Photoresist Remover

Abstract

Cleaning compositions and methods of using the same are disclosed, which include one or more alkanolamines, one or more ether alcohol solvents or aromatic-containing alcohols, one or more corrosion inhibitors, and optionally one or more secondary solvents.

Description

Technical Field

[0001] The disclosed and claimed subject matter generally relates to compositions having the ability to effectively remove photoresist from a substrate, and methods for using such compositions.

Background Art

[0002] There are many stripping solutions for removing photoresist, such as those disclosed in US Patent Application Publication No. 2001034313A1 and US Patent Application Publication No. 20180143531A1. With the increasing demands of wafer manufacturers for performance improvement, there is a need for improvement in stripping solution compositions. Among the various materials used on substrates for various functions, the stripping agent may come into contact with those materials, and it is necessary to have the ability to remove the stripping agent and compatibility with the materials that are not removed on the substrate. Furthermore, solvents used in stripping agent formulations, such as N-methyl-2-pyrrolidone (NMP) and dimethyl sulfoxide (DMSO), have recently been regulated, and new formulations containing more environmentally friendly solvents are needed.

Summary of the Invention

Means for Solving the Problems

[0003] In one aspect of the disclosed and claimed subject matter, a photoresist stripping solution for efficiently removing or stripping photoresist from a substrate is provided. The stripping solution of the present invention does not contain or substantially does not contain NMP and DMSO, is particularly useful for removing positive photoresist, and does not harm materials present on the substrate, such as passivation layers of polyimide (PI) and polybenzoxazole (PBO).

[0004] The compositions according to the disclosed and claimed subject matter comprise (i) one or more organic solvents, (ii) one or more alkanolamines and / or amines, and (iii) one or more corrosion inhibitors. In further embodiments, the composition comprises (iv) one or more secondary solvents. In further embodiments of this embodiment, the disclosed and claimed chemical formulation comprises (i), (ii), and (iii). In further embodiments of this embodiment, the disclosed and claimed chemical formulation comprises (i), (ii), (iii), and (iv). In yet another further embodiment of this embodiment, the disclosed and claimed chemical formulation comprises (i), (ii), (iii), and (iv).

[0005] In further embodiments, one or more corrosion inhibitors comprise two or more corrosion inhibitors. Some embodiments are water-free or substantially water-free and / or water-free or substantially water-free (e.g., KOH, quaternary ammonium hydroxide).

[0006] In another embodiment, the composition comprises (i) one or more alkanolamines, (ii) one or more ether alcohol solvents or aromatic ring-containing alcohols, and (iii) one or more corrosion inhibitors. Further embodiments according to the Disclosure may include additional or secondary solvents. Preferred secondary solvents include aliphatic alcohols. Further embodiments according to the Disclosure may include amines or combinations of amines and alkanolamines. Further embodiments according to the Disclosure may include two additional corrosion inhibitors.

[0007] A second aspect of the present disclosure provides a method for removing photoresist from a substrate using the stripping solution described above. Photoresist can be removed from a selected substrate having photoresist on it by contacting the substrate with the stripping solution for a time sufficient to remove a desired amount of photoresist, removing the substrate from the stripping solution, washing the stripping solution off the substrate with a solvent, and drying the substrate.

[0008] In one embodiment, the release agent comprises from about 20% to about 90% diethylene glycol monobutyl ether, from about 0.01% to about 5% of one or more corrosion inhibitors, and from about 5% to about 40% of one or more alkanolamines, the alkanolamine having at least two carbon atoms, at least one amino substituent, and at least one hydroxyl substituent, with the amino and hydroxyl substituents attached to two different carbon atoms.

[0009] In a further aspect, the alkanolamine has the formula:

Chemical formula

[0010] In one embodiment, the formulation of the present invention comprises an alkanolamine of formula (I) in which one or both of R 1 and R 2 are H.

[0011] In one embodiment, the formulation of the present invention is R 1 , R 2 and R 3 Alkanolamines of formula (I) where each of these is H: [ka] Includes.

[0012] In one embodiment, the formulation of the present invention is R 1 and R 2 One of them is H, and R 1 and R 2 Another one is the -CH3 group, R 3 Alkanolamines of formula (I) where H: [ka] Includes.

[0013] In one embodiment, the formulation of the present invention is R 1 , R 2 and R 3 Alkanolamines of formula (I) where each of these is -CH3: [ka] Includes.

[0014] In one embodiment, the formulation of the present invention is R 1 , R 2 Each of these is hydrogen, and R 3 Alkanolamines of formula (I) where -CH3: [ka] Includes.

[0015] In one embodiment, the formulation of the present invention is R 1 and R 2 One of them is H, and R 1 and R 2 Another one is a substituted C1-C6 alkyl of the formula -CH2CH2OH, R3 Alkanolamines of formula (I) where H: [ka] Includes.

[0016] In one embodiment, the formulation of the present invention is R 1 and R 2 Both are substituted C1-C6 alkyl groups of the formula -CH2CH2OH, and R 3 Alkanolamines of formula (I) where H: [ka] Includes.

[0017] In one embodiment, the formulation of the present invention is R 1 and R 2 One of them is H, and R 1 and R 2 Another one is a substituted C1-C6 alkyl of the formula -CH2CH2NH2, R 3 Alkanolamines of formula (I) where H: [ka] Includes.

[0018] In one embodiment, the formulation of the present invention is R 1 and R 2 These are -CH3 and R 3 Alkanolamines of formula (I) where H: [ka] Includes.

[0019] The disclosed and claimed subject matter further covers the use and synthesis of the disclosed and claimed chemical formulations.

[0020] In another embodiment, the composition may include an additional or secondary solvent. Preferred secondary solvents include glycols, polyhydroxyl compounds, and the like.

[0021] A third aspect of this disclosure includes electronic devices manufactured by the novel methods disclosed.

[0022] Other features and advantages of the disclosed and claimed subject matter, along with illustrative solutions illustrating the principles of the disclosed and claimed subject matter, will become apparent from the following more detailed description.

[0023] This summary does not specifically describe all embodiments and / or progressive novel aspects of the disclosed and claimed subject matter. Instead, this summary provides only a preliminary discussion of different embodiments and the corresponding points of novelty over the prior art and known art. For further details and / or possible aspects of the disclosed and claimed subject matter and embodiments, readers are directed to the detailed description section of this disclosure, which will be discussed further below.

[0024] The order in which the various steps described herein are discussed is for clarity only. In general, the steps disclosed herein can be performed in any preferred order. Furthermore, each of the various features, technologies, and structures disclosed herein may be described in various places within this disclosure, but each concept is intended to be performed independently of or in appropriate combination with one another. Thus, the disclosed and claimed subject matter can be embodied and seen in many different ways. [Modes for carrying out the invention]

[0025] For the purpose of facilitating an understanding of what is claimed, the embodiments are described herein with reference to the illustrated embodiments and in a specific language. Nevertheless, it will be understood that no limitation of the scope of what is claimed is intended thereby, and that changes and further modifications as well as further applications of the principle thereof, as shown herein, are intended to occur as would ordinarily to those skilled in the art relating to this disclosure.

[0026] All documents cited herein, including publications, patent applications, and patents, are incorporated herein by reference as if they were included in their entirety, with each reference individually and specifically indicated as being incorporated by reference.

[0027] The use of the terms “a,” “an,” and “the” and similar reference terms in the context describing the disclosed and claimed subject matter (particularly in the context of the following claims) shall be interpreted as encompassing both singular and plural unless otherwise indicated herein or clearly contradicted by the context. The terms “comprising,” “having,” “including,” and “containing” shall be interpreted as non-restrictive terms (i.e., “including, but not limited to”) unless otherwise indicated herein. The descriptions of value ranges herein are intended solely as a shorthand method for referring to each distinct value that falls within the range individually, unless otherwise indicated herein, and each distinct value is incorporated herein as it would be if described individually herein. All methods described herein may be performed in any appropriate order unless otherwise indicated herein or clearly contradicted by the context. Any use of examples or illustrative language provided herein (e.g., "etc.") is intended solely to better clarify the subject matter being disclosed and claimed, and, unless otherwise asserted, does not limit its scope. Nothing in this specification should be construed as indicating that any unclaimed element is essential for the implementation of the disclosed and claimed subject matter.

[0028] Preferred embodiments of the disclosed and claimed subject matter, including the best modes known to the inventors for carrying out the disclosed and claimed subject matter, are described herein. Variations of those preferred embodiments will be apparent to those skilled in the art by reading the foregoing description. The inventors of the present invention anticipate that those skilled in the art will appropriately adopt such variations, and they intend that the disclosed and claimed subject matter will be carried out in ways other than those specifically described herein. Accordingly, the disclosed and claimed subject matter includes all modifications and equivalents of the subject matter described in the claims appended herein, as permitted by applicable law. Furthermore, any combination of the above elements in all possible variations thereof is encompassed by the disclosed and claimed subject matter unless otherwise indicated herein or unless it is clearly inconsistent with the context.

[0029] For ease of reference, “microelectronic devices” or “semiconductor substrates” refer to semiconductor wafers, flat panel displays, phase-change memory devices, solar panels, and other products manufactured for use in microelectronics, integrated circuits, or computer chip applications, including solar substrates, photovoltaics, and microelectromechanical systems (MEMS). Examples of 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 may be doped or undoped. The term “microelectronic devices” should be understood not as limiting, but as including substrates that ultimately become microelectronic devices or microelectronic assemblies. Microelectronic devices or semiconductor substrates may include low dielectric constant dielectric materials, barrier materials, and one or more passivation layers such as AlCu alloys, metals such as W, Ti, and TiN, polyimide, or polybenzoxazole, as well as other materials on the same.

[0030] In this document, "low dielectric material" refers to any material used as a dielectric material in layered microelectronic devices, wherein the dielectric constant is less than approximately 3.5. Preferably, low dielectric materials include low-polarity materials such as silicon-containing organic polymers, silicon-containing hybrid organic / inorganic materials, organosilicate glass (OSG), TEOS, fluorosilicate glass (FSG), silicon dioxide, and carbon-doped oxide (CDO) glass. It should be understood that low dielectric materials can have a variety of densities and porosities.

[0031] As defined in this book, the term “barrier material” refers to any material used in the art to seal the interconnections of metal wires, such as copper, and to minimize the diffusion of the metal, such as copper, into a dielectric material. Preferred barrier layer materials include tantalum, titanium, ruthenium, hafnium, and refractory metals, as well as their nitrides and silicides.

[0032] In this specification, “substantially free” is defined as less than about 1% by mass, more preferably less than about 0.5% by mass, and most preferably less than about 0.2% by mass. “Substantially free” also includes about 0.0% by mass. The term “free of” means 0.0% by mass.

[0033] In some embodiments, when describing a composition that is substantially water-free, it is intended that water may be added along with the components, but the amount of water added along with the components should be less than about 0.1% by mass, and the water may be absorbed from the atmosphere during production and use. In other embodiments, "substantially water-free" may mean a composition in which water is not present in any more than about 1% by mass. In other embodiments, "substantially water-free" may mean a composition in which water is not present in any more than about 3% by mass.

[0034] When used in relation to a measurable numerical variable, the terms "about" or "approximately" refer to all values ​​of the variable that are greater than the indicated value and the experimental error of the indicated value (e.g., within the 95% confidence interval of the mean) or within a percentage of the indicated value (e.g., ±10%, ±5%).

[0035] In all such compositions, certain components of the composition are discussed in relation to a mass percentage range including zero, but such components may or may not be present in various specific embodiments of the composition, and if present, they may be present at a low concentration of as little as 0.001 mass percent based on the total mass of the composition in which they are used. Note that, unless otherwise indicated, all defined mass percentages of components are relative to the total mass of the composition. Furthermore, unless otherwise indicated, all mass percentages are "neat," meaning they do not include aqueous solutions present when they are added to the composition. References to "at least one" can be replaced with "one or more." "At least one" and / or "one or more" include "at least two" or "two or more" and "at least three" and "three or more," etc.

[0036] The composition of the present invention comprises one or more organic solvents, one or more alkanolamines and / or one or more amines; one or more corrosion inhibitors; and optionally one or more secondary solvents.

[0037] In further embodiments, the compositions of the present invention essentially consist of (i) one or more alkanolamines, (ii) one or more ether alcohol solvents or aromatic alcohols, and (iii) one or more corrosion inhibitors, at various concentrations. In such embodiments, the total amount of (i), (ii), and (iii) is not equal to 100% by mass and may include other components (e.g., additional solvents (one or more), including water, general additives, and / or impurities) that do not significantly alter the effect of the cleaning composition.

[0038] In another embodiment, the composition of the present invention comprises, at various concentrations, (i) one or more alkanolamines, (ii) one or more ether alcohol solvents or aromatic alcohols, and (iii) one or more corrosion inhibitors. In such embodiments, the total amount of (i), (ii), and (iii) is equal to about 100% by mass, but other small and / or trace amounts of impurities may be included, present in amounts so small as not to significantly alter the effect of the composition. For example, in one such embodiment, the cleaning composition may contain 2% by mass or less of impurities. In another embodiment, the cleaning composition may contain 1% by mass or less of impurities. In a further embodiment, the cleaning composition may contain 0.05% by mass or less of impurities.

[0039] When the compositions of the present invention described herein are referred to in units of mass%, it is understood that in no case shall the mass percentage of all components, including non-essential components such as impurities, exceed 100% by mass. In compositions "essentially consisting of" the components described herein, such components may be added up to or less than 100% by mass of the composition. If the components total less than 100% by mass, such compositions may contain some small amounts of non-essential contaminants or impurities. For example, in one such embodiment, the composition may contain 2% by mass or less of impurities. In another embodiment, the rinse may contain 1% by mass or less of impurities. In a further embodiment, the composition may contain 0.05% by mass or less of impurities. In other such embodiments, the components may form at least 90% by mass, more preferably at least 95% by mass, more preferably at least 99% by mass, more preferably at least 99.5% by mass, and most preferably at least 99.9% by mass, and may include other components that do not significantly affect the performance of the wet etching solution. Otherwise, it is understood that, in the absence of significant non-essential impurities, the composition of all essential components will essentially be 100% by mass.

[0040] solvent

[0041] Typically, the compositions according to this disclosure comprise one or more organic solvents. One type of solvent that can be used in the compositions is an ether alcohol solvent or an aromatic ring-containing alcohol solvent, or a mixture thereof. The ether alcohol solvent may be a glycol ether or another alcohol having an ether group. One or more ether alcohol solvents, including a glycol ether solvent, can be used in the compositions. 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-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), or dipropylene glycol. Examples of alcohol ether solvents that are not glycol ethers include 3-methoxy-3-methyl-1-butanol (MMB), furfuryl alcohol, and tetrahydrofurfuryl alcohol. Examples of aromatic ring-containing alcohol solvents useful in compositions include benzyl alcohol and alkanol-substituted benzenes such as benzylethanol and benzylpropanol. Each solvent can be used alone, in mixtures of the same type, or in combination of any or all of different types.

[0042] In most applications, one or more alcohol ether solvents and / or aromatic alcohols are considered to constitute, for example, about 50% to about 90% or 55% to about 90% by mass of the composition. Other preferred embodiments of the disclosed and claimed subject matter may include about 60% to about 88% or 65% to 85% by mass of glycol ether solvents and / or aromatic alcohols. The alcohol ether solvent(s) and / or aromatic alcohols may be present in amounts that fall within the range defined by the following list of mass percentages: 50, 55, 58, 60, 62, 65, 67, 70, 72, 75, 77, 80, 82, 85, 88, and 90. Aromatic ring-containing alcohols and / or aromatic-containing alcohols may be present in the composition in amounts that fall within the range defined by the following list of mass percentages: 50, 55, 58, 60, 62, 65, 67, 70, 72, 75, 77, 80, 82, 85, 88, and 90. In other embodiments, one or more ether alcohol solvents and / or aromatic-containing alcohols constitute about 80% to about 85% by mass of the composition. In other embodiments, one or more ether alcohol solvents and / or aromatic-containing alcohols constitute about 30% to about 50% by mass of the composition.

[0043] In some embodiments, the ether alcohol solvent or aromatic ring-containing alcohol solvent may contain about 10% to about 50% of a secondary solvent. Alternatively, in some embodiments, the stripping solution may be free of or substantially free of a secondary solvent.

[0044] The secondary organic solvent alcohol can be a linear, branched, aliphatic, or aromatic alcohol. Examples of secondary alcohols that the composition may contain include methanol, ethanol, propanol, isopropyl alcohol, butanol, tert-butyl alcohol, tert-amyl alcohol, 3-methyl-3-pentanol, 1-octanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 9-hexadecen-1-ol, 1-heptadecanol, 1-octadecanol, 1-nonadecanol, 1-eicosanol, 1-heneicosanol, 1-docosanol, 13-docosen-1-ol, 1-tetracosanol, 1-hexacosanol, 1-heptacosanol, 1-octacosanol, 1-triacontanol, 1-dotriacontanol, 1-tetratriacontanol, cetearyl alcohol, propylene glycol, ethylene glycol, and glycerol.

[0045] When used, the secondary organic solvent may constitute about 0.02% to about 45%, or about 0.08% to about 38%, or about 0.1% to about 35%, or about 0.2% to about 33%, or about 0.3% to about 20% of the composition. In alternative embodiments, the secondary solvent may be present in any amount defined by endpoints selected from the following mass percent: 0.02, 0.08, 0.1, 0.2, 0.3, 0.4, 0.5, 0.7, 0.9, 1, 3, 5, 8, 10, 12, 15, 17, 20, 23, 25, 38, 30, 32, 35, 37, 40, 43, and 45.

[0046] Alkanolamine

[0047] A suitable alkanolamine has at least two carbon atoms, at least one amino substituent, and at least one hydroxyl substituent, wherein the amino and hydroxyl substituents are attached to two different carbon atoms.

[0048] In some embodiments, the alkanolamine is derived from formula (I): [ka] It is a 1,2-alkanolamine, In the formula, R 1 , R 2 and R 3 Each of these is independently selected from H, unsubstituted C1-C6 alkyl, substituted C1-C6 alkyl, branched C3-C6 alkyl, and C1-C6 alkylamino. In some embodiments, R 1 and R 2 Each is independently selected from H, C1-C4 alkyl, or C1-C4 alkylamino. In one embodiment, R 1 is -H or -CH2CH2NH2, and R 2 In another embodiment, R 1 is -CH2CH2NH2, and R 2 In another embodiment, R 1 and R 2 Both are -H. In another embodiment, R 1 and R 2 Both are -CH2CH2OH. In another embodiment, R 3 It is -CH3.

[0049] In one embodiment, the formulation of the present invention is R 1 and R 2 It contains an alkanolamine of formula (I) in which one or both are H.

[0050] In one embodiment, the formulation of the present invention is R 1 , R 2 and R 3 Alkanolamines of formula (I) where each of these is H: [ka] Includes.

[0051] In one embodiment, the formulation of the present invention is R 1 and R 2 One of them is H, and R 1 and R 2Another one is the -CH3 group, R 3 Alkanolamines of formula (I) where H: [ka] Includes.

[0052] In one embodiment, the formulation of the present invention is R 1 , R 2 and R 3 Alkanolamines of formula (I) where each of these is -CH3: [ka] Includes.

[0053] In one embodiment, the formulation of the present invention is R 1 , R 2 Each of these is hydrogen, and R 3 Alkanolamines of formula (I) where -CH3: [ka] Includes.

[0054] In one embodiment, the formulation of the present invention is R 1 and R 2 One of them is H, and R 1 and R 2 Another one is a substituted C1-C6 alkyl of the formula -CH2CH2OH, R 3 Alkanolamines of formula (I) where H: [ka] Includes.

[0055] In one embodiment, the formulation of the present invention is R 1 and R 2 Both are substituted C1-C6 alkyl groups of the formula -CH2CH2OH, and R 3 Alkanolamines of formula (I) where H: [ka] comprises.

[0056] In one embodiment, the formulation of the present invention is R 1 and R 2 one of which is H, and R 1 and R 2 the other of which is a substituted C1-C6 alkyl of the formula -CH2CH2NH2, and R 3 is H, an alkanolamine of formula (I):

Chemical formula

[0057] In one embodiment, the formulation of the present invention is R 1 and R 2 are each -CH3, and R 3 is H, an alkanolamine of formula (I):

Chemical formula

[0058] Suitable alkanolamines include ethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, N-methylisopropanolamine, N-ethylisopropanolamine, N-propylisopropanolamine, 2-aminopropan-1-ol, N-methyl-2-aminopropan-1-ol, N-ethyl-2-aminopropan-1-ol, 1-aminopropan-3-ol, N-methyl-1-aminopropan-3-ol, N-ethyl-1-aminopropan-3-ol, 1-aminobutan-2-ol, N-methyl-1-aminobutan-2-ol, N-ethyl-1-aminobutan-2-ol, 2-aminobutan-1-ol, N-methyl-2-A Minobutan-1-ol, N-ethyl-2-aminobutan-1-ol, 3-aminobutan-1-ol, N-methyl-3-aminobutan-1-ol, N-ethyl-3-aminobutan-1-ol, 1-aminobutan-4-ol, N-methyl-1-aminobutan-4-ol, N-ethyl-1-aminobutan-4-ol, 1-amino-2-methylpropane-2-ol, 2-amino-2-methylpropane-1-ol, 1-aminopentan-4-ol, 2-amino- Examples include, but are not limited to, 4-methylpentan-1-ol, 2-aminohexane-1-ol, 3-aminoheptan-4-ol, 1-aminooctan-2-ol, 5-aminooctan-4-ol, 1-aminopropane-2,3-diol, 2-aminopropane-1,3-diol, tris(oxymethyl)aminomethane, 1,2-diaminopropane-3-ol, 1,3-diaminopropane-2-ol, and 2-(2-aminoethoxy)ethanol.

[0059] The preferred level required for at least one of the alkanolamine and / or amine can be in the range of about 5% to about 50% of the composition. In some embodiments, the alkanolamine and / or amine is about 10% to about 30% of the composition. In alternative embodiments, the alkanolamine and / or amine can be present in any amount defined by an endpoint selected from the following mass percentages: 2, 5, 8, 10, 12, 15, 17, 20, 22, 25, 27, 30, 32, 35, 38, 40, 42, 45, 48, and 50.

[0060] The total mass percentage of organic solvents, which may be alcohol ether solvents and secondary solvents, and the mass percentage of alkanolamines and / or amines in the composition can be about 90% to about 99.9%. In other embodiments, the composition may contain about 55% to about 99%, or about 65% to about 98%, or about 70% to about 97%, or about 75% to about 99.9%, or about 80% to about 98%, or about 85% to about 99%, or about 85% to about 96%, or about 90% to about 97%, or about 75% to about 90% of organic solvents and alkanolamines and / or amines. In some embodiments, the mass percentage is greater than the mass percentage of alkanolamines and / or amines, and the organic solvent may be present in the composition in amounts of 20% to about 90%, or 30% to about 90%, or 50% to about 80%, or 60% to about 80%. In some embodiments, the solution may contain about 20% to about 90%, or about 55% to about 60%, or 30% to about 50%, or 35% to about 45%, or about 55% to about 75% glycol ether.

[0061] Corrosion inhibitor

[0062] The composition contains one or more, or two or more, corrosion inhibitors. Suitable corrosion inhibitors include organic corrosion inhibitors, such as aromatic hydroxyl compounds and aromatic polyhydroxyl compounds such as catechol and resorcinol; alkylcatechols such as methylcatechol, ethylcatechol, t-butylcatechol, phenol, and pyrogallol; aromatic triazoles such as benzotriazole; aminobenzotriazoles such as alkylbenzotriazole and 1-aminobenzotriazole; thiazoles such as 2-aminobenzothiazole (ABT); sugar alcohols such as glycerol, xylitol, and sorbitol; and sebacic acid, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, benzoic acid, phthalic acid, 1,2,3-benzenetricarboxylic acid, glycolic acid, lactic acid, malic acid, citric acid, acetic anhydride, phthalic anhydride, maleic anhydride, succinic anhydride, salicylic acid, and gallic acid. Examples of such compounds include, but are not limited to, carboxylic acids, gallic acid esters such as methyl gallate and propyl gallate; metal salts such as copper(II) nitrate, copper(II) bromide, copper(II) chlorate, copper(II) chloride, copper(II) fluorosilicate, copper(II) formate, copper(II) selenate, and copper(II) sulfate; organic salts of carboxyls containing the above organic compounds, and similar compounds; and chelate compounds, such as phosphoric acid-based chelate compounds including 1,2-propanediaminetetramethylenephosphonic acid and hydroxyethanephosphonic acid, carboxylic acid-based chelate compounds such as ethylenediaminetetraacetic acid and its sodium and ammonium salts, dihydroxyethylglycine and nitrilotriacetic acid, amine-based chelate compounds such as bipyridine, tetraphenylporphyrin and phenanthroline, and oxime-based chelate compounds such as dimethylglyoxime and diphenylglyoxime. In other embodiments, one or more corrosion inhibitors may include one or more copper salts such as copper(II) nitrate; copper(II) bromide; copper(II) chlorate; copper(II) chloride; copper(II) fluorosilicate; copper(II) formate; and / or copper(II) sulfate alone.In yet another embodiment, the composition may include one or more of the above-mentioned organic corrosion inhibitors and / or chelating compounds, as well as one or more copper salts. In yet another embodiment, one or more corrosion inhibitors may be copper(II) nitrate (e.g., copper(II) nitrate hemi (pentahydrate - oxidizing agent) with about 42% NADA and about 26.3% NADA / 1N), copper(II) bromide, copper(II) chlorate, copper(II) chloride, copper(II) fluorosilicate, copper(II) formate, copper(II) selenite, copper(II) sulfate, and / or resorcinol. In yet another embodiment, the corrosion inhibitor may include copper(II) nitrate (i.e., NADA or NADA / 1N) and resorcinol.

[0063] In other embodiments, the corrosion inhibitor is an aliphatic or aromatic polyhydroxyl compound, such as ethylene glycol; 1,2-propanediol (propylene glycol); 1,3-propanediol, 1,2,3-propanetriol; 1,2-butanediol; 1,3-propanediol; 2,3-butanediol; 1,4-butanediol; 1,2,3-butanetriol; 1,2,4-butanetriol; 1,2-pentanediol; 1,3-pentanediol; 1,4-pentanediol Lu; 2,3-pentanediol; 2,4-pentanediol; 3,4-pentanediol; 1,2,3-pentanetriol; 1,2,4-pentanetriol; 1,2,5-pentanetriol; 1,3,5-pentanetriol; etohexadiol; p-methane-3,8-polyhydroxyl compound; 2-methyl-2,4-pentanediol; 2,2-dimethyl-1,3-propanediol; glycerin; tolylnetylpropane; xylitol; arabitol; 1,2- or 1,3 -Cyclopentanediol; 1,2- or 1,3-cyclohexanediol; 2,3-norbornanediol; 1,8-octanediol; 1,2-cyclohexanedimethanol; 1,3-cyclohexanedimethanol; 1,4-cyclohexanedimethanol; 2,2,4-trimethyl-1,3-pentanediol; hydroxypivalylhydroxypivalate; 2-methyl-1,3-propanediol; 2-butyl-2-ethyl-1,3-propanediol; 2-ethyl-2-isobutyl This may include -1,3-propanediol; 1,6-hexanediol; 2,2,4,4-tetramethyl-1,6-hexanediol; 1,10-decanediol; 1,4-benzenedimethanol; hydrogenated bisphenol A; 1,1,1-trimethylolpropane; 1,1,1-trimethylolethane; pentaerythritol; erythritol; treitol; dipentaerythritol; sorbitol; and similar compounds, as well as combinations of two or more of the aforementioned polyhydroxyl compounds.

[0064] In some embodiments, one or more organic corrosion inhibitors selected from the above list may be present in the useful composition at levels ranging from about 0.005% by mass to about 10% by mass. In one embodiment, the solution may contain about 0.25% by mass to about 5% by mass, or 0.1% by mass to about 4% by mass, or 0.25% by mass to about 2% by mass. One or more corrosion inhibitors may be present in any amount defined by an endpoint selected from the following mass percent: 0.005, 0.02, 0.08, 0.1, 0.2, 0.25, 0.3, 0.4, 0.5, 0.7, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. The first and second corrosion inhibitors can be used in the composition. Preferred first and / or second corrosion inhibitors are copper nitrates (e.g., NADA or NADA / 1N) and resorcinol. The disclosed and claimed subject matter includes a method for treating a semiconductor substrate with a composition to remove a photoresist without damaging any films, layers, metals, or other structures present on the substrate, including passivation layers such as PI or PBO. A preferred temperature for treating the semiconductor substrate is about 50°C. For most applications, temperatures of about 45°C to about 85°C or about 50°C to about 75°C are useful. Lower contact temperatures are appropriate for specific applications where the substrate is sensitive or a longer removal time is required. For example, when reworking a substrate, it may be appropriate to maintain the stripping solution at a temperature of at least 20°C for a longer period of time to remove the photoresist and avoid damaging the substrate.

[0065] As described above, in one embodiment, one or more corrosion inhibitors constitute about 0.005% to about 10% by mass of the composition. In a further embodiment of this embodiment, one or more corrosion inhibitors constitute about 0.25% to about 5% by mass of the composition. In a further embodiment of this embodiment, one or more corrosion inhibitors constitute about 0.1% to about 4% by mass of the composition. In a further embodiment of this embodiment, one or more corrosion inhibitors constitute about 0.25% to about 2% by mass of the composition. In a further embodiment of this embodiment, one or more corrosion inhibitors constitute about 0.005% by mass of the composition. In a further embodiment of this embodiment, one or more corrosion inhibitors constitute about 0.02% by mass of the composition. In a further embodiment of this embodiment, one or more corrosion inhibitors constitute about 0.08% by mass of the composition. In a further embodiment of this embodiment, one or more corrosion inhibitors constitute about 0.1% by mass of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors constitute about 0.2% by mass of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors constitute about 0.25% by mass of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors constitute about 0.3% by mass of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors constitute about 0.4% by mass of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors constitute about 0.5% by mass of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors constitute about 0.7% by mass of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors constitute about 0.9% by mass of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors constitute about 1% by mass of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors constitute about 2% by mass of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors constitute about 3% by mass of the composition. In a further embodiment of this model, one or more corrosion inhibitors constitute about 4% by mass of the composition. In a further embodiment of this model, one or more corrosion inhibitors constitute about 5% by mass of the composition.In a further aspect of this embodiment, one or more corrosion inhibitors constitute about 6% by mass of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors constitute about 7% by mass of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors constitute about 8% by mass of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors constitute about 9% by mass of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors constitute about 10% by mass of the composition.

[0066] In another embodiment, one or more corrosion inhibitors comprise catechol. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 0.5% to about 1.5% by mass of catechol. In a further aspect of this embodiment, one or more corrosion inhibitors essentially consist of catechol. In a further aspect of this embodiment, one or more corrosion inhibitors essentially consist of about 0.5% to about 1.5% by mass of catechol. In a further aspect of this embodiment, one or more corrosion inhibitors consist of catechol. In a further aspect of this embodiment, one or more corrosion inhibitors consist of about 0.5% to about 1.5% by mass of catechol.

[0067] In another embodiment, one or more corrosion inhibitors comprise resorcinol. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 0.5% to about 1.5% by mass of resorcinol. In a further aspect of this embodiment, one or more corrosion inhibitors essentially consist of resorcinol. In a further aspect of this embodiment, one or more corrosion inhibitors essentially consist of about 0.5% to about 1.5% by mass of resorcinol. In a further aspect of this embodiment, one or more corrosion inhibitors consist of resorcinol. In a further aspect of this embodiment, one or more corrosion inhibitors consist of about 0.5% to about 1.5% by mass of resorcinol

[0068] In another embodiment, one or more corrosion inhibitors comprise glycerol. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 0.5% to about 1.5% by mass of glycerol. In a further aspect of this embodiment, one or more corrosion inhibitors essentially consist of glycerol. In a further aspect of this embodiment, one or more corrosion inhibitors essentially consist of about 0.5% to about 1.5% by mass of glycerol. In a further aspect of this embodiment, one or more corrosion inhibitors consist of about 0.5% to about 1.5% by mass of glycerol.

[0069] In another embodiment, one or more corrosion inhibitors comprise sebaciic acid. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 0.5% to about 1.5% by mass of sebaciic acid. In a further aspect of this embodiment, one or more corrosion inhibitors essentially consist of sebaciic acid. In a further aspect of this embodiment, one or more corrosion inhibitors essentially consist of about 0.5% to about 1.5% by mass of sebaciic acid. In a further aspect of this embodiment, one or more corrosion inhibitors consist of sebaciic acid. In a further aspect of this embodiment, one or more corrosion inhibitors consist of about 0.5% to about 1.5% by mass of sebaciic acid.

[0070] In another embodiment, one or more corrosion inhibitors comprise a copper nitrate and resorcinol. In a further aspect of this embodiment, one or more corrosion inhibitors essentially consist of a copper nitrate and resorcinol. In a further aspect of this embodiment, one or more corrosion inhibitors consist of a copper nitrate and resorcinol.

[0071] In another embodiment, one or more corrosion inhibitors comprise a copper nitrate. In a further aspect of this embodiment, one or more corrosion inhibitors essentially consist of a copper nitrate. In a further aspect of this embodiment, one or more corrosion inhibitors consist of copper nitrate.

[0072] When immersing the substrate, stirring the composition further facilitates the removal of the photoresist. Stirring can be achieved through mechanical stirring, circulation, or by bubbling an inert gas through the composition. Once the desired amount of photoresist has been removed, the substrate is removed from contact with the stripping solution and rinsed with water or alcohol. Deionized water is the preferred form of water, and isopropanol (IPA) is the preferred form of alcohol, although rinsing with alcohol is optional. For substrates with easily oxidizable components, rinsing under an inert atmosphere is preferable. The preferred stripping solution according to this disclosure has improved loading capacities for photoresist material compared to current commercial products, allowing a given volume of stripping solution to process more substrates.

[0073] The stripping solution provided in this disclosure can be used to remove polymer resist material present in single-layer or certain types of double-layer resists. For example, a double-layer resist typically has a first inorganic layer covered with a second polymer layer, or it may have two polymer layers. By using the method 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 double-layer structure consisting of a first inorganic layer and a second or outer polymer layer. Furthermore, two polymer layers can be effectively removed from a wafer having a double-layer film consisting of two polymer layers.

[0074] This disclosure describes chemical solutions used for removing thick and thin-film photoresists. For advanced packaging applications of semiconductor devices, thick-film photoresists may be resists of about 5 μm to about 100 μm or more, or about 15 μm to 100 μm, or about 20 μm to about 100 μm. In other cases, the chemical solutions can be used to remove photoresists of about 1 μm to about 100 μm or more, or about 2 μm to 100 μm, or about 3 μm to about 100 μm. In one embodiment, the described solution contains glycol ether, monoethanolamine (MEA), and at least two corrosion inhibitors. The stripping solution is also, or alternatively, substantially free of strong bases (e.g., quaternary ammonium hydroxide, KOH) and / or water.

[0075] Some embodiments of the compositions of the present invention may substantially omit, or be free of, one or more of the following in any combination (these terms are as defined above): nitrogen-containing solvents, bischoline salts, tricholine salts, oxoammonium compounds, hydroxylamines and their derivatives, hydrogen peroxide, oxidizing agents, inorganic acids, inorganic bases, metal hydroxides, NMPs, surfactants, metal-containing compounds, and any combination thereof. In other embodiments, the compositions will substantially omit (or be free of) sodium, and / or calcium, and / or aminocarboxylic acids, and / or alcohols, and / or ethylenediamine, and / or ethyllentriamine, and / or thiophenol. In some embodiments, the compositions disclosed herein are formulated to substantially omit, or be free of, at least one of the following chemical compounds: alkylthiols and organosilanes. In some embodiments, the compositions disclosed herein are formulated to substantially omit, or be free of, one or more of the following halide-containing compounds, for example, it may substantially omit, or be free of one or more of the following fluoride, bromine, chlorine, or iodine-containing compounds. In other embodiments, the composition may be substantially free of or may not contain sulfonic acid and / or phosphoric acid and / or sulfuric acid and / or nitric acid and / or hydrochloric acid. In other embodiments, the composition may be substantially free of or may not contain sulfates and / or nitrates and / or sulfites and / or nitrites. In other embodiments, the composition may be substantially free of or may not contain ethyldiamine, 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 and / or silane-containing compounds and / or phosphorus-containing compounds. Some embodiments may be substantially free of or may not contain surfactants. Some embodiments may be substantially free of or may not contain amphoteric salts and / or cationic surfactants and / or anionic surfactants and / or zwitterionic surfactants and / or nonionic surfactants.Some embodiments may substantially omit or be deficient in imidisoles and / or anhydrides. Some embodiments may substantially omit or be deficient in pyrrolidone and / or acetamide. Some embodiments may substantially omit or be deficient in any amine (other than alkanolamines). Some embodiments may substantially omit or be deficient in peroxy compounds and / or peroxides and / or persulfates and / or percarbonates, as well as their acids and salts. Some embodiments may substantially omit or be deficient in iodates and / or perboric acid and / or percarbonates and / or peroxides and / or cerium compounds and / or cyanides and / or periodic acid and / or ammonium molybdate and / or ammonia and / or abrasives. Components that may be deficient in a composition may be any combination of components, as all combinations are described herein.

[0076] The compositions of the disclosed and claimed subject matter may also include one or more of the following additives: dyes and biocides. The additives(s) may be added in amounts typically up to about 5% by mass of the total composition, such that they do not adversely affect the performance of the composition. In other embodiments, the compositions may be substantially free of, or not contain, dyes, biocides, and / or other additives. [Examples]

[0077] Examples

[0078] Herein, we refer to more specific embodiments of the present disclosure and experimental results supporting such embodiments. These examples are provided below to more fully illustrate the disclosed subject matter and should not be construed as limiting the disclosed subject matter in any way.

[0079] It will be apparent to those skilled in the art that various modifications and variations are possible in the disclosed subject matter and the specific examples shown herein without departing from the intent or scope of the disclosed subject matter. Accordingly, the disclosed subject matter, including the examples shown below, is intended to cover modifications and variations of the disclosed subject matter that fall within the scope of any claim and its equivalents.

[0080] Materials and methods

[0081] All materials used in this patent were purchased and / or made available from Sigma Aldrich and used in the formulation as received.

[0082] The resist cleaning performance and compatibility with polyimide (PI) or polybenzoxazole (PBO) were investigated using an optical microscope and a scanning electron microscope. The etching rate of copper was determined by measuring the film thickness before and after processing using a 4-probe RESMAP.

[0083] The following abbreviations are used for the various compositions in the table below. [Table 1]

[0084] In this example, various stripping compositions (examples and comparative examples) containing the formulations specified in the table below were tested for their ability to remove photoresist from semiconductor wafer samples. The semiconductor wafer coupon-sized samples were silicon wafers plated with Cu pillars and Sn / Ag solder caps with a thick layer of spin-on photoresist on top of them. Photoresist removal was performed using a beaker immersion process. The photoresist on the test coupon was a positive-type spin-on photoresist. Other test coupons had a polyimide (PI) passivation layer on top of them. Still other test coupons had a polybenzoxazole (PBO) passivation layer on top of them.

[0085] Table 1 lists the results of tests conducted on NMP regarding PI / PBO compatibility and photoresist stripping effect. The test results reported in Table 1 relate to photoresist removal from photoresist coupons and compatibility with separate coupons, each having either a PBO passivation layer or a PI passivation layer, under specified process conditions (temperature and time). [Table 2] [Table 3] [Table 4] [Table 5] [Table 6] [Table 7] [Table 8] [Table 9] [Table 10] [Table 11]

[0086] Analysis of Example Formulations

[0087] Analysis 1A: Resist cleaning performance

[0088] Tables 11-14 list various stripping compositions of the present invention and comparative examples tested using a semiconductor wafer with a CR4000 positive spin-on photoresist with a thickness of 50 μm, a Sn / Ag solder cap and plated Cu pillar, and an immersion step. In the immersion step, a coupon-sized sample of the semiconductor wafer was processed in a beaker. 100.0 grams of the stripping composition was placed in the beaker and heated to a target temperature of 50°C or 60°C. Once the stripping composition reached the processing temperature, the coupon was placed in a holder in the beaker and gently stirred with a starburst. The temperature was maintained at the processing temperature while in contact with the coupon during the washing step. After the predetermined processing, the coupon was removed from the beaker, washed with deionized water and IPA, and dried with a nitrogen stream.

[0089] Resist removal is defined as "clean" if all resist is removed from the wafer coupon surface, "almost clean" if at least 95% of the resist is removed from the surface, and "partially clean" if approximately 80% of the resist is removed from the surface. The NMP comparative example was unable to completely remove the resist after 15 minutes at 80°C, while the other exemplary compositions were able to completely remove the resist after 15 minutes at 50°C or 60°C, except for Examples 13, 19, and 25, where the coupon was partially clean after 15 minutes.

[0090] Analysis 1B: PI / PBO compatibility

[0091] Tables 11-14 also show the results of evaluations using low-temperature cured polyimide (PI) and polybenzoxazole (PBO) films. These tests were performed using semiconductor wafers patterned with cured PI or cured PBO films. In the immersion step, coupon-sized samples of semiconductor wafers were processed in a beaker. 100 grams of the release composition were placed in the beaker and heated to the target temperature. Once the release composition reached the processing temperature, the coupon was placed in a holder in the beaker and gently stirred with a starburst. The temperature was maintained at the processing temperature throughout the process. After 60 or 120 minutes of processing, the coupon was removed from the beaker, rinsed with deionized water and IPA, and dried under a nitrogen stream.

[0092] The polyimide film patterns were monitored using an optical microscope and a scanning electron microscope before and after treatment of each tested coupon. The presence of cracks was considered an indicator of poor compatibility between PI and PBO. Factors affecting the compatibility between PI and PBO include the solvent and alkanolamines or amines. Slight cracks were observed in the NMP-treated PI after 120 minutes. Formulations 7-14, 18, 19, 24 and 25 showed good compatibility with PI after 120 minutes, while formulations 1-6 and 20-23 showed poor compatibility with PI after 120 minutes. The comparative examples and formulations 1-25 of the present invention all showed good compatibility with PBO after 120 minutes. [Table 12] [Table 13] [Table 14] [Table 15]

[0093] Analysis 2: Corrosion inhibitors and etching rates

[0094] Tables 15-18 list various inventive and comparative stripping compositions tested for Analysis 2 using an immersion step to measure the Cu etching rate. The tests were performed using blanket Cu wafers. In the immersion step, three coupon-sized samples of semiconductor wafers were processed in a beaker. 100 grams of stripping composition were placed in the beaker and heated to the target temperature. Once the stripping composition reached the target temperature, the three coupons were placed in a holder in the beaker and gently stirred with a starburst. The temperature was maintained at the processing temperature throughout the process. After a total processing time of 15 minutes, the coupons were removed from the beaker, rinsed with deionized water and IPA, and dried under a nitrogen stream.

[0095] Using RESMAP, the thickness of the Cu layer was measured before and after each coupon treatment, and the change in thickness and etch rate were calculated. Tables 15 and 16 examine the individual corrosion inhibitors by monitoring the Cu etching rate. 0.5% cysteine ​​(formulation 31) resulted in the lowest Cu etching rate. 0.5% 8-hydroquinoline (formulation 28) and 0.5% glycerol (formulation 33) did not affect Cu protection. 0.5% catechol (formulation 29), resorcinol (formulation 27), and 2-aminobenzotriazole (formulation 30) reduced the Cu etching rate by 50% compared to formulation 27, which did not contain any corrosion inhibitor, while D-sorbitol (formulation 32) and sebacic acid (formulation 16) reduced the Cu etching rate to some extent. 1% glycerol (formulation 8) significantly reduced the Cu etching rate. Resorcinol reduced the Cu etching rate when its concentration was increased from 0.5% to 1.5% (formulations 34, 35, and 15), but did not significantly reduce the Cu etching rate even when the concentration was further increased from 1.5% to 3% (formulations 35-38). Table 17 shows the effects of combinations of NADA with other corrosion inhibitors by monitoring the Cu etching rate. Combinations of NADA with resorcinol, catechol, and sebacic acid each showed a significant reduction in the Cu etching rate (formulations 40, 42, and 46). Combinations of NADA with D-sorbitol and glycerol did not affect copper protection (formulations 44, 45). The combination of NADA with aminobenzotriazole (formulation 43) showed an increase in the Cu etching rate, while 8-hydroquinoline (formulation 41) showed a slight decrease in the Cu etching rate. Table 18 shows that combinations of corrosion inhibitors without NADA solution reduced the Cu etching rate. [Table 16] [Table 17] [Table 18] [Table 19]

[0096] Summary of results

[0097] DB is the fastest stripping solvent for CR4000 removal among all solvents tested with 15% MEA added. At a 30% MEA level, alkanolamines showed better resist cleaning performance than amines at 10 minutes, and CR4000 could be washed away in 10 minutes regardless of the solvent used.

[0098] MMB and water showed better compatibility with PI than DB solvents.

[0099] When 15% amine or alkanolamine was added, all formulations showed good compatibility with PI after 120 minutes. In general, higher MEA concentrations resulted in better resist exfoliation but worse compatibility with PI.

[0100] Cysteine ​​showed good performance as a single corrosion inhibitor to reduce the etching rate of Cu.

[0101] Resorcinol reduced the Cu etching rate when its concentration was increased from 0.5% to 1.5%, but further increasing the concentration from 1.5% to 3% did not significantly reduce the Cu etching rate.

[0102] The combinations of NADA with resorcinol, catechol, and sebacic acid each showed a significant reduction in the Cu etching rate. For example, NADA, catechol, resorcinol, and 2-aminobenzotriazole reduced the Cu etching rate by 50% compared to a control without corrosion inhibitors.

[0103] Several combinations of corrosion inhibitors (e.g., resorcinol and sebacic acid) showed copper etching rates approximately seven times lower than controls without corrosion inhibitors.

[0104] While the disclosed and claimed subject matter has been described and illustrated with a certain degree of specificity, the disclosure is merely illustrative, and it is understood that numerous changes in the conditions and order of the steps can be left to those skilled in the art without departing from the intent and scope of the disclosed and claimed subject matter. Therefore, it will be understood that various modifications can be made and equivalents can be used in place of the elements without departing from the scope of the disclosed and claimed subject matter. Furthermore, many modifications can be made to adapt specific circumstances or materials to the teachings of the disclosed and claimed subject matter without departing from its essential scope. In addition, numerical values ​​specified in the detailed description shall be interpreted as both exact values ​​and approximations being explicitly specified.

Claims

1. 1. A cleaning composition comprising: (i) one or more alkanolamines; (ii) one or more ether alcohol solvents or aromatic-containing alcohols, and (iii) one or more corrosion inhibitors A cleaning composition comprising:

2. 1. A cleaning composition comprising: (i) one or more alkanolamines; (ii) one or more ether alcohol solvents or aromatic-containing alcohols, and (iii) one or more corrosion inhibitors A cleaning composition consisting essentially of:

3. 1. A cleaning composition comprising: (i) one or more alkanolamines; (ii) one or more ether alcohol solvents or aromatic-containing alcohols, and (iii) one or more corrosion inhibitors A cleaning composition comprising:

4. The one or more alkanolamines are of formula (I): 【Chemistry 1】 and a 1,2-alkanolamine of the formula: R １ , R ２ and R ３ are H, unsubstituted C, １ -C ６ Alkyl, substituted C １ -C ６ Alkyl, branched C ３ -C ６ Alkyl and C １ -C ６ alkylamino; The composition according to any one of claims 1 to 3.

5. The composition of claim 4, wherein the one or more alkanolamines comprise a 1,2-alkanolamine.

6. The composition of claim 4, wherein the composition comprises about 5% to 50% by weight of a 1,2-alkanolamine.

7. The composition of claim 4, wherein the composition comprises about 10% to 40% by weight of a 1,2-alkanolamine.

8. The composition of claim 4, wherein the composition comprises about 15% to 35% by weight of a 1,2-alkanolamine.

9. The composition of claim 4, wherein the composition comprises about 20% to 30% by weight of a 1,2-alkanolamine.

10. The composition of claim 4, wherein the composition comprises about 15% to 20% by weight of a 1,2-alkanolamine.

11. The composition of claim 4, wherein the composition comprises about 10% to 20% by weight of a 1,2-alkanolamine.

12. The composition of claim 4, wherein the composition comprises about 10% by weight of a 1,2-alkanolamine.

13. The composition of claim 4, wherein the composition comprises about 15% by weight of a 1,2-alkanolamine.

14. The composition of claim 4, wherein the composition comprises about 20% by weight of a 1,2-alkanolamine.

15. The composition of claim 4, wherein the composition comprises about 25% by weight of a 1,2-alkanolamine.

16. The composition of claim 4, wherein the composition comprises about 30% by weight of a 1,2-alkanolamine.

17. the one or more alkanolamines 【Chemistry 2】 The composition of claim 4 comprising:

18. The composition comprises about 15% by weight of 【Transformation 3】 The composition of claim 4 comprising:

19. The composition comprises about 30% by weight of 【Chemistry 4】 The composition of claim 4 comprising:

20. the one or more alkanolamines 【Transformation 5】 The composition of claim 4 comprising:

21. The composition comprises about 15% by weight of 【Transformation 6】 The composition of claim 4 comprising:

22. The composition comprises about 30% by weight of 【Transformation 7】 The composition of claim 4 comprising:

23. the one or more alkanolamines 【Transformation 8】 The composition of claim 4 comprising:

24. The composition comprises about 15% by weight of 【Chemistry 9】 The composition of claim 4 comprising:

25. The composition comprises about 30% by weight of 【Chemistry 10】 The composition of claim 4 comprising:

26. the one or more alkanolamines 【Chemistry 11】 The composition of claim 4 comprising:

27. The composition comprises about 15% by weight of 【Chemistry 12】 The composition of claim 4 comprising:

28. The composition comprises about 30% by weight of 【Chemistry 13】 The composition of claim 4 comprising:

29. the one or more alkanolamines 【Chemistry 14】 The composition of claim 4 comprising:

30. The composition comprises about 15% by weight of 【Chemistry 15】 The composition of claim 4 comprising:

31. The composition comprises about 30% by weight of 【Chemistry 16】 The composition of claim 4 comprising:

32. the one or more alkanolamines 【Chemistry 17】 The composition of claim 4 comprising:

33. The composition comprises about 15% by weight of [Chemistry 18] The composition of claim 4 comprising:

34. The composition comprises about 30% by weight of 【Chemistry 19】 The composition of claim 4 comprising:

35. the one or more alkanolamines 【Chemistry 20】 The composition of claim 4 comprising:

36. The composition comprises about 15% by weight of 【Chemistry 21】 The composition of claim 4 comprising:

37. The composition comprises about 30% by weight of 【Chemistry 22】 The composition of claim 4 comprising:

38. the one or more alkanolamines 【Chemistry 23】 The composition of claim 4 comprising:

39. The composition comprises about 15% by weight of 【Chemistry 24】 The composition of claim 4 comprising:

40. The composition comprises about 30% by weight of 【Chemistry 25】 The composition of claim 4 comprising:

41. the one or more alkanolamines may be selected from the group consisting of ethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, N-methylisopropanolamine, N-ethylisopropanolamine, N-propylisopropanolamine, 2-aminopropan-1-ol, N-methyl-2-aminopropan-1-ol, N-ethyl-2-aminopropan-1-ol, 1-aminopropan-3-ol, N-methyl-1-aminopropan-3-ol, N-ethyl-1-aminopropan-3-ol, 1-aminobutan-2-ol, N-methyl-1-aminobutan-2-ol, N-ethyl-1-aminobutan-2-ol, 2-aminobutan-1-ol, N-methyl-2-aminobutan -1-ol, N-ethyl-2-aminobutan-1-ol, 3-aminobutan-1-ol, N-methyl-3-aminobutan-1-ol, N-ethyl-3-aminobutan-1-ol, 1-aminobutan-4-ol, N-methyl-1-aminobutan-4-ol, N-ethyl-1-aminobutan-4-ol, 1-amino-2-methylpropan-2-ol, 2-amino-2-methylpropan-1-ol, 1-aminopentan-4-ol, 2-amino-4-methylpentane 5. The composition of claim 1, further comprising one or more of the following: 1,2-diaminopropan-3-ol, 2-aminohexan-1-ol, 3-aminoheptan-4-ol, 1-aminooctan-2-ol, 5-aminooctan-4-ol, 1-aminopropane-2,3-diol, 2-aminopropane-1,3-diol, tris(oxymethyl)aminomethane, 1,2-diaminopropan-3-ol, 1,3-diaminopropan-2-ol, and 2-(2-aminoethoxy)ethanol.

42. 5. The composition of any of claims 1 to 4, wherein the one or more ether alcohol solvents or aromatic-containing alcohols comprise one or more of 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-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), or dipropylene glycol, 3-methoxy-3-methyl-1-butanol (MMB), furfuryl alcohol, tetrahydrofurfuryl alcohol, benzyl alcohol, benzyl ethanol, and benzyl propanol.

43. The composition of any of claims 1 to 4, wherein the one or more ether alcohol solvents or aromatic-containing alcohols comprise one or more glycol ethers.

44. The composition of any of claims 1 to 4, wherein the one or more ether alcohol solvents or aromatic-containing alcohols comprise one or more alcohols having an ether group.

45. The composition of any of claims 1 to 4, wherein the one or more ether alcohol solvents or aromatic-containing alcohols comprise one or more alkanol-substituted benzenes.

46. The composition of any of claims 1 to 4, wherein the one or more ether alcohol solvents or aromatic-containing alcohols comprise from about 50% to about 90% by weight of the composition.

47. The composition of any of claims 1 to 4, wherein the one or more ether alcohol solvents or aromatic-containing alcohols comprise from about 55% to about 90% by weight of the composition.

48. The composition of any of claims 1 to 4, wherein the one or more ether alcohol solvents or aromatic-containing alcohols comprise from about 60% to about 88% by weight of the composition.

49. The composition of any of claims 1 to 4, wherein the one or more ether alcohol solvents or aromatic-containing alcohols comprise from about 65% to about 85% by weight of the composition.

50. The composition of any of claims 1 to 4, wherein the one or more ether alcohol solvents or aromatic-containing alcohols comprise from about 80% to about 85% by weight of the composition.

51. The composition of any of claims 1 to 4, wherein the one or more ether alcohol solvents or aromatic-containing alcohols comprise from about 30% to about 50% by weight of the composition.

52. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise from about 0.005% to about 10% by weight of the composition.

53. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise from about 0.25 weight percent to about 5 weight percent of the composition.

54. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise from about 0.1 weight percent to about 4 weight percent of the composition.

55. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise from about 0.25 weight percent to about 2 weight percent of the composition.

56. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise about 0.005% by weight of the composition.

57. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise about 0.02% by weight of the composition.

58. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise about 0.08% by weight of the composition.

59. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise about 0.1% by weight of the composition.

60. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise about 0.2% by weight of the composition.

61. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise about 0.25% by weight of the composition.

62. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise about 0.3% by weight of the composition.

63. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise about 0.4% by weight of the composition.

64. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise about 0.5% by weight of the composition.

65. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise about 0.7% by weight of the composition.

66. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise about 0.9% by weight of the composition.

67. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise about 1% by weight of the composition.

68. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise about 2% by weight of the composition.

69. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise about 3% by weight of the composition.

70. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise about 4% by weight of the composition.

71. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise about 5% by weight of the composition.

72. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise about 6% by weight of the composition.

73. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise about 7% by weight of the composition.

74. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise about 8% by weight of the composition.

75. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise about 9% by weight of the composition.

76. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise about 10% by weight of the composition.

77. 5. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise aromatic hydroxyl compounds, aromatic polyhydroxyl compounds, alkyl catechols, phenols, aromatic triazoles, alkyl benzotriazoles, aminobenzotriazoles, thiazoles, sugar alcohols, carboxylic acids, and metal salts.

78. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise a metal salt.

79. The one or more corrosion inhibitors may be selected from the group consisting of catechol, resorcinol, methylcatechol, ethylcatechol, t-butylcatechol, phenol, pyrogallol, benzotriazole, 1-aminobenzotriazole, 2-aminobenzothiazole (ABT), glycerol, xylitol, sorbitol, sebacic acid, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, benzoic acid, phthalic acid, 1,2,3-benzenetricarboxylic acid, glycolic acid, lactic acid, malic acid, citric acid, acetic anhydride, phthalic anhydride, maleic anhydride, succinic anhydride, salicylic acid, gallic acid, 5. The composition of any of claims 1 to 4, comprising one or more of the following: carboxylic acid, methyl gallate and propyl gallate, copper(II) nitrate, copper(II) bromide, copper(II) chlorate, copper(II) chloride, copper(II) fluorosilicate, copper(II) formate, copper(II) selenite, copper(II) sulfate, 1,2-propanediaminetetramethylenephosphonic acid, hydroxyethanephosphonic acid, ethylenediaminetetraacetic acid and its sodium and ammonium salts, dihydroxyethylglycine, nitrilotriacetic acid, bipyridine, tetraphenylporphyrin, phenanthroline, dimethylglyoxime, and diphenylglyoxime.

80. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise catechol.

81. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise resorcinol.

82. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise glycerol.

83. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise sebacic acid.

84. 5. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise from about 0.5% to about 1.5% by weight of catechol.

85. 5. The composition of claim 1, wherein the one or more corrosion inhibitors comprises from about 0.5% to about 1.5% by weight of resorcinol.

86. 5. The composition of claim 1, wherein the one or more corrosion inhibitors comprises from about 0.5% to about 1.5% by weight of glycerol.

87. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprises from about 0.5% to about 1.5% by weight of sebacic acid.

88. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors consist essentially of catechol.

89. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors consist essentially of resorcinol.

90. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors consist essentially of glycerol.

91. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors consist essentially of sebacic acid.

92. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors consist essentially of from about 0.5% to about 1.5% by weight of catechol.

93. 5. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors consist essentially of from about 0.5% to about 1.5% by weight of resorcinol.

94. 5. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors consists essentially of from about 0.5% to about 1.5% by weight of glycerol.

95. 5. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors consist essentially of from about 0.5% to about 1.5% by weight of sebacic acid.

96. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise catechol.

97. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise resorcinol.

98. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors consist of glycerol.

99. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise sebacic acid.

100. 5. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors consist of about 0.5% to about 1.5% by weight of catechol.

101. 5. The composition of claim 1, wherein the one or more corrosion inhibitors consist of from about 0.5% to about 1.5% by weight of resorcinol.

102. 5. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors consist of about 0.5% to about 1.5% by weight of glycerol.

103. 5. The composition of claim 1, wherein the one or more corrosion inhibitors comprises from about 0.5% to about 1.5% by weight of sebacic acid.

104. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise copper nitrate and resorcinol.

105. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors consist essentially of copper nitrate salts and resorcinol.

106. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors consist of copper nitrate salts and resorcinol.

107. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise a copper nitrate salt.

108. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors consist essentially of copper nitrate salts.

109. The composition of any of claims 1 to 4, wherein the one or more corrosion inhibitors comprise a copper nitrate salt.

110. the one or more corrosion inhibitors are selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2,3-propanetriol, 1,2-butanediol, 1,3-propanediol, 2,3-butanediol, 1,4-butanediol, 1,2,3-butanetriol, 1,2,4-butanetriol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 2,3-pentanediol, 2,4-pentanediol; 3,4-pentanediol, 1,2,3-pentanetriol, 1,2,4-pentanetriol, 1,2,5-pentanetriol, 1,3,5-pentanetriol, ethohexadiol, p-methane-3,8-polyhydroxyl compounds, 2-methyl-2,4-pentanediol, 2,2-dimethyl-1,3-propanediol, glycerin, tolylmethylolpropane, xylitol, arabitol, 1,2-cyclopentanediol, 1,3-cyclopentanediol 1,2-cyclohexanediol, 1,3-cyclohexanediol, 2,3-norbornanediol, 1,8-octanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol, hydroxypivalyl hydroxypivalate, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-ethyl-2 5. The composition of claim 1, further comprising one or more of the following: 1,3-isobutyl-1,3-propanediol, 1,6-hexanediol, 2,2,4,4-tetramethyl-1,6-hexanediol, 1,10-decanediol, 1,4-benzenedimethanol, hydrogenated bisphenol A, 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, pentaerythritol, erythritol, threitol, dipentaerythritol, and sorbitol.

111. 3. The composition of claim 1 or 2, further comprising one or more secondary solvents.

112. 3. The composition of claim 1 or 2, further comprising about 10% to about 50% of a secondary solvent.

113. 3. The composition of claim 1 or 2, further comprising from about 10% to about 50% of a secondary solvent that is one or more of a straight chain aliphatic alcohol, a branched chain aliphatic alcohol, and an aromatic alcohol.

114. Methanol, ethanol, propanol, isopropyl alcohol, butanol, tert-butyl alcohol, tert-amyl alcohol, 3-methyl-3-pentanol, 1-octanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 9-hexadecen-1-ol, 1-heptadecanol, 1-octadecanol, 1-nonadecanol, 1-ethyl-1-methylpropan ...

3. The composition of claim 1 or 2, further comprising from about 10% to about 50% of a secondary solvent that is one or more of: cosanol, 1-heneicosanol, 1-docosanol, 13-docosene-1-ol, 1-tetracosanol, 1-hexacosanol, 1-heptacosanol, 1-octacosanol, 1-triacontanol, 1-dotriacontanol, 1-tetratriacontanol, cetearyl alcohol, propylene glycol, ethylene glycol, and glycerol.

115. 1. A method of using a cleaning composition, comprising: contacting a semiconductor substrate having a photoresist thereon with the composition of any of claims 1 to 114 A method comprising: