 1967 in his doctoral thesis as a way to predict whether one material would dissolve in another to form a solution. They are based on the idea that like dissolves like, which defines one molecule as "like" another if it bonds to itself in a similar way. Specifically, each molecule is given three Hansen parameters, each generally expressed as (MPa) 1 / 2 Measured in: - δ d :Energy from intermolecular dispersion forces - δ p : Energy from dipolar intermolecular forces between molecules (referred to in the text as "Hansen polar solubility parameter") - δ h : Energy from hydrogen bonds between molecules

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

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

[0070] Furthermore, it has been found in own experiments that cleaning compositions according to the invention, comprising one or more alkyl glycol ethers (E) as defined above, and comprising as one, or at least one, or all, of the polar aprotic organic solvents (C) a 2-imidazolidinone, in particular 1,3-dimethyl-2-imidazolidinone, substituted once or twice with a branched or unbranched alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, exhibit a particularly good stability when used in combination with one or more oxidizing agents according to the invention as defined herein (or preferably in combination with one or more oxidizing agents according to the invention as described above or below). The particularly good stability (against one or more oxidizing agents, in particular against hydrogen peroxide) is due to the relatively high affinity of Ti, TiN, Ta, TaN, Al and HfO of the cleaning composition, compared to the use of a similar cleaning composition comprising one or more alkyl glycol ethers (E) but not comprising a 2-imidazolidinone (as defined above) as the polar aprotic organic solvent (C). xand / or a layer or mask comprising or consisting of a material selected from the group consisting of tungsten carbide (WC x ) and tungsten nitride (WN x ), in particular resulting in a longer lasting and higher (selective) activity of etching a layer or mask comprising or consisting of TiN (as defined above).

[0071] The use of a cleaning composition in combination with one or more oxidizing agents according to the invention as defined herein (or in combination with one or more oxidizing agents according to the invention as defined above or below as preferred, in particular in combination with one or more oxidizing agents according to the invention as defined below as "one preferred particular variant of the invention") is therefore preferred, The cleaning composition comprises: 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-imidazolidinones, preferably 1,3-dimethyl-2-imidazolidinone, substituted once or twice with 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 invention as defined herein (or the use of a cleaning composition in combination with one or more oxidizing agents according to the invention as described above or below as preferred) in which one, or at least one, or all of the polar aprotic organic solvents (C) are preferably alkyl sulfone compound(s) of formula IV (or alkyl sulfone compounds of formula IV as described herein as preferred) and may comprise, as further component (E), one or more alkyl glycol ethers or it may not comprise such further component (E). In many cases, a cleaning composition for use in combination with one or more oxidizing agents according to the invention as defined herein (or the use of a cleaning composition in combination with one or more oxidizing agents according to the invention as defined herein as preferred) in which one, or at least one, or all of the polar aprotic organic solvents (C) are preferably alkyl sulfone compound(s) of formula IV (or alkyl sulfone compounds of formula IV as described herein as preferred) and may comprise, as further component (E), one or more alkyl glycol ethers (as defined above).

[0073] Also preferred is the use of a cleaning composition in combination with one or more oxidizing agents according to the invention as defined herein (or as preferred above or below with one or more oxidizing agents according to the invention), which cleaning composition further comprises: (F) a buffer system suitable for buffering the pH of the cleaning composition to a range of 6 to 9, preferably to a range of 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;Hydroxyquinoline Nolinsulfonic 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 a one or more chelating agents preferably selected from the group consisting of diamine;methylamine;dimethylamine;ethylamine;triethylamine;isobutylamine;diisobutylamine, tert-butylamine;tributylamine;dipropylamine;diglycolamine;diisopropylamine;pentamethyldiethylenetriamine;monoethanolamine;triethanolamine;methyldiethanolamine;acetylacetonate;acetylacetone;2,2'-azanediyldiacetic acid;ammonium carbamate;ammonium pyrrolidine dithiocarbamate;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;gamma-butyrolactone; and mixtures thereof, Preferably, the one or more chelating agents are selected from the group consisting of 1,2-cyclohexylene dinitrilotetraacetic acid, N,N,N,N-ethylenediaminetetrakis(methylenephosphonic acid), and mixtures thereof, preferably in the range of 0.01% to 3% by weight, more preferably in the range of 0.1% to 2% by weight, and even more preferably in the range of 0.15% to 1.5% by weight, relative to the total weight of the cleaning composition; and / or (H) one or more surfactants (as defined below), preferably including one or more fluorosurfactants.

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

[0075] The use of a cleaning composition in combination with one or more oxidizing agents according to the invention is preferred, in which the buffer system of component (F) is a combination of a weak acid (e.g. phosphoric acid) and a salt of a weak acid as known in the art. The buffer system may contain, as an acidic element (weak acid) compound which is also a chelating agent (G), in particular 1,2-cyclohexylene dinitrilotetraacetic acid and / or N,N,N,N-ethylenediaminetetrakis(methylenephosphonic acid). A preferred salt of a weak acid of the buffer system comprises an ammonium compound of formula III: [N(R 4 )4]OH(III) [In the formula, R 4 are independently selected from hydrogen and branched or unbranched alkyl groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. For 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 invention as defined above, the one or more chelating agents (G) can generally in each case be used alone (as one single compound) or in combination with other chelating agents (G).

[0077] Also preferred is the use of a cleaning composition in combination with one or more oxidizing agents according to the invention, wherein the one or more surfactants (H) of the cleaning composition, if present, as defined above, are selected from the group consisting of: (i) fluorosurfactants preferably selected from the group consisting of sodium lauryl sulfate, perfluorinated alkylsulfonamide salts (preferably perfluorinated N-substituted alkylsulfonamide ammonium salts PNAAS), perfluorooctane sulfonate, perfluorobutane sulfonate, perfluorononanoate, and perfluorooctanoate; anionic surfactants preferably selected from the group consisting of alkylaryl ether phosphates and alkyl ether phosphates; (ii) a zwitterionic surfactant preferably selected from the group consisting of 3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulfonate ("CHAPS"), cocamidopropyl hydroxysultaine (CAS RN 68139-30-0), {[3-(dodecanoylamino)propyl](dimethyl)ammonio}acetate, phosphatidylserine, phosphatidylethanolamine, phosphatidylcholine, and (iii) A nonionic surfactant preferably selected from the group consisting of glucoside alkyl ethers, glycerol alkyl ethers, cocamide ethanolamine, and lauryl dimethylamine oxide.

[0078] More preferred surfactants (H) in the composition according to the first preferred variant of the invention are or contain perfluorinated N-substituted alkylsulfonamide ammonium salts. Preferred surfactants (H) in the composition according to the invention do not contain metals or metal ions.

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

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

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

[0082] The etching solution comprising a total amount of fluoride anions of <0.001 wt. % (as defined above) based on the total weight of the cleaning composition is preferably selected from the group consisting of ammonium fluoride, ammonium acid fluoride, triethanolammonium fluoride, diglycolammonium fluoride, methyldiethanolammonium fluoride, tetramethylammonium fluoride, triethylamine trihydrofluoride, hydrogen fluoride, fluoroboric acid, tetrafluoroboric acid, ammonium tetrafluoroborate, fluoroacetic acid, ammonium fluoroacetic acid, trifluoroacetic acid, fluorosilicic acid, ammonium fluorosilicate, tetrabutylammonium tetrafluoroborate, and mixtures thereof.

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

[0084] In a first preferred alternative, the use of a cleaning composition in combination with one or more oxidizing agents according to the invention as defined herein (or in combination with one or more oxidizing agents according to the invention as described above or below as preferred) is preferred, in which the total amount of one or more polar aprotic organic solvents (C), preferably selected from the group consisting of dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, propylene carbonate, sulfolane, tetrahydrofuran, and mixtures thereof, ranges from 5% to 15% by weight relative to the total weight 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 invention as defined herein (or the use of a cleaning composition in combination with one or more oxidizing agents according to the invention as defined above or below as preferred) is preferred, in which the total amount of one or more polar aprotic organic solvents (C), preferably selected from the group consisting of dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, propylene carbonate, sulfolane, tetrahydrofuran, and mixtures thereof, ranges from 30% to 40% by weight relative to the total weight 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 for the use of a cleaning composition in combination with one or more oxidizing agents according to the present invention as described or described below as preferred), the oxidizing agent is preferably applied in an amount relative to the cleaning composition as explained and defined below for the wet etching composition according to the present invention (or for any variant or preferred variant thereof).

[0087] One preferred particular variant of the present invention relates to the use of a cleaning composition in combination with one or more oxidizing agents according to the invention as defined herein (or, as preferred, in combination with one or more oxidizing agents according to the invention as described above or below), which cleaning composition comprises or consists of the following components: (A) 4-methylmorpholine-4-oxide as a solubilizing agent, in a total amount ranging from 2% to 12% by weight, more preferably from 3% to 10% by weight, based on the total weight of the cleaning composition; (B) one or more corrosion inhibitors selected from the group consisting of benzotriazoles that are unsubstituted or substituted independently one or two times with unbranched alkyl having one, two, three, or four carbon atoms, and mixtures thereof, in a total amount ranging from 0.2% to 6% by weight, preferably ranging from 0.5% to 5% by weight, based on the total weight of the cleaning composition; (C) one or more polar aprotic organic solvents selected from the group consisting of dimethyl sulfoxide, sulfolane, and mixtures thereof, in a total amount ranging from 3% by weight to 45% by weight, preferably from 5% by weight to 15% by weight, based on the total weight of the cleaning composition; (D) water, making up the remainder of the cleaning composition to 100% by weight; (E) one or more alkyl glycol ethers of formula II in a total amount ranging from 10% to 40% by weight, preferably from 15% to 35% by weight, based on the total weight of the cleaning composition [ka] [In the formula, R 2 is an unbranched alkylene group having 2 to 4 carbon atoms; R 3 is a branched or unbranched alkyl group having 1 to 6 carbon atoms. and n is an integer ranging from 2 to 6; (F) a buffer system suitable for buffering the pH of the cleaning composition to a range of 6 to 9, preferably to a range of 7 to 8.5; and (G) One or more chelating agents selected from the group consisting of 1,2-cyclohexylene dinitrilotetraacetic acid; N,N,N,N-ethylenediaminetetrakis(methylenephosphonic acid), and mixtures thereof, in a total amount ranging from 0.1% to 2% by weight, preferably from 0.15% to 1.5% by weight, based on the total weight of the cleaning composition.

[0088] Another preferred particular variant of the present invention relates to the use of a cleaning composition in combination with one or more oxidizing agents according to the invention as defined herein (or preferably in combination with one or more oxidizing agents according to the invention as described above or below), the cleaning composition comprising or consisting of the following components: (A) 4-methylmorpholine-4-oxide as a solubilizing agent, in a total amount ranging from 1% to 15% by weight, more preferably from 8% to 15% by weight, based on the total weight of the cleaning composition; (B) one or more corrosion inhibitors selected from the group consisting of benzotriazoles that are unsubstituted or substituted independently one or two times with unbranched alkyl having one, two, three, or four carbon atoms, and mixtures thereof, in a total amount ranging from 0.2% to 6% by weight, preferably ranging from 0.5% to 5% by weight, based on the total weight of the cleaning composition; (C) one or more polar aprotic organic solvents in a total amount ranging from 10% to 50% by weight, preferably ranging from 15% to 45% by weight, more preferably ranging from >30% to 45% by weight, based on the total weight of the cleaning composition, wherein all of the one or more 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 alkyl sulfone compound of formula IV (alkyl sulfone compound) is sulfolane; (D) water, preferably making up the remainder of the cleaning composition to 100% by weight; (F) a buffer system suitable for buffering the pH of the cleaning composition to a range of 6 to 9, preferably to a range of 7 to 8.5; (G) one or more chelating agents preferably selected from the group consisting of 1,2-cyclohexylene dinitrilotetraacetic acid, in a total amount ranging from 0.1% to 2% by weight, preferably ranging from 0.15% to 1.5% by weight, relative to the total weight of the cleaning composition; ammonium compounds of formula III as defined above (or as defined above as preferred), and mixtures thereof. and (H) (if present) preferably one or more surfactants, preferably including one or more fluorosurfactants, in a total amount ranging from 0.01% to 2% by weight, preferably from 0.02% to 1% by weight, based on the total weight of the cleaning composition.

[0089] Further preferred is the use of a cleaning composition 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), which use comprises removing post-etch or post-ash residues from a 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 subtended tungsten; and low-k materials; and / or - the use comprises cleaning a semiconductor substrate comprising at least one material selected from the group consisting of copper, cobalt, preferably tungsten, more preferably subtended tungsten; and low-k materials: and / or - the use comprises removing post-etch or post-ash residues from a 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 subtended tungsten; and low-k materials, The post-etch or post-ash residue comprises one or more residues selected from the group consisting of: one or more fluorine-containing or non-fluorine-containing organic compounds, preferably organic polymers, - metal-organic complexes, and - a metallic material, preferably titanium and / or titanium oxide and / or titanium nitride; and / or - the use comprises removing residues and contaminants from a surface of a semiconductor substrate comprising at least one material selected from the group consisting of copper, cobalt, preferably tungsten, more preferably subtended tungsten; and low-k materials; Preferably, the residues and contaminants comprise or consist of fluorine-containing or non-fluorine-containing organic compounds, preferably organic polymers.

[0090] As used herein, the term "underlying tungsten" means that tungsten (as tungsten metal or tungsten material), as defined above, is underlain (fully covered by) at least one layer of low-k material, and preferably also at least one etch stop layer comprising or consisting of one or more aluminum compounds (which, if present, is typically located between the at least one layer of low-k material and the tungsten and separates all sides of the at least one layer of low-k material from the surface of the tungsten). Thus, preferably, the underlying tungsten is not directly exposed to a cleaning composition (in combination with one or more oxidizers) or wet etching composition (both as defined herein) during a process for the manufacture of a semiconductor device (preferably as defined herein), but may be contacted by a cleaning composition (in combination with one or more oxidizers) and / or a wet etching composition, when the cleaning composition (in combination with one or more oxidizers) or wet etching composition penetrates or diffuses through the at least one layer of low-k material and, if applicable, through the at least one etch stop layer comprising or consisting of one or more aluminum compounds.

[0091] The use of the cleaning composition in combination with one or more oxidizing agents according to the invention as defined herein (or as preferred above or below) is also preferred, the use being of Ti, TiN, Ta, TaN, Al and HfO x A layer or mask comprising or consisting of a material selected from the group consisting of, preferably hard mask, and / or tungsten carbide (WC x ) and tungsten nitride (WN x(oxidative) etching or partially (oxidative) etching a layer or mask, preferably a hard mask, which comprises or consists of a material selected from the group consisting of: - preferably a Ti hardmask, a TiN hardmask, a Ta hardmask, a TaN hardmask, an Al hardmask, and a HfO hardmask in the presence of at least one material selected from the group consisting of copper, cobalt, preferably tungsten, more preferably lower tungsten; and low-k materials. x hard mask, and / or tungsten carbide (WC x ) hard mask and tungsten nitride (WN x ) a hardmask comprising a metal selected from the group consisting of: a TiN hardmask; and / or - etching, preferably oxidative etching or partial etching, preferably partial oxidative etching, in the presence of at least one material selected from the group consisting of copper, cobalt, preferably tungsten, more preferably underlying tungsten; and low-k materials on the surface of the semiconductor substrate; and / or - etching, preferably selectively etching, the layer comprising an aluminide in the presence of a layer of low-k material and / or preferably a tungsten, more preferably an underlying tungsten-containing layer; and / or a layer comprising copper and / or cobalt; and / or - removing, preferably selectively removing, from a semiconductor substrate a layer of low-k material and / or a layer preferably comprising tungsten, more preferably an underlying layer comprising tungsten and / or copper and / or cobalt, and / or - removing, preferably selectively removing, from the surface of a semiconductor substrate, a layer comprising an aluminide in the presence of a layer of low-k material and / or preferably a layer comprising tungsten, more preferably an underlying layer comprising tungsten, and / or copper and / or cobalt.

[0092] In a particularly preferred variant of the invention, the use of a cleaning composition in combination with one or more oxidizing agents according to the invention as defined herein (or in combination with one or more oxidizing agents according to the invention as described above or below as being preferred) is preferably - The cleaning composition is used in combination with one or more oxidizing agents in a one-step process to remove: (i) Ti hard mask, TiN hard mask, Ta hard mask, TaN hard mask, Al hard mask, and HfO x hard mask, and / or tungsten carbide (WC x ) hard mask and tungsten nitride (WN x ) a hardmask, more preferably a TiN hardmask; and (ii) an aluminide etch stop layer deposited on a copper-containing layer, preferably a copper layer, and / or on a cobalt-containing layer, preferably a cobalt layer, in the presence of tungsten, which is preferably completely covered by at least one layer of low-k material (and preferably further by at least one etch stop layer comprising or consisting of one or more aluminides located between the tungsten and the at least one layer of low-k material); and / or - the cleaning composition is used in combination with one or more oxidizing agents in separate steps or simultaneously in the same step, preferably simultaneously in the same step; and / or - the one or more oxidizing agents are selected from the group consisting of hydrogen peroxide, urea peroxide, peroxodisulfuric acid, ammonium persulfate, peroxomonosulfuric acid, pyrosulfuric acid, 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 ranging from 2% to 25% by weight, preferably in the range from 5% to 20% by weight, more preferably in the range from 7.5% to 20% by weight, even more preferably in the range from 10% to 17.5% by weight, relative to the total weight 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, preferably selected from the group consisting of amine-N-oxides; 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 the cleaning composition (including all its variants and preferred variants) in combination with one or more oxidizing agents according to the invention as defined above.

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

[0095] The cleaning composition according to the invention as defined herein (or preferably as described above or below) preferably comprises - the total amount of etching solution containing fluoride anions is <0.001% by weight based on the total weight of the cleaning composition, preferably the cleaning composition does not contain any etching solution containing fluoride anions; and / or The cleaning composition comprises (F) comprising a buffer system suitable for buffering the pH of the cleaning composition to a range of 6 to 9; and / or The cleaning composition comprises as component (E) one or more alkyl glycol ethers of formula II, in which - R 2 is a branched or unbranched alkylene group having 3 to 4 carbon atoms; and / or - R 3 is a branched or unbranched alkyl group having 1, 2, 3, 5, or 6 carbon atoms; and / or - n is an integer ranging from 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 the use of a cleaning composition as defined above) for removing post-etch or post-ash residues from the surface of a semiconductor substrate.

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

[0098] It has been found in own experience that cleaning compositions according to the invention as defined above, in particular cleaning compositions in which one, or at least one, or (in a particularly preferred variant of this aspect of the invention) all of the polar aprotic organic solvents (C) are an alkylsulfone compound(s) of formula IV (or alkylsulfone compounds of formula IV as described herein as preferred), are particularly suitable for: (a) reducing the number of nanometer-scale particles (e.g., from the environment) that may be present or settle on the surface of the semiconductor substrate (or, for example, avoiding the introduction or adsorption of such nanometer-scale particles from the environment on the surface of the semiconductor substrate): reducing the number of such nanometer-scale particles (e.g., SiO x , SiC, SiOC, or Ti ion particles) tend to gradually agglomerate to sub-micrometer or micrometer scales, and if introduced or adsorbed onto the surface of the semiconductor substrate (and are not removed by application of the cleaning composition according to the present invention), may cause defects in the semiconductor products manufactured from the semiconductor substrate; and / or (b) removing particles, particularly post-etch or post-ash residue particles, from the surface of the semiconductor substrate;

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

[0100] It has further been found by own experience that cleaning compositions according to the invention as defined above, in particular cleaning compositions in which one, or at least one, or (in a particularly preferred variant of this aspect of the invention) all of the polar aprotic organic solvents (C) are an alkylsulfone compound(s) of formula IV (or alkylsulfone compounds of formula IV as described herein as preferred), have a particularly low tendency towards haze.

[0101] To remove post-etch or post-ash residues from the surface of a semiconductor substrate, the use of a cleaning composition as defined above (or of a cleaning composition as defined above as preferred) is preferred. the semiconductor substrate comprises at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and low-k materials; and / or - the use comprises cleaning a semiconductor substrate comprising at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and low-k materials; and / or - the use comprises removing post-etch or post-ash residues from a 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 materials, The post-etch or post-ash residue comprises one or more residues selected from the group consisting of: one or more fluorine-containing or non-fluorine-containing organic compounds, preferably organic polymers, - metal-organic complexes, and - a metallic material, preferably titanium and / or titanium oxide and / or titanium nitride; and / or - the use comprises removing residues and contaminants from a surface of a semiconductor substrate comprising at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and low k value materials; Preferably, the residues and contaminants comprise or consist of fluorine-containing or non-fluorine-containing organic compounds, preferably organic polymers.

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

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

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

[0105] Analogously to what has been described above in the context of the use of a cleaning composition in combination with one or more oxidizing agents of the invention, it has been found in own experience that wet etching compositions according to the invention as defined above (in particular the wet etching compositions according to the invention described herein as being preferred), in particular wet etching compositions in which one, or at least one, or (in a particularly preferred variant of this aspect of the invention) all of the polar aprotic organic solvents (C) are an alkylsulfone compound(s) of formula IV (or alkylsulfone compounds of formula IV described herein as being preferred), exhibit the following beneficial effects: - on the surface of the semiconductor substrate, in particular Ti, TiN, Ta, TaN, Al and HfO, in the presence of at least one material selected from the group consisting of copper, cobalt, preferably tungsten and low-k materials; x and / or a layer or mask comprising or consisting of a material selected from the group consisting of tungsten carbide (WC x ) and tungsten nitride (WN x) , in particular a high selectivity for etching, in particular an oxidative etching or partial etching, in particular a partial oxidative etching of layers or masks comprising or consisting of a material selected from the group consisting of TiN; and - High etch rate stability over time. High etch rate stability is achieved for Ti, TiN, Ta, TaN, Al, and HfO x and / or a layer or mask comprising or consisting of a material selected from the group consisting of tungsten carbide (WC x ) and tungsten nitride (WN x In particular, they provide a high (selective) etching rate over a long period of time for a layer or mask that comprises or consists of a material that comprises or consists of TiN (as defined above). For example, the wet etching composition may protect a high selective etching rate over a layer or mask that comprises or consists of TiN for a long period of time of 24 hours or more (see also the Examples section).

[0106] Furthermore, the present invention also relates to the use of a wet etching composition as defined above (or preferably to the use of a wet etching composition as defined above) for: - preferably a Ti hardmask, a TiN hardmask, a Ta hardmask, a TaN hardmask, an Al hardmask, and a HfO hardmask in the presence of at least one material selected from the group consisting of preferably copper, cobalt, preferably tungsten, more preferably lower tungsten; and low-k materials. x hard mask and / or tungsten carbide (WC x ) hard mask and tungsten nitride (WN x ) a hardmask comprising a metal selected from the group consisting of hardmasks; more preferably a TiN hardmask that is removed or partially removed. and / or - Preferably, on the surface of the semiconductor substrate, at least one material selected from the group consisting of copper, cobalt, preferably tungsten, more preferably underlying tungsten; and low-k materials, such as Ti, TiN, Ta, TaN, Al, and HfO x and / or a layer or mask comprising or consisting of a material selected from the group consisting of tungsten carbide (WC x ) and tungsten nitride (WN x ) selected from the group consisting of; preferably etching, preferably oxidatively etching or partially etching, preferably partially oxidatively etching, a layer or mask comprising or consisting of a material preferably comprising or consisting of TiN; and / or - etching, preferably selectively etching, the layer comprising an aluminide in the presence of a layer of low-k material and / or a layer comprising copper and / or cobalt and / or preferably a layer comprising tungsten, more preferably an underlying layer comprising tungsten; and / or - removing, preferably selectively removing, a layer comprising an aluminide from a semiconductor substrate in the presence of a layer of low-k material and / or a layer comprising copper and / or cobalt and / or preferably a layer comprising tungsten, more preferably an underlying layer comprising tungsten; and / or - removing, preferably selectively removing, a layer comprising an aluminide from a surface of a semiconductor substrate in the presence of a layer of low-k material and / or a layer comprising copper and / or cobalt and / or preferably a layer comprising tungsten, more preferably an underlying layer comprising tungsten; and / or - removing post-etch or post-ash residues from the surface of the semiconductor substrate, preferably in the presence of at least one material selected from the group consisting of copper, cobalt, preferably tungsten, more preferably underlying tungsten, and low-k materials; The post-etch or post-ash residue preferably comprises one or more residues selected from the group consisting of or including: one or more fluorine-containing or non-fluorine-containing organic compounds, preferably organic polymers, - metal-organic complexes, and A metallic material, preferably titanium and / or titanium oxide and / or titanium nitride.

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

[0108] In a further aspect, the present invention also relates to a process for the manufacture of a semiconductor device from a semiconductor substrate, comprising the steps of: P1) preparing a wet etching composition by mixing a cleaning composition according to the invention as defined above (or a cleaning composition according to the invention as defined above as preferred), in which one or more oxidizing agents are preferably selected from the group consisting of hydrogen peroxide, urea peroxide, peroxodisulfuric acid, ammonium persulfate, peroxomonosulfuric acid, pyrosulfuric acid, ozone and mixtures thereof, or resulting in a wet etching composition according to the invention as defined above (or a wet etching composition according to the invention as defined above as preferred), 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 low-k materials, contacting the wet etching composition received or provided in step P1) at least once with: - 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 a HfO x layers or masks, and / or tungsten nitride (WN x ) layer or mask and tungsten carbide (WC x ) layers or masks; more preferably TiN layers or masks, and / or an etch stop layer comprising or consisting of one or more aluminium compounds deposited on a copper-containing layer, preferably a copper layer, and / or on a cobalt-containing layer, preferably a cobalt layer, on the surface of the semiconductor substrate, Preferably, as follows: - Etching, preferably selectively oxidatively etching, or partially etching, preferably selectively partially oxidatively etching, the layer or mask. and / or - removing, preferably selectively removing, an etch stop layer comprising an aluminide from the surface of the semiconductor substrate; and / or - removing post-etch or post-ash residues from a surface of a semiconductor substrate, preferably in a one-step process;

[0109] In general, all aspects of the present invention discussed herein in the context of the use of the cleaning composition in combination with one or more oxidizing agents of the present invention, the cleaning composition of the present invention, the use of the cleaning composition for removing post-etch or post-ash residues of the present invention, the wet etching composition of the present invention, and / or the use of the wet etching composition of the present invention, apply mutatis mutandis to the process of manufacturing a semiconductor device according to the present invention as defined herein above and below. Similarly, all aspects of the process of manufacturing a semiconductor device according to the present invention as discussed herein apply mutatis mutandis to the use of the cleaning composition in combination with one or more oxidizing agents of the present invention, the cleaning composition of the present invention, the use of the cleaning composition for removing post-etch or post-ash residues of the present invention, the wet etching composition of the present invention, and / or the use of the wet etching composition of the present invention.

[0110] In a further aspect, the present invention also relates to a method for removing post-etch or post-ash residues on, and / or from, a surface of a semiconductor substrate, comprising the steps of: x and / or a layer or mask comprising or consisting of a material selected from the group consisting of tungsten carbide (WC x ) and tungsten nitride (WN x ), preferably for etching, preferably for oxidative etching or partially etching, preferably for partially oxidative etching, a layer or mask comprising or consisting of a material selected from the group consisting of: TiN, and / or for etching, preferably for selectively etching, a layer comprising or consisting of one or more aluminium compounds in the presence of a layer of low-k material on the surface of a semiconductor substrate, and / or preferably a layer comprising tungsten, more preferably an underlying layer comprising tungsten, and / or copper and / or cobalt, As individual components: (K1) a cleaning composition according to the invention as defined above (or a cleaning composition according to the invention as defined above as preferred) and (K2) one or more oxidizing agents preferably selected from the group consisting of hydrogen peroxide, urea peroxide, peroxodisulfuric acid, ammonium persulfate, peroxomonosulfuric acid, pyrosulfuric acid, ozone, and mixtures thereof; more preferably one of the one or more oxidizing agents is hydrogen peroxide; and optionally further comprising or in combination with, as individual components, component (K1) and / or component (K2): (K3) preferably comprises one or more stabilizers selected from the group consisting of amine-N-oxides; 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] Generally, all aspects of the present invention discussed herein in the context of the use of the cleaning composition in combination with one or more oxidizing agents of the present invention, the cleaning composition of the present invention, the use of the cleaning composition for removing post-etch or post-ash residues of the present invention, the wet etching composition of the present invention, the use of the wet etching composition of the present invention, and / or the inventive process of manufacturing a semiconductor device, apply mutatis mutandis to the kit according to the present invention as defined herein above and below. Similarly, all aspects of the kit according to the present invention as discussed herein apply mutatis mutandis to the use of the cleaning composition in combination with one or more oxidizing agents of the present invention, the cleaning composition of the present invention, the use of the cleaning composition for removing post-etch or post-ash residues of the present invention, the wet etching composition of the present invention, the use of the wet etching composition of the present invention, and / or the inventive process of manufacturing a semiconductor device.

[0112] The cleaning composition according to the present invention (including all its variants and preferred variants as defined herein), the wet etching composition according to the present invention (including all its variants and preferred variants as defined herein) and / or the kit according to the present invention (including all its variants and preferred variants as defined herein) are designed and intended for use or application in a process for the manufacture of semiconductor devices (including all its variants and preferred variants as defined herein).

[0113] The present invention, or its variants, is defined as follows in the following aspects A1 to A15:

[0114] A1. Use of a cleaning composition comprising at least the following components: (A) One or more compounds of formula I as solubilizing agents:

[0115] [ka] [In the formula, R 1 is selected from the group consisting of branched or unbranched alkyl having 1, 2, 3, or 4 carbon atoms; (B) one or more corrosion inhibitors selected from the group consisting of benzotriazoles, which are unsubstituted or branched or unbranched alkyl having 1, 2, 3, or 4 carbon atoms, aminoalkyl having 1, 2, 3, or 4 carbon atoms, branched or unbranched alkyl, phenyl, thiophenyl, halogen, hydroxy, nitro, and / or thiol, 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-etch or post-ash residues from a surface of a semiconductor substrate and / or - Ti, TiN, Ta, TaN, Al, and HfO x4. The method of claim 1, further comprising the steps of: (a) providing a cleaning composition for etching or partially etching a layer or mask comprising or consisting of a material selected from the group consisting of:

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

[0117] A3.- Component (E) has a Hansen polar solubility parameter δ p is ≦8(MPa) 1 / 2 and n is an integer from 1 to 3. The alkyl glycol ethers are selected from the group consisting of and / or Use according to aspect A2, in which the cleaning composition comprises as component (E) one or more alkyl glycol ethers of formula II: [ka] [In the formula, R 2 is a branched or unbranched alkylene group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms; R 3 is a branched or unbranched alkyl group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms. and and n is an integer ranging from 1 to 6, preferably from 2 to 6.

[0118] A4. The cleaning composition further comprises: (F) a buffer system suitable for buffering the pH of the cleaning composition to a range of 6 to 9, preferably to a range of 7 to 8.5; and / or (G) one or more chelating agents, preferably in a total amount ranging from 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, based on the total mass of the cleaning composition; and / or (H) The use according to any one of the aspects A1 to A3, comprising one or more surfactants, preferably including one or more fluorosurfactants.

[0119] A5. In the cleaning composition, the or at least one of the solubilizing agents (A) is or comprises 4-methylmorpholine-4-oxide; and / or the or at least one of the corrosion inhibitors (B) is selected from the group consisting of benzotriazoles, unsubstituted or substituted independently once or twice by branched or unbranched alkyl having 1, 2, 3 or 4 carbon atoms and / or halogens, preferably selected from the group consisting of chlorine or bromine, and mixtures thereof; and / or the or at least one polar aprotic organic solvent (C) is selected from the group consisting of dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, propylene carbonate, sulfolane, tetrahydrofuran, and mixtures thereof; Preferably, the or at least one of the polar aprotic organic solvents (C) is dimethyl sulfoxide, and / or - the total amount of etching solution containing fluoride anions is <0.001% by weight based on the total weight of the cleaning composition, preferably the cleaning composition does not contain any etching solution containing fluoride anions; and / or in the one or more alkyl glycol ethers of formula II, - R 2 is a branched or unbranched alkylene group having 3 to 4 carbon atoms; and / or - R 3 is a branched or unbranched alkyl group having 1, 2, 3, 5, or 6 carbon atoms; and / or - n is an integer ranging from 2 to 4; and / or The use according to any one of the aspects A1 to A4, wherein the specific compound butyl diglycol is not included.

[0120] A6. In cleaning compositions the total amount of the one or more solubilizing agents (A), preferably 4-methylmorpholine-4-oxide, is in the range of 1% to 15% by weight, preferably in the range of 2% to 12% by weight, more preferably in the range of 3% to 10% by weight, relative to the total weight of the cleaning composition; and / or the total amount of one or more corrosion inhibitors (B), preferably selected from the group consisting of benzotriazoles unsubstituted or substituted once or twice independently by branched or unbranched alkyl with 1, 2, 3 or 4 carbon atoms, and / or by halogen, and mixtures thereof, is in the range of 0.1% to 6% by weight, preferably in the range of 0.2% to 6% by weight, more preferably in the range of 0.5% to 5% by weight, relative to the total weight 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, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, propylene carbonate, sulfolane, tetrahydrofuran, and mixtures thereof, is in the range of 1% by weight to 50% by weight, preferably in the range of 3% by weight to 45% by weight, more preferably in the range of 5% by weight to 40% by weight, based on the total weight of the cleaning composition; and / or the total amount of the one or more alkyl glycol ethers (E), preferably the one or more alkyl glycol ethers of formula II, is in the range from 5% to 50% by weight, preferably in the range from 10% to 40% by weight, more preferably in the range from 15% to 35% by weight, relative to the total weight of the cleaning composition; and / or - the cleaning composition comprises at least components (A), (B), (C), (D), (E), and (F); and / or The use according to any one of the aspects A1 to A5, wherein water (D) makes up the remainder of the cleaning composition to make up 100% by weight.

[0121] A7. Use includes removing post-etch or post-ash residues from a surface of a semiconductor substrate; the semiconductor substrate comprises at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and low-k materials; and / or - the use comprises cleaning a semiconductor substrate comprising at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and low-k materials; and / or - the use comprises removing post-etch or post-ash residues from a 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 materials, The post-etch or post-ash residue comprises one or more residues selected from the group consisting of: one or more fluorine-containing or non-fluorine-containing organic compounds, preferably organic polymers, - metal-organic complexes, and - a metallic material, preferably titanium and / or titanium oxide and / or titanium nitride; and / or - the use comprises removing residues and contaminants from a surface of a semiconductor substrate comprising at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and low k value materials, - Use according to any one of the aspects A1 to A6, wherein preferably the residues and contaminants comprise or consist of fluorine-containing or non-containing organic compounds, preferably organic polymers.

[0122] A8. Uses Ti, TiN, Ta, TaN, Al, and HfO xand etching, preferably oxidatively etching or partially etching, preferably partially oxidatively etching, a layer or mask, preferably a hard mask, comprising or consisting of a material selected from the group consisting of: - preferably a Ti hardmask, a TiN hardmask, a Ta hardmask, a TaN hardmask, an Al hardmask, and a HfO hardmask in the presence of at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and low-k materials; x removing, preferably partially removing, a hardmask preferably comprising a metal selected from the group consisting of hardmasks, more preferably a TiN hardmask; and / or - etching, preferably oxidative etching or partial etching, preferably partial oxidative etching, in the presence of at least one material selected from the group consisting of copper, cobalt, preferably tungsten and low-k materials, on the surface of the semiconductor substrate; and / or - etching, preferably selectively etching, a layer comprising an aluminide in the presence of a layer of a low-k material and / or preferably a layer comprising tungsten and / or a layer comprising copper and / or cobalt; and / or - removing, preferably selectively removing, a layer comprising an aluminide from a semiconductor substrate in the presence of a layer of a low-k material and / or a layer preferably comprising tungsten and / or a layer comprising copper and / or cobalt, and / or The use according to any one of the aspects A1 to A7 for removing, preferably selectively removing, a layer comprising an aluminide from a surface of a semiconductor substrate in the presence of a layer of a low-k material and / or a layer preferably comprising tungsten and / or a layer comprising 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: (i) Ti hard mask, TiN hard mask, Ta hard mask, TaN hard mask, Al hard mask, and HfO x A hardmask comprising a metal preferably selected from the group consisting of hardmasks, more preferably a TiN hardmask. and (ii) an aluminide etch stop layer deposited on a copper-containing layer, preferably a copper layer, and / or on a cobalt-containing layer, preferably a cobalt layer, in the presence of tungsten, preferably completely covered by at least one layer of a low-k material; and / or - the cleaning composition is used in combination with one or more oxidizing agents in separate steps or simultaneously in the same step, preferably simultaneously in the same step; and / or - the one or more oxidizing agents are selected from the group consisting of hydrogen peroxide, urea peroxide, peroxodisulfuric acid, ammonium persulfate, peroxomonosulfuric acid, pyrosulfuric acid, 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 ranging from 2% to 25% by weight, preferably in the range from 5% to 20% by weight, more preferably in the range from 7.5% to 20% by weight, even more preferably in the range from 10% to 17.5% by weight, relative to the total weight of the cleaning composition; and / or - Use according to any one of the aspects A1 to A8, wherein the one or more stabilizers are used in combination with the one or more oxidizing agents and / or in combination with the cleaning composition, and are preferably selected from the group consisting of amine-N-oxides; 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.

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

[0125] A11. Use of a cleaning composition according to embodiment 10 for removing post-etch or post-ash residues from a surface of a semiconductor substrate, preferably as defined in embodiment 1 and / or 7.

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

[0127] A13. Method of using the wet etching composition according to embodiment 12 for - preferably a Ti hardmask, a TiN hardmask, a Ta hardmask, a TaN hardmask, an Al hardmask, and a HfO hardmask in the presence of at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and low-k materials; x removing, preferably partially removing, a hard mask comprising a metal preferably selected from the group consisting of hard masks of and / or - preferably on the surface of the semiconductor substrate, in the presence of at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and low-k materials, Ti, TiN, Ta, TaN, Al, and HfO xetching, preferably oxidatively etching or partially etching, preferably partially oxidatively etching, a layer or mask comprising or consisting of a material selected from the group consisting of, preferably comprising or consisting of TiN; and / or - etching, preferably selectively etching, a layer comprising an aluminide in the presence of a layer of low-k material and / or a layer comprising copper and / or cobalt and / or preferably a layer comprising tungsten; and / or - removing, preferably selectively removing, a layer comprising an aluminide from a semiconductor substrate in the presence of a layer of a low-k material and / or a layer comprising copper and / or cobalt and / or preferably a layer comprising tungsten; and / or - removing, preferably selectively removing, a layer comprising an aluminide from the surface of a semiconductor substrate in the presence of a layer of low-k material and / or a layer comprising copper and / or cobalt and / or preferably a layer comprising tungsten; and / or - removing post-etch or post-ash residues from the surface of the semiconductor substrate, preferably in the presence of at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and low-k materials, The post-etch or post-ash residue preferably comprises one or more residues selected from the group consisting of or including: one or more fluorine-containing or non-fluorine-containing organic compounds, preferably organic polymers, - metal-organic complexes, and A 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 steps of: P1) Producing a wet etching composition by mixing the cleaning composition according to any one of the embodiments 1 to 6, preferably according to any one of the embodiments 2 to 6, with one or more oxidizing agents preferably selected from the group consisting of hydrogen peroxide, urea peroxide, peroxodisulfuric acid, ammonium persulfate, peroxomonosulfuric acid, pyrosulfuric acid, ozone and mixtures thereof; or providing a wet etching composition according to embodiment 12, and P2) preferably in the presence of at least one material selected from the group consisting of copper, cobalt, preferably tungsten, and low-k materials, contacting the wet etching composition received or provided in step P1) at least once with: - on a surface of a semiconductor substrate, 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 a HfO x a layer or hard mask preferably selected from the group consisting of layers or masks, more preferably a TiN layer or mask; and / or an etch stop layer comprising or consisting of one or more aluminium compounds, deposited on the surface of the semiconductor substrate on a layer comprising copper, preferably on a copper layer, and / or on a layer comprising cobalt, preferably on a cobalt layer, Preferably, as follows: - Etching, preferably selectively oxidatively etching, or partially etching, preferably selectively partially oxidatively etching, the layer or mask. and / or - removing, preferably selectively removing, an etch stop layer comprising or consisting of one or more aluminium compounds from the surface of the semiconductor substrate; and / or A method for removing post-etch or post-ash residues from a surface of a semiconductor substrate, preferably in a one-step process.

[0129] A15. A kit for removing post-etching or post-ashing residues from a surface of a semiconductor substrate, and / or for etching, preferably oxidatively etching or partially etching, preferably partially oxidatively etching, a layer or mask comprising or consisting of TiN on a surface of a semiconductor substrate, and / or for etching, preferably selectively etching, a layer comprising or consisting of one or more aluminum compounds on a surface of a semiconductor substrate, in the presence of a layer of a low-k material and / or preferably a layer comprising tungsten, more preferably an underlying layer comprising tungsten, and / or copper and / or cobalt, As individual components: (K1) the cleaning composition according to any one of aspects 1 to 6; and (K2) one or more oxidizing agents preferably selected from the group consisting of hydrogen peroxide, urea peroxide, peroxodisulfuric acid, ammonium persulfate, peroxomonosulfuric acid, pyrosulfuric acid, ozone, and mixtures thereof; more preferably one of the one or more oxidizing agents is hydrogen peroxide; and optionally further comprising or in combination with, as individual components, component (K1) and / or component (K2): (K3) A kit comprising one or more stabilizers preferably selected from the group consisting of amine-N-oxides; 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 examples are meant to further explain and illustrate the invention without limiting its scope.

[0131] The following abbreviations are used in the Examples section: *: Also acts as a weak acid component in the buffer system (F) 5-Me-BTA: 5-methyl-benzotriazole (as defined above) b: Remaining (up to 100% by mass) BTA: Benzotriazole (unsubstituted) BDG: Butyl diglycol BTG: butyl triglycol CDTA: 1,2-cyclohexylenedinitrilotetraacetic 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] Preparation of cleaning compositions according to the present invention The following cleaning compositions according to the invention (CCI1 to CCI7 and CCI8 to CCI5) were prepared by mixing in each case components (A) to (H) (as appropriate). Details are given below in Tables 1a and 1b. The designations of components (A) to (H) correspond to the designations of the components as defined above.

[0133] [Table 1]

[0134] [Table 2]

[0135] [Example 2] Preparation 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) were prepared by mixing the respective cleaning compositions of the present invention CCI1-CCI7, or CCI8-CCI11, or CCI15 (see Example 1), in each case receiving a sufficient amount of hydrogen peroxide (HO, 31% in water) to a final concentration or mass ratio as shown in Tables 2a and 2b below, where "wt% HO" in each case is given relative to the total mass of the respective cleaning composition (CCI1-CCI7, CCI8-CCI11, and CCI15) utilized to produce a given wet etching composition, and "wt% HO" 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 etch losses for TiN. The etching loss of the TiN layer caused by the inventive wet etching composition of Example 2 was determined according to or in a similar manner to the method described in WO 2015 / 173730 A1. The wet etching compositions were prepared by mixing the respective cleaning composition with a specific amount of hydrogen peroxide immediately before performing the etch rate experiment.

[0139] Si test wafers with a layer of TiN (TiN layer thicknesses ranged from 200 to 300 nm, as physical vapor deposition TiN "PVD TiN") were selected from a suitable commercial source and divided into smaller coupons. The layer thickness and etching rate were then measured by X-ray fluorescence analysis (XRF) in a manner known per se. XRF is suitable for the non-contact and non-destructive measurement of the thickness of thin layers and for the determination of their chemical composition. For this type of measurement, the X-ray source and the detector are located on the same side of the sample. When X-rays are applied to a layer on a substrate, if the layer is somewhat thin enough, the radiation will penetrate the layer according to its thickness and in turn cause a characteristic fluorescence radiation in the underlying material of the substrate. This fluorescence radiation will be absorbed and attenuated in 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 of the substrate material.

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

[0141] The wet etching composition was then brought to the test temperature (59° C. for this Example 3 experiment) and mechanically stirred. The wafer coupon was secured to a mechanical holder and contacted with the wet etching composition in a beaker for a reaction time (1 min for this Example 3 experiment). The coupon was then pulled out of the wet etching composition and washed with ultrapure water, or with isopropyl alcohol, or with a mixture of ultrapure water and isopropyl alcohol for about 1 min. The coupon was then dried with nitrogen gas. The residual thickness of the TiN layer after etching was measured again 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 stated, all values ​​for the etching loss measured in Examples 3-5 are given in Å.

[0142] [Example 4] Aluminum oxide (AlO x ), cobalt, and copper etch loss measurements The thickness of the outer layer of appropriate type (Co layer ranged from 25 to 200 nm; AlO x Si wafers or wafer pieces (collectively referred to below as "test wafers") with layers of AlO (all outer layers suitable for performing etching loss experiments were thick enough to allow obtaining meaningful measurements after the etching process) were obtained from commercial sources. The test wafers were pretreated as applicable: Cu and Co were immersed in an oxalic acid solution for 20-30 seconds each, then rinsed with water and dried. x The coated surface was not pretreated.

[0143] Aluminum oxide (AlO x ) coated surface was used as a representative model for a layer (as defined above) comprising or consisting of one or more aluminum compounds.

[0144] A wet etching composition (see Example 2 and Table 2 above) was prepared and test wafers (see above) were etched with AlO x The surfaces were contacted with the wet etching composition in a glass beaker at a temperature of 59° C. for a reaction time of 10 minutes in the case of the Cu surface and 5 minutes in the case of the Cobalt surface, and then withdrawn 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 wafers were determined by X-ray fluorescence analysis (as described above in Example 3) before and after contact with the test compositions. At least three experiments were performed to ensure reproducibility.

[0146] Copper, cobalt, or AlO x The thickness of each of the layers is measured before and after contact with the wet etching composition. xThe difference between the thickness of each of the layers and the measurement after its contact with the wet etching composition was determined in each case as the resulting etching loss of each layer (as explained in Example 3 above). x The etch losses for each of the layers 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 etch losses on underlying tungsten layers (i) a layer of low-k material (top layer, layer thickness: 75 Å); (ii) an etch stop layer of one or more aluminum compounds (AlO as the first underlying layer below the top layer). x A Si test wafer was fabricated with successive layers of (i) a low-k material layer, (ii) an etch stop layer, (iii) a tungsten layer (a layer comprising tungsten metal as a second underlying layer below the first underlying layer, layer thickness: 50 Å, located on the surface of the Si test wafer). The Si test wafer stack thus fabricated and comprising (in a given order) (i) a low-k material layer, (ii) an etch stop layer, (iii) a tungsten layer, and (iv) a surface of the Si test wafer was sealed on all sides such that a wet etching composition applied to the top layer (i) of the stack could contact the tungsten layer (iii) only by (permeating or diffusing) through (i) the top layer and (ii) the etch stop layer (first underlying layer) (as is done in this experiment).

[0148] The Si test wafer stack was then etched by contacting with the wet etching composition prepared according to Example 2 above in an etching process equivalent to that described in Example 3 above (applicable test temperature in this Example 5: 59° C., applicable reaction time in this Example 5: 1 min). The thickness of the tungsten layer before and after etching was then determined according to the method described in Example 3 above, and the etching loss of each of the tungsten layers was 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 effective for selectively etching TiN (for selectively etching a hard mask containing or consisting of TiN) and AlO x It can be seen that the etch rate selectivity for Cu (to selectively remove an etch stop layer containing or consisting of one or more aluminum compounds), Cu (to protect to the highest extent possible any copper present in the etching process), and Co (to protect to the highest extent possible any copper present in the etching process) was excellent. Therefore, it can be concluded that all wet etching compositions WEI1 to WEI7 are suitable for application in manufacturing processes for 10 nm or sub-10 nm structures, such as 7 nm structures, on semiconductor substrates, including the one-step triple removal step of the process as described above.

[0151] The results shown in Table 3 above further show that the wet etching compositions WEI4, WEI5, WEI6, and WEI7 according to the present invention (all showing beneficial etch loss for W layers below <10 nm under the test conditions of Example 5) are excellently suitable for application in manufacturing processes for 7 nm or sub-7 nm structures, such as 5 nm structures, on semiconductor substrates, including the one-step triple removal step of the process as described above.

[0152] [Example 6] Measurement of etch loss for TiN as a function of time in wet etching compositions As in Example 3 above, the etching loss of TiN caused by the inventive wet etching compositions WEI8 to WEI11 and WEI15 of Example 2 above (see Table 2b) was determined according to or in a similar manner to the method described in WO 2015 / 173730(A1).

[0153] In this example 6, Si test wafers (12 inches) with a layer of TiN (thickness of TiN layer: about 300 nm as PVD TiN) were filled with 100 mL of wet etching composition as specified in Table 4 below and were kept in each case at a temperature of 60 ° C. for time intervals as further specified in Table 4 below. After each time interval, the residual thickness of the TiN layer on the test wafer was determined as explained in Example 3 above and compared with the thickness of the TiN layer of the same test wafer at the beginning of the experiment. The residual activity of the wet etching composition tested in this experiment after a given time interval is then given in the form of an etching rate in angstroms per minute (Å / min), as is usual in the field. The results of this experiment are shown in Table 4 below (the figures shown in Table 4 are within the accuracy of measurement of the applied method).

[0154] [Table 6]

[0155] From the results shown in Table 4 above, it can be seen that wet etching compositions according to the invention provide stable etching rates for TiN layers over time, especially when they contain (only) an alkyl sulfone compound of formula IV as the polar aprotic organic solvent (C), and more especially when they contain sulfolane or ethyl isopropyl sulfone as the polar aprotic organic solvent (C) (but no alkyl glycol ether (E)). In this experiment, the etching rates of such wet etching compositions according to the invention (see, for example, WEI8 and WEI9) performed on TiN layers were stable and did not decrease (within the measurement accuracy of the test method) for at least 24 hours.

[0156] The results shown in Table 4 above show that wet etching compositions containing one or more alkyl glycol ethers (E) as defined herein (but not containing a polar aprotic organic solvent (C)) provided a stable etch rate for the TiN layer over a somewhat shorter period of time.

[0157] The results shown in Table 4 above further show that the wet etching compositions comprising one or more alkyl glycol ethers (E) as defined herein and a polar aprotic organic solvent (C), but not comprising an alkyl sulfone compound of formula IV as defined above, provided a stable etch rate for the TiN layer over a slightly shorter period of time.

[0158] Furthermore, the results shown in Table 4 above show that the etch rates of wet etching compositions comprising 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 comprising an alkyl sulfone compound of formula IV as defined herein, see e.g., WEI15) exhibited etch rates for TiN layers at levels approximately equivalent to those of wet etching compositions comprising an alkyl sulfone compound of formula IV as a polar aprotic organic solvent (C) for at least 24 hours.

[0159] [Example 7] Determination of the number of particles in the nanometer to micrometer range in cleaning compositions Cleaning compositions CCI12, CCI13, and CCI14 (200 mL each) were prepared and filtered as described above in Example 1. After filtration, the amount of liquid particles with diameters of 0.15 μm, 0.2 μm, 0.3 μm, and 0.5 μm was determined by a liquid particle counter (Rion KS 40 A or Rion KS 19F, Rion Co., 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 this result, it can be concluded that cleaning composition CCI14 (comprising an alkylsulfone compound of formula IV (sulfolane) as the polar aprotic organic solvent (C)) had the most beneficial inhibitory effect on particle aggregation of the cleaning compositions tested.

[0161] [Example 8] Measuring the number of particles 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 full 300 mm non-patterned wafer. The wafer was then rinsed and fully processed, including drying. The processed wafer surfaces were then inspected for particle counts on their surfaces with an industrial non-patterned wafer surface inspection system (KLA Tencor Corporation (USA): Surfscan™ SP3, SP5, or SP7, respectively).

[0162] It was found that wafers treated with cleaning composition CCI1 in this experiment exhibited particularly low particle counts on their surfaces after treatment.

[0163] [Example 9] Aluminum oxide (AlO) as a function of pH value of wet etching composition x Measurement of etching loss for the .DELTA. ... As in Example 4 above, three different types of AlO x A test wafer with an outer layer was obtained.

[0164] Wet etching compositions (see Example 2 and Table 2 above) were prepared and the etch rates of the wet etching compositions were determined as described in Example 4 above or similarly as described in Example 4 above at a temperature of 60° C.

[0165] The etch rates of the wet etching compositions according to the invention were determined on two sets of different wafer surfaces as described above in Example 3 or Example 4, or in a similar manner: three different types of AlO that were not plasma etched, x On a set of wafer surfaces supporting the outer layer (control) and three different types of AlO that were plasma etched x On another set of wafer surfaces bearing the outer layer. The results of this experiment are shown in Table 5 below.

[0166] [Table 7]

[0167] Wet etching compositions WEI1 and WEI8 were prepared as described above (see Examples 1 and 2). Wet etching composition WEI16 was prepared similarly to cleaning composition WEI1, which was identical to CCI1, except that the content of tetramethylammonium hydroxide (TEAH) was lower in the cleaning composition used to prepare wet etching composition WEI16, ranging from 0.1 to 0.4 wt. % based on the total weight of the cleaning composition. The pH of wet etching composition WEI16 was 6.5.

[0168] From the results in Table 5 above, it can be seen that the wet etching composition according to the present invention having a pH value in the range of 6 to 9, preferably in the range of 6.5 to 8.0, can effectively inhibit the formation of different types of layers containing aluminum compounds (different types of AlO xThe etching rates for the outer layer (and possibly the outer layer) are shown, which makes the wet etching composition eminently suitable for the very controlled and specific etching of layers comprising or consisting of one or more aluminum compounds.

Claims

1. A method of using a cleaning composition comprising at least the following components: (A) One or more compounds of formula I as solubilizing agents: 【Chemistry 1】 [In the formula, R １ is selected from the group consisting of branched or unbranched alkyl having 1, 2, 3, or 4 carbon atoms. a solubilizing agent in the range of 1% to 15% by weight based on the total weight of the cleaning composition; (B) one or more corrosion inhibitors selected from the group consisting of unsubstituted, branched or unbranched alkyl having 1, 2, 3, or 4 carbon atoms, benzotriazoles substituted independently once or twice with alkyl, branched or unbranched and having 1, 2, 3, or 4 carbon atoms, aminoalkyl, phenyl, thiophenyl, halogen, hydroxy, nitro, and / or thiol, and mixtures thereof; a corrosion inhibitor in the range of 0.1% to 6% by weight based on the total weight of the cleaning composition; (C) one or more polar aprotic organic solvents, The polar aprotic organic solvent (C) may be one or at least one of the following: - alkylsulfone compounds of formula IV 【Chemistry 2】 [In the formula, R ５ is a branched or unbranched alkyl group having 1 to 5 carbon atoms; R ６ is a branched or unbranched alkyl group having 1 to 5 carbon atoms; or R ５ and R ６ together form a branched or unbranched alkylene group having 3 to 5 carbon atoms, one or two carbon atoms of the alkylene group being -O-R ７ and R ７ is a branched or unbranched alkyl group having 1 to 4 carbon atoms; and - Mixtures of these is selected from the group consisting of In the range of 30% to 36% by weight based on the total weight of the cleaning composition; Polar aprotic organic solvents; and (D) water in combination with one or more oxidizing agents, The one or more oxidizing agents are selected from the group consisting of hydrogen peroxide, urea peroxide, peroxydisulfuric acid, ammonium persulfate, peroxymonosulfuric acid, pyrosulfuric acid, ozone, and mixtures thereof. - Ti, TiN, Ta, TaN, Al, and HfO ｘ and / or a layer or mask comprising or consisting of a material selected from the group consisting of tungsten carbide and tungsten nitride, Including, Etching or partially etching the layer or mask may include - etching a layer containing an aluminide in the presence of a layer of a low-k material and / or a layer containing copper and / or cobalt; and / or - removing a layer containing an aluminide in the presence of a layer of a low-k material and / or a layer containing copper and / or cobalt from a semiconductor substrate; and / or Removal of layers containing aluminides in the presence of layers of low-k materials and / or layers containing copper and / or cobalt from the surface of a semiconductor substrate. Including, Methods of using the cleaning composition.

2. 2. The process of claim 1, wherein one, or at least one, or all of the polar aprotic organic solvents (C) are alkyl sulfone compounds of formula IV according to claim 1 and are selected from the group consisting of ethyl methyl sulfone, ethyl isopropyl sulfone, ethyl isobutyl sulfone, isopropyl isobutyl sulfone, sulfolane, 3-methoxysulfolane, and mixtures thereof.

3. The cleaning composition comprises: (F) a buffer 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 a total amount ranging from 0.01% to 3% by weight, based on the total weight of the cleaning composition; and / or (H) One or more surfactants The method of claim 1 or 2, further comprising:

4. In the cleaning composition, the or at least one of the solubilizing agents (A) is or comprises 4-methylmorpholine-4-oxide; and / or the or at least one of the corrosion inhibitors (B) is selected from the group consisting of benzotriazoles, unsubstituted or substituted once or twice, independently, by branched or unbranched alkyl having 1, 2, 3 or 4 carbon atoms, and / or by halogens selected from the group consisting of chlorine and bromine, and mixtures thereof; and / or the total amount of etching solution containing fluoride anions is <0.001% by weight, based on the total weight of the cleaning composition; 4. The method according to any one of claims 1 to 3.

5. In cleaning compositions the total amount of one or more solubilizing agents (A) ranges from 2% to 12% by weight, relative to the total weight of the cleaning composition; and / or the total amount of one or more corrosion inhibitors (B) ranges from 0.2% to 6% by weight, relative to the total weight of the cleaning composition; and / or the cleaning composition comprises components (A), (B), (C), (D), (F), (G), and (H); and / or - Water (D) makes up the remainder of the cleaning composition to make up 100% by weight; 5. The method according to any one of claims 1 to 4.

6. The method includes removing post-etch or post-ash residue from a surface of a semiconductor substrate. the semiconductor substrate comprises at least one material selected from the group consisting of copper, cobalt and low-k materials; and / or the method includes cleaning a semiconductor substrate comprising at least one material selected from the group consisting of copper, cobalt, and low-k materials; and / or the method comprises removing post-etch or post-ash residues from a surface of a semiconductor substrate in the presence of at least one material selected from the group consisting of copper, cobalt, and low-k materials; Post-etch or post-ash residues include one or more fluorine-containing or non-fluorine-containing organic polymers, - metal-organic complexes, and - metallic materials containing titanium and / or titanium oxides and / or titanium nitrides or comprising one or more residues selected from the group consisting of: and / or the method comprises removing residues and contaminants from a surface of a semiconductor substrate comprising at least one material selected from the group consisting of copper, cobalt, and low-k materials; 6. The method according to any one of claims 1 to 5.

7. The method includes the steps of: Ti, TiN, Ta, TaN, Al, and HfO ｘ and / or a layer or mask comprising or consisting of a material selected from the group consisting of tungsten carbide (WC) ｘ ) and tungsten nitride (WN ｘ and etching or partially etching a layer or mask comprising or consisting of a material selected from the group consisting of: - Ti hardmask, TiN hardmask, Ta hardmask, TaN hardmask, Al hardmask, and HfO hardmask in the presence of at least one material selected from the group consisting of copper, cobalt, and low-k materials. ｘ removing or partially removing a hardmask comprising a metal selected from the group consisting of hardmasks and / or selected from the group consisting of tungsten carbide hardmasks and tungsten nitride hardmasks; and / or - Etching or partially etching the surface of the semiconductor substrate in the presence of at least one material selected from the group consisting of copper, cobalt and low-k materials; The method of any one of claims 1 to 6, comprising:

8. The cleaning composition is used in combination with one or more oxidizing agents in a one-step process that removes: (i) Ti hard mask, TiN hard mask, Ta hard mask, TaN hard mask, Al hard mask, and HfO ｘ hardmasks and / or comprising a metal selected from the group consisting of tungsten carbide hardmasks and tungsten nitride hardmasks; and (ii) an aluminide etch stop layer deposited on the copper-containing layer and / or on the cobalt-containing layer; and / or - the cleaning composition is used in combination with one or more oxidizing agents in separate steps or simultaneously in the same step; and / or the one or more oxidizing agents are in a total amount ranging from 2% to 25% by weight relative to the total weight of the cleaning composition; and / or said oxidizing agent is hydrogen peroxide, said oxidizing agent being used in a total amount ranging from 7.5% to 20% by weight relative to the total weight 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, such as amine-N-oxides; 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.

8. The method according to any one of claims 1 to 7.

9. A cleaning composition described in any one of claims 1 to 5.

10. 10. The cleaning composition of claim 9, (F) comprising a buffer system suitable for buffering the pH of the cleaning composition to a range of 6 to 9; A cleaning composition, wherein the total amount of etchants comprising fluoride anions is <0.001 wt. %, based on the total weight of the cleaning composition.

11. A method of using a cleaning composition according to claim 9 or 10 for removing post-etch or post-ash residues according to claims 1 and / or 6 from the surface of a semiconductor substrate.

12. (W1) A cleaning composition according to any one of claims 1 to 5. and (W2) one or more oxidizing agents selected from the group consisting of hydrogen peroxide, urea peroxide, peroxodisulfuric acid, ammonium persulfate, peroxomonosulfuric acid, pyrosulfuric acid, and ozone; 1. A wet etching composition comprising:

13. The wet etching composition of claim 12, comprising one or more oxidizing agents, component (W2), in a total amount ranging from 2% by weight to 25% by weight based on the total weight of the cleaning composition.

14. - etching a layer containing an aluminide in the presence of a layer of a low-k material and / or a layer containing copper and / or cobalt; and / or removing an aluminide-containing layer from a semiconductor substrate in the presence of a layer of low-k material and / or a layer containing copper and / or cobalt; and / or - removing a layer containing an aluminide from the surface of a semiconductor substrate in the presence of a layer of a low-k material and / or a layer containing copper and / or cobalt; and / or - a method of using the wet etching composition according to claim 12 or 13 for removing post-etch or post-ash residues from a surface of a semiconductor substrate in the presence of at least one material selected from the group consisting of copper, cobalt and low-k materials, comprising: Post-etch or post-ash residues include one or more fluorine-containing or non-fluorine-containing organic polymers, - metal-organic complexes, and - metallic materials containing titanium and / or titanium oxides and / or titanium nitrides The method of claim 1, further comprising one or more residues selected from the group consisting of:

15. The following steps: P1) Mixing the cleaning composition according to any one of claims 1 to 5 with one or more oxidizing agents selected from the group consisting of hydrogen peroxide, urea peroxide, peroxodisulfuric acid, ammonium persulfate, peroxomonosulfuric acid, pyrosulfuric acid, ozone, and mixtures thereof to produce a wet etching composition; or Providing a wet etching composition according to claim 12 or 13; and P2) the wet etching composition received or prepared in step P1); - To etch a layer or a mask and / or - to remove an etch stop layer comprising or consisting of one or more aluminides from the surface of the semiconductor substrate, and / or - to remove post-etching or post-ashing residues from the surface of the semiconductor substrate, 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 a HfO layer or mask on the surface of a semiconductor substrate. ｘ a layer or hardmask selected from the group consisting of a tungsten carbide hardmask and a tungsten nitride hardmask; and / or - contacting at least once an etch stop layer comprising or consisting of one or more aluminium compounds deposited on the surface of the semiconductor substrate, on a layer comprising copper and / or on a layer comprising cobalt, A method for manufacturing a semiconductor device from a semiconductor substrate, comprising:

16. 1. A kit for etching a layer comprising or consisting of one or more aluminum compounds in the presence of a layer of low-k material and / or a layer comprising copper and / or cobalt on a surface of a semiconductor substrate, comprising: As individual components: (K1) a cleaning composition according to any one of claims 1 to 5; and (K2) One or more oxidizing agents selected from the group consisting of hydrogen peroxide, urea peroxide, peroxodisulfuric acid, ammonium persulfate, peroxomonosulfuric acid, pyrosulfuric acid, ozone, and mixtures thereof. A kit comprising:

17. The compound further comprises, as individual components, component (K1) and / or component (K2) or in combination: (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; 17. The kit of claim 16, comprising one or more stabilizers selected from the group consisting of succinic acid; glutaric acid; maleic acid, and mixtures thereof.

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