Compositions and methods for improving the fabrication of metal structures by wet chemical etching - Patents.com

Abstract

One aspect of the invention is a photoresist composition comprising a thiol derivative having a thiol moiety attached to an SP2 carbon that is part of a ring having the structure (H1), (H2), (H3) or (H4), the thiol additive being present in a range of about 0.5% to about 3% by weight of total solids. Another aspect of the invention is the use of the photoresist composition on a metal substrate to form a patterned photoresist that is used as an etch mask in anisotropic wet chemical etching of the metal substrate to produce a patterned metal substrate. Yet another aspect of the invention is a method of treating a metal substrate that allows the use of a composition comprising the thiol derivative in a spin casting solution, as well as an overlying patterned photoresist as an etch mask for wet chemical etching to produce anisotropic etching of the metal substrate, thereby also producing a patterned metal substrate. TIFF2024542436000091.tif19170

Description

[Technical field]

[0001] The disclosed invention relates to photoresist and spin-cast solvent compositions containing thiol derivatives and processes for their use to improve metal feature fabrication by wet chemical etching. [Background technology]

[0002] Photoresist compositions are used in microlithography processes for the production of miniaturized electronic components, such as in the production of computer chips, integrated circuits, light emitting diode (LED) devices, and displays. These processes typically involve first applying a film of a photoresist composition to a substrate, such as silicon wafers used in the production of integrated circuits. The coated substrate is then baked to evaporate any solvent in the photoresist composition and to fix the coating on the substrate. The coated and baked surface of the substrate is then subjected to imagewise exposure to imaging radiation.

[0003] This radiation exposure causes a chemical change in the exposed areas of the coated surface. Visible light, ultraviolet (UV), electron beam, and X-ray radiant energy are the imaging radiation types commonly used today in microlithography processes. After this imagewise exposure, the coated substrate is treated with a developer solution to dissolve and remove either the radiation exposed or unexposed areas of the coated surface of the substrate.

[0004] There are two types of photoresist compositions that are developable in aqueous base: negative-working and positive-working. Furthermore, these two types of photoresist compositions may be chemically amplified photoresists in which the quantum yield of the photochemical events that produce the different dissolution characteristics that enable the imageability of these photoresists are amplified by catalytic chain length, resulting in increased sensitivity of these chemically amplified photoresists to radiation compared to their non-chemically amplified counterparts, while in such non-chemically amplified photoresists, the photochemical events that produce the different dissolution characteristics that enable the imageability of these photoresists are predicted only by the quantum yield of the photosensitive moieties within the photoresist, and the conversion upon irradiation is not amplified by catalytic events.

[0005] Imagewise exposure of a positive-working photoresist composition to radiation renders the resist composition in the radiation-exposed areas more soluble in a developer solution. In this type of chemically amplified photoresist, the solubility is achieved by catalytic release of base-solubilizing groups, usually by the action of photogenerated acid; this is in contrast to non-chemically amplified photoresists, in which base solubility is usually achieved by photolysis of a dissolution inhibitor such as DNQ-PAC, the quantum yield of which is not amplified by a catalytic event and is therefore not chemically amplified. In both cases, the unexposed areas of the photoresist coating remain relatively insoluble in aqueous base. Thus, treatment of an exposed positive-working resist with a developer removes the photoresist coating in the exposed areas to form a positive image in the coating, thereby uncovering the desired portions of the surface of the underlying substrate where the photoresist composition was originally deposited.

[0006] Imagewise exposure of a negative-working photoresist composition to radiation renders the resist composition insoluble in developer solutions in the areas exposed to radiation, while the unexposed areas remain soluble in aqueous base. In this type of chemically amplified photoresist, the insolubility is achieved by catalytic release of reactive moieties, such as carbocations, which can interact with crosslinkers or the resin itself to render the exposed areas insoluble. In contrast, in non-chemically amplified photoresists, base insolubility is usually achieved by photogeneration of radicals that interact with crosslinkers, usually acrylate-based additives, to induce crosslinking of the exposed areas, thus rendering them insoluble in aqueous base. In both cases, the unexposed areas of the photoresist coating remain soluble in such solutions. Thus, treatment of an exposed negative-working resist with a developer removes the photoresist coating in the unexposed areas, forming a negative image in the coating, thereby uncovering the desired portions of the surface of the underlying substrate on which the photoresist composition was originally deposited.

[0007] In thick film photoresists, the resins are aqueous base soluble resins or derivatives thereof, usually novolac resins containing either carboxylic acid or phenolic base solubilizing groups, (meth)acrylate based copolymers with various methacrylate based repeat units or repeat units derived from hydroxystyrene, or mixtures of these different polymers. In positive chemically amplified photoresists, these resins have at least one of these base solubilizing resins in one or more of the polymers with acid labile groups that can be removed by photoacid generated by a photoacid generator (PAG).

[0008] Semiconductor assembly process has been improved with the introduction of wafer level packaging (WLP) in mass production. Copper (Cu) redistribution layer (RDL) scaling is one of the key processes for the manufacturing of smaller, thinner and lighter chips. Fine pitch redistribution layer (RDL) is a market trend of high density wafer level fan-out (HDWLFO) packaging for semiconductors.

[0009] The subtractive method of structuring conductor metals by wet chemical etching was the main technique in the early IC (integrated circuit) industry when Al was the dominant conductor material. As the trend of miniaturization according to Moore's law is pushing towards new CD (critical dimension) nodes, the subtractive method of structuring metal structures, especially by wet chemical etching, can no longer meet the industrial demands. This is mainly due to the isotropic nature of wet chemical etching, which cannot provide a high enough fidelity. In the substrate process (FEOL) wiring formation, alternative subtractive techniques such as plasma dry etching or additive techniques such as physical vapor deposition (PVD) or atomic layer deposition (ALD) have begun to prevail, and in the wiring process (BEOL), additive techniques such as electroplating in lift-off processes (1. NEGATIVE-ACTING CHEMICALLY AMPLIFIED PHOTORESIST COMPOSITION, EP1297386B1 (Patent Document 1), 2. NEGATIVE RESIST FORMULATION FOR PRODUCING UNDERCUT PATTERN PROFILES, WO2018 / 197379Al (Patent Document 2)) have begun to be used, along with the conductor material shift from Al to Cu and other metals such as Co or Rh. However, the throughput of additive approaches to structuring conductor metals is impaired due to additional process steps or due to the inherent slow speed of certain steps such as PVD. Also, wet etching of metal substrates using an overlying patterned photoresist pattern suffers from poor adhesion of the metal to the overlying patterned photoresist, resulting in isotropic etching of the underlying metal that is poorly repeatable and limits the feature size of the patterned metal that results after wet etching. This is primarily due to the isotropic nature of wet chemical etching not providing high enough fidelity, but the throughput of additional approaches to structuring of interconnects is hampered due to additional process steps or due to the inherent slow speed of certain steps such as PVD.However, metal wet chemical etching remains the preferred technique in many applications such as discrete devices and MEMS (microelectromechanical systems), especially where the requirements for resolution are relatively modest and cost benefits are more important.There is therefore a need for compositions and methods that can improve the wet etching of metal substrates during lithographic processing, such that the wet etching is anisotropic and produces etched metal patterns with good uniformity, and can also resolve relatively small etched metal features.

[0010] For conventional lithographic patterning with photoresist, smaller features have been reported by using self-assembled monolayers (SAMs) as ultrathin resists patterned by microcontact printing, but wet chemical etching can only be considered for features >3 μm due to its isotropic nature ("Microcontact Printing of Alkanethiols on Copper and Its Application in Microfabrication", Y. Xia et al., Chem. Mater. 1996, 8, 601-603 1). In addition, typical harsh etching chemistries and time-consuming processes can lead to undesirable defects ranging from "mouse bites" or notching, photoresist cracking, to photoresist peeling in extreme cases. Poor adhesion of resist on substrate has been commonly considered as the root cause of these defects, which cause poor reproducibility and limit the feature size of patterned metals after wet etching. However, unlike the well-known adhesion promotion strategy using HMDS (hexamethyldisilazane) to prime the substrate surface in the case of Si ("Wet etchants penetration through photoresist during wet patterning", P. Garnier, et al., Solid State Phenomena, 2018, 141-146 (Non-Patent Document 2)), no similar strategy or materials exist for metal substrates ("Improved adhesion of novolac and epoxy based resists by cationic organic materials on critical substrates for high volume patterning applications" A. Voigt, et al., Proc. SPIE 9051, Advances in Patterning Materials and Processes XXXI, 2014, 90511K (Non-Patent Document 3)). [Prior art documents] [Chartered documents]

[0011]

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Non-licensed literature

[0012] [Non-licensed document 1] "Microcontact Printing of Alkanethiols on Copper and Its Application in Microfabrication",Y.Xia et al.,Chem.Mater.1996,8,601-603 1

Non-licensed Document 2

[0013] Surprisingly, it has been found that the wet etching performance of metal substrates during lithographic patterning and processing of metal substrates can be improved by applying various thiol derivatives as metal primers to obtain improved photoresist adhesion to metal substrates, which eliminates the problems typically associated with defects described above. These thiol derivative metal primers can be applied as separate coatings, as formulations including the thiol derivative primers and organic spin-casting solvents, prior to coating of photoresist, or alternatively, can be applied as additives in various different types of photoresists, including both chemically amplified and non-chemically amplified positive and negative photoresists. By using either approach during conventional wet etching of metal substrates covered with imaged photoresist, the improved adhesion of the imaged photoresist pattern on the metal leads to anisotropically etched metal substrates with well-defined and large sidewall angles, which avoids the problems of isotropic etching of metals caused by poor adhesion of photoresist to metal substrates.

[0014] One aspect of the invention is a photoresist composition comprising a thiol derivative, the thiol moiety of which is attached to an SP2 carbon that is part of a ring having the structure (H1), (H2), (H3) or (H4), the thiol derivative being present in a range of from about 0.5% to about 3% by weight of total solids: In the structure (H1), Xt is selected from the group consisting of N(Rt3), C(Rt1)(Rt2), O, S, Se, and Te; In the structure (H2), Y is selected from the group consisting of C(Rt3) and N; In the structure (H3), Z is selected from the group consisting of C(Rt3) and N; and In the structure (H4), Arene is selected from unsubstituted phenyl, substituted phenyl, an unsubstituted polycyclic arene moiety, and a substituted polycyclic arene moiety; Rt1, Rt2, and Rt3 are independently H, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkenyl group having 2 to 8 carbon atoms, an unsubstituted alkenyl group having 2 to 8 carbon atoms, a substituted alkynyl group having 2 to 8 carbon atoms, an unsubstituted alkynyl group having 2 to 8 carbon atoms, a substituted aromatic group having 6 to 20 carbon atoms, a substituted heteroaromatic group having 3 to 20 carbon atoms, an unsubstituted aryl group having 6 to 20 carbon atoms, a substituted heteroaromatic group having 3 to 20 carbon atoms, a ... Rt4 is independently selected from the group consisting of H, OH, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkenyl group having 2 to 8 carbon atoms, an unsubstituted alkenyl group having 2 to 8 carbon atoms, a substituted alkynyl group having 2 to 8 carbon atoms, an unsubstituted alkynyl group having 2 to 8 carbon atoms, a substituted aromatic group having 6 to 20 carbon atoms, a substituted heteroaromatic group having 3 to 20 carbon atoms, an unsubstituted aromatic group having 6 to 20 carbon atoms, and an unsubstituted heteroaromatic group having 3 to 20 carbon atoms.

[0015] [ka] Another aspect of the invention is the use of the photoresist composition on a metal substrate to form a patterned photoresist that is used as an etch mask in the anisotropic wet chemical etching of the metal substrate to produce a patterned metal substrate.

[0016] Yet another aspect of the present invention is a composition comprising the above-described thiol derivative in a spin-casting solvent and a method of treating a metal substrate with the solution, using the substrate to image a photoresist, and using the imaged photoresist as a mask for wet chemical etching to effect anisotropic etching of the metal substrate to produce a patterned metal substrate.

[0017] The accompanying drawings provide a further understanding of the disclosed invention, and are incorporated in and constitute a part of this specification, illustrating embodiments of the disclosed invention and, together with the detailed description of the invention, serve to explain the principles of the disclosed invention. [Brief description of the drawings]

[0018] [Figure 1] FIG. 1 shows non-limiting examples of DNQ PAC compounds that may be used as free PAC components and / or that may be used to form PAC moieties attached to polymeric components via acetal-containing linking groups on phenolic moieties. [Diagram 2] FIG. 2 shows non-limiting examples of photoacid generators that generate sulfonic acids and other strong acids. [Diagram 3] FIG. 3 shows non-limiting examples of photoacid generators that generate HCl or HBr. [Figure 4] Figure 4 shows cross-sectional SEM images showing the wet etching performance of copper wafers using the two-step process: Examples 1 and 2 where the Cu wafer was primed with PMT, a reference example which was an untreated Cu wafer, and Comparative Example 1 where the wafer was treated with an aliphatic thiol. [Diagram 5]FIG. 5 shows cross-sectional SEM images showing the wet etching performance of copper wafers using the two-step process: Examples 3 and 4 where the Cu wafer was primed with HPMT, and a reference example which is an untreated Cu wafer. [Figure 6] FIG. 6 shows cross-sectional SEM images comparing the wet etch performance of copper wafers using Example 5, Comparative Example 2, and a reference Cu wafer without any additive added to the photoresist. [Figure 7] 1 shows cross-sectional SEM images of Examples 6, 7 and 8, in which various amounts of PMT were used as an additive to the photoresist. [Figure 8] 1 shows cross-sectional SEM images of Examples 9 and 10 using various amounts of HPMT. [Figure 9] 1 shows cross-sectional SEM images of Examples 11, 12 and 13 using various amounts of HPMT. [Figure 10] 1 shows cross-sectional SEM images of Examples 14 and 15 showing a comparison of using either PMT or HPMT doped photoresist on a 4.7 micron Cu layer (top) or a thicker 9 micron Cu layer (bottom). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] It is to be understood that both the general description above and the detailed description below are exemplary and explanatory, and are not intended to be limiting with respect to the invention as claimed. In this application, unless specifically stated otherwise, the use of the singular includes the plural, the singular means "at least one," and the use of "or" means "and / or." Furthermore, the use of the term "comprises" as well as other verb forms such as "comprises" is not limiting. Also, the use of terms such as "element" or "component" includes elements and components that contain one unit, as well as elements or components that contain more than one unit, unless specifically stated otherwise. Unless otherwise indicated, the conjunction "and" as used herein is intended to be inclusive, and the conjunction "or" is not intended to be exclusive. For example, the phrase "or instead of" is intended to be exclusive. As used herein, the conjunction "and / or" refers to any combination of the aforementioned elements, including the use of a single element.

[0020] The section headings used herein are for organizational purposes only and should not be construed as limiting the subject matter described. All references or portions of references cited herein, including but not limited to patents, patent applications, papers, books, and treatises, are incorporated herein in their entirety for all purposes. In the event that the definition of a term in one or more of the references and similar materials incorporated herein conflicts with that herein, the definition in the present application shall control.

[0021] Unless otherwise indicated, "alkyl" refers to a hydrocarbon group that can be linear, branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, and the like), or cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, and the like), polycyclic (e.g., norbornyl, adamantyl, and the like). These alkyl moieties may be substituted or unsubstituted as described below. The term "alkyl" refers to such moieties having C1 to C20 carbons. For structural reasons, it is understood that linear alkyls start at C1, while branched and cyclic alkyls start at C3, and polycyclic alkyls start at C5. Furthermore, moieties derived from alkyls described below, such as alkyloxy, are understood to have the same carbon number range, unless otherwise stated. In the event that a different alkyl group length is specified, the above definition of alkyl is still valid in that it encompasses all types of alkyl moieties described above, and the above structural considerations regarding the minimum carbon number of a given type of alkyl group still apply.

[0022] Alkyloxy (also known as alkoxy) refers to an alkyl group attached through an oxy (-O-) moiety (e.g., methoxy, ethoxy, propoxy, butoxy, 1,2-isopropoxy, cyclopentyloxy, cyclohexyloxy, and the like). These alkyloxy moieties may be substituted or unsubstituted as described below.

[0023] Halo or halide refers to a halogen, F, Cl, Br, or I, attached to an organic moiety by one bond.

[0024] Haloalkyl refers to a saturated linear, cyclic or branched alkyl group, such as those described above, in which at least one of the hydrogens is replaced by a halide selected from the group F, Cl, Br, I, or mixtures thereof when more than one halo moiety is present. Fluoroalkyl is a specific subgroup of these moieties.

[0025] Fluoroalkyl refers to linear, cyclic or branched saturated alkyl groups as defined above in which hydrogen has been partially or fully replaced by fluorine (e.g., trifluoromethyl, perfluoroethyl, 2,2,2-trifluoroethyl, perfluoroisopropyl, perfluorocyclohexyl, and the like). These fluoroalkyl moieties, if not fully fluorinated, may be substituted or unsubstituted as described below.

[0026] Fluoroalkyloxy refers to a fluoroalkyl group, as defined above, attached through an oxy (-O-) moiety, which may be fully fluorinated (also known as perfluorinated) or alternatively partially fluorinated (e.g., trifluoromethyloxy, perfluoroethyloxy, 2,2,2-trifluoroethoxy, perfluorocyclohexyloxy, and the like). These fluoroalkyl moieties, if not fully fluorinated, may be substituted or unsubstituted as described below.

[0027] As used herein, when referring to alkyl, alkyloxy, fluoroalkyl, fluoroalkyloxy moieties having a possible range of carbon atoms starting from C1, such as, as non-limiting examples, "C1-C20 alkyl" or "C1-C20 fluoroalkyl," this range includes linear alkyl, alkyloxy, fluoroalkyl, and fluoroalkyloxy starting from C1, but only C3 and above are specified for branched alkyl, branched alkyloxy, cycloalkyl, cycloalkyloxy, branched fluoroalkyl, and cyclic fluoroalkyl.

[0028] The term "alkylene" refers to a hydrocarbon group that can be linear, branched, or cyclic and has two or more points of attachment (two points of attachment include, for example, methylene, ethylene, 1,2-isopropylene, 1,4-cyclohexylene, and the like, and three points of attachment include, for example, 1,1,1-substituted methanes, 1,1,2-substituted ethanes, 1,2,4-substituted cyclohexanes, and the like). Again, when specifying a range of possible carbon numbers, such as, for example, C1-C20 as a non-limiting example, this range includes linear alkylenes starting at C1, but specifies only C3 and above for branched alkylenes or cycloalkylenes. These alkylene moieties may be substituted or unsubstituted as follows:

[0029] As used herein, the term solid components refers to components other than the organic spin-cast solvent component, and therefore "wt %" of total solids refers to the weight % of each individual solid component relative to the sum of all solid components.

[0030] The term "mono- and oligomeric alkyleneoxyalkylene" includes both simple alkyleneoxyalkylene moieties, such as ethyleneoxyethylene (-CH-CH-O-CH-CH-), propyleneoxypropylene (-CH-CH-CH-O-CH-CH-CH-CH-), and the like, as well as oligomeric materials, such as di(ethyleneoxy)ethylene (-CH-CH-O-CH-CH-O-CH-CH-), di(propyleneoxy)propylene (-CH-CH-O-CH-CH-CH-O-CH-CH-CH-), and the like.

[0031] The term "aryl" or "aromatic group" refers to such groups containing 6 to 24 carbon atoms, e.g., phenyl, tolyl, xylyl, naphthyl, anthracyl, biphenyls, bis-phenyls, tris-phenyls, and the like. These aryl groups may be further substituted with any of the appropriate substituents described above, such as alkyl, alkoxy, acyl, or aryl groups described above.

[0032] The term "novolak" (also known as Novolac), as used herein, in the absence of other modifications of the structure, refers to a novolak resin that is soluble in an aqueous base, such as tetramethylammonium hydroxide (TMAH).

[0033] The term "PAG", unless otherwise stated, refers to a photoacid generator capable of generating an acid (also called a photoacid) under deep UV or UV radiation, e.g., 200-300 nm, i-line, h-line, g-line and / or broadband radiation. The acid may be sulfonic acids, HCl, HBr, HAsF6, and the like. This includes, by way of non-limiting example, onium salts and other photosensitive compounds known in the art that can photochemically generate strong acids such as alkylsulfonic acids, arylsulfonic acids, HAsF6, HSbF6, HBF4, HPF6, CF3SO3H, HC(SO2CF3)2, HC(SO2CF3)3, HN(SO2CF3)2, HB(CH5)4, HB(CF5)4, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate acid, p-toluenesulfonic acid, HB(CF3)4, and cyclopentadienes penta-substituted with electron-withdrawing groups, e.g., cyclopenta-1,3-diene-1,2,3,4,5-pentacarbonitrile. Other photoacid generators include trihalomethyl compounds and photosensitive derivatives of trihalomethyl heterocyclic compounds that can generate hydrogen halides such as HBr or HCl.

[0034] Photoresist compositions containing thiol derivatives and methods of using them to produce anisotropically etched metal substrates - Patents.com Photoresist Composition In one of its aspects, the invention is a photoresist composition comprising a thiol derivative, the thiol moiety of which is attached to an SP2 carbon that is part of a ring having the structure (H1), (H2), (H3) or (H4), the thiol derivative being present in a range of from about 0.5% to about 3% by weight of total solids: In the structure (H1), Xt is selected from the group consisting of N(Rt3), C(Rt1)(Rt2), O, S, Se, and Te; In the structure (H2), Y is selected from the group consisting of C(Rt3) and N; In the structure (H3), Z is selected from the group consisting of C(Rt3) and N; and In the structure (H4), Arene is selected from unsubstituted phenyl, substituted phenyl, an unsubstituted polycyclic arene moiety, and a substituted polycyclic arene moiety; Rt1, Rt2, and Rt3 are independently selected from the group consisting of H, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkenyl group having 2 to 8 carbon atoms, an unsubstituted alkenyl group having 2 to 8 carbon atoms, a substituted alkynyl group having 2 to 8 carbon atoms, an unsubstituted alkynyl group having 2 to 8 carbon atoms, a substituted aromatic group having 6 to 20 carbon atoms, a substituted heteroaromatic group having 3 to 20 carbon atoms, an unsubstituted aromatic group having 6 to 20 carbon atoms, and an unsubstituted heteroaromatic group having 3 to 20 carbon atoms; Rt4 is independently selected from the group consisting of H, OH, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkenyl group having 2 to 8 carbon atoms, an unsubstituted alkenyl group having 2 to 8 carbon atoms, a substituted alkynyl group having 2 to 8 carbon atoms, an unsubstituted alkynyl group having 2 to 8 carbon atoms, a substituted aromatic group having 6 to 20 carbon atoms, a substituted heteroaromatic group having 3 to 20 carbon atoms, an unsubstituted aromatic group having 6 to 20 carbon atoms, and an unsubstituted heteroaromatic group having 3 to 20 carbon atoms.

[0035] [ka] In one aspect of the invention, the thiol derivative is a heterocyclic thiol selected from the general structures (H1), (H2) or (H3) above or tautomers thereof, where such heterocyclic thiol may be selected from, but is not limited to, the following compounds (H5)-(H23) in unsubstituted or substituted form:

[0036] [ka] In another aspect of the embodiment, where the composition of the invention comprises at least one heterocyclic thiol having the general structure (H1), (H2) or (H3) or a tautomer thereof, such heterocyclic thiol may be selected from thiouracil derivatives such as 2-thiouracil, including, but not limited to, 5-methyl-2-thiouracil, 5,6-dimethyl-2-thiouracil, 6-ethyl-5-methyl-2-thiouracil, 6-methyl-5-n-propyl-2-thiouracil, 5-ethyl-2-thiouracil, 5-n-propyl-2-thiouracil, 5-n-butyl-2-thiouracil, 5-n-hexyl-2-thiouracil, 5-n-butyl-6-ethyl-2-thiouracil, 5-hydroxy-2-thiouracil, 5,6-dithiouracil, 5-methyl ... Hydroxy-2-thiouracil, 5-hydroxy-6-n-propyl-2-thiouracil, 5-methoxy-2-thiouracil, 5-n-butoxy-2-thiouracil, 5-methoxy-6-n-propyl-2-thiouracil, 5-bromo-2-thiouracil, 5-chloro-2-thiouracil, 5-fluoro-2-thiouracil, 5-amino-2-thiouracil, 5-amino-6-methyl-2-thiouracil, 5-amino-6-phenyl-2-thiouracil, 5,6-diamino-2-thiouracil, 5-allyl-2-thiouracil, 5-allyl-3-ethyl-2-thiouracil, 5-allyl-6-phenyl-2-thiouracil, 5-benzyl-2-thiouracil, 5-benzyl-6-methyl-2-thiouracil, 5-acetamido-2-thiouracil, 6-methyl-5-nitro-2-thiouracil, 6-amino-2-thiouracil, 6-amino-5-methyl-2-thiouracil, 6-amino-5-n-propyl-2-thiouracil, 6-bromo-2-thiouracil, Thiouracil, 6-chloro-2-thiouracil, 6-fluoro-2-thiouracil, 6-bromo-5-methyl-2-thiouracil, 6-hydroxy-2-thiouracil, 6-acetamido-2-thiouracil, 6-n-octyl-2-thiouracil, 6-dodecyl-2-thiouracil, 6-tetradodecyl-2-thiouracil, 6-hexadecyl-2-thiouracil, 6-(2-hydroxyethyl)-2-thiouracil, 6-(3-isopropyloctyl)-5-methyl-2-thiouracil , 6-(m-nitrophenyl)-2-thiouracil, 6-(m-nitrophenyl)-5-n-propyl-2-thiouracil, 6-α-naphthyl-2-thiouracil, 6-α-naphthyl-5-tert-butyl-2-thiouracil, 6-(p-chlorophenyl)-2-thiouracil, 6-(p-chlorophenyl)-2-ethyl-2-thiouracil, 5-ethyl-6-eicosyl-2-thiouracil, 6-acetamido-5-ethyl-2-thiouracil, 6-eicosyl-5-allyl-2-thiouracil, Thiouracil, 5-amino-6-phenyl-2-thiouracil, 5-amino-6-(p-chlorophenyl)-2-thiouracil, 5-methoxy-6-phenyl-2-thiouracil, 5-ethyl-6-(3,3-dimethyloctyl)-2-thiouracil, 6-(2-bromoethyl)-2-thiouracil, 1-phenyl-1H-tetrazole-5-thiol, 4-(5-mercapto-1H-tetrazol-1-yl)phenol, tautomers thereof, and combinations thereof.

[0037] In another embodiment, where the composition of the present invention comprises at least one heterocyclic thiol selected from the general structures (H1), (H2) or (H3) or tautomers thereof, such heterocyclic thiol may be selected from the group consisting of unsubstituted triazole thiol, substituted triazole thiol, unsubstituted imidazole thiol, substituted imidazole thiol, substituted triazine thiol, unsubstituted triazine thiol, substituted mercaptopyrimidine, unsubstituted mercaptopyrimidine, substituted thiadiazole thiol, unsubstituted thiadiazole thiol, substituted indazole thiol, unsubstituted indazole thiol, tautomers thereof, and combinations thereof.

[0038] In the photoresist compositions described herein, the thiol derivative of structure (H1), (H2), (H3), or (H4) is present in an amount from about 0.6% to about 3% by weight of total solids. In another aspect of this embodiment, the thiol compound is present in an amount from about 0.7% to about 3% by weight of total solids. In another aspect of this embodiment, the thiol compound is present in an amount from about 0.8% to about 3% by weight of total solids. In another aspect of this embodiment, the thiol compound is present in an amount from about 0.9% to about 3% by weight of total solids. In another aspect of this embodiment, the thiol compound is present in an amount from about 1% to about 3% by weight of total solids.

[0039] In another aspect of the photoresist compositions described herein, the thiol derivative of structure (H1), (H2), (H3), or (H4) is present in an amount of from about 0.5% to about 2.5% by weight of total solids. In another aspect of this embodiment, the thiol derivative is present in an amount of from about 0.5% to about 2.0% by weight of total solids. In another aspect of this embodiment, the thiol derivative is present in an amount of from about 0.5% to about 1.5% by weight of total solids. In another aspect of this embodiment, the thiol derivative is present in an amount of from about 0.5% to about 1.4% by weight of total solids. In another aspect of this embodiment, the thiol derivative is present in an amount of from about 0.5% to about 1.3% by weight of total solids. In another aspect of this embodiment, the thiol derivative is present in an amount of from about 0.5% to about 1.2% by weight of total solids. In another aspect of this embodiment, the thiol derivative is present in an amount from about 0.5% to about 1.1% by weight of total solids. In another aspect of this embodiment, the thiol derivative is present in an amount from about 0.5% to about 1% by weight of total solids.

[0040] In another aspect of the photoresist compositions described herein, the thiol derivative has the structure (H2).

[0041] In another aspect of the photoresist compositions described herein, the thiol derivative has the structure (H3).

[0042] In another aspect of the photoresist composition described herein, the thiol derivative has the structure (H1).

[0043] In another aspect of the photoresist composition described herein, the thiol derivative has the structure (H1) and Xt is N(Rt3).

[0044] In one aspect of the photoresist composition described herein, where the thiol derivative has structure (H1) and Xt is N(Rt3), it has structure (H1-A), where X1 is N, X2 and X3 are individually selected from the group consisting of N and C(Rt3), and Rx1, Rx2, Rx3, Rx4 and Rx5 are individually selected from the group consisting of H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylene hydroxy (-alkylene-OH), C2-C8 alkylene oxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkylene oxyalkyl (-(alkylene-O-alkyl), pa -alkyl), where pa is an integer ranging from 2 to 4, and in C(Rt3), Rt3 is independently selected from the group consisting of H, substituted alkyl groups having 1 to 8 carbon atoms, unsubstituted alkyl groups having 1 to 8 carbon atoms, substituted alkenyl groups having 2 to 8 carbon atoms, unsubstituted alkenyl groups having 2 to 8 carbon atoms, substituted alkynyl groups having 2 to 8 carbon atoms, unsubstituted alkynyl groups having 2 to 8 carbon atoms, substituted aromatic groups having 6 to 20 carbon atoms, substituted heteroaromatic groups having 3 to 20 carbon atoms, unsubstituted aromatic groups having 6 to 20 carbon atoms, and unsubstituted heteroaromatic groups having 3 to 20 carbon atoms.

[0045] [ka] In one aspect of the photoresist composition described herein where the thiol derivative has structure (H1) and Xt is N(Rt3), it has structure (H1-B), where Rx is H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa -alkyl), where pa is an integer ranging from 2 to 4. Rc2 is selected from H and C1-C8 alkyl, and Rc1 is selected from H and C1-C8 alkyl.

[0046] [ka] In one aspect of the photoresist composition described herein where the thiol derivative has structure (H1) and Xt is N(Rt3), it has structure (H1-C) where Rc2 is selected from H and C1-C8 alkyl and Rx is H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa -alkyl), where pa is an integer ranging from 2 to 4.

[0047] [ka] In one aspect of the photoresist composition described herein where the thiol derivative has structure (H1) and Xt is N(Rt3), it has structure (H1-D), where Rc1 is selected from H and C1-C8 alkyl, and Rx is selected from H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa -alkyl), where pa is an integer ranging from 2 to 4.

[0048] [ka] In one aspect of the photoresist composition described herein where the thiol derivative has structure (H1) and Xt is N(Rt3), it has structure (H1-E), where Rx is H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa -alkyl), where pa is an integer ranging from 2 to 4.

[0049] [ka] In one aspect of the photoresist composition described herein where the thiol derivative has structure (H1) and Xt is N(Rt3), it has structure (H1-EA), where Rx is H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa -alkyl), where pa is an integer ranging from 2 to 4.

[0050] [ka] In one aspect of the photoresist composition described herein where the thiol derivative has structure (H1) and Xt is N(Rt3), it has structure (H1-EB), where Rx is H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa -alkyl), where pa is an integer ranging from 2 to 4.

[0051] [ka] In one aspect of the photoresist composition described herein, where the thiol derivative has structure (H1) and Xt is N(Rt3), it has structure (H1-EC) or structure (H1-ED). In one aspect of this embodiment, it has structure (H1-EC). In one aspect of this embodiment, it has structure (H1-ED).

[0052] [ka] In one aspect of the photoresist composition described herein where the thiol derivative has the structure (H1) and Xt is N(Rt3), it has the structure (H1-EE).

[0053] [ka] In one aspect of the photoresist composition described herein, wherein the thiol derivative has structure (H4), Arene is selected from unsubstituted phenyl, substituted phenyl, unsubstituted polycyclic arene moieties, and substituted polycyclic arene moieties. In one aspect of this embodiment, the Arene is a substituted or unsubstituted polycyclic arene. In another aspect of this embodiment, the Arene is selected from naphthalene, anthracene, and pyrene. In yet another aspect of this embodiment, the Arene is a substituted or unsubstituted phenyl. In one aspect of this embodiment, the Arene is phenyl.

[0054] In one aspect of the photoresist composition described herein, the thiol derivative has the structure (H4), which more specifically has the structure (H4-A), where R H4a , R H4b , R H4c , R H4d , R H4eare individually defined as H, OH, halide, C1-C8 alkyl, an unsubstituted aromatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms substituted with at least one hydroxyl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa -alkyl), where pa is an integer ranging from 2 to 4.

[0055] [ka] In one aspect of the photoresist composition described herein, the thiol derivative has the structure (H4), which more specifically has the structure (H4-B), where R H4 is H, OH, halide, C1-C8 alkyl, an unsubstituted aromatic group having 6-20 carbon atoms, an aromatic group having 6-20 carbon atoms substituted with at least one hydroxyl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa -alkyl), where pa is an integer ranging from 2 to 4.

[0056] [ka] In one aspect of the photoresist composition described herein, the thiol derivative has the structure (H4), which more specifically has the structure (H4-C), where R 4H is H, OH, halide, C1-C8 alkyl, an unsubstituted aromatic group having 6-20 carbon atoms, an aromatic group having 6-20 carbon atoms substituted with at least one hydroxyl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa-alkyl), where pa is an integer ranging from 2 to 4.

[0057] [ka] In one aspect of the photoresist composition described herein, the thiol derivative has structure (H4), which more specifically has structure (H4-D), where Rx1 is selected from H, OH, halide, C1-C8 alkyl, an unsubstituted aromatic group having 6-20 carbon atoms, an aromatic group having 6-20 carbon atoms substituted with at least one hydroxy, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa -alkyl), where pa is an integer ranging from 2 to 4.

[0058] [ka] In one aspect of the photoresist composition described herein, the thiol derivative has the structure (H4), which more specifically has the structure (H4-E).

[0059] [ka] In one aspect of the photoresist composition described herein, the thiol derivative has the structure (H4), which more specifically has the structure (H4-F).

[0060] [ka] In one aspect of the photoresist composition, it is a positive non-chemically amplified photoresist that is developable in an aqueous base solution.

[0061] In one aspect of the photoresist composition, it is a positive non-chemically amplified photoresist developable in an aqueous base, comprising: at least one novolak type resin soluble in about 0.26N TMAH; At least one DNQ PAC component, and Organic spin-casting solvents, The photoresist is a photoresist comprising:

[0062] In one aspect of the photoresist composition, it is a positive non-chemically amplified photoresist developable in an aqueous base, comprising: at least one novolak type resin soluble in about 0.26N TMAH; At least one DNQ PAC component; Photobleachable dyes, and Organic spin-casting solvents, The photoresist is a photoresist comprising:

[0063] In one aspect of the photoresist composition, it is a positive non-chemically amplified photoresist developable in an aqueous base, comprising: at least one novolak type resin soluble in about 0.26N TMAH; At least one DNQ PAC component; Surfactants from 2000 ppm to 14,000 ppm, and Organic spin-casting solvents, The photoresist is a photoresist comprising:

[0064] In one aspect of the photoresist composition, it is a positive non-chemically amplified photoresist developable in an aqueous base, comprising: at least one meth(acrylate) copolymer comprising repeat units derived from (meth)acrylic acid, in about a 0.26 N solution in TMAH; at least one novolak type resin soluble in about 0.26N TMAH; At least one DNQ PAC component, and Organic spin-casting solvents, The photoresist is a photoresist comprising:

[0065] In one aspect of the photoresist composition, it is a positive chemically amplified photoresist composition that is developable in an aqueous base solution. In one aspect of the photoresist composition, it is a positive chemically amplified photoresist composition developable in an aqueous base, comprising: At least one photoacid generator; at least one polymer comprising one or more (meth)acrylate repeat units and further comprising one or more repeat units having at least one acid-cleavable group; Organic spin-casting solvents, and This photoresist composition does not contain a novolak resin.

[0066] In one aspect of the photoresist composition, it is a positive chemically amplified photoresist composition developable in an aqueous base, comprising: At least one photoacid generator; at least one polymer comprising one or more (meth)acrylate repeat units and further comprising one or more repeat units having at least one acid-cleavable group; At least one novolac-type resin, and Organic spin-casting solvents, A photoresist composition comprising:

[0067] In one aspect of the photoresist composition, it is a positive chemically amplified photoresist composition developable in an aqueous base, comprising: At least one photoacid generator; At least one DNQ PAC component; at least one novolac resin, at least one polymer comprising one or more (meth)acrylate repeat units and further comprising one or more repeat units having at least one acid-cleavable group; Organic spin-casting solvents, A photoresist composition comprising:

[0068] In one aspect of the photoresist composition, it is a positive chemically amplified photoresist composition developable in an aqueous base, comprising: At least one photoacid generator; at least one polymer comprising one or more (meth)acrylate repeat units and further comprising one or more repeat units having at least one acid-cleavable group; photobleachable dye, Organic spin-casting solvents, A photoresist composition comprising:

[0069] In one aspect of the photoresist composition, it is a positive chemically amplified photoresist composition developable in an aqueous base, comprising: at least one polymer comprising one or more (meth)acrylate repeat units and further comprising one or more repeat units having at least one acid-cleavable group; at least one novolak type resin soluble in about 0.26N TMAH; at least one photoacid generator (PAG); and Organic spin-casting solvents, A photoresist composition comprising:

[0070] In one aspect of the photoresist composition, it is a positive chemically amplified (meth)acrylate-based photoresist developable in an aqueous base, comprising: at least one (meth)acrylate copolymer comprising (meth)acrylic acid derived repeat units, the carboxylic acid of which is functionalized with an acid labile group, repeat units derived from at least one of styrene and benzyl (meth)acrylate, which becomes soluble in about 0.26 N TMAH when the acid labile group is cleaved by photogenerated acid from a PAG; At least one type of PAG, Organic spin-casting solvents, The photoresist is a photoresist comprising:

[0071] In one aspect of the photoresist composition, the photoresist composition is an aqueous base developable positive chemically amplified (meth)acrylate photoresist, at least one (meth)acrylate copolymer comprising (meth)acrylic acid derived repeat units, the carboxylic acid of which is functionalized with an acid labile group, repeat units derived from at least one of styrene and benzyl (meth)acrylate, which becomes soluble in 0.26N TMAH when the acid labile group is cleaved by photogenerated acid from a PAG; at least one novolak type resin soluble in about 0.26N TMAH; At least one PAG, and Organic spin-casting solvents, The photoresist is a photoresist comprising:

[0072] In one aspect of the photoresist composition, it is a positive chemically amplified photoresist developable in an aqueous base, comprising: (i) a novolac polymer, (ii) a polymer comprising substituted or unsubstituted hydroxystyrene and an acrylate, methacrylate, or a mixture of acrylates and methacrylates, the acrylates and / or methacrylates being protected with acid labile groups that require high activation energy for deblocking, and (iii) a component comprising a reaction product formed in the absence of an acid catalyst between a compound selected from vinyl ethers and unsubstituted or substituted unsaturated heteroalicyclics; At least one type of PAG, Organic spin-casting solvents, The photoresist is a photoresist comprising:

[0073] In one aspect of the photoresist composition, it is a positive chemically amplified photoresist developable in an aqueous base, comprising: (i) a novolac polymer, (ii) a polymer comprising substituted or unsubstituted hydroxystyrene and an acrylate, methacrylate, or a mixture of acrylates and methacrylates, the acrylates and / or methacrylates being protected with acid labile groups that require high activation energy for deblocking, and (iii) a component comprising a reaction product formed in the absence of an acid catalyst between a compound selected from vinyl ethers and unsubstituted or substituted unsaturated heteroalicyclics; At least one polymer comprising repeat units derived from 4-hydroxystyrene, repeat units derived from acetal-protected 4-hydroxystyrene, and repeat units derived from (meth)acrylic acid protected with a high-energy protecting group; At least one type of PAG, Organic spin-casting solvents, The photoresist is a photoresist comprising:

[0074] In one aspect of the photoresist composition, it is a negative non-chemically amplified photoresist that is developable in an aqueous base solution.

[0075] In one aspect of the photoresist composition, it is a negative non-chemically amplified photoresist developable in an aqueous base, comprising: At least one alkali-soluble polymer comprising at least one unit of the structure (INR),

[0076] [ka] wherein R' is independently selected from hydrogen, (C1-C4) alkyl, chlorine and bromine, and m is an integer from 1 to 4. At least one monomer of the structure (IINR),

[0077] [ka] (Wherein, W is a polyvalent linking group, R1 to R6 are independently hydrogen, hydroxy, (C1-C 20 ) alkyl and chlorine, and X1 and X2 are independently oxygen or N-R7, where R7 is hydrogen or (C1-C 20 ) alkyl, and n is an integer equal to or greater than 1. At least one radical photoinitiator, and Organic spin-casting solvents, The photoresist is a photoresist comprising:

[0078] In one aspect of the photoresist composition, it is a negative non-chemically amplified photoresist developable in an aqueous base, comprising: at least one novolak type resin soluble in about 0.26N TMAH; at least one radical photoinitiator; At least one (meth)acrylate crosslinker, and Organic spin-casting solvents, The photoresist is a photoresist comprising:

[0079] In one aspect of the photoresist composition, it is a negative non-chemically amplified (meth)acrylate photoresist developable in an aqueous base, comprising: at least one (meth)acrylate polymer comprising repeat units derived from (meth)acrylic acid, repeat units derived from at least one of styrene and benzyl (meth)acrylate, and soluble in about 0.26 N TMAH; at least one radical photoinitiator; At least one (meth)acrylate crosslinker, and Organic spin-casting solvents, The photoresist is a photoresist comprising:

[0080] In one aspect of the photoresist composition, it is a negative chemically amplified photoresist developable in an aqueous base solution.

[0081] In one aspect of the photoresist composition, it is a negative chemically amplified photoresist developable in an aqueous base, comprising: at least one phenolic film-forming polymeric binder resin having ring-bound hydroxyl groups selected from novolac resins, hydroxystyrene copolymers, and mixtures thereof, the at least one phenolic film-forming polymeric binder resin being soluble in about 0.26N TMAH; At least one type of PAG, a crosslinker that forms a carbonium ion when exposed to acid photogenerated by the PAG and comprises an etherified aminoplast polymer or oligomer; and Organic spin-casting solvents, The photoresist is a photoresist comprising:

[0082] Methods of using photoresist compositions containing thiol derivatives to produce anisotropically etched metal substrates - Patents.com Another aspect of the invention is a method for patterning a metal substrate to produce an anisotropically etched metal substrate, comprising the steps of: i) washing the metal substrate covering the semiconductor with a 1-5 wt% aqueous solution of a tri- or dicarboxylic acid, followed by rinsing with distilled water to obtain a washed metal substrate; ii) spin drying the cleaned metal substrate; iii) applying the composition of the present invention onto the cleaned and dried metal substrate to obtain a photoresist coating; iv) baking the photoresist coating at a temperature between 90° C. and 120° C. to remove the solvent; v) patterning the photoresist using UV radiation and then developing with an aqueous base developer to obtain a patterned photoresist etch barrier covering the metal substrate; vi) treating with a wet acidic chemical etchant using the patterned photoresist as an etch barrier to produce an anisotropically etched metal pattern covered with a patterned photoresist etch barrier; vii) removing the patterned photoresist etch barrier overlying the top surface with a stripper to produce an anisotropically etched metal substrate; The method comprises:

[0083] In another aspect of the method of patterning a metal substrate to produce an anisotropically etched metal substrate, the metal substrate is a metal substrate overlying a semiconductor substrate, and step vii) produces an anisotropically etched metal substrate overlying the semiconductor substrate.

[0084] In another aspect of this method, the metal substrate is selected from a copper substrate, an aluminum substrate, an aluminum alloy substrate, silver, gold, nickel, and tungsten. In another aspect of this embodiment, the metal substrate is a copper substrate. In another aspect of this embodiment, the metal substrate is aluminum. In another aspect of this embodiment, the metal substrate is an aluminum alloy. In another aspect of this embodiment, the metal substrate is a silver substrate. In another aspect of this embodiment, the metal substrate is a gold substrate. In another aspect of this embodiment, the metal substrate is a nickel substrate. In another aspect of this embodiment, the metal substrate is a tungsten substrate. Learn more about other ingredients suitable for photoresist formulations

[0085] Novolac Components In the non-chemically amplified and chemically amplified photoresist formulations described herein that include a novolac resin, this component is a novolac resin that is soluble in an aqueous developer such as 0.26N TMAH at 23° C. The novolac resin may include repeating units of structure (N), where Ra1, Ra2, and Ra3 are each independently (i) hydrogen, (ii) an unsubstituted C1-C4 alkyl, (iii) a substituted C1-C4 alkyl, (iv) an unsubstituted -X-phenol group (where X is -O-, -C(CH3)2-, -CH2-, -(C=O)-, or -SO2-), or (v) a substituted -X-phenol group (where X is -O-, -C(CH3)2-, -CH2-, -C(=O)-, or -SO2-). In another aspect of this embodiment, Ra1 and Ra2 are each hydrogen and Ra3 is an unsubstituted C1-C4 alkyl. In yet another aspect of this embodiment, each of Ra1 and Ra2 is hydrogen, and Ra3 is -CH3. In yet another aspect of this embodiment, the repeating unit (N) has the structure (NA). In another aspect of this embodiment, the novolac-based resin component further comprises one or more repeating units of the structure (NB), where (i) Ra1, Ra2, and Ra3 are each independently hydrogen, unsubstituted C1-C4 alkyl, or substituted C1-C4 alkyl, (ii) X is -O-, -C(CH3)2-, -CH2-, -C(=O)-, or -SO2-, and (iii) each Ra4 is independently hydrogen, unsubstituted C1-C4 alkyl, or substituted C1-C4 alkyl, and in a specific aspect of this embodiment, the structure (NB) has the more specific structure (NC).

[0086] [ka]

[0087] DNQ PAC ingredients In other embodiments of the photoresist compositions described herein in which a DNQ PAC component is present, it may be derived from a 1,2-diazonaphthoquinone-5-sulfonate compound or a 1,2-diazonaphthoquinone-4-sulfonate compound. Figure 1 shows non-limiting examples of these types of DNQ PACs that may be used as free PAC components; in this figure, the moiety D is H or a moiety selected from the structures (DNQa) and (DNQb), where in each compound shown in Figure 1, at least one D is a moiety of the structures (DNQa) or (DNQb).

[0088] [ka] In other embodiments of the photoresist compositions described herein, the DNQ PAC component is either a single DNQ PAC compound having the structure (DNQc) or a mixture of DNQ PAC compounds, where D 1c , D 2c , D 3c and D. 4c is independently selected from H or a moiety having the structure (DNQa), and further 1c , D 2c , D 3c Or D 4c At least one of the moieties has the structure (DNQa).

[0089] [ka] In other embodiments of the photoresist compositions described herein that include a DNQ PAC component, the DNQ PAC component is either a single DNQ PAC compound having the structure (DNQc) or a mixture of PAC compounds, where D 1c , D 2c , D 3c and D. 4c is independently selected from H or a moiety having the structure (DNQb), and further 1c , D 2c , D 3c Or D 4cAt least one of the is a moiety having the structure (DNQb).

[0090] [ka] In other embodiments of the photoresist compositions described herein that include a free PAC component, the PAC component is either a single PAC compound or a mixture of PAC compounds having the structure (DNQd), where D 1d , D 2d , D 3d and D. 4d is independently selected from H or a moiety having the structure (DNQa), and further 1d , D 2d , D 3d Or D 4d At least one of the is a moiety having the structure (DNQa).

[0091] [ka] In other embodiments of the photoresist compositions described herein that include a DNQ PAC component, the DNQ PAC component is a single DNQ PAC compound or a mixture of PAC compounds having the structure (DNQd), where D 1d , D 2d , D 3d and D. 4d is independently selected from H or a moiety having the structure (DNQb), and further 1d , D 2d , D 3d Or D 4d At least one of the is a moiety having the structure (DNQb).

[0092] [ka] In other embodiments of the photoresist compositions described herein that include a DNQ PAC component, the DNQ PAC component is either a single DNQ PAC compound having the structure (DNQe) or a mixture of PAC compounds, where D1e , D 2e , and D 3e is independently selected from H or a moiety having the structure (DNQa), and further 1e , D 2e Or D 3e At least one of the is a moiety having the structure (DNQa).

[0093] [ka] In other embodiments of the photoresist compositions described herein that include a free PAC component, the PAC component is either a single PAC compound or a mixture of PAC compounds having the structure (DNQe), where D 1e , D 2e , and D 3c is independently selected from H or a moiety having the structure (DNQb), and further 1e , D 2e Or D 3e At least one of the is a moiety having the structure (DNQb).

[0094] [ka]

[0095] Photoacid generator (PAG) component In the chemically amplified photoresist formulations described herein that include a PAG component, this component is a material that is sensitive to radiation, such as UV radiation (e.g., broadband, i-line, g-line, 248 nm, 193 nm, and EUV), which upon exposure to this radiation releases an acid (also called a photoacid), which cleaves acid labile groups, such as tert-alkyl esters or acetals, thereby releasing base-solubilizing groups in the resin used to render these exposed areas base-soluble, thus producing a positive image, in a positive chemically amplified photoresist, or alternatively, cleaving groups to generate carbocations that can react with the photoresist resin to crosslink the base-soluble resin, rendering it insoluble in the exposed areas, thus producing a negative image, in a negative chemically amplified photoresist. The photoacid can be sulfonic acids, HCl, HBr, HAsF6, and the like. This includes, by way of non-limiting example, onium salts and other photosensitive compounds known in the art that can photochemically generate strong acids such as alkylsulfonic acids, arylsulfonic acids, HAsF6, HSbF6, HBF4, HPF6, CF3SO3H, HC(SO2CF3)2, HC(SO2CF3)3, HN(SO2CF3)2, HB(CH5)4, HB(CF5)4, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate acid, p-toluenesulfonic acid, HB(CF3)4, and cyclopentadienes penta-substituted with electron-withdrawing groups, e.g., cyclopenta-1,3-diene-1,2,3,4,5-pentacarbonitrile. Other photoacid generators include trihalomethyl compounds and photosensitive derivatives of trihalomethyl heterocyclic compounds that can generate hydrogen halides such as HBr or HCl. The PAG may be an aromatic imide N-oxysulfonate derivative of an organic sulfonic acid, an aromatic sulfonium salt of an organic sulfonic acid, a trihalotriazine derivative, or a mixture thereof.

[0096] FIG. 2 shows non-limiting examples of photoacid generators that generate sulfonic acids and other strong acids.

[0097] FIG. 3 shows non-limiting examples of photoacid generators that generate either HCl or HBr.

[0098] In one aspect of this embodiment, it has the structure (P), where R 1p is a fluoroalkyl moiety, and R 2p is H, an alkyl, oxyalkyl, thioalkyl, or aryl moiety. Alternatively, the PAG may have the structure (PA), where R 3p is a fluoroalkyl, alkyl, or aryl moiety, and R4p is H, an alkyl, oxyalkyl, thioalkyl, or aryl moiety. Another aspect of the compositions of the invention described herein is where the photoacid generator (PAG) component, component d), comprises 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl trifluoromethanesulfonate (NIT PAG).

[0099] The PAG component described herein can range from about 0.1% to about 2% by weight of the total weight percent solids.

[0100] [ka]

[0101] Base Additive Ingredients In the chemically amplified photoresist formulations described herein that include a PAG, an optional component that can be added is a base component to mitigate acid diffusion in exposed areas of the photoresist resulting from photoacid. The base component can be any base component that is basic enough to neutralize the photoacid. Another aspect of the compositions of the invention described herein is the base additive of component e), which includes, but is not limited to, base additives having a boiling point above 100° C. at atmospheric pressure and a pK of at least 1. aSuch acid quenchers may include basic materials or combinations of materials, such as amine compounds having the structures (BIa), (BIb), (BIc), (BId), (BIe), (BIf), (BIg), (BIh), (BIi), (BIj), (BIk), and (BIl), or mixtures of compounds from this group, where R b1 is a C1-C20 saturated alkyl chain or a C2-C20 unsaturated alkyl chain; R b2 , R b3 , R b4 , R b5 , R b6 , R b7 , R b8 , R b9 , R b10 , R b11 , R b12 and R b13 is independently selected from the group of H and C1-C20 alkyl.

[0102] [ka] The base additive component can be selected from a basic material or combination of materials, including, but not limited to, tetraalkylammonium or trialkylammonium salts of dicarboxylic acids or mixtures thereof. Specific non-limiting examples are mono(tetraalkylammonium) salts of dicarboxylic acids, di(tetraalkylammonium) salts of dicarboxylic acids, mono(trialkylammonium) salts of dicarboxylic acids, or di(trialkylammonium) salts of dicarboxylic acids. Non-limiting examples of suitable dicarboxylic acids for these salts are oxalic acid, maleic acid, malonic acid, fumaric acid, phthalic acid, and the like. Structures (BIma), (BImb), (BImc) or (BImd) provide general structural formulas for such materials, where Rqa, Rqb and Rqc are independently a C4-C8 alkyl group and Rqe is a valence bond, an arylene moiety, a C1-C4 alkylene moiety, an alkenyl moiety (-C(Rqf)=C(Rqg)-, where Rqf and Rqg are independently H or a C1-C4 alkyl group. Structure (BIme) provides a specific example of such a material.

[0103] [ka] This base additive component, when present, ranges from about 0.0001% to about 0.020% by weight of total solids.

[0104] Acrylic resins with acid-cleavable groups for positive chemically amplified photoresists For positive chemically amplified photoresists containing the acrylate resins described herein, suitable resins include those that contain acid-cleavable groups that, when cleaved by photoacid, render the resin soluble in an aqueous base developer, non-limiting examples of which include those described in US 8,017,296 (Patent Document 3), US 9,012,126 (Patent Document 4), US 8,841,062 (Patent Document 5), WO 2021 / 094350 (Patent Document 6), and WO 2020 / 048957 (Patent Document 7).

[0105] Hydroxystyrene resins with acid-cleavable groups for positive chemically amplified photoresists For positive chemically amplified photoresists described herein that include hydroxystyrene resins, suitable resins of this type are those that have acid-cleavable groups that, when cleaved by photoacid, render the resin soluble in an aqueous base developer, such as, but not limited to, those described in WO2019 / 224248 (Patent Document 8) and US20200183278 (Patent Document 9). Acrylic resins for positive non-chemically amplified photoresists For the positive non-chemically amplified photoresists described herein, suitable resins are acrylate resins that are soluble in aqueous base developers, such as, but not limited to, those described in WO2021 / 094423 (Patent Document 10).

[0106] Phenolic resins soluble in aqueous base for use in positive non-chemically amplified photoresists. For the positive non-chemically amplified photoresists described herein, including phenolic resins such as novolaks and resins derived from hydroxystyrenes, suitable novolak resins are again, by way of non-limiting example, those described in US Pat. No. 6,852,465 and WO 2021 / 094423.

[0107] Acrylate resins for negative chemically amplified photoresists For negative chemically amplified photoresists described herein that include an acrylate-based resin, suitable resins are acrylic resins that are soluble in aqueous base developers, such as, but not limited to, those described in U.S. Pat. No. 6,576,394.

[0108] Acrylate resins for negative non-chemically amplified photoresists For negative non-chemically amplified photoresists comprising an acrylate-based resin as described herein, suitable resins are acrylate-based resins that are soluble in aqueous base developers, such as those described in US 8,906,594 (Patent Document 13) or US 20200393758 (Patent Document 14), as non-limiting examples.

[0109] Hydroxystyrene resins for negative non-chemically amplified photoresists. For negative non-chemically amplified photoresists comprising a hydroxystyrene resin as described herein, suitable resins are, by way of non-limiting example, hydroxystyrene resins that may contain optional acrylate repeat units that are soluble in aqueous base developers, such as, by way of non-limiting example, those described in U.S. Pat. No. 7,601,482.

[0110] Organic spin-casting solvent In the non-chemically amplified and chemically amplified photoresist formulations described herein, the organic spin-cast solvent component may be butyl acetate, amyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, cyclopentanone, ethyl-3-ethoxypropanoate, methyl-3-ethoxypropanoate, methyl-3-methoxypropanoate, methyl acetoacetate, ethyl acetoacetate, diacetone alcohol, methyl pyruvate, ethyl pyruvate, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monomethyl ether propanoate, propylene glycol monoethyl ether propanoate, ethylene glycol The organic spin casting solvent may include one or more of ethanol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, N-methylpyrrolidone, dimethylsulfoxide, gamma-butyrolactone, propylene glycol methyl ether acetate (PGMEA), propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, methyl lactate, ethyl lactate, propyl lactate, tetramethylene sulfone, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol dimethyl ether or diethylene glycol dimethyl ether and gamma-butyrolactone. In one aspect of this embodiment, the organic spin casting solvent is a single solvent. In another aspect of this embodiment, the organic spin casting solvent is a mixture of two or more solvents. In another aspect, it is a mixture of three solvents, and in one aspect of this embodiment, the solvent is a mixture of PGMEA, 3-methoxybutyl acetate and gamma-butyrolactone. In another aspect of this embodiment, the solvent mixture is one in which PGMEA ranges from about 55% to about 80% by weight, 3-methoxybutyl acetate ranges from about 5% to about 20% by weight, and gamma butyrolactone ranges from about 1% to about 2% by weight, where the sum of the weight percentages of these individual components equals 100% by weight.

[0111] Optional Ingredients The photoresist formulations described herein may optionally further comprise at least one optional surface leveling agent, such as one or more surfactants. In this embodiment, the surfactant is not particularly limited, and examples thereof include polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene olein ether; polyoxyethylene alkylaryl 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, polyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorinated surfactants, such as F-Top EF301, EF303, and EF352 (manufactured by Gemco), Megafac F171, F172, F173, R08, R30, R90 and R94 (manufactured by Dainippon Ink and Chemicals), Florad FC-430, FC-431, FC-4430 and FC-4432 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-381, S-382, S-386, SC101, SC102, SC103, SC104, SC105, SC106, Surfinol 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 acid polymers such as Polyflow No. 75 and No. 95 (Kyoeisha Chemical Co., Ltd.) In one embodiment, when a surfactant is present, it ranges from about 0.01% to about 0.3% by weight of the total solids.

[0112] Compositions Comprising Thiol Derivatives and Organic Spin-Casting Solvents and Methods of Using Them to Produce Anisotropically Etched Metal Substrates - Patent application Composition containing a thiol derivative and an organic spin-casting solvent Another aspect of the present invention is A thiol derivative, wherein the thiol moiety is attached to an SP2 carbon that is part of a ring having the structure (H1), (H2), (H3) or (H4); and Organic spin-casting solvents, wherein the thiol derivative comprises from about 1% to about 10% by weight of the composition, and wherein the thiol derivative comprises from about 98% to 100% by weight of the total solids, and further In the structure (H1), Xt is selected from the group consisting of N(Rt3), C(Rt1)(Rt2), O, S, Se, and Te; In the structure (H2), Y is selected from the group consisting of C(Rt3) and N; In the structure (H3), Z is selected from the group consisting of C(Rt3) and N; and In the structure (H4), Arene is selected from unsubstituted phenyl, substituted phenyl, unsubstituted polycyclic arene moieties, and substituted polycyclic arene moieties; Rt1, Rt2, and Rt3 are independently selected from the group consisting of H, substituted alkyl groups having 1 to 8 carbon atoms, unsubstituted alkyl groups having 1 to 8 carbon atoms, substituted alkenyl groups having 2 to 8 carbon atoms, unsubstituted alkenyl groups having 2 to 8 carbon atoms, substituted alkynyl groups having 2 to 8 carbon atoms, unsubstituted alkynyl groups having 2 to 8 carbon atoms, substituted aromatic groups having 6 to 20 carbon atoms, substituted heteroaromatic groups having 3 to 20 carbon atoms, unsubstituted aromatic groups having 6 to 20 carbon atoms, and unsubstituted heteroaromatic groups having 3 to 20 carbon atoms; Rt4 is independently selected from the group consisting of H, OH, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkenyl group having 2 to 8 carbon atoms, an unsubstituted alkenyl group having 2 to 8 carbon atoms, a substituted alkynyl group having 2 to 8 carbon atoms, an unsubstituted alkynyl group having 2 to 8 carbon atoms, a substituted aromatic group having 6 to 20 carbon atoms, a substituted heteroaromatic group having 3 to 20 carbon atoms, an unsubstituted aromatic group having 6 to 20 carbon atoms, and an unsubstituted heteroaromatic group having 3 to 20 carbon atoms. It is a composition.

[0113] [ka] In one aspect of the composition of the thiol derivative in an organic solvent, the composition consists solely of these two components.

[0114] In one aspect of the composition of the thiol derivative in an organic spin-casting solvent, the thiol derivative is present in an amount of about 1.25% to about 10% by weight of the composition. In one aspect of this embodiment, it is present in an amount of about 1.5% to about 9.75% by weight of the composition. In one aspect of this embodiment, it is present in an amount of about 1.75% to about 9.50% by weight of the composition. In one aspect of this embodiment, it is present in an amount of about 2% to about 9.25% by weight of the composition. In one aspect of this embodiment, it is present in an amount of about 2.25% to about 9% by weight of the composition. In one aspect of this embodiment, it is present in an amount of about 2.5% to about 8.75% by weight of the composition. In one aspect of this embodiment, it is present in an amount of about 2.75% to about 8.5% by weight of the composition. In one aspect of this embodiment, it is present in an amount of about 3% to about 8.25% by weight of the composition. In one aspect of this embodiment, it is present in an amount of about 3.25% to about 8% by weight of the composition. In one aspect of this embodiment, it is present in an amount of about 3.5% to about 7.75% by weight of the composition. In one aspect of this embodiment, it is present in an amount of about 3.75% to about 7.5% by weight of the composition. In one aspect of this embodiment, it is present in an amount of about 4% to about 7.25% by weight of the composition. In one aspect of this embodiment, it is present in an amount of about 4.25% to about 7% by weight of the composition.

[0115] In one aspect of the thiol derivative composition in an organic spin-casting solvent, the thiol derivative is a heterocyclic thiol derivative having any of the structures (H1), (H2) or (H3). In this embodiment, it may be selected from any of the heterocyclic thiol derivatives described above as suitable for use in the photoresist composition, such as any of the heterocyclic thiol compounds listed by their chemical names in the section relating to heterocyclic thiol materials having structures (H5)-(H23) or photoresist compositions containing these materials.

[0116] In one aspect of the composition of the thiol derivative in an organic spin-casting solvent, the thiol derivative has the structure (H2):

[0117] In one aspect of the composition of the thiol derivative in an organic spin-casting solvent, the thiol derivative has the structure (H3):

[0118] In one aspect of the composition of the thiol derivative in an organic spin-casting solvent, the thiol derivative has the structure (H1):

[0119] In one aspect of the composition of the thiol derivative in an organic spin-casting solvent, the thiol derivative has the structure (H1) and Xt is N(Rt3).

[0120] In one aspect of the composition of the thiol derivative in an organic spin-casting solvent, the thiol derivative has the structure (H1-A), where X1 is N, X2 and X3 are individually selected from the group consisting of N and C(Rt3), and Rx1, Rx2, Rx3, Rx4, and Rx5 are individually selected from the group consisting of H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylene hydroxy (-alkylene-OH), C2-C8 alkylene oxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkylene oxyalkyl (-(alkylene-O-alkyl), pa -alkyl) (where pa is an integer ranging from 2 to 4), and Rt3 in C(Rt3) is independently selected from the group consisting of H, substituted alkyl groups having 1 to 8 carbon atoms, unsubstituted alkyl groups having 1 to 8 carbon atoms, substituted alkenyl groups having 2 to 8 carbon atoms, unsubstituted alkenyl groups having 2 to 8 carbon atoms, substituted alkynyl groups having 2 to 8 carbon atoms, unsubstituted alkynyl groups having 2 to 8 carbon atoms, substituted aromatic groups having 6 to 20 carbon atoms, substituted heteroaromatic groups having 3 to 20 carbon atoms, unsubstituted aromatic groups having 6 to 20 carbon atoms, and unsubstituted heteroaromatic groups having 3 to 20 carbon atoms.

[0121] [ka] In one aspect of the composition of the thiol derivative in an organic spin casting solvent, the thiol derivative has the structure (H1-B), where Rx is H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa -alkyl), where pa is an integer ranging from 2 to 4; Rc2 is selected from H and C1-C8 alkyl; and Rc1 is selected from H and C1-C8 alkyl.

[0122] [ka] In one aspect of the composition of the thiol derivative in an organic spin casting solvent, the thiol derivative has the structure (H1-C), where Rc2 is selected from H and C1-C8 alkyl, and Rx is selected from H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa -alkyl), where pa is an integer ranging from 2 to 4.

[0123] [ka] In one aspect of the composition of the thiol derivative in an organic spin casting solvent, the thiol derivative has the structure (H1-D), where Rc1 is selected from H and C1-C8 alkyl, and Rx is selected from H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa -alkyl), where pa is an integer ranging from 2 to 4.

[0124] [ka] In one aspect of the composition of the thiol derivative in an organic spin casting solvent, the thiol derivative has the structure (H1-E), where Rx is H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa -alkyl), where pa is an integer ranging from 2 to 4.

[0125] [ka] In one aspect of the composition of the thiol derivative in an organic spin casting solvent, the thiol derivative has the structure (H1-EA), where Rx is H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa -alkyl), where pa is an integer ranging from 2 to 4.

[0126] [ka] In one aspect of the composition of the thiol derivative in an organic spin casting solvent, the thiol derivative has the structure (H1-EB), where Rx is H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa -alkyl), where pa is an integer ranging from 2 to 4.

[0127] [ka] In one aspect of the composition of the thiol derivative in an organic spin-casting solvent, the thiol derivative has the structure (H1-EC) or (H1-ED).

[0128] [ka] In one aspect of the composition of the thiol derivative in an organic spin-casting solvent, the thiol derivative has the structure (H1-EC).

[0129] [ka] In one aspect of the composition of the thiol derivative in an organic spin-casting solvent, the thiol derivative has the structure (H1-ED).

[0130] [ka] In one aspect of the composition of the thiol derivative in an organic spin-casting solvent, the thiol derivative has the structure (H1-EE).

[0131] [ka] In one aspect of the composition of the thiol derivative in an organic spin casting solvent, the thiol derivative has the structure (H4), where the Arene moiety is selected from an unsubstituted phenyl, a substituted phenyl, an unsubstituted polycyclic arene moiety, and a substituted polycyclic arene moiety.

[0132] In one aspect of the composition of the thiol derivative in an organic spin-casting solvent, the Arene is a substituted or unsubstituted polycyclic arene.

[0133] In one aspect of the composition of the thiol derivative in an organic spin-casting solvent, the Arene is selected from naphthalene, anthracene, and pyrene.

[0134] In one aspect of the composition of the thiol derivative in an organic spin-casting solvent, the thiol derivative has the structure (H4) and the Arene is a substituted or unsubstituted phenyl.

[0135] In one aspect of the composition of the thiol derivative in an organic spin-casting solvent, the thiol derivative has the structure (H4) and the Arene is an unsubstituted phenyl.

[0136] In one aspect of the composition of the thiol derivative in an organic spin-casting solvent, the thiol derivative has the structure (H4-A), where R H4a , R H4b , R H4c , R H4d , R H4e are individually defined as H, OH, halide, C1-C8 alkyl, an unsubstituted aromatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms substituted with at least one hydroxyl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa-alkyl), where pa is an integer ranging from 2 to 4.

[0137] [ka] In one aspect of the composition of the thiol derivative in an organic spin-casting solvent, the thiol derivative has the structure (H4-B), where R H4 is H, OH, halide, C1-C8 alkyl, an unsubstituted aromatic group having 6-20 carbon atoms, an aromatic group having 6-20 carbon atoms substituted with at least one hydroxyl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa -alkyl), where pa is an integer ranging from 2 to 4.

[0138] [ka] In one aspect of the composition of the thiol derivative in an organic spin-casting solvent, the thiol derivative has the structure (H4-C), where R 4H is H, OH, halide, C1-C8 alkyl, an unsubstituted aromatic group having 6-20 carbon atoms, an aromatic group having 6-20 carbon atoms substituted with at least one hydroxyl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa -alkyl), where pa is an integer ranging from 2 to 4.

[0139] [ka] In one aspect of the composition of the thiol derivative in an organic spin casting solvent, the thiol derivative has the structure (H4-D), where Rx1 is selected from H, OH, halide, C1-C8 alkyl, an unsubstituted aromatic group having 6-20 carbon atoms, an aromatic group having 6-20 carbon atoms substituted with at least one hydroxy, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa -alkyl), where pa is an integer ranging from 2 to 4.

[0140] [ka] In one aspect of the composition of the thiol derivative in an organic spin-casting solvent, the thiol derivative has the structure (H4-E).

[0141] [ka] In one aspect of the composition of the thiol derivative in an organic spin-casting solvent, the thiol derivative has the structure (H4-F).

[0142] [ka] In one aspect of the composition of the thiol derivative in an organic spin casting solvent, the organic spin casting solvent component is selected from the group consisting of butyl acetate, amyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, cyclopentanone, ethyl 3-ethoxypropanoate, methyl 3-ethoxypropanoate, methyl 3-methoxypropanoate, methyl acetoacetate, ethyl acetoacetate, diacetone alcohol, methyl pivalate, ethyl pivalate, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monomethyl ether propanoate, propylene glycol monoethyl ... The active ingredient(s) may include one or more of propylene glycol methyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, N-methylpyrrolidone, dimethyl sulfoxide, gamma-butyrolactone, propylene glycol methyl ether acetate (PGMEA), propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, methyl lactate, ethyl lactate, propyl lactate, tetramethylene sulfone, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol dimethyl ether, or diethylene glycol dimethyl ether.

[0143] In one aspect of the composition of the thiol derivative in an organic spin-casting solvent, the organic spin-casting solvent is selected from propylene glycol monomethyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), and mixtures thereof.

[0144] In one aspect of all of the compositions of said thiol derivatives in organic spin-casting solvents for use in a two-step process, when the composition is used to coat a metallic substrate prior to coating with a photoresist, patterning and wet etching as described herein, it may contain, as an optional component, a surfactant or leveling agent as described herein for the photoresist formulations containing said thiol derivatives.

[0145] Methods for patterning metal substrates using compositions of said thiol derivatives in organic spin-casting solvents Another aspect of the present invention is a method of patterning a metal substrate to produce an anisotropically etched metal substrate, comprising the steps of: ia) washing the metal substrate covering the semiconductor with a 1-5 wt% aqueous solution of a tri- or dicarboxylic acid, followed by rinsing with distilled water to obtain a washed metal substrate; iia) spin drying the cleaned metal substrate; iiia) applying a composition of said thiol derivative in an organic spin-casting solvent as described herein onto said cleaned and dried metal substrate to obtain a treated metal substrate; iva) baking the treated metal substrate at a temperature between 90°C and 120°C to remove the solvent and then rinsing with an organic spin-casting solvent; va) applying a UV-exposed, aqueous base-developable photoresist to the treated and dried metal substrate to form a photoresist coating; via) baking the photoresist coating at a temperature between 90° C. and 120° C. to remove the solvent; viia) patterning a photoresist with UV radiation followed by development with an aqueous base to obtain a patterned photoresist etch barrier covering said metal substrate; vii) treating with a wet acidic chemical etchant using the patterned photoresist as an etch barrier to produce an anisotropically etched metal pattern overcoated with a patterned photoresist etch barrier; viva) Removing the patterned photoresist etch barrier overlying the top surface with a stripper to produce an anisotropically etched metal substrate.

[0146] In one aspect of the method, the metal substrate is a metal substrate overlying a semiconductor substrate, and further, step viva) produces an anisotropically etched metal substrate overlying the semiconductor substrate.

[0147] In another aspect of this method, the metal substrate is selected from a copper substrate, an aluminum substrate, an aluminum alloy substrate, silver, gold, nickel, and tungsten.

[0148] In another aspect of this embodiment, the metal substrate is a copper substrate. In another aspect of this embodiment, the metal substrate is aluminum. In another aspect of this embodiment, the metal substrate is an aluminum alloy. In another aspect of this embodiment, the metal substrate is a silver substrate. In another aspect of this embodiment, the metal substrate is a gold substrate. In another aspect of this embodiment, the metal substrate is a nickel substrate. In another aspect of this embodiment, the metal substrate is a tungsten substrate. EXAMPLES

[0149] More specific embodiments of the present disclosure and experimental results supporting such embodiments are described below. These examples are provided below to more fully explain the disclosed invention, and should not be construed as limiting the disclosed invention in any way.

[0150] It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed invention and the specific examples provided herein without departing from the spirit or scope of the disclosed invention. Thus, the disclosed invention, including the description provided by way of the following examples, is intended to cover modifications and variations of the disclosed invention that come within the scope of any claims and their equivalents.

[0151] chemicals All chemicals were obtained from Millipore Sigma unless otherwise indicated. Commercial photoresists and rinses were obtained from EMD Performance Materials Corp. unless otherwise indicated.

[0152] Coating of the formulation: All formulations were tested on 6 or 8 inch diameter Si and Cu wafers. The Si wafers were dehydration baked and vapor primed with hexamethyldisilazane (HMDS). The Cu wafers were silicon wafers coated with 5,000 Angstroms of silicon dioxide, 250 Angstroms of tantalum nitride, and 3,500 Angstroms of Cu (PVD deposited).

[0153] Image formation: The wafers were exposed on a SUSS MA200CC mask aligner or an ASML 250 i-line stepper. The resist was held for 10-60 minutes without a post-exposure bake, then puddle developed in AZ® 300MIF (a 0.26N aqueous solution of tetramethylammonium hydroxide = TMAH) at 23 °C for 120-360 seconds. The developed resist images were examined using a Hitachi S4700 or AMRAY 4200L electron microscope.

[0154] Coating of the formulation All formulations were tested on 8 inch diameter Si and Cu wafers.

[0155] contact angle measurement The contact angles of the surfaces were determined using the Dataphysics Contact Angle System OCA.

[0156] Imaging of Coated Wafers The coated wafers were exposed on a SUSS MA200 CC mask aligner or an ORC i-line stepper. The wafers were baked at 100°C for 100 seconds and then puddle developed in AZ® 300MIF (a 0.26N aqueous solution of tetramethylammonium hydroxide = TMAH) at 23°C for 120-360 seconds. The developed resist images on the metal substrates were examined with a Hitachi S4700 or AMRAY 4200L electron microscope.

[0157] Metal Etching Metal substrates etched using any of the following one-step or two-step procedure examples were etched with specific wet etchants defined by the specific metal or metal stack to remove metal in areas not covered by the patterned photoresist. Table 1 outlines the etching conditions used for the various metals.

[0158] In a two-step procedure, a thiol derivative of the present invention in which sulfur is attached to the SP2 carbon in a spin-cast solvent solution was used to prime a metal substrate prior to coating with a photoresist, then the photoresist was coated on the primed substrate, imaged, developed, and the metal substrate not covered with the patterned photoresist was wet etched.

[0159] In a two-step process, the thiol derivatives of the present invention were added to a commercial photoresist and the modified commercial photoresist was coated onto a metal substrate, imaged, developed, and the metal not covered by the patterned photoresist was wet etched.

[0160] [Table 1]

[0161] Two-step process Primer for metal substrates PMT (5-mercapto-1-phenyl-1H-tetrazole) or its analogues, such as 1-(4-hydroxyphenyl)-5-mercapto-1H-tetrazole), 5-mercapto-1-(4-methoxyphenyl)-1H-tetrazole, 1-(4-ethoxyphenyl)-5-mercapto-1H-tetrazole, etc., were dissolved in an organic solvent (e.g. PGMEA) to prepare a 1-5 wt% solution. The resulting solution was used to spin coat onto a metal substrate (AlSiCu, Cu, Ag, etc.). After soft baking at 90-120°C, the excess of PMT-type material was rinsed off using AZ® EBR 70 / 30 to form a PMT primed metal substrate, which had a different water contact angle than the unprimed metal substrate. The general procedure was as follows: The metal substrate was cleaned with a 2% aqueous citric acid solution (puddled for 2 minutes, then rinsed with deionized water and spun dry).

[0162] The priming solution was spin-coated (1500 rpm, 30 seconds) onto the cleaned metal substrate.

[0163] The coated substrate was baked (110° C. for 1-2 minutes) to allow chemical grafting of the primer to the metal substrate.

[0164] The excess of primer was then rinsed off with an AZ® EBR 70 / 30 puddle and spray, followed by spin drying to yield a primed metal substrate.

[0165] Photoresist patterning A photoresist (e.g., novolac-DNQ type, chemically amplified type, or photopolymer type) was applied and patterned onto the PMT-primed metal substrate using standard photolithography techniques to yield a metal substrate patterned with the selected photoresist, as follows.

[0166] The primed metal substrate was coated with a selected photoresist (specific coating parameters were determined by the resist selected and the desired resist film thickness).

[0167] The resulting substrates coated with the selected resist were exposed in a typical exposure tool (SUSS broadband aligner or ASLM i-line stepper). The specific exposure parameters are determined by the desired resist film thickness.

[0168] The exposed substrates were developed with a resist developer (eg AZ MIF300) to produce patterned metal substrates.

[0169] Metal Etching Metal Etching Using a Two-Step Process The resulting metal substrate primed and patterned with the thiol derivative solution-containing photoresist of the present invention was treated with a specific wet etchant defined for the specific metal or metal stack to remove the unwanted metal not protected by the photoresist to produce certain metal features defined by the mask pattern. A hard bake prior to wet etching is often required to allow for the steepest possible metal sidewall profile, and the optimal hard bake temperature varies for each specific photoresist. Table 1 shows the general etching conditions for various metals.

[0170] The general process is as follows: The resist-patterned metal substrate was first baked at 90-120° C. depending on the resist selected.

[0171] This resist-patterned metal substrate was then immersed sequentially in multiple etchant baths and etched under specific conditions selected depending on the particular metal stack.

[0172] Between each etchant, a deionized water rinse was performed. At the end of the through stack etch, the substrate was rinsed with deionized water at 50° C. and dried under N2.

[0173] Post-etch substrates can be treated with a remover (e.g., AZ® 910) to stripe the resist for better analysis of the etch results.

[0174] Example 1 The electrodeposited copper wafers were primed using the following process: Washed with 2% aqueous citric acid and then spun dry; spin-coated with 2 mL of a 5 wt % solution of 1-(phenyl)-5-mercapto-1H-tetrazole) in PGMEA; baked at 110°C for 1 min; Rinsed with AZ® EBR 70 / 30.

[0175] The water contact angle of this primed Cu wafer is about 58° compared to about 66° for the untreated Cu wafer.

[0176] The primed wafer was then patterned with AZ® P4620M (Novolac-DNQ positive tone photoresist). After etching the copper in a H3PO4 / H2O2 based etchant, steep metal sidewalls with a taper angle of about 65° were obtained, in contrast to a reference sample of an untreated copper wafer patterned with AZ® P4620M, which had a taper angle of about 35°.

[0177] Example 2 The electrodeposited copper wafers were primed using the following process: Washed with 2 wt % citric acid aqueous solution and then spun dry; spin-coated with 2 mL of a 5 wt % solution of 1-(phenyl)-5-mercapto-1H-tetrazole) in PGMEA; baked at 110°C for 1 min; Rinsed with AZ® EBR 70 / 30.

[0178] The water contact angle of this primed Cu wafer is about 16° compared to about 66° for the untreated Cu wafer.

[0179] The primed wafer was then patterned with AZ® P4620M (Novolac-DNQ positive tone photoresist). After etching the copper in a H3PO4 / H2O2 based etchant, steep metal sidewalls with a taper angle of about 65° were obtained, in contrast to a taper angle of about 35° for a reference sample of untreated copper wafer patterned with AZ® P4620M.

[0180] Comparative Example 1 The electrodeposited copper wafers were primed using the following process: Washed with 2 wt % citric acid aqueous solution and then spun dry; spin-coated with 2 mL of 5 wt % 3-(2′-ethyl-4′-(4-pentylcyclohexyl)-[1,1′-biphenyl]-4-yl)propane-1-thiol in PGMEA; baked at 110°C for 1 min; Rinsed with AZ® EBR 70 / 30.

[0181] The water contact angle of this primed Cu wafer is about 65° compared to about 66° for the untreated Cu wafer.

[0182] The primed wafer was then patterned with AZ® P4620M (Novolac-DNQ positive tone photoresist). After etching the copper in a H3PO4 / H2O2 based etchant, steep metal sidewalls with a taper angle of about 35° were obtained, in contrast to the taper angle of about 35° for a reference sample of untreated copper wafer patterned with AZ® P4620M. In addition, due to the much larger undercut, the resist peeled off from the metal structures during the etching process.

[0183] FIG. 4 shows cross-sectional SEM images comparing the patterned photoresist resulting from Examples 1 and 2, where the Cu wafer was primed with the thiol derivative 1-(phenyl)-5-mercapto-1H-tetrazole as a solution in PGMEA, which shows anisotropic wet etching of Cu, indicated by the large angle of the etched Cu with the substrate. FIG. 4 also shows the wet etching results obtained with a reference Cu wafer not treated with this solution, where a much shallower angle was obtained, suggesting isotropic etching resulting from poor adhesion of the top layer patterned photoresist to the underlying Cu. FIG. 4 also shows the wet etching results of Comparative Example 1, where an aliphatic thiol derivative (in this case the thiol is not bonded to the SP2 carbon) as a solution in PGMEA was used to treat the Cu wafer; in this case, a very shallow angle was observed in the etched Cu, similar to the untreated Cu wafer, suggesting isotropic etching. Surprisingly, treatment with this aliphatic thiol gave even poorer results as the overlying patterned photoresist lost adhesion during the chemical wet etch.

[0184] Example 3 The electrodeposited copper wafers were primed using the following process: Washed with 2 wt % citric acid aqueous solution and then spun dry; spin-coated with 2 mL of a 5 wt % solution of 5-mercapto-1-phenyl-1H-tetrazole in PGMEA; baked at 110°C for 1 min; Rinsed with AZ® EBR 70 / 30.

[0185] The water contact angle of the primed Cu wafer was about 58° compared to about 66° for the untreated Cu wafer.

[0186] The primed wafer was then patterned with AZ® 15nXT, a chemically amplified negative-tone photoresist. After etching the copper in a H3PO4 / H2O2-based etchant, steep metal sidewalls with a taper angle of about 65° were obtained, in contrast to a taper angle of about 33° for a reference sample of untreated copper wafer patterned with AZ® 15nXT.

[0187] Example 4 The electrodeposited copper wafers were primed using the following process: Washed with 2 wt % citric acid aqueous solution and then spun dry; spin-coated with 2 mL of 5 wt % 1-(4-hydroxyphenyl)-5-mercapto-1H-tetrazole in PGMEA; baked at 110°C for 1 min; Rinsed with AZ® EBR 70 / 30.

[0188] The water contact angle of this primed Cu wafer is about 16° compared to about 66° for the untreated Cu wafer.

[0189] The primed wafer was then patterned with AZ® 15nXT, a chemically amplified negative-tone photoresist. After etching the copper in a H3PO4 / H2O2-based etchant, steep metal sidewalls with a taper angle of about 60° were obtained, in contrast to a taper angle of about 33° for a reference sample of untreated copper wafer patterned with AZ® 15nXT.

[0190] Figure 5 shows cross-sectional SEM images comparing the patterned photoresist resulting from Examples 3 and 4, where the Cu wafer was primed with the thiol derivative 1-(4-hydroxyphenyl)-5-mercapto-1H-tetrazole as a solution in PGMEA, which shows anisotropic wet etching of Cu as indicated by the large angle of the etched Cu with the substrate. Figure 5 also shows the wet etching results obtained with a reference Cu wafer not treated with this solution, where a much shallower angle was obtained, suggesting isotropic etching resulting from poor adhesion of the top layer patterned photoresist to the underlying Cu.

[0191] The electrodeposited copper wafers were primed using the following process: Washed with 2 wt % citric acid aqueous solution and then spun dry; spin-coated with 2 mL of 1 wt % 4-mercaptophenol in PGMEA; baked at 110°C for 1 min; Rinsed with AZ® EBR 70 / 30.

[0192] The water contact angle of this primed Cu wafer is about 25° compared to about 66° for the untreated Cu wafer.

[0193] The primed wafer was then patterned with AZ® 15nXT, a chemically amplified negative-tone photoresist. After etching the copper in a H3PO4 / H2O2-based etchant, steep metal sidewalls with a taper angle of about 73° were obtained, in contrast to a taper angle of about 33° for a reference sample of untreated copper wafer patterned with AZ® 15nXT.

[0194] Comparative Example 2 The electrodeposited copper wafers were primed using the following process: Washed with 2 wt % citric acid aqueous solution and then spun dry; spin-coated with 2 mL of 1 wt % 4-(5-methyl-1H-tetrazol-1-yl)phenol in PGMEA; baked at 110°C for 1 min; Rinsed with AZ® EBR 70 / 30.

[0195] The water contact angle of this primed Cu wafer is about 25° compared to about 66° for the untreated Cu wafer.

[0196] The primed wafer was then patterned with AZ® 15nXT, a chemically amplified negative-tone photoresist. After etching the copper in a H3PO4 / H2O2-based etchant, steep metal sidewalls with a taper angle of about 13° were obtained, in contrast to a reference sample of an untreated copper wafer patterned with AZ® 15nXT, which had a taper angle of about 33°.

[0197] FIG. 6 shows cross-sectional SEM images comparing the patterned photoresist resulting from Example 5, where the priming solution included 4-mercaptophenol in solution in PGMEA, indicating anisotropic wet etching of Cu, as indicated by the large angle of the etched Cu with the substrate. FIG. 5 shows wet etching results obtained with a reference Cu wafer not treated with this solution, where a much shallower angle was obtained, suggesting isotropic etching resulting from poor adhesion of the top layer patterned photoresist to the Cu. Finally, Comparative Example 2, where the priming solution was 4-(5-methyl-1H-tetrazol-1-yl)phenol (a material that does not contain a thiol bonded to the SP2 carbon) in PGMEA, resulted in a much shallower angle, suggesting isotropic etching resulting from poor adhesion of the top layer patterned photoresist to the underlying Cu. All three of these experiments shown in FIG. 6 were performed on 350 nm Cu.

[0198] One-Step Process Photoresist Formulation Each photoresist formulation was prepared as follows: PMT (5-mercapto-1-phenyl-1H-tetrazole) or its analogues, such as 1-(4-hydroxyphenyl)-5-mercapto-1H-tetrazole, 5-mercapto-1-(4-methoxyphenyl)-1H-tetrazole, 1-(4-ethoxyphenyl)-5-mercapto-1H-tetrazole, etc., were used as one of the components of the photoresist formulation to provide in-situ priming on metal substrates (AlSiCu, Cu, Ag, etc.). The main photoresist resin can be a chemically amplified novolak-DNQ type. The content of the PMT type additive was 0.3-3 wt% of the total solids used in the photoresist formulation.

[0199] Photoresist patterning Photoresists (eg, novolac-DNQ type, chemically amplified type, or photopolymer type) containing the PMT-like additive were applied and patterned onto metal substrates using standard photolithography processes.

[0200] The primed metal substrate was coated with a selected photoresist (specific coating parameters were determined by the resist selected and the desired resist film thickness).

[0201] The resulting substrates coated with the selected resist were exposed in a typical exposure tool (SUSS Broadband Aligner or ASL Mi-Line Stepper). The specific exposure parameters are determined by the desired resist film thickness.

[0202] The exposed substrate was developed using a typical resist developer (eg AZ MIF300) to produce a patterned metal substrate.

[0203] Metal Etching Using a One-Step Process The resulting metal substrate patterned with the PMT-containing photoresist was treated with a specific wet etchant defined by the metal or metal step to remove the unwanted metal not protected by the photoresist, thereby creating certain metal features defined by the mask pattern. A hard bake prior to the wet etch is often required to allow for the steepest possible metal sidewall profile, and the optimal hard bake temperature varies for each specific photoresist. Table 1 shows the general etching conditions for various metals.

[0204] The resist-patterned metal substrate was first baked at 90-120° C. depending on the resist selected.

[0205] The resist-patterned metal substrate was then immersed in multiple etchant baths sequentially and etched under specific conditions selected depending on the particular metal stack; between each etchant, it was rinsed with deionized water. At the end of the through-stack etch, the substrate was rinsed with 50°C deionized water and dried under N2.

[0206] Post-etch substrates can be treated with a typical remover (e.g. AZ® 910) to stripe the resist for better analysis of the etch results.

[0207] Example 6 First, the electrodeposited copper wafer was cleaned with 2 wt% aqueous citric acid and then patterned with AZ® P4620M, a novolac-DNQ positive tone photoresist containing 0.5 wt% of 5-mercapto-1-phenyl-1H-tetrazole. After etching the copper in a H3PO4 / H2O2-based etchant, steep metal sidewalls with a taper angle of about 50° were obtained. In contrast, the taper angle of the reference sample copper wafer patterned with AZ® P4620M was about 35°.

[0208] Example 7 First, the electrodeposited copper wafer was cleaned with 2 wt% aqueous citric acid and then patterned with AZ® P4620M, a novolac-DNQ positive tone photoresist containing 1 wt% of 5-mercapto-1-phenyl-1H-tetrazole. After etching the copper in a H3PO4 / H2O2 based etchant, steep metal sidewalls with a taper angle of about 65° were obtained. In contrast, the taper angle of the reference sample copper wafer patterned with AZ® P4620M was about 35°.

[0209] Example 8 First, the electrodeposited copper wafer was cleaned with 2 wt% aqueous citric acid and then patterned with AZ® P4620M, a novolac-DNQ positive tone photoresist containing 3 wt% 5-mercapto-1-phenyl-1H-tetrazole. After etching the copper in a H3PO4 / H2O2 based etchant, steep metal sidewalls with a taper angle of about 75° were obtained. In contrast, the taper angle of the reference sample copper wafer patterned with AZ® P4620M was about 35°.

[0210] FIG. 7 shows the wet-etched SEM cross-sectional profiles obtained in Examples 6-7.

[0211] Example 9 First, the electrodeposited copper wafer was washed with 2 wt% citric acid in water and then patterned with AZ® 15nXT, a chemically amplified negative-tone photoresist containing 1 wt% 1-(4-hydroxyphenyl)-5-mercapto-1H-tetrazole. After etching the copper in a H3PO4 / H2O2-based etchant, steep metal sidewalls with a taper angle of about 70° were obtained. In contrast, the taper angle of the AZ® 15nXT-patterned copper wafer reference sample was about 33°.

[0212] Example 10 First, the electrodeposited copper wafer was washed with 2 wt% aqueous citric acid and then patterned with AZ® 15nXT, a chemically amplified negative-tone photoresist containing 3 wt% 1-(4-hydroxyphenyl)-5-mercapto-1H-tetrazole. After etching the copper in a H3PO4 / H2O2-based etchant, steep metal sidewalls with a taper angle of about 75° were obtained. In contrast, the taper angle of a reference sample of copper wafer patterned with AZ® 15nXT was about 33°.

[0213] FIG. 8 shows the wet etched SEM cross-sectional profiles obtained in Examples 9 and 10.

[0214] Example 11 First, the electrodeposited copper wafer was cleaned with 2 wt% aqueous citric acid and then patterned with AZ® TD2010, a novolac-DNQ positive tone photoresist containing 0.1 wt% of 5-mercapto-1-phenyl-1H-tetrazole. After etching the copper in a H3PO4 / H2O2 based etchant, steep metal sidewalls with a taper angle of about 48° were obtained. In contrast, the taper angle of the reference sample of the copper wafer patterned with AZ® TD2010 was about 30°.

[0215] Example 12 First, the electrodeposited copper wafer was cleaned with 2 wt% aqueous citric acid and then patterned with AZ® TD2010, a novolac-DNQ positive tone photoresist containing 0.75 wt% of 5-mercapto-1-phenyl-1H-tetrazole. After etching the copper in a H3PO4 / H2O2 based etchant, steep metal sidewalls with a taper angle of about 55° were obtained. In contrast, the taper angle of the reference sample of the copper wafer patterned with AZ® TD2010 was about 30°.

[0216] Example 13 First, the electrodeposited copper wafer was cleaned with 2 wt% aqueous citric acid and then patterned with AZ® TD2010, a novolac-DNQ positive tone photoresist containing 1 wt% of 5-mercapto-1-phenyl-1H-tetrazole. After etching the copper in a H3PO4 / H2O2 based etchant, steep metal sidewalls with a taper angle of about 80° were obtained. In contrast, the taper angle of the reference sample of the copper wafer patterned with AZ® TD2010 was about 30°.

[0217] FIG. 9 shows the wet etched SEM cross-sectional profiles obtained in Examples 11, 12 and 13.

[0218] Example 14 Example 6 was repeated, but this time using 9 micron thick Cu instead of 4.7 micron thick Cu. Figure 10 shows a comparison of the etch results using 4.7 micron (top) and 9.0 micron (bottom); the resulting etched images showed good anisotropic etching of the Cu underneath the protective patterned P4520M photoresist, as shown by the steep metal sidewalls with taper angles of about 70° obtained for the etched Cu when this much thicker Cu substrate was used.

[0219] Example 15 Example 9 was repeated, but in this case 9 micron thick Cu was used instead of 4.7 micron thick Cu. Figure 10 shows a comparison of the etching results using 4.7 micron (top) and 9.0 micron (bottom); the resulting etched images showed good anisotropic etching of the Cu underneath the protective patterned P4520M photoresist, as shown by the steep metal sidewalls with taper angles of about 70° obtained for the etched Cu when this much thicker Cu substrate was used.

Claims

1. 1. A photoresist composition comprising a thiol derivative wherein the thiol moiety is attached to an SP2 carbon that is part of a ring having the structure (H1), (H2), (H3), or (H4), wherein the thiol derivative is present in an amount ranging from 0.5% to 3% by weight of total solids, with the proviso that: In the structure (H1), Xt is N(Rt ３ ), C(Rt １ ) (Rt ２ ), selected from the group consisting of O, S, Se, and Te; In the structure (H2), Y is C(Rt ３ ) and N; In the structure (H3), Z is C(Rt ３ ) and N; and In structure (H4), Arene is selected from unsubstituted phenyl, substituted phenyl, unsubstituted polycyclic arene moieties, and substituted polycyclic arene moieties; Rt １ , Rt ２ , and Rt ３ are independently selected from the group consisting of H, substituted alkyl groups having 1 to 8 carbon atoms, unsubstituted alkyl groups having 1 to 8 carbon atoms, substituted alkenyl groups having 2 to 8 carbon atoms, unsubstituted alkenyl groups having 2 to 8 carbon atoms, substituted alkynyl groups having 2 to 8 carbon atoms, unsubstituted alkynyl groups having 2 to 8 carbon atoms, substituted aromatic groups having 6 to 20 carbon atoms, substituted heteroaromatic groups having 3 to 20 carbon atoms, unsubstituted aromatic groups having 6 to 20 carbon atoms, and unsubstituted heteroaromatic groups having 3 to 20 carbon atoms; Rt ４ are independently selected from the group consisting of H, OH, substituted alkyl groups having 1 to 8 carbon atoms, unsubstituted alkyl groups having 1 to 8 carbon atoms, substituted alkenyl groups having 2 to 8 carbon atoms, unsubstituted alkenyl groups having 2 to 8 carbon atoms, substituted alkynyl groups having 2 to 8 carbon atoms, unsubstituted alkynyl groups having 2 to 8 carbon atoms, substituted aromatic groups having 6 to 20 carbon atoms, substituted heteroaromatic groups having 3 to 20 carbon atoms, unsubstituted aromatic groups having 6 to 20 carbon atoms, and unsubstituted heteroaromatic groups having 3 to 20 carbon atoms; Photoresist compositions. 【Chemistry 1】

2. 10. The composition of claim 1, wherein the thiol derivative is present in an amount of from 0.6% to 3% by weight of total solids.

3. 3. The composition of claim 1 or 2, wherein the thiol derivative has the structure (H2).

4. 3. The composition of claim 1 or 2, wherein the thiol derivative has the structure (H3).

5. 3. The composition of claim 1 or 2, wherein the thiol derivative has the structure (H1):

6. The thiol derivative has the structure (H1) and Xt is N(Rt ３ 3. The composition according to claim 1 or 2, wherein

7. The thiol derivative has the structure (H1-A), where X １ is N and X ２ and X ３ are N and C(Rt ３ ) and Rx １ , Rx ２ , Rx ３ , Rx ４ , and Rx ５ are individually H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) ｐａ -alkyl), where pa is an integer ranging from 2 to 4, and Rt ３ are independently selected from the group consisting of H, substituted alkyl groups having 1 to 8 carbon atoms, unsubstituted alkyl groups having 1 to 8 carbon atoms, substituted alkenyl groups having 2 to 8 carbon atoms, unsubstituted alkenyl groups having 2 to 8 carbon atoms, substituted alkynyl groups having 2 to 8 carbon atoms, unsubstituted alkynyl groups having 2 to 8 carbon atoms, substituted aromatic groups having 6 to 20 carbon atoms, substituted heteroaromatic groups having 3 to 20 carbon atoms, unsubstituted aromatic groups having 6 to 20 carbon atoms, and unsubstituted heteroaromatic groups having 3 to 20 carbon atoms. 【Chemistry 2】

8. The thiol derivative has the structure (H1-B), where Rx is H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) ｐａ -alkyl), where pa is an integer ranging from 2 to 4; ２ is selected from H and C1-C8 alkyl; Rc １ The composition of claim 1 or 2, wherein is selected from H and C1-C8 alkyl. 【Transformation 3】

9. The thiol derivative has the structure (H1-C), where Rc ２ is selected from H and C1-C8 alkyl, and Rx is selected from H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) ｐａ 3. The composition of claim 1, wherein pa is an integer ranging from 2 to 4. 【Chemistry 4】

10. The thiol derivative has the structure (H1-D), wherein Rc １ is selected from H and C1-C8 alkyl, and Rx is selected from H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) ｐａ 3. The composition of claim 1, wherein pa is an integer ranging from 2 to 4. 【Transformation 5】

11. The thiol derivative has the structure (H1-E), where Rx is H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) ｐａ 3. The composition of claim 1, wherein pa is an integer ranging from 2 to 4. 【Transformation 6】

12. The thiol derivative has the structure (H1-EA), where Rx is selected from the group consisting of H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) ｐａ 3. The composition of claim 1, wherein pa is an integer ranging from 2 to 4. 【Transformation 7】

13. The thiol derivative has the structure (H1-EB), where Rx is selected from the group consisting of H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) ｐａ 3. The composition of claim 1, wherein pa is an integer ranging from 2 to 4. 【Transformation 8】

14. The composition of claim 1 or 2, wherein the thiol derivative has the structure (H1-EC). 【Chemistry 9】

15. The composition of claim 1 or 2, wherein the thiol derivative has the structure (H1-ED). 【Chemistry 10】

16. The composition of claim 1 or 2, wherein the thiol derivative has the structure (H1-EE). 【Chemistry 11】

17. 3. The composition of claim 1 or 2, wherein the thiol derivative has the structure (H4), where Arene is selected from unsubstituted phenyl, substituted phenyl, unsubstituted polycyclic arene moieties, and substituted polycyclic arene moieties.

18. 3. The composition of claim 1 or 2, wherein the thiol derivative has the structure (H4) and the Arene is a substituted or unsubstituted phenyl.

19. 3. The composition of claim 1, which is a positive non-chemically amplified photoresist developable in an aqueous base.

20. 1. A positive non-chemically amplified photoresist developable in an aqueous base, comprising: at least one novolak-type resin soluble in 0.26N TMAH; at least one DNQ PAC component, and Organic spin-cast solvents, 3. The composition of claim 1, which is a photoresist comprising:

21. 1. A positive non-chemically amplified photoresist developable in an aqueous base, comprising: at least one novolak-type resin soluble in 0.26N TMAH; at least one DNQ PAC component; photobleachable dyes, and Organic spin-cast solvents, 3. The composition of claim 1, which is a photoresist comprising:

22. 1. A positive non-chemically amplified photoresist developable in an aqueous base, comprising: at least one novolak-type resin soluble in 0.26N TMAH; at least one DNQ PAC component; 2000 ppm to 14,000 ppm surfactant, and Organic spin-cast solvents, 3. The composition of claim 1, which is a photoresist comprising:

23. 1. A positive non-chemically amplified photoresist developable in an aqueous base, comprising: at least one meth(acrylate) copolymer comprising repeat units derived from (meth)acrylic acid, in solution in 0.26 N TMAH; at least one novolak-type resin soluble in 0.26N TMAH; at least one DNQ PAC component, and Organic spin-cast solvents, 3. The composition of claim 1, which is a photoresist comprising:

24. A positive chemically amplified photoresist developable in aqueous base, wherein the thiol derivative has the structure (H1-E) or (H4), wherein Rx is selected from H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa -alkyl), where pa is an integer ranging from 2 to 4, Arene is selected from unsubstituted phenyl, substituted phenyl, unsubstituted polycyclic arene moieties, and substituted polycyclic arene moieties, and Rt 4 are independently selected from the group consisting of H, OH, substituted alkyl groups having 1 to 8 carbon atoms, unsubstituted alkyl groups having 1 to 8 carbon atoms, substituted alkenyl groups having 2 to 8 carbon atoms, unsubstituted alkenyl groups having 2 to 8 carbon atoms, substituted alkynyl groups having 2 to 8 carbon atoms, unsubstituted alkynyl groups having 2 to 8 carbon atoms, substituted aromatic groups having 6 to 20 carbon atoms, substituted heteroaromatic groups having 3 to 20 carbon atoms, unsubstituted aromatic groups having 6 to 20 carbon atoms, and unsubstituted heteroaromatic groups having 3 to 20 carbon atoms. 【Chemistry 12】

25. 1. A positive chemically amplified photoresist developable in an aqueous base, comprising: at least one photoacid generator; at least one polymer comprising one or more (meth)acrylate repeat units and further comprising one or more repeat units having at least one acid-cleavable group; Organic spin-cast solvents, and further comprising: Novolac resins included 25. The composition of claim 24.

26. 1. A positive chemically amplified photoresist developable in an aqueous base, comprising: at least one photoacid generator; at least one polymer comprising one or more (meth)acrylate repeat units and further comprising one or more repeat units having at least one acid-cleavable group; at least one novolac-type resin, and Organic spin-cast solvents, 25. The composition of claim 24 which is a photoresist comprising:

27. 1. A positive chemically amplified photoresist developable in an aqueous base, comprising: at least one photoacid generator; at least one DNQ PAC component; at least one novolac resin, at least one polymer comprising one or more (meth)acrylate repeat units and further comprising one or more repeat units having at least one acid-cleavable group; and Organic spin-cast solvents, 25. The composition of claim 24 which is a photoresist comprising:

28. 1. A positive chemically amplified photoresist developable in an aqueous base, comprising: at least one photoacid generator; at least one polymer comprising one or more (meth)acrylate repeat units and further comprising one or more repeat units having at least one acid-cleavable group; photobleachable dyes, and Organic spin-cast solvents, 25. The composition of claim 24 which is a photoresist comprising:

29. at least one polymer comprising one or more (meth)acrylate repeat units and further comprising one or more repeat units having at least one acid-cleavable group; at least one novolak-type resin soluble in 0.26N TMAH; at least one photoacid generator (PAG), and Organic spin-cast solvents, 25. The composition of claim 24 which is a positive chemically amplified photoresist comprising:

30. A positive chemically amplified (meth)acrylate photoresist developable in an aqueous base, comprising: at least one (meth)acrylate copolymer comprising (meth)acrylic acid derived repeat units, the carboxylic acid of which is functionalized with an acid labile group, repeat units derived from at least one of styrene and benzyl (meth)acrylate, which becomes soluble in 0.26 N TMAH when the acid labile group is cleaved by photogenerated acid from a PAG; at least one PAG, and Organic spin-cast solvents, 25. The composition of claim 24 which is a photoresist comprising:

31. A positive chemically amplified (meth)acrylate photoresist developable in an aqueous base, comprising: at least one (meth)acrylate copolymer comprising (meth)acrylic acid derived repeat units, the carboxylic acid of which is functionalized with an acid labile group, repeat units derived from at least one of styrene and benzyl (meth)acrylate, which becomes soluble in 0.26 N TMAH when the acid labile group is cleaved by photogenerated acid from a PAG; at least one novolak-type resin soluble in 0.26N TMAH; at least one PAG, and Organic spin-cast solvents, 25. The composition of claim 24 which is a photoresist comprising:

32. (i) a novolac polymer; (ii) a polymer comprising substituted or unsubstituted hydroxystyrene and an acrylate, methacrylate, or a mixture of acrylate and methacrylate, wherein the acrylate and / or methacrylate are protected with acid labile groups that require high activation energy for deblocking; and (iii) a component comprising a reaction product formed in the absence of an acid catalyst between a compound selected from vinyl ethers and unsubstituted or substituted unsaturated heteroalicyclics; at least one PAG, and Organic spin-cast solvents, 25. The composition of claim 24 which is a positive chemically amplified photoresist comprising:

33. 1. A positive chemically amplified photoresist developable in an aqueous base, comprising: (i) a novolac polymer; (ii) a polymer comprising substituted or unsubstituted hydroxystyrene and an acrylate, methacrylate, or a mixture of acrylate and methacrylate, wherein the acrylate and / or methacrylate are protected with acid labile groups that require high activation energy for deblocking; and (iii) a component comprising a reaction product formed in the absence of an acid catalyst between a compound selected from vinyl ethers and unsubstituted or substituted unsaturated heteroalicyclics; at least one polymer comprising a repeating unit derived from 4-hydroxystyrene, a repeating unit derived from acetal-protected 4-hydroxystyrene, and a repeating unit derived from (meth)acrylic acid protected with a high-energy protecting group; at least one PAG, Organic spin-cast solvents, 25. The composition of claim 24 which is a positive chemically amplified photoresist comprising:

34. 3. The composition of claim 1 or 2, which is a negative, non-chemically amplified photoresist developable in aqueous base, wherein the thiol derivative has the structure (H1-E), where Rx is selected from H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa -alkyl), where pa is an integer ranging from 2 to 4. 【Chemistry 13】

35. 1. A negative non-chemically amplified photoresist developable in an aqueous base, comprising: at least one alkali-soluble polymer comprising at least one unit of the structure (INR), 【Chemistry 14】 (wherein R' is independently hydrogen, (C １ -C ４ ) selected from alkyl, chlorine and bromine, and m is an integer from 1 to 4. At least one monomer of structure (IINR), 【Chemistry 15】 (Wherein W is a polyvalent linking group, R １ ~R ６ are independently hydrogen, hydroxy, (C １ -C ２０ ) alkyl and chlorine; X １ and X ２ are independently oxygen or N—R ７ where R ７ is hydrogen or (C １ -C ２０ ) alkyl, and n is an integer equal to or greater than 1. at least one radical photoinitiator, and Organic spin-cast solvents, 3. The composition of claim 1, which is a photoresist comprising:

36. 1. A negative non-chemically amplified photoresist developable in an aqueous base, comprising: at least one novolak-type resin soluble in 0.26N TMAH; at least one radical photoinitiator; at least one (meth)acrylate crosslinker, and Organic spin-cast solvents, 3. The composition of claim 1, which is a photoresist comprising:

37. 1. A negative non-chemically amplified (meth)acrylate photoresist developable in an aqueous base, comprising: at least one (meth)acrylate polymer comprising repeat units derived from (meth)acrylic acid, repeat units derived from at least one of styrene and benzyl (meth)acrylate, and soluble in 0.26N TMAH; at least one radical photoinitiator; at least one (meth)acrylate crosslinker, and Organic spin-cast solvents, 3. The composition of claim 1, which is a photoresist comprising:

38. 3. The composition of claim 1, which is a negative chemically amplified photoresist developable in an aqueous base.

39. 1. A negative chemically amplified photoresist developable in an aqueous base, comprising: at least one phenolic film-forming polymeric binder resin having ring-bonded hydroxyl groups selected from novolac resins, hydroxystyrene copolymers, and mixtures thereof, which is soluble in 0.26 N TMAH; at least one PAG, a crosslinker that forms carbonium ions when exposed to acid photogenerated by the PAG and comprises an etherified aminoplast polymer or oligomer; and Organic spin-cast solvents, 3. The composition of claim 1, which is a photoresist comprising:

40. 1. A method for patterning a metal substrate, comprising: i) washing the metal substrate coated with the semiconductor with a 1-5 wt % aqueous solution of a tri- or dicarboxylic acid, followed by rinsing with distilled water to obtain a washed metal substrate; ii) spin-drying the cleaned metal substrate; iii) applying the composition of claim 1 or 2 onto the cleaned and dried metal substrate to obtain a photoresist coating; iv) baking the photoresist coating at a temperature between 90°C and 120°C to remove the solvent; v) patterning the photoresist using UV radiation and then developing with an aqueous base developer to obtain a patterned photoresist etch barrier overlying the metal substrate; vi) treating with a wet acidic chemical etchant using the patterned photoresist as an etch barrier to produce an anisotropically etched metal pattern covered with a patterned photoresist etch barrier; vii) removing the overlying patterned photoresist etch barrier with a stripper to produce an anisotropically etched metal substrate; A method comprising:

41. 41. The method of claim 40, wherein the metal substrate is a metal substrate overlying a semiconductor substrate, and step vii) results in an anisotropically etched metal substrate overlying the semiconductor substrate.

42. A thiol derivative having a thiol moiety attached to an SP2 carbon that is part of a ring having the structure (H2) or the structure (H1-E), and Organic spin-cast solvents, A composition comprising: with the proviso that the thiol derivative is present in an amount of from 1% to 10% by weight of the composition, and the thiol derivative comprises from 98% to 100% by weight of the total solids, and further In the structure (H2), Y is C(Rt ３ ) and N; Rt ３ is selected from the group consisting of H, substituted alkyl groups having 1 to 8 carbon atoms, unsubstituted alkyl groups having 1 to 8 carbon atoms, substituted alkenyl groups having 2 to 8 carbon atoms, unsubstituted alkenyl groups having 2 to 8 carbon atoms, substituted alkynyl groups having 2 to 8 carbon atoms, unsubstituted alkynyl groups having 2 to 8 carbon atoms, substituted aromatic groups having 6 to 20 carbon atoms, substituted heteroaromatic groups having 3 to 20 carbon atoms, unsubstituted aromatic groups having 6 to 20 carbon atoms, and unsubstituted heteroaromatic groups having 3 to 20 carbon atoms; Rx is selected from H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa -alkyl), where pa is an integer ranging from 2 to 4; composition. 【Chemistry 16】

43. 43. The composition of claim 42, wherein the thiol derivative is present in an amount of from 1.25% to 10% by weight of the composition.

44. 1. A method of patterning a metal substrate to produce an anisotropically etched metal substrate, comprising the steps of: ia) washing the metal substrate covering the semiconductor with a 1-5 wt % aqueous solution of a tri- or dicarboxylic acid, followed by rinsing with distilled water to obtain a washed metal substrate; iia) spin-drying the cleaned metal substrate; iiia) applying a composition onto the cleaned and dried metal substrate to obtain a treated metal substrate, said composition comprising: Thiol derivatives having a thiol moiety attached to an SP2 carbon that is part of a ring having the structure (H1), (H2), (H3) or (H4), and Organic spin-cast solvents, Including, with the proviso that the thiol derivative is present in an amount of from 1% to 10% by weight of the composition, and the thiol derivative comprises from 98% to 100% by weight of the total solids, and further In said structure (H1), Xt is selected from the group consisting of N(Rt 3 ), C(Rt 1 )(Rt 2 ), O, S, Se, and Te; In the structure (H2), Y is selected from the group consisting of C(Rt 3 ) and N; In the structure (H3), Z is selected from the group consisting of C(Rt 3 ) and N; and In structure (H4), Arene is selected from unsubstituted phenyl, substituted phenyl, unsubstituted polycyclic arene moieties, and substituted polycyclic arene moieties; Rt 1 , Rt 2 , and Rt 3 are independently selected from the group consisting of H, substituted alkyl groups having 1 to 8 carbon atoms, unsubstituted alkyl groups having 1 to 8 carbon atoms, substituted alkenyl groups having 2 to 8 carbon atoms, unsubstituted alkenyl groups having 2 to 8 carbon atoms, substituted alkynyl groups having 2 to 8 carbon atoms, unsubstituted alkynyl groups having 2 to 8 carbon atoms, substituted aromatic groups having 6 to 20 carbon atoms, substituted heteroaromatic groups having 3 to 20 carbon atoms, unsubstituted aromatic groups having 6 to 20 carbon atoms, and unsubstituted heteroaromatic groups having 3 to 20 carbon atoms; Rt 4 is independently selected from the group consisting of H, OH, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkenyl group having 2 to 8 carbon atoms, an unsubstituted alkenyl group having 2 to 8 carbon atoms, a substituted alkynyl group having 2 to 8 carbon atoms, an unsubstituted alkynyl group having 2 to 8 carbon atoms, a substituted aromatic group having 6 to 20 carbon atoms, a substituted heteroaromatic group having 3 to 20 carbon atoms, an unsubstituted aromatic group having 6 to 20 carbon atoms, and an unsubstituted heteroaromatic group having 3 to 20 carbon atoms; a composition comprising: 【Chemistry 17】 iv) baking the treated metal substrate at a temperature between 90°C and 120°C to remove the solvent, followed by rinsing with an organic spin-casting solvent; a) applying a UV-irradiated, aqueous base-developable photoresist to the treated and dried metal substrate to form a photoresist coating; via) baking the photoresist coating at a temperature between 90°C and 120°C to remove the solvent; viia) patterning a photoresist with UV radiation and subsequently developing with an aqueous base developer to obtain a patterned photoresist etch barrier covering said metal substrate; viii) treating with a wet acidic chemical etchant using the patterned photoresist as an etch barrier to produce an anisotropically etched metal pattern covered with a patterned photoresist etch barrier; viva) removing the overlying patterned photoresist etch barrier with a stripper to produce an anisotropically etched metal substrate; The method comprising:

45. 45. The method of claim 44, wherein the metal substrate is a metal substrate overlying a semiconductor substrate, and further wherein step viva) results in an anisotropically etched metal substrate overlying a semiconductor substrate.

46. ​​The photoresist composition of claim 1 or 2, comprising a thiol derivative, The thiol derivative is the thiol derivatives having the structure (H1-B), wherein Rx is selected from the group consisting of H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa -alkyl), where pa is an integer ranging from 2 to 4, Rc 2 is selected from H and C1-C8 alkyl, and Rc 1 is selected from H and C1-C8 alkyl; [Chemistry 18] thiol derivatives having the structure (H1-C), where Rc 2 is selected from H and C1-C8 alkyl, and Rx is selected from H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa -alkyl), where pa is an integer ranging from 2 to 4; 【Chemistry 19】 thiol derivatives having the structure (H1-D), where Rc 1 is selected from H and C1-C8 alkyl, and Rx is selected from H, OH, halide, C1-C8 alkyl, aryl, C1-C8 alkylenehydroxy (-alkylene-OH), C2-C8 alkyleneoxyalkyl (-alkylene-O-alkyl), and C5-C15 polyalkyleneoxyalkyl (-(alkylene-O) pa -alkyl), where pa is an integer ranging from 2 to 4; 【Chemistry 20】 Thiol derivatives having the structure (H1-EC); 【Chemistry 21】 Thiol derivatives having the structure (H1-EE); 【Chemistry 22】 Structure (H4) Rt 4 -Arene-SH (H4) wherein Arene is selected from unsubstituted phenyl, substituted phenyl, unsubstituted polycyclic arene moieties, and substituted polycyclic arene moieties, and Rt 4 is independently selected from the group consisting of H, OH, substituted alkyl groups of 1 to 8 carbon atoms, unsubstituted alkyl groups of 1 to 8 carbon atoms, substituted alkenyl groups of 2 to 8 carbon atoms, unsubstituted alkenyl groups of 2 to 8 carbon atoms, substituted alkynyl groups of 2 to 8 carbon atoms, unsubstituted alkynyl groups of 2 to 8 carbon atoms, substituted aromatic groups of 6 to 20 carbon atoms, substituted heteroaromatic groups of 3 to 20 carbon atoms, unsubstituted aromatic groups of 6 to 20 carbon atoms, and unsubstituted heteroaromatic groups of 3 to 20 carbon atoms; The photoresist composition is selected from the group consisting of:

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