JP4499751B2 - Formulation for removing photoresist, etch residue and BARC and method comprising the same - Google Patents

Description

  The manufacture of microelectronic structures involves a number of steps. Within integrated circuit processing manufacturing schemes, selective etching of the semiconductor surface is sometimes required. Historically, a number of very different types of etching processes for selective material removal have been successfully utilized to varying degrees. Furthermore, selective etching of the various layers within the microelectronic structure is considered a critical and critical step in the integrated circuit processing process.

  In the manufacture of semiconductors and semiconductor microcircuits, it is often necessary to coat the substrate material with a polymeric organic material. Examples of some substrate materials include silicon wafers coated with silicon dioxide, which may contain metallic elements such as titanium, copper, and also titanium, copper, and the like. Generally, the polymeric organic material is a photoresist material. This is a material for forming an etch mask in development after exposure to light. In subsequent process steps, at least a portion of the photoresist is removed from the surface of the substrate. One common method of removing the photoresist from the substrate is by wet chemical means. A wet chemical composition formulated to remove photoresist from a substrate corrodes, dissolves and / or cloudes the surface of any metal circuit; chemically converts to an inorganic substrate; and The photoresist must be removed without attacking the substrate itself. Another method of removing the photoresist is by dry ashing, where the photoresist is removed by plasma ashing using either a forming gas such as oxygen or hydrogen. The residue or by-product may be the photoresist itself or a combination of photoresist, underlying substrate and / or etch gas. These residues or by-products are often referred to as sidewall polymers, veils or fences.

  Increasingly, reactive ion etching (RIE) is an optimal process for pattern transfer during the formation of vias, metal lines and trenches. For example, complex semiconductor devices such as advanced DRAMs and microprocessors (which require multiple layers behind the interconnect wiring lines) use RIE to create vias, metal lines and trench structures To do. Vias are used through the interlayer dielectric to provide contact between one level of silicon, silicon compound or metal wiring and the level of the adjacent wiring. Metal lines are conductive structures used as device interconnects. The trench structure is used in forming a metal line structure. Bottom (formed under the resist) anti-reflective coating (BARC) and void filling materials (which are generally highly crosslinked organic polymeric materials) are widely used in semiconductor substrates including copper. The BARC material may also include, for example, silicon. Vias, metal lines and trench structures are generally metals and alloys, such as Al-Cu, Cu, Ti, TiN, Ta, TaN, W, TiW, silicon or silicon compounds (eg tungsten, titanium or cobalt silicon compounds). To expose. The RIE process is generally used to define residues that may contain re-sputtered oxide material, as well as possibly organic material derived from photoresist and lithographically via, metal line or trench structures. The protective coating material is also left behind.

  Therefore, it is possible to remove residues such as residual photoresist, BARC and / or process residues (for example, residues resulting from selective etching using plasma and / or RIE). It would be desirable to provide a clean cleaning composition and process. In addition, residues such as photoresist, BARC and etch residues can be removed, including metals, high dielectric constant materials (referred to herein as “high-k”), silicon, silicon compounds and / or High for residue compared to interlevel dielectric materials including low dielectric constant materials such as deposited oxides (herein referred to as “low-k”) that may be exposed to the cleaning composition It would be desirable to provide selective cleaning compositions and processes that exhibit selectivity. It would be desirable to provide a composition that is compatible with and can be used together with delicate low-k films such as HSQ, MSQ, FOx, black diamond and TEOS (tetraethyl silicate).

  The formulations disclosed herein can selectively remove residues (e.g., photoresists, ion-implanted photoresists, void fillers, BARCs and / or other polymeric materials), and / or inorganic materials and process residues. Can be removed from the substrate without attacking any undesired areas of metal, low-k dielectric, and / or high-k dielectric material that may be exposed to the formulation It is. Formulations for removing photoresist, etch residue or BARC include ammonium hydroxide and 2-aminobenzothiazole, residual water. Preferred formulations are tetramethylammonium hydroxide, tolyltriazole, propylene glycol, 2-aminobenzothiazole, dipropylene glycol monomethyl ether, residual water: more preferably 1-15% by weight tetramethylammonium hydroxide, 1-5% % Tolyltriazole, 5-15% by weight propylene glycol, 1-10% by weight 2-aminobenzothiazole, 20-45% by weight dipropylene glycol monomethyl ether, residual water. Certain more preferred formulations are 6.5% by weight tetramethylammonium hydroxide, 3% by weight tolyltriazole, 10% by weight propylene glycol, 6% by weight 2-aminobenzothiazole, 39% by weight dipropylene glycol. Contains monomethyl ether and residual water. Another particular more preferred formulation is 5% by weight tetramethylammonium hydroxide, 3% by weight tolyltriazole, 12.13% by weight propylene glycol, 1.5% by weight 2-aminobenzothiazole, 40% by weight. Of dipropylene glycol monomethyl ether and residual water. The present invention is also a method of removing a material selected from the group consisting of photoresist, etch residue, BARC, and combinations thereof from a substrate, the formulation described above for removing the material from the substrate. Applying an object to a substrate.

  Selective residues (eg, photoresist, ion-implanted photoresist, void filler, bottom anti-reflective coating (BARC) and other polymeric materials) and / or process residues (eg, residues produced by etching) Described herein are formulations for removal and methods involving the same. In cleaning methods involving practical substrates for microelectronic devices, typical contaminants that are removed include, for example, exposed and / or ashed photoresist materials, ashed photo Organic compounds such as resist residues, UV- or X-ray-cured photoresists, C-F-containing polymers, low and high molecular weight polymers, and other organic etch residues; chemical mechanical planarization (CMP) Inorganic compounds such as ceramic particles derived from slurry, metal oxides and other inorganic etch residues; metal-containing compounds such as organometallic residues and metal organic compounds; produced by processes such as planarization and etching processes It may include ionic and neutral, light and heavy inorganic (metal) species, moisture, and insoluble materials, including particles. In one particular embodiment, the residue removed from the substrate comprises a silicon-containing BARC residue.

Residue is generally present in the substrate, which may also be metal, silicon, silicon compounds and / or interlevel dielectric materials (eg, deposited silicon oxide and derivatized silicon oxide (eg, HSQ, MSQ, FOX, TEOS and spin-on glass)), chemical vapor deposition dielectric materials, low-k materials and / or high-k materials (eg hafnium silicate, hafnium oxide, barium strontium titanate (BST), TiO ₂ , TaO ₅ ) Where the residue and the metal, silicon, silicate, interlevel dielectric material, low-k material and / or high-k material are both in contact with the cleaning formulation. The formulations and methods disclosed herein provide photoresists, ion-implanted photoresists, without significantly attacking metals, silicon, silicon dioxide, interlevel dielectric materials, low-k materials and / or high-k materials, It provides for the selective removal of residues such as BARC, void fillers, and / or process residues. In certain embodiments, the substrate may comprise a metal such as, but not limited to, copper, copper alloys, titanium, titanium nitride, tantalum, tantalum nitride, tungsten, and / or titanium / tungsten alloys. In certain embodiments, the formulations disclosed herein may be suitable for substrates having delicate low-k membranes. In certain embodiments, the substrate may comprise a low-k material, a high-k material, or a combination thereof.

In one aspect, a formulation for removing residues from a substrate comprising BARC is provided, the formulation comprising dipropylene glycol monomethyl ether, tetramethylammonium hydroxide, tolyltriazole, propylene glycol, 2-aminobenzothiazole, and Contains deionized water. More preferably the formulation is 20-45% by weight dipropylene glycol monomethyl ether, 1-15% by weight tetramethylammonium hydroxide, 1-5% by weight tolyltriazole, 5-15% by weight propylene glycol, 10% by weight of 2-aminobenzothiazole and residual deionized water. Certain more preferred formulations are 6.5% by weight tetramethylammonium hydroxide, 3.0% by weight tolyltriazole, 10% by weight propylene glycol, 6% by weight 2-aminobenzothiazole, 39% by weight di-dioxide. Contains propylene glycol monomethyl ether and residual water. Another particular more preferred formulation is 5% by weight tetramethylammonium hydroxide, 3% by weight tolyltriazole, 12.13% by weight propylene glycol, 1.5% by weight 2-aminobenzothiazole, 40% by weight. Of dipropylene glycol monomethyl ether and residual water. This hydroxide should be contaminated with metals such as K, Na, etc. at 100 ppm or less. The formulations disclosed herein include oxidants, abrasive particles, or optional additive ingredients that adversely affect the stripping and cleaning capabilities of the formulation or damage one or more surfaces of the underlying substrate. Absent. Examples of oxidizing agents include, but are not limited to, hydrogen peroxide (H ₂ O ₂ ), monopersulfate, iodate, magnesium perphthalate, peracetic acid and other peracids, persulfate, bromate , Periodate, nitrate, nitric acid, iron salt, cerium salt, Mn (III), Mn (IV) and Mn (VI) salt, silver salt, copper salt, chromium salt, cobalt salt, halogen hypochlorite As well as mixtures thereof. Examples of abrasive particles include diamond particles as well as metal oxides, borides, carbides, alumina, ceria and silica and mixtures thereof. In certain embodiments, the formulation is used to remove residues such as abrasive particles contained in a CMP solution derived from a CMP process. The formulations disclosed herein are preferably free of such particles.

  Water is also present in the formulations disclosed herein. Water is present in an amount ranging from about 1% to about 95%, or from about 1% to about 75%, or from about 1 to about 50% by weight. It can be incidentally present as a component of other elements, such as, for example, an aqueous solution containing a fluoride ion source or a quaternary ammonium compound, or it can be added separately. . Some non-limiting examples of water include deionized water, ultrapure water, distilled water, doubly distilled water, or deionized water having a low metal content.

In certain embodiments, the formulations disclosed herein may include an organic solvent that is preferably water soluble as an optional component. The water soluble organic solvent is present in an amount ranging from about 0% to about 60%, or from about 0% to about 55%, or from about 0% to about 50% by weight. Examples of the water-soluble organic solvent include, but are not limited to, dimethylacetamide (DMAC), N-methylpyrrolidinone (NMP), dimethylsulfoxide (DMSO), dimethylformamide, N-methylformamide, formamide, dimethyl-2-piperidone ( DMPD), tetrahydrofurfuryl alcohol, glycerol, ethylene glycol, and other amides, alcohols or sulfoxides, or polyfunctional compounds (eg, hydroxyamides or aminoalcohols). Further examples of the water-soluble organic solvent comprises a _(C 2 _{-C 20)} alkanediols and _(C 3 _{-C 20)} diols such as alkane triol and polyol, cyclic alcohols and substituted alcohols. Specific examples of these water-soluble organic solvents include propylene glycol, tetrahydrofurfuryl alcohol, diacetone alcohol and 1,4-cyclohexanedimethanol. In certain embodiments, the organic polar solvent may be DMSO, NMP, and / or DMAC. The water-soluble organic solvents listed above may be used alone or in combination with two or more solvents.

  In certain embodiments, the water-soluble organic solvent may comprise a glycol ether. Examples of glycol ethers are ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol Monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monobenzyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, poly Tylene glycol monomethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, di Propylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol diisopropyl ether, tripropylene glycol monomethyl ether, 1-methoxy-2- Including ethanol, 2-methoxy-1-butanol, 2-methoxy-2-methylbutanol, 1,1-dimethoxyethane and 2- (2-butoxyethoxy) ethanol.

In certain embodiments, the formulation may optionally comprise from about 0.1% to about 5% by weight of substituted hydroxylamine or an acid salt thereof. Typical hydroxylamines include diethylhydroxylamine and their lactate and citrate.

  In certain embodiments, the formulation may optionally include an organic acid. The organic acid is present in an amount ranging from about 0% to about 10%, or from about 0% to 5%, or from about 0% to about 2% by weight of the formulation. Typical organic acids include, but are not limited to, citric acid, anthranilic acid, gallic acid, benzoic acid, malonic acid, maleic acid, fumaric acid, D, L-malic acid, isophthalic acid, phthalic acid, and lactic acid .

  In certain embodiments, the formulations described herein may optionally include one or more corrosion inhibitors. The sulfonic acid or corresponding salt is present in an amount ranging from about 0% to about 20%, or from about 0% to about 10%, or from about 0% to about 5% by weight of the formulation. Examples of suitable corrosion inhibitors include, but are not limited to, organic acid salts, resorcinol, other phenols, acids, or triazoles, maleic anhydride, phthalic anhydride, catechol, pyrogallol, esters of gallic acid, benzotriazole (BZT ), Carboxybenzotriazole, fructose, ammonium thiosulfate, glycine, tetramethylguanidine, iminodiacetic acid, dimethylacetoacetamide, trihydroxybenzene, dihydroxybenzene, salicylhydroxamic acid, and mixtures thereof.

The formulation may also include one or more of the following additives: surfactants, chelating agents, chemical modifiers, dyes, biocides, and other additives. Stripping and cleaning ability of formulations, or metal underlying, silicon, silicon dioxide, interlevel dielectric materials, unless adversely affect the integrity of the low-k and / or high-k materials (integrity), added Agents may be added to the formulations described herein. For example, when a formulation is used to treat a substrate that includes copper, the formulation does not include additional additives that will increase the rate of etching the copper of the formulation. Some examples of representative additives are acetylene alcohols and their derivatives, acetylenic diols (nonionic alkoxylated and / or self-emulsifying acetylenic diol surfactants) and their derivatives, alcohols Quaternary amines and diamines, amides (including aprotic solvents such as dimethylformamide and dimethylacetamide), alkylalkanolamines (eg diethanolethylamine), and beta-diketones, beta-ketoimines, carboxylic acids, apples Chelating agents such as tartaric acid and their derivatives based on acids and esters and diesters, and tertiary amines, diamines and triamines.

  The formulations disclosed herein are compatible with substrates including low-k films such as HSQ (FOx), MSQ, SiLK, and the like. The formulations also include photoresists including positive and negative photoresists and plasma etch residues (eg, organic residues, organometallic residues, inorganic residues, metal oxides), or copper and / or titanium containing groups. Effective in stripping low temperature photoresist composites with very little corrosion of the material. Furthermore, the formulation is compatible with a variety of metals, silicon, silicon dioxide, interlevel dielectric materials, low-k and / or high-k materials.

  During the manufacturing process, a photoresist layer is coated on the substrate. A pattern is defined in the photoresist layer using a photolithographic process. The patterned photoresist layer is therefore subject to plasma etching, which transfers the pattern to the substrate. Etch residues are produced at the etch stage. Some substrates used in the present invention are ashed, while some are not ashed. If the substrate is ashed, the major residue that will be cleaned is the etchant residue. If the substrate is not ashed, the major residues that will be cleaned or stripped at this time are both etch residues and photoresist.

  The methods described herein are detailed with substrates having metals, organic or metal-organic polymers, inorganic salts, oxides, hydroxides, or composites or combinations thereof present as a film or residue. It is carried out by contacting the formulation. Actual conditions such as temperature, time, etc. will depend on the nature and thickness of the material to be removed. Generally, the substrate is contacted or dipped into a container containing a formulation that is at a temperature in the range of 20 ° C to 85 ° C, or 20 ° C to 60 ° C, or 20 ° C to 40 ° C. The standard time that the substrate is exposed to the formulation may be, for example, in the range of 0.1-60 minutes, or 1-30 minutes, or 1-15 minutes. After contact with the formulation, the substrate may be rinsed and then dried. Drying is generally carried out under an inert atmosphere. In certain embodiments, a rinse containing deionized water or other additives and deionized water is employed before, during, and / or after contacting the substrate with the formulation described herein. Also good. However, the formulation may be used in any manner known in the art that utilizes a cleaning solution for removal of photoresist, ion-implanted photoresist, BARC, ash, or etch residues and / or residues. Is possible.

The following are acronyms used in this specification.
DPM Dipropylene glycol monomethyl ether TMAH Tetramethylammonium hydroxide TMAF Fluorotetramethylammonium DI water Deionized water PG Propylene glycol ABT 2-Aminobenzothiazole TTL Tolyltriazole

  Example formulations are listed in Table 1.

  A summary of etch rates for the blanket low-k dielectric is given in Table 2. At all the following etch rates, measurements were performed at a temperature of 40 ° C. with exposures of 5, 10, 20, 40 and 60 minutes. Thickness measurements were measured between etch times and graphed for each typical composition result using a “least squares fit” model. The calculated slope of the “least squares fit” model for each composition is the resulting etch rate, given in angstroms / minute (Å / min). In measuring the dielectric etch rate, the wafer had a blanket layer of known thickness deposited on the Si wafer. Initial thickness was measured using a Filmtec 2000SE spectroscopic ellipsometer / reflectometer. Approximately 200 ml of the test solution was set in a 250 ml beaker, with stirring and if necessary heated to a specific temperature. When only one wafer was set in the beaker containing the solution, a dummy wafer was set in the beaker. After measurement of the initial thickness, the test wafer was immersed in a typical composition. After 5 minutes, the test wafer was removed from the test solution, rinsed with deionized water for 3 minutes and completely dried under nitrogen. The thickness of each wafer was measured and the procedure was repeated on a test wafer if necessary.

  Examples A, B, D, E and F were evaluated for low-k compatibility. However, Example C did not evaluate for low-k compatibility. However, as shown in Table 3, all six examples were evaluated for their ability to remove photoresist, BARC and post etch residues. Based on the results obtained for the patterned wafer, Example C did not damage the porous ILD and was effective in removing the photoresist and BARC material.

  Table 3 demonstrates the effectiveness of the preferred composition for removing photoresist, BARC and etch residues from the test substrate. The wafer had a 193 nm photoresist layer, a 193 nm BARC layer, an unknown ultra low-k layer and a silicon oxide layer. The substrate was then treated by immersing the substrate in the preferred composition. In this procedure, one or more test wafers were set in a 600 ml beaker containing 400 ml of each composition. The 600 ml beaker further contained a 1 inch stir bar rotating 400 revolutions per minute. The composition containing the wafer there was then heated at the times and temperatures given in Table 3. After exposure to the preferred composition, the wafer was rinsed with deionized water and dried with nitrogen gas. The wafer was split to provide an edge and then measured using a scanning electron microscope (SEM) for various pre-measurement points on the wafer. The cleaning ability and damage to the underlying interlevel dielectric (ILD) were then visually clarified and encoded as given in Table 3 as follows. That is, for washing, “+” indicates excellent, “P” indicates partial removal, and “−” indicates poor quality. And for ILD damage, "+" indicates no damage and "-" indicates damage.

  Based on the results obtained for the patterned wafer, Examples C, B, D, E and F did not damage the porous ILD. All six examples were effective in removing the photoresist. On the other hand, Examples B, C, E and F were effective in removing BARC material.

  While specific embodiments have been described in detail, those skilled in the art will recognize that various modifications and alternatives can be made to these details in light of the general teachings of the disclosure. Accordingly, the particular arrangements disclosed are meant to be illustrative only and are not intended to limit the scope of the invention, which is intended to limit the scope of the appended claims and all their equivalents. Effectiveness extends.

Claims (23)

  Formulation for removing photoresist, ion-implanted photoresist, BARC and / or etch residue, comprising ammonium hydroxide and 2-aminobenzothiazole, residual water, the hydroxide having 100 ppm metal contamination A formulation that is:   The formulation according to claim 1, which does not contain oxidants and abrasive particles. Ammonium hydroxide Ru tetramethylammonium der hydroxide, formulation as claimed in claim 1 or 2. Dimethylacetamide (DMAC), N-methylpyrrolidinone (NMP), dimethylsulfoxide (DMSO), dimethylformamide, N-methylformamide, formamide, dimethyl-2-piperidone (DMPD), tetrahydrofurfuryl alcohol, glycerol, ethylene glycol, amide , Alcohol, sulfoxide , hydroxyamide, amino alcohol diol and polyol, (C ₂ -C ₂₀ ) alkanediol, (C ₃ -C ₂₀ ) alkanetriol, cyclic alcohol, propylene glycol , diacetone alcohol, 1,4-cyclohexane further seen containing dimethanol, 0-60 wt% of a water-soluble organic solvent selected from the group consisting of glycol ethers and mixtures thereof, wherein _{(C 2 -C 20), (} C 3 -C 20) Each number of carbon atoms constituting the alkane backbone, indicating that it is an 2～20,3～20, by formulation according to claim 1. The formulation according to any of claims 1 to 4, further comprising 0.1% to 5% by weight of substituted hydroxylamine or an acid salt thereof.   0% by mass or more selected from the group consisting of citric acid, anthranilic acid, gallic acid, benzoic acid, malonic acid, maleic acid, fumaric acid, D, L-malic acid, isophthalic acid, phthalic acid, lactic acid and mixtures thereof The formulation according to any of claims 1 to 5, further comprising 10% by weight of an organic acid.   Organic acid salt, phenol, acid, triazole, benzotriazole (BZT), resorcinol, maleic anhydride, phthalic anhydride, catechol, pyrogallol, ester of gallic acid, carboxybenzotriazole, fructose, ammonium thiosulfate, glycine, tetramethylguanidine, The composition further comprises 0% to 20% by weight of a corrosion inhibitor selected from the group consisting of iminodiacetic acid, dimethylacetoacetamide, trihydroxybenzene, dihydroxybenzene, salicylhydroxamic acid, and mixtures thereof. A formulation as described in any of the above. Further comprising an additive selected from the group consisting of surfactants, chelating agents , dyes , and mixtures thereof, wherein the additive is capable of stripping and cleaning the formulation, or underlying metal, silicon, silicon dioxide, level during dielectric material is one that does not adversely affect the intact (integrity) of the low-k and / or high-k materials, formulations according to any of claims 1 to 7.   Formulation for removing photoresist, ion-implanted photoresist, BARC and / or etch residue, tetramethylammonium hydroxide, tolyltriazole, propylene glycol, 2-aminobenzothiazole, dipropylene glycol monomethyl ether, A formulation comprising residual water, the hydroxide having a metal contamination of 100 ppm or less.   1-15 wt% tetramethylammonium hydroxide, 1-5 wt% tolyltriazole, 5-15 wt% propylene glycol, 1-10 wt% 2-aminobenzothiazole, 20-45 wt% dipropylene 10. A formulation according to claim 9, comprising glycol monomethyl ether, residual water.   Contains 6.5 wt% tetramethylammonium hydroxide, 3 wt% tolyltriazole, 10 wt% propylene glycol, 6 wt% 2-aminobenzothiazole, 39 wt% dipropylene glycol monomethyl ether, residual water The formulation according to claim 9 or 10, comprising   5% by weight tetramethylammonium hydroxide, 3% by weight tolyltriazole, 12.13% by weight propylene glycol, 1.5% by weight 2-aminobenzothiazole, 40% by weight dipropylene glycol monomethyl ether, residual water A formulation according to claim 9 or 10, comprising   A method for removing from a substrate a material selected from the group consisting of photoresist, ion-implanted photoresist, etch residue, BARC, and combinations thereof, wherein the material is removed from the substrate. Applying the formulation to a substrate.   The method of claim 13, wherein the formulation is free of oxidizers and abrasive particles. The formulation is dimethylacetamide (DMAC), N-methylpyrrolidinone (NMP), dimethylsulfoxide (DMSO), dimethylformamide, N-methylformamide, formamide, dimethyl-2-piperidone (DMPD), tetrahydrofurfuryl alcohol, glycerol, Ethylene glycol, amide, alcohol, sulfoxide , hydroxyamide, amino alcohol diol and polyol, (C ₂ -C ₂₀ ) alkanediol, (C ₃ -C ₂₀ ) alkanetriol, cyclic alcohol, propylene glycol , diacetone alcohol, 1 , 4-cyclohexanedimethanol, further seen contains 0-60% by weight of a water-soluble organic solvent selected from the group consisting of glycol ethers and mixtures thereof, wherein _{(C 2 -C 20), (} C 3 The method according to claim 13 or 14 , wherein -C20 ) represents that the number of carbon atoms constituting the alkane main chain is 2 to _{20, 3 to 20,} respectively . The method according to any of claims 13 to 15, wherein the formulation further comprises 0.1% to 5% by weight of substituted hydroxylamine or an acid salt thereof.   The formulation was selected from the group consisting of citric acid, anthranilic acid, gallic acid, benzoic acid, malonic acid, maleic acid, fumaric acid, D, L-malic acid, isophthalic acid, phthalic acid, lactic acid and mixtures thereof The method according to claim 13, further comprising 0% by mass to 10% by mass of an organic acid.   The formulation is an organic acid salt, phenol, acid, triazole, benzotriazole (BZT), resorcinol, maleic anhydride, phthalic anhydride, catechol, pyrogallol, ester of gallic acid, carboxybenzotriazole, fructose, ammonium thiosulfate, glycine, Further comprising 0 wt% to 20 wt% corrosion inhibitor selected from the group consisting of tetramethylguanidine, iminodiacetic acid, dimethylacetoacetamide, trihydroxybenzene, dihydroxybenzene, salicylhydroxamic acid, and mixtures thereof. Item 18. The method according to any one of Items 13 to 17. The formulation further comprises an additive selected from the group consisting of surfactants, chelating agents , dyes , and mixtures thereof, wherein the additive is capable of stripping and cleaning the formulation, or the underlying metal, silicon, those that do not adversely silicon dioxide, interlevel dielectric materials, a negative effect on intact (integrity) of the low-k and / or high-k material, the method described in any one of claims 13 to 18.   A method for removing from a substrate a material selected from the group consisting of photoresist, ion-implanted photoresist, etch residue, BARC, and combinations thereof, wherein the material is removed from the substrate. Applying the formulation to a substrate.   1-15% by weight tetramethylammonium hydroxide, 1-5% by weight tolyltriazole, 5-15% by weight propylene glycol, 1-10% by weight 2-aminobenzothiazole, 20-45% by weight 21. A process according to claim 20, comprising dipropylene glycol monomethyl ether, residual water.   Formulation 6.5% by weight tetramethylammonium hydroxide, 3% by weight tolyltriazole, 10% by weight propylene glycol, 6% by weight 2-aminobenzothiazole, 39% by weight dipropylene glycol monomethyl ether, the balance The method according to claim 20 or 21, comprising water.   Formulation 5% by weight tetramethylammonium hydroxide, 3% by weight tolyltriazole, 12.13% by weight propylene glycol, 1.5% by weight 2-aminobenzothiazole, 40% by weight dipropylene glycol monomethyl ether The method according to claim 20 or 21, comprising residual water.