Photoresist remover

Abstract

A cleaning composition and a method of using the same are disclosed, wherein the composition comprises one or more alkanolamines, one or more ether alcohol solvents or aromatic-containing alcohols, one or more corrosion inhibitors, and optionally one or more second solvents.

Description

Technology Field

[0001] The subject matter disclosed and claimed generally relates to a composition having the ability to effectively remove photoresist from a substrate, and a method of using such composition. Background Technology

[0002] There are many stripper solutions for the removal of photoresist, such as those disclosed in US2001034313 AA and US20180143531A1. Improved stripper solution compositions are required due to the increasing demands of wafer manufacturers for enhanced performance. Along with the various materials used on substrates for various functions, strippers may come into contact with such materials; therefore, the ability to remove the stripper and compatibility with materials on the substrate that should not be removed are required. Furthermore, due to recent restrictions on solvents used in stripper formulations, such as limitations on N-methyl-2-pyrrolidone (NMP) and dimethyl sulfoxide (DMSO), new formulations with more environmentally friendly solvents are needed.

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

[0004] The composition according to the disclosed and claimed subject comprises (i) one or more organic solvents, (ii) one or more alkanolamines and / or amines, and (iii) one or more corrosion inhibitors. In a further aspect, the composition comprises (iv) one or more second solvent(s). In a further aspect of this embodiment, the disclosed and claimed chemical formulation essentially consists of (i), (ii), and (iii). In a further aspect of this embodiment, the disclosed and claimed chemical formulation essentially consists of (i), (ii), (iii), and (iv). In another aspect of this embodiment, the disclosed and claimed chemical formulation consists of (i), (ii), and (iii). In yet another aspect of this embodiment, the disclosed and claimed chemical formulation consists of (i), (ii), (iii), and (iv).

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

[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 present disclosure may contain an additional or second solvent. A preferred second solvent comprises an aliphatic alcohol. Further embodiments according to the present disclosure may contain an amine or a combination of an amine and an alkanolamine. Further embodiments according to the present disclosure further contain two types of corrosion inhibitors.

[0007] A second aspect of the present disclosure provides a method for removing photoresist from a substrate using the stripper solution described above. The 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 using a solvent, and drying the substrate.

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

[0009] In addition, the alkanolamine is a 1,2-alkanolamine of the following chemical formula:

[0010] (I)

[0011] Here, R 1 , R 2 and R 3 Each 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 is H. In another embodiment, R 1 is -CH2CH2NH2 and R 2 is -H. In another embodiment, R 1 and R 2Both are -H. In another embodiment, R 1 and R 2 Both are -CH2CH2OH. In another aspect of this embodiment, R 3 It is -CH3. .

[0012] In one embodiment, the formulation is R 1 and R 2 It includes alkanolamines of chemical formula (I) in which one or both are H.

[0013] In one embodiment, the formulation is R 1 , R 2 and R 3 Each contains an alkanolamine of chemical formula (I) in which H is present:

[0014] .

[0015] In one embodiment, the formulation is R 1 and R 2 One of them is H, and R 1 and R 2 The other one is the -CH3 group, and R 3 This includes an alkanolamine of the chemical formula (I) which is H:

[0016] .

[0017] In one embodiment, the formulation is R 1 , R 2 and R 3 Each contains an alkanolamine of chemical formula (I) that is -CH3:

[0018] .

[0019] In one embodiment, the formulation is R 1 , R 2 Each is hydrogen and R 3 This includes an alkanolamine of the chemical formula (I) which is -CH3:

[0020] .

[0021] In one embodiment, the formulation is R1 and R 2 One of them is H, and R 1 and R 2 The other one is a substituted C1-C6 alkyl of the chemical formula -CH2CH2OH, and R 3 This includes an alkanolamine of the chemical formula (I) which is H:

[0022] .

[0023] In one embodiment, the formulation is R 1 and R 2 Both of them are substituted C1-C6 alkyls of the chemical formula -CH2CH2OH, and R 3 This includes an alkanolamine of the chemical formula (I) which is H:

[0024] .

[0025] In one embodiment, the formulation is R 1 and R 2 One of them is H, and R 1 and R 2 The other one is a substituted C1-C6 alkyl of the chemical formula -CH2CH2NH2, and R 3 This includes an alkanolamine of the chemical formula (I) which is H:

[0026] .

[0027] In one embodiment, the formulation is R 1 and R 2 Each is -CH3, and R 3 This includes an alkanolamine of the chemical formula (I) which is H:

[0028] .

[0029] The subject matter disclosed and claimed additionally relates to the use and synthesis of the disclosed and claimed chemical formulation.

[0030] In another embodiment, the above-described composition comprises an additional or second solvent. A preferred second solvent comprises glycol, a polyhydroxyl compound, etc.

[0031] A third aspect of the present disclosure includes an electronic device manufactured by the disclosed novel method.

[0032] Other features and benefits of the disclosed and claimed subject matter will be apparent from the following more detailed description, taken together with an exemplary solution illustrating the principles of the disclosed and claimed subject matter.

[0033] This summary section does not specify all embodiments and / or progressively novel aspects of the disclosed and claimed subject matter. Instead, this summary provides only a preliminary discussion of corresponding points of novelty and different embodiments with respect to the prior art and known art. For additional details and / or possible aspects of the disclosed and claimed subject matter and embodiments, the reader turns to the detailed description section of the disclosure, as further discussed below.

[0034] The order of discussion of the different steps described herein is provided for clarity. In general, the steps disclosed herein may be performed in any suitable order. Furthermore, although each of the different features, techniques, gradients, etc. disclosed herein may be discussed at different locations within the disclosure, it is intended that each concept may be practiced independently of one another or appropriately combined with one another. Accordingly, the subject matter disclosed and claimed may be embodied and examined in many different ways. Specific details for implementing the invention

[0035] To facilitate understanding of the claimed, reference will now be made to the embodiments exemplified, and specific language will be used to describe them. Nevertheless, no limitation is intended on the scope of the claimed, and it will be understood that such changes and further modifications and such further applications of the principles as exemplified herein are to be considered as generally occurring to a person skilled in the art to which this disclosure relates.

[0036] All references cited herein, including publications, patent applications, and patents, are included by reference to the same extent as if each reference were indicated as being included by reference individually and specifically, and the full text thereof were presented herein.

[0037] In the context of describing the subject matter disclosed and claimed (particularly in the context of the claims below), the use of singular terms and similar referents shall be interpreted as encompassing both singular and plural forms, unless otherwise indicated herein or otherwise evident in the context. The terms “comprising,” “having,” “comprising,” and “containing” shall be interpreted as open-ended terms (i.e., meaning “comprising, but not limited thereto”) unless otherwise stated. References to ranges of values ​​in this document are intended merely to serve as a shortened method of individually referring to each individual value within the range, unless otherwise indicated herein, and each individual value is included in the specification as if individually referred to in this document. All methods described herein may be performed in any suitable order, unless otherwise indicated herein or otherwise evident in the context. Any and all examples provided herein, or the use of exemplary language (e.g., “e.g., for example”), are intended merely to better illuminate the subject matter disclosed and claimed and do not limit its scope unless otherwise stated. No language in the specification shall be interpreted as indicating any unclaimed element essential to the practice of the disclosed and claimed subject matter.

[0038] Preferred embodiments of the disclosed and claimed subject are described herein, including the best mode known to the inventors for carrying out the disclosed and claimed subject. Variations of such preferred embodiments may become apparent to a person skilled in the art upon reading the foregoing description. The inventors expect that a person skilled in the art will make appropriate use of such variations, and the inventors intend that the disclosed and claimed subject be practiced differently from as specifically described herein. Accordingly, the disclosed and claimed subject includes all modifications and equivalents of the subject mentioned in the appended claims as permitted by applicable law. Furthermore, any combination of the elements described above in all possible variations thereof is encompassed in the disclosed and claimed subject unless otherwise indicated herein or otherwise clearly contradictory in the context.

[0039] For convenience of reference, “microelectronic device” or “semiconductor substrate” corresponds to semiconductor wafers, flat panel displays, phase change memory devices, solar panels, and solar substrates, photovoltaics, and other products including MEMS (microelectromechanical systems) manufactured for use in 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 may or may not be doped. The term “microelectronic device” is to be understood to include any substrate that will eventually become a microelectronic device or microelectronic assembly, without being intended to be limiting in any way. A microelectronic device or semiconductor substrate may include a low-k dielectric material, a barrier material, and a metal, such as AlCu alloy, W, Ti, TiN, one or more passivation layers, such as polyimide or polybenzoxazole, as well as other materials thereon.

[0040] As defined herein, "low-k dielectric" corresponds to any material used as a dielectric in layered microelectronic devices, said material having a dielectric constant of less than about 3.5. Preferably, the low-k dielectric comprises low-polarity materials such as silicon-containing organic polymers, silicon-containing hybrid organic / inorganic materials, organosilicate glass (OSG), TEOS, fluorinated silicate glass (FSG), silicon dioxide, and carbon-doped oxide (CDO) glass. It should be understood that the low-k dielectric may have various densities and various porosities.

[0041] As defined herein, the term “barrier material” corresponds to any material used in the relevant art to seal metal lines, e.g., copper interconnects, to minimize the diffusion of the metal, e.g., copper, into the dielectric. Preferred barrier layer materials include tantalum, titanium, ruthenium, hafnium, and other refractory metals and their nitrides and silicides.

[0042] "Substantially absent" is defined herein as less than approximately 1 wt.%, more preferably less than approximately 0.5 wt.%, and most preferably less than approximately 0.2 wt.%. "Substantially absent" also includes approximately 0.0 wt.%. The term "without" means 0.0 wt.%.

[0043] In some embodiments, when describing a composition substantially free of water, this is intended to mean that water may be added with the ingredients; however, the amount of water added with the ingredients should be approximately less than 0.1 wt%; water may be absorbed from the atmosphere during manufacturing and use. In other embodiments, substantially free of water may refer to a composition in which water is not present in greater than approximately 1 wt%. In other embodiments, substantially free of water may refer to a composition in which water is not present in greater than approximately 3 wt%.

[0044] When used in relation to a measurable numerical variable, the terms “about” or “approximately” refer to any value of the variable that is greater than the indicated value and within the experimental error of the indicated value (e.g., 95% confidence limit for the mean) or within a percentage of the indicated value (e.g., ± 10%, ± 5%).

[0045] In all such compositions where specific components of the composition are discussed with reference to weight percentage ranges including zero lower limits, it will be understood that such components may be present or absent in various specific embodiments of the composition, and where such components are present, they may be present at a concentration as low as 0.001 weight percent based on the total weight of the composition in which such components are utilized. It should be noted that all defined weight percentages of components are based on the total weight of the composition unless otherwise indicated. Additionally, all weight percentages are "neat" unless otherwise indicated, meaning that they do not include aqueous solutions in which they are present when added to the composition. Any reference to "at least one" may 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.

[0046] The composition 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 second solvents.

[0047] In additional embodiments, the composition is essentially composed of (i) one or more alkanolamines, (ii) one or more ether alcohol solvents or aromatic-containing alcohols, and (iii) one or more corrosion inhibitors in varying concentrations. In these embodiments, the sum of (i), (ii), and (iii) is not equal to 100 weight percent and may include other components (e.g., additional solvent(s) including water, common additives, and / or impurities) that do not significantly alter the effectiveness of the cleaning composition.

[0048] In another embodiment, the composition comprises, in varying concentrations, (i) one or more alkanolamines, (ii) one or more ether alcohol solvents or aromatic-containing alcohols, and (iii) one or more corrosion inhibitors. In this embodiment, the sum of (i), (ii), and (iii) is approximately 100 weight percent, but may contain other small and / or trace impurities present in such small amounts that do not significantly alter the efficacy of the composition. For example, in one such embodiment, the cleaning composition may contain 2 weight percent or less of impurities. In another embodiment, the cleaning composition may contain 1 weight percent or less of impurities. In a further embodiment, the cleaning composition may contain 0.05 weight percent or less of impurities.

[0049] When referring to the composition of the composition of the present invention described herein in weight percent, it is understood that the weight percent of all components, including non-essential components such as impurities, in any case does not exceed 100 weight percent in total. In a composition "essentially made up" of the mentioned components, the total of these components may be 100 weight percent of the composition or less than 100 weight percent. If the total of the components is less than 100 weight percent, such composition may contain some small amount of non-essential contaminants or impurities. For example, in one such embodiment, the composition may contain 2 weight percent or less of impurities. In another embodiment, the rinse may contain 1 weight percent or less of impurities. In a further embodiment, the composition may contain 0.05 weight percent or less of impurities. In other such embodiments, the component may form at least 90 wt%, more preferably at least 95 wt%, more preferably at least 99 wt%, more preferably at least 99.5 wt%, most preferably at least 99.9 wt%, and may include other components that do not significantly affect the performance of the wet etching agent. Otherwise, it is understood that if no significant non-essential impurity components are present, the composition of all essential components will essentially be 100 wt% in total.

[0050] menstruum

[0051] A composition according to the present disclosure typically comprises one or more organic solvents. One type of solvent that may be used in the composition 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 other alcohol having an ether group. One or more ether alcohol solvents, including a glycol ether solvent, may be used in the composition. 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 dimethyl ether, diethylene glycol (DEG), or dipropylene glycol. Examples of alcohol ether solvents other than glycol ethers are 3-methoxy-3-methyl-1-butanol (MMB), furfuryl alcohol, and tetrahydrofurfuryl alcohol. Aromatic ring-containing alcohol solvents useful in the above composition are alkanol-substituted benzenes, e.g., benzyl alcohol, benzyl ethanol, and benzyl propanol. Each solvent may be used alone, as a mixture of the same type, or as a combination of any or all of different types.

[0052] In most applications, it is believed that one or more alcohol ether solvents and / or aromatic-containing alcohols comprise, for example, about 50% to about 90% by weight of the composition, or 55% to about 90% by weight. Other preferred embodiments of the disclosed and claimed subject matter may comprise about 60% to about 88% by weight, or 65% to 85% by weight of glycol ether solvents and / or aromatic-containing alcohols. Alcohol ether solvent(s) and / or aromatic-containing alcohol may be present in amounts falling within the ranges defined by the following weight percentage list: 50, 55, 58, 60, 62, 65, 67, 70, 72, 75, 77, 80, 82, 85, 88, and 90. Aromatic ring-containing alcohol and / or aromatic-containing alcohol may be present in the composition in amounts falling within the ranges defined by the following weight percentage list: 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 wt% to about 85 wt% of the composition. In another embodiment, one or more ether alcohol solvents and / or aromatic-containing alcohols constitute about 30 wt% to about 50 wt% of the composition.

[0053] Some embodiments may contain about 10% to about 50% of a second solvent in addition to the ether alcohol solvent or aromatic ring-containing alcohol solvent described above. Alternatively, in some embodiments, the stripper solution may have no or substantially no second solvent.

[0054] The second organic solvent alcohol may be a linear or branched aliphatic or aromatic alcohol. Examples of a second alcohol that the composition may 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-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. It includes 1-dotriacontanol, 1-tetratriacontanol, cetearyl alcohol, propylene glycol, ethylene glycol, and glycerol.

[0055] When used, the second organic solvent may comprise about 0.02% to about 45% of the composition, 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%. In an alternative embodiment, the second solvent may be present in any amount defined by an endpoint selected from the following weight percentages: 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.

[0056] alkanolamine

[0057] Suitable alkanolamines have at least two carbon atoms, at least one amino substituent and at least one hydroxyl substituent, and said amino and hydroxyl substituents are attached to two different carbon atoms.

[0058] In some embodiments, the alkanolamine is a 1,2-alkanolamine of formula (I):

[0059] (I)

[0060] Here, R 1 , R 2 and R 3 Each 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 is H. In another embodiment, R 1 is -CH2CH2NH2 and R 2 is -H. In another embodiment, R 1 and R 2 Both are -H. In another embodiment, R 1 and R 2 Both are -CH2CH2OH. In another aspect, R 3 It is -CH3. .

[0061] In one embodiment, the formulation is R 1 and R 2 It includes alkanolamines of chemical formula (I) in which one or both are H.

[0062] In one embodiment, the formulation is R 1 , R 2 and R 3 Each contains an alkanolamine of chemical formula (I) in which H is present:

[0063] .

[0064] In one embodiment, the formulation is R 1 and R 2 One of them is H, and R 1 and R 2 The other one is the -CH3 group, and R 3 This includes an alkanolamine of the chemical formula (I) which is H:

[0065] .

[0066] In one embodiment, the formulation is R 1 , R 2 and R 3 Each contains an alkanolamine of chemical formula (I) that is -CH3:

[0067] .

[0068] In one embodiment, the formulation is R 1 , R 2 Each is hydrogen and R 3 This includes an alkanolamine of the chemical formula (I) which is -CH3:

[0069] .

[0070] In one embodiment, the formulation is R 1 and R 2 One of them is H, and R 1 and R 2 The other one is a substituted C1-C6 alkyl of the chemical formula -CH2CH2OH, and R 3 This includes an alkanolamine of the chemical formula (I) which is H:

[0071] .

[0072] In one embodiment, the formulation is R 1 and R 2 Both of them are substituted C1-C6 alkyls of the chemical formula -CH2CH2OH, and R 3 This includes an alkanolamine of the chemical formula (I) which is H:

[0073] .

[0074] In one embodiment, the formulation is R 1 and R 2 One of them is H, and R 1 and R 2 The other one is a substituted C1-C6 alkyl of the chemical formula -CH2CH2NH2, and R 3 This includes an alkanolamine of the chemical formula (I) which is H:

[0075] .

[0076] In one embodiment, the formulation is R 1 and R 2 Each is -CH3, and R 3 This includes an alkanolamine of the chemical formula (I) which is H:

[0077] .

[0078] Suitable alkanolamines are 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-methylpentan-1-ol, 2-aminohexane-1-ol, 3-aminoheptan-4-ol, 1-aminooctan-2-ol, 5-aminooctan-4-ol, 1-aminopropan-2,3-diol, 2-aminopropan-1,3-diol, It includes, but is not limited to, tris(oxymethyl)aminomethane, 1,2-diaminopropan-3-ol, 1,3-diaminopropan-2-ol, and 2-(2-aminoethoxy)ethanol.

[0079] A suitable level required for at least one of the alkanolamine and the amine may 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 may be present in any amount defined by an endpoint selected from the following weight percentages: 2, 5, 8, 10, 12, 15, 17, 20, 22, 25, 27, 30, 32, 35, 38, 40, 42, 45, 48, and 50.

[0080] The sum of the weight percentage of the organic solvent, which may be an alcohol ether solvent and a second solvent, and the weight percentage of the alkanolamine and / or amine in the composition may 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 the organic solvent and alkanolamine and / or amine. In some embodiments, the weight percentage is greater than the weight percentage of the alkanolamine and / or amine, and the organic solvent may be present in the composition in an amount of 20% to about 90%, or 30% to about 90%, or 50% to about 90%, or 60% to about 80%. In some embodiments, the solvent may comprise 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% of glycol ether.

[0081] corrosion inhibitor

[0082] The composition contains one or more, or two or more, corrosion inhibitors. Suitable corrosion inhibitors include organic corrosion inhibitors, e.g., aromatic hydroxyl compounds, and aromatic polyhydroxyl compounds, e.g., catechol and resorcinol; alkylcatechols, e.g., methylcatechol, ethylcatechol and t-butylcatechol, phenol and pyrogallol; aromatic triazoles, e.g., benzotriazole; alkylbenzotriazole and aminobenzotriazole, e.g., 1-aminobenzotriazole; triazoles, e.g., 2-aminobenzothiazole (ABT); sugar alcohols, e.g., glycerol, xylitol and sorbitol; Carboxylic acids, e.g., 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 and gallic acid esters, e.g., methyl gallate and propyl gallate; metal salts, e.g., copper(II) nitrate; copper(II) bromide; copper(II) chlorate; copper(II) chloride; copper(II) fluorosilicate; copper(II) formate; copper(II) selenate; copper(II) sulfate; The above-described carboxyl-containing organic compounds, etc., and chelate compounds such as phosphate-based chelate compounds, e.g., 1,2-propanediaminetetramethylenephosphonic acid and hydroxyethanephosphonic acid; carboxylic acid-based chelate compounds, e.g., ethylenediaminetetraacetic acid and its sodium and ammonium salts, dihydroxyethylglycine and nitrilotriaacetic acid; amine-based chelate compounds, e.g., bipyridine, tetraphenylporphyrin and phenanthroline; and oxime-based chelate compounds, e.g., dimethylglyoxime and diphenylglyoxime, but are not limited thereto.In another embodiment, one or more corrosion inhibitors may comprise one or more copper salts, e.g., copper(II) nitrate; copper(II) bromide; copper(II) chlorate; copper(II) chloride; copper(II) fluorosilicate; copper(II) formate; copper(II) selenate; and / or copper(II) sulfate alone. In yet another embodiment, the composition may comprise one or more of the above organic corrosion inhibitors and / or chelate compounds and one or more copper salts. In yet another embodiment, one or more corrosion inhibitors may comprise copper(II) nitrate (e.g., NADA is about 42% copper(II) nitrate hemi (pentahydrate-oxidizer) and NADA / 1N is about 26.3% copper(II) nitrate hemi (pentahydrate-non-oxidizer), copper(II) bromide; copper(II) chlorate; copper(II) chloride; copper(II) fluorosilicate; copper(II) formate; copper(II) selenate; It may be copper(II) sulfate and / or resorcinol. In another embodiment, the corrosion inhibitor may be copper(II) nitrate (i.e., NADA or NADA / 1N) and resorcinol.

[0083] In another embodiment, the corrosion inhibitor is 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; 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 compound; 2-methyl-2,4-pentanediol; 2,2-dimethyl-1,3-propanediol; glycerin; trimethylolpropane; 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; hydroxypivalyl hydroxypivalate; 2-methyl-1,3-propanediol; 2-butyl-2-ethyl-1,3-propanediol; 2-ethyl-2-isobutyl-1,3-propanediol; It may include 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; sorbitol; etc., and aliphatic or aromatic polyhydroxyl compounds comprising a combination of two or more of the aforementioned polyhydroxyl compounds.

[0084] In some embodiments, one or more organic corrosion inhibitors selected from the list described above may be present in a useful composition at a level ranging from about 0.005 wt% to about 10 wt%. In one embodiment, the solution may contain about 0.25 wt% to about 5 wt% or 0.1 wt% to about 4 wt% or 0.25 wt% to about 2 wt%. One or more corrosion inhibitors may be present in any amount defined by an endpoint selected from the following wt%s: 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 may be used in the composition. Preferred first and / or second corrosion inhibitors are copper nitrate salts (e.g., NADA or NADA / 1N) and resorcinol. The subject matter disclosed and claimed includes a method of treating a semiconductor substrate with said composition to remove photoresist without damaging films, layers, metals, or other structures present on the substrate, including passivation layers such as PI and 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. For specific applications where the substrate is sensitive or requires a longer removal time, a lower contact temperature is appropriate. For example, when reworking the substrate, it may be appropriate to maintain the stripper solution at a temperature of at least 20°C for a longer period to remove the photoresist and avoid substrate damage.

[0085] As mentioned above, in one embodiment, one or more corrosion inhibitors comprise about 0.005 wt% to about 10 wt% of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 0.25 weight percent to about 5 weight percent of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 0.1 weight percent to about 4 weight percent of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 0.25 weight percent to about 2 weight percent of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 0.005 wt% of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 0.02 wt% of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 0.08 wt% of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 0.1 wt% of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 0.2 wt% of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 0.25 wt% of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 0.3 wt% of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 0.4 wt% of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 0.5 wt% of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 0.7 wt% of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 0.9 wt% of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 1 wt% of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 2 wt% of the composition.In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 3 wt% of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 4 wt% of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 5 wt% of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 6 wt% of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 7 wt% of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 8 wt% of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 9 wt% of the composition. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 10 wt% of the composition.

[0086] 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 wt% to about 1.5 wt% 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 wt% to about 1.5 wt% 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 wt% to about 1.5 wt% of catechol.

[0087] 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 wt% to about 1.5 wt% 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 wt% to about 1.5 wt% 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 wt% to about 1.5 wt% of resorcinol.

[0088] 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 wt% to about 1.5 wt% of glycerol. In a further aspect of this embodiment, one or more corrosion inhibitors are essentially composed of glycerol. In a further aspect of this embodiment, one or more corrosion inhibitors are essentially composed of about 0.5 wt% to about 1.5 wt% of glycerol. In a further aspect of this embodiment, one or more corrosion inhibitors are composed of glycerol. In a further aspect of this embodiment, one or more corrosion inhibitors are composed of about 0.5 wt% to about 1.5 wt% of glycerol.

[0089] In another embodiment, one or more corrosion inhibitors comprise sebacic acid. In a further aspect of this embodiment, one or more corrosion inhibitors comprise about 0.5 wt% to about 1.5 wt% of sebacic acid. In a further aspect of this embodiment, one or more corrosion inhibitors are essentially composed of sebacic acid. In a further aspect of this embodiment, one or more corrosion inhibitors are essentially composed of about 0.5 wt% to about 1.5 wt% of sebacic acid. In a further aspect of this embodiment, one or more corrosion inhibitors are composed of sebacic acid. In a further aspect of this embodiment, one or more corrosion inhibitors are composed of about 0.5 wt% to about 1.5 wt% of sebacic acid.

[0090] In another embodiment, one or more corrosion inhibitors comprise copper nitrate salt and resorcinol. In a further aspect of this embodiment, one or more corrosion inhibitors essentially consist of copper nitrate salt and resorcinol. In a further aspect of this embodiment, one or more corrosion inhibitors consist of copper nitrate salt and resorcinol.

[0091] In another embodiment, one or more corrosion inhibitors comprise a copper nitrate salt. In a further aspect of this embodiment, one or more corrosion inhibitors essentially consist of a copper nitrate salt. In a further aspect of this embodiment, one or more corrosion inhibitors consist of copper nitrate.

[0092] When immersing the substrate, stirring of the composition further facilitates the removal of the photoresist. Stirring may be influenced by mechanical stirring, circulation, or bubbling of an inert gas through the composition. Once the desired amount of photoresist has been removed, the substrate is removed from contact with the stripper solution and washed with water or alcohol. Deionized water (DI water) is the preferred form of water, and isopropanol (IPA) is the preferred alcohol; rinsing with alcohol is optional. For substrates containing oxidizing components, the substrate is preferably washed under an inert atmosphere. The preferred stripper solution according to the present disclosure has an improved loading capacity for photoresist material compared to currently commercially available products and can process a larger number of substrates with a given volume of stripper solution.

[0093] The stripper solution provided in this disclosure can be used to remove polymeric resist material present in a single layer or a specific type of double layer resist. For example, a double layer resist may typically have a first inorganic layer covered by a second polymer layer or may have two polymer layers. By utilizing the method taught below, a single layer of 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 composed 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 double layer composed of two polymer layers.

[0094] The present disclosure describes a chemical solution used for removing thick and thin photoresists. The thick photoresist may be a resist 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 advanced packaging applications for semiconductor devices. In other cases, the chemical solution may be used to remove a photoresist 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 a glycol ether, monoethanolamine (MEA), and at least two corrosion inhibitors. The stripper solution is also or alternatively substantially free of a strong base (e.g., quaternary ammonium hydroxide, KOH) and / or water.

[0095] Some embodiments of the composition may be substantially absent or alternatively absent one or more of the following in any combination (these terms are as defined above): nitrogen-containing solvents, bis-choline salts, tricholine salts, oxoammonium compounds, hydroxylamine and its derivatives, hydrogen peroxide, oxidizing agents, inorganic acids, inorganic bases, metal hydroxides, NMPs, surfactants, metal-containing compounds, and combinations of any of these. In other embodiments, the composition will be substantially absent (or will be absent) of sodium, and / or calcium, and / or aminocarboxylic acids, and / or alcohols, and / or ethylenediamine, and / or ethylenetriamine, and / or thiophenol. In some embodiments, the composition disclosed herein is formulated to be substantially absent or without at least one of the following chemical compounds: alkyl thiols, and organosilanes. In some embodiments, the composition disclosed herein is formulated to be substantially absent or without one or more of the following: halide-containing compounds, for example, to be substantially absent or without one or more of the following: fluoride-, bromine-, chlorine-, or iodine-containing compounds. In other embodiments, the composition may be substantially absent or without 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 absent or without sulfates and / or nitrates and / or sulfites and / or nitrites. In other embodiments, the composition may be substantially absent or without ethyl diamine, 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 absent or without surfactants.Some embodiments may substantially lack or be absent amphoteric salts, and / or cationic surfactants, and / or anionic surfactants, and / or zwitterionic surfactants, and / or nonionic surfactants. Some embodiments may substantially lack or be absent imidazole, and / or anhydrides. Some embodiments may substantially lack or be absent pyrrolidone, and / or acetamide. Some embodiments may substantially lack or be absent any amine (other than alkanolamine). Some embodiments may substantially lack or be absent peroxy compounds, and / or peroxides, and / or persulfates, and / or percarbonates, and their acids, and their salts. Some embodiments may be substantially absent or lack iodate, and / or perboric acid, and / or percarbonate, and / or peroxyacid, and / or cerium compound, and / or cyanide, and / or periodic acid and / or ammonium molybdate, and / or ammonia and / or abrasive. Any component that may be absent from the composition may be any combination of components as all combinations are presented herein.

[0096] The composition of the disclosed and claimed subject matter may also include one or more of the following additives: dyes and biocides. The additive(s) may be added in an amount typically of about 5 weight percent or less of the total composition, to an extent that does not adversely affect the performance of the composition. In other embodiments, the composition will be substantially free of dyes, biocides, and / or other additives.

[0097] Examples

[0098] We will now refer to more specific embodiments of the present disclosure and experimental results that support such embodiments. Examples are given below to more fully illustrate the subject matter of the disclosed subject matter and should not be construed as limiting the subject matter of the disclosed subject matter in any way.

[0099] It will be apparent to those skilled in the art that various modifications and variations may be made to the subject matter and specific embodiments disclosed herein without departing from the spirit or scope of the subject matter disclosed. Accordingly, the subject matter disclosed, including the description provided by the following embodiments, is intended to encompass modifications and variations of the subject matter disclosed within the scope of the claims and their equivalents.

[0100] Materials and Methods:

[0101] All materials used in this patent are available for purchase and / or acquisition from Sigma Aldrich and were used in the formulation as received.

[0102] The resist cleaning performance and compatibility with polyimide (PI) or polybenzoxazole (PBO) were checked using an optical microscope and a scanning electron microscope. The Cu etching rate was determined by measuring the film thickness using a 4-point probe RESMAP before and after formulation treatment.

[0103] The following abbreviations are used in the various compositions of the table below:

[0104]

[0105] Low-temperature curing PI is a polyimide passivation layer (or insulating layer) that cures at approximately 220°C or less.

[0106] In the examples, various stripping compositions (examples and comparative examples) comprising the formulations identified in the table below were tested for their ability to remove photoresist from semiconductor wafer samples. The coupon-sized semiconductor wafer samples were silicon wafers plated with Cu pillars and Sn / Ag solder caps having a thick layer of spin-on photoresist on them. Photoresist removal was performed using an immersion process in a beaker. The photoresist on the test coupons was positive spin for the photoresist. Another test coupon had a passivation layer of polyimide (PI) on it. Yet another test coupon also had a passivation layer of polybenzoxazole (PBO) on it.

[0107] Table 1 lists the results of testing NMP for PI / PBO compatibility and photoresist removal effectiveness. The test results reported in Table 1 were for photoresist removal from photoresist coupons and compatibility with individual coupons having a PBO passivation layer coupon or a PI passivation layer, respectively, under specific process conditions (temperature and time).

[0108] Comparative Example Formulation—NMP

[0109]

[0110] Example Formulations

[0111]

[0112] Example Formulations

[0113]

[0114] Example Formulations

[0115]

[0116] Example Formulations

[0117]

[0118] Example Formulations

[0119]

[0120] Example Formulations

[0121]

[0122] Example Formulations

[0123]

[0124] Example Formulations

[0125]

[0126] Example Formulations

[0127]

[0128] Analysis of the formulation in the example

[0129] Analysis 1A: Resist Cleaning Performance

[0130] Tables 11 through 14 list various stripping compositions of the present invention and comparative compositions tested using a semiconductor wafer having a 50 μm thick CR4000 positive spin-on photoresist plated with a Cu pillar and Sn / Ag solder cap and an immersion process. For the immersion process, a coupon-sized semiconductor wafer sample was processed in a beaker. The beaker was filled with 100.0 g of the stripping composition and heated to a target temperature of 50°C or 60°C. When the stripping composition was at the process temperature, the coupon was placed in the holder of the beaker and a little stirring was provided by a stirring rod. The temperature was maintained at the process temperature while in contact with the coupon during the cleaning process. After the curing treatment, the coupon was removed from the beaker, washed with deionized water and IPA, and dried with a nitrogen stream.

[0131] Resist removal is defined as "clean" if all resist is removed from the wafer coupon surface; "mostly clean" if at least 95% of the resist is removed from the surface; and "partially clean" if about 80% of the resist is removed from the surface. Except for Examples 13, 19, and 25, where the NMP comparative example could not completely remove the resist after 15 minutes at 80°C and the coupon was partially clean after 15 minutes, all other illustrated compositions could completely remove the resist after 15 minutes at 50°C or 60°C.

[0132] Analysis 1B: PI / PBO Compatibility

[0133] Tables 11 through 14 also provide the results evaluated for low-temperature cured polyimide (PI) films and polybenzoxazole (PBO) films. These tests were performed using semiconductor wafers patterned with cured PI films or cured PBO films. For the immersion process, a coupon-sized semiconductor wafer sample was processed in a beaker. The beaker was filled with 100 grams of stripping composition and heated to a target temperature. When the stripping composition was at the process temperature, the coupon was placed in the holder of the beaker and lightly stirred by a stirring rod. The temperature was maintained at the process temperature throughout the process. After a total processing time of 60 or 120 minutes, the coupon was removed from the beaker, washed with deionized water and IPA, and dried with a nitrogen stream.

[0134] The pattern of the polyimide films was monitored using an optical microscope and a scanning electron microscope before and after treatment for each tested coupon. Any cracking was recorded as an indicator of poor compatibility between PI and PBO. Factors affecting the compatibility of PI and PBO include solvents and alkanolamines or amines. NMP-treated PI exhibited minor cracking 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. All comparisons and formulation 1-25 of the present invention had good compatibility with PBO after 120 minutes.

[0135] Solvent Effects on Resist Removal and PI / PBO Compatibility

[0136]

[0137] Effects of Solvents or Solvent Mixtures on Resist Removal and PI / PBO Compatibility

[0138]

[0139] Effects of Amine / Alkanolamine on Resist Removal and PI / PBO Compatibility

[0140]

[0141] Effect of Alkanolamine Concentration on Resist Removal and PI / PBO Compatibility

[0142]

[0143] Analysis 2: Corrosion Inhibitors and Etching Rates

[0144] Tables 15 through 18 list various inventive and comparative stripping compositions tested for Analysis 2 using an immersion process to measure the Cu etching rate. Tests were performed using blanket Cu wafers. For the immersion process, three coupon-sized semiconductor wafer samples were processed in a beaker. The beaker was filled with 100 grams of the stripping composition and heated to the target temperature. When the stripping composition was at the target temperature, the three coupons were placed in the holder of the beaker and lightly stirred by a stirring rod. Throughout the process, the temperature was maintained at the process temperature shown in the table. After a total processing time of 15 minutes, the coupons were removed from the beaker, washed with deionized water and IPA, and dried with a nitrogen stream.

[0145] The thickness of the Cu layer was measured for each coupon before and after treatment using RESMAP to calculate the etching rate and thickness change. In Tables 15 and 16, single corrosion inhibitors were studied by monitoring the Cu etching rate. 0.5% cysteine ​​(Formulation 31) had the lowest Cu etching rate. 0.5% 8-hydroquinoline (Formulation 28) and 0.5% glycerol (Formulation 33) had no effect on 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 had no 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 as the concentration was increased from 0.5% to 1.5% (Formulations 34, 35, and 15), but the Cu etching rate did not significantly decrease from 1.5% to 3% even with further increases in concentration (Formulations 35-38). In Table 17, combinations of NADA and other corrosion inhibitors were investigated 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 were found to have no effect on Cu protection (Formulations 44, 45). The combination of NADA and aminobenzotriazole (Formulation 43) showed an increased Cu etching rate, while 8-hydroquinoline (Formulation 41) showed a slight decrease in the Cu etching rate. Table 18 illustrates combinations of corrosion inhibitors that reduced the Cu etching rate without using NADA solution.

[0146] Effect of Corrosion Inhibitor on Cu Etching Rate

[0147]

[0148] Effect of Corrosion Inhibitor on Cu Etching Rate

[0149]

[0150] Effect of Corrosion Inhibitor on Cu Etching Rate

[0151]

[0152] Performance of powerful corrosion inhibitors

[0153]

[0154] Results Summary

[0155] DB is a fast stripping solvent for CR4000 removal among all solvents tested at a 15% MEA loading. Alkanolamine exhibited better resist cleaning performance than amine within 10 minutes at a 30% MEA level, where CR4000 could be cleaned within 10 minutes regardless of the solvent used.

[0156] MMB and water showed better compatibility with PI than DB solvent.

[0157] With a 15% loading of amine or alkanolamine, all formulations exhibited good compatibility with PI after 120 minutes. In general, higher MEA concentrations resulted in better resist stripping but showed poorer compatibility with PI.

[0158] Cysteine ​​performed well as a single corrosion inhibitor to reduce the Cu etching rate.

[0159] Resorcinol reduced the Cu etching rate as the concentration was increased from 0.5% to 1.5%, but the Cu etching rate did not decrease significantly from 1.5% to 3% even when the concentration was further increased.

[0160] The combination 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 group without any corrosion inhibitors.

[0161] Some corrosion inhibitor pairs (e.g., resorcinol and sebacic acid) exhibited a Cu etching rate approximately 7 times lower than the control group without corrosion inhibitors.

[0162] Although the subject matter disclosed and claimed has been described and exemplified to some extent in detail, it is understood that the disclosure is merely for illustrative purposes and that numerous changes to the conditions and order of steps can be determined by a person skilled in the art without departing from the spirit and scope of the subject matter disclosed and claimed. Accordingly, it will be understood by a person skilled in the art that various changes may be made and equivalents substitute for its elements without departing from the scope of the subject matter disclosed and claimed. Furthermore, many modifications may be made to apply specific situations or materials to the teachings of the subject matter disclosed and claimed without departing from its essential scope. Furthermore, all numerical values ​​identified in the detailed description should be interpreted as if both exact and approximate values ​​are explicitly identified.

Claims

Claim 1 (i) 1 or more alkanolamines 5 wt% to 30 wt%, (ii) 1 or more ether alcohol solvents or aromatic-containing alcohols in an amount of 55 wt% to 90 wt%, and (iii) A cleaning composition comprising 0.005 wt% to 10 wt% of one or more corrosion inhibitors, comprising a first corrosion inhibitor comprising a copper salt and a second corrosion inhibitor comprising at least one of sebacic acid, catechol, resorcinol, glycerol, sorbitol, and 8-hydroquinoline, wherein the cleaning composition comprises less than 0.1 wt% water and is free of a strong base selected from DMSO, quaternary ammonium hydroxide, and KOH. Claim 2 In paragraph 1, one or more alkanolamines A composition comprising Claim 3 In claim 1, one or more alkanolamines are 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-methylpentan-1-ol, 2-aminohexane-1-ol, 3-aminoheptan-4-ol, 1-aminooctan-2-ol, 5-aminooctan-4-ol, 1-aminopropan-2,3-diol, A composition comprising one or more of 2-aminopropane-1,3-diol, tris(oxymethyl)aminomethane, 1,2-diaminopropan-3-ol, 1,3-diaminopropan-2-ol, and 2-(2-aminoethoxy)ethanol. Claim 4 In claim 1, one or more ether alcohol solvents or aromatic-containing alcohols are 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), or dipropylene glycol, A composition comprising one or more of 3-methoxy-3-methyl-1-butanol (MMB), furfuryl alcohol, tetrahydrofurfuryl alcohol, benzyl alcohol, benzyl ethanol, and benzyl propanol. Claim 5 A composition according to claim 1, wherein one or more ether alcohol solvents or aromatic-containing alcohols comprise one or more glycol ethers. Claim 6 A composition according to claim 1, wherein one or more ether alcohol solvents or aromatic-containing alcohols comprise one or more alcohols having ether groups. Claim 7 A composition according to claim 1, wherein one or more ether alcohol solvents or aromatic-containing alcohols comprise one or more alkanol-substituted benzenes. Claim 8 A composition according to claim 1, wherein the second corrosion inhibitor comprises one or more of catechol, resorcinol, glycerol, sorbitol, and sebacic acid. Claim 9 A composition according to claim 1, wherein the second corrosion inhibitor comprises 0.5 wt% to 1.5 wt% of one or a combination of catechol, resorcinol, and sebacic acid. Claim 10 A composition according to claim 1, wherein the second corrosion inhibitor comprises 0.5 wt% to 1.5 wt% of resorcinol. Claim 11 A composition according to claim 1, wherein one or more corrosion inhibitors comprise copper nitrate salt and resorcinol. Claim 12 A composition according to claim 1, wherein the first corrosion inhibitor comprises a copper nitrate salt. Claim 13 A composition according to claim 1, wherein the second corrosion inhibitor comprises sorbitol. Claim 14 A composition according to claim 1, further comprising 10% to 50% of a second solvent which is one or more of a linear aliphatic alcohol, a branched-chain aliphatic alcohol, and an aromatic alcohol. Claim 15 In claim 1, 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-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, A composition further comprising 10% to 50% of a second solvent selected from one or more of 1-dotriacontanol, 1-tetratriacontanol, cetearyl alcohol, propylene glycol, ethylene glycol, and glycerol. 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