Compositions for removing photoresist and etch residue, methods of use, and uses thereof

Abstract

A method and cleaning composition for microelectronic devices or semiconductor substrates comprising (i) at least one organic solvent; (ii) at least one amine free of carboxylic acid moieties; (iii) water; and (iv) a corrosion inhibitor comprising one or more of (a) an amino acid, (b) an azole, and (c) a phenolic acid, wherein the remover solution is free of dimethyl sulfoxide, N-methyl pyrrolidone, and dimethylacetamide.

Description

Technical Field

[0001] The disclosed and claimed subjects relate to compositions for removing photoresist and etching residues from a substrate, and methods for manufacturing them and / or using them in the manufacture of semiconductor devices. Background Technology

[0002] In semiconductor wafer manufacturing, wafer-level packaging (WLP) is a technique used to package integrated circuits at the wafer level, involving adding protective layers and electrical connections to a substrate before dicing. Typically, interconnects are metal bumps created through various processes, including photolithography and metal deposition. Structures with deep holes are created during photolithography, and solder bump metal is then filled into these holes. The bumps are then formed by removing the photoresist mask layer.

[0003] Photoresist layers are typically removed using photoresist strippers via wet processes. Effective photoresist strippers require not only high efficiency in photoresist removal but also good compatibility with the exposed substrate (e.g., metal bumps and copper substrates). Photoresist strippers and etching residue removers used in wafer-level packaging typically consist of various combinations of solvents, alkalis, corrosion inhibitors, optional co-solvents, and other additives. Conventional removers use DMSO or NMP as solvents and amines or quaternary ammonium hydroxides or inorganic bases, or combinations thereof, as alkalis. Alkali is a crucial component for photoresist and etching residue removal. However, during the photoresist layer removal process, the copper substrate exposed to the photoresist stripper is susceptible to undesirable etching. Therefore, it is critical for photoresist strippers and etching residue removers to prevent copper corrosion during the cleaning process, which can be achieved by introducing effective and robust copper corrosion inhibitors.

[0004] Corrosion inhibitors are used to suppress the etching of exposed copper substrates. Much effort has been made to find good copper inhibitors in photoresist strippers. Well-known copper corrosion inhibitors, such as benzotriazole, are effective in aqueous solutions. However, benzotriazole is not effective in strippers rich in organic solvents (especially those containing amines as strong bases). Metal salts, such as copper salts, are used as effective corrosion inhibitors, but these salts have solubility and stability issues in photoresist strippers. Sugar alcohols are also used as copper corrosion inhibitors, but their efficiency in such organic solvent-rich strippers is insufficient for copper protection.

[0005] Furthermore, many photoresist strippers and post-etch cleaning solutions contain environmentally unfriendly organic solvents, such as N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), and dimethylacetamide (DMAC). The development of new photoresist strippers and post-etch cleaning solutions requires replacing these organic solvents with more environmentally friendly alternatives.

[0006] Therefore, there is a need to develop photoresist strippers with high efficiency in photoresist removal. These strippers contain copper inhibitors to effectively protect copper substrates, while being free of environmentally unfriendly organic solvents such as NMP, DMAC, and DMSO. Summary of the Invention

[0007] This overview does not specifically describe every embodiment and / or additional novel aspect of the disclosed and claimed subject matter. Rather, this overview provides only a preliminary discussion of different embodiments and corresponding novel points relative to conventional and known technologies. For additional details and / or feasible perspectives on the disclosed and claimed subject matter and embodiments, the reader is directed to the detailed description and corresponding figures of this disclosure discussed further below.

[0008] The disclosed and claimed subject matter relates to photoresist stripping agents and etching residue removal solutions (collectively, “removal solutions”) for removing or stripping (i) positive or negative photoresist, (ii) photoresist etching residues after an etching process, and / or (iii) etching residues from a substrate. The disclosed and claimed removal compositions are particularly compatible with copper, even at high rotational speeds during application.

[0009] The disclosed subject matter relates to a removal agent solution, which comprises, is substantially composed of, or is composed of the following:

[0010] (i) at least one organic solvent;

[0011] (ii) at least one amine that does not contain a carboxylic acid moiety;

[0012] (iii) Water;

[0013] (iv) Corrosion inhibitors, comprising one or more of the following:

[0014] (a) amino acids,

[0015] (b) azole, and

[0016] (c) Phenolic acids

[0017] The removal solution does not contain dimethyl sulfoxide, N-methylpyrrolidone, or dimethylacetamide.

[0018] In another aspect of this embodiment, (iv) the corrosion inhibitor comprises two or more of (a) an amino acid, (b) a azole, and (c) a phenolic acid. In one embodiment, (iv) the corrosion inhibitor comprises (a) an amino acid and (b) a azole. In another embodiment, (iv) the corrosion inhibitor comprises (a) an amino acid and (c) a phenolic acid. In yet another aspect of this embodiment, (iv) the corrosion inhibitor comprises one or more of each of (a) an amino acid, (b) a azole, and (c) a phenolic acid.

[0019] The disclosed and claimed subject matter also includes the uses of the disclosed and claimed remover solutions. Among other things, the remover solutions can also be used to remove polymeric resist materials present in single-layer or certain types of bilayer resists. For example, bilayer resists typically have a first inorganic layer covered by a second polymer layer, or may have two polymer layers.

[0020] Other features and advantages of the disclosed and claimed subject matter will become apparent from the following more detailed description in conjunction with example solutions (which illustrate the principles of the disclosed and claimed subject matter).

[0021] The order in which the different steps are discussed herein is for clarity. Generally, the steps disclosed herein can be performed in any suitable order. Furthermore, although the different features, techniques, configurations, etc., disclosed herein may be discussed in different parts of this disclosure, it is intended that each concept can be implemented independently of or in combination with each other, as appropriate. Therefore, the disclosed and claimed subject matter can be embodied and viewed in many different ways.

[0022] Detailed Explanation

[0023] All references cited in this article, including publications, patent applications and patents, are incorporated herein by reference to the extent that each reference is individually and specifically stated to be incorporated by reference and fully presented in this article.

[0024] In the context of describing the disclosed and claimed subject matter (especially in the context of the following claims), the use of the terms “a,” “an,” and “the,” and similar references, shall be construed as encompassing both the singular and plural, unless otherwise indicated herein or clearly contradicted by the context. The terms “comprising,” “having,” “including,” and “containing” shall be construed as open-ended terms (i.e., meaning “including but not limited to”), unless otherwise stated. The description of ranges of values ​​herein is intended merely as a way of abbreviating each individual value falling within that range, unless otherwise stated herein, and each individual value is incorporated into the specification as if it were separately described herein. Any methods described herein may be performed in any suitable order, unless otherwise stated herein or clearly contradicted by the context. Any and all instances or exemplary language provided herein (e.g., “such as”) are intended only to better illustrate the disclosed and claimed subject matter and do not constitute a limitation on the scope of the disclosed and claimed subject matter, unless otherwise claimed. No language in the specification should be construed as indicating that any non-claimed element is essential for implementing the disclosed and claimed subject matter.

[0025] Preferred embodiments of the disclosed and claimed subject matter are described herein, including the best modes known to the inventors for carrying out the disclosed and claimed subject matter. Variations of these preferred embodiments may become apparent to those skilled in the art upon reading the foregoing description. The inventors anticipate that those skilled in the art will employ such variations as appropriate, and that the inventors intend to implement the disclosed and claimed subject matter in a manner different from that specifically described herein. Therefore, the disclosed and claimed subject matter includes all modifications and equivalents to the subject matter recited in the appended claims as permitted by applicable law. Furthermore, unless otherwise stated herein or clearly contradicted by the context, the disclosed and claimed subject matter encompasses any combination of the foregoing elements in all possible variations.

[0026] For ease of reference, "microelectronic device" or "semiconductor substrate" refers to semiconductor wafers, flat panel displays, phase-change memory devices, solar panels, and other products, including solar substrates, photovoltaic devices, and microelectromechanical systems (MEMS), manufactured for microelectronic, integrated circuit, or computer chip applications. Solar substrates include, but are not limited to, silicon, amorphous silicon, polycrystalline silicon, monocrystalline silicon, CdTe, copper indium selenide, copper indium sulfide, and gallium arsenide on gallium. Solar substrates can be doped or undoped. It should be understood that the term "microelectronic device" is not limited in any way and includes any substrate that will ultimately become a microelectronic device or microelectronic assembly. Microelectronic devices or semiconductor substrates may include low-k dielectric materials, barrier materials, and metals such as AlCu alloys, W, Ti, TiN, and other materials thereon.

[0027] As defined herein, a “low-k dielectric material” corresponds to any material used as a dielectric material in layered microelectronic devices, wherein the material has a dielectric constant of less than about 3.5. Preferably, low-k dielectric materials include low-polarity materials, such as silicon-containing organic polymers, silicon-containing hybrid organic / inorganic materials, organosilicon glasses (OSG), TEOS, fluorinated silicate glasses (FSG), silicon dioxide, and carbon-doped oxide (CDO) glasses. It should be understood that low-k dielectric materials can have different densities and different porosities.

[0028] As defined herein, the term "barrier material" refers to any material in the art used to seal metal wires (e.g., copper interconnects) to minimize the diffusion of said metal (e.g., copper) into the dielectric material. Preferred barrier layer materials include tantalum, titanium, ruthenium, hafnium, and other refractory metals and their nitrides and silicides.

[0029] In this document, "substantially free of" is defined as less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.5% by weight, and most preferably less than 0.1% by weight. "Substantially free of" also includes 0.0% by weight. The term "free of" means 0.0% by weight.

[0030] As used herein, the terms “about” and “approximately” are each intended to correspond to ±5% of the stated value.

[0031] As used herein, “net” refers to the weight percentage of undiluted acid or other material. For example, 100g of 85% phosphoric acid contains 85g of acid and 15g of diluent.

[0032] In all such compositions, including those with a weight percentage range of zero, it will be understood that such components may or may not be present in various specific embodiments of the composition, and where such components are present, they may be present at concentrations as low as 0.001 weight percentages, based on the total weight of the composition employing such components. It should be noted that all defined weight percentages of components are based on the total weight of the composition unless otherwise indicated. Furthermore, all weight percentages are “net” unless otherwise indicated, meaning they do not include aqueous compositions present therein when added to the composition. Any reference to “at least one” may be replaced by “one or more.” “At least one” and / or “one or more” includes “at least two” or “two or more” and “at least three” and “three or more”, etc.

[0033] In broad practice, the disclosed and claimed subject matter relates to the aforementioned removal agent solutions, which comprise, are substantially composed of, or consist of components (i), (ii), (iii), and (iv). In some embodiments, the removal agent solution may contain other components. In some embodiments, the removal agent solutions disclosed herein are formulated to be free of or substantially free of at least one of the following chemical compounds: inorganic bases, quaternary ammonium hydroxides, ammonium hydroxides, amino acids, organic acids, azoles, halide ions (e.g., fluoride ions, chloride ions), metal-containing chemicals, reducing agents, alkanolamines, hydroxylamines, hydroxylamine derivatives, amine oxime compounds, organic solvents, surfactants, and abrasives.

[0034] In another embodiment, the remover solution is essentially composed of different concentrations of (i), (ii), (iii), and (iv). In such an embodiment, the combined amount of (i), (ii), (iii), and (iv) is not equal to 100% by weight and may include other components that do not materially alter the effectiveness of the remover solution.

[0035] In another embodiment, the remover solution comprises different concentrations of (i), (ii), (iii), and (iv). In such an embodiment, the combined amount of (i), (ii), (iii), and (iv) is equal to or approximately equal to 100% by weight, but may contain other small and / or trace amounts of impurities, present in small quantities that do not materially alter the effectiveness of the composition. For example, in one such embodiment, the remover solution may contain 2% by weight or less of impurities. In another embodiment, the remover solution may contain 1% by weight or less of impurities. In yet another embodiment, the remover solution may contain 0.05% by weight or less of impurities.

[0036] When the composition of the inventive compositions described herein is referred to as a percentage by weight (%), it should be understood that in any case the total percentage by weight of all components (including non-essential components, such as impurities) will not exceed 100% by weight. In compositions “consisting substantially of the described components,” such components may total 100% by weight of the composition, or may total less than 100% by weight. Where the total percentage by weight of components is less than 100% by weight, such compositions may contain small amounts of non-essential contaminants or impurities. For example, in one such embodiment, the remover solution may contain 2% by weight or less of impurities. In another embodiment, the remover solution may contain 1% by weight or less of impurities. In yet another embodiment, the remover solution may contain 0.05% by weight or less of impurities. In other such embodiments, the components may constitute at least 90% by weight, more preferably at least 95% by weight, more preferably at least 99% by weight, more preferably at least 99.5% by weight, most preferably at least 99.9% by weight, and may contain other components that will not substantially affect the performance of the remover solution. Otherwise, if there is no significant amount of non-essential impurity components, it should be understood that the combination of all essential components will substantially total 100% by weight.

[0037] The following detailed description provides only preferred exemplary embodiments and is not intended to limit the scope, applicability, or configuration of the disclosed and claimed subject matter. Rather, the detailed description of the following preferred exemplary embodiments will provide those skilled in the art with a facilitating description of preferred exemplary embodiments for implementing the disclosed and claimed subject matter. Various changes may be made to the function and arrangement of the elements without departing from the spirit and scope of the disclosed and claimed subject matter as set forth in the appended claims.

[0038] Remover solution

[0039] It should be understood that the foregoing general description and the following detailed description are illustrative and explanatory, and do not limit the subject matter claimed. The purpose, features, advantages, and concepts of the disclosed subject matter will be readily apparent to those skilled in the art from the description provided in the specification, and those skilled in the art will readily implement the disclosed subject matter based on the description herein. The inclusion of “preferred embodiments” and / or examples illustrating preferred modes for implementing the disclosed subject matter is for illustrative purposes and is not intended to limit the scope of the claims.

[0040] It will be apparent to those skilled in the art that various modifications can be made to how the disclosed subject matter is implemented based on the aspects described in the specification without departing from the spirit and scope of the subject matter disclosed herein.

[0041] In particular, the disclosed and claimed removal agent solutions contain, are substantially composed of, or consist of the following:

[0042] (i) at least one organic solvent;

[0043] (ii) at least one amine that does not contain a carboxylic acid moiety;

[0044] (iii) Water;

[0045] (iv) Corrosion inhibitors, comprising one or more of the following:

[0046] (a) amino acids,

[0047] (b) azole, and

[0048] (c) Phenolic acids

[0049] The removal agent solution is free of dimethyl sulfoxide, N-methylpyrrolidone, and dimethylacetamide.

[0050] In another aspect of this embodiment, (iv) the corrosion inhibitor comprises two or more of (a) an amino acid, (b) a azole, and (c) a phenolic acid. In one embodiment, (iv) the corrosion inhibitor comprises (a) an amino acid and (b) a azole. In another embodiment, (iv) the corrosion inhibitor comprises (a) an amino acid and (c) a phenolic acid. In yet another aspect of this embodiment, (iv) the corrosion inhibitor comprises one or more of each of (a) an amino acid, (b) a azole, and (c) a phenolic acid.

[0051] In some aspects of this embodiment, the remover solution may contain other optional components.

[0052] I. Organic solvents

[0053] As described above, the remover solution contains at least one organic solvent that is not dimethyl sulfoxide, N-methylpyrrolidone, or dimethylacetamide. One class of solvents that can be used in the compositions of the disclosed and claimed solutions are ether alcohol solvents or amide-type solvents other than DMAC, or mixtures thereof. The ether alcohol solvent can be a glycol ether or other alcohol having an ether group. One or more ether alcohol solvents, including glycol ether solvents, can be used in the disclosed and claimed solutions. Suitable glycol ether solvents include diethylene glycol butyl ether (DB), diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol propyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol propyl ether, dipropylene glycol propyl ether, propylene glycol phenyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, ethylene glycol phenyl ether, tripropylene glycol methyl ether, dipropylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol (DEG), dipropylene glycol, or propylene glycol phenyl ether (glycol ether PPH). Examples of non-glycol ether alcohol ether solvents are 3-methoxy-3-methyl-1-butanol (MMB), furfuryl alcohol, and tetrahydrofurfuryl alcohol. Examples of amide solvents useful in disclosed and claimed solutions include, but are not limited to, N,N-dimethylformamide, diethylformamide (DEF), dimethylacetamide, and cyclic amides. Each solvent can be used alone, in a mixture of the same type, or in any or all different types of combinations.

[0054] The remover solution will contain about 20% to about 70% or about 30% to about 65% by weight of at least one organic solvent. Other preferred embodiments of the disclosed and claimed solutions contain about 30% to about 62%, about 40% to about 62%, about 50% to about 62%, about 30% to about 50%, or about 30% to about 40% by weight of a glycol ether solvent. One or more alcohol ether solvents or ether alcohol solvents may be present in amounts falling within the ranges defined by the following weight percentage list: 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, and 70. In one embodiment, the alcohol ether solvent may be present in the composition in the ranges of about 20% to about 70%, about 20% to about 60%, about 25% to about 45%, and about 30% to about 62%. Amide solvents may be present in amounts falling within the ranges defined by the following weight percentage list: 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, and 70. In one embodiment, the amide solvent may be present in the composition in the range of about 20% to about 70%, about 20% to about 60%, about 25% to about 45%, and about 30% to about 62%.

[0055] Some embodiments may contain about 5% to about 30% of a second solvent, such as benzyl alcohol or propylene glycol, which differs from the aforementioned ether alcohol or amide solvents. Alternatively, in some embodiments, the stripper solution may contain no or substantially no second solvent.

[0056] The second organic solvent alcohol can be a straight-chain or branched aliphatic or aromatic alcohol. Examples of second alcohols that may be included in the composition include benzyl alcohol, propylene glycol, ethylene glycol, methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, tert-amyl alcohol, 3-methyl-3-pentanol, 1-octanol, 1-decanol, 1-undecanool, 1-dodecanool, 1-tridecanool, 1-tetradecanool, 1-pentadecanol, 1-hexadecanool, 9-hexadecen-1-ol, 1-heptadecanool, 1-octadecanool, 1-nonadecanol, 1-eicosenool, 1-timodecanool, 1-timodecanool, 1-timodecanool, 1-timodecanool, 1-timodecanool, 1-timodecanool, 1-timodecanool, 1-timodecanool, 1-timodecanool, and cetearyl alcohol.

[0057] When used, the second organic solvent may comprise about 3% to about 45% of the composition, or about 5% to about 35%, or about 8% to about 30%, or about 10% to about 30%. In alternative embodiments, the second solvent may be present in any amount defined by the endpoints selected from the following weight percentages: 3, 5, 8, 10, 12, 15, 17, 20, 23, 25, 38, 30, 32, 35, 37, 40, 43, and 45.

[0058] II. Amines lacking a carboxylic acid moiety

[0059] As described above, the remover solution contains at least one amine that does not contain a carboxylic acid moiety. Suitable amines include, but are not limited to, alkanolamines, including one or more of the following: ethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, dimethylethanolamine, diethylethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, N-methylisopropanolamine, N-ethylisopropanolamine, N-propylisopropanolamine, 2-aminopropanolamine, etc. Alkyl-1-ol, N-methyl-2-aminopropane-1-ol, N-ethyl-2-aminopropane-1-ol, 1-aminopropane-3-ol, N-methyl-1-aminopropane-3-ol, N-ethyl-1-aminopropane-3-ol, 1-aminobutane-2-ol, N-methyl-1-aminobutane-2-ol, N-ethyl-1-aminobutane-2-ol, 2-aminobutane-1-ol, N-methyl-2-aminobutane-1-ol, N-ethyl-2- Aminobutane-1-ol, 3-aminobutane-1-ol, N-methyl-3-aminobutane-1-ol, N-ethyl-3-aminobutane-1-ol, 1-aminobutane-4-ol, N-methyl-1-aminobutane-4-ol, N-ethyl-1-aminobutane-4-ol, 1-amino-2-methylpropane-2-ol, 2-amino-2-methylpropane-1-ol, 1-aminopentane-4-ol, 2-amino-4-methylpentane-1-ol, 2-amino The preferred alkanolamines include hexane-1-ol, 3-aminoheptane-4-ol, 1-aminooctane-2-ol, 5-aminooctane-4-ol, 1-aminopropane-2,3-diol, 2-aminopropane-1,3-diol, tris(oxomethyl)aminomethane, 1,2-diaminopropane-3-ol, 1,3-diaminopropane-2-ol, 2-(2-aminoethoxy)ethanol, 4-(2-hydroxyethyl)morpholine, 1-(2-hydroxyethyl)piperidine, and 1-(2-hydroxyethyl)piperazine. Preferred alkanolamines include N-methylethanolamine, triethanolamine, N-ethylethanolamine, ethanolamine, N-methyldiethanolamine, monoisopropanolamine, and aminoethoxyethanol.

[0060] Suitable amines also include hydroxyl-free amines, including diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), aminoethylpiperazine, 3-morpholinopropylamine (APM), benzylamine (BA), 1,5-diamino-2-methylpentane, 1,3-diaminopentane, piperazine, 1-(2-aminoethyl)piperazine, 1,2-diaminocyclohexane, 1,3-diaminopropane, 1-(2-aminoethyl)piperidine, pentamethyldiethylenetriamine, and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Preferred hydroxyl-free amines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, aminoethylpiperazine, 3-morpholinopropylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and benzylamine.

[0061] The desired suitable level of at least one amine can be from about 2% by weight to about 60% by weight of the composition. In some embodiments, the amine is from about 3% by weight to about 50% by weight of the composition. In alternative embodiments, the amine can be present in any amount defined by the endpoints selected from the following weight percentages: 3, 5, 20, 25, 30, 35, 40, 45, 50, 55 and 60.

[0062] In one embodiment, the solution contains about 2% to about 60% by weight of an amine. In one embodiment, the solution contains about 3% to about 60% by weight of an amine. In one embodiment, the solution contains about 10% to about 45% by weight of an amine. In one embodiment, the solution contains about 10% to about 40% by weight of an amine. In one embodiment, the solution contains about 10% to about 35% by weight of an amine. In one embodiment, the solution contains about 10% to about 30% by weight of an amine. In one embodiment, the solution contains about 10% to about 25% by weight of an amine. In one embodiment, the solution contains about 10% to about 20% by weight of an amine. In one embodiment, the solution contains about 20% to about 60% by weight of an amine. In one embodiment, the solution contains about 20% to about 50% by weight of an amine. In one embodiment, the solution contains about 20% to about 45% by weight of an amine. In one embodiment, the solution contains about 20% to about 40% by weight of an amine. In one embodiment, the solution contains about 20% to about 35% by weight of an amine. In one embodiment, the solution contains about 20% to about 30% by weight of an amine. In one embodiment, the solution contains about 30% to about 60% by weight of an amine. In one embodiment, the solution contains about 30% to about 50% by weight of an amine. In one embodiment, the solution contains about 30% to about 40% by weight of an amine.

[0063] III. Water

[0064] As described above, the remover solution contains water. Suitable water levels can be from about 0.1% by weight to about 35% by weight of the composition. In some embodiments, water comprises from about 5% by weight to about 25% by weight of the composition. In alternative embodiments, amines may be present in any amount defined by the endpoints selected from the following weight percentages: 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 5, 7.5, 10, 12.5, 15, 17.5, 20, 22.5, 25, 30, 35.

[0065] In one embodiment, the solution contains about 0.1 wt% to about 30 wt% water. In one embodiment, the solution contains about 5 wt% to about 30 wt% water. In one embodiment, the solution contains about 5 wt% to about 25 wt% water. In one embodiment, the solution contains about 5 wt% to about 22 wt% water. In one embodiment, the solution contains about 5 wt% to about 20 wt% water. In one embodiment, the solution contains about 5 wt% to about 17.5 wt% water. In one embodiment, the solution contains about 5 wt% to about 15 wt% water. In one embodiment, the solution contains about 5 wt% to about 12.5 wt% water. In one embodiment, the solution contains about 10 wt% to about 25 wt% water. In one embodiment, the solution contains about 10 wt% to about 22.5 wt% water. In one embodiment, the solution contains about 10 wt% to about 20 wt% water. In one embodiment, the solution contains about 10 wt% to about 17.5 wt% water. In one embodiment, the solution contains about 10 wt% to about 15 wt% water. In one embodiment, the solution contains about 10 wt% to about 12.5 wt% water.

[0066] IV. Corrosion Inhibitor

[0067] As described above, the removal agent solution contains a corrosion inhibitor, which comprises one or more of (a) an amino acid, (b) an azole, and (c) a phenolic acid. In some embodiments, the corrosion inhibitor comprises two or more of (a) an amino acid, (b) an azole, and (c) a phenolic acid (i.e., the corrosion inhibitor may comprise an amino acid and an azole; an amino acid and a phenolic acid; or an azole and a phenolic acid). In some embodiments, the corrosion inhibitor comprises one or more of each of (a) an amino acid, (b) an azole, and (c) a phenolic acid (i.e., comprising at least one amino acid, at least one azole, and at least one phenolic acid).

[0068] (a) amino acids

[0069] Amino acids suitable for use in the disclosed and claimed removal agent solutions contain at least one amino group and one carboxylic acid group. Suitable amino acid corrosion inhibitors include, but are not limited to, glycine, histidine, arginine, alanine, isoleucine, cysteine, asparagine, leucine, glutamine, aspartic acid, lysine, glutamic acid, methionine, proline, serine, phenylalanine, tyrosine, threonine, tryptophan, valine, n-(2-hydroxyethyl)ethylenediamine-N,N,N-triacetic acid, 2-pyridinecarboxylic acid, L-cysteine, 3,4-diaminobenzoic acid, and iminoacetic acid. Glycine is a preferred amino acid for use in the disclosed and claimed removal agent solutions.

[0070] Based on the total weight of the composition, the amino acids may be present in any net amount, ranging from about 0.01 wt% to about 10 wt%, about 0.05 wt% to about 10 wt%, 0.01 wt% to about 5 wt%, or about 0.05 wt% to about 2 wt%, or about 0.05 wt% to about 1 wt%, or about 0.1 wt% to about 5 wt%, or about 0.1 wt% to about 3 wt%, or about 0.1 wt% to about 2 wt%, or about 0.1 wt% to about 1 wt%, or about 0.3 wt% to about 5 wt%, or about 0.3 wt% to about 1 wt%. In some preferred compositions, the amino acids are present in about 0.1 wt% to 1 wt%. In some preferred compositions, the amino acids are present in about 0.3 wt% to 1 wt%. In some preferred compositions, the amino acids are present in about 0.5 wt% to 1 wt%.

[0071] (b) azole

[0072] Suitable azoles for use as corrosion inhibitors include, but are not limited to, benzotriazole, benzotriazole-5-carboxylic acid, 1,2,4-triazole, 5-aminotetrazole, 5-methyl-1H-benzotriazole, 1-hydroxybenzotriazole, 5-amino-1,3,4-thiadiazole-2-thiol, 3-amino-1H-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, tolyltriazole, 5-phenyl-benzotriazole, 5-nitro-benzotriazole, 3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole, 2-(5-aminopentyl)-benzotriazole, 1-amino-1,2,3-triazole, and 1-amino-5- Methyl-1,2,3-triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, 5-phenylthio-benzotriazole, naphthiatriazole, 1H-tetrazole-5-acetic acid, 2-mercaptobenzothiazole (2-MBT), 1-phenyl-2-tetrazole-5-thione, 2-mercaptobenzimidazole (2-MBI), 4-methyl-2-phenylimidazolium, 2-mercaptothiazoline, 2,4-diamino-6-methyl-1,3,5-triazine, thiazole, imidazole, benzimidazole, triazine, 5-methyl-1H-benzotriazole, 4-methylbenzotriazole, 1-methylbenzotriazole, 1-methyltetrazole, and 5-methyl-1H-tetrazole. Preferred azoles for use in the disclosed and claimed removal agent solutions are toluenetriazole (TTL) and benzotriazole (BZT).

[0073] Based on the total weight of the composition, the azole inhibitor may be present in any net amount, ranging from about 0.01 wt% to about 10 wt%, about 0.05 wt% to about 10 wt%, 0.01 wt% to about 5 wt%, or about 0.05 wt% to about 2 wt%, or about 0.05 wt% to about 1 wt%, or about 0.1 wt% to about 5 wt%, or about 0.1 wt% to about 3 wt%, or about 0.1 wt% to about 2 wt%, or about 0.1 wt% to about 1 wt%, or about 0.3 wt% to about 5 wt%, or about 0.3 wt% to about 1 wt%. In some preferred compositions, the azole is present in about 0.1 wt% to 1 wt%. In some preferred compositions, the azole inhibitor is present in about 0.3 wt% to 1 wt%. In some preferred compositions, the azole inhibitor is present in about 0.5 wt% to 1 wt%.

[0074] (c) Phenolic acid

[0075] Phenolic acids suitable for use as corrosion inhibitors are hydroxybenzoic acids having one or more hydroxyl groups and at least one carboxyl group attached to a benzene ring. Such phenolic acids include, but are not limited to, gallic acid, phloroglucinol carboxylic acid, 2,3-dihydroxybenzoic acid (hypogallic acid), 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid (gentianic acid), 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid (protocatechuic acid), 3,5-dihydroxybenzoic acid, vanillic acid, syringic acid, veratric acid, 2-hydroxybenzoic acid (salicylic acid), 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, and pyrogallol. Gallic acid is a preferred phenolic acid for use in disclosed and claimed removal agent solutions.

[0076] Based on the total weight of the composition, phenolic acids may be present in any net amount, ranging from about 0.01 wt% to about 10 wt%, from about 0.05 wt% to about 10 wt%, from 0.01 wt% to about 5 wt%, or from about 0.05 wt% to about 2 wt%, or from about 0.05 wt% to about 1 wt%, or from about 0.1 wt% to about 5 wt%, or from about 0.1 wt% to about 3 wt%, or from about 0.1 wt% to about 2 wt%, or from about 0.1 wt% to about 1 wt%, or from about 0.3 wt% to about 5 wt%, or from about 0.3 wt% to about 1 wt%. In some preferred compositions, phenolic acids are present in about 0.1 wt% to 1 wt%. In some preferred compositions, phenolic acids are present in about 0.3 wt% to 1 wt%. In some preferred compositions, phenolic acid inhibitors are present in about 0.5 wt% to 1 wt%.

[0077] Excluded ingredients

[0078] In some embodiments, the removal agent solutions disclosed herein are formulated to be free of or substantially free of at least one of the following chemical compounds: inorganic bases, inorganic acids, quaternary ammonium hydroxides, ammonium hydroxides, organic acids, sulfur-containing organic chemicals, phosphorus-containing organic chemicals, halide ions (e.g., fluoride ions, chloride ions), metal-containing chemicals, reducing agents, oxidizing agents, hydrogen peroxide, hydroxylamine, hydroxylamine derivatives, amine oxime compounds, organic solvents, organosilanes, surfactants, and abrasives.

[0079] In some embodiments, the solution may be substantially free of or free of halogen-containing compounds, for example, it may be substantially free of or free of one or more of the following substances: fluorine-containing, bromine-containing, chlorine-containing, or iodine-containing compounds. In other embodiments, the solution may be substantially free of or free of sulfates and / or nitrates and / or sulfites and / or nitrites.

[0080] In some embodiments, the disclosed and claimed removal agent solutions are substantially free of or contain no ammonium hydroxide and / or ethylenediamine. In other embodiments, the solution may be substantially free of or contain no sodium-containing compounds and / or calcium-containing compounds and / or manganese-containing compounds or magnesium-containing compounds and / or chromium-containing compounds and / or sulfur-containing compounds. In other embodiments, the solution may be substantially free of or contain no amine oxime compounds and / or abrasives.

[0081] In some embodiments, the disclosed and claimed removal agent solutions are substantially free of or contain no other ammonium salts and / or quaternary ammonium hydroxides, quaternary ammonium salts, and metal ions.

[0082] In some embodiments, the disclosed and claimed solutions are substantially free of or contain no sulfonic acid and / or phosphoric acid and / or sulfuric acid and / or nitric acid and / or hydrochloric acid.

[0083] In some embodiments, the disclosed and claimed solutions are substantially free of or contain no amphoteric salts and / or cationic surfactants and / or anionic surfactants and / or amphoteric surfactants and / or nonionic surfactants.

[0084] In some embodiments, the disclosed and claimed solutions are substantially free of or contain no pyrrolidone and / or acetamide.

[0085] In some embodiments, the disclosed and claimed solutions are substantially free of or contain no peroxides and / or peroxides and / or persulfates and / or percarbonates, their acids and salts.

[0086] In some embodiments, the disclosed and claimed solutions are substantially free of or contain no iodates and / or perboric acid and / or percarbonate and / or peroxyacid and / or cerium compounds and / or cyanides and / or periodic acid and / or ammonium molybdate and / or ammonia and / or abrasives.

[0087] In some embodiments, the disclosed and claimed solutions are substantially free of or contain no oxidation products of one or more antioxidants, reducing agents, and phenolic acids.

[0088] In some implementations, the disclosed and claimed solutions are substantially free of or contain no sugar alcohols (one or more).

[0089] pH

[0090] The disclosed and claimed solutions have a pH of about 9 or greater, for example, about 9 to about 14 or about 10 to about 12, or any pH within the range of starting and ending points of 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, or 14. In one embodiment, the disclosed and claimed removal agent solution has a pH greater than about 9. In one embodiment, the disclosed and claimed removal agent solution has a pH greater than about 9.5. In one embodiment, the disclosed and claimed removal agent solution has a pH greater than about 10. In one embodiment, the disclosed and claimed removal agent solution has a pH greater than about 10.5. In one embodiment, the disclosed and claimed removal agent solution has a pH greater than about 11. In one embodiment, the disclosed and claimed removal agent solution has a pH greater than about 11.5. In one embodiment, the disclosed and claimed removal agent solution has a pH greater than about 12. In one embodiment, the disclosed and claimed removal agent solution has a pH greater than about 12.5. In another embodiment, the disclosed and claimed removal agent solution has a pH greater than about 13.

[0091] Exemplary Implementation

[0092] All values ​​in the following exemplary implementations are net values ​​unless otherwise stated.

[0093] In one exemplary embodiment, the disclosed and claimed removal agent solution comprises, is substantially composed of, or is composed of the following:

[0094] (i) Approximately 30% to approximately 62% organic solvent;

[0095] (ii) about 10% to about 40% of at least one amine that does not contain a carboxylic acid moiety;

[0096] (iii) Approximately 5% to approximately 30% water; and

[0097] (iv) A corrosion inhibitor comprising, substantially comprising, or consisting of: (a) about 0.1% to about 1.5% of an amino acid; (b) about 0.1% to about 1.5% of an azole; and (c) about 0.1% to about 1.5% of a phenolic acid.

[0098] The removal solution does not contain dimethyl sulfoxide, N-methylpyrrolidone, or dimethylacetamide.

[0099] In one aspect of this embodiment, the removal agent solution comprises, is substantially composed of, or consists of: (i) about 40% to about 45% diethylene glycol monoethyl ether; (ii) about 30% to about 35% n-methylethanolamine; (iii) about 22.5% to about 25% water; and (iv) (a) about 0.1% to about 0.5% glycine, (b) about 0.75% to about 1.25% benzotriazole and (c) about 0.25% to about 0.75% gallic acid.

[0100] In one exemplary embodiment, the disclosed and claimed removal agent solution comprises, is substantially composed of, or is composed of the following:

[0101] (i) Approximately 30% to approximately 62% organic solvent;

[0102] (ii) about 10% to about 40% of at least one amine that does not contain a carboxylic acid moiety;

[0103] (iii) Approximately 5% to approximately 30% water; and

[0104] (iv) A corrosion inhibitor comprising, substantially comprising, or consisting of: (a) about 0.1% to about 1.5% amino acids; (b) about 0.1% to about 1.5% azoles.

[0105] The removal solution does not contain dimethyl sulfoxide, N-methylpyrrolidone, or dimethylacetamide.

[0106] In one aspect of this embodiment, the removal agent solution comprises, is substantially composed of, or consists of: (i) about 40% to about 45% diethylene glycol monoethyl ether; (ii) about 30% to about 35% n-methylethanolamine; (iii) about 22.5% to about 25% water; and (iv) (a) about 0.1% to about 0.5% glycine, and (b) about 0.75% to about 1.25% benzotriazole.

[0107] In one exemplary embodiment, the disclosed and claimed removal agent solution comprises, is substantially composed of, or is composed of the following:

[0108] (i) Approximately 30% to approximately 62% organic solvent;

[0109] (ii) about 10% to about 40% of at least one amine that does not contain a carboxylic acid moiety;

[0110] (iii) Approximately 5% to approximately 20% water; and

[0111] (iv) Approximately 0.1% to approximately 1.5% of a corrosion inhibitor, comprising, substantially comprising, or consisting of an azole corrosion inhibitor.

[0112] The removal solution does not contain dimethyl sulfoxide, N-methylpyrrolidone, or dimethylacetamide.

[0113] In one aspect of this embodiment, the removal solution comprises, is substantially composed of, or consists of: (i) about 50% to about 60% diethylene glycol monoethyl ether; (ii) about 7.5% to about 12.5% ​​triethanolamine and about 15% to about 25% n-methylethanolamine; (iii) about 10% to about 15% water; and (iv) about 1% to about 1.5% toluenetriazole.

[0114] In one exemplary embodiment, the disclosed and claimed removal agent solution comprises, is substantially composed of, or is composed of the following:

[0115] (i) Approximately 40% to approximately 80% organic solvent;

[0116] (ii) about 5% to about 40% of at least one amine that does not contain a carboxylic acid moiety;

[0117] (iii) Approximately 2% to approximately 40% of a second amine lacking a carboxylic acid moiety;

[0118] (iv) Approximately 5% to approximately 20% water; and

[0119] (v) Approximately 0.3% to approximately 1.8% of a corrosion inhibitor, comprising, substantially comprising, or consisting of an azole corrosion inhibitor.

[0120] The removal solution does not contain dimethyl sulfoxide, N-methylpyrrolidone, or dimethylacetamide.

[0121] In one aspect of this embodiment, the removal agent solution comprises, is substantially composed of, or consists of: (i) about 70.0% to about 75.0% of diethylformamide; (ii) about 7.5% to about 12.5% ​​of 3-morpholinopropylamine and about 2.5% to about 5% of 1,8-diazabicyclo[5.4.0]undec-7-ene; (iii) about 10% to about 15% of water; and (iv) about 1% to about 1.5% of toluenetriazole.

[0122] Applications and methods

[0123] The disclosed and claimed subjects also include methods for removing one or more photoresist or etching residues or similar materials from a substrate, wholly or partially, by using one or more disclosed and claimed photoresist stripping agents and etching residue removal solutions. As described above, the disclosed and claimed photoresist stripping agents and etching residue removal solutions can be used to remove polymer resist materials present in a single layer or certain types of dual-layer resists. Using the methods taught below, a single-layer polymer resist can be effectively removed from a standard wafer having a single polymer layer. The same method can also be used to remove a single polymer layer from a wafer having a dual layer consisting of a first inorganic layer and a second or outer polymer layer. Finally, two polymer layers can be effectively removed from a wafer having a dual layer consisting of two polymer layers.

[0124] In one aspect of this embodiment, the process or method for removing photoresist or etching residues from a substrate includes the following steps:

[0125] (i) Contact the substrate with one or more photoresist stripping agents and etching residue remover solutions for a sufficient time to remove the required amount of photoresist or similar material;

[0126] (ii) Remove the substrate from the solution;

[0127] (iii) Rinse the solution off the substrate with deionized water or solvent; and

[0128] (iv) Optionally dry the substrate.

[0129] In one embodiment, step (i) includes immersing the substrate in one or more solutions of photoresist stripper and etching residue remover, and optionally agitating the substrate to facilitate the removal of photoresist. Such agitation can be achieved by mechanical stirring, circulation, or by bubbling an inert gas through the composition.

[0130] In one embodiment, step (ii) includes rinsing the substrate with water or alcohol. In one aspect of this embodiment, DI water is a preferred form of water. In another aspect of this embodiment, isopropanol (IPA) is a preferred solvent. In yet another aspect of this embodiment, the oxidized components are rinsed under an inert atmosphere or may be rinsed under an inert atmosphere.

[0131] Using the methods described above (and variations thereof), the disclosed and claimed photoresist stripping and etching residue removal solutions can be used to remove thick and thin positive-tone or negative-tone photoresists. Thick photoresists can be about 5 μm to about 100 μm or larger, or about 15 μm to 100 μm, or about 20 μm to about 100 μm, in advanced packaging applications for semiconductor devices. In other cases, chemical solutions can be used to remove photoresists about 0.1 μm to about 100 μm or larger, or about 0.2 μm to 100 μm, or about 0.3 μm to about 100 μm. Detailed Implementation

[0132] Example

[0133] Reference will now be made to more specific embodiments of this disclosure and experimental results supporting such embodiments. Examples are given below to illustrate the subject matter of the disclosure more fully and should not be construed as limiting the subject matter in any way.

[0134] It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed subject matter and the specific examples provided herein without departing from the spirit or scope of the disclosed subject matter. Therefore, the disclosed subject matter (including the description provided by the examples below) is intended to cover modifications and variations of the disclosed subject matter that fall within the scope of any claims and their equivalents.

[0135] Materials and methods:

[0136] All materials used in this patent are purchased from and / or available from Sigma Aldrich and are used in formulations as received. Unless otherwise stated, where appropriate, the amounts of materials in all tables are reported as weight percent and reflect “net” values. The remaining weight of the formulation is derived from water present in the raw materials.

[0137] Testing was performed using a blank Cu wafer. For the immersion process, two coupon-sized semiconductor wafer samples were processed in a beaker. The beaker was filled with 100 g of the release composition and heated to the target temperature. When the release composition was at the target temperature of 50°C, the two wafers were placed in a support within the beaker. The temperature was maintained at the process temperature throughout the process. After a total processing time of 1 minute, 5 minutes, or 30 minutes, with agitation at 1200 rpm, the copper substrate was rinsed with water and dried by blowing nitrogen.

[0138] The Cu etching rate was determined by measuring the film thickness in the formulation before and after processing using a CDE four-point probe RESMAP. For copper substrates, a typical initiation layer thickness is 1000 Å.

[0139] The following abbreviations are used for the various compositions in the table below:

[0140]

[0141] Unless otherwise stated, all amounts of materials in the tables are reported as weight percent and reflect “net” values ​​where appropriate. Exemplary and comparative formulations show all listed ingredients totaling 100% by weight.

[0142] Table 1 shows the effect of single corrosion inhibitors on the Cu etching rate. Compared with the control group without any corrosion inhibitor, both BZT and glycine significantly reduced the Cu etching rate. Gallic acid, on the other hand, increased the Cu etching rate.

[0143]

[0144] Table 1. Effect of a single corrosion inhibitor on Cu etching rate

[0145] Tables 2-4 show the effect of the combination of two corrosion inhibitors on the Cu etching rate. Table 2 shows that the combination of BZT and glycine significantly reduced the Cu etching rate compared to BZT or glycine alone in Examples 2 and 6. Table 3 shows that the addition of gallic acid to the BZT-containing formulation further reduced the Cu etching rate. Table 3 shows that the addition of gallic acid to the glycine-containing formulation increased the Cu etching rate. However, the addition of BZT significantly reduced the Cu etching rate, even less than the combination of BZT and glycine in the formulation.

[0146]

[0147] Table 2. Effect of the combination of BZT and glycine on Cu etching rate

[0148]

[0149] Table 3. Effect of the combination of gallic acid and BZT on Cu etching rate

[0150]

[0151] Table 4. Effect of the combination of gallic acid and glycine on Cu etching rate

[0152]

[0153] Table 5. Effect of azole inhibitors on Cu etching rate

[0154]

[0155] Table 6. Effects of alkanolamine and TTL concentrations on Cu etching rate

[0156] Table 5 shows the effect of different azole inhibitors on the Cu etching rate. Compared with BZT and ABT in formulations with different alkanolamine concentrations, TTL showed the lowest Cu etching rate, while ABT showed the highest. The higher alkanolamine concentrations of NMEA and TEA resulted in higher Cu etching rates. In Examples 5-6, the Cu etching rate was 1.07 (Cu-1000A E / R (Å / min)). At 5 min / 800 rpm / 40 °C, the Al etching rate was 9.93 (Al -800 Å E / R (Å / min)). (1 min / 800 rpm / 40℃).

[0157] Table 6 shows the effect of alkanolamine and TTL concentrations on the Cu etching rate in formulations with a lower water concentration of 12.5%. Higher alkanolamine concentrations in NMEA and TEA resulted in higher Cu etching rates at the same TTL concentration, while higher TTL concentrations resulted in lower Cu etching rates at the same alkanolamine concentration.

[0158] Table 7 shows the Cu etching rates when using various amino acids to replace glycine. At a 0.5% loading with DE as the solvent, glycine is the best amino acid for inhibiting Cu etching.

[0159]

[0160] Table 7. Effects of various amino acids on Cu etching rate

[0161] Table 8 shows the Cu etching rates achieved by replacing glycine with various amino acids using MMB solvent. At a 0.1% loading with MMB as the solvent, glycine was the best amino acid for inhibiting Cu etching.

[0162]

[0163] Table 8. Effects of various amino acids on Cu etching rate

[0164] Table 9 shows the Cu etching rates using DE and DEF solvents. DE solvent showed a lower Cu etching rate than DEF.

[0165]

[0166] Table 9. Effects of DEF and DE solvents on Cu etching rate

[0167] Table 10 shows the Cu etching rates using various solvents. There were no significant differences in Cu etching rates among the ether solvents when all three corrosion inhibitor combinations were used.

[0168]

[0169] Table 10. Effects of various solvents on Cu etching rate

[0170] Table 11 shows the Cu etching rates using various amines with DEF as the solvent. With BZT as the corrosion inhibitor alone, TEA and N-MDEA showed significantly lower Cu etching rates than the other amines tested (including DETA, DGA, and benzylamine).

[0171]

[0172] Table 11. Effects of various amines using DEF as a solvent on Cu etching rate

[0173] Table 12 shows the Cu etching rates for water contents ranging from 12% to 27%. Within this range, 24.5% water yielded the lowest Cu etching rate. Further optimization of the inhibitor concentration significantly reduced the Cu etching rate.

[0174]

[0175] Table 12. Effect of water content on Cu etching rate

[0176] Table 13 shows the Cu etching rates with various secondary solvents. PPH shows a slightly lower Cu etching rate than all other secondary solvents.

[0177]

[0178] Table 13. Effects of various secondary solvents on Cu etching rate

[0179] Although the invention has been described and illustrated with a particular degree of specificity, it is understood that disclosure has been made by way of example only, and that many changes in the order of conditions and steps may be made by those skilled in the art without departing from the spirit and scope of the invention.

Claims

1. A removal agent solution comprising: (i) at least one organic solvent; (ii) at least one amine that does not contain a carboxylic acid moiety; (iii) Water; and (iv) Corrosion inhibitors, comprising one or more of the following: (a) Amino acids; (b) azole; and (c) Phenolic acids; The removal agent solution is free of dimethyl sulfoxide, N-methylpyrrolidone, and dimethylacetamide.

2. The removal agent solution according to claim 1, wherein the at least one organic solvent comprises one or more of an ether alcohol solvent or an amide solvent other than dimethylacetamide.

3. The removal agent solution according to claim 1, wherein the at least one organic solvent comprises one or more ether alcohol solvents.

4. The removal agent solution according to claim 1, wherein the at least one organic solvent comprises one or more of the following: diethylene glycol butyl ether (DB), diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol propyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol propyl ether, dipropylene glycol propyl ether, propylene glycol phenyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, ethylene glycol phenyl ether, tripropylene glycol methyl ether, dipropylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol (DEG), dipropylene glycol, and propylene glycol phenyl ether (diol ether PPH).

5. The removal agent solution according to claim 1, wherein the at least one organic solvent comprises one or more of 3-methoxy-3-methyl-1-butanol (MMB), furfuryl alcohol, and tetrahydrofurfuryl alcohol.

6. The removal agent solution according to claim 1, wherein the at least one organic solvent comprises one or more of N,N-dimethylformamide, diethylformamide (DEF), dimethylacetamide, and cycloamide.

7. The removal agent solution according to claim 1, wherein the at least one organic solvent accounts for about 20% to about 70% of the removal agent solution.

8. The removal agent solution according to claim 1, wherein the at least one organic solvent accounts for about 20% to about 60% of the removal agent solution.

9. The removal agent solution according to claim 1, wherein the at least one organic solvent accounts for about 30% to about 65% of the removal agent solution.

10. The removal agent solution according to claim 1, wherein the at least one organic solvent accounts for about 30% to about 62% of the removal agent solution.

11. The removal agent solution according to claim 1, wherein the at least one organic solvent accounts for about 40% to about 62% of the removal agent solution.

12. The removal agent solution according to claim 1, wherein the at least one organic solvent accounts for about 50% to about 62% of the removal agent solution.

13. The removal agent solution according to claim 1, wherein the at least one organic solvent accounts for about 30% to about 50% of the removal agent solution.

14. The removal agent solution according to claim 1, wherein the at least one organic solvent accounts for about 30% to about 40% of the removal agent solution.

15. The removal agent solution according to claim 1, wherein the at least one organic solvent accounts for about 25% to about 45% of the removal agent solution.

16. The removal agent solution according to claim 1, wherein the at least one amine without a carboxylic acid structural moiety comprises one or more alkanolamines.

17. The removal agent solution according to claim 1, wherein the at least one amine without a carboxylic acid moiety comprises one or more alkanolamines selected from the group consisting of: ethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, dimethylethanolamine, diethylethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, N-methylisopropanolamine, N-ethyl ... Propanolamine, N-propylisopropanolamine, 2-aminopropane-1-ol, N-methyl-2-aminopropane-1-ol, N-ethyl-2-aminopropane-1-ol, 1-aminopropane-3-ol, N-methyl-1-aminopropane-3-ol, N-ethyl-1-aminopropane-3-ol, 1-aminobutane-2-ol, N-methyl-1-aminobutane-2-ol, N-ethyl-1-aminobutane-2-ol, 2-aminobutane-1-ol, N-methyl-2-aminobutane -1-ol, N-ethyl-2-aminobutane-1-ol, 3-aminobutane-1-ol, N-methyl-3-aminobutane-1-ol, N-ethyl-3-aminobutane-1-ol, 1-aminobutane-4-ol, N-methyl-1-aminobutane-4-ol, N-ethyl-1-aminobutane-4-ol, 1-amino-2-methylpropane-2-ol, 2-amino-2-methylpropane-1-ol, 1-aminopentane-4-ol, 2-amino-4-methylpentane-1-ol - Alcohols, 2-aminohexane-1-ol, 3-aminoheptane-4-ol, 1-aminooctane-2-ol, 5-aminooctane-4-ol, 1-aminopropane-2,3-diol, 2-aminopropane-1,3-diol, tris(hydroxymethyl)aminomethane, 1,2-diaminopropane-3-ol, 1,3-diaminopropane-2-ol, 2-(2-aminoethoxy)ethanol, 4-(2-hydroxyethyl)morpholine, 1-(2-hydroxyethyl)piperidine, and 1-(2-hydroxyethyl)piperazine.

18. The removal agent solution according to claim 1, wherein the at least one amine without a carboxylic acid structural moiety comprises one or more alkanolamines selected from the group consisting of: N-methylethanolamine, triethanolamine, N-ethylethanolamine, ethanolamine, N-methyldiethanolamine, monoisopropanolamine, and aminoethoxyethanol.

19. The removal agent solution according to claim 1, wherein the at least one amine without a carboxylic acid structural moiety comprises one or more amines without a hydroxyl group.

20. The removal agent solution according to claim 1, wherein the at least one amine without a carboxylic acid structural moiety comprises one or more hydroxyl-free amines selected from the group consisting of: diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), aminoethylpiperazine, 3-morpholinopropylamine, benzylamine (BA), 1,5-diamino-2-methylpentane, 1,3-diaminopentane, piperazine, 1-(2-aminoethyl)piperazine, 1,2-diaminocyclohexane, 1,3-diaminopropane, 1-(2-aminoethyl)piperidine, pentamethyldiethylenetriamine, and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

21. The removal agent solution according to claim 1, wherein the at least one amine without a carboxylic acid structural moiety comprises one or more hydroxyl-free amines selected from the group consisting of: diethylenetriamine, triethylenetetramine, tetraethylenepentamine, aminoethylpiperazine, 3-morpholinopropylamine, and benzylamine.

22. The removal agent solution according to claim 1, wherein the at least one amine without a carboxylic acid structural moiety comprises about 10% to about 60% by weight of the removal agent solution.

23. The removal agent solution according to claim 1, wherein the at least one amine without a carboxylic acid structural moiety accounts for about 10% to about 50% by weight of the removal agent solution.

24. The removal agent solution according to claim 1, wherein the at least one amine without a carboxylic acid structural moiety comprises about 10% to about 45% by weight of the removal agent solution.

25. The removal agent solution according to claim 1, wherein the at least one amine without a carboxylic acid structural moiety accounts for about 10% to about 40% by weight of the removal agent solution.

26. The removal agent solution according to claim 1, wherein the at least one amine without a carboxylic acid structural moiety comprises about 10% to about 35% by weight of the removal agent solution.

27. The removal agent solution according to claim 1, wherein the at least one amine without a carboxylic acid structural moiety accounts for about 10% to about 30% by weight of the removal agent solution.

28. The removal agent solution according to claim 1, wherein the at least one amine without a carboxylic acid structural moiety accounts for about 10% to about 25% by weight of the removal agent solution.

29. The removal agent solution according to claim 1, wherein the at least one amine without a carboxylic acid structural moiety accounts for about 10% to about 20% by weight of the removal agent solution.

30. The removal agent solution according to claim 1, wherein the at least one amine without a carboxylic acid structural moiety accounts for about 20% to about 60% by weight of the removal agent solution.

31. The removal agent solution according to claim 1, wherein the at least one amine without a carboxylic acid structural moiety accounts for about 20% to about 50% by weight of the removal agent solution.

32. The removal agent solution according to claim 1, wherein the at least one amine without a carboxylic acid structural moiety accounts for about 20% to about 45% by weight of the removal agent solution.

33. The removal agent solution according to claim 1, wherein the at least one amine without a carboxylic acid structural moiety accounts for about 20% to about 40% by weight of the removal agent solution.

34. The removal agent solution according to claim 1, wherein the at least one amine without a carboxylic acid structural moiety accounts for about 20% to about 35% by weight of the removal agent solution.

35. The removal agent solution according to claim 1, wherein the at least one amine without a carboxylic acid structural moiety accounts for about 20% to about 30% by weight of the removal agent solution.

36. The removal agent solution according to claim 1, wherein the at least one amine without a carboxylic acid structural moiety accounts for about 30% to about 60% by weight of the removal agent solution.

37. The removal agent solution according to claim 1, wherein the at least one amine without a carboxylic acid structural moiety accounts for about 30% to about 50% by weight of the removal agent solution.

38. The removal agent solution according to claim 1, wherein the at least one amine without a carboxylic acid structural moiety accounts for about 30% to about 40% by weight of the removal agent solution.

39. The removal agent solution according to claim 1, wherein the water accounts for about 0.1% to about 30% by weight of the removal agent solution.

40. The removal agent solution according to claim 1, wherein the water accounts for about 5% to about 30% by weight of the removal agent solution.

41. The removal agent solution according to claim 1, wherein the water accounts for about 5% to about 25% by weight of the removal agent solution.

42. The removal agent solution according to claim 1, wherein the water accounts for about 5% to about 22% by weight of the removal agent solution.

43. The removal agent solution according to claim 1, wherein the water accounts for about 5% to about 20% by weight of the removal agent solution.

44. The removal agent solution according to claim 1, wherein the water accounts for about 5% to about 17.5% by weight of the removal agent solution.

45. The removal agent solution according to claim 1, wherein the water accounts for about 5% to about 15% by weight of the removal agent solution.

46. ​​The removal agent solution according to claim 1, wherein the water accounts for about 5% to about 12.5% ​​by weight of the removal agent solution.

47. The removal agent solution according to claim 1, wherein the water accounts for about 10% to about 25% by weight of the removal agent solution.

48. The removal agent solution according to claim 1, wherein the water accounts for about 10% to about 22.5% by weight of the removal agent solution.

49. The removal agent solution according to claim 1, wherein the water accounts for about 10% to about 20% by weight of the removal agent solution.

50. The removal agent solution according to claim 1, wherein the water accounts for about 10% to about 17.5% by weight of the removal agent solution.

51. The removal agent solution according to claim 1, wherein the water accounts for about 10% to about 15% by weight of the removal agent solution.

52. The removal agent solution according to claim 1, wherein the water accounts for about 10% to about 12.5% ​​by weight of the removal agent solution.

53. The removal agent solution according to claim 1, wherein the corrosion inhibitor comprises one or more amino acids.

54. The removal agent solution according to claim 1, wherein the corrosion inhibitor comprises one or more azoles.

55. The removal agent solution according to claim 1, wherein the corrosion inhibitor comprises one or more phenolic acids.

56. The removal agent solution according to claim 1, wherein the corrosion inhibitor comprises two or more of (a) amino acids, (b) azoles and (c) phenolic acids.

57. The removal agent solution according to claim 1, wherein the corrosion inhibitor comprises (a) an amino acid and (b) an azole.

58. The removal agent solution according to claim 1, wherein the corrosion inhibitor comprises (a) an amino acid and (c) a phenolic acid.

59. The removal agent solution according to claim 1, wherein the corrosion inhibitor comprises (b) azole and (c) phenolic acid.

60. The removal agent solution according to claim 1, wherein the corrosion inhibitor comprises one or more of each of (a) an amino acid, (b) an azole and (c) a phenolic acid.

61. The removal agent solution according to claim 1, wherein the corrosion inhibitor comprises one or more amino acids, wherein the amino acid comprises at least one amine group and one carboxylic acid group.

62. The removal agent solution according to claim 1, wherein the corrosion inhibitor comprises one or more amino acids selected from the group consisting of glycine, histidine, arginine, alanine, isoleucine, cysteine, asparagine, leucine, glutamine, aspartic acid, lysine, glutamic acid, methionine, proline, serine, phenylalanine, tyrosine, threonine, tryptophan, valine, n-(2-hydroxyethyl)ethylenediamine-N,N,N-triacetic acid, 2-pyridinecarboxylic acid, L-cysteine, 3,4-diaminobenzoic acid, and iminodiacetic acid.

63. The removal agent solution according to claim 1, wherein the corrosion inhibitor comprises glycine.

64. The removal agent solution according to claim 1, wherein the amino acid accounts for about 0.01% to about 10% by weight of the removal agent solution.

65. The removal agent solution according to claim 1, wherein the amino acid accounts for about 0.05% to about 10% by weight of the removal agent solution.

66. The removal agent solution according to claim 1, wherein the amino acid accounts for about 0.01% to about 5% by weight of the removal agent solution.

67. The removal agent solution according to claim 1, wherein the amino acid accounts for about 0.05% to about 2% by weight of the removal agent solution.

68. The removal agent solution according to claim 1, wherein the azole accounts for about 0.05% to about 1% by weight of the removal agent solution.

69. The removal agent solution according to claim 1, wherein the amino acid accounts for about 0.1% to about 5% by weight of the removal agent solution.

70. The removal agent solution according to claim 1, wherein the amino acid accounts for about 0.1% to about 3% by weight of the removal agent solution.

71. The removal agent solution according to claim 1, wherein the amino acid accounts for about 0.1% to about 2% by weight of the removal agent solution.

72. The removal agent solution according to claim 1, wherein the amino acid accounts for about 0.1% to about 1% by weight of the removal agent solution.

73. The removal agent solution according to claim 1, wherein the amino acid accounts for about 0.3% to about 5% by weight of the removal agent solution.

74. The removal agent solution according to claim 1, wherein the amino acid accounts for about 0.3% to about 1% by weight of the removal agent solution.

75. The removal agent solution according to claim 1, wherein the amino acid accounts for about 0.5% to about 1% by weight of the removal agent solution.

76. The removal agent solution according to claim 1, wherein the corrosion inhibitor comprises one or more azoles selected from the group consisting of: benzotriazole, benzotriazole-5-carboxylic acid, 1,2,4-triazole, 5-aminotetrazole, 5-methyl-1H-benzotriazole, 1-hydroxybenzotriazole, 5-amino-1,3,4-thiadiazole-2-thiol, 3-amino-1H-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, tolyltriazole, 5-phenyl-benzotriazole, 5-nitro-benzotriazole, 3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole, 2-(5-amino-pentyl)-benzotriazole, 1-amino-1, 2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, 5-phenylthio-benzotriazole, naphthiazole, 1H-tetrazole-5-acetic acid, 2-mercaptobenzothiazole (2-MBT), 1-phenyl-2-tetrazolin-5-thione, 2-mercaptobenzimidazole (2-MBI), 4-methyl-2-phenylimidazolium, 2-mercaptothiazoline, 2,4-diamino-6-methyl-1,3,5-triazine, thiazole, imidazole, benzimidazole, triazine, 5-methyl-1H-benzotriazole, 4-methylbenzotriazole, 1-methylbenzotriazole, 1-methyltetrazole, and 5-methyl-1H-tetrazole.

77. The removal agent solution according to claim 1, wherein the corrosion inhibitor comprises toluenetriazole (TTL).

78. The removal agent solution according to claim 1, wherein the corrosion inhibitor comprises benzotriazole (BZT).

79. The removal agent solution according to claim 1, wherein the azole accounts for about 0.01% to about 10% by weight of the removal agent solution.

80. The removal agent solution according to claim 1, wherein the azole accounts for about 0.05% to about 10% by weight of the removal agent solution.

81. The removal agent solution according to claim 1, wherein the azole accounts for about 0.01% to about 5% by weight of the removal agent solution.

82. The removal agent solution according to claim 1, wherein the azole accounts for about 0.05% to about 2% by weight of the removal agent solution.

83. The removal agent solution according to claim 1, wherein the azole accounts for about 0.05% to about 1% by weight of the removal agent solution.

84. The removal agent solution according to claim 1, wherein the azole accounts for about 0.1% to about 5% by weight of the removal agent solution.

85. The removal agent solution according to claim 1, wherein the azole accounts for about 0.1% to about 3% by weight of the removal agent solution.

86. The removal agent solution according to claim 1, wherein the azole accounts for about 0.1% to about 2% by weight of the removal agent solution.

87. The removal agent solution according to claim 1, wherein the azole accounts for about 0.1% to about 1% by weight of the removal agent solution.

88. The removal agent solution according to claim 1, wherein the azole accounts for about 0.3% to about 5% by weight of the removal agent solution.

89. The removal agent solution according to claim 1, wherein the azole accounts for about 0.3% to about 1% by weight of the removal agent solution.

90. The removal agent solution according to claim 1, wherein the azole accounts for about 0.5% to about 1% by weight of the removal agent solution.

91. The removal agent solution according to claim 1, wherein the corrosion inhibitor comprises one or more phenolic acids, the phenolic acid comprising hydroxybenzoic acid having one or more hydroxyl groups and at least one carboxyl group attached to a benzene ring.

92. The removal agent solution according to claim 1, wherein the corrosion inhibitor comprises one or more phenolic acids selected from the group consisting of: gallic acid, phloroglucinol carboxylic acid, 2,3-dihydroxybenzoic acid (hypogallic acid), 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid (gentianic acid), 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid (protocatechuic acid), 3,5-dihydroxybenzoic acid, vanillic acid, syringic acid, veratric acid, 2-hydroxybenzoic acid (salicylic acid), 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, and pyrogallol.

93. The removal agent solution according to claim 1, wherein the corrosion inhibitor comprises gallic acid.

94. The removal agent solution according to claim 1, wherein the phenolic acid accounts for about 0.01% to about 10% by weight of the removal agent solution.

95. The removal agent solution according to claim 1, wherein the phenolic acid accounts for about 0.05% to about 10% by weight of the removal agent solution.

96. The removal agent solution according to claim 1, wherein the phenolic acid accounts for about 0.01% to about 5% by weight of the removal agent solution.

97. The removal agent solution according to claim 1, wherein the phenolic acid accounts for about 0.05% to about 2% by weight of the removal agent solution.

98. The removal agent solution according to claim 1, wherein the phenolic acid accounts for about 0.05% to about 1% by weight of the removal agent solution.

99. The removal agent solution according to claim 1, wherein the phenolic acid accounts for about 0.1% to about 5% by weight of the removal agent solution.

100. The removal agent solution according to claim 1, wherein the phenolic acid accounts for about 0.1% to about 3% by weight of the removal agent solution.

101. The removal agent solution according to claim 1, wherein the phenolic acid accounts for about 0.1% to about 2% by weight of the removal agent solution.

102. The removal agent solution according to claim 1, wherein the phenolic acid accounts for about 0.1% to about 1% by weight of the removal agent solution.

103. The removal agent solution according to claim 1, wherein the phenolic acid accounts for about 0.3% to about 5% by weight of the removal agent solution.

104. The removal agent solution according to claim 1, wherein the phenolic acid accounts for about 0.3% to about 1% by weight of the removal agent solution.

105. The removal agent solution according to claim 1, wherein the phenolic acid accounts for about 0.5% to about 1% by weight of the removal agent solution.

106. The removal agent solution according to claim 1, wherein the removal agent comprises (i) Approximately 30% to approximately 62% organic solvent; (ii) about 10% to about 40% of at least one amine that does not contain a carboxylic acid moiety; (iii) Approximately 5% to approximately 30% water; and (iv) Corrosion inhibitors, comprising, essentially consisting of, or consisting of the following: (a) about 0.1% to about 1.5% of amino acids; (b) about 0.1% to about 1.5% of azoles; and (c) about 0.1% to about 1.5% of phenolic acids; The removal agent solution is free of dimethyl sulfoxide, N-methylpyrrolidone, and dimethylacetamide.

107. The removal agent solution according to claim 1, wherein the removal agent comprises (i) about 40% to about 45% of diethylene glycol monoethyl ether; (ii) about 30% to about 35% of n-methylethanolamine; (iii) about 22.5% to about 25% of water; and (iv) (a) about 0.1% to about 0.5% of glycine, (b) about 0.75% to about 1.25% of benzotriazole and (c) about 0.25% to about 0.75% of gallic acid.

108. The removal agent solution according to claim 1, wherein the removal agent comprises (i) Approximately 30% to approximately 62% organic solvent; (ii) about 10% to about 40% of at least one amine that does not contain a carboxylic acid moiety; (iii) Approximately 5% to approximately 30% water; and (iv) Corrosion inhibitors, comprising, essentially consisting of, or consisting of the following: (a) about 0.1% to about 1.5% of amino acids; (b) about 0.1% to about 1.5% of azoles; The removal agent solution is free of dimethyl sulfoxide, N-methylpyrrolidone, and dimethylacetamide.

109. The removal agent solution according to claim 1, wherein the removal agent comprises (i) about 40% to about 45% of diethylene glycol monoethyl ether; (ii) about 30% to about 35% of n-methylethanolamine; (iii) about 22.5% to about 25% of water; and (iv) (a) about 0.1% to about 0.5% of glycine, and (b) about 0.75% to about 1.25% of benzotriazole.

110. The removal agent solution according to claim 1, wherein the removal agent comprises (i) Approximately 30% to approximately 62% organic solvent; (ii) about 10% to about 40% of at least one amine that does not contain a carboxylic acid moiety; (iii) Approximately 5% to approximately 20% water; and (iv) about 0.1% to about 1.5% of a corrosion inhibitor, which comprises, is substantially composed of or consists of an azole corrosion inhibitor; The removal agent solution is free of dimethyl sulfoxide, N-methylpyrrolidone, and dimethylacetamide.

111. The removal agent solution according to claim 1, wherein the removal agent comprises (i) about 50% to about 60% of diethylene glycol monoethyl ether; (ii) about 7.5% to about 12.5% ​​of triethanolamine and about 15% to about 25% of n-methylethanolamine; (iii) about 10% to about 15% of water; and (iv) about 1% to about 1.5% of toluenetriazole.

112. The removal agent solution according to claim 1, wherein the removal agent comprises (i) Approximately 40% to approximately 80% organic solvent; (ii) about 5% to about 40% of at least one amine that does not contain a carboxylic acid moiety; (iii) Approximately 2% to approximately 40% of a second amine lacking a carboxylic acid moiety; (iv) Approximately 5% to approximately 20% water; and (v) about 0.3% to about 1.8% of corrosion inhibitors, which contain, are substantially composed of or consist of azole corrosion inhibitors; The removal agent solution is free of dimethyl sulfoxide, N-methylpyrrolidone, and dimethylacetamide.

113. The removal agent solution according to claim 1, wherein the removal agent comprises (i) about 70.0% to about 75.0% of diethylformamide; (ii) about 7.5% to about 12.5% ​​of 3-morpholinopropylamine and about 2.5% to about 5% of 1,8-diazabicyclo[5.4.0]undec-7-ene; (iii) about 10% to about 15% of water; and (iv) about 1% to about 1.5% of toluenetriazole.

114. The removal agent solution according to any one of claims 1-113, wherein the removal agent solution has a pH of about 9 to about 14.

115. The removal agent solution according to any one of claims 1-113, wherein the removal agent solution has a pH of about 10 to about 12.

116. The removal agent solution according to any one of claims 1-113, wherein the removal agent solution has a pH greater than about 9.

117. The removal agent solution according to any one of claims 1-113, wherein the removal agent solution has a pH greater than about 9.

5.

118. The removal agent solution according to any one of claims 1-113, wherein the removal agent solution has a pH greater than about 10.

119. The removal agent solution according to any one of claims 1-113, wherein the removal agent solution has a pH greater than about 10.

5.

120. The removal agent solution according to any one of claims 1-113, wherein the removal agent solution has a pH greater than about 11.

121. The removal agent solution according to any one of claims 1-113, wherein the removal agent solution has a pH greater than about 11.

5.

122. The removal agent solution according to any one of claims 1-113, wherein the removal agent solution has a pH greater than about 12.

123. The removal agent solution according to any one of claims 1-113, wherein the removal agent solution has a pH greater than about 12.

5.

124. The removal agent solution according to any one of claims 1-113, wherein the removal agent solution has a pH greater than about 13.

125. A method for removing photoresist or etching residues from a substrate, comprising the following steps: (i) Contact the substrate with the removal agent solution according to any one of claims 1-124 for a sufficient time to remove the required amount of photoresist or similar material; (ii) Remove the substrate from the removal agent solution; (iii) Rinse the substrate with deionized water or a solvent; and (iv) Optionally, the substrate is dried.

126. The method of claim 125, wherein step (i) comprises immersing the substrate in the photoresist solution and optionally agitating the substrate to facilitate the removal of the photoresist.

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