Photoresist Remover Composition

Abstract

The present invention relates to a composition, which comprises at least one sulfosalicylic acid having structure (I) or its hydrate and mixtures thereof, and a sulfosalicylic acid having structure (I) or its hydrate, a main solvent selected from acetone and methyl ethyl ketone or mixtures of these solvents, an optional auxiliary solvent which is a glycolic acid derivative or a mixture of at least two glycolic acid derivatives, and an optional surfactant.

Description

Technical Field

[0001] The present invention relates to a composition of a low pK a remover solution, the composition consisting of: a sulfonic acid selected from sulfosalicylic acid having structure (I), a primary solvent selected from acetone and methyl ethyl ketone, or a mixture of such primary solvents, and an optional co-solvent as a glycolic derivative. Background Art

[0002] The present invention relates to a chemical stripper composition that uses the remover composition of the present invention to remove a crosslinked polymer coating, the remover composition not promoting the corrosion of a metal substrate, but unexpectedly also not requiring the presence of a metal protection chelating compound or a polymer having charge complexing properties to prevent significant corrosion.

[0003] Materials removed by these formulations of the present invention include positive and negative chemically amplified types (such as epoxy resins) and acid-catalyzed photoimageable coatings. Many commercially available strippers for microelectronic coatings perform inadequately to meet minimum manufacturing requirements. The present invention provides a commercial framework for a removal product for a crosslinked system that responds in an acidic medium without the deleterious etching and damage effects typically observed on devices containing metals such as copper or tin, but at the same time does not contain metal chelating compounds that can detrimentally form particulate matter during the removal / stripping process.

[0004] For various processing conditions, up to and including hard bake, or otherwise referred to as full cure, the composition will remove and dissolve the chemically amplified reaction compound within minutes using conventional dipping conditions at high temperature, without deleterious effects on sensitive metals such as copper or tin. It has been found that such fully cured coatings are resistant to conventional organic strippers that typically contain basic components, as exemplified in U.S. Patent No. 6,551,973. When using these conventional strippers, no dissolution occurs. Instead, it is observed that these conventional basic strippers remove the coating by a lifting or flaking mechanism. This lift-off mechanism results in incomplete removal from complex three-dimensional topographies common in microelectromechanical systems (MEMS) devices. Undissolved material will generate particles that circulate throughout the bath, causing the undissolved pieces to redeposit on other areas of the device. Such contamination occurring on these tiny, computer-controlled gears, sensors, springs, pumps, and associated micron or nanoscale fixtures leads to contamination and device failure. An object of the present invention is to achieve complete dissolution of the undesired polymeric material during a given stripping and removal.

[0005] Some low pK for removing crosslinked coatings aThe system does this by complete dissolution rather than stripping. However, these materials contain metal corrosion inhibitors that 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 corrosion of the metal substrate by the low pK a remover during the removal process. Examples of such corrosion inhibitors are small molecules, oligomers or polymers containing moieties with enol species (e.g., 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 type; these inhibitors are, for example, fumarated rosin. Particles formed by the metal corrosion inhibitors in the low pK a remover can deposit onto other areas of the device, harmfully affecting the performance of the final device. Non-limiting examples of such low pK a remover systems containing such metal corrosion inhibitors are described in WO2016 / 142507.

[0006] During the fabrication of these microcircuits or microdevices, various inorganic substrates such as single-crystalline silicon and polycrystalline silicon, compound semiconductors such as gallium arsenide, and metals are coated with an organic coating ("photoresist" or "resist"), which forms a resist framework of a permanent or temporary design and exhibits a pattern after undergoing a lithography process. Photoresists can be utilized to isolate conductors or protect selected regions of the substrate surface (such as silicon, silicon dioxide, or aluminum) from chemicals in both wet (chemicals) and dry (plasma) forms. In the case of using a material as a photoresist, the exposed regions of the substrate can undergo the required etching (removal) or deposition (addition) processes. After this operation is completed and after subsequent rinsing or conditioning, it is necessary to remove the resist and any applied post-etch residues to permit the basic finishing operations. After removing the photoresist, a specific micro-etching or deposition pattern remains. The mask and patterning processes are repeated several times to produce a layered configuration of the technology that includes the final device. Each step requires complete resist stripping and dissolution to ensure that the final-form device is produced with relatively high yield and satisfactory performance, without particle formation, and that the photoresist film is completely dissolved, rather than just delaminated. Depending on the type of photoresist employed, these materials can contain additives that can readily form particles, such as photoactive compounds (e.g., DNQ), photoacid generators (PAG), and photoradical generators. Any particles deposited into the active regions during this process detrimentally affect the yield and performance of the device. Additionally, another problem to be solved is the ability to very rapidly remove the photoresist, and completely dissolve it, in photoresists for metal stripping applications. This is because the metal covers the entire photoresist pattern, with very few regions for the penetrant chemicals of the remover. Therefore, a remover solution is required to rapidly dissolve the photoresist to achieve rapid metal stripping. Summary of the Invention

[0007] The present invention is an improved stripping composition that will remove a wide range of different patterned photoresist films, including those formed by both different types of negative and positive resist systems, and can remove thick photoresist films in 2 minutes or less even when these photoresist films are under a metal film. Among these different types, examples are resists that can be imaged by visible light, broadband i-line, g-line, h-line, UV, 248 nm, 193 nm, 193 nm immersion, deep UV, EUV, electron, or electron beam. In particular, the improved stripping composition of the present invention can provide rapid and complete dissolution of all components in thick photoresist films in 2 minutes or less. Additionally, this photoresist removal is performed from the substrate without etching the underlying exposed silver, copper, and / or tin, as well as other metals, and without using metal corrosion inhibitor additives (since such additives are also prone to promoting particle formation during resist pattern removal).

[0008] The inventive remover composition confers these advantageous properties by extremely rapid and complete dissolution of photoresist patterns formed from many different types of photoresists, typically in 30 to 20 seconds or less for photoresist films having a thickness of about 10 μm to about 100 μm, depending on the thickness, pattern type, and photoresist type. This removal is effected without forming a peeling resist film or particles from the resin or additives in the remover and without corroding the metal substrate coated with the photoresist film. When such a photoresist film inhibits access of the remover beneath the metal layer of the photoresist film, depending on the bimetallic geometry, the inventive formulation can remove the film in as little as about 2 minutes or less, about 2 to about 10 times faster than other removers. At the same time, unexpectedly, this remover composition does not require the presence of any inhibitor additives to inhibit corrosion (no significant corrosion), does not cause corrosion of metal substrates such as silver, copper, tin, and the like, and does not have a precipitation problem of metal corrosion inhibitors during the removal process using these inventive remover compositions. It has been found that these inventive remover compositions and their use processes are particularly suitable for the manufacture of semiconductor wafers, MEMS devices, and displays. In summary, these inventive remover compositions have the following advantages: (1) do not require corrosion inhibitors; (2) dissolve the photoresist film rather than merely delaminate it; (3) maintain an extremely rapid dissolution rate even when beneath a metal layer. Accordingly, these inventive remover compositions are capable of rapidly removing photoresist in photoresists for metal lift-off applications. A non-limiting example of such a photoresist is a negative i-line photoresist and a broadband photoresist containing a novolak resin.

[0009] In one of its aspects, the invention relates to a composition consisting essentially of: at least one sulfosalicylic acid having structure (I), its hydrate, or a mixture of the sulfosalicylic acid and its hydrate; a primary solvent selected from acetone and methyl ethyl ketone or a mixture of these solvents, an optional co-solvent (which is a glycolic acid derivative or a mixture of at least two glycolic acid derivatives), and an optional surfactant.

[0010]

[0011] In another aspect, the invention relates to the use of the above composition to remove a photoresist film from a substrate. Detailed Description

[0012] It should be understood that both the foregoing general description and the following detailed description are illustrative and explanatory and do not limit the claimed subject matter. In this application, unless otherwise specifically stated, the use of the singular includes the plural, the term "a / an" means "at least one", and the use of "or" means "and / or". Further, the use of the term "including" and other forms (such as "includes" and "included") is not restrictive. Additionally, unless otherwise specifically stated, terms such as "element" or "component" cover both elements and components that include one unit and elements or components that include more than one unit. As used herein, unless otherwise indicated, 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" means any combination of the foregoing elements using a single element.

[0013] The term (meth)acrylate is a term that includes both acrylate and methacrylate in one term.

[0014] The term "stripping agent" is synonymous with "removing agent".

[0015] The expression "consisting essentially of" has the following meaning: the ingredients form at least 90 wt%, more preferably at least 95 wt%, and most preferably at least 99 wt% of the composition.

[0016] The term "substantially" is intended to mean that no other components similar to the listed components are present in the composition.

[0017] According to one embodiment of the present invention, the term "consisting essentially of" may be replaced by "consisting of", whereby there are no other components in the composition.

[0018] The section headings used herein should not be construed as limiting the described subject matter for organizational purposes. All documents or portions of documents (including but not limited to patents, patent applications, articles, books, and papers) cited in this application are hereby expressly incorporated herein by reference in their entirety for any purpose. In the event that one or more of the incorporated documents and similar materials define a term in a manner that contradicts the definition of that term in this application, this application shall control.

[0019] The term alkyl refers to C-1 to C-8 straight-chain alkyls, C-2 to C-9 branched-chain alkyls, and C-5 to C-8 cycloalkyls.

[0020] The term alkyl carboxylate refers to part alkyl-(C=O)-O-[alkyl CO2-].

[0021] When referring to a composition in wt%, it should be understood that in any case, the wt% of all components, including non-essential components (such as impurities), totals no more than 100 wt%. In the case where the composition contains some minor non-essential contaminants or impurities, the composition of all essential components may total less than 100 wt%. Otherwise, if there are no significant non-essential impurity components, it should be understood that the composition of all essential components will essentially total 100 wt%.

[0022] As used herein, the term glycolic acid derivatives refers to alkylene diols, oligo(alkyleneoxyalkylene) diols [HO-(alkylene - O - alkylene - O) n -H] (n = 1 to 4); monoalkyl ethers and dialkyl ethers of alkylene diols, oligo(alkyleneoxyalkylene) diols [HO-(alkylene - O - alkylene - O) n -H] (n = 1 to 4); monoalkyl carboxylates and dialkyl carboxylates of alkylene diols, oligo(alkyleneoxyalkylene) diols [HO-(alkylene - O - alkylene - O) n -H] (n = 1 to 4); oligo(alkyleneoxyalkylene) diols [HO-(alkylene - O - alkylene - O) n -H] (n = 1 to 4) in which one hydroxyl group is functionalized as an alkyl ether and the other hydroxyl group is functionalized as an alkyl carboxylate.

[0023] In one of its aspects, the present invention relates to a composition consisting essentially of:

[0024] a) a sulfosalicylic acid having structure (I), its hydrate, or a mixture of the sulfosalicylic acid and its hydrate;

[0025] b) a main solvent selected from acetone and methyl ethyl ketone, or a mixture of these solvents,

[0026] c) an optional auxiliary solvent which is a glycolic acid derivative or a mixture of at least two glycolic acid derivatives; and

[0027] d) an optional surfactant, described herein separately, at different concentrations.

[0028] In this embodiment, the combined amounts of the above components do not have to equal 100 wt% (for example, the components can form at least 90 wt%, more preferably at least 95 wt%, more preferably at least 99 wt%, more preferably at least 99.5 wt%, most preferably at least 99.9 wt%), and may include other components that do not substantially affect the performance of the remover. In another aspect of this embodiment, the composition consists of components a), b), c), and d).

[0029]

[0030] Some embodiments of the composition of the present invention consist essentially of:

[0031] a) at least one of sulfosalicylic acid having structure (I), its hydrate, or a mixture of the sulfosalicylic acid and its hydrate;

[0032] b) a main solvent selected from acetone and methyl ethyl ketone, or a mixture of these solvents; and

[0033] c) an auxiliary solvent which is a glycolic acid derivative or a mixture of at least two glycolic acid derivatives; described herein at different concentrations.

[0034] In this embodiment, the combined amount of the above components does not exceed 100 wt%, but does not have to be equal to 100 wt% (for example, the components can form at least 90 wt%, more preferably at least 95 wt%, more preferably at least 99 wt%, more preferably at least 99.5 wt%, most preferably at least 99.9 wt% of the composition), and can include other components that do not substantially affect the performance of the remover. In another aspect of this embodiment, the composition of the present invention consists of the above components a), b), and c).

[0035] In one of its aspects, the present invention relates to a composition which consists essentially of:

[0036] a) at least one of sulfosalicylic acid having structure (I), its hydrate, or a mixture of the sulfosalicylic acid and its hydrate;

[0037] b) a main solvent selected from acetone and methyl ethyl ketone, or a mixture of these solvents; and

[0038] c) and a surfactant.

[0039] In this embodiment, the combined amount of components a), b), and c) does not exceed 100 wt%, but does not necessarily equal 100 wt%. These materials that do not affect the performance of the remover formulation can be present if other materials do not affect the performance of this remover material. In one embodiment, components a), b), and c) form at least 90 wt%, more preferably at least 95 wt%, more preferably at least 99 wt%, more preferably at least 99.5 wt%, most preferably at least 99.9 wt% of the composition.

[0040] In one of its aspects, the present invention relates to a composition which consists of:

[0041] a) at least one of sulfosalicylic acid having structure (I), its hydrate, or a mixture of the sulfosalicylic acid and its hydrate;

[0042] b) a main solvent selected from acetone and methyl ethyl ketone, or a mixture of these solvents; and

[0043] c) and a surfactant.

[0044] In this embodiment, the combined amount of the above components is 100 wt% and no other materials are significantly present.

[0045] In one of its aspects, the present invention relates to a composition consisting of:

[0046] a) at least one of sulfosalicylic acid having structure (I), its hydrate, or a mixture of the sulfosalicylic acid and its hydrate;

[0047] b) a main solvent selected from acetone and methyl ethyl ketone, or a mixture of these solvents.

[0048] In this embodiment, the combined amount of the above components is 100 wt% and no other materials are significantly present.

[0049] In one of its aspects, the present invention relates to a composition consisting essentially of:

[0050] a) at least one of sulfosalicylic acid having structure (I), its hydrate, or a mixture of the sulfosalicylic acid and its hydrate;

[0051] b) a main solvent selected from acetone and methyl ethyl ketone, or a mixture of these solvents.

[0052] In this embodiment, the combined amount of components a) and b) does not exceed 100 wt%, but is not necessarily equal to 100 wt%. These materials that do not affect the performance of the remover formulation may be present if they do not affect the performance of this remover material. In one embodiment, components a) and b) 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% of the composition.

[0053] In embodiments of the composition in which sulfosalicylic acid having structure (I) (or its hydrate) is one of its components, more specific embodiments of these are selected from those having structure (Ia), (Ib), (Ic), (Id) (or their hydrates) and mixtures thereof.

[0054]

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

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

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

[0058] In some embodiments, the sulfosalicylic acid (or its hydrate) of structure (I) is a compound (or its hydrate) having structure (Id).

[0059] In another embodiment of any of the above aspects of this composition, the sulfosalicylic acid component is sulfosalicylic acid having structure (I) (or is a hydrate), and it has a wt% loading in the total wt of the solution in the range of about 0.5 wt% to about 10 wt%. In another aspect of this embodiment, the wt% loading of this acid is about 0.75 wt% to about 7.00 wt%. In another aspect of this embodiment, the wt% loading of this acid is about 1.00 wt% to about 6.00 wt%. In another aspect of this embodiment, the wt% is about 1.50 wt% to about 5.00 wt%. In another aspect of this embodiment, the wt% is about 1.50 wt% to about 4.00 wt%. In another aspect of this embodiment, the wt% is about 1.75 wt% to about 3.00 wt%. In another aspect of this embodiment, the wt% is about 1.80 wt% to about 2.75 wt%. In another aspect of this embodiment, the wt% is about 1.90 wt% to about 2.50 wt%. 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%. In another aspect of this embodiment, the sulfosalicylic acid can be sulfosalicylic acid having structure (Ib) (or its hydrate). In another aspect of this embodiment, the sulfosalicylic acid can be sulfosalicylic acid having structure (Ic) (or its hydrate). In another aspect of this embodiment, the sulfosalicylic acid can be sulfosalicylic acid having structure (Id) (or its hydrate).

[0060] In one embodiment of the composition described herein, the main solvent is acetone.

[0061] In one embodiment of the composition described herein, the main solvent is methyl ethyl ketone.

[0062] In one embodiment of the composition described herein, the primary solvent is a mixture of acetone and methyl ethyl ketone. In one aspect of this embodiment, the wt% of acetone in the primary solvent mixture ranges from about 1 wt% to about 99.5 wt%. In one aspect of this embodiment, there is no auxiliary glycolic acid derivative solvent component in the composition. In another aspect of this embodiment, there is also an auxiliary glycolic acid derivative solvent component. In another aspect of this primary solvent mixture, it contains about 95 wt% acetone. In another aspect, this primary solvent mixture contains about 90 wt% acetone. In yet another aspect of this primary solvent mixture, it contains about 85 wt% acetone. In yet another aspect of this primary solvent mixture, it contains about 80 wt% acetone. In yet another aspect of this embodiment, this primary solvent mixture contains about 75 wt% acetone. In yet another aspect of this primary solvent mixture, it contains about 65 wt% acetone. In yet another aspect of this primary solvent mixture, it contains about 60 wt% acetone. In yet another aspect of this primary solvent mixture, it contains about 55 wt% acetone. In yet another aspect of this primary solvent mixture, it contains about 50 wt% acetone. In yet another aspect of this primary solvent mixture, it contains about 45 wt% acetone. In yet another aspect of this primary solvent mixture, it contains about 40 wt% acetone. In yet another aspect of this primary solvent mixture, it contains about 35 wt% acetone. In yet another aspect of this primary solvent mixture, it contains about 30 wt% acetone. In yet another aspect of this primary solvent mixture, it contains about 25 wt% acetone. In yet another aspect of this primary solvent mixture, it contains about 20 wt% acetone. In yet another aspect of this primary solvent mixture, it contains about 15 wt% acetone. In yet another aspect of this primary solvent mixture, it contains about 10 wt% acetone. In yet another aspect of this primary solvent mixture, it contains about 5 wt% acetone.

[0063] In embodiments of the compositions described herein that contain a co-glycolic acid derivative solvent component, this co-glycolic acid derivative solvent component is one of two things: a single co-glycolic acid derivative solvent or a mixture of at least two of these types of solvents. This co-glycolic acid derivative solvent component is present in an amount of about 1 wt% to about 30 wt% of the combined primary solvent and co-glycolic acid derivative solvent component. In one embodiment, it is about 1 wt% of the combined solvent component. In another embodiment, it is about 2 wt% of the combined solvent component. In another embodiment, it is about 3 wt% of the combined solvent component. In another embodiment, it is about 4 wt% of the combined solvent component. In another embodiment, it is about 5 wt% of the combined solvent component. In another embodiment, it is about 6 wt% of the combined solvent component. In another embodiment, it is about 7 wt% of the combined solvent component. In another embodiment, it is about 8 wt% of the combined solvent component. In another embodiment, it is about 9 wt% of the combined solvent component. In another embodiment, it is about 10 wt% of the combined solvent component. In another embodiment, it is about 11 wt% of the combined solvent component. In another embodiment, it is about 12 wt% of the combined solvent component. In another embodiment, it is about 13 wt% of the combined solvent component. In another embodiment, it is about 14 wt% of the combined solvent component. In another embodiment, it is about 15 wt% of the combined solvent component. In another embodiment, it is about 16 wt% of the combined solvent component. In another embodiment, it is about 17 wt% of the combined solvent component. In another embodiment, it is about 18 wt% of the combined solvent component. In another embodiment, it is about 19 wt% of the combined solvent component. In another embodiment, it is about 20 wt% of the combined solvent component. In another embodiment, it is about 21 wt% of the combined solvent component. In another embodiment, it is about 23 wt% of the combined solvent component. In another embodiment, it is about 23 wt% of the combined solvent component. In another embodiment, it is about 24 wt% of the combined solvent component. In another embodiment, it is about 25 wt% of the combined solvent component. In another embodiment, it is about 26 wt% of the combined solvent component. In another embodiment, it is about 27 wt% of the combined solvent component. In another embodiment, it is about 28 wt% of the combined solvent component. In another embodiment, it is about 29 wt% of the combined solvent component. In another embodiment, it is about 30 wt% of the combined solvent component.

[0064] In another aspect of these embodiments, the auxiliary glycolic acid derivative solvent component is selected from alkylene glycols, oligo(alkyleneoxyalkylene) glycols [HO-(alkylene-O-alkylene-O) n -H] (n = 1 to 4), monoalkyl ethers of alkylene glycols, monoalkyl ethers of oligo(alkyleneoxyalkylene) glycols, dialkyl ethers of alkylene glycols, dialkyl ethers of oligo(alkyleneoxyalkylene) glycols, alkylene glycols in which one of the hydroxyl groups is functionalized as an alkyl carboxylate and the other is functionalized as an ether, oligo(alkyleneoxyalkylene) glycols in which one of the hydroxyl groups is functionalized as an alkyl carboxylate and the other is functionalized as an ether, alkylene glycols in which one of the hydroxyl groups is functionalized as an alkyl carboxylate, oligo(alkyleneoxyalkylene) glycols in which one of the hydroxyl groups is functionalized as an alkyl carboxylate, alkylene glycols in which both hydroxyl groups are functionalized as alkyl carboxylates, oligo(alkyleneoxyalkylene) glycols in which both hydroxyl groups are functionalized as alkyl carboxylates, or a mixture of at least two selected from these solvent types.

[0065] In another aspect of these embodiments, the auxiliary glycolic acid derivative solvent component is an alkylene glycol.

[0066] In another aspect of these embodiments, the auxiliary glycolic acid derivative solvent component is an oligo(alkyleneoxyalkylene) glycol [HO-(alkylene-O-alkylene-O) n -H] (n = 1 to 4).

[0067] In another aspect of these embodiments, the auxiliary glycolic acid derivative solvent component is a monoalkyl ether of an alkylene glycol.

[0068] In another aspect of these embodiments, the auxiliary glycolic acid derivative solvent component is a monoalkyl ether of an oligo(alkyleneoxyalkylene) glycol [HO-(alkylene-O-alkylene-O) n -H] (n = 1 to 4).

[0069] In another aspect of these embodiments, the auxiliary glycolic acid derivative solvent component is a dialkyl ether of an alkylene glycol.

[0070] In another aspect of these embodiments, the auxiliary glycolic acid derivative solvent component is a dialkyl ether of an oligo(alkyleneoxyalkylene) glycol [HO-(alkylene-O-alkylene-O) n -H] (n = 1 to 4).

[0071] In another aspect of these embodiments, the auxiliary glycolic acid derivative solvent component is an alkylene glycol in which one hydroxyl group is functionalized as an alkyl ether and the other hydroxyl group is functionalized as an alkyl carboxylate.

[0072] In another aspect of these embodiments, the auxiliary glycolic acid derivative solvent component is an oligo(alkyleneoxyalkylene) diol [HO-(alkylene-O-alkylene-O) n -H] (n = 1 to 4), where one hydroxyl group is functionalized as an alkyl ether and the other hydroxyl group is functionalized as an alkyl carboxylate.

[0073] In another aspect of these embodiments, the auxiliary glycolic acid derivative solvent component is an alkylene diol, where one of the hydroxyl groups is functionalized as an alkyl carboxylate.

[0074] In another aspect of these embodiments, the auxiliary glycolic acid derivative solvent component is an oligo(alkyleneoxyalkylene) diol [HO-(alkylene-O-alkylene-O) n -H] (n = 1 to 4), where one of the hydroxyl groups is functionalized as an alkyl carboxylate.

[0075] In another aspect of these embodiments, the auxiliary glycolic acid derivative solvent component is an alkylene diol, where both hydroxyl groups are functionalized as alkyl carboxylates.

[0076] In another aspect of these embodiments, the auxiliary glycolic acid derivative solvent component is an oligo(alkyleneoxyalkylene) diol [HO-(alkylene-O-alkylene-O) n -H] (n = 1 to 4), where both hydroxyl groups are functionalized as alkyl carboxylates.

[0077] In another aspect of these embodiments, the auxiliary glycolic acid derivative solvent component is an oligo(alkyleneoxyalkylene) diol [HO-(alkylene-O-alkylene-O) n -H] (n = 1 to 4).

[0078] In a more specific embodiment of the auxiliary glycolic acid derivative solvent component, the alkylene moiety is selected from C-2 to C-6 straight-chain alkylene, or C-3 to C-7 branched-chain alkylene, or in the case of oligo(alkyleneoxyalkylene) diols, a mixture of these. In a more specific embodiment, the alkylene moiety is C-3 alkylene.

[0079] In a more specific embodiment of the auxiliary glycolic acid derivative where the hydroxyl group is functionalized as an alkyl ether (as a monoalkyl ether or a dialkyl ether), the alkyls are independently selected from methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl.

[0080] In a more specific embodiment of the auxiliary glycolic acid derivative where the hydroxyl group is functionalized with an alkyl carboxylate, these alkyl carboxylates are selected from acetate, propionate, isobutyrate, and butyrate.

[0081] In another specific embodiment in this regard of the glycolic acid derivative solvents, they are selected from ethylene glycol, propylene glycol, 1-methoxy-2-propyl acetate (PGMEA), 1-methoxy-2-propanol (PGME), dipropylene glycol monomethyl ether (II) having the formula (CH3O)C3H6OC3H6(OH) (CAS#34590-94-8.), dipropylene glycol dimethyl ether (III) (DPGDME) (CAS#111109-77-4), and dipropylene glycol (IV) (CAS#25265-71-8 25265-71), or a mixture of at least two of these solvents. In a more specific aspect of this embodiment, the auxiliary glycolic acid derivative solvent is ethylene glycol. In a more specific aspect of this embodiment, the auxiliary glycolic acid derivative solvent is propylene glycol. In a more specific aspect of this embodiment, the auxiliary glycolic acid derivative solvent is 1-methoxy-2-propyl acetate. In a more specific aspect of this embodiment, the auxiliary glycolic acid derivative solvent is 1-methoxy-2-propanol. In a more specific aspect of this embodiment, the auxiliary glycolic acid derivative solvent is dipropylene glycol monomethyl ether. In a more specific aspect of this embodiment, the auxiliary glycolic acid derivative solvent is dipropylene glycol dimethyl ether (III).

[0082] The aforementioned dipropylene glycol monomethyl ether (II) auxiliary glycolic acid derivative solvent is a complex mixture containing the following isomeric compounds: 1-(2-methoxypropoxy)-2-propanol (CAS 13429-07-7) (IIa); 1-(2-methoxy-1-methylethoxy)-2-propanol (CAS 20324-32-7) (IIb), 2-(2-methoxypropoxy)-1-propanol (CAS 13588-28-8) (IIc); 2-(2-(2-methoxypropoxy)-1-propanol (CAS 55956-21-3) (IId), and their optical isomers. In another embodiment of the inventive composition described herein containing an auxiliary glycolic acid derivative solvent, these individual solvents or a mixture of at least two of IIa to IId (and their optical isomers) are the auxiliary glycolic acid derivative solvents.

[0083]

[0084] The foregoing dipropylene glycol dimethyl ether (III) auxiliary glycolic acid derivative solvent is a complex mixture containing the following isomeric compounds: 2-methoxy-1-(2-methoxypropoxy)propane (CAS#63019-84-1) (IIIa); 2-methoxy-1-((1-methoxypropan-2-yl)oxy)propane (CAS 89399-28-0) (IIIb), 2-methoxy-1-((1-methoxypropan-2-yl)oxy)propane (CAS#189354-80-1) (IIIc), which have the following general structures IIIa, IIIb and IIIc, and their optical isomers. In another embodiment of the inventive compositions described herein containing an auxiliary glycolic acid derivative solvent, these individual solvents or a mixture of at least two of IIIa to IIIc (and their optical isomers) are the auxiliary glycolic acid derivative solvents.

[0085]

[0086] The foregoing dipropylene glycol monomethyl ether (IV) auxiliary glycolic acid derivative solvent is a complex mixture containing the following isomeric compounds: bis(2-hydroxypropyl) ether (CAS#110-98-5) (IVa); 2-(2-hydroxypropoxy)-1-propanol (CAS#106-62-7) (IVb), 2,2'-oxybis[1-propanol] (CAS#189354-80-1) (IVc), which have the following general structures IVa, IVb and IVc, and their optical isomers. In another embodiment of the inventive compositions described herein containing an auxiliary glycolic acid derivative solvent, these individual solvents or a mixture of at least two of IVa to IVc (and their optical isomers) are the auxiliary glycolic acid derivative solvents.

[0087]

[0088] In the embodiments of the present invention compositions described herein containing a surfactant, there are no specific limitations on the surfactant, and examples thereof include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, decaglycol monododecyl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleinether; polyoxyethylene alkaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, and sorbitan monostearate; nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene 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.); silicone polymers such as KP-341, X-70-092, and X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd.); and acrylic or methacrylic acid polymers such as Polyflow TM No. 75 and No. 95 (manufactured by Kyoeisha Yushikagaku Kogyo K.K.).

[0089] In another embodiment of the foregoing compositions 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%.

[0090] In another embodiment of any of the above-described compositions, the surfactant is a polymeric surfactant having structure (III), where 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 (IIIa).

[0091]

[0092] In an embodiment of the present invention, the composition contains a surfactant having structure (III) or (IIIa), and each surfactant can be present in the composition individually at about 0.005 wt% to about 0.100 wt%. In another embodiment, about 0.010 wt% to about 0.050 wt%. In yet another embodiment, about 0.015 wt% to about 0.040 wt%. In still another embodiment, about 0.020 wt% to about 0.035 wt%. In yet another embodiment, about 0.022 wt% to about 0.030 wt%. In still another embodiment, about 0.023 wt% to about 0.028 wt%. In yet another embodiment, about 0.024 wt% to about 0.026 wt%. In still another embodiment, about 0.025 wt%. In some of these embodiments, when the surfactant is present, it is further defined as the surfactant corresponding to structure (III) or (IIIa), and preferably no other surfactants different from these structures are present in the composition.

[0093] In one aspect of the present invention, a class of materials that can substantially change the effectiveness of the remover due to particle deposition is specifically excluded from the compositions of the present invention described herein. Examples of these excluded materials are particles, pigments, dyes, antioxidants, and inhibitors of the rosin type; such as fumarated rosin and other materials that can form particles and deposit on the substrate during stripping.

[0094] In another aspect of the present invention, another class of materials that can substantially change the effect of the remover by causing corrosion of the metal substrate is pK aOther acidic materials having a pH less than 5, which acidic materials are specifically excluded from the inventive compositions described herein. Examples of such acidic materials are sulfonic acids, other types of sulfonic acids of which non-limiting examples, apart from the sulfonic acids having structure (I) (and substructures (Ia), (Ib), (Ic), (Id)) present in the inventive compositions described herein, are arylsulfonic acids (e.g., benzenesulfonic acid, naphthalenesulfonic acid, alkylbenzenesulfonic acids (e.g., p-toluenesulfonic acid, dodecylbenzenesulfonic acid), alkylsulfonic acids (e.g., methanesulfonic acid, butanesulfonic acid), trifluoromethanesulfonic acid, perfluoroalkylsulfonic acids (e.g., perfluorobutanesulfonic acid), partially fluorinated alkylsulfonic acids (e.g., 2,2,2-trifluoroethanesulfonic acid), other arylsulfonic acids (substituted or unsubstituted, e.g., benzenesulfonic acid, fluorobenzenesulfonic acid, difluorobenzenesulfonic acid, pentafluorobenzenesulfonic acid, propylbenzenesulfonic acid), nitrobenzenesulfonic acid, dinitrobenzenesulfonic acid, benzenedisulfonic acid and the like. Also excluded are sulfamic acids, such as non-limiting examples sulfamic acid, cyclamic acid and methylsulfamic acid. Also excluded are strong inorganic acids (pK a less than 0), such as non-limiting examples fluorosulfonic acid, nitric acid, sulfuric acid, hydrochloric acid and the like. pK a Inorganic acids having a pK greater than 0, hydrofluoric acid, phosphorus-containing oxoacids containing P in the oxidation state +1 [e.g., H3PO2 (or H2PO(OH)), hypophosphorous acid or hypophosphinic acid, monoprotic acid]; phosphorus-containing oxoacids containing P in the oxidation state +3 [e.g., (H3PO3 (or HPO(OH)2), phosphorous acid or phosphonic acid, diprotic acid], phosphorus-containing oxoacids containing P in the oxidation state +5 (e.g., phosphoric acid: H3PO4 (or PO(OH)3), phosphoric acid, triprotic acid phosphoric acid). Also excluded are carboxylic acids, such as non-limiting examples formic acid, alkylcarboxylic acids (e.g., acetic acid, propionic acid and similar acids), perfluoroalkylcarboxylic acids (e.g., trifluoroacetic acid and similar acids), arylcarboxylic acids (e.g., benzoic acid and similar acids), alkylbenzoic acids (e.g., toluic acid and similar acids), arylalkanoic acids (e.g., phenylacetic acid, phenylpropionic acid and similar acids), dicarboxylic acids (e.g., oxalic acid, maleic acid, malonic acid and the like), tricarboxylic acids (e.g., citric acid, isocitric acid, aconitic acid, propane-1,2,3-trihydroxyacid, symmetric benzene-1,2,3-tricarboxylic acid and the like). In another aspect of this embodiment, materials such as those described above having a pK a less than 0 are excluded from the stripper formulation. In one aspect of this embodiment, materials having a pK a less than 0 are excluded from the formulation.

[0095] In another aspect of the present invention, two classes of materials that can substantially alter the effectiveness of the removal agent composition by causing particle deposition or by causing metal corrosion, as separately described herein in its different aspects, are excluded from the components.

[0096] Another embodiment of the present invention is a method comprising the following steps:

[0097] i) Thermally condition the temperature of any one of the compositions of the present invention described above to a temperature of about 15°C to about 80°C to produce a thermally conditioned composition.

[0098] ii) Treat a substrate coated with a photoresist film with the thermally conditioned composition for a time of about 1 minute to about 60 minutes until a substrate with the photoresist film removed is produced.

[0099] iii) After step ii), rinse the substrate with one of isopropyl alcohol, a mixture of isopropyl alcohol and water, or water to remove any residual composition from step ii), thereby producing a clean substrate.

[0100] iv) Dry the clean substrate.

[0101] In a more specific embodiment of this method, in step i), the composition is thermally conditioned to about 20°C to about 60°C. In another specific embodiment of this method, in step i), the composition is thermally conditioned to about 20°C to about 40°C. In yet another specific embodiment, in step ii), the substrate is a metal. In yet another specific embodiment, in step ii), the substrate is copper. In yet another specific embodiment, in step ii), the substrate is tin. In yet another specific embodiment, in step ii), the substrate is silver. In still another specific embodiment, in step ii), the treatment of the substrate lasts for about 1 minute to about 20 minutes. In still another specific embodiment, in step iii), the rinsing is carried out with a mixture of water and isopropyl alcohol, and the mixture has a water composition in the range of about 5 wt% to about 95 wt%.

[0102] In one embodiment of the above-described method of the present invention, the treatment of the photoresist film removed in step ii) is a treatment selected from the group consisting of 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.

[0103] In one embodiment of the above-described method of the present invention, in step ii), the treatment is carried out by immersing the substrate in the composition of the present invention, spraying with the thermally conditioned composition of the present invention, or by puddling the thermally conditioned composition onto the photoresist film. In one aspect of this embodiment, immersion is used. In another aspect of this embodiment, spraying is used. In another aspect of this embodiment, puddling is used.

[0104] In another embodiment of the method of the present invention described above, in step i), the composition is thermally conditioned to from about 30 °C to about 65 °C.

[0105] In another embodiment of the method of the present invention described above, in step iv), the clean substrate is dried by centrifugal drying in air, drying with an air stream (such as nitrogen, air or some other inert gas), isopropyl alcohol (IPA) drying or Marangoni drying. In one aspect, the drying is carried out by centrifugal drying. In another aspect, the drying is carried out by using the air stream. In another aspect, the drying is carried out by using IPA drying. In yet another aspect, the drying is carried out by the Marangoni drying.

[0106] In one aspect of the method of the present invention described above, the photoresist film is a negative photoresist film.

[0107] In one aspect of the method of the present invention described above, the photoresist film is a positive photoresist film.

[0108] In another aspect of the method of the present invention described above, the photoresist film is a chemically amplified photoresist film.

[0109] 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. In one aspect, it is a patterned negative photoresist film. In another aspect, it is a blanket-exposed negative photoresist film. In one aspect of these embodiments, the negative photoresist is a chemically amplified photoresist.

[0110] A patterned photoresist film as described herein refers to a photoresist film that has been exposed or developed with an aqueous alkali developer or a solvent-based developer to produce the patterned photoresist film, depending on the type of photoresist used to form the film, and the development can occur after a post-exposure bake.

[0111] A blanket-exposed photoresist film refers to a photoresist film that has been exposed to radiation (such as i-line, g-line, UV, deep UV, broadband, EUV, electron beam and the like), but where a mask is not used during the exposure to produce an exposed pattern that will produce a patterned photoresist film after development.

[0112] In another embodiment of the method of the present invention described above, in step ii), the substrate is a metal. In one aspect of this embodiment, the metal is selected from copper, aluminum, aluminum / copper alloy, silver, tin, titanium, tungsten, and nickel. In another aspect of this embodiment of the method, the metal is selected from aluminum, aluminum / copper alloy, and copper. In yet another embodiment of the method of the present invention described above, in step ii), the substrate is copper. In yet another embodiment of the method of the present invention described above, in step ii), the substrate is tin.

[0113] In yet another embodiment of the method of the present invention described above, in step ii), the substrate is a substrate having a bimetallic pattern, and the bimetallic pattern is composed of two different metals selected from aluminum, aluminum / copper alloy, tin, silver, and copper. In one aspect, the bimetallic pattern is one of copper and tin. In another aspect, the bimetal is silver and aluminum. In yet another aspect, the bimetallic pattern has one of silver and aluminum / copper alloy. In yet another embodiment, the bimetallic pattern is one of silver and tin. In yet another embodiment, the bimetallic pattern is one of silver and copper. In yet another embodiment, the bimetallic pattern is one of silver and titanium. In yet another embodiment, the bimetallic pattern is one of silver and tungsten. In yet another embodiment, the bimetallic pattern is one of silver and nickel.

[0114] In another embodiment of the method of the present invention described above, in step ii), the substrate is processed for about 1 minute to about 20 minutes. In another aspect of this embodiment, in step ii), the substrate is processed for about 5 minutes to about 20 minutes.

[0115] In another embodiment of the method of the present invention described above, in step iii), rinsing is carried out with water.

[0116] The remover composition of the present invention can be used in the above-described inventive method to remove patterns from many different types of photoresist patterns as follows.

[0117] Depending on the application, for IC devices, IC device interconnects, circuit boards, solder board applications, MEMs, displays, and the like, the remover of the present invention can be used to remove patterned resist films having various thicknesses. Generally, the thickness is consistent with the size of the device being manufactured, starting from about dozens of nanometers for prior art ICs, ranging to several micrometers for larger IC devices, and up to 10 to 500 micrometers for extremely large devices such as MEMs.

[0118] The remover of the present invention can be used with a resist pattern generated from a negative and positive photoresist material capable of forming a pattern, which can be selected from materials that can be patterned using different types of radiation. For example, as non-limiting examples, the removed resist pattern can be formed from i-line photoresist, g-line photoresist, 248 nm photoresist, 193 nm photoresist, extreme ultraviolet photoresist, electron beam photoresist, and particle beam photoresist. The remover of the present invention can be used with a photoresist pattern that can be generated from a photoresist, and the photoresist can be further classified as follows based on the type of chemical used to obtain the pattern.

[0119] For example, the remover of the composition of the present invention can be used to remove positive patterns generated by exposure to visible light, i-line, h-line, and g-line and developed with an alkaline aqueous solution using a photoresist sensitized with a novolak resin and a diazonaphthoquinone (DNQ) sensitizer material. These types of resist systems can also produce negative images via a tone reversal process. Diazonaphthoquinone-based resists are described in (Diazonapththoquinone-based Resists, Chapter 2, Basic Chemistry of DNQ / Novolak resists, SPIE Optional Engineering Press, Volume TT11, page 9, 1993), which is incorporated herein by reference in its entirety.

[0120] In addition, the remover of the composition of the present invention can be used to remove resist films and patterns generated from both negative and positive photoresists developed with an alkaline aqueous solution or a solvent.

[0121] In addition, the remover of the composition of the present invention can be used to remove chemically amplified and alkaline aqueous solution-developable resists. Generally, resist patterns are formed by 248 nm, 193 nm, EUV to achieve higher resolution patterns, but longer wavelengths (such as visible light, broadband UV, i-line, g-line, and h-line) can also be used to produce photoresist patterns.

[0122] The remover of the present invention can be used to remove resist patterns generated from positive chemically amplified resists. Potentially, resins that are soluble in an alkaline aqueous solution (such as (meth)acrylate copolymers, styrenic copolymers, novolaks, phenolic resins) are made soluble in an alkaline aqueous solution by deprotecting acid-cleavable groups that shield the alkaline aqueous solution solubilizing moiety. The base-solubilizing moiety can be a carboxylic acid, a phenol, or generally has a pK of less than 11 aOther portions thereof are such that the alkaline aqueous solution will ionize it to a large extent. An acid is generated in the exposed area of the photoresist film by a photoacid generating compound. This acid deprotects the acid-cleavable group via an acidolysis or hydrolysis process, releasing the free base solubilizing moiety, thereby allowing the photoresist film to be soluble in the alkaline aqueous solution in the exposed area.

[0123] The remover of the present invention can be used to remove resist patterns generated by negative chemically amplified resists whose inherent solubility in alkaline aqueous solution is not masked by any protecting group. Instead, in this method, inherently base-soluble resins (binder resins) such as alkali aqueous solution-soluble (meth)acrylate copolymers, styrenic copolymers, novolacs and the like are catalytically crosslinked by a photoacid via acid crosslinking moieties. These moieties can be attached to the binder resin itself, present on a crosslinking additive (crosslinker) or present on both the resin and the additive. The acid-catalyzed crosslinking in the exposed area is affected by the photoacid generated by the PAG, which produces a negative image after alkaline aqueous solution development. Generally, when a crosslinking additive is employed, the crosslinking additive is a moiety capable of forming a carbonium ion upon interaction with the photoacid (such as an aminoplast) or an additive containing an acid-crosslinkable group (such as an epoxide). Similarly, if the crosslinking moiety is present on the resin, it can be a moiety capable of forming a carbonium ion with the acid or a moiety crosslinkable with the acid (such as an epoxy moiety). The following reference is a review of chemically amplified resists: H. Itoh, Adv Polym Sci, 2005, I 72, page 37.

[0124] The remover of the present invention can be used to remove photoresist patterns generated from negative chemically amplified resists, where the binder resin can include novolac, such as novolac derived from substituted phenols, such as o-cresol, m-cresol, p-cresol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, thymol, and mixtures thereof, which have been condensed with aldehydes such as formaldehyde. In other methods, the binder resin can also include poly(vinylphenol), such as poly(p-hydroxystyrene); poly(p-hydroxy-α-methylstyrene); copolymers of p-hydroxystyrene or p-hydroxy-α-methylstyrene with styrene, acetoxystyrene, or acrylic acid and / or methacrylic acid; homopolymers of hydroxyphenylalkylmethanol; or novolac / poly(vinylphenol) copolymers. The crosslinking additive for such negative chemically amplified resists can be an etherified aminoplast crosslinking functional group contained in small compounds, organic oligomers, or polymers. Such aminoplasts provide carbocation ions after acid cleavage and are used to crosslink the binder resin in the presence of an acid generated by radiation (preferably imaging radiation). This crosslinking renders the binder resin insoluble in alkaline media in the exposed areas. Such crosslinking agents can be prepared by combining various aminoplasts with compounds or low molecular weight polymers containing multiple hydroxyl, carboxyl, amide, or imide groups. Some examples of aminooligomers or polymers are aminoplasts obtained by reacting amines such as urea, melamine, or glycolurea with aldehydes such as formaldehyde. Suitable aminoplasts can include urea formaldehyde, melamine formaldehyde, benzoguanamine formaldehyde, and glycolurea formaldehyde resins, and combinations of any of these. In some applications, the aminoplast is a hexakis(methoxymethyl)melamine oligomer. Non-limiting examples of such materials are described in U.S. Patent No. 6,576,394.

[0125] Examples

[0126] Reference is now made to more specific embodiments of the present invention and the experimental results supporting these embodiments. However, the applicant cautions 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.

[0127] Chemicals

[0128] Photoresist products used in these examples nLOF 2070, 3DT, 4620, 15nXT were all obtained from EMD Performance Materials, Branchburg, NJ 08876. All other chemicals were purchased from Millipore Sigma (3050 Spruce St., St. Louis, MO 63103).

[0129] Treatment

[0130] For the photoresist stripping test, a silicon wafer was used as the inorganic substrate, and a chemically amplified negative photoresist was coated and treated on the inorganic substrate nLOF 2070 (product of EMD Performance Materials, Branchburg, NJ 08876). The treatment consisted of spin-coating the resist to the desired thickness and applying a soft bake at 110 °C for 90 seconds on a hot plate to form a 10-μm thick film. Subsequently, the resist was exposed to light at 220 mJ / cm 2 After exposure baking at 110 °C for 90 seconds on a hot plate, the resist was then developed. Development was carried out in two puddles with AZ 300MIF developer for 60 seconds each, followed by rinsing with deionized water.

[0131] A 200-mm (8-inch) silicon wafer with a 150-nm silver sputter coating was used for the silver corrosion test. The silver-coated silicon wafer specimen was immersed in the photoresist remover solution for a period sufficient to strip the photoresist. Regular inspections were carried out to examine the metal surface condition by visual and microscopic examination for the presence of surface turbidity as an indication of corrosion. Surface turbidity could be identified and confirmed at a level more sensitive than gravimetric analysis

[0132] Silver corrosion and photoresist stripping test 1

[0133] The photoresist remover solution was prepared by dissolving 2 wt% 5-sulfosalicylic acid dihydrate (CAS: 5965-83-3) in acetone (CAS: 67-64-1). The room temperature solution was placed in a 150-ml beaker with a magnetic stir bar (300 rpm). The silicon wafer specimen with the nLOF 2070 photoresist pattern was immersed in the solution. The photoresist dissolved within 20 seconds. The same solution and equipment were used for the silver corrosion test. The silver wafer specimen was immersed in the solution for 60 minutes. By visual and microscopic examination, the silver surface had no turbidity and was substantially intact, and there was no deposition of any particles.

[0134] Silver corrosion and photoresist stripping test 2

[0135] The photoresist remover solution was prepared by dissolving 2 wt% 5-sulfosalicylic acid dihydrate (CAS: 5965-83-3) in methyl ethyl ketone (CAS: 78-93-3). The room temperature solution was placed in a 150-ml beaker with a magnetic stir bar (300 rpm). The silicon wafer specimen with A silicon wafer specimen with an nLOF 2070 photoresist pattern was immersed in the solution. The photoresist dissolved within 20 seconds. The same solution and equipment were used for the silver corrosion test. A silver wafer specimen was immersed in the solution for 60 minutes. By visual and microscopic inspection, the silver surface had no turbidity and was substantially intact, and there was no deposition of any particles.

[0136] Silver Corrosion and Photoresist Stripping Test 3

[0137] A photoresist remover solution was prepared by dissolving 2 wt% 5-sulfosalicylic acid dihydrate (CAS: 5965-83-3) in a mixture of acetone (CAS: 67-64-1) and di(propylene glycol) methyl ether (CAS: 34590-94-8) (weight ratio: 80:20). The room temperature solution was placed in a 150 ml beaker with a magnetic stir bar (300 rpm). A silicon wafer specimen with an nLOF 2070 photoresist pattern was immersed in the solution. The photoresist dissolved within 20 seconds. The same solution and equipment were used for the silver corrosion test. A silver wafer specimen was immersed in the solution for 60 minutes. By visual and microscopic inspection, the silver surface had no turbidity and was substantially intact, and there was no deposition of any particles.

[0138] Silver Corrosion and Photoresist Test 4

[0139] A photoresist remover solution was prepared by dissolving 10 wt% 5-sulfosalicylic acid dihydrate (CAS: 5965-83-3) in a mixture of acetone (CAS: 67-64-1) and di(propylene glycol) methyl ether (CAS: 34590-94-8) (weight ratio: 80:20). The room temperature solution was placed in a 150 ml beaker with a magnetic stir bar (300 rpm). A silicon wafer specimen with an nLOF2070 photoresist pattern was immersed in the solution. The photoresist dissolved within 20 seconds. The same solution and equipment were used for the silver corrosion test. A silver wafer specimen was immersed in the solution for 60 minutes. By visual and microscopic inspection, the silver surface had no turbidity and was substantially intact, and there was no deposition of any particles.

[0140] Silver Corrosion and Photoresist Test 5

[0141] A photoresist remover solution was prepared by dissolving 2 wt% 5-sulfosalicylic acid dihydrate (CAS: 5965-83-3) in a mixture of acetone (CAS: 67-64-1) and PGMEA (weight ratio: 80:20). The room temperature solution was placed in a 150 ml beaker with a magnetic stir bar (300 rpm). A silicon wafer specimen with an A silicon wafer specimen with an nLOF 2070 photoresist pattern was immersed in the solution. The photoresist dissolved within 20 seconds. The same solution and equipment were used for the silver corrosion test. A silver wafer specimen was immersed in the solution for 60 minutes. By visual and microscopic inspection, the silver surface had no turbidity and was substantially intact, and there was no deposition of any particles.

[0142] Silver Corrosion and Photoresist Test 6

[0143] A photoresist remover solution was prepared by dissolving 2 wt% 5-sulfosalicylic acid dihydrate (CAS: 5965-83-3) in a mixture of acetone (CAS: 67-64-1) and PGME (weight ratio: 80:20). The solution at room temperature was placed in a 150 ml beaker with a magnetic stir bar (300 rpm). A silicon wafer specimen with A silicon wafer specimen with an nLOF 2070 photoresist pattern was immersed in the solution. The photoresist dissolved within 20 seconds. The same solution and equipment were used for the silver corrosion test. A silver wafer specimen was immersed in the solution for 60 minutes. By visual and microscopic inspection, the silver surface had no turbidity and was substantially intact, and there was no deposition of any particles.

[0144] Silver Corrosion and Photoresist Test 7

[0145] A photoresist remover solution was prepared by dissolving 2 wt% 5-sulfosalicylic acid dihydrate (CAS: 5965-83-3) in a mixture of acetone (CAS: 67-64-1) and propylene glycol (CAS No.: 57-55-6) (weight ratio: 80:20). The solution at room temperature was placed in a 150 ml beaker with a magnetic stir bar (300 rpm). A silicon wafer specimen with A silicon wafer specimen with an nLOF 2070 photoresist pattern was immersed in the solution. The photoresist dissolved within 20 seconds. The same solution and equipment were used for the silver corrosion test. A silver wafer specimen was immersed in the solution for 60 minutes. By visual and microscopic inspection, the silver surface had no turbidity and was substantially intact, and there was no deposition of any particles.

[0146] Silver Corrosion and Photoresist Test 8

[0147] A photoresist remover solution was prepared by dissolving 2 wt% 5-sulfosalicylic acid dihydrate (CAS: 5965-83-3) in a mixture of acetone (CAS: 67-64-1) and dipropylene glycol dimethyl ether (CAS: 111109-77-4) (weight ratio: 80:20). The solution at room temperature was placed in a 150 ml beaker with a magnetic stir bar (300 rpm). A silicon wafer specimen with A silicon wafer specimen with an nLOF2070 photoresist pattern was immersed in the solution. The photoresist dissolved within 20 seconds. The same solution and equipment were used for the silver corrosion test. A silver wafer specimen was immersed in the solution for 60 minutes. By visual and microscopic inspection, the silver surface had no turbidity and was substantially intact, and there was no deposition of any particles.

[0148] Silver Corrosion and Photoresist Test 9

[0149] A photoresist remover solution was prepared by dissolving 10 wt% 5-sulfosalicylic acid dihydrate (CAS: 5965-83-3) in a mixture of acetone (CAS: 67-64-1) and propylene glycol (CAS No.: 57-55-6) (weight ratio: 80:20). The room temperature solution was placed in a 150 ml beaker with a magnetic stir bar (300 rpm). A silicon wafer specimen with an nLOF 2070 photoresist pattern was immersed in the solution. The photoresist dissolved within 20 seconds. The same solution and equipment were used for the silver corrosion test. A silver wafer specimen was immersed in the solution for 60 minutes. By visual and microscopic inspection, the silver surface had no turbidity and was substantially intact, and there was no deposition of any particles.

[0150] Stripping of Other Types of Photoresists

[0151] Silver corrosion and photoresist stripping tests 1 were conducted for other types of photoresists, all of which demonstrated rapid removal (20 seconds or less) of thick photoresist films without corroding metals such as silver or copper and without any particle deposition, as outlined in Table 1.

[0152] Table 1

[0153]

[0154] Comparative Photoresist Stripping Test 1

[0155] A photoresist remover solution was prepared by dissolving 2 wt% 5-sulfosalicylic acid dihydrate (CAS: 5965-83-3) in di(propylene glycol) methyl ether (CAS: 34590-94-8). The room temperature solution was placed in a 150 ml beaker with a magnetic stir bar (300 rpm). A silicon wafer specimen with an nLOF 2070 photoresist pattern was immersed in the solution. The photoresist took at least 20 minutes to dissolve.

[0156] Comparative Photoresist Stripping Test 2

[0157] A photoresist remover solution was prepared by dissolving 2 wt% 5-sulfosalicylic acid dihydrate (CAS: 5965-83-3) in 2-heptanone (CAS: 110-43-0). The room temperature solution was placed in a 150 ml beaker with a magnetic stir bar (300 rpm). A silicon wafer specimen with nLOF 2070 photoresist pattern was immersed in the solution. It took at least 20 minutes for the photoresist to dissolve.

[0158] Comparative Photoresist Stripping Test 3

[0159] A photoresist remover solution was prepared by dissolving 2 wt% 5-sulfosalicylic acid dihydrate (CAS: 5965-83-3) in cyclohexanone (CAS: 108-94-1). The room temperature solution was placed in a 150 ml beaker with a magnetic stir bar (300 rpm). A silicon wafer specimen with nLOF 2070 photoresist pattern was immersed in the solution. It took at least 20 minutes for the photoresist to dissolve.

[0160] Comparative Photoresist Stripping Test 4

[0161] A photoresist remover solution was prepared by dissolving 2 wt% 5-sulfosalicylic acid dihydrate (CAS: 5965-83-3) in di(propylene glycol) dimethyl ether (CAS: 111109-77-4). The room temperature solution was placed in a 150 ml beaker with a magnetic stir bar (300 rpm). A silicon wafer specimen with nLOF 2070 photoresist pattern was immersed in the solution. It took at least 20 minutes for the photoresist to dissolve.

[0162] Comparative Metal Corrosion Test 1

[0163] A photoresist remover solution was prepared by dissolving 2 wt% dodecylbenzenesulfonic acid (CAS: 68584-22-5) in acetone. The solution was placed in a 150 ml beaker with a magnetic stir bar (300 rpm). A silver wafer specimen was immersed in the solution. After 5 minutes, the silver layer on the silicon wafer became cloudy, indicating corrosion.

Claims

1. A stripping composition comprising at least 99 wt% of the following components: At least one of sulfosalicylic acid having structure (I), its hydrate, or a mixture of the sulfosalicylic acid and its hydrate; A main solvent selected from acetone and methyl ethyl ketone, or a mixture of these solvents, An auxiliary solvent which is a glycolic acid derivative or a mixture of at least two glycolic acid derivatives, Wherein the auxiliary solvent is selected from the group consisting of: alkylene glycols, oligo(alkyleneoxyalkylene) glycols, monoalkyl ethers of alkylene glycols, monoalkyl ethers of oligo(alkyleneoxyalkylene) glycols, dialkyl ethers of alkylene glycols, dialkyl ethers of oligo(alkyleneoxyalkylene) glycols, alkylene glycols in which one of the hydroxyl groups is functionalized as an alkyl carboxylate and the other is functionalized as an ether, oligo(alkyleneoxyalkylene) glycols in which one of the hydroxyl groups is functionalized as an alkyl carboxylate and the other is functionalized as an ether, alkylene glycols in which one of the hydroxyl groups is functionalized as an alkyl carboxylate, oligo(alkyleneoxyalkylene) glycols in which one of the hydroxyl groups is functionalized as an alkyl carboxylate, alkylene glycols in which both hydroxyl groups are functionalized as alkyl carboxylates, and oligo(alkyleneoxyalkylene) glycols in which both hydroxyl groups are functionalized as alkyl carboxylates; And optionally a surfactant; 2. The composition according to claim 1, wherein the auxiliary solvent is selected from [HO-(alkylene-O-alkylene-O) n -H], where n = 1 to 4.

3. The composition according to claim 1, consisting of the following components: At least one of sulfosalicylic acid having structure (I), its hydrate, or a mixture of the sulfosalicylic acid and its hydrate; A main solvent selected from acetone and methyl ethyl ketone, or a mixture of these solvents, An auxiliary solvent which is a glycolic acid derivative or a mixture of at least two glycolic acid derivatives, and Optionally a surfactant; 4. The composition according to any one of claims 1 to 3, wherein the sulfosalicylic acid is sulfosalicylic acid having structure (Ia) or its hydrate:

5. The composition according to any one of claims 1 to 3, wherein the sulfosalicylic acid is sulfosalicylic acid having structure (Ib) or its hydrate:

6. The composition according to any one of claims 1 to 3, wherein the sulfosalicylic acid is sulfosalicylic acid having structure (Ic) or its hydrate:

7. The composition according to any one of claims 1 to 3, wherein the sulfosalicylic acid is sulfosalicylic acid having structure (Id) or its hydrate:

8. The composition according to any one of claims 1 to 3, wherein the main solvent is acetone or methyl ethyl ketone.

9. The composition according to any one of claims 1 to 3, wherein the main solvent is a mixture of acetone and methyl ethyl ketone.

10. The composition according to any one of claims 1 to 3, wherein the auxiliary solvent is selected from one of the following two: a solvent selected from the group consisting of PGME, PGMEA, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, and dipropylene glycol dimethyl ether, or a mixture of at least two of these solvents.

11. The composition according to claim 10, wherein the auxiliary solvent is dipropylene glycol monomethyl ether.

12. A composition comprising at least 99 wt% of the following components: At least one of sulfosalicylic acid having structure (I), its hydrate, or a mixture of the sulfosalicylic acid and its hydrate; A main solvent selected from acetone and methyl ethyl ketone, or a mixture of these solvents, An optional co-solvent which is a glycolic acid derivative or a mixture of at least two glycolic acid derivatives, and An optional surfactant; wherein the sulfosalicylic acid having structure (I) or its hydrate is selected from sulfosalicylic acid having structure (Ib), (Ic), (Id) or its hydrate, a mixture thereof, and a mixture thereof with sulfosalicylic acid having structure (Ia) or its hydrate, 13. The composition according to claim 12, which consists of the following components: At least one of sulfosalicylic acid having structure (I), its hydrate, or a mixture of the sulfosalicylic acid and its hydrate; A main solvent selected from acetone and methyl ethyl ketone, or a mixture of these solvents, An optional co-solvent which is a glycolic acid derivative or a mixture of at least two glycolic acid derivatives, and An optional surfactant; wherein the sulfosalicylic acid having structure (I) or its hydrate is selected from sulfosalicylic acid having structure (Ib), (Ic), (Id) or its hydrate, a mixture thereof, and a mixture thereof with sulfosalicylic acid having structure (Ia) or its hydrate, 14. A method comprising the following steps: i) Thermally regulating the composition to a temperature of 15°C to 80°C to produce a thermally regulated composition, wherein the composition comprises at least 99 wt% of the following components: At least one of sulfosalicylic acid having structure (I), its hydrate, or a mixture of the sulfosalicylic acid and its hydrate; A main solvent selected from acetone and methyl ethyl ketone, or a mixture of these solvents, An optional co-solvent which is a glycolic acid derivative or a mixture of at least two glycolic acid derivatives, and An optional surfactant; ii) Treating a substrate coated with a photoresist film with the thermally regulated composition for a time of 1 minute to 60 minutes until a substrate with the photoresist film removed is produced, iii) After step ii), rinsing the substrate with the photoresist film removed with one of isopropyl alcohol, a mixture of isopropyl alcohol and water, or water to remove any residual composition from step ii) to produce a clean substrate, iv) Drying the clean substrate.

15. The method according to claim 14, wherein the composition is the composition according to any one of claims 1 to 13.

16. Use of a composition as defined in any one of claims 1 to 13 or claim 14 for removing a photoresist film from a substrate.

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