Photoresist remover composition

Abstract

The present invention relates to a composition comprising a sulfonic acid and a solvent dipropylene glycol dimethyl ether [CAS Registry Number 111109-77-4] (III), wherein the sulfonic acid is selected from the group consisting of an alkylbenzenesulfonic acid having structure (I) or a hydrate thereof (wherein n is an integer from 6 to 16), a sulfosalicylic acid having structure (II) or a hydrate thereof, and a mixture thereof;

Description

Field of the Invention

[0001] The present invention relates to low pK a Stripper solution compositions consisting of specific alkylbenzene sulfonic acids, sulfosalicylic acid and the solvent dipropylene glycol dimethyl ether [CAS Reg. No. 111109-77-4], and compositions containing these components and a surfactant. These stripper solutions exhibit clean removal of photoresist films from substrates, showing complete dissolution of the removed resist pattern without particle formation or deposition. In addition, when the substrate is a metal such as copper or tin, the removal of the patterned resist causes little (i.e., no significant) or no corrosion to the metal substrate.

[0002] background

[0003] The present invention is directed to chemical stripper compositions that remove crosslinked polymer coatings using the stripper compositions of the present invention that do not promote corrosion of metal substrates, but which unexpectedly also do not require the presence of metal protecting chelating compounds or compounds or polymers having charge complexing properties to prevent significant corrosion.

[0004] Materials removed by the formulations of the present invention include positive tone and negative tone chemically amplified (e.g. epoxy) and acid catalyzed photoimageable coatings. Many commercial strippers for microelectronic coatings perform inadequately to meet minimal manufacturing requirements. The present invention provides a commercial framework to produce stripping products for crosslinked systems that react in acidic media without the deleterious etching and damaging effects typically observed on devices containing metals (e.g. copper or tin) but without metal chelating compounds that may deleteriously form particulate matter during the removal / stripping process.

[0005] For various processing conditions up to and including hard baking or what is called full cure, using conventional high temperature immersion conditions, the composition will remove and dissolve chemically amplified reactive compounds within a few minutes without damaging effects on sensitive metals such as copper or tin. Such fully cured coatings are found to be resistant to conventional organic strippers that typically contain alkaline components as shown in U.S. Patent No. 6,551,973 (2003) to Moore et al. When these conventional strippers are used, no dissolution occurs. Instead, it is observed that these conventional alkaline strippers remove the coating by a mechanism of lifting up or breaking into pieces. As is common in micro-electromechanical systems (MEMS) devices, this lifting mechanism produces incomplete removal from complex three-dimensional topography. Undissolved material will produce particles that circulate throughout the bath, causing undissolved pieces to be redeposited on other areas of the device. This contamination that occurs on these tiny, computer-controlled gears, sensors, springs, pumps, and related micro- or nano-scale fixtures leads to contamination and device failure. It is an object of the present invention to achieve complete dissolution of unwanted polymeric material within a given stripping and removal cycle.

[0006] Some low pK a Systems remove crosslinked coatings by complete dissolution rather than stripping, however, these materials contain metal corrosion inhibitors, which unexpectedly cause particle problems due to precipitation of these inhibitor components during the removal process. These corrosion inhibitors are metal complexing additives that are added to prevent low pK corrosion during the removal process by complexing with the metal substrate. a The corrosion inhibitors are small molecules, oligomers or polymers containing an enol moiety, for example containing an unsaturated carbon chain adjacent to an alcohol functional group. Representative enol inhibitors include fumaric acid, maleic acid and phthalic acid. More specific examples of inhibitors are those of the rosin class; for example, these are fumaric rosins. a Particles formed by metal inhibitors in the remover may deposit on other areas of the device and adversely affect the performance of the final device. a Non-limiting examples of remover systems are described in WO20126 / 142507.

[0007] In the manufacturing process of these microcircuits or microdevices, various inorganic substrates (such as single crystal silicon and polycrystalline silicon, mixed semiconductors such as gallium arsenide and metals) are coated with organic coatings ("photoresists" or "resists") to form a permanent or temporary designed resist frame and present a pattern after undergoing a photolithography process. Photoresists can be used to insulate conductors or protect selected areas of the substrate surface (such as silicon, silicon dioxide or aluminum) from the action of wet (chemical) and dry (plasma) forms of chemicals. In the case where the material is used as a photoresist, the exposed areas of the substrate can be subjected to the desired etching (removal) or deposition (addition) process. After this operation and subsequent rinsing or adjustment are completed, the resist and any applied post-etching residues must be removed to allow the necessary trimming operations. After removing the photoresist, a specific micro-etching or deposition pattern is left. The masking and patterning process is repeated several times to produce a layered arrangement including the final device technology. Each step requires complete resist stripping and dissolution to ensure that the final form of the device is produced with a relatively high yield and satisfactory performance. During this process, any particle deposition into the active region has a detrimental effect on device yield and performance.

[0008] An object of the present invention is to provide an improved stripping composition that will remove a wide range of different patterns of photoresist films including those formed by different types of negative and positive resist systems. Among these different types, examples are resists that can be imaged by visible light, broadband i-line, g-line, h-line, UV, 248nm, 193nm, 193nm immersion, deep UV, EUV, electrons or electron beams. Depending on which type is used, these materials may contain additives, such as photoactive compounds (e.g., DNQ), photoacid generators (PAGs) and photoradical generators, which may easily form particles. Therefore, another object of the present invention is to be able to remove patterns formed by these types of resists in minutes rather than hours, so that all components, resins and additives are completely dissolved without forming particles. Another object of the present invention is to remove such photoresists from substrates without corroding the copper and / or tin and other metals exposed below, without using metal corrosion inhibitor additives, because such additives are also prone to promote particle formation during the removal of the resist pattern. Another object of the present invention is to perform the photoresist pattern removal and metal protection by using safe and unrestricted chemistries that are not harmful to workers or the environment and avoid the use of low flash point solvents, especially solvents with boiling points below about 150°C.

[0009] The stripper compositions of the present invention impart these advantageous properties by completely dissolving photoresist patterns from patterns formed by many different types of resists without forming lifted resist films or particles formed by resins or additives. At the same time, unexpectedly, these inventive stripper compositions contain a low pK in the solvent dipropylene glycol dimethyl ether [CAS Reg. No. 111109-77-4]. a The stripper compositions of the present invention do not require the presence of any inhibitor additives to inhibit corrosion (no significant corrosion), or do not corrode metal substrates such as copper, tin, etc. Therefore, there are no problems associated with the precipitation of metal corrosion inhibitors during the removal process using the compositions of the present invention. These stripper compositions of the present invention and methods of use thereof have been found to be particularly useful in the manufacture of semiconductor wafers, MEMS devices, and displays. In addition, these stripper compositions of the present invention have the following advantages: (1) no anti-corrosion agent is required; (2) the photoresist film is dissolved rather than simply delaminated; (3) all ingredients are water-soluble (most anti-corrosion agents used in the prior art are water-insoluble), so only water rinsing is required; (4) no protective layer is formed on the substrate when the anti-corrosion agent is used; and (5) environmentally friendly solvents are used. SUMMARY OF THE INVENTION

[0011] In one aspect, the present invention relates to a composition consisting essentially of a sulfonic acid and a solvent dipropylene glycol dimethyl ether [CAS Registry Number 111109-77-4] (III), wherein the sulfonic acid is selected from the group consisting of an alkylbenzene sulfonic acid or a hydrate thereof having structure (I), a sulfosalicylic acid or a hydrate thereof having structure (II), and a mixture thereof, wherein n is an integer from 6 to 16. In another aspect, the present invention relates to a composition consisting essentially of a sulfonic acid and a solvent dipropylene glycol dimethyl ether [CAS Registry Number 111109-77-4] (III), wherein the sulfonic acid is selected from the group consisting of an alkylbenzene sulfonic acid or a hydrate thereof having structure (I), a sulfosalicylic acid or a hydrate thereof having structure (II), and a mixture thereof, wherein n is an integer from 6 to 16,

[0012]

[0013]

[0014] In another aspect, the present invention relates to a composition consisting essentially of (I), (II), (III) and a surfactant. In another aspect, the present invention relates to a composition consisting essentially of (I), (II), (III) and a surfactant.

[0015] Finally, the present invention also relates to the use of the above composition to remove a photoresist film from a substrate.

[0016] Details

[0017] It should be understood that the foregoing general description and the following detailed description are illustrative and explanatory, rather than limiting, of the subject matter claimed. In this application, unless otherwise specifically stated, the use of the singular includes the plural, the word "a" or "an" means "at least one (kind)", and the use of "or" means "and / or".

[0018] Furthermore, the use of the term "includes" and other forms such as "comprises" and "containing" is not limiting. In addition, unless otherwise specifically stated, terms such as "element" or "component" include elements and components that comprise one unit as well as elements or components that comprise more than one unit. As used herein, unless otherwise stated, the conjunction "and" is intended to be inclusive and the conjunction "or" is not intended to be exclusive. For example, the phrase "or, alternatively" is intended to be exclusive. As used herein, the term "and / or" refers to any combination of the aforementioned elements, including the use of a single element.

[0019] The term (meth)acrylate is a term that includes both acrylate and methacrylate in one term.

[0020] The terms "stripper" and "removal agent" are synonymous.

[0021] The section headings used herein are for organizational purposes and should not be construed as limiting the subject matter described. All documents or portions of documents cited in this application, including but not limited to patents, patent applications, articles, books, and articles, are hereby expressly incorporated by reference in their entirety for any purpose. In the event that one or more of the incorporated literature citations and similar materials define a term in a manner inconsistent with the definition of the term in this application, the present application shall prevail.

[0022] When expressing the composition in wt%, it should be understood that the wt% of all components (including non-essential components, such as impurities) should not be increased to more than 100 wt% in any case. In those cases where the composition contains some small amounts of non-essential contaminants or impurities, all the essential components of the composition may add up to less than 100 wt%. Otherwise, if there are no significant non-essential impurity components, it should be understood that the composition of all the essential components adds up to substantially 100 wt%.

[0023] Some embodiments of the compositions of the present invention consist essentially of varying concentrations of sulfonic acid and solvent dipropylene glycol dimethyl ether (III) [CAS Registry Number 111109-77-4], wherein the sulfonic acid is selected from alkylbenzene sulfonic acid or its hydrate having structure (I), sulfosalicylic acid or its hydrate having structure (II), and mixtures thereof, wherein n is an integer from 6 to 16, wherein structures (I) and (II) respectively include varying concentrations of substructures (Ia), (Ib), (Ic), (II), (IIa), (IIb), (IIc) and (IId) described herein; in such embodiments, the total amount of the above components does not have to be equal to 100 wt % (e.g., the components 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 99.9 wt %), and may include other ingredients that do not significantly affect the performance of the remover.

[0024] Some embodiments of the compositions of the present invention consist essentially of varying concentrations of sulfonic acid and solvent dipropylene glycol dimethyl ether (III) [CAS Registry Number 111109-77-4] and a surfactant, wherein the sulfonic acid is selected from an alkylbenzene sulfonic acid or a hydrate thereof having structure (I), a sulfosalicylic acid or a hydrate thereof having structure (II), and mixtures thereof, wherein n is an integer from 6 to 16, wherein structures (I) and (II) respectively include varying concentrations of substructures (Ia), (Ib), (Ic), (II), (IIa), (IIb), (IIc) and (IId) described herein; in this embodiment, the total amount of the above components does not have to be equal to 100% by weight (for example, the components may form at least 90% by weight of the composition, more preferably at least 95% by weight, more preferably at least 99% by weight, more preferably at least 99.5% by weight, and most preferably at least 99.9% by weight), and may include other ingredients that do not significantly affect the performance of the remover. In some of these embodiments, when the surfactant is further defined as a surfactant corresponding to structure (VI) or (VIa), preferably no other surfactants other than these structures are present in the composition.

[0025] Materials that do not affect the performance of the remover, such as non-acidic impurities, free water [except when using hydrates of structures (I) and / or (II) and their corresponding substructures (Ia), (Ib), (Ic), (II), (IIa), (IIb), (IIc) and (IId)] may be present at these levels in accordance with the definition of "essentially consisting of..."; that is, in one embodiment, up to about 10 wt%, preferably up to about 5 wt%, more preferably up to about 1 wt%, more preferably up to 0.5 wt%, and most preferably up to 0.1 wt%.

[0026] Various materials can significantly change the effectiveness of the composition as a stripper and are excluded from the compositions of the present invention described herein. Examples of these excluded materials are rosin-based particles, pigments, dyes, antioxidants and inhibitors; for example, rosin fumarate and other materials that can form particles and deposits on the substrate during the stripping process. Also excluded are any other types of acidic materials that can adversely affect the resist stripping and / or corrosiveness to metals of the stripping compositions of the present invention. For example, in addition to those having structures (I) and / or (II) (and substructures (Ia), (Ib), (Ic) and / or (IIa), (IIb), (IIc), (IId)) described herein that are present in the compositions of the present invention, other types of sulfonic acids that can affect the resist stripping and / or metal corrosion properties of the stripping compositions of the present invention; non-limiting examples of such other types of sulfonic acids are alkyl sulfonic acids (e.g., methanesulfonic acid, butanesulfonic acid), trifluoromethanesulfonic acid, perfluoroalkyl sulfonic acids (e.g., perfluorobutanesulfonic acid), partially fluorinated alkyl sulfonic acids (e.g., 2,2,2-trifluoroethanesulfonic acid), other aryl sulfonic acids (substituted or unsubstituted, such as benzenesulfonic acid, fluorobenzenesulfonic acid, difluorobenzenesulfonic acid, pentafluorobenzenesulfonic acid, alkylbenzenesulfonic acids in which the alkyl group has less than 8 carbon atoms (e.g., p-toluenesulfonic acid (tosic acid), 4-ethylbenzenesulfonic acid, propylbenzenesulfonic acid), nitrobenzenesulfonic acid, dinitrobenzenesulfonic acid, benzene disulfonic acid, etc. Also excluded are aminosulfonic acids, such as the non-limiting examples aminosulfonic acid, cyclohexylaminosulfonic acid, and methylaminosulfonic acid. Also excluded are strong inorganic acids (pK a Less than 0), such as, by way of non-limiting example, fluorosulfonic acid, nitric acid, sulfuric acid, hydrochloric acid, etc. pK aInorganic acids greater than 0, hydrofluoric acid, phosphorus oxyacids containing P in oxidation state +1 [such as H3PO2 (or H2PO(OH)), hypophosphorous acid or phosphinic acid, monoprotic acid]; phosphorus oxyacids containing P in oxidation state +3 [such as (H3PO3 (or HPO(OH)2), phosphorous acid or phosphonic acid, diprotic acid], phosphorus oxyacids containing P in oxidation state +5 (such as phosphoric acid: H3PO4 (or PO(OH)3), phosphoric acid, tribasic acid phosphoric acid). Also excluded are carboxylic acids, such as non-limiting examples of formic acid, alkyl carboxylic acids (such as acetic acid, propionic acid, etc.), perfluoroalkyl carboxylic acids (such as trifluoroacetic acid, etc.), aryl carboxylic acids (such as benzoic acid, etc.), alkylbenzene carboxylic acids (such as toluic acid, etc.), arylalkylene carboxylic acids (such as phenylacetic acid, phenylpropionic acid, etc.), dicarboxylic acids (such as oxalic acid, maleic acid, malonic acid All other solvents that promote corrosion of metals (such as copper and / or tin as described herein, and / or other metal substrates and bimetallic substrates, with particular emphasis on tin-containing substrates) are also excluded [except for the solvent component (III) of the present invention, dipropylene glycol dimethyl ether [CAS Registry No. 111109-77-4]]. Specific non-limiting examples of such excluded solvents are polar aprotic solvents, dialkyl sulfoxides, and solvents having structures (Is), (IIs), (IIIs), (IVs), (Vs), (VIs), (VIIs), (VIIIs), (IXs), (Xs), (XIs), and (XIIs), wherein R S Selected from -(-O-CH2-CH2-) ns -OH, -OH, -OC(=O)-CH3, where ns=1 or 2, R s1 is H or a C-1 to C-4 alkyl moiety, and R s2 It is a C-1 to C-18 alkyl group.

[0027]

[0028] Dipropylene glycol monomethyl ether (Vs) [CAS#34590-94-8],

[0029] As mentioned above, the solvent excluded from the composition of the present invention under the term "dipropylene glycol monomethyl ether (VIs) (DPGME)" is a mixture of isomeric compounds having CAS# 34590-94-8. The mixture has the general formula (CH3O)C3H6OC3H6(OH). The mixture also has the synonym dipropylene glycol methyl ether. Dipropylene glycol monomethyl ether, including the following isomeric compounds having the following structures and their optical isomers: 1-(2-methoxypropoxy)-2-propanol (CAS 13429-07-7) (VIsa); 1-(2-methoxy-1-methylethoxy)-2-propanol (CAS 20324-32-7) (VIsb), 2-(2-methoxypropoxy)-1-propanol (CAS 13588-28-8) (VIsc); 2-(2-(2-methoxypropoxy)-1-propanol (CAS 55956-21-3) (VIsd); these individual solvent components (VIsa to VIsd) of dipropylene glycol monomethyl ether and their optical isomers are also excluded as individual components in the composition of the present invention:

[0030]

[0031] According to one embodiment of the present invention, the term "consisting essentially of can be replaced by "consisting of", thereby not allowing other components in the composition. For example, in the present composition described herein without a surfactant component, different concentrations of alkylbenzene sulfonic acid or its hydrate having structure (I), sulfosalicylic acid or its hydrate having structure (II), and mixtures thereof, wherein n is an integer from 6 to 16, and the total amount of solvent dipropylene glycol dimethyl ether (III) [CAS Registry No. 111109-77-4], wherein structures (I) and (II) include substructures (Ia), (Ib), (Ic), (II), (IIa), (IIb), (IIc) and (IId), respectively, the total amount of the above components is Similarly, in the compositions of the present invention containing surfactant components described herein, different concentrations of alkylbenzenesulfonic acid or its hydrate having structure (I), sulfosalicylic acid or its hydrate having structure (II), and mixtures thereof, wherein n is an integer from 6 to 16, and solvent dipropylene glycol dimethyl ether (III) [CAS Registry Number 111109-77-4], wherein structures (I) and (II) include substructures (Ia), (Ib), (Ic), (II), (IIa), (IIb), (IIc) and (IId), respectively, and the total amount of surfactant, the total amount of the above components must be equal to about 100% by weight to allow for the presence of impurities.

[0032] In one aspect, the present invention relates to a composition consisting essentially of a sulfonic acid and a solvent dipropylene glycol dimethyl ether [CAS Reg. No. 111109-77-4] (III), wherein the sulfonic acid is selected from the group consisting of an alkylbenzene sulfonic acid or a hydrate thereof having structure (I), a sulfosalicylic acid or a hydrate thereof having structure (II), and a mixture thereof, wherein n is an integer from 6 to 16. In another aspect, the present invention relates to a composition consisting essentially of a sulfonic acid and a solvent dipropylene glycol dimethyl ether [CAS Reg. No. 111109-77-4] (III), wherein the sulfonic acid is selected from the group consisting of an alkylbenzene sulfonic acid or a hydrate thereof having structure (I), a sulfosalicylic acid or a hydrate thereof having structure (II), and a mixture thereof, wherein n is an integer from 6 to 16.

[0033]

[0034] In another aspect, the present invention relates to a composition consisting essentially of (I), (II), (III) and a surfactant. In another aspect, the present invention relates to a composition consisting essentially of (I), (II), (III) and a surfactant.

[0035] In all embodiments of the compositions of the present invention described herein, the solvent represented by dipropylene glycol dimethyl ether, code (III) or the abbreviation DPGDME is a complex mixture of isomeric compounds having CAS# 111109-77-4. The general formula of the mixture is CH3OC3H6OC3H6OCH3. The mixture also has the synonymous names oxybis[methoxypropane], DMFG, dipropylene glycol dimethyl ether, Proglyde TM , DMM, Proglyme TM The mixture contains the following isomeric compounds having the following general structures (IIIa, IIIb, IIIc): 2-methoxy-1-(2-methoxypropoxy)propane (CAS#63019-84-1) (IIIa); 2-methoxy-1-((1-methoxyprop-2-yl)oxy)propane (CAS 89399-28-0) (IIIb), 2-methoxy-1-((1-methoxyprop-2-yl)oxy)propane (CAS#189354-80-1) (IIIc), and since these structures contain optically active carbons, they are also mixtures of enantiomers and diastereomers resulting from the optical activity of these carbons:

[0036]

[0037]

[0038] In the embodiment of the present composition containing a surfactant described herein, there is no particular limitation on the surfactant, and examples thereof include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, decaethylene glycol monododecyl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monovalerate and sorbitan monostearate; nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate; fluorinated surfactants such as F-Top EF301, EF303 and EF352 (manufactured by Jemco Inc.), Megafac F171, F172, F173, R08, R30, R90 and R94 (manufactured by Dainippon Ink & Chemicals, Inc.), FC-430, FC-431, FC-4430 and FC-4432 (manufactured by Sumitomo 3M Ltd.), Asahi Guard AG710, Surflon S-381, S-382, S-386, SC101, SC102, SC103, SC104, SC105, SC106, E1004, KH-10, KH-20, KH-30 and KH-40 (manufactured by Asahi Glass Co., Ltd.); organosiloxane polymers such as KP-341, X-70-092 and X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd.); and acrylic or methacrylic polymers such as Polyflow TM No.75 and No.95 (manufactured by Kyoeisha Yushikagaku Kogyo KK).

[0039]

[0040] In another embodiment of the aforementioned composition of the present invention, the surfactant is present in an amount less than 1 wt% of the total weight of the composition. In another embodiment, the surfactant is present in an amount less than about 0.1 wt%.

[0041] In another embodiment of any of the above compositions, the surfactant is a polymeric surfactant having structure (VI), wherein n'' is the number of repeating units in the polymer and na is the number of CH2 spacer moieties, which is an integer from 8 to 14. In another embodiment of this aspect of the composition, the polymeric surfactant has structure (VIa).

[0042] In embodiments of the present invention containing a surfactant having structure (VI) or (VIa), each of them can be present in the composition at about 0.005wt% to about 0.100wt%. In another embodiment, about 0.010wt% to about 0.050wt%. In yet another embodiment, about 0.015wt% to about 0.040wt%. In yet another embodiment, about 0.020wt% to about 0.035wt%. In yet another embodiment, about 0.022wt% to about 0.030wt%. In yet another embodiment, about 0.023wt% to about 0.028wt%. In yet another embodiment, about 0.024wt% to about 0.026wt%. In another embodiment, about 0.025wt%.

[0043] In another embodiment of any of the above compositions, the alkylbenzene sulfonic acid n of structure (I) is an integer from 8 to 16. In another aspect of this embodiment, n is an integer from 8 to 14. In yet another embodiment of this aspect, n is an integer from 8 to 10. In yet another embodiment, n is an integer from 6 to 10.

[0044] In one embodiment of the above composition, the sulfonic acid component is only the alkylbenzenesulfonic acid of structure (I) or its hydrate.

[0045] In another embodiment of the above composition, the sulfonic acid component is only sulfosalicylic acid of structure (II) or a hydrate thereof.

[0046] In another embodiment of the above composition, the sulfonic acid component is a mixture of an alkylbenzenesulfonic acid of structure (I) or a hydrate thereof and a sulfosalicylic acid of structure (II) or a hydrate thereof.

[0047] In embodiments of the compositions described herein containing an alkylbenzene sulfonic acid of structure (I) (or a hydrate thereof) as one of its components, in a more specific embodiment, the sulfonic acid is a sulfonic acid having the more specific structure (Ia).

[0048]

[0049] In embodiments of the compositions described herein containing an alkylbenzenesulfonic acid (or a hydrate thereof) of structure (I) as one of its components, in more specific embodiments of these, n is an integer from 6 to 16, and the acid has a more specific structure (Ib), wherein nb is an integer from 6 to 16. In a more specific aspect of this embodiment, nb is an integer from 10 to 14. In yet another aspect of this embodiment, nb is an integer from 8 to 10. In yet another embodiment of this aspect, it has a more specific structure (Ic).

[0050]

[0051] In embodiments of the compositions described herein that contain an alkylbenzene sulfonic acid of structure (I) (or a hydrate thereof) as one of its components, in more specific embodiments of these, n is an integer from 8 to 16. In another aspect, n is an integer from 8 to 14. In yet another aspect, n is an integer from 8 to 10. Within any of the above ranges, the alkylbenzene sulfonic acid can be an alkylbenzene sulfonic acid having structure (Ia).

[0052] In the embodiments of the compositions described herein containing sulfosalicylic acid of structure (II) (or its hydrate) as one of its components, more specific embodiments of these are selected from those having structures (IIa), (IIb), (IIc), (IId) (or its hydrate) and mixtures thereof.

[0053]

[0054] In some embodiments, the sulfosalicylic acid of structure (II) (or a hydrate thereof) is a compound having structure (IIa) (or a hydrate thereof).

[0055] In some embodiments, the sulfosalicylic acid of structure (II) (or its hydrate) is a compound having structure (lib) (or its hydrate).

[0056] In some embodiments, the sulfosalicylic acid of structure (II) (or its hydrate) is a compound having structure (IIc) (or its hydrate).

[0057] In some embodiments, the sulfosalicylic acid of structure (II) (or its hydrate) is a compound having structure (IId) (or its hydrate).

[0058] In another embodiment of any of the above-mentioned aspects of the composition, the sulfonic acid component is a component with structure (I) (or a hydrate), which has a wt% load in the range of about 0.5wt% to about 10wt% in the gross weight of the solution. In another aspect of this embodiment, the wt% load of the acid is about 0.75wt% to about 7.00wt%. In another aspect of this embodiment, the wt% load of the acid is about 1.00wt% to about 6.00wt%. In another aspect of this embodiment, wt% is about 1.50wt% to about 5.00wt%. In another aspect of this embodiment, wt% is about 1.50wt% to about 4.00wt%. In another aspect of this embodiment, wt% is about 1.75wt% to about 3.00wt%. In another aspect of this embodiment, wt% is about 1.80wt% to about 2.75wt%. In another aspect of this embodiment, wt% is about 1.90wt% to about 2.50wt%. In another aspect of this embodiment, the wt% is about 1.90 wt% to about 2.30 wt%. In another aspect of this embodiment, the wt% is about 1.90 wt% to about 2.20 wt%. In another aspect of this embodiment, the wt% is about 2 wt%.

[0059] In another embodiment of any of the above aspects of the composition, the sulfonic acid component is a component with structure (Ib) (or a hydrate), which has a wt% load in the range of about 0.5wt% to about 10wt% in the gross weight of the solution. In another aspect of this embodiment, the wt% load of the acid is about 0.75wt% to about 7.00wt%. In another aspect of this embodiment, the wt% load of the acid is about 1.00wt% to about 6.00wt%. In another aspect of this embodiment, wt% is about 1.50wt% to about 5.00wt%. In another aspect of this embodiment, wt% is about 1.50wt% to about 4.00wt%. In another aspect of this embodiment, wt% is about 1.75wt% to about 3.00wt%. In another aspect of this embodiment, wt% is about 1.80wt% to about 2.75wt%. In another aspect of this embodiment, wt% is about 1.90wt% to about 2.50wt%. In another aspect of this embodiment, wt% is about 1.90wt% to about 2.30wt%. In another aspect of this embodiment, wt% is about 1.90wt% to about 2.20wt%. In another aspect of this embodiment, wt% is about 2wt%. In another aspect of this embodiment, the alkylbenzene sulfonic acid can be an alkylbenzene sulfonic acid having structure (Ic).

[0060] In another embodiment of any of the above aspects of the composition, the sulfonic acid component is a component with structure (II) (or a hydrate), which has a wt% load capacity in the range of about 0.5wt% to about 10wt% in the gross weight of the solution. In another aspect of this embodiment, the wt% load capacity of the acid is about 0.75wt% to about 7.00wt%. In another aspect of this embodiment, the wt% load capacity of the acid is about 1.00wt% to about 6.00wt%. In another aspect of this embodiment, wt% is about 1.50wt% to about 5.00wt%. In another aspect of this embodiment, wt% is about 1.50wt% to about 4.00wt%. In another aspect of this embodiment, wt% is about 1.75wt% to about 3.00wt%. In another aspect of this embodiment, wt% is about 1.80wt% to about 2.75wt%. In another aspect of this embodiment, wt% is about 1.90wt% to about 2.50wt%. In another aspect of this embodiment, wt% is about 1.90wt% to about 2.30wt%. In another aspect of this embodiment, wt% is about 1.90wt% to about 2.20wt%. In another aspect of this embodiment, wt% is about 2wt%. In another aspect of this embodiment, the sulfonic acid component is a component having structure (IIa).

[0061] In another embodiment of any of the above aspects of the composition, the sulfonic acid component is a mixture of components with structures (I) and (II) (or their hydrates), which has a wt% loading in the range of about 0.5wt% to about 10wt% in the gross weight of the solution. In another aspect of this embodiment, the wt% loading of the acid is about 0.75wt% to about 7.00wt%. In another aspect of this embodiment, the wt% loading of the acid is about 1.00wt% to about 6.00wt%. In another aspect of this embodiment, wt% is about 1.50wt% to about 5.00wt%. In another aspect of this embodiment, wt% is about 1.50wt% to about 4.00wt%. In another aspect of this embodiment, wt% is about 1.75wt% to about 3.00wt%. In another aspect of this embodiment, wt% is about 1.80wt% to about 2.75wt%. In another aspect of this embodiment, wt% is about 1.90wt% to about 2.50wt%. In another aspect of this embodiment, wt% is about 1.90wt% to about 2.30wt%. In another aspect of this embodiment, wt% is about 1.90wt% to about 2.20wt%. In another aspect of this embodiment, wt% is about 2wt%. In another aspect of this embodiment, the sulfonic acid component is a mixture of sulfonic acid components with structures (Ib) and (IIa) (or their hydrates), wherein nb is an integer from 8 to 16. In another aspect of this embodiment, the sulfonic acid component is a mixture of sulfonic acid components with structures (Ib) and (IIa) (or their hydrates), wherein nb is an integer from 8 to 14. In yet another embodiment, the sulfonic acid with structure (Ib) in the sulfonic acid mixture is a sulfonic acid in which nb is an integer from 8 to 10. In another aspect of this embodiment, the sulfonic acid component is a mixture of sulfonic acid components with structures (Ic) and (IIa) (or their hydrates).

[0062] In any of the above embodiments of the composition, wherein the sulfonic acid component is a mixture of components having structures (I) and (II) (or their hydrates), or a mixture of these sulfonic acids having more specific structures (Ib) and (IIa), the weight ratio of the sulfonic acid having structure (I) (or Ic) to the sulfonic acid having structure (II) (or IIa) is in the range of about 100:1 to about 1:1. In more specific examples, the ratio is in the range of about 10:1 to about 1:1. In more specific examples, the ratio is in the range of about 5:1 to about 1:1.

[0063] Another embodiment of the present invention is a method comprising the following steps;

[0064] i) heating any one of the above compositions of the present invention at a temperature of about 20° C. to about 100° C. to form a heated composition;

[0065] ii) treating the substrate coated with the photoresist film with the heated composition for a period of about 1 minute to about 60 minutes until the substrate with the photoresist film removed is obtained,

[0066] iii) after step ii), rinsing the substrate from which the photoresist film has been removed with isopropyl alcohol, water or a mixture of isopropyl alcohol and water to remove any residual composition from step ii) to produce a clean substrate,

[0067] iv) drying the cleaned substrate.

[0068] In one embodiment of the above-mentioned method of the present invention, the treatment of the photoresist film removed in the step ii) is selected from a patterned photoresist film, a blanket-exposed photoresist film without a pattern, and an unexposed photoresist film. In one embodiment, it is a patterned photoresist film. In another embodiment, it is an unexposed photoresist film. In another embodiment, it is a blanket-exposed photoresist film.

[0069] In one embodiment of the above-mentioned method of the present invention, in step ii), the treatment is carried out by dipping it into the heated composition of the present invention, spraying it with the heated composition of the present invention, or pouring the heated composition onto the photoresist film. In one aspect of this embodiment, dipping is used. In another aspect of this embodiment, spraying is used. In another aspect of this embodiment, pouring is used.

[0070] In another embodiment of the above method of the present invention, in step i), the composition is heated from about 30°C to about 65°C.

[0071] In another embodiment of the above-mentioned inventive method, in step iv), the cleaned substrate is dried by spin drying, isopropyl alcohol (IPA) drying or Marangoni drying in air using a gas stream such as nitrogen, air or some other inert gas. In one aspect, the drying is carried out by spinning, in another aspect, the drying is carried out by using the gas stream. In another aspect, the drying is carried out by using IPA drying. In another aspect, the drying is carried out by the Marangoni drying.

[0072] In one aspect of the above-mentioned method of the present invention, the photoresist film is a negative photoresist film.

[0073] In one aspect of the above-mentioned method of the present invention, the photoresist film is a positive photoresist film.

[0074] In another aspect of any of the above methods of the present invention, the photoresist film is a chemically amplified photoresist film.

[0075] In another aspect of any of the above embodiments, the photoresist film is a patterned negative photoresist film or a blanket-exposed negative photoresist film. On the one hand, it is a patterned negative photoresist film. On the other hand, it is a blanket-exposed negative photoresist film. In one aspect of these embodiments, the negative photoresist is a chemically amplified photoresist.

[0076] The patterned photoresist film described herein refers to a photoresist film that has been exposed and developed with an alkaline aqueous developer or a solvent-based developer to produce the patterned photoresist film, and the development may be performed after post-exposure baking, depending on the type of photoresist used to form the film.

[0077] Blanket exposed photoresist film refers to a photoresist film that has been exposed to radiation (i-line, g-line, UV, deep UV, broadband, EUV, electron beam, etc.), but wherein no mask is used during the exposure to produce an exposure pattern that will produce a patterned photoresist film when developed.

[0078] In another embodiment of the above-mentioned inventive method, in step ii), the substrate is a metal. In one aspect of this embodiment, the metal is selected from aluminum, aluminum / copper alloys, copper, tin, titanium, tungsten and nickel. In another aspect of this embodiment of the method, the metal is selected from aluminum, aluminum / copper alloys and copper. In another embodiment of the above-mentioned inventive method, in step ii), the substrate is copper. In another embodiment of the above-mentioned inventive method, in step ii), the substrate is tin.

[0079] In another embodiment of the above-mentioned method of the present invention, in step ii), the substrate is a substrate comprising a bimetallic pattern, which is composed of two different metals selected from aluminum, aluminum / copper alloy, tin and copper. In one aspect, the bimetallic pattern is a bimetallic pattern of one of copper and tin.

[0080] In another embodiment of the above method of the present invention, in step ii), the substrate is treated for about 1 minute to about 20 minutes. In another aspect of this embodiment, in step ii), the substrate is treated for about 5 minutes to about 20 minutes.

[0081] In another embodiment of the above-mentioned method of the present invention, in step iii), rinsing is carried out with water.

[0082] The stripper compositions of the present invention can be used in the above-described methods of the present invention to remove patterns from many different types of photoresist patterns as described below.

[0083] The removers of the present invention can be used to remove patterned resist films having various thicknesses depending on the application, IC devices, IC device interconnects, circuit boards, solder board applications, MEMs, displays, etc. Typically, the thickness is consistent with the size of the device being manufactured, starting from about tens of nanometers for prior art ICs, to a range of several microns for larger IC devices, to 10 to 500 microns for very large devices such as MEMs.

[0084] The remover of the present invention can be used for resist patterns, and the resist patterns are produced by negative and positive photoresist materials capable of forming patterns, and the patterns can be selected from those of patterns that can be formed using different types of radiation. For example, as a non-limiting example, the resist pattern for removal can be formed by i-line photoresists, g-line photoresists 248nm photoresists, 193nm photoresists, extreme ultraviolet photoresists, electron beam photoresists and particle beam photoresists. The remover of the present invention can be used for photoresist patterns that can be produced by photoresists, and the photoresists can be further classified as follows by the chemical type used to obtain the pattern.

[0085] For example, the remover of the composition of the present invention can be used to remove positive patterns, which are produced by exposure to visible light, i-line, h-line and g-line and by alkaline aqueous solution development, using photoresists based on novolak resins and diazonaphthoquinone type sensitizers (DNQ) sensitizer materials, and these types of resist systems can also produce negative images by tone reversal processes. Resists based on diazonaphthoquinone-novolak are described in (Diazonapththoquinone-basedResists, Chapter 2, Basic Chemistry of DNQ / Novolak resists, SPIE OptionalEngineering Press volume TT 11, page 9, 1993), which is incorporated herein by reference in its entirety.

[0086] Furthermore, the remover of the composition of the present invention can be used to remove resist films and patterns produced by both negative or positive photoresists that can be developed by aqueous alkali solution or solvent.

[0087] In addition, the remover of the composition of the present invention can be used to remove chemically amplified and alkaline aqueous solution developable resists. Typically, resist patterns are formed by 248nm, 193nm, EUV to achieve higher resolution patterns, but resist patterns can also be produced using longer wavelengths, such as visible light, broadband UV, i-line, g-line and h-line.

[0088] The remover of the present invention can be used to remove resist patterns produced by positive tone chemically amplified resists, and can make latent alkali aqueous solution soluble resins, such as (meth) acrylate copolymers, styrene copolymers, novolacs, phenolic resins, alkali aqueous solution soluble by deprotecting the acid cleavable groups of the alkali aqueous solution solubilizing portion. The alkali solubilizing portion can be a carboxylic acid, a phenol or a phenolic acid having a pK value of less than 11. a The photoresist film is soluble in aqueous alkali solution in the exposed area of ​​the photoresist film. The photoacid generator compound generates an acid in the exposed area of ​​the photoresist film. The acid deprotects the acid-cleavable group by an acidolysis or hydrolysis process, releasing the free alkali solubilizing part, thereby making the photoresist film soluble in aqueous alkali solution in the exposed area.

[0089] Remover of the present invention can be used for removing the resist pattern produced by negative tone chemical amplification, and the inherent alkali aqueous solution solubility of the resist pattern is not masked by any protective group. On the contrary, in this method, inherent alkali soluble resin (binder resin), for example, those based on (methyl) acrylate copolymer, styrene copolymer, novolac etc. that are soluble in alkali aqueous solution, are crosslinked by light-acid catalysis through acid crosslinking part. These parts can be the side groups of binder resin itself, present on crosslinking additive (crosslinking agent) or present on both resin and additive. The light-acid produced by PAG affects the crosslinking of acid catalysis in the exposure area, which is produced in the negative tone image after alkali aqueous solution development. Usually, when using crosslinking additive, it is a part that can form carbonium ion when interacting with light acid such as amino plastic, or an additive such as epoxy compound containing acid crosslinkable group. Similarly, if crosslinking part is present on resin, it can be a part that can form carbonium ion with acid, or a part such as epoxy part that can be crosslinked with acid. The following reference is a review of chemically amplified resists: H. Ito, Adv Polym Sci 2005 I72 p.37.

[0090] The remover of the present invention can be used to remove a resist pattern produced by a negative chemically amplified resist, which can be produced by a negative chemically amplified resist, wherein the binder resin may contain a novolac, such as a novolac derived from a substituted phenol (e.g., o-cresol; m-cresol; p-cresol; 2,4-xylenol; 2,5-xylenol; 3,4-xylenol; 3,5-xylenol; thymol and mixtures thereof) condensed with an aldehyde (e.g., formaldehyde). In other methods, the binder resin may also contain a poly(vinylphenol), such as poly(p-hydroxystyrene); poly(p-hydroxy-α-methylstyrene); a copolymer of p-hydroxystyrene or p-hydroxy-α-methylstyrene and styrene, a copolymer of acetoxystyrene or acrylic acid and / or methacrylic acid; a hydroxyphenylalkylmethanol homopolymer; or a novolac / poly(vinylphenol) copolymer. The crosslinking additive for such a negative chemically amplified resist may be an etherified aminoplast crosslinking functional group contained in a small compound, an organic oligomer or a polymer. This aminoplast provides carbonium ions when acid cleavage occurs and is used to crosslink the binder resin in the presence of an acid produced by radiation, preferably imaging radiation. This crosslinking makes the binder resin insoluble in alkaline media in the exposed area. This crosslinking agent can be prepared by a variety of aminoplasts and compounds or low molecular weight polymers containing multiple hydroxyls, carboxyls, amides or imides. Some examples of amino oligomers or polymers are aminoplasts obtained by the reaction of amines such as urea, melamine or ethanol urea with aldehydes such as formaldehyde. Suitable aminoplasts can include urea-formaldehyde, melamine-formaldehyde, benzoguanamine-formaldehyde and ethanol urea-formaldehyde resins, and any combination of these. In some applications, the aminoplast is a hexa(methoxymethyl)melamine oligomer. Non-limiting examples of this material are described in U.S. Patent No. 6,576,394.

[0091] For the low pK aRemover composition and method, the remover of the present invention can be used for negative resist pattern, it can be produced by negative crosslinked resist based on crosslinking caused by photo radical generator rather than photoacid generator. In this case, the same type of binder resin as described above for chemical amplification type negative photoresist can be used. However, in this case, there is a crosslinking additive comprising at least two olefin parts that are prone to free radical crosslinking. Examples of these parts are vinyl aryl parts such as styrene, and acrylate or methacrylate parts. Depending on the purpose, the non-restrictive more specific examples of these free radical crosslinking additives can be appropriately selected from acrylic acid derivatives such as acrylate and methacrylic acid derivatives such as methacrylate. These can have low molecular weight (monomer properties) or high molecular weight (oligomer or polymer properties). In this case, the additive can be a small molecule, containing multiple oligomers or polymers that can be crosslinked by free radicals. Some of these free radical crosslinking additives can have acid cleavable structures therein. Such a structure can be used in the further processing of patterned film, such as promoting the stripping of resist after the pattern is transferred to the substrate. Examples of such acid cleavable groups are tertiary ethers, tertiary carboxylic acid esters, etc., which are susceptible to acidolytic cleavage in the absence of favorable water, or alternatively acid cleavable moieties which can be readily hydrolytically cleaved with photoacid-favored water in resist films such as acetals, ketals, and alkylsilyl ethers. Non-limiting examples of such materials are described in U.S. Pat. No. 7,601,482. Example

[0092] Reference will now be made to more specific embodiments of the present disclosure and to experimental results providing support for these embodiments. Applicants note, however, that the following disclosure is for illustrative purposes only and is not intended to limit the scope of the claimed subject matter in any way.

[0093] Chemicals

[0094] DBSA (dodecylbenzenesulfonic acid; CAS: 68584-22-5) was obtained from Stepan (22 West Frontage RD., Northfield, IL 60093). All other chemicals were purchased from Sigma Aldrich (3050 Spruce ST., St. Louis, MO 63103).

[0095] deal with

[0096] Silicon 200 mm (8") wafers with 150 nm copper sputter coating were used for copper corrosion testing. Copper coated silicon wafer specimens were immersed in a preheated photoresist stripper solution for a period of time greater than sufficient to strip the photoresist. Regular observations were made to check the condition of the metal surface by visual and microscopic observation for the presence of surface haze as an indication of corrosion. Surface haze can be analyzed gravimetrically More sensitive levels are identified and confirmed.

[0097] For tin corrosion testing, a similar procedure as for copper corrosion testing is used, except that the top Tin layer Titanium covered with Thermal oxide layer of silicon wafer.

[0098] For the photoresist stripping tests, unless otherwise stated, silicon wafers with 150 nm sputtered copper were used as substrates on which chemically amplified negative photoresists were applied and processed. -15nXT (a product of EMD Performance Materials, Branchburg, NJ08876). The treatment consisted of spin coating the resist to 12 μm thickness and applying a soft bake on a hot plate at 110°C for 180 seconds. The resist was then exposed to 900 mJ / cm 2 Before developing the resist, a 60 second post-exposure bake was completed on a hot plate at 120 °C. 300 MIF developer was developed in two puddle washes for 60 seconds each, with a deionized ("DI") water rinse after each.

[0099] Copper Corrosion and Photoresist Stripping Test 1

[0100] A photoresist remover solution was prepared by dissolving 2 wt% DBSA in dipropylene glycol dimethyl ether (CAS#111109-77-4). The solution was heated to 60°C on a hot plate in a 150 ml beaker with a magnetic stir bar (300 rpm). A copper wafer sample was immersed in the heated solution for 30 minutes. The copper surface had no turbidity and was essentially intact by visual and microscopic observation.

[0101] Use the same composition, temperature and settings to remove the photoimaged -15nXT photoresist pattern. The cross-linked photoresist pattern was dissolved within 5 minutes. In addition, after rinsing with deionized water for 1 minute and blowing dry with a nitrogen gun, the substrate was free of any particles.

[0102] Copper Corrosion and Photoresist Stripping Test 2

[0103] A photoresist remover solution was prepared by dissolving 1 wt% DBSA and 1 wt% 5-sulfosalicylic acid dihydrate (CAS: 5965-83-3) in dipropylene glycol dimethyl ether (CAS: 111109-77-4). The solution was heated to 65°C on a hot plate in a 150 ml beaker with a magnetic stir bar (300 rpm). A copper wafer sample was immersed in the heated solution for 30 minutes. The copper surface had no turbidity and was essentially intact by visual and microscopic observation.

[0104] Use the same composition, temperature and settings to remove the photoimaged -15nXT photoresist pattern. The cross-linked photoresist pattern was dissolved within 5 minutes. In addition, after rinsing with deionized water for 1 minute and blowing dry with a nitrogen gun, the substrate was free of any particles.

[0105] Copper Corrosion and Photoresist Stripping Test 3

[0106] A photoresist remover solution was prepared by dissolving 2 wt % of 5-sulfosalicylic acid dihydrate (CAS: 5965-83-3) in dipropylene glycol dimethyl ether (CAS: 111109-77-4). The solution was heated to 60° C. on a hot plate in a 150 ml beaker with a magnetic stir bar (300 rpm). A copper wafer sample was immersed in the heated solution for 30 minutes. The copper surface had no turbidity and was substantially intact by visual and microscopic observation.

[0107] Use the same composition, temperature and settings to remove the photoimaged -15nXT photoresist pattern. The cross-linked photoresist pattern was dissolved within 5 minutes. In addition, after rinsing with deionized water for 1 minute and blowing dry with a nitrogen gun, the substrate was free of any particles.

[0108] Tin corrosion and photoresist stripping test 1

[0109] A photoresist remover solution was prepared by dissolving 2 wt% DBSA in dipropylene glycol dimethyl ether (CAS#111109-77-4). The solution was heated to 60°C on a hot plate in a 150 ml beaker with a magnetic stir bar (300 rpm). A tin wafer sample was immersed in the heated solution for 30 minutes. The tin surface had no turbidity and was essentially intact by visual and microscopic observation.

[0110] Use the same composition, temperature and settings to remove the photoimaged -15nXT photoresist pattern. The cross-linked photoresist pattern was dissolved within 5 minutes. In addition, after rinsing with deionized water for 1 minute and blowing dry with a nitrogen gun, the substrate was free of any particles.

[0111] The above tests show that strong benzenesulfonic acid without an anticorrosive agent will not attack copper or tin when formulated in a selected solvent and that the composition is effective for stripping chemically amplified negative photoresists. The following comparative examples will show that this acid will attack copper or tin when formulated in different solvents.

[0112] Comparative copper corrosion test 1

[0113] A photoresist remover solution was prepared by dissolving 2 wt% DBSA in dipropylene glycol monomethyl ether (CAS: 34590-94-8). The solution was heated to 60°C on a hot plate in a 150 ml beaker with a magnetic stir bar (300 rpm). A copper wafer sample was immersed in the heated solution. After 5 minutes, the copper layer on the silicon wafer became cloudy, indicating corrosion.

[0114] Comparative tin corrosion test 1

[0115] A photoresist remover composition was prepared by dissolving 2 wt% DBSA in tetraethylene glycol (CAS#31692-85-0). The solution was heated to 60°C on a hot plate in a 150 ml beaker with a magnetic stir bar (300 rpm). Tin layer Titanium covered with The sample was made from a silicon wafer with a thermal oxide layer. The sample was immersed in the heated solution for 30 minutes. Due to the high etching rate of the chemical, the tin surface was no longer intact by visual inspection.

[0116] Additional Metal Etch Rate Test 1

[0117] A photoresist remover solution was prepared by dissolving 2wt% DBSA in dipropylene glycol dimethyl ether (CAS: 111109-77-4). 100 ml of the solution was heated to 60°C in a 250 ml beaker with a magnetic stirring bar (300 rpm) using a hot plate. Wafer samples with various metal coatings were immersed in the solution for 30 and 60 minutes. The film thickness of the metal layer was measured using a Jandel 4-point probe. The film thickness was measured at 0 (before immersion), 30 minutes, and 60 minutes. A curve of film thickness versus time was plotted. A linear regression was performed on the data. The slope of the linear regression is the measured etching rate value, as shown in the table below. The results show that the photoresist remover composition has low etching for both copper and tin.

[0118] Table 1

[0119]

[0120] Additional Metal Etch Rate Test 2

[0121] A photoresist remover solution was prepared by dissolving 1 wt% DBSA and 1 wt% 5-sulfosalicylic acid dihydrate (CAS: 5965-83-3) in dipropylene glycol dimethyl ether (CAS: 111109-77-4). 100 ml of the solution was heated to 60°C in a 250 ml beaker with a magnetic stirring bar (300 rpm) using a hot plate. Wafer specimens with various metal coatings were immersed in the solution for 30 and 60 minutes. The film thickness of the metal layer was measured using a Jandel 4-point probe. The film thickness was measured at 0 (before immersion), 30 minutes, and 60 minutes. A curve of film thickness versus time was plotted. A linear regression was performed on the data. The slope of the linear regression is the measured etching rate value, as shown in the table below. The results show that the photoresist remover composition has low etching for both copper and tin.

[0122] Table 2

[0123]

[0124] The above tests show that strong benzenesulfonic acid without an anticorrosive agent does not corrode copper or tin when formulated in a selected solvent and that the composition is effective for stripping chemically amplified negative photoresists. The above comparative examples show that stripper formulations containing dodecylbenzenesulfonic acid, 5-sulfosalicylic acid, or a mixture thereof in a solvent other than dipropylene glycol dimethyl ether corrode copper or tin or both. Unexpectedly, stripper formulations containing dodecylbenzenesulfonic acid, 5-sulfosalicylic acid, or a mixture thereof in dipropylene glycol dimethyl ether effectively and cleanly remove photoresist coatings on substrates containing copper or tin without the formation of resist lift-off or corrosion of copper or tin in the substrate.

Claims

1. A composition comprising a sulfonic acid and a solvent, dipropylene glycol dimethyl ether (III), wherein the sulfonic acid is a mixture of an alkylbenzenesulfonic acid or a hydrate thereof having structure (I) and sulfosalicylic acid or a hydrate thereof having structure (II), or sulfosalicylic acid or a hydrate thereof having structure (II), wherein n is an integer from 6 to 16, 2. A composition comprising a sulfonic acid, a solvent dipropylene glycol dimethyl ether (III) and a surfactant, wherein the sulfonic acid is a mixture of an alkylbenzenesulfonic acid or a hydrate thereof having structure (I) and a sulfosalicylic acid or a hydrate thereof having structure (II), or a sulfosalicylic acid or a hydrate thereof having structure (II), wherein n is an integer from 6 to 16, 3. The composition of claim 1 or 2, wherein the sulfosalicylic acid is sulfosalicylic acid having structure (IIa) or a hydrate thereof, 4. A method comprising the following steps: i) heating the composition according to any one of claims 1 to 3 at a temperature of 20°C to 100°C, ii) treating the substrate coated with the photoresist film with the heated composition for a period of 1 minute to 60 minutes until the substrate with the photoresist film removed is obtained, iii) after step ii), rinsing the substrate from which the photoresist film has been removed with isopropyl alcohol, water, or a mixture of isopropyl alcohol and water to remove any residual composition from step ii) to produce a clean substrate, iv) drying the cleaned substrate.

5. The method of claim 4, wherein in step i), the composition is heated from 30°C to 65°C. The method of claim 4 , wherein in step ii), the substrate is a metal.

7. The method of claim 4, wherein in step ii), the substrate is copper.

8. The method of claim 4, wherein in step ii), the substrate is tin.

9. The method of claim 4, wherein in step ii), the substrate is treated for 1 minute to 20 minutes.

10. The method of claim 4, wherein in step iii), the rinsing is performed with water.

11. Use of the composition according to any one of claims 1 to 3 for removing a resist film or a resist pattern from a substrate.

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