Positive-working photoresist composition with improved pattern profile and depth of focus (DOF)

Abstract

The disclosed invention relates to a resist composition comprising the following components: component a) a blend of two novolak polymers having structures (I) and (II); component b) a diazo-naphthoquinone sulfonate (DNQ-PAC) component, which is a single material or a mixture of materials having the general formula also having structure (III) or having the general formula (III-1); component c) a dissolution promoter component comprising a polyphenol-based compound, which is a single compound or a mixture of at least two compounds selected from the group consisting of oligomeric fractionated novolaks, compounds having the general formula (VI), and compounds having the general formula (VII), with the proviso that R de1 , R de2 , R de3 , R de4 and R de5 are individually selected from C1-C4 alkyl; component d) a surfactant; and component e) an organic spin-casting solvent, and optionally component f) a heterocyclic thiol.

Description

[Technical Field]

[0001] The disclosed invention relates to positive-working, radiation-sensitive, aqueous, base-soluble photoresist compositions used to manufacture integrated circuits (ICs), light-emitting diode (LED) devices, and display devices. [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 a silicon wafer used in the production of integrated circuits. The coated substrate is then baked to evaporate any solvent in the photoresist composition and fix the coating onto the substrate. The coated and baked surface of the substrate is then subjected to imagewise exposure.

[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 radiation species commonly used today in microlithography processes for forming images. 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] Photoresist compositions are of two types: negative-working and positive-working. 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 (e.g., by release of base-labile groups or photolysis of a dissolution inhibitor), while the photoresist coating in the unexposed areas remains relatively insoluble in such solutions. Therefore, treatment of the exposed positive-working resist with a developer removes the photoresist coating in the exposed areas, forming a positive image in the coating, thereby uncovering desired portions of the underlying substrate surface where the photoresist composition was originally deposited.

[0005] The use of positive-working photosensitive photoresist compositions developable with aqueous base is known. Most of these compositions are either chemically amplified photoresists based on phenolic or (meth)acrylate resins, or non-chemically amplified photoresists based on novolak / diazonaphthoquinone (DNQ). In novolak / DNQ photoresists, positive images are formed via photodecomposition of diazonaphthoquinone compounds (PACs), which leads to faster dissolution of the novolak resin in aqueous base in exposed resist areas. These types of photoresists are used at longer UV wavelengths, such as i-line (365 nm), and have been the workhorse photoresists in integrated circuit (IC) manufacturing for many years.

[0006] The semiconductor assembly process has been improved with the introduction of wafer-level packaging (WLP) in mass production. Copper (Cu) redistribution layer (RDL) miniaturization is one of the key processes for the fabrication of small, thin, and lightweight chips. Fine-pitch RDL is a market trend for high-density wafer-level fan-out (HDWLFO) packaging for semiconductors. The realization of this technology on topographic substrates requires the development of photoresists with high resolution and transmittance. Chemically amplified (CA) photoresists have demonstrated stable sensitivity and high resolution at various thicknesses due to their high transmittance at i-line (365 nm) exposure. However, their high cost and poor environmental stability limit their application in RDL fabrication for outsourced semiconductor assembly and test (OSAT) companies. Compared with CA-type photoresists, DNQ-based photoresists offer the advantages of lower cost, better environmental stability, and no need for post-exposure bake (PEB), which are favorable for OSAT companies. However, when resolving fine-pitch features, DNQ-based photoresists exhibit significant top loss (rounding) and footing due to bleaching of i-line (365 nm) exposure by diazonaphthoquinone (DNQ) photoactive compounds (PACs). In Cu-RDL fabrication by electroplating, photoresist top loss is unacceptable because the copper line profile produced from a top-loss / footing photoresist profile is unstable (wide top / narrow bottom).

[0007] To improve the profile of a photoresist pattern, process modification is a commonly used strategy, for example, hard-baking the photoresist lines (after development) above their glass transition temperature (Tg) to thermally reflow the photoresist structure to achieve the desired profile, but this method reduces wafer throughput due to the additional process steps. Summary of the Invention

[0008] To meet the demand for improved profiles in semiconductor packaging without the need for a profile hard bake and to address the problem of reduced wafer throughput, new novolac / DNQ-based photoresist formulations have been developed for high resolution and vertical pattern profiles. These new novolac / DNQ-based photoresist formulations contain two novolac resins, one a DNQ PAC and one a speed enhancer (dissolution promoter), and unexpectedly exhibit high resolution and vertical profiles down to 0.9 μm lines / spaces at 5.0 μm film thickness. Unexpectedly, the new novolac / DNQ-based photoresist formulations also have significantly less top loss and significantly improved depth of focus (DOF) without further process modifications. These novel novolak / DNQ-based photoresist formulations provide vertical profiles with low top loss without the need for a post-exposure bake (PEB) or post-exposure hard bake, have high resolution and fast photospeed, and exhibit a larger process window (wider DOF) compared to conventional novolak / DNQ-based photoresist formulations. These novel novolak / DNQ-based photoresist formulations are environmentally stable with good shelf life, use low-cost components, and have easy-to-prepare formulas.

[0009] In one aspect, these novel compositions consist essentially of the following components a), b), c), d), and e), or consist essentially of the following components a), b), c), d), e), and f).

[0010] Component a) is a blend of two novolac polymers having structures (I) and (II); wherein R1-R9 are individually selected from C1-C4 alkyl, and x, y, and z represent mole percent based on the total number of moles of repeat units in the polymer of structure (I); k, l, and m represent mole percent based on the total number of moles of repeat units in the polymer of structure (II), and further wherein x ranges from about 10 to about 20 mole percent, y ranges from about 50 to about 60 mole percent, and z ranges from about 30 to about 50 mole percent. wherein x, y, and z are in the range of from about 10 to about 20 mole percent, l is in the range of from about 40 to about 50 mole percent, and m is in the range of from about 30 to about 40 mole percent; and wherein, in structure (I), the sum of x, y, and z is 100 mole percent, and in structure (II), the sum of k, l, and m is 100 mole percent; the weight percent solids content of said novolac polymers of structures (I) and (II) is preferably each independently in the range of from about 25 to about 60 weight percent solids.

[0011] [ka] Component b) is a diazo-naphthoquinone sulfonate (DNQ-PAC) component, which is a single material or a mixture of materials having the general formula (III) or the general formula (III-1); 1c , D 2c , D 3c , D 4c and D 5c are individually selected from H or a moiety having structure (IV) or (V), and further, in structure (III), D 1c , D 2c , D 3c or D 4c is a moiety having structure (IV) or (V), and in structure (III-1), D 1c , D 2c , D 3c , D 4c , D 5cat least one of which is a moiety having structure (IV) or (V); wherein said DNQ-PAC preferably ranges from about 10% to about 15% by weight of the total solids.

[0012] [ka] Component c) is a solubility promoter component comprising a polyphenolic compound, the polyphenolic compound being a single compound or a mixture of at least two compounds selected from the group consisting of oligomeric fractionated novolaks, compounds having the general structural formula (VI) and compounds having the general structural formula (VII), wherein R de1 , R de2 , R de3 , R de4 and R de5 are individually selected from C1-C4 alkyl.

[0013] [ka] Component d) is a surfactant and ranges from about 0% to about 0.2% by weight of solids.

[0014] Component e) is an organic spin-casting solvent.

[0015] Component f) is a heterocyclic thiol.

[0016] Additionally, with the weight percent solids content calculated from the total weight of components a), b), c) and d) or components a), b), c), d) and f), which together add up to 100 weight percent solids content, the weight percent solids content ranges for components a), b), c) and d), or components a), b), c), d) and f), are as follows: Component a) is a novolac polymer of structures (I) and (II) wherein the weight percent solids content is each independently in the range of from about 23 weight percent to about 70 weight percent; component b) in the range of about 9% to about 15% by weight; Component c) ranges from about 4% to about 15% by weight, and Component d) ranges from about 0% to about 0.2% by weight, and further This composition does not contain a hexamethylmelamine crosslinker or a photoacid generator.

[0017] The disclosed invention also relates to a method of coating the resist composition onto a substrate as part of a lithographic process.

[0018] The accompanying drawings provide a further understanding of the disclosed invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosed invention, and together with the description, serve to explain the principles of the disclosed invention. [Brief explanation of the drawings]

[0019] FIG. 1 shows depth of focus (DOF) curves for Example 2 and Comparative Example 1. [Figure 2] SEM verification of depth of focus (DOF) for Example 2 with a film thickness (FT) of 5 μm [Figure 3] Linearity for Example 2 at 5 μmFT DETAILED DESCRIPTION OF THE INVENTION

[0020] Both the foregoing general description and the following detailed description are intended for purposes of illustration and example only and are not intended to be limiting of the claimed invention. As used herein, the use of the singular includes the plural, and unless specifically stated otherwise, the singular means "at least one," and the use of "or" means "and / or." Furthermore, the use of "comprises" and other verb forms, such as "comprises," is not limiting. Also, references to "elements" or "components" include both elements and components containing one unit and elements or components containing more than one unit, unless specifically stated otherwise. As used herein, the conjunction "and" is intended to be inclusive, and the conjunction "or" is not intended to be exclusive, unless otherwise specified. For example, the phrase "or instead" is intended to be exclusive. As used herein, the conjunction "and" refers to any combination of the aforementioned elements, including the use of a single element.

[0021] 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 thereof 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 cited herein conflicts with that herein, the definition herein shall control.

[0022] The term "linkage point", in each case when referring to a polymer of the present invention, refers to a point of branching and / or cross-linking to other polymer chains, provided that the branching and / or cross-linking is to the extent that the resulting branched and / or cross-linked polymer still has a sufficiently small molecular weight to avoid reaching a gel point where the polymer becomes insoluble in solvents such as spin-casting solvents.

[0023] Unless otherwise specified, "alkyl" refers to a hydrocarbon group that can be linear, branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, etc.), cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, etc.), or polycyclic (e.g., norbornyl, adamantyl, etc.). 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 begin at C1, while branched and cyclic alkyls begin at C3 and polycyclic alkyls begin at C5. Furthermore, moieties derived from alkyls described below, such as alkyloxy and haloalkyloxy, are understood to have the same carbon number range unless otherwise specified. When a different alkyl group length is specified, the above definition of alkyl group still applies in that it encompasses all types of alkyl moieties described above, and the structural considerations regarding the number of carbon atoms for a given type of alkyl group still apply.

[0024] 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, etc.) These alkyloxy moieties may be substituted or unsubstituted as described below.

[0025] Halo or halide refers to a halogen, F, Cl, Br, or I, attached to an organic moiety by one bond.

[0026] Haloalkyl refers to a saturated linear, cyclic, or branched alkyl group, such as those described above, in which at least one of the hydrogens has been 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.

[0027] Fluoroalkyl refers to a linear, cyclic, or branched saturated alkyl group as defined above in which hydrogen has been partially or fully replaced by fluorine (e.g., trifluoromethyl, perfluoroethyl, 2,2,2-trifluoroethyl, perfluoroisopropyl, perfluorocyclohexyl, etc.) These fluoroalkyl moieties, if not fully fluorinated, may be substituted or unsubstituted as described below.

[0028] Fluoroalkyloxy refers to a fluoroalkyl group as described above attached through an oxy (—O—) moiety, which may be fully fluorinated (also known as perfluorinated) or alternatively, may be partially fluorinated (e.g., trifluoromethyloxy, perfluoroethyloxy, 2,2,2-trifluoroethoxy, perfluorocyclohexyloxy, etc.). These fluoroalkyl moieties, when not fully fluorinated, may be substituted or unsubstituted as described below.

[0029] When referring herein 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 specifies only branched alkyl, branched alkyloxy, cycloalkyl, cycloalkyloxy, branched fluoroalkyl, and cyclic fluoroalkyl starting from C3.

[0030] The term "alkylene" refers to a hydrocarbon group that can be linear, branched, or cyclic and has two or more bonds (e.g., those having two bonds include methylene, ethylene, 1,2-isopropylene, and 1,4-cyclohexylene; those having three bonds include 1,1,1-substituted methane, 1,1,2-substituted ethane, and 1,2,4-substituted cyclohexane). Again, when specifying a range of possible carbon numbers, such as, as a non-limiting example, C1 to C20, this range includes linear alkylene starting from C1, but specifies only branched alkylene or cycloalkylene starting from C3. These alkylene moieties may be substituted or unsubstituted, as described below.

[0031] The term solid components as used herein refers to components that are not solvent component e), i.e., in one embodiment, components a), b), c), and d), and in another embodiment, components a), b), c), d), and f), including optional heterocyclic component f).

[0032] The term "mono- and oligomeric alkyleneoxyalkylene" encompasses both simple alkyleneoxyalkylene moieties, such as ethyleneoxyethylene (-CH-CH-O-CH-CH-), propyleneoxypropylene (-CH-CH-CH-O-CH-CH-CH-), and the like, as well as oligomeric materials, such as tri(ethyleneoxyethylene) (-CH-CH-O-CH-CH-O-CH-CH-), tri(propyleneoxypropylene) (-CH-CH-CH-O-CH-CH-CH-O-CH-CH-CH-), and the like.

[0033] The term "aryl" or "aromatic group" refers to such groups containing 6 to 24 carbon atoms, including phenyl, tolyl, xylyl, naphthyl, anthracyl, biphenyls, bis-phenyls, tris-phenyls, etc. These aryl groups may be further substituted with any of the suitable substituents described above, for example, any of the alkyl, alkoxy, acyl, or aryl groups described above.

[0034] The term "novolac," as used herein, in the absence of other structural modifications, refers to a novolac resin that is soluble in aqueous base, such as tetramethylammonium hydroxide.

[0035] The term "arylene" refers to an aromatic hydrocarbon moiety having two or more bonds (e.g., 2 to 5), which may be a single benzene moiety (e.g., 1,4-phenylene, 1,3-phenylene, and 1,2-phenylene having two bonds; 1,2,4-substituted benzene, 1,3,5-substituted benzene, etc. having three bonds), a polycyclic aromatic moiety having two bonds, such as those derived from naphthalene, anthracene, pyrene, etc., or a plurality of linked benzene rings having two bonds (e.g., biphenylene). In instances where the aromatic moieties are fused aromatic rings, these may be referred to as fused-ring arylenes, more specifically, for example, naphthalenylene, anthracenylene, pyrenylene, etc. Fused-ring arylenes may be substituted or unsubstituted as described below, and additionally, these fused-ring arylenes may contain a hydrocarbon substituent on the fused ring having two binding sites, thereby forming an additional aliphatic or unsaturated ring, which upon bonding to the fused ring may form a ring having from 5 to 10 carbon atoms.

[0036] The term "PAG," unless otherwise specified, refers to a photoacid generator capable of generating an acid (also known as a photoacid) under deep UV or UV radiation, such as 200-300 nm, i-line, h-line, g-line, and / or broadband radiation. The acid may be sulfonic acids, HCl, HBr, HAsF, etc. This includes, by way of non-limiting example, strong acids such as alkylsulfonic acids, arylsulfonic acids, HAsF6", HSbF6", HBF4", HPF6", CF3SO3H, HC(SO2CF3)2", HC(SO2CF3)3, HN(SO2CF3)2", HB(C6H5)4, HB(C6F5)4, bis(trifluoromethylphenyl)borate acid, p-toluenesulfonic acid, HB(CF3)4, onium salts and other photosensitive compounds known in the art capable of photochemically generating trihalomethyls, and photosensitive derivatives of trihalomethyl heterocyclic compounds capable of generating hydrogen halides such as HBr or HCl.

[0037] The term "arene" includes aromatic hydrocarbon moieties containing one ring or two to eight carbon-based aromatic rings fused together.

[0038] The term "heteroarene" refers to an arene that contains one or more trivalent or tetravalent heteroatoms, respectively, to the extent that its aromaticity is maintained. Examples of such heteroatoms are N, O, P, and S. As a non-limiting example, such a heteroarene may contain 1 to 3 such heteroatoms.

[0039] Unless otherwise indicated herein, the term "substituted," when referring to aryl, alkyl, alkyloxy, fluoroalkyl, fluoroalkyloxy, fused aromatic ring, arene, heteroarene, includes unsubstituted alkyl, substituted alkyl, unsubstituted aryl, alkyloxyaryl (alkyl-O-aryl-), dialkyloxyaryl ((alkyl-O-)2-aryl), haloaryl, alkyloxy, alkylaryl, haloalkyl, halide, hydroxyl, cyano, nitro, acetyl, alkylcarbonyl, formyl, ethenyl (CH2=CH-), phenylethenyl (Ph-CH=CH-), arylethenyl (aryl-CH=CH), and ethenylenearylene moieties (e.g., Ar(-CH=CH-Ar-)). z (z is 1 to 3)). Specific non-limiting examples of substituted aryl and substituted arylethenyl substituents are as follows, where:

[0040] [ka] represents a bond:

[0041] [ka] The terms substituted aryl and substituted ethenyls refer to these moieties in which the substituents are selected from any of the substituents described herein. Similarly, the term "unsubstituted" refers to these same moieties in which there are no substituents other than hydrogen.

[0042] In one of its aspects, the invention relates to a composition consisting essentially of or consisting of components a), b), c), d), e), and f), wherein Component a) is a blend of two novolac polymers having structures (I) and (II); wherein R1-R9 are individually selected from C1-C4 alkyl, and x, y, and z represent mole percent based on the total number of moles of repeat units in the polymer of structure (I); and k, l, and m represent mole percent based on the total number of moles of repeat units in the polymer of structure (II), wherein x ranges from about 10 to about 20 mole percent, y ranges from about 50 to about 60 mole percent, z ranges from about 30 to about 40 mole percent, k ranges from about 10 to about 20 mole percent, l ranges from about 40 to about 50 mole percent, and m ranges from about 30 to about 40 mole percent; and further, in structure (I), the sum of x, y, and z is 100 mole percent, and in structure (II), the sum of k, l, and m is 100 mole percent. Further, the weight percent solids content of said novolac polymers of structures (I) and (II) each independently ranges from about 23 to about 70 weight percent, preferably from about 25 to about 60 weight percent solids, based on the total weight of the solid components of components a), b), c), and d), where the sum of the individual weight percent solids contents of these components equals 100%.

[0043] [ka] Component b) is a diazo-naphthoquinone sulfonate (DNQ-PAC) component, which is a single material or a mixture of materials having the general formula (III) or the general formula (III-1); where D 1c , D 2c , D 3c , D 4c and D 5c are individually selected from H or a moiety having structure (IV) or (V), wherein further, in structure (III), D 1c , D 2c , D 3c or D 4c is a moiety having structure (IV) or (V), and in structure (III-1), D 1c , D 2c , D 3c , D4c , D 5c at least one of which is a moiety having structure (IV) or (V), further wherein this component ranges from about 9% to about 15%, preferably from about 10% to about 15%, by weight of the solids.

[0044] [ka] Component c) is a solubility promoter component comprising a polyphenolic compound, the polyphenolic compound being a single compound or a mixture of at least two compounds selected from the group consisting of oligomeric fractionated novolaks, compounds having the general structural formula (VI) and compounds having the general structural formula (VII), wherein R de1 , R de2 , R de3 , R de4 and R de5 are individually selected from C1-C4 alkyl; and further, this component ranges from about 4% to about 15% by weight of the solids.

[0045] [ka] Component d) is a surfactant, which ranges from about 0% to about 0.2% by weight of solids.

[0046] Component e) is an organic spin-casting solvent.

[0047] Component f) is a heterocyclic thiol.

[0048] Furthermore, this composition consisting essentially of components a), b), c), d), and e) or components a), b), c), d), e), and f) does not contain a hexamethylmelamine-based crosslinker or a photoacid generator.

[0049] In one embodiment, the composition consists essentially of components a), b), c), d), and e).

[0050] In one embodiment, the composition consists essentially of components a), b), c), d), e), and f).

[0051] In one embodiment, the composition consists of components a), b), c), d) and e).

[0052] In one embodiment, the composition consists of components a), b), c), d), e) and f).

[0053] In one embodiment of the composition according to the present invention, component a) is such that R1 to R9 are methyl.

[0054] In another embodiment of the compositions according to the invention described herein, for the polymer of structure (I), x ranges from about 15 to about 20 mole %, y ranges from about 50 to about 55 mole %, and z ranges from about 30 to about 35 mole %.

[0055] In another embodiment of the compositions of the invention described herein, for the polymer of structure (I), the repeat units of structure (Ia) wherein the mole % of x ranges from about 10 to about 25 mole % comprise a mixture of isomeric repeat units having structures (Iax1), (Iax2), (Iax3), (Iax4), (Iax5), and (Iax6), which repeat units have mole % values ​​of x1, x2, x3, x4, x5, and x6 based on the total amount of repeat units of structure (Ia), wherein: the mole percent value of repeat units of structure (Iax1), x1, ranges from 0 to about 5 mole percent; the mole percent value of repeat units of structure (Iax2), x2, ranges from 0 to about 5 mole percent; the mole percent x3 of repeat units of structure (Iax3) ranges from about 20 to about 25 mole percent; the mole percent value of repeat units of structure (Iax4), x4, is in the range of about 20 to about 25 mole percent; the mole percent x5 of repeat units of structure (Iax5) ranges from about 20 to about 25 mole percent; The mole percent value of x6 of the repeating unit of Structure (Iax6) ranges from about 20 to about 25 mole percent, the sum of x1, x2, x3, x4, x5, and x6 is from about 10 mole percent to about 25 mole percent based on the novolac polymer of Structure (I), and the sum of x1, x2, x3, x4, x5, x6, y, and z equals 100 mole percent based on the novolac polymer of Structure (I).

[0056] [ka] In another embodiment of the compositions of the invention described herein, for the polymer of structure (II), the repeat units of structure (IIa) having a mole % of k ranging from about 10 mole % to about 20 mole % comprise a mixture of isomeric repeat units having structures (IIax1), (IIax2), (IIax3), (IIax4), (IIax5), and (IIax6), which repeat units have mole % values ​​of k1, k2, k3, k4, k5, and k6, respectively, wherein the sum of these mole % values ​​ranges from about 10 mole % to about 20 mole %, and wherein the mole percent k1 of repeat units of structure (IIak1) ranges from about 10 to about 20 mole percent; the mole percent k2 of repeat units of structure (IIak2) ranges from 0 to about 5 mole percent; the mole percent value of repeat units of structure (IIak3), k3, ranges from 0 to about 5 mole percent; the mole percent value of repeat units of structure (IIak4), k4, ranges from 0 to about 5 mole percent; the mole percent value of repeat units of structure (IIak5), k5, ranges from 0 to about 5 mole percent; The mole percent value k6 of repeat units of structure (IIak6) ranges from 0 to about 5 mole percent, further wherein the sum of k1, k2, k3, k4, k5, k6, l, and m equals 100 mole percent.

[0057] [ka] In another embodiment of the described inventive composition, the polymer of structure (II) has the more specific structure (II-1), wherein k1 ranges from about 10 to about 20 mol %, l ranges from about 40 to about 50 mol %, and m ranges from about 30 to about 40 mol %, and further wherein, for structure (II-1), the sum of k1, l, and m is 100 mol %.

[0058] [ka] In another embodiment of the compositions according to the invention described herein, k is in the range of about 15 to about 20 mole %, l is in the range of about 40 to about 50 mole %, and m is in the range of about 35 to about 40 mole %, with respect to the polymer of structure (II).

[0059] In another embodiment of component a) of the present invention, the weight percent solids content of the novolac copolymer of structure (I) ranges from about 23 weight percent to about 55 weight percent total solids, and the novolac polymer of structure (II) ranges from about 25 weight percent to about 56 weight percent total solids, wherein the weight percent of the total solids content of the combined weight percent solids content of these two polymer components ranges from about 75 weight percent to about 85 weight percent. In another aspect, they independently range from about 35 weight percent to about 50 weight percent solids. In yet another aspect of this embodiment, the novolac polymer of structure (I) ranges from about 23.5 weight percent to about 52 weight percent total solids, and the novolac polymer of structure (II) ranges from about 28 weight percent to about 55.5 weight percent total solids.

[0060] In another embodiment of the compositions of the invention described herein, with respect to component b), the DNQ PAC is D 1c , D 2c , D 3c and D 4c are individually selected from H or a moiety having the structure (IV), and further 1c , D 2c , D 3c or D4c at least one of which is a moiety having structure (IV).

[0061] In another embodiment of the compositions of the invention described herein, the DNQ PAC of component b) is D 1c , D 2c , D 3c and D 4c are individually selected from H or a moiety having the structure (V), and further, D 1c , D 2c , D 3c or D 4c at least one of which is a moiety having the structure (V).

[0062] In another embodiment of the compositions of the invention described herein, the speed enhancer, component c), is present in a range of about 5% to about 15% by weight. In another aspect of this embodiment, it is present in a range of about 6% to about 14% by weight. In another aspect of this embodiment, it is present in a range of about 6.5% to about 13% by weight. In another aspect of this embodiment, it is present in a range of about 6.5% to about 12% by weight.

[0063] In another embodiment of the compositions of the present invention described herein, the speed enhancer, component c), is an oligomeric fractionated novolak. In one aspect of this embodiment, the speed enhancer ranges from about 5% to about 14% by weight. In another aspect of this embodiment, it ranges from about 5% to about 13% by weight. In another aspect of this embodiment, it ranges from about 6.0% to about 12% by weight. In another aspect of this embodiment, it ranges from about 6.5% to about 11% by weight. In another aspect of this embodiment, it ranges from about 6.5% to about 10% by weight. In another aspect of this embodiment, it ranges from about 6.5% to about 10% by weight. In another aspect of this embodiment, it ranges from about 6.5% to about 9% by weight. In another aspect of this embodiment, it ranges from about 6.5% to about 8% by weight. In another aspect of this embodiment, it is about 7% by weight.

[0064] In another embodiment of the compositions of the invention described herein, component c), the speed enhancer, is a compound of structure (VI), a compound of structure (VII), or a mixture thereof. In one aspect of this embodiment, in the compound of structure (VI), R de1 , R de2 , and R de3 are all selected from the same C1-C4 alkyl.

[0065] In another embodiment of the compositions of the invention described herein, the speed enhancer, component c), has structure (VI). In another aspect of this embodiment, the speed enhancer ranges from about 5% to about 14% by weight. In another aspect of this embodiment, it ranges from about 5% to about 13% by weight. In another aspect of this embodiment, it ranges from about 6.0% to about 12% by weight. In another aspect of this embodiment, it ranges from about 6.5% to about 11% by weight. In another aspect of this embodiment, it ranges from about 6.5% to about 10% by weight. In another aspect of this embodiment, it ranges from about 6.5% to about 10% by weight. In another aspect of this embodiment, it ranges from about 6.5% to about 9% by weight. In another aspect of this embodiment, it ranges from about 6.5% to about 8% by weight. In another aspect of this embodiment, it is about 7% by weight.

[0066] In another embodiment of the compositions of the invention described herein, component c), the speed enhancer, is a mixture of different compounds having structure (VI). In another aspect of this embodiment, the speed enhancer ranges from about 5% to about 14% by weight. In another aspect of this embodiment, it ranges from about 5% to about 13% by weight. In another aspect of this embodiment, it ranges from about 6.0% to about 12% by weight. In another aspect of this embodiment, it ranges from about 6.5% to about 11% by weight. In another aspect of this embodiment, it ranges from about 6.5% to about 10% by weight. In another aspect of this embodiment, it ranges from about 6.5% to about 10% by weight. In another aspect of this embodiment, it ranges from about 6.5% to about 9% by weight. In another aspect of this embodiment, it ranges from about 6.5% to about 8% by weight. In another aspect of this embodiment, it is about 7% by weight.

[0067] In another embodiment of the compositions of the invention described herein, the speed enhancer, component c), has structure (VII). In another aspect of this embodiment, the speed enhancer ranges from about 5% to about 15% by weight. In another aspect of this embodiment, it ranges from about 6% to about 14% by weight. In another aspect of this embodiment, it ranges from about 7% to about 13% by weight. In another aspect of this embodiment, it ranges from about 8% to about 12.5% ​​by weight. In another aspect of this embodiment, it ranges from about 8% to about 12.5% ​​by weight. In another aspect of this embodiment, it ranges from about 9% to about 12.5% ​​by weight. In another aspect of this embodiment, it ranges from about 10% to about 12.5% ​​by weight. In another aspect of this embodiment, it ranges from about 11% to about 12.5% ​​by weight. In another aspect of this embodiment, it is about 12% by weight.

[0068] In another embodiment of the compositions of the invention described herein, component c), the speed enhancer, is a mixture of different compounds having structure (VII). In another aspect of this embodiment, this ranges from about 6% to about 14% by weight. In another aspect of this embodiment, this ranges from about 7% to about 13% by weight. In another aspect of this embodiment, this ranges from about 8% to about 12.5% ​​by weight. In another aspect of this embodiment, this ranges from about 8% to about 12.5% ​​by weight. In another aspect of this embodiment, this ranges from about 9% to about 12.5% ​​by weight. In another aspect of this embodiment, this ranges from about 10% to about 12.5% ​​by weight. In another aspect of this embodiment, this ranges from about 11% to about 12.5% ​​by weight. In another aspect of this embodiment, this ranges about 12% by weight.

[0069] In another embodiment of the compositions of the invention described herein, component c), the speed enhancer, is a mixture of speed enhancers of structures (VI) and (VII).

[0070] In another embodiment of the compositions of the invention described herein, component c), the speed enhancer, is selected from those having structure (VIa) or structure (VIIa), or is a mixture of speed enhancers of structure (VIa) and (VIIa). In one aspect of this embodiment, it has structure (VIa). In another aspect of this embodiment, the speed enhancer has structure (VIIa). In another aspect of this embodiment, the speed enhancer is a mixture of structures (VIa) and (VIIa).

[0071] In another embodiment of the compositions of the invention described herein, the speed enhancer, component c), has structure (VIa), and is present in a range of about 5% to about 14% by weight. In another aspect of this embodiment, it is present in a range of about 5% to about 13% by weight. In another aspect of this embodiment, it is present in a range of about 6.0% to about 12% by weight. In another aspect of this embodiment, it is present in a range of about 6.5% to about 11% by weight. In another aspect of this embodiment, it is present in a range of about 6.5% to about 10% by weight. In another aspect of this embodiment, it is present in a range of about 6.5% to about 10% by weight. In another aspect of this embodiment, it is present in a range of about 6.5% to about 9% by weight. In another aspect of this embodiment, it is present in a range of about 6.5% to about 8% by weight. In another aspect of this embodiment, it is present in a range of about 7% by weight.

[0072] In another embodiment of the compositions of the invention described herein, the speed enhancer, component c), has structure (VIIa), and is present in a range of about 6% to about 14% by weight. In another aspect of this embodiment, it is present in a range of about 7% to about 13% by weight. In another aspect of this embodiment, it is present in a range of about 8% to about 12.5% ​​by weight. In another aspect of this embodiment, it is present in a range of about 8% to about 12.5% ​​by weight. In another aspect of this embodiment, it is present in a range of about 9% to about 12.5% ​​by weight. In another aspect of this embodiment, it is present in a range of about 10% to about 12.5% ​​by weight. In another aspect of this embodiment, it is present in a range of about 11% to about 12.5% ​​by weight. In another aspect of this embodiment, it is present in a range of about 12% by weight.

[0073] [ka] Component d) Surfactant In another embodiment of the composition of the present invention described herein, the surfactant of component d) 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, Inc.), Florad FC-430, FC-431, FC-4430 and FC-4432 (manufactured by Sumitomo 3M Company, Limited), 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 (manufactured by Kyoeisha Chemical Co., Ltd.).

[0074] In another embodiment of the compositions of the invention described herein, the total weight of components a), b), c), and d), or a), b), c), d), and f), when combined with solvent component e), results in a weight percent of all of these solid components in solvent ranging from about 30% to about 40%.

[0075] In another embodiment of the composition, component e), the organic spin solvent, 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 ether propanoate, ethylene glycol monomethyl The solvent component may comprise one or more of propylene glycol monomethyl 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, and gamma-butyrolactone. In one aspect of this embodiment, the solvent component comprises propylene glycol monomethyl ether (PGME). In another aspect of this embodiment, the solvent component comprises propylene glycol monomethyl ether acetate (PGMEA).

[0076] Component f) Heterocyclic thiol In one embodiment of the composition of the present invention described above, the composition further comprises at least one optional heterocyclic thiol component. In one aspect of this embodiment, the heterocyclic thiol component is at least one heterocyclic thiol compound comprising a ring structure selected from the general structural formulas (H1), (H2), or (H3), or tautomers thereof; and the ring structure is a single ring structure having 4 to 8 atoms or a polycyclic ring structure having 5 to 20 atoms; and wherein the single ring structure or polycyclic ring structure comprises an aromatic, non-aromatic, or heteroaromatic ring. In structure (H1), Xt is selected from the group consisting of N(Rt3), C(Rt1)(Rt2), O, S, Se, and Te. In structure (H2), Y is selected from the group consisting of C(Rt3) and N. In structure (H3), Z is selected from the group consisting of C(Rt3) and N. In these structures, 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. In one embodiment, the heterocyclic thiol compound is present at from about 0.5% to about 1.5% by weight total solids.

[0077] [ka] In another embodiment, the composition of the present invention comprises at least one heterocyclic thiol selected from the general structural formula (H1), (H2), or (H3) or a tautomer thereof. These may be selected from, but are not limited to, substituted or unsubstituted triazole thiols, substituted or unsubstituted imidazole thiols, substituted or unsubstituted triazine thiols, substituted or unsubstituted mercaptopyrimidines, substituted or unsubstituted thiathiazole thiols, substituted or unsubstituted indazole thiols, tautomers thereof, or combinations thereof. Substituents may include, but are not limited to, saturated or unsaturated hydrocarbon groups, substituted or unsubstituted aromatic rings, aliphatic, aromatic, or heteroaromatic alcohols, amines, amides, imides, carboxylic acids, esters, ethers, halides, and the like. Such substituents may be used in conjunction with the heterocyclic thiol to improve solubility, improve substrate interaction, enhance exposure, or function as an antihalation dye.

[0078] In another embodiment, wherein the composition of the present invention comprises at least one heterocyclic thiol selected from the general structural formula (H1), (H2), or (H3) above, or a tautomer thereof, such heterocyclic thiol may be selected from, but is not limited to, the following compounds (H4)-(H23) in unsubstituted or substituted form:

[0079] [Table 1] JPEG0007763254000015.jpg229170

[0080] In another aspect of the embodiment, wherein the composition of the present invention comprises at least one heterocyclic thiol having the general structural formula (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 ...butyl-6-ethyl-2-thiouracil, 5-hydroxy-2-thiouracil, 5,6-dithiouracil, 5-methyl-2-thiouracil, 5-n-propyl-2-thiouracil, 5-n-butyl-2-thiouracil, 5-n-butyl-6-ethyl-2-thiouracil, 5-hydroxy-2-thiouracil, 5,6-dithiouracil, 5-n-butyl-6-ethyl-2-thiouracil, 5-n-butyl-6-ethyl-2-thiouracil, 5-hydroxy-2-thiouracil, 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, 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, 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 are included.

[0081] In another embodiment, wherein the composition of the present invention comprises at least one heterocyclic thiol selected from the general structural formula (H1), (H2), or (H3), or a tautomer thereof, the 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.

[0082] In another embodiment, wherein the composition of the present invention includes component g), the heterocyclic thiol is at least one heterocyclic thiol selected from the group consisting of 1,3,5-triazine-2,4,6-trithiol, 2-mercapto-6-methylpyrimidin-4-ol, 3-mercapto-6-methyl-1,2,4-triazin-5-ol, 2-mercaptopyrimidine-4,6-diol, 1H-1,2,4-triazole-3-thiol, 1H-1,2,4-triazole-5-thiol, 1H-imidazole-2-thiol, 1H-imidazole-5-thiol, and 1H-imidazole-5-thiol.

[0033] The 5-mercapto-1H-imidazole-4-thiol may be selected from the group consisting of 1H-imidazole-4-thiol, 2-azabicyclo[3.2.1]oct-2-ene-3-thiol, 2-azabicyclo[2.2.1]hept-2-ene-3-thiol, 1H-benzo[d]imidazole-2-thiol, 2-mercapto-6-methylpyrimidin-4-ol, 2-mercaptopyrimidin-4-ol, 1-methyl-1H-imidazole-2-thiol, 1,3,4-thiadiazole-2,5-dithiol, 1H-indazole-3-thiol, 1-phenyl-1H-tetrazole-5-thiol, 4-(5-mercapto-1H-tetrazol-1-yl)phenol, tautomers thereof, and combinations thereof.

[0083] In another aspect of the compositions comprising at least one heterocyclic thiol selected from the general structural formula (H1), (H2), or (H3) described herein, the heterocyclic thiol is present in a content ranging from about 0.001% to about 1.5% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol ranges from about 0.010% to about 1.5% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol ranges from about 0.1% to about 1.5% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol ranges from about 0.2% to about 1.5% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol ranges from about 0.3% to about 1.5% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from about 0.4% to about 1.5% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol is present in a range of about 0.6% to about 1.4% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol is present in a range of about 0.7% to about 1.3% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound is present in a range of about 0.8% to about 1.2% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound is present in a range of about 0.9% to about 1.1% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound is present in a range of about 1% by weight of total solids.

[0084] In another aspect of the compositions comprising at least one heterocyclic thiol selected from general structural formula (H1), (H2), or (H3) described herein, the heterocyclic thiol compound described herein ranges from about 0.01% to about 0.49% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from about 0.04% to about 0.49% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from about 0.08% to about 0.49% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from about 0.09% to about 0.49% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from about 0.10% to about 0.49% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from about 0.15% to about 0.49% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.20% to about 0.49% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.25% to about 0.48% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.47% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.47% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.49% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.45% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.45% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.45% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.44% by weight of total solids.In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.43% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.42% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.41% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.40% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound is about 0.35% by weight of total solids.

[0085] Component e) Organic Spin-Casting Solvent The photosensitive compositions disclosed herein may be dissolved in an organic solvent. Examples of suitable organic solvents include, but are not limited to, 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, propylene glycol monoethyl ether, propylene glycol monomethyl ether propanoate, propylene glycol monoethyl ether propanoate, ethylene glycol monomethyl ether, ethyl Examples of suitable solvents include 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, diethylene glycol dimethyl ether, gamma-butyrolactone, etc. These solvents may be used alone or as a mixture of two or more.

[0086] Other optional ingredients In one embodiment of the composition of the present invention described above, it further comprises at least one optional surface leveling agent, which may include a surfactant. 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, Inc.), Florad FC-430, FC-431, FC-4430 and FC-4432 (manufactured by Sumitomo 3M Company, Limited), 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.) When a surfactant is present, in one embodiment it ranges from about 0.01% to about 0.3% by weight of the total solids.

[0087] processing Another aspect of the present invention is a method of coating any one of the compositions described herein onto a substrate.

[0088] Another aspect of the present invention is a method for imaging a resist comprising the steps of: i) coating any one of the compositions described herein onto a substrate to form a resist film; ii) selectively exposing the resist film to UV light using a mask to form a selectively exposed resist film; iii) developing the selectively exposed film to form a positive imaged resist film on the substrate.

[0089] Another aspect of the present invention is a method for imaging a resist comprising the steps of: ia) coating any one of the compositions described herein onto a substrate to form a resist film; iia) selectively exposing the resist film to UV light using a mask to form a selectively exposed resist film; iiia) baking the selectively exposed resist film to form a selectively exposed and baked resist film; iva) developing the selectively exposed and baked resist film to form a positive imaged resist film on the substrate.

[0090] Another aspect of the present invention is the use of the compositions described herein to coat a substrate or to produce an imaged resist film on a substrate. [Example]

[0091] 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.

[0092] 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 example below, is intended to cover modifications and variations of the disclosed invention that come within the scope of any claims and their equivalents.

[0093] Coating formulation: All formulations were tested on 6- or 8-inch diameter Si and Cu wafers. The Si wafers were rehydration baked and vapor primed with hexamethyldisilazane (HMDS). The Cu wafers were coated with 5,000 Å of silicon dioxide, 250 Å of tantalum nitride, and 3,500 Å of Cu (PVD-deposited).

[0094] Resist coatings were prepared by spin-coating the resist samples and applying a soft bake at 110°C for 120 seconds on a standard wafer track hotplate in contact mode. The spin speed was adjusted to obtain resist films 5-10 microns thick. All film thickness measurements were performed on Si wafers using optical metrology.

[0095] Image formation: These wafers were exposed on a SUSS MA200CC mask aligner or an ASML 250i line stepper. The resist was held for 10-60 minutes without a post-exposure bake, then puddle developed in AZ300MIF (a 0.26N aqueous solution of tetramethylammonium hydroxide = TMAH) for 120-360 seconds at 23 °C. The developed resist images were examined using a Hitachi S4700 or AMRAY 4200L electron microscope.

[0096] material SPN400 Slow is an m-cresol / p-cresol / dimethylphenol / formaldehyde novolac polymer sold under the name Alnovol SPN400 44% PGMEA, supplied by Allnex USA Inc. The novolac has an average molecular weight of 18,282 MW. The dissolution rate of this novolac is 63 Å / s in 0.26N aqueous TMAH developer. MIPHOTO NOVOL T106S is an m-cresol / p-cresol / dimethylphenol / formaldehyde novolac polymer sold under the name MIPHOTO NOVOL T106S, supplied by Miwon Commercial Co., Ltd. The novolac has an average molecular weight of 8,136 MW and a PDI of 6.51. The dissolution rate of this novolac is 309 Å / s in 0.26N aqueous TMAH developer. MIPHOTO PAC BP524 is a DNQ PAC sold under this name by Miwon Commercial Co., Ltd. It is a mixture of materials having the general formula (III) in which D1c, D2c, D3c, and D4c are individually selected from H or moieties having structure (IV), with the proviso that at least one of D1c, D2c, D3c, or D4c is a moiety having structure (IV).

[0097] [ka] BI26X-SA is bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, a dissolution enhancer sold under this name by Asahi Organic Chemicals.

[0098] TPPA (4,4'-(1-(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl)ethane-1,1-diyl)diphenol), available from Millipore Sigma USA, a subsidiary of Merck KGaA (Darmstadt, Germany).

[0099] APS-437 (also known as KF-353A) is a surfactant from Shin-Etsu Chemical Co., Ltd. (Tokyo, Japan).

[0100] PGMEA (1-methoxy-2-propanyl acetate); solvents used for the example photoresist formulations were obtained from Sigma-Aldrich, a subsidiary of Merck KGaA (Darmstadt, Germany).

[0101] AZ300MIF developer was obtained from EMD Performance Materials Corp., a subsidiary of Merck KGaA, Darmstadt, Germany (also known as 2.38% tetramethylammonium hydroxide (TMAH)).

[0102] All other chemicals were obtained from Millipore Sigma USA, a subsidiary of Merck KGaA (Darmstadt, Germany) unless otherwise stated.

[0103] The molecular weight of the polymer was determined by gel permeation chromatography (GPC).

[0104] The novolac / DNQ photoresist composition contains two novolac resins, a DNQ photoactive compound, a dissolution promoter, a surfactant, and a solvent. The two novolac resins used in the photoresist composition consist of different monomers and composition ratios. The photoresist was spin-coated onto silicon wafers and soft-baked on a hotplate, then exposed using a gh-line or i-line stepper. The exposed wafers were then developed using AZ® 300 MIF developer to remove the exposed areas. Finally, the wafers were rinsed with DI water and then spin-dried to obtain a photoresist pattern.

[0105] Comparative example 1 (H476-SPN400 Slow, BP524, BI26X-SA, APS437, PGMEA): A novolak / DNQ photoresist composition was prepared by dissolving a 42.7% PGMEA solution of novolak resin SPN400 Slow (64.54 grams), 4.69 grams of MIPHOTO PAC BP524, 2.76 grams of dissolution promoter BI26X-SA, and 0.42 grams of surfactant APS-437 (also known as KF-353A) in 28.02 grams of propylene glycol monomethyl ether acetate (PGMEA). This resulted in a positive photoresist composition with a solids content of 35.0 wt. %. The photoresist composition was spin-coated onto a silicon wafer substrate and soft-baked at 110°C for 120 seconds to yield a 5.0 μm-thick film. The coated film was then exposed by an ASML i-line stepper (NA=0.48, sigma=0.55) through a pattern mask for measuring the resolution, followed by a post-exposure bake (PEB) at 100°C for 60 seconds, and then developed with AZ® 300MIF developer (2.38% TMAH, tetramethylammonium hydroxide aqueous solution) for three 60-second puddles (3 x 60 seconds). 1.0 μmL / S (line / space) was 360 mJ / cm. 2 and showed a top CD of 0.551 μm and a bottom CD of 1.151 μm.

[0106] Solid content of raw material %- Novolac resin PN400 Slow:78.6458% MIPHOTO PAC BP524:13.3698% Speed ​​Enhancer BI26X-SA: 7.8646% Surfactant APS437 (KF353A): 0.1199% Solid content: 35.04%

[0107] Comparative example 2 (H457-T106S, BP524, BI26X-SA, APS437, PGMEA): A novolak / DNQ photoresist composition was prepared by mixing a 30.0% PGMEA solution of novolak resin MIPHOTO NOVOL T106S (94.61 grams), 3.97 grams of MIPHOTO PAC BP524, 1.42 grams of dissolution promoter BI26X-SA, and 0.41 grams of surfactant APS-437 (also known as KF-353A) in 10.0% PGMEA. This resulted in a positive photoresist composition with a solids content of 33.82 wt %. This composition was evaluated in the same manner as Comparative Example 1. A 1.0 μmL / S (line / space) of 100 mJ / cm was obtained. 2 and showed a top CD of 0.832 μm and a bottom CD of 0.716 μm.

[0108] Solid content of raw material %- MIPHOTO NOVOL T106S: 83.9329% MIPHOTO PAC BP524:11.7506% Speed ​​Enhancer BI26X-SA: 4.1967% Surfactant APS437 (KF353A): 0.1199% Solid content: 33.8153%

[0109] Example 1 (Comparative example 1 / Comparative example 2 = 66 / 34, solid content ratio) A novolak / DNQ photoresist composition was prepared by mixing Comparative Example 1 (32.53 grams) and Comparative Example 2 (17.37 grams). This resulted in a positive photoresist composition with a solids content of 34.50% by weight. This composition was evaluated in the same manner as Comparative Example 1. The 1.0 μmL / S (line / space) yielded a 240 mJ / cm 2 and showed a top CD of 0.725 μm and a bottom CD of 1.180 μm.

[0110] Solid content of raw material %- Novolac resin SPN400 Slow: 51.9063% Novolac resin MIPHOTO NOVOL T106S: 28.5371% MIPHOTO PAC BP524:12.8191% Speed ​​Enhancer BI26X-SA: 6.6176% Surfactant APS437 (KF353A): 0.1198% Solid content: 34.50%

[0111] Example 2 (Comparative example 1 / Comparative example 2 = 50 / 50, solid content ratio) A novolak / DNQ photoresist composition was prepared by mixing Comparative Example 1 (24.55 grams) and Comparative Example 2 (25.45 grams). This resulted in a positive photoresist composition with a solids content of 34.38% by weight. This composition was evaluated in the same manner as Comparative Example 1. A 1.0 μmL / S (line / space) of 200 mJ / cm 2 and showed a top CD of 0.764 μm and a bottom CD of 1.112 μm.

[0112] Solid content of raw material %- Novolac resin SPN400 Slow: 39.323% Novolac resin MIPHOTO NOVOL T106S: 41.966% MIPHOTO PAC BP524: 12.56% Speed ​​Enhancer BI26X-SA: 6.031% Surfactant APS437 (KF353A): 0.119% Solid content: 34.38%

[0113] Example 3 (Comparative example 1 / Comparative example 2 = 34 / 66, solid content ratio) A novolak / DNQ photoresist composition was prepared by mixing Comparative Example 1 (16.60 grams) and Comparative Example 2 (33.40 grams). This resulted in a positive photoresist composition with a solids content of 34.18% by weight. This composition was evaluated in the same manner as Comparative Example 1. The 1.0 μmL / S (line / space) yielded 140 mJ / cm. 2 and showed a top CD of 0.861 μm and a bottom CD of 1.151 μm.

[0114] Solid content of raw material %- Novolac resin SPN400 Slow: 26.7396% Novolac resin MIPHOTO NOVOL T106S: 55.3955% MIPHOTO PAC BP524:12.3012% Speed ​​Enhancer BI26X-SA: 5.4438% Surfactant APS437 (KF353A): 0.1199% Solid content: 34.18%

[0115] Example 4 A novolak / DNQ photoresist composition was prepared by mixing 21.15 grams of a 42.7% PGMEA solution of novolak resin SPN400 Slow, 66.21 grams of a 30.01% PGMEA solution of novolak resin MIPHOTO NOVOL T106S, 3.71 grams of MIPHOTO PAC BP524, 4.47 grams of the dissolution promoter TPPA, 0.375 grams of the adhesion additive PMT, 0.446 grams of a 10.0% PGMEA solution of surfactant APS-437 (also known as KF-353A), and 3.636 grams of PGMEA, resulting in a positive photoresist composition with a solids content of 37.5% by weight.

[0116] Solid content of raw material %- Novolac resin SPN400 Slow: 24.088% Novolac resin MIPHOTO NOVOL T106S: 52.987% MIPHOTO PAC BP524:9.899% Speed ​​Enhancer TPPA: 11.907% Adhesion additive PMT: 1.00% Surfactant APS437 (KF353A): 0.119% Solid content: 37.5%

[0117] FIG. 1 compares the depth of focus (DOF) curves of Example 2 and Comparative Example 1 side-by-side in a graph, highlighting the unexpected improvement of the novel formulation of the present invention described herein.

[0118] FIG. 2 shows a scanning electron microscope (SEM) examination demonstrating the good depth of focus (DOF) of Example 2 when coated and imaged as a 5 μm film thickness.

[0119] FIG. 3 shows a scanning electron microscope (SEM) examination demonstrating the good linearity of Example 2 when coated and imaged at a 5 μm film thickness.

[0120] FIG. 4 shows Table 1, which provides a summary of the lithographic performance of Examples 1, 2, and 3 compared to Comparative Example 1, again highlighting the unexpected improvement of the novel formulations of the present invention described herein. While this application is directed to the invention set forth in the claims, the disclosure of this application also includes: 1. A composition consisting essentially of the following components a), b), c), d), and e) or consisting essentially of the following components a), b), c), d), e) and f): a) a blend of two novolac polymers having structures (I) and (II); 1 ~R 9 are individually selected from C1-C4 alkyl, and x, y, and z represent mole % based on the total number of moles of repeat units in the polymer of Structure (I); k, l, and m represent mole % based on the total number of moles of repeat units in the polymer of Structure (II), wherein further, x ranges from about 10 to about 20 mole %, y ranges from about 50 to about 60 mole %, z ranges from about 30 to about 40 mole %, k ranges from about 10 to about 20 mole %, l ranges from about 40 to about 50 mole %, and m ranges from about 30 to about 40 mole %, and further, wherein, for Structure (I), the sum of x, y, and z is 100 mole %, and in Structure (II), the sum of k, l, and m is 100 mole %. b) a diazo-naphthoquinone sulfonate (DNQ-PAC) component, which is a single material or a mixture of materials having the general formula (III) or the general formula (III-1); provided that D 1c 、D 2c 、D 3c 、D 4c and D 5c are individually selected from H or a moiety having structure (IV) or (V), wherein further, in structure (III), D 1c 、D 2c 、D 3c or D 4c at least one of which is a moiety having structure (IV) or (V), and in structure (III-1), D 1c 、D 2c 、D 3c 、D 4c 、D 5c at least one of which is a moiety having structure (IV) or (V): c) a solubility enhancer component comprising a polyphenolic compound, which is a single compound or a mixture of at least two compounds selected from the group consisting of oligomeric fractionated novolaks, compounds having the general structural formula (VI) and compounds having the general structural formula (VII); provided that R de1 、R de2 、R de3 、Rde4 and R de5 are individually selected from C1-C4 alkyl; d) surfactants, e) organic spin-casting solvents; provided that, using weight percent solids calculated from the total weights of components a), b), c), and d) that add up to 100 weight percent solids, the weight percent solids ranges for components a), b), c), and d) are as follows: Component a) is a novolac polymer of structures (I) and (II) wherein the weight percent solids content is each independently in the range of from about 23 weight percent to about 70 weight percent; component b) in the range of about 9% to about 15% by weight; Component c) ranges from about 4% to about 15% by weight, and Component d) ranges from about 0% to about 0.2% by weight, and further The composition is free of a hexamethylmelamine crosslinker and a photoacid generator. f) optionally, a heterocyclic thiol moiety.

change

change

change

change

change

change

Claims

1. A composition consisting essentially of or consisting essentially of the following components a), b), c), e), optionally and d): a) a blend of two novolac polymers having structures (I) and (II); １ ~R ９ are individually selected from C1-C4 alkyl, and x, y, and z represent mole % based on the total number of moles of repeat units in the polymer of Structure (I); k, l, and m represent mole % based on the total number of moles of repeat units in the polymer of Structure (II), wherein further, x ranges from 10 to 20 mole %, y ranges from 50 to 60 mole %, z ranges from 30 to 40 mole %, k ranges from 10 to 20 mole %, l ranges from 40 to 50 mole %, and m ranges from 30 to 40 mole %, and further, wherein, for Structure (I), the sum of x, y, and z is 100 mole %, and in Structure (II), the sum of k, l, and m is 100 mole %. b) a diazo-naphthoquinone sulfonate (DNQ-PAC) component, which is a single material or a mixture of materials having the general formula (III) or the general formula (III-1); １ｃ , D ２ｃ , D ３ｃ , D ４ｃ and D ５ｃ are individually selected from H or a moiety having structure (IV) or (V), wherein further, in structure (III), D １ｃ , D ２ｃ , D ３ｃ or D ４ｃ is a moiety having structure (IV) or (V), and in structure (III-1), D １ｃ , D ２ｃ , D ３ｃ , D ４ｃ , D ５ｃ is a moiety having structure (IV) or (V): c) a solubility promoter component comprising a polyphenolic compound, which is a single compound or a mixture of at least two compounds selected from the group consisting of oligomeric fractionated novolaks, compounds having the general structural formula (VI) and compounds having the general structural formula (VII); provided that R ｄｅ１ , R ｄｅ２ , R ｄｅ３ , R ｄｅ４ and R ｄｅ５ are individually selected from C1-C4 alkyl; d) surfactants, e) organic spin-casting solvents; provided that, using weight percent solids calculated from the total weights of components a), b), c), and d) that add up to 100 weight percent solids, the weight percent solids ranges for components a), b), c), and d) are as follows: Component a) is a novolac polymer of structure (I) and (II) wherein the weight percent solids content is each independently in the range of from 23 to 70 weight percent; component b) in the range of 9% to 15% by weight; Component c) ranges from 4% to 15% by weight, and Component d) ranges from 0 to 0.2 wt %; and The composition is free of a hexamethylmelamine crosslinker and a photoacid generator. f) Heterocyclic thiol moieties. 【Chemistry 1】 【change】

2. R １ ~R ９ The composition of claim 1 wherein is methyl.

3. In the polymer of structure (I): x is in the range of 15 to 20 mol %; y is in the range of 50 to 55 mol %, and z is in the range of 30 to 35 mol %; The composition according to claim 1 or 2.

4. In the polymer of structure (I), the repeat units of structure (Ia) in which the mole % of x ranges from 10 to 20 mole % comprise a mixture of isomeric repeat units having structures (Iax1), (Iax2), (Iax3), (Iax4), (Iax5), and (Iax6), having mole % values ​​of x1, x2, x3, x4, x5, and x6, respectively, based on the total amount of repeat units of structure (Ia), wherein: The mole percent value of repeat units of structure (Iax1), x1, ranges from 0 to 5 mole percent; The mole percent value of repeat units of structure (Iax2), x2, ranges from 0 to 5 mole percent; the mole percent value of repeat units of structure (Iax3), x3, is in the range of 20 to 25 mole percent; the mole percent value of repeat units of structure (Iax4), x4, is in the range of 20 to 25 mole percent; the mole percent value of repeat units of structure (Iax5), x5, is in the range of 20 to 25 mole percent; The mole percent of repeat units of structure (Iax6), x6, ranges from 20 to 25 mole percent, and further the sum of x1, x2, x3, x4, x5, and x6 ranges from 10 mol % to 20 mol % based on the novolac polymer of structure (I), and the sum of x1, x2, x3, x4, x5, x6, y, and z equals 100 mol % based on the novolac polymer of structure (I); and R 1 and R 2 have the same meaning as in claim 1 or 2; The composition according to any one of claims 1 to 3. 【Chemistry 2】

5. In the polymer of structure (II), the repeat units of structure (IIa) having a mole % of k ranging from 10 mole % to 20 mole % comprise a mixture of isomeric repeat units having structures (IIak1), (IIak2), (IIak3), (IIak4), (IIak5), and (IIak6) having mole % values ​​of k1, k2, k3, k4, k5, and k6, respectively, the sum of which mole % values ​​ranging from 10 mole % to 20 mole %, wherein the mole percent value of repeat units of structure (IIak1), k1, is in the range of 10 to 20 mole percent; the mole percent value of repeat units of structure (IIak2), k2, ranges from 0 to 5 mole percent; the mole percent value of repeat units of structure (IIak3), k3, ranges from 0 to 5 mole percent; the mole percent value of repeat units of structure (IIak4), k4, ranges from 0 to 5 mole percent; the mole percent value of repeat units of structure (IIak5), k5, ranges from 0 to 5 mole percent; The mole percent value of repeat units of structure (IIak6), k6, ranges from 0 to 5 mole percent; Further, wherein the sum of k1, k2, k3, k4, k5, k6, and l and m is equal to 100 mole percent; and R 5 , R 6 and R 7 have the same meaning as in claim 1 or 2; The composition according to any one of claims 1 to 4. 【Transformation 3】

6. 6. The composition of any one of claims 1 to 5, wherein said polymer of structure (II) has the more specific structure (II-1), wherein k1 ranges from 10 to 20 mol %, l ranges from 40 to 50 mol %, and m ranges from 30 to 40 mol %, and further wherein, for structure (II-1), the sum of k1, l, and m is 100 mol %, and R 5 , R 6 , R 7 , R 8 , and R 9 have the same meaning as in claim 1 or 2. 【Chemistry 4】

7. In the polymer of structure (II): k is in the range of 15 to 20 mol %; 1 is in the range of 40 to 50 mol %, and m is in the range of 35 to 40 mol %; The composition according to any one of claims 1 to 6.

8. The DNQ PAC of component b) is D １ｃ , D ２ｃ , D ３ｃ and D ４ｃ are individually selected from H or a moiety having the structure (IV), and further １ｃ , D ２ｃ , D ３ｃ or D ４ｃ The composition of any one of claims 1 to 7, wherein at least one of: is a moiety having structure (IV).

9. The composition of any one of claims 1 to 8, wherein the solubility promoter of component c) is an oligomeric fractionated novolak.

10. 9. The composition of any one of claims 1 to 8, wherein the solubility promoter of component c) is a compound of structure (VI), a compound of structure (VII), or a mixture thereof.

11. The solubility promoter of component c) has structure (VI) and further comprises R ｄｅ１ , R ｄｅ２ , and R ｄｅ３ The composition of any one of claims 1 to 8, wherein all are selected from the same C1 to C4 alkyl.

12. 9. The composition of any one of claims 1 to 8, wherein said solubility enhancer of component c) is selected from those having structure (VIa) or structure (VIIa), or is a mixture of solubility enhancers of structures (VIa) and (VIIa). 【Transformation 5】

13. Component f) is at least one heterocyclic thiol compound comprising a ring structure selected from the general structural formula (H1), (H2) or (H3) or a tautomer thereof; and the ring structure is a single ring structure having 4 to 8 atoms or a polycyclic ring structure having 5 to 20 atoms; and wherein the single ring structure or the polycyclic ring structure comprises an aromatic, non-aromatic or heteroaromatic ring, and in structural formula (H1), Xt is selected from the group consisting of N(Rt3), C(Rt １ ) (Rt ２ ), O, S, Se, and Te, and in the structural formula (H2), Y is selected from the group consisting of C(Rt ３ ) and N, and in the structural formula (H3), Z is selected from the group consisting of C(Rt ３ ) and N, wherein 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; The composition according to any one of claims 1 to 12. 【Transformation 6】

14. 1. A method of imaging a resist comprising the steps of: ia) coating the composition according to any one of claims 1 to 13 onto a substrate to form a resist film; iia) selectively exposing the resist film to UV light using a mask to form a selectively exposed resist film; iiia) optionally baking the selectively exposed resist film to form a selectively exposed and baked resist film; iv) developing the selectively exposed and optionally baked resist film to form a positive imaged resist film on the substrate; The method comprising:

15. Use of a composition according to any one of claims 1 to 13 for coating a substrate or for producing an imaged resist film on a substrate.

Images