Composition for removing photoresist from a substrate and use of said composition - Patents.com

Abstract

The disclosed and claimed subject matter relates to photoresist stripper solutions that include (i) one or more inorganic bases; (ii) two or more organic solvents; (iii) one or more corrosion inhibitors, and may optionally include (iv) one or more second solvents.

Description

[Technical field]

[0001] Generally, the disclosed and claimed subject matter relates to compositions capable of effectively removing photoresist from a substrate, and methods for using such compositions. The disclosed compositions are stripper solutions for the removal of photoresist that may be substantially free of DMSO, NMP, and TMAH, and are preferably compatible with metals and passivation materials, such as polyimides. [Background technology]

[0002] Photoresist strippers for the removal of thick photoresists used in wafer level packaging typically contain different combinations of solvents, amines, quaternary ammonium hydroxides, inorganic hydroxides, co-solvents, corrosion inhibitors and other additives. Many products for this application contain DMSO or NMP as the solvent and either amines or quaternary ammonium hydroxides or both. Tetramethylammonium hydroxide (TMAH) is the most commonly used quaternary ammonium hydroxide due to its lower cost and better performance than other quaternary hydroxides. However, there are well-known potential health effects associated with TMAH. Alternatives to TMAH-containing stripper compositions are desired.

[0003] Inorganic bases, especially alkali metal hydroxides, offer advantageous properties when used in photoresist strippers without the potential health effects associated with TMAH. Inorganic bases have low cost and good thermal stability, resulting in photoresists with longer bath life compared to photoresist strippers using TMAH. However, one problem with alkali metal hydroxides is that they tend to react with carbon dioxide from the atmosphere to form carbonates. Carbonates are water-soluble, but typically are not very soluble in organic solvents. Thus, photoresist strippers that typically use alkali metal hydroxides have problems with precipitation or sludge due to the formation of carbonate crystals that are insoluble in the organic solvent of the stripper; this can cause tool clogging and pose safety concerns for the operation of the tool. Removal of precipitated carbonates can require extra cleaning of the process tool using water to dissolve and / or rinse them, increasing maintenance costs. Thus, it is important to solve the sludge problem in organic solvent-based strippers that use inorganic bases, especially alkali metal hydroxides.

[0004] There are many stripper solutions for removing photoresist (for example, US Patent Application Publication No. 2019 / 0317409 describes a stripper solution for removing photoresist from a substrate, comprising a primary solvent, a secondary solvent, an inorganic base, an amine, and a corrosion inhibitor). Improved stripper solution compositions are required due to the increased demand for improved performance from wafer manufacturers. When different materials are used in the substrate for different functions, the stripper may come into contact with those materials and therefore needs to have the ability to remove photoresist and compatibility with materials on the substrate that should not be removed. Furthermore, given the recent constraints on the solvents used in stripper formulations, such as N-methyl-2-pyrrolidone (NMP) and dimethyl sulfoxide (DMSO), new formulations with more environmentally friendly solvents are required. Summary of the Invention

[0005] overview This summary section is not intended to identify every embodiment and / or incrementally novel aspect of the disclosed and claimed subject matter. Rather, this summary merely provides a preliminary discussion of different embodiments and corresponding points that are novel over the prior art and known art. For further details and / or a possible overall picture of the disclosed and claimed subject matter and embodiments, please refer to the detailed description section and corresponding figures of the present disclosure, further discussed below.

[0006] The disclosed and claimed subject matter is directed to a photoresist stripper solution for effectively removing or stripping positive or negative photoresist, photoresist after an etching process, or etching residue from a substrate. The disclosed and claimed photoresist stripper solution has the ability to remain liquid when faced with temperatures below normal room temperature typically encountered during shipping, storage, and use in some manufacturing facilities, and has a particularly high loading capacity for resist materials.

[0007] The disclosed and claimed photoresist stripper solution contains inorganic hydroxide, which reduces carbonate crystal formation and extends bath life.The disclosed and claimed photoresist stripper solution does not contain NMP and DMSO, and is particularly useful for removing both positive and negative liquid photoresists.The disclosed and claimed photoresist stripper solution does not harm the materials present on the substrate, especially on metals, silicon, and passivation materials such as polyimide.

[0008] The disclosed and claimed photoresist stripper solution comprises: (i) one or more inorganic bases; (ii) two or more organic solvents; and (iii) one or more corrosion inhibitors In a further aspect, the solution comprises (iv) one or more secondary solvents. In a further aspect of this embodiment, the solution consists essentially of (i), (ii), and (iii). In a further aspect of this embodiment, the solution consists essentially of (i), (ii), (iii), and (iv). In another further aspect of this embodiment, the solution consists of (i), (ii), and (iii). In another further aspect of this embodiment, the solution consists of (i), (ii), (iii), and (iv).

[0009] In one other embodiment, the solution comprises (i) one or more inorganic bases selected from NaOH, KOH, and combinations thereof. In one aspect of this embodiment, the (i) one or more inorganic bases comprise NaOH. In one other aspect of this embodiment, the (i) one or more inorganic bases comprise KOH. In one other aspect of this embodiment, the (i) one or more inorganic bases comprise a combination of NaOH and KOH.

[0010] In one other embodiment, the solution comprises (ii) two or more organic solvents, where (a) a first solvent is selected from glycol ether solvents, ether alcohol solvents, and aromatic ring-containing alcohols, and combinations thereof, and (b) a second solvent is a polyol solvent (i.e., a polyhydroxy-containing solvent). In one aspect of this embodiment, the (ii) two or more organic solvents comprise a glycol ether solvent. In one aspect of this embodiment, the (ii) two or more organic solvents comprise an ether alcohol solvent. In one aspect of this embodiment, the (ii) two or more organic solvents comprise an aromatic ring-containing alcohol. In one aspect of this embodiment, the (ii) two or more organic solvents comprise a glycol ether solvent and an ether alcohol solvent. In one aspect of this embodiment, the (ii) two or more organic solvents comprise a glycol ether solvent and an aromatic ring-containing alcohol. In one aspect of this embodiment, the (ii) two or more organic solvents comprise an ether alcohol solvent and an aromatic ring-containing alcohol.

[0011] In one exemplary embodiment of the disclosed and claimed subject matter, the photoresist stripper solution comprises: (i) one or more inorganic bases, including about 0.5 wt % to about 5 wt % potassium hydroxide; (ii) two or more organic solvents, including: a. about 30 wt % to about 90 wt % triethylene glycol monomethyl ether; and b. about 5 wt % to about 30 wt % diethylene glycol; and (iii) from about 0.01 wt % to about 5 wt % of one or more corrosion inhibitors Includes.

[0012] In one exemplary embodiment of the disclosed and claimed subject matter, the photoresist stripper solution comprises: (i) one or more inorganic bases, including about 0.5% to about 5% potassium hydroxide; (ii) two or more organic solvents comprising: a. about 30 wt % to about 90 wt % triethylene glycol monomethyl ether; and b. about 5 wt % to about 30 wt % diethylene glycol; (iii) from about 0.01 wt % to about 5 wt % of one or more corrosion inhibitors; and (iv) one or more secondary solvents, including from about 5 wt % to about 30 wt % of a polyol solvent; Includes.

[0013] In one other embodiment, the disclosed and claimed subject matter is directed to a method of removing photoresist and associated polymeric materials from a substrate using the disclosed and claimed photoresist stripper solutions. In one aspect of this embodiment, the photoresist is removed from the substrate by contacting the substrate having photoresist thereon with one or more photoresist stripper solutions for a time sufficient to remove a desired amount of photoresist, removing the substrate from the stripper solutions, rinsing the stripper solutions from the substrate with DI water or a solvent, and drying the substrate.

[0014] Additionally, the disclosed and claimed subject matter is directed to the use and synthesis of the disclosed and claimed chemical formulations.

[0015] In one other embodiment, the disclosed and claimed subject matter is directed to electronic devices manufactured by the disclosed novel methods.

[0016] Other features and advantages of the disclosed and claimed subject matter will become apparent from the following more detailed description, taken in conjunction with example solutions that illustrate the principles of the disclosed and claimed subject matter.

[0017] Embodiments of the disclosed and claimed subject matter provide one or more of the following advantages: low precipitation of solids upon use, the ability of the composition to remain liquid at temperatures below normal room temperature and at temperatures often encountered during shipping and storage, the composition having a flash point well above normal processing temperatures, the photoresist stripper having good cleaning capabilities, high loading capacity, reduced crystallization and precipitation of alkali metal carbonates or other alkali metal compounds even when the stripper solution contains alkali metal hydroxides, compatibility with metals, silicon, and passivation materials such as polyimides, and extended bath life.

[0018] The order of discussion of the different steps described herein is provided for purposes of clarity. In general, the steps disclosed herein can be performed in any suitable order. Moreover, although each of the different features, techniques, configurations, etc. disclosed herein may be discussed in different parts of the disclosure, each of these concepts can be implemented independently of each other or in suitable combination with each other. Thus, the subject matter disclosed and claimed can be embodied and viewed in many different ways.

[0019] definition To facilitate understanding of the claimed subject matter, reference will be made hereinafter to illustrative embodiments and specific terms will be used to describe the same. However, no limitation of the claimed subject matter is intended, and it should be understood that modifications, further variations and further applications of the principles of the claimed subject matter as exemplified in the claims are contemplated as would normally occur to one of ordinary skill in the art to which this disclosure pertains.

[0020] All references cited in this specification, including publications, patent applications, and patents, are herein incorporated by reference to the same extent as if each reference was individually and specifically indicated to be incorporated by reference in its entirety.

[0021] The use of the terms "a" and "an" and "the" and similar referential words in the context of describing the disclosed and claimed subject matter (especially in the claims that follow) shall be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms "comprising," "having," "including," and "containing" shall be construed as open-ended terms (i.e., meaning "including, but not limited to"), unless otherwise indicated. The recitation of ranges of values ​​herein, unless otherwise indicated herein, is merely intended to serve as a shorthand method of individually referring to each individual value falling within the range, and each individual value is incorporated herein as if it were set forth separately herein. All methods described herein may be performed in any suitable order, unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples or exemplary words (e.g., "such as") provided herein is intended merely to facilitate understanding of the disclosed and claimed subject matter, and does not limit the scope of the disclosed and claimed subject matter, unless otherwise stated in the claims. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the disclosed and claimed subject matter.

[0022] Preferred embodiments of the disclosed and claimed subject matter are described herein, including the best mode known to the inventors for carrying out the disclosed and claimed subject matter. Variations of those preferred embodiments will become apparent to those skilled in the art upon reading the following description. The inventors anticipate that those skilled in the art will employ such variations as appropriate, and intend for the disclosed and claimed subject matter to be practiced differently than specifically described herein. Accordingly, this disclosure and claimed subject matter includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the disclosed and claimed subject matter, unless otherwise indicated herein or clearly contrary to context.

[0023] For ease of reference, "microelectronic device" or "semiconductor substrate" corresponds to semiconductor wafers, flat panel displays, phase change memory devices, solar panels and other products comprising solar substrates, photovoltaic cells and microelectromechanical systems (MEMS) manufactured for use in microelectronic, integrated circuit or computer chip applications. The term "microelectronic device" is not meant to be limited in any manner and is understood to include any substrate that will ultimately become a microelectronic device or microelectronic assembly. Microelectronic devices and semiconductor substrates may include low-k dielectric materials, barrier materials and metals such as Al, Cu, SnAg alloys, W, Ti, TiN, one or more passivation layers such as polyimide or polybenzoxazole, and Si and other materials thereon.

[0024] As defined herein, a "low k dielectric material" corresponds to any material used as a dielectric material in integrated microelectronic devices and having a modulus of less than about 3.5. Preferably, the low k dielectric material includes 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 is recognized that the low k dielectric material may have variable density and variable porosity.

[0025] As defined herein, the term "barrier material" corresponds to any material used in the art to seal metal wiring, e.g., copper interconnects, to minimize diffusion of the metal, e.g., copper, into dielectric materials. Preferred barrier layer materials include tantalum, titanium, titanium tungsten, ruthenium, hafnium and other refractory metals and their nitrides and silicides.

[0026] In this specification, "substantially free" is defined as less than approximately 1 wt%, more preferably less than approximately 0.5 wt%, and most preferably less than approximately 0.2 wt%. "Substantially free" further includes approximately 0.0 wt%. The term "free" means 0.0 wt%. In some embodiments, when describing a composition that is substantially free of water, it is intended to mean that water may be added as an impurity with the components; however, the amount of water added with the components should be less than approximately 0.1 wt%; however, during manufacture and use, water may be absorbed from the atmosphere. In other embodiments, substantially free of water may refer to a composition in which water is not present in excess of approximately 1 wt%. In other embodiments, substantially free of water may refer to a composition in which water is not present in excess of approximately 3 wt%. In other embodiments, water may be added as part of the raw materials, and the water level may be greater than 2 wt% and less than 5%.

[0027] The terms "about" or "approximately," when used in conjunction with a measurable, numerical variable, refer to the value of the specified variable and all values ​​of that variable that are within experimental error of the specified value (e.g., within a 95% confidence limit for the mean) or within a percentage of the specified value (e.g., ±10%, ±5%), whichever is wider.

[0028] In all such compositions where specific components of the composition are discussed in terms of wt% ranges including a lower limit of 0, it is understood that such components may be present or absent in various specific embodiments of the composition, for example, when such components are present, they may be present at concentrations as low as 0.001 wt% based on the total weight of the composition in which they are used. Unless otherwise stated, all stated wt% of the composition are based on the total weight of the composition. Furthermore, unless otherwise stated, all wt% are "neat", meaning that they do not include the aqueous solution in which they are present when added to the composition. Any reference to "at least one" can be replaced with "one or more". "At least one" and / or "one or more" includes "at least two" or "two or more" and "at least three" and "three or more", etc.

[0029] The compositions include an inorganic base; two or more organic solvents; one or more corrosion inhibitors; and optionally one or more secondary solvents.

[0030] In a further embodiment, the composition comprises various concentrations of (i) inorganic hydroxides; (ii) two or more glycol ethers, ether alcohol solvents, or aromatic-containing alcohols; and (iii) one or more corrosion inhibitors; and (iv) optionally, one or more secondary solvents for the polyol; In such embodiments, the combined amount of (i), (ii), (iii), and (iv) does not equal 100 wt % and may include other ingredients (e.g., additional solvents, including water, common additives, and / or impurities) that do not significantly alter the effectiveness of the cleaning composition.

[0031] In one other embodiment, the composition comprises various concentrations of (i) inorganic hydroxides; (ii) two or more ether alcohol solvents or aromatic-containing alcohols; and (iii) one or more corrosion inhibitors In such an embodiment, the combined amount of (i), (ii) and (iii) is approximately equal to 100 wt%, but may include other minor and / or trace amounts of impurities present in such small amounts that they do not significantly alter the effectiveness of the composition. For example, in one such embodiment, the cleaning composition may contain 2 wt% or less of impurities. In one other embodiment, the cleaning composition may contain 1 wt% or less of impurities. In a further embodiment, the cleaning composition may contain 0.05 wt% or less of impurities.

[0032] With respect to wt%, when referring to the composition of the composition of the present invention described herein, it is understood that in no case will the wt% of all components, including non-essential components such as impurities, total more than 100 wt%. In a composition "consisting essentially of" a described component, such components can total 100 wt% of the composition or total less than 100 wt%. When the components total less than 100 wt%, such a composition may contain some small amount of non-essential contaminants or impurities. For example, in one such embodiment, the composition may contain 2 wt% or less of impurities. In one other embodiment, the rinse may contain 1 wt% or less of impurities. In a further embodiment, the composition may contain 0.05 wt% or less of impurities. In one other such embodiment, the ingredients 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%, and most preferably at least 99.8 wt%, and may include other ingredients that do not affect the performance of the cleaning composition. Otherwise, the composition of all essential ingredients adds up to essentially 100 wt%, in the absence of significant non-essential impurity ingredients. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0033] Detailed Description It is understood that both the general description above and the detailed description below are exemplary and explanatory and are not intended to limit the claimed subject matter. The objects, features, advantages and ideas of the disclosed subject matter will be apparent to those skilled in the art from the description provided herein, and the disclosed subject matter can be readily implemented by those skilled in the art based on the description set forth herein. Any "preferred embodiment" and / or example descriptions showing preferred modes for implementing the disclosed subject matter are included for illustrative purposes and are not intended to limit the scope of the claims.

[0034] It will also be apparent to those skilled in the art that, based on the embodiments described herein, various modifications can be made in how to implement the disclosed subject matter without departing from the spirit and scope of the subject matter disclosed herein.

[0035] As mentioned above, the subject of disclosure is: (i) one or more inorganic bases; (ii) two or more organic solvents, where (a) a first solvent is selected from glycol ether solvents, ether alcohol solvents, and aromatic ring-containing alcohols, and combinations thereof, and (b) a second solvent is a polyol solvent; and (iii) one or more corrosion inhibitors In a further aspect, the solution further optionally comprises, consists essentially of, or consists of (iv) one or more secondary solvents.

[0036] In a solution comprising or consisting essentially of the listed components, the sum of the wt% of components (i), (ii), (iii) or (i), (ii), (iii) and (iv) is less than or equal to 100 wt%. In a solution consisting of the listed components, the sum of the wt% of components (i), (ii), (iii) or (i), (ii), (iii) and (iv) is equal to 100 wt%.

[0037] In one exemplary embodiment, the photoresist stripper solution comprises: (i) from about 0.5 wt % to about 5 wt % of one or more neat inorganic bases; (ii) about 90 wt % to about 97 wt % of two or more organic solvents that are different from each other, comprising: (a) a first solvent comprising one or more of a glycol ether solvent, an ether alcohol solvent, and an aromatic ring-containing alcohol solvent, or a mixture thereof; and (b) a second solvent comprising one or more polyol solvents; (iii) from about 0.01 wt % to about 2 wt % of one or more corrosion inhibitors; and (iv) optionally, one or more secondary solvents; wherein the combined wt% of components (i), (ii), (iii) and (iv) is less than or equal to 100 wt%. In a further aspect of this embodiment, the one or more neat inorganic bases comprise KOH.

[0038] In one exemplary embodiment, the photoresist stripper solution comprises: (i) from about 1.0 wt % to about 2.5 wt % of one or more neat inorganic bases; (ii) about 90 wt % to about 97 wt % of two or more organic solvents that are different from each other, comprising: (a) a first solvent comprising one or more of a glycol ether solvent, an ether alcohol solvent, and an aromatic ring-containing alcohol solvent, or a mixture thereof; and (b) a second solvent comprising one or more polyol solvents; (iii) from about 0.01 wt % to about 2 wt % of one or more corrosion inhibitors; and (iv) optionally, one or more secondary solvents; wherein the sum of the wt% of components (i), (ii), (iii) and (iv) is less than or equal to 100 wt%. In a further aspect of this embodiment, the one or more neat inorganic bases comprises KOH.

[0039] In one exemplary embodiment, the photoresist stripper solution comprises: (i) from about 0.5 wt % to about 5 wt % of one or more neat inorganic bases; (ii) about 90 wt % to about 97 wt % of two or more organic solvents that are different from each other, comprising: (a) a first solvent comprising one or more of a glycol ether solvent, an ether alcohol solvent, and an aromatic ring-containing alcohol solvent, or a mixture thereof; and (b) a second solvent comprising one or more polyol solvents; (iii) from about 0.01 wt % to about 2 wt % of one or more corrosion inhibitors; and (iv) optionally, one or more secondary solvents; wherein the sum of the wt% of components (i), (ii), (iii) and (iv) is less than or equal to 100 wt%. In a further aspect of this embodiment, the one or more neat inorganic bases comprises KOH.

[0040] In one exemplary embodiment, the photoresist stripper solution comprises: (i) from about 1.0 wt % to about 2.5 wt % of one or more neat inorganic bases; (ii) about 90 wt % to about 97 wt % of two or more organic solvents that are different from each other, comprising: (a) a first solvent comprising one or more of a glycol ether solvent, an ether alcohol solvent, and an aromatic ring-containing alcohol solvent, or a mixture thereof; and (b) a second solvent comprising one or more polyol solvents; (iii) from about 0.01 wt % to about 2 wt % of one or more corrosion inhibitors; and (iv) optionally, one or more secondary solvents; wherein the sum of the wt% of components (i), (ii), (iii) and (iv) is less than or equal to 100 wt%. In a further aspect of this embodiment, the one or more neat inorganic bases comprises KOH.

[0041] In one exemplary embodiment, the photoresist stripper solution comprises: (i) from about 0.5 wt % to about 5 wt % of one or more neat inorganic bases; (ii) about 90 wt % to about 97 wt % of two or more organic solvents that are different from each other, comprising: (a) a first solvent comprising one or more of a glycol ether solvent, an ether alcohol solvent, and an aromatic ring-containing alcohol solvent, or a mixture thereof; and (b) a second solvent comprising one or more polyol solvents; (iii) from about 0.01 wt % to about 2 wt % of one or more corrosion inhibitors; and (iv) optionally, one or more secondary solvents; wherein the sum of wt% of components (i), (ii), (iii) and (iv) is equal to 100 wt. In a further aspect of this embodiment, the one or more neat inorganic bases comprise KOH.

[0042] In one exemplary embodiment, the photoresist stripper solution comprises: (i) from about 1.0 wt % to about 2.5 wt % of one or more neat inorganic bases; (ii) about 90 wt % to about 97 wt % of two or more organic solvents that are different from each other, comprising: (a) a first solvent comprising one or more of a glycol ether solvent, an ether alcohol solvent, and an aromatic ring-containing alcohol solvent, or a mixture thereof; and (b) a second solvent comprising one or more polyol solvents; (iii) from about 0.01 wt % to about 2 wt % of one or more corrosion inhibitors; and (iv) optionally, one or more secondary solvents; wherein the sum of the wt% of components (i), (ii), (iii) and (iv) equals 100 wt%. In a further aspect of this embodiment, the one or more neat inorganic bases comprise KOH.

[0043] In particular, photoresist stripper solutions can be used to remove polymeric resist materials present in single layer or certain types of bilayer resists. For example, bilayer resists typically have either a first inorganic layer covered by a second polymer layer or have two polymer layers.

[0044] Photoresist Stripper Solution Components (i) Inorganic base As stated above, the disclosed and claimed subject matter includes one or more inorganic bases. Preferably, the one or more inorganic bases include at least one alkali metal hydroxide, or a mixture of different alkali metal hydroxides. Suitable inorganic bases include, but are not limited to, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, and cesium hydroxide. In some embodiments, preferably, sodium hydroxide is included. In such embodiments, sodium hydroxide is used as an aqueous solution, for example, a 48 wt% aqueous solution. In other such embodiments, sodium hydroxide is used as a solid, for example, 85 wt% or 90 wt% flakes.

[0045] The metal hydroxide may be present in any neat amount ranging from about 0.1% to about 5%, or from about 0.1 wt% to about 4 wt%, or from about 0.9 wt% to about 4 wt%, or from about 0.1 wt% to about 0.8 wt%, or from about 0.4 wt% to about 0.5 wt%, or from about 0.1 wt% to about 0.2 wt%, based on the total weight of the composition. More preferably, the metal hydroxide is present in an amount of 3.5 wt% or less. In certain preferred compositions, the metal hydroxide is present at about 1.0 wt% to about 2.5 wt%. In certain preferred compositions, the metal hydroxide is present at about 1.5 wt% to about 2.25 wt%.

[0046] In one embodiment, the solution comprises about 1.0 wt% to about 2.5 wt% neat KOH. In a further aspect of this embodiment, the solution comprises about 1.75 wt% to about 2.25 wt% neat KOH. In one other aspect of this embodiment, the solution comprises about 1.75 wt% to about 2.1 wt% neat KOH. In one other aspect of this embodiment, the solution comprises about 1.75 wt% to about 2.05 wt% neat KOH. In one other aspect of this embodiment, the solution comprises about 1.75 wt% to about 2.0 wt% neat KOH. In one other aspect of this embodiment, the solution comprises about 1 wt% neat KOH. In one other aspect of this embodiment, the solution comprises about 1.25 wt% neat KOH. In another aspect of this embodiment, the solution comprises about 1.5 wt% neat KOH. In another aspect of this embodiment, the solution comprises about 1.75 wt% neat KOH. In another aspect of this embodiment, the solution comprises about 1.8 wt% neat KOH. In another aspect of this embodiment, the solution comprises about 1.9 wt% neat KOH. In another aspect of this embodiment, the solution comprises about 2.0 wt% neat KOH. In another aspect of this embodiment, the solution comprises about 2.05 wt% neat KOH. In another aspect of this embodiment, the solution comprises about 2.1 wt% neat KOH. In another aspect of this embodiment, the solution comprises about 2.15 wt% neat KOH. In another aspect of this embodiment, the solution comprises about 2.2 wt% neat KOH. In one alternative aspect of this embodiment, the solution comprises about 2.25 wt% neat KOH. In one alternative aspect of this embodiment, the solution comprises about 2.3 wt% neat KOH.

[0047] In one embodiment, the solution comprises about 1.0 wt% to about 2.5 wt% neat NaOH. In a further aspect of this embodiment, the solution comprises about 1.75 wt% to about 2.25 wt% neat NaOH. In one other aspect of this embodiment, the solution comprises about 1.75 wt% to about 2.1 wt% neat NaOH. In one other aspect of this embodiment, the solution comprises about 1.75 wt% to about 2.05 wt% neat NaOH. In one other aspect of this embodiment, the solution comprises about 1.75 wt% to about 2.0 wt% neat NaOH. In one other aspect of this embodiment, the solution comprises about 1 wt% neat NaOH. In one other aspect of this embodiment, the solution comprises about 1.25 wt% neat NaOH. In one other aspect of this embodiment, the solution comprises about 1.5 wt% neat NaOH. In one other aspect of this embodiment, the solution comprises about 1.75 wt% neat NaOH. In one other aspect of this embodiment, the solution comprises about 1.8 wt% neat NaOH. In one other aspect of this embodiment, the solution comprises about 1.9 wt% neat NaOH. In one other aspect of this embodiment, the solution comprises about 2.0 wt% neat NaOH. In one other aspect of this embodiment, the solution comprises about 2.05 wt% neat NaOH. In one other aspect of this embodiment, the solution comprises about 2.1 wt% neat NaOH. In one other aspect of this embodiment, the solution comprises about 2.15 wt% neat NaOH. In one other aspect of this embodiment, the solution comprises about 2.2 wt% neat NaOH. In one alternative aspect of this embodiment, the solution comprises about 2.25 wt% neat NaOH. In one alternative aspect of this embodiment, the solution comprises about 2.3 wt% neat NaOH.

[0048] (ii) Organic Solvent The solutions of the disclosed and claimed subject matter include two or more organic solvents (i.e., a first solvent and a second solvent), where (a) the first solvent is selected from glycol ether solvents, ether alcohol solvents, and aromatic ring-containing alcohols, and combinations thereof, and (b) the second solvent is a polyol solvent, the two solvents being different from each other.

[0049] In one embodiment, the solution comprises about 90 wt% to about 97 wt% of the two or more organic solvents. In a further aspect of this embodiment, the solution comprises about 94 wt% to about 97 wt% of the two or more organic solvents. In a further aspect of this embodiment, the two or more organic solvents comprise (a) about 60 wt% to about 80 wt% of a first solvent and (b) about 10 wt% to about 30 wt% of a second solvent. In a further aspect of this embodiment, the two or more organic solvents comprise (a) about 68 wt% to about 77 wt% of a first solvent and (b) about 11 wt% to about 28 wt% of a second solvent.

[0050] First Solvent In some embodiments, the first solvent is selected from ether alcohol, aromatic ring-containing alcohol solvent or mixture thereof. One type of ether alcohol solvent may be glycol ether. Suitable glycol ether solvents include, but are not limited to, 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, triethylene glycol monomethyl ether (TEGME), triethylene glycol monomethyl ether, triethylene glycol monopropyl ether and triethylene glycol monobutyl ether. Other suitable types of ether alcohol solvents are not glycol ethers (i.e., other alcohols with ether groups). Examples include 3-methoxy-3-methyl-1-butanol (MMB), furfuryl alcohol, and tetrahydrofurfuryl alcohol.

[0051] Suitable aromatic ring-containing alcohol solvents include substituted benzenes such as benzyl alcohol, benzyl ethanol and benzyl propanol.

[0052] In one embodiment, the first solvent comprises triethylene glycol monomethyl ether (TEGME). In a further aspect of this embodiment, the first solvent is about 60 wt% to about 80 wt% triethylene glycol monomethyl ether (TEGME). In a further aspect of this embodiment, the first solvent is about 68 wt% to about 77 wt% triethylene glycol monomethyl ether (TEGME).

[0053] Second Solvent As described above, the second solvent is different from the first solvent and is a polyol solvent. In some embodiments, the second solvent includes, but is not limited to, one or more of ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG), dipropylene glycol, glycerol, and propylene glycol (PG). In a further aspect of this embodiment, the second solvent includes about 10 wt% to about 30 wt% of ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG), dipropylene glycol, glycerol, and propylene glycol (PG). In a further aspect of this embodiment, the second solvent includes about 10 wt% to about 30 wt% of diethylene glycol (DEG) and propylene glycol (PG). In a further aspect of this embodiment, the second solvent includes about 11 wt% to about 28 wt% of diethylene glycol (DEG) and propylene glycol (PG).

[0054] In one embodiment, the two or more organic solvents include (a) a first solvent comprising from about 60 wt% to about 80 wt% of one or more of an ether alcohol, an aromatic ring-containing alcohol solvent, or a mixture thereof, and (b) a second solvent comprising from about 10 wt% to about 30 wt% of one or more of a polyol solvent. In a further aspect of this embodiment, the two or more organic solvents include (a) a first solvent comprising from about 68 wt% to about 77 wt% of one or more of an ether alcohol, an aromatic ring-containing alcohol solvent, or a mixture thereof, and (b) a second solvent comprising from about 11 wt% to about 28 wt% of one or more of a polyol solvent.

[0055] In one embodiment, the two or more solvents include (a) a first solvent comprising about 60 wt % to about 80 wt % triethylene glycol monomethyl ether (TEGME) and (b) a second solvent comprising about 10 wt % to about 30 wt % of one or more polyol solvents.

[0056] In one embodiment, the two or more organic solvents include (a) about 60 wt % to about 80 wt % of a first solvent, which is one or more of an ether alcohol, an aromatic ring-containing alcohol, or a mixture thereof; and (b) about 10 wt % to about 30 wt % of a second solvent, which is one or more of ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG), glycerol, propylene glycol (PG), and a mixture thereof.

[0057] In one embodiment, the two or more organic solvents include (a) a first solvent comprising about 68 wt% to about 77 wt% triethylene glycol monomethyl ether (TEGME) and (b) a second solvent comprising about 11 wt% to about 28 wt% ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG), glycerol, propylene glycol (PG) and mixtures thereof. In a further aspect of this embodiment, the two or more organic solvents include (a) a first solvent comprising about 68 wt% to about 77 wt% triethylene glycol monomethyl ether (TEGME) and (b) a second solvent comprising about 11 wt% to about 28 wt% diethylene glycol (DEG) and propylene glycol (PG).

[0058] In other embodiments, the two or more organic solvents comprise from about 50 wt% to about 90 wt%, or from 55 wt% to about 90 wt%, based on the weight of the composition. Other embodiments of the disclosed and claimed subject matter include from about 60 wt% to about 88 wt%, or from 65% to 85% glycol ether solvent and / or aromatic-containing alcohol. The two or more organic solvents, individually or collectively, may be within the ranges bounded by the following list of weight percents: 50, 55, 58, 60, 62, 65, 67, 70, 72, 75, 77, 80, 82, 85, 88, and 90.

[0059] In some embodiments, the solution is free or essentially free of amide-containing solvents, where essentially free means less than 1 percent, or less than 0.1 wt%, or less than 0.01 wt%, or less than 0.001 wt%, or free, where free is undetectable or zero.

[0060] In other embodiments, the solution may be free or essentially free of sulfur-containing solvents. In a further aspect of this embodiment, the composition is free or essentially free of dimethylsulfoxide (DMSO) and n-methyl-2-pyrrolidone (NMP). Essentially free means less than 1 percent, or less than 0.1 wt%, or less than 0.01 wt%, or less than 0.001 wt%, or free, where free is undetectable or 0.

[0061] (iii) Corrosion inhibitors The solutions of the disclosed and claimed subject matter include one or more corrosion inhibitors. Suitable corrosion inhibitors include, but are not limited to, aromatic hydroxyl and aromatic polyhydroxyl compounds such as catechol and resorcinol; alkyl catechols such as methyl catechol, ethyl catechol, and t-butyl catechol, phenol and pyrogallol; aromatic triazoles such as benzotriazole; alkyl benzotriazoles and aminobenzotriazoles such as 1-aminobenzotriazole; thiazoles such as 2-aminobenzothiazole (ABT); sugar alcohols such as glycerol, xylitol, and sorbitol; 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; copper(II) sulfate; carboxylic acids such as sebacic acid, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fumanic acid, butyl ester ... and organic corrosion inhibitors including carboxylic 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 such as methyl gallate and propyl gallate; organic salts of carboxylic acids containing the above organic compounds, and chelates such as phosphonic acid based chelates (including 1,2-propanediaminetetramethylene phosphonate and hydroxyethane phosphonate), carboxylic acid based chelates (such as ethylenediaminetetraacetic acid and its sodium and ammonium salts, dihydroxyethylglycine and nitrilotriacetic acid), amine based chelates (such as bipyridine, tetraphenylporphyrin and phenanthroline) and oxime based chelates (such as dimethylglyoxime and diphenylglyoxime). In other embodiments, the one or more corrosion inhibitors may include only 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; copper(II) selenate, and / or copper(II) sulfate.In yet another embodiment, the composition may include the organic corrosion inhibitor and / or chelating compound described above and one or more copper salts. In yet another embodiment, the one or more corrosion inhibitors may be copper(II) nitrate (e.g., NADA / 1N is about 26.3% copper(II) nitrate hemi(pentahydrate-non-oxidizing agent)), copper(II) bromide; copper(II) chlorate; copper(II) chloride; copper(II) fluorosilicate; copper(II) formate; copper(II) selenate; copper(II) sulfate and / or resorcinol. In yet another embodiment, the corrosion inhibitor may include copper(II) nitrate and resorcinol.

[0062] In other embodiments, the corrosion inhibitor may comprise an aliphatic or aromatic polyhydroxyl compound, which may be ethylene glycol; 1,2-propanediol (propylene glycol); 1,3-propanediol; 1,2,3-propanediol; 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;Trimethylolpropane;Xylitol 1,2- or 1,3-cyclopentanediol;2,3-norbornanediol;1,8-octanediol;1,2-cyclohexane-dimethanol;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-1,3-propanediol Polyhydroxyl compounds include, but are not limited to, polyphenylene sulfide; 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; mannitol; resorcinol; catechol; and the like, as well as combinations of two or more of the foregoing polyhydroxyl compounds.

[0063] In some embodiments, the one or more corrosion inhibitors are present in the solution at a level of about 0.005 wt% to about 10 wt%. In one embodiment, the solution contains about 0.25 wt% to about 5 wt%, or 0.1 wt% to about 4 wt%, or 0.25 wt% to about 2 wt%. The one or more corrosion inhibitors may be present in any amount bounded by an endpoint selected from the following wt%: 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. First and second corrosion inhibitors can be used in the composition. This disclosure and claimed subject matter includes a method of treating a semiconductor substrate with the composition to remove photoresist without damaging a passivation layer, such as a film, layer, metal, or other structure on the substrate, including PI and PBO. A preferred temperature for treating the semiconductor substrate is about 70° C. For many applications, temperatures of about 45° C. to about 90° C. or about 50° C. to about 75° C. are useful. In certain applications where the substrate is sensitive or longer removal times are required, lower contact temperatures are appropriate. For example, for reprocessing substrates, it may be appropriate to maintain the stripper solution at a temperature of at least 20° C. for a longer period of time to remove the photoresist and avoid damage to the substrate.

[0064] In some embodiments, the one or more corrosion inhibitors include one or more of BZT, sorbitol, resorcinol, sebacic acid, glycerol, and copper (II) nitrate. In some embodiments, these corrosion inhibitors (alone or in combination) are present at about 0.01 wt% to about 2 wt%. In some embodiments, these corrosion inhibitors (alone or in combination) are present at about 0.2 wt% to about 1 wt%. In some embodiments, these corrosion inhibitors (alone or in combination) are present at about 0.5 wt%.

[0065] In some embodiments, the one or more corrosion inhibitors include BZT. In one aspect of this embodiment, the solution includes about 0.5 wt% to about 1 wt% BZT. In one other aspect of this embodiment, the solution includes about 0.5 wt% BZT. In one other aspect of this embodiment, the solution includes about 1.0 wt% BZT.

[0066] In some embodiments, the one or more corrosion inhibitors include sorbitol. In one aspect of this embodiment, the solution includes about 0.2 wt% to about 1 wt% sorbitol. In one other aspect of this embodiment, the solution includes about 0.2 wt% sorbitol. In one other aspect of this embodiment, the solution includes about 0.5 wt% sorbitol. In one other aspect of this embodiment, the solution includes about 1.0 wt% sorbitol.

[0067] In some embodiments, the one or more corrosion inhibitors include resorcinol. In one aspect of this embodiment, the solution includes about 0.2 wt% to about 1 wt% resorcinol. In one other aspect of this embodiment, the solution includes about 0.2 wt% resorcinol. In one other aspect of this embodiment, the solution includes about 0.5 wt% resorcinol. In one other aspect of this embodiment, the solution includes about 1.0 wt% resorcinol.

[0068] In some embodiments, one or more of the corrosion inhibitors comprises glycerol. In one aspect of this embodiment, the solution comprises about 0.2 wt% to about 1 wt% glycerol. In one other aspect of this embodiment, the solution comprises about 0.2 wt% glycerol. In one other aspect of this embodiment, the solution comprises about 0.5 wt% glycerol. In one other aspect of this embodiment, the solution comprises about 1.0 wt% glycerol.

[0069] In some embodiments, the one or more corrosion inhibitors include sebacic acid. In one aspect of this embodiment, the solution includes about 0.2 wt% to about 1 wt% sebacic acid. In one other aspect of this embodiment, the solution includes about 0.2 wt% sebacic acid. In one other aspect of this embodiment, the solution includes about 0.5 wt% sebacic acid. In one other aspect of this embodiment, the solution includes about 1.0 wt% sebacic acid.

[0070] In some embodiments, the one or more corrosion inhibitors include copper nitrate. In one other aspect of this embodiment, the solution includes about 0.005 wt% to about 0.5 wt% copper nitrate. In one other aspect of this embodiment, the solution includes about 0.01 wt% copper nitrate. In one other aspect of this embodiment, the solution includes about 0.2 wt% copper nitrate. In one other aspect of this embodiment, the solution includes 0.5 wt% copper nitrate.

[0071] (iv) Secondary Solvent (Optional) Some embodiments may contain a secondary solvent in addition to the solvents listed above. Alternatively, in some embodiments, the stripper solution may be free or substantially free of secondary solvents.

[0072] In some embodiments, the secondary solvent comprises water or an alcohol containing one hydroxyl group.

[0073] The secondary organic solvent may be a linear or branched aliphatic or aromatic alcohol. Examples of secondary alcohols 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-docosene-1-ol, 1-tetracosanol, 1-hexacosanol, 1-heptacosanol, 1-octacosanol, 1-triacontanol, 1-dotriacontanol, 1-tetratriacontanol and cetearyl alcohol.

[0074] When used, the secondary organic solvent may comprise from about 0.02% to about 50%, or from about 0.08% to about 38%, or from about 0.1% to about 35%, or from about 0.2% to about 33%, or from about 0.3% to about 20%, or from about 1% to about 15% of the composition. In alternative embodiments, the secondary solvent may be present in any amount bounded by an endpoint selected from the following wt %: 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, 28, 30, 32, 35, 37, 40, 43, 45, 47, and 50.

[0075] Other optional or not considered ingredients In some embodiments, the disclosed and claimed solutions are substantially free or free of one or more of the following, in any combination: nitrogen-containing solvents, bischoline salts, tricholine salts, oxoammonium compounds, hydroxylamines and their derivatives, hydrogen peroxide, oxidizing agents, surfactants, and combinations thereof (as these terms are defined above).

[0076] In some embodiments, the compositions disclosed herein are formulated to be substantially free of, or free of, at least one of the following chemical compounds: alkylthiols and organosilanes.

[0077] In some embodiments, the disclosed and claimed solutions are formulated to be substantially free or free of one or more of halide-containing compounds, for example, may be substantially free or free of one or more of the following: fluorine, bromine, chlorine, or iodine-containing compounds.

[0078] In some embodiments, the disclosed and claimed solutions are substantially free or free of sulfonic acid and / or phosphonic acid and / or sulfuric acid and / or nitric acid and / or hydrochloric acid.

[0079] In some embodiments, the disclosed and claimed solutions are substantially free or free of 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.

[0080] In some embodiments, the disclosed and claimed solutions are substantially free or free of surfactants.

[0081] In some embodiments, the disclosed and claimed solutions are substantially free or free of amphoteric salts, and / or cationic surfactants, and / or anionic surfactants, and / or zwitterionic surfactants, and / or non-ionic surfactants.

[0082] In some embodiments, the disclosed and claimed solutions are substantially free or free of imidazole and / or anhydride.

[0083] In some embodiments, the disclosed and claimed solutions are substantially free or free of pyrrolidone and / or acetamide.

[0084] In some embodiments, the disclosed and claimed solutions are substantially free or free of any amines and alkanolamines.

[0085] In some embodiments, the disclosed and claimed solutions are substantially free or free of peroxy compounds, and / or peroxides, and / or persulfides, and / or percarbonates, and acids thereof, and salts thereof.

[0086] In some embodiments, the disclosed and claimed solutions are substantially free or free of iodates, and / or perborates, and / or percarbonates, and / or peracids, and / or cerium compounds, and / or cyanides, and / or periodic acid, and / or ammonium molybdate, and / or ammonia, and / or abrasives.

[0087] How to use The disclosed and claimed subject matter further includes a method for removing, in whole or in part, one or more photoresists or similar materials from a substrate using one or more of the disclosed and claimed photoresist stripper solutions. As described above, the disclosed and claimed photoresist stripper solutions can be used to remove polymeric resist materials present in a single layer or in a certain type of bilayer resist. By using the method described below, a single layer of polymeric resist can be effectively removed from a standard wafer having a single polymer layer. Furthermore, the method can be used to remove a single polymer layer from a wafer having a bilayer 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 bilayer composed of two polymer layers.

[0088] In one aspect of this embodiment, a process or method for removing photoresist or similar material from a substrate comprises: (i) contacting the substrate with one or more photoresist stripper solutions for a time sufficient to remove a desired amount of photoresist or similar material; (ii) removing the substrate from the stripper solution; (iii) rinsing the stripper solution from the substrate with DI water or a solvent; and (iv) optionally drying the substrate Includes.

[0089] In one embodiment, step (i) comprises immersing the substrate in one or more photoresist stripper solutions and, optionally, agitating the substrate to facilitate removal of the photoresist. Such agitation can be effected by mechanical agitation, by circulation, or by bubbling an inert gas through the composition.

[0090] In one embodiment, step (ii) comprises rinsing the rinsed substrate with water or alcohol. In one aspect of this embodiment, DI water is the preferred form of water. In one other aspect of this embodiment, isopropanol (IPA) is the preferred solvent. In one other aspect of this embodiment, the components that undergo oxidation may be rinsed or rinsed under an inert atmosphere.

[0091] Using the above methods (and variations thereof), the disclosed and claimed photoresist stripper solutions can be used for the removal of thick positive or negative photoresists, and thin positive or negative photoresists. In advanced packaging applications for semiconductor devices, the thick photoresist can be 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 solution can be used to remove about 1 μm to about 100 μm or more, or about 2 μm to 100 μm, or about 3 μm to 100 μm of photoresist. EXAMPLES

[0092] Reference is made hereinafter to more specific embodiments of the present disclosure and experimental results, which provide support for such embodiments. 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.

[0093] It will be apparent to those skilled in the art that various modifications and variations can be made in the disclosed subject matter and the specific examples provided herein without departing from the spirit and scope of the disclosed subject matter. Thus, the subject matter of the present disclosure, including the description provided by way of the following examples, is intended to cover modifications and variations of the disclosed subject matter that come within the scope of the appended claims and their equivalents.

[0094] Materials and Methods All materials used in this patent application were purchased and / or available from Sigma Aldrich and were used in the formulations as delivered.

[0095] The cleaning performance and polyimide (PI) compatibility were examined using optical and scanning electron microscopy. The Cu and Al etch rates are determined by measuring the film thickness using a four-point probe RESMAP before and after treatment in the formulations.

[0096] In the various compositions of the tables that follow, the following abbreviations are used: [Table 1] Low temperature cure PI is a polyimide passivation layer (or insulator layer) that is cured at approximately less than 250°C.

[0097] In the examples, various stripper compositions (Examples and Comparative Examples) including the formulations identified in the following tables were tested for their ability to remove photoresist from semiconductor wafer samples. The semiconductor wafer coupon-sized samples were plated silicon wafers with Cu pillars and Sn / Ag solder caps with a thickness of spin-on photoresist thereon. Photoresist removal was performed using an immersion process in a beaker. The photoresist on the test coupons was a negative spin-on photoresist. The other test coupons had a passivation layer of polyimide (PI) on them. Unless otherwise noted, where necessary, the amounts of materials in all tables are reported in wt% values ​​and reflect "neat" values. The remainder of the formulation weight is derived from water present in the raw materials.

[0098] Table 1 lists the Cu and Al etch rates, PI compatibility and photoresist removal efficiency. The test results recorded in Table 1 are for photoresist removal from the patterned coupon and compatibility with a separate coupon with a PI passivation layer at specific processing conditions (temperature and time). Table 1. Comparative Example Formulations [Table 2] Table 2. Example Formulations [Table 3] Table 3. Example Formulations [Table 4]

[0099] Analysis of Example Formulations Analysis 1: Corrosion Inhibitors and Etch Rates Tables 4 and 5 list (i) comparative stripper solutions and (ii) solutions according to the disclosed and claimed subject matter that were tested using an immersion process to measure Cu and Al etch rates. Tests were performed using blanket Cu and Al wafers. For the immersion process, three coupon-sized samples of semiconductor wafers were processed in a beaker. The beaker was charged with 100 grams of the stripper composition and heated to the target temperature. When the stripper composition was at the target temperature, the three coupons were placed in a holder in the beaker and slightly agitated by a stir bar. The temperature was maintained at the process temperature in the table throughout the process. After a total process time of 25 minutes, the coupons were removed from the beaker, rinsed with DI water and IPA, and dried with a stream of nitrogen.

[0100] RESMAP was used to measure the thickness of the Cu or Al layer before and after treatment for each coupon, and the change in thickness and etch rate was calculated. In Tables 4 and 5, a single corrosion inhibitor or a combination of two corrosion inhibitors was investigated by monitoring the Cu etch rate and the aluminum etch rate. All of the corrosion inhibitors listed in Tables 4 and 5 reduce Cu etching to different degrees (formulations 1-17) compared to no corrosion inhibitor (Comparative Example 2). The solutions of the disclosed and claimed subject matter shown in Tables 4 and 5 reduce the Al etch rate significantly more than Comparative Examples 1 and 2, except for formulations 4-7. Table 4. Effect of corrosion inhibitors on Cu and Al etch rates [Table 5] Table 5. Effect of corrosion inhibitors on Cu and Al etch rates [Table 6]

[0101] Analysis 2: Resist cleaning performance Table 6 lists various (i) comparative stripping solutions and (ii) solutions according to the disclosed and claimed subject matter that were tested using immersion processes and semiconductor wafers having 65 μm thick negative tone spin-on photoresist plated with Cu pillars and Sn / Ag solder caps. For the immersion processes, coupon sized semiconductor wafer samples were processed in a beaker. The beaker was filled with 100 grams of stripping solution and heated to a target temperature of 80° C. When the stripping solution was at the target temperature, the coupon was placed in a holder in the beaker and slightly agitated by a stir bar. The coupon was contacted during the cleaning process while the temperature was maintained at the processing temperature. After one set of processes, the coupon was removed from the beaker, rinsed with DI water and IPA, and dried with a stream of nitrogen.

[0102] Resist removal was defined as "clean" when all resist was removed from the wafer coupon surface; "almost clean" when at least 95% of the resist was removed from the surface; and "partially clean" when about 80% of the resist was removed. All formulations were able to completely remove the positive photoresist at 80°C for 50 minutes, except for Examples 8, 12, and 16, where the coupons were almost clean after 50 minutes. Table 6: Resist removal performance [Table 7]

[0103] Analysis 4: Polyimide Compatibility Table 7 lists the results for (i) comparative stripping solutions and (ii) solutions according to the disclosed and claimed subject matter evaluated with low temperature cured polyimide (PI) films. These tests were performed using semiconductor wafers patterned with cured PI films. For the immersion process, coupon-sized semiconductor wafer samples were processed in a beaker. The beaker was charged with 100 grams of stripping solution and heated to the target temperature. When the stripping solution was at the processing temperature, the coupon was placed in a holder in the beaker and slightly agitated by a stir bar. The temperature was maintained at the processing temperature throughout the process. After a total processing time of 90 minutes, the coupon was removed from the beaker, rinsed with DI water and IPA, and dried with a stream of nitrogen.

[0104] The PI film pattern was monitored using optical and scanning electron microscopy before and after treatment for each coupon tested. Note that cracks or visible damage on the film surface are indicative of poor compatibility of the PI. All examples of the disclosed and claimed subject matter except for Example 13 had good compatibility after 90 minutes, while Comparative Example 1 showed PI attack. Table 7: PI compatibility [Table 8]

[0105] While the disclosed and claimed subject matter has been described and illustrated with a certain degree of particularity, it will be understood that the disclosure is for purposes of illustration only and that many variations in the conditions and sequence of steps could be made by one skilled in the art without departing from the spirit and scope of the disclosed and claimed subject matter.

[0106] Thus, one skilled in the art may make various modifications and equivalents may be substituted for elements thereof without departing from the scope of the disclosed and claimed subject matter. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the disclosed and claimed subject matter without departing from the essential scope of the disclosed and claimed subject matter. In addition, all numerical values ​​specified in the detailed description are intended to be explicitly specified both as exact values ​​and as approximate values.

Claims

1. (i) from about 1.0 wt % to about 2.5 wt % of one or more neat inorganic bases; (ii) about 90 wt % to about 97 wt % of two or more organic solvents that are different from each other, comprising: (a) a first solvent comprising one or more of a glycol ether solvent, an ether alcohol solvent, and an aromatic ring-containing alcohol solvent, or a mixture thereof; and (b) a second solvent comprising one or more polyol solvents; (iii) from about 0.01 wt % to about 2 wt % of one or more corrosion inhibitors; and (iv) optionally, one or more secondary solvents; wherein the sum of components (i), (ii), (iii) and (iv) is 100 wt % or less.

2. 10. The photoresist stripper solution of claim 1, wherein the one or more neat inorganic bases comprise about 1.75 wt % to about 2.25 wt % neat KOH.

3. 10. The photoresist stripper solution of claim 1, wherein the one or more neat inorganic bases comprise one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, and cesium hydroxide.

4. 2. The photoresist stripper solution of claim 1, wherein the two or more organic solvents comprise: (a) a first solvent comprising from about 60 wt % to about 80 wt % of one or more of an ether alcohol, an aromatic ring-containing alcohol solvent, or a mixture thereof; and (b) a second solvent comprising from about 10 wt % to about 30 wt % of one or more polyol solvents, wherein the first solvent and the second solvent are different from each other.

5. 2. The photoresist stripper solution of claim 1, wherein the two or more organic solvents comprise: (a) a first solvent comprising about 60 wt % to about 80 wt % triethylene glycol monomethyl ether (TEGME); and (b) a second solvent comprising about 10 wt % to about 30 wt % one or more of ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG), glycerol, propylene glycol (PG), and mixtures thereof, wherein the first solvent and the second solvent are different from each other.

6. 10. The photoresist stripper solution of claim 1, wherein the one or more corrosion inhibitors include one or more of BZT, sorbitol, resorcinol, sebacic acid, glycerol, and copper (II) nitrate.

7. 10. The photoresist stripper solution of claim 1, wherein the one or more corrosion inhibitors comprise about 0.5 wt% to about 1 wt% BZT.

8. 10. The photoresist stripper solution of claim 1, wherein the one or more corrosion inhibitors comprise about 0.2 wt % to about 1 wt % sorbitol.

9. 10. The photoresist stripper solution of claim 1, wherein the one or more corrosion inhibitors comprise about 0.2 wt % to about 1 wt % resorcinol.

10. 10. The photoresist stripper solution of claim 1, wherein the one or more corrosion inhibitors comprise about 0.2 wt% to about 1 wt% glycerol.

11. 10. The photoresist stripper solution of claim 1, wherein the one or more corrosion inhibitors comprise about 0.2 wt % to about 1 wt % sebacic acid.

12. 10. The photoresist stripper solution of claim 1, wherein the one or more corrosion inhibitors comprise about 0.005 wt % to about 1 wt % copper nitrate.

13. 10. The photoresist stripper solution of claim 1 which is free of amide-containing solvents.

14. 10. The photoresist stripper solution of claim 1 which is free of sulfur-containing solvents.

15. 10. The photoresist stripper solution of claim 1 which is free of dimethylsulfoxide (DMSO).

16. 10. The photoresist stripper solution of claim 1 which does not contain n-methyl-2-pyrrolidone (NMP).

17. 10. The photoresist stripper solution of claim 1, which is free of dimethylsulfoxide (DMSO) and n-methyl-2-pyrrolidone (NMP).

18. 10. The photoresist stripper solution of claim 1 further comprising a secondary solvent comprising water.

19. 10. The photoresist stripper solution of claim 1 comprising from about 2.03 wt% KOH, about 12.75 wt% propylene glycol, about 69.5 wt% triethylene glycol monomethyl ether and about 15 wt% diethylene glycol, about 0.5 wt% sorbitol.

20. 1. A method for removing photoresist or similar material from a substrate, comprising: (i) contacting a substrate with one or more of the photoresist stripper solutions of claim 1 for a time sufficient to remove a desired amount of the photoresist or similar material; (ii) removing the substrate from the photoresist stripper solution; (iii) rinsing the photoresist stripper solution from the substrate with DI water or a solvent; (iv) optionally drying the substrate. A method comprising: