Positive tone ultra thick photoresist composition

Abstract

1. A positive-working, chemically amplified photosensitive composition comprising: as component a), at least one random copolymer having structure (A); as component b), at least one acrylic polymer component having structure (B) containing repeat units selected from those having structures (1), (2), (3), (4), (5), (6) and (7); as component c), at least one novolac polymer; as component d), at least one photoacid generator (PAG); as component e), at least one base additive; as component f), at least one heterocyclic thiol compound; and as component g), an organic spin-cast solvent. JPEG2024541353000073.jpg69170

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 to actinic 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 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-solubilizing 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] Semiconductor assembly processes have 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 production of small, thin, and lightweight chips. Fine-pitch redistribution layer (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 shown 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. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] US20190064662A1 Summary of the Invention [Problem to be solved by the invention]

[0008] One problem with thick chemically amplified photoresist formulations greater than 150 microns is wetting on the substrate, which results in a non-perpendicular profile in the imaged film. Another problem with these thick chemically amplified photoresists is the relatively long processing times due to a lack of sensitivity and low dissolution rates, which have a negative impact on the throughput of IC manufacturing techniques that use such thick chemically amplified photoresists. Therefore, there is a need for thick chemically amplified photoresist formulations that avoid these problems. Additionally, there is a need for thick photoresists used in lithographic processes such as metal plating that also exhibit better wetting on the substrate. [Means for solving the problem]

[0009] To meet the requirements for improving the profile in semiconductor manufacturing using thick chemically amplified photoresists, for improving the wetting of these materials, and for preserving imaged patterns with these vertical profiles while maintaining very little unexposed area erosion of less than 1 micron, and for avoiding the problem of reduced wafer throughput, new thick chemically amplified photoresist formulations have been developed that have high resolution with good photosensitivity, good dissolution rate, and exhibit vertical pattern profiles and provide good wetting on the substrate. These disclosed new thick photoresist formulations, as described below, contain two copolymer components, one of which contains repeat units derived from acrylic acids, and the other copolymer component is an acrylate copolymer containing repeat units derived from an acrylate derivative with acid-cleavable groups and benzylic acrylates, styrenes, or mixtures of benzylic acrylates and styrenes.

[0010] In one aspect, the novel positive-working chemically amplified photosensitive composition comprises the following components: Component a) at least one random copolymer having structure (A), wherein: the repeat units of structure (I) range from about 17 mole % to about 70 mole %; the repeat units of structure (II) range from 0 to about 70 mole %; the repeat units of structure (III) range from 0 to about 70 mole %; the sum of repeat units of structures (II) and (III) ranges from about 30 mole % to about 70 mole %; The repeat units of structure (IV) range from about 0 mole % to about 35 mole %, wherein the sum of the mole % of repeat units of structures (I), (II), (III) and (IV) does not exceed 100 mole %, or equals 100 mole % if no other types of repeat units are present, and Ril, Ri2, Ri 14 and Ri 13are independently selected from H or C1-C4 alkyl, and R, ... 10 , Ri 11 , and Ri 12 are individually selected from H, C1-C8 alkyl, C1-C4 alkoxy, phenyl, substituted phenyl, and mixtures thereof; Li1 is a C2-C6 alkylene moiety; ni, mi, oi, and pi are the number of repeat units of structures (I), (II), (III), and (IV), respectively; and further, the copolymer of structure (A) has a minimum dissolution rate of 500 Å / sec in 0.26 N tetramethylammonium hydroxide at 23° C. and does not contain any repeat units with acid-cleavable groups;

[0011] [ka] Component b) at least one acrylic copolymer component of Structure (B) comprising repeating units selected from those having Structures (1), (2), (3), (4), (5), (6), and (7), wherein R1, R2, R3, R4, R5, R6, and R7 are independently selected from H, F, C1-C4 perfluoroalkyl, or C1-C4 alkyl; R8 and R9 are independently selected from H, C1-C4 alkyl, C1-C4 alkyloxyalkyl, and halogen; R 10 is selected from the group consisting of C1 to C8 primary alkyl, C3 to C8 secondary alkyl, C3 to C8 cyclic secondary alkyl, and C7 to C14 secondary alicyclic alkyl; R 11 is a C2-C8 (hydroxy) alkylene moiety, R 12 is a tertiary alkyl acid cleavable group, and R 13 is a C3-C12 (alkyloxy) alkylene moiety; and further These repeat units collectively make up 100 mole % of the repeat units in said functionalized acrylic copolymer, wherein the repeat units of structure (I) range from about 0 mol % to about 20 mol %; the repeat units of structure (2) range from about 0 mol % to about 20 mol % of said acrylic copolymer; the repeat units of structure (3) range from about 5 mol % to about 55 mol % of said acrylic copolymer; the repeat units of structure (4) range from about 0 mol % to about 30 mol % of said acrylic copolymer; the repeat units of structure (5) range from about 15 mol % to about 55 mol % of said acrylic copolymer; the repeat units of structure (6) range from about 18 mol % to about 40 mol % of the acrylic copolymer; the repeat units of structure (7) range from about 0 mol % to about 40 mol % of said acrylic copolymer;

[0012] [ka] Component c) at least one novolac polymer; Component d) at least one photoacid generator (PAG); Component e) at least one base additive; Component f) at least one heterocyclic thiol compound; Component g) Organic spin-cast solvent.

[0013] The disclosed invention also relates to a method of coating the resist composition onto a substrate as part of a lithographic process.

[0014] 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 of the invention, serve to explain the principles of the disclosed invention. [Brief explanation of the drawings]

[0015] [Figure 1]Lithographic performance of comparative formulations. [Figure 2] Lithographic performance of Formulation 7. DETAILED DESCRIPTION OF THE INVENTION

[0016] It is to be understood that both the foregoing general description and the following detailed description are for purposes of explanation and illustration only, and are not intended to limit the invention as claimed. As used herein, unless specifically stated otherwise, the use of the singular includes the plural, and the singular means "at least one," and the use of "or" means "and / or." Furthermore, the use of the term "comprises" and other verb forms, such as "comprises," is not limiting. Furthermore, the use of terms such as "element" or "component" includes 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 indicated. 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.

[0017] The section headings used herein are for organizational purposes only and should not be construed as limiting the technical 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.

[0018] 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), cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, and the like), or 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, linear alkyls are understood to 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 indicated. Where the length of an alkyl group is specified differently from those described above, the above definition of alkyl still applies in that it encompasses all types of alkyl moieties described above, and structural considerations regarding the minimum carbon number for a given type of alkyl group still apply.

[0019] 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.

[0020] Halo or halide refers to a halogen, F, Cl, Br, or I, attached to an organic moiety by one bond.

[0021] 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.

[0022] 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, and the like). These fluoroalkyl moieties, if not fully fluorinated, may be substituted or unsubstituted as described below.

[0023] 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.

[0024] When referring herein to alkyl, alkyloxy, fluoroalkyl, fluoroalkyloxy moieties having a possible range of carbon atoms starting from C1, such as, as a non-limiting example, "C1-C20 alkyl" or "C1-C20 fluoroalkyl," this range includes those starting from C1 for linear alkyl, alkyloxy, fluoroalkyl, and fluoroalkyloxy, but only those starting from C3 for branched alkyl, branched alkyloxy, cycloalkyl, cycloalkyloxy, branched fluoroalkyl, and cyclic fluoroalkyl.

[0025] The term "alkylene" refers to a hydrocarbon group that can be linear, branched, or cyclic, having two or more points of attachment (e.g., methylene, ethylene, 1,2-isopropylene, 1,4-cyclohexylene, and the like, having two points of attachment; 1,1,1-substituted methanes, 1,1,2-substituted ethanes, 1,2,4-substituted cyclohexanes, and the like, having three points of attachment). Again, when specifying a range of possible carbon numbers, such as C1 to C20 as a non-limiting example, this range includes those starting at C1 for linear alkylene, but only those starting at C3 for branched alkylene or cycloalkylene. These alkylene moieties can be substituted or unsubstituted, as described below.

[0026] As used herein, the term solid components refers to components that are not solvent component g), i.e., in one embodiment, components a), b), c), d), e) and f).

[0027] 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-), and the like, and oligomeric materials such as di(ethyleneoxy)ethylene (-CH-CH-O-CH-CH-O-CH-CH-), di(propyleneoxy)propylene (-CH-CH-CH-O-CH-CH-CH-O-CH-CH-), and the like.

[0028] The term "aryl" or "aromatic group" refers to groups containing from 6 to 24 carbon atoms, including 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, such as alkyl, alkoxy, acyl, or aryl groups described above.

[0029] The term "Novolak" (also known as Novolac), when used herein without other modifications of structure, refers to novolak resins that are soluble in aqueous bases such as tetramethylammonium hydroxide and the like.

[0030] 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, 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(C6H5)4, HB(C6F5)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 photosensitive derivatives of trihalomethyl compounds and trihalomethyl heterocyclic compounds that can generate hydrogen halides, such as HBr or HCl.

[0031] In one of its aspects, the present invention is a positive-working, chemically amplified photosensitive composition comprising the following components a), b), c), d), e), f), and g): Component a) Component a) is at least one random copolymer having structure (A), where: the repeat units of structure (I) range from about 17 mole % to about 70 mole %; the repeat units of structure (II) range from 0 to about 70 mole %; the repeat units of structure (III) range from 0 to about 70 mole %; the sum of repeat units of structures (II) and (III) ranges from about 30 mole % to about 70 mole %; The repeat units of structure (IV) range from about 0 mole % to about 35 mole %, wherein the sum of the mole % of repeat units of structures (I), (II), (III) and (IV) does not exceed 100 mole %, or equals 100 mole % if no other type of repeat units are present; and R, R 14、 Ri2 and Ri 13 are independently selected from H or C1-C4 alkyl, and R, ... 10 , Ri 11 , and Ri 12 are individually selected from H, C1-C8 alkyl, C1-C4 alkoxy, phenyl, substituted phenyl, and mixtures thereof; Li1 is a C2-C6 alkylene moiety; ni, mi, oi, and pi are the number of repeat units of structures (I), (II), (III), and (IV), respectively; and further, the copolymer of structure (A) has a minimum dissolution rate of 500 Å / sec in 0.26 N tetramethylammonium hydroxide at 23° C. and does not contain any repeat units having acid-cleavable groups.

[0032] [ka] component b) Component b) is at least one acrylic copolymer component of structure (B) comprising repeating units selected from those having structures (1), (2), (3), (4), (5), (6), and (7), wherein R1, R2, R3, R4, R5, R6, and R7 are independently selected from H, F, C1-C4 perfluoroalkyl, or C1-C4 alkyl; R8 and R9 are independently selected from H, C1-C4 alkyl, C1-C4 alkyloxyalkyl, and halogen; R 10is selected from the group consisting of C1 to C8 primary alkyl, C3 to C8 secondary alkyl, C3 to C8 cyclic secondary alkyl, and C7 to C14 secondary alicyclic alkyl; R 11 is a C2-C8 (hydroxy) alkylene moiety, R 12 is a tertiary alkyl acid cleavable group, and R 13 is a C3-C12 (alkyloxy) alkylene moiety, and further These repeat units collectively make up 100 mole % of the repeat units in said functionalized acrylic copolymer, wherein the repeat units of structure (1) range from about 0 mol % to about 20 mol % of said acrylic copolymer; the repeat units of structure (2) range from about 0 mol % to about 20 mol % of said acrylic copolymer; the repeat units of structure (3) range from about 5 mol % to about 55 mol % of said acrylic copolymer; the repeat units of structure (4) range from about 0 mol % to about 30 mol % of said acrylic copolymer; the repeat units of structure (5) range from about 15 mol % to about 55 mol % of said acrylic copolymer; the repeat units of structure (6) range from about 18 mol % to about 40 mol % of the acrylic copolymer; The repeat units of structure (7) range from about 0 mole % to about 40 mole % of the acrylic copolymer.

[0033] [ka] Ingredient c) Component c) is at least one novolac polymer. ingredient d) Component d) is at least one photoacid generator (PAG). Component e) Component e) is at least one base additive. Component f) Component f) is at least one heterocyclic thiol compound. Ingredient g) Component g) is an organic spin-casting solvent.

[0034] A more detailed description of specific embodiments of these components follows: Component a) One aspect of the composition of the present invention is where component a) is a copolymer comprising repeating units of structures (I) and (II). Another aspect of this embodiment is where component a) is a copolymer comprising repeating units of structures (I) and (III).

[0035] Another aspect of the composition of the present invention is where component a) is a copolymer comprising repeating units of structures (I), (II) and (III).

[0036] Another aspect of the composition of the present invention is where component a) is a copolymer comprising repeating units of structures (I), (II) and (IV).

[0037] Another aspect of this embodiment is when component a) is a copolymer consisting of repeating units of structures (I), (III) and (IV).

[0038] Another aspect of the composition of the present invention is where component a) is a copolymer consisting of repeating units of structures (I), (II), (III) and (IV).

[0039] In another aspect of the compositions of the present invention, component a) described herein is one in which the repeat units of structure (I) are from about 17 mol % to about 65 mol %. In another aspect of this embodiment, this is from about 20 mol % to about 65 mol %. In one aspect of this embodiment, Ril is H. In another aspect, Ril is C1-C4 alkyl. In yet another aspect, Ril is methyl.

[0040] In another aspect of the compositions of the present invention, component a) described herein comprises a repeat unit of structure (II). In one aspect of this embodiment, Ri2 is H. In another aspect of this embodiment, Ri2 is C1-C4 alkyl. In yet another aspect, Ri2 is methyl.

[0041] Another aspect of the compositions of the present invention is where component a) described herein is one where repeat units of structure (III) are present. In one aspect of this embodiment, Ri 14 is H. In another aspect of this embodiment, Ri 14 is C1-C4 alkyl. In yet another aspect, Ri 14 is methyl.

[0042] Another aspect of the compositions of the present invention is where component a) described herein is one where repeat units of structure (IV) are present. In one aspect of this embodiment, Ri 13 is H. In another aspect of this embodiment, Ri 13 is C1-C4 alkyl. In yet another aspect, Ri 13 is methyl.

[0043] Another aspect of the compositions of the present invention is where component a) described herein has the structure (A-1).

[0044] [ka] Another aspect of the composition of the present invention is where component a) described herein has structure (A-2). In one aspect of this embodiment, the repeat units of structure (Ia) range from about 20 mol% to about 70 mol%. In another aspect of this embodiment, the repeat units of structure (Ia) range from about 30 mol% to about 70 mol%. In yet another aspect of this embodiment, the repeat units of structure (Ia) range from about 40 mol% to about 70 mol%. In yet another aspect, the repeat units of structure (Ia) range from about 50 mol% to about 70 mol%. In yet another aspect, the repeat units of structure (Ia) range from about 60 mol% to about 70 mol%. In one aspect of this embodiment, the repeat units of structure (Ia) are about 50 mol%. In another aspect, the repeat units of structure (Ia) are about 60 mol%.

[0045] [ka] Another aspect of the composition of the present invention is where component a) described herein has structure (A-3). In one aspect of this embodiment, the repeat units of structure (Ia) range from about 20 mol% to about 70 mol%. In another aspect of this embodiment, the repeat units of structure (Ia) range from about 30 mol% to about 70 mol%. In yet another aspect of this embodiment, the repeat units of structure (Ia) range from about 40 mol% to about 70 mol%. In yet another aspect, the repeat units of structure (Ia) range from about 50 mol% to about 70 mol%. In yet another aspect, the repeat units of structure (Ia) range from about 60 mol% to about 70 mol%. In one aspect of this embodiment, the repeat units of structure (Ia) are about 50 mol%. In another aspect, the repeat units of structure (Ia) are about 60 mol%.

[0046] [ka] Another aspect of the compositions of the present invention is where component a) described herein has structure (A-4). In another aspect of this embodiment, the repeat units of structure (Ia) range from about 17 mol% to about 70 mol% (preferably up to about 60 mol%), and the sum of the repeat units of structures (IIa) and (IIIa) range from about 40 mol% to about 60 mol%. In yet another aspect of this embodiment, the repeat units of structure (Ia) range from about 17 mol% to about 60 mol% (preferably up to about 55 mol%), and the sum of the repeat units of structures (IIa) and (IIIa) range from about 45 mol% to about 65 mol%. In yet another aspect, the repeat units of structure (Ia) range from about 17 mol% to about 50 mol%, and the sum of the repeat units of structures (IIa) and (IIIa) range from about 45 mol% to about 65 mol%. In yet another aspect, the repeat units of structure (Ia) range from about 17 mol% to about 40 mol%, and the sum of repeat units of structures (IIa) and (IIIa) range from about 45 mol% to about 65 mol%. In yet another aspect, the repeat units of structure (Ia) range from about 17 mol% to about 30 mol%, and the sum of repeat units of structures (IIa) and (IIIa) range from about 45 mol% to about 55 mol%. In yet another aspect, the repeat units of structure (Ia) range from about 17 mol% to about 30 mol%, and the sum of repeat units of structures (IIa) and (IIIa) range from about 45 mol% to about 50 mol%. In yet another aspect, the repeat units of structure (Ia) range from about 17 mol% to about 25 mol%, and the sum of the repeat units of structures (IIa) and (IIIa) range from about 45 mol% to about 50 mol%. In one aspect of this embodiment, the repeat units of structure (Ia) are about 25 mol%, and the sum of the repeat units of structures (IIa) and (IIIa) are about 45 mol%. In one aspect of this embodiment, (Ia) is about 25 mol%, (IIa) is about 10 mol%, (IIIa) is about 35 mol%, and (IVa) is about 30 mol%.Furthermore, in all of these embodiments having structure (A-4), the mole percent values ​​of repeat units having structures (Ia), (IIa), (IIIa), and (IVa) are selected within those ranges such that the sum of the mole percents equals but does not exceed 100 mole percent.

[0047] [ka] Another aspect of the compositions of the present invention is where component a) described herein has structure (A-5). In another aspect of this embodiment, the repeat units of structure (Ia) range from about 17 mol% to about 70 mol% (preferably up to about 60 mol%), and the repeat units of structure (IIIa) range from about 40 mol% to about 60 mol%. In yet another aspect of this embodiment, the repeat units of structure (Ia) range from about 17 mol% to about 60 mol% (preferably up to about 55 mol%), and the repeat units of structure (IIIa) range from about 45 mol% to about 65 mol%. In yet another aspect, the repeat units of structure (Ia) range from about 17 mol% to about 50 mol% and the repeat units of structure (IIIa) range from about 45 mol% to about 65 mol%. In yet another aspect, the repeat units of structure (Ia) range from about 17 mol% to about 40 mol%, and the repeat units of structure (IIIa) range from about 45 mol% to about 65 mol%. In yet another aspect, the repeat units of structure (Ia) range from about 17 mol% to about 30 mol%, and the repeat units of structure (IIIa) range from about 45 mol% to about 55 mol%. In yet another aspect, the repeat units of structure (Ia) range from about 17 mol% to about 30 mol%, and the repeat units of structure (IIIa) range from about 45 mol% to about 50 mol%. In yet another aspect, the repeat units of structure (Ia) range from about 17 mol% to about 25 mol%, and the repeat units of structure (IIIa) range from about 45 mol% to about 50 mol%. In one aspect of this embodiment, the repeat units of structure (Ia) are about 20 mol % and the repeat units of structure (IIIa) are about 50 mol %. In one aspect of this embodiment, (Ia) is about 20 mol %, (IIIa) is about 50 mol %, and (IVa) is about 30 mol %. Furthermore, in all of these embodiments having structure (A-5), the mole % values ​​of the repeat units having structures (Ia), (IIIa), and (IVa) are selected within those ranges such that the sum of the mole % values ​​equals but does not exceed 100 mol %.

[0048]

change

[0049] [ka] Another aspect of the compositions of the present invention is where component a) described herein has structure (A-7). In another aspect of this embodiment, the repeat units of structure (Ia) range from about 17 mol% to about 70 mol% (preferably up to about 60 mol%), and the repeat units of structure (IIIa) range from about 40 mol% to about 60 mol%. In yet another aspect of this embodiment, the repeat units of structure (Ia) range from about 17 mol% to about 60 mol% (preferably up to about 55 mol%), and the repeat units of structure (IIIa) range from about 45 mol% to about 65 mol%. In yet another aspect, the repeat units of structure (Ia) range from about 17 mol% to about 50 mol% and the repeat units of structure (IIIa) range from about 45 mol% to about 65 mol%. In yet another aspect, the repeat units of structure (Ia) range from about 17 mol% to about 40 mol%, and the repeat units of structure (IIIa) range from about 45 mol% to about 65 mol%. In yet another aspect, the repeat units of structure (Ia) range from about 17 mol% to about 30 mol%, and the repeat units of structure (IIIa) range from about 45 mol% to about 55 mol%. In yet another aspect, the repeat units of structure (Ia) range from about 17 mol% to about 30 mol%, and the repeat units of structure (IIIa) range from about 45 mol% to about 50 mol%. In yet another aspect, the repeat units of structure (Ia) range from about 17 mol% to about 25 mol%, and the repeat units of structure (IIIa) range from about 45 mol% to about 50 mol%. In one aspect of this embodiment, the repeating units of structure (Ia) are about 20 mol % and the repeating units of structure (IIIa) are about 50 mol %. In one aspect of this embodiment, structure (Ia) is about 20 mol %, structure (IIIa) is about 50 mol %, and structure (IVb) is about 30 mol %. Furthermore, in all of these embodiments having structure (A-5), the mole % values ​​of the repeating units having structures (Ia), (IIIa), and (IVa) are selected within those ranges such that the sum of the mole % values ​​equals but does not exceed 100 mol %.

[0050]

change

[0051] [ka] Another aspect of the compositions of the present invention is where component a) described herein has structure (A-9). In another aspect of this embodiment, the repeat units of structure (Ia) range from about 17 mol% to about 70 mol% (preferably up to about 60 mol%), and the repeat units of structure (IIa) range from about 40 mol% to about 60 mol%. In yet another aspect of this embodiment, the repeat units of structure (Ia) range from about 17 mol% to about 60 mol% (preferably up to about 55 mol%), and the repeat units of structure (IIa) range from about 45 mol% to about 65 mol%. In yet another aspect, the repeat units of structure (Ia) range from about 17 mol% to about 50 mol% and the repeat units of structure (IIa) range from about 45 mol% to about 65 mol%. In yet another aspect, the repeat units of structure (Ia) range from about 17 mol% to about 40 mol%, and the repeat units of structure (IIa) range from about 45 mol% to about 65 mol%. In yet another aspect, the repeat units of structure (Ia) range from about 17 mol% to about 30 mol%, and the repeat units of structure (IIa) range from about 45 mol% to about 55 mol%. In yet another aspect, the repeat units of structure (Ia) range from about 17 mol% to about 30 mol%, and the repeat units of structure (IIa) range from about 45 mol% to about 50 mol%. In yet another aspect, the repeat units of structure (Ia) range from about 17 mol% to about 25 mol%, and the repeat units of structure (IIa) range from about 45 mol% to about 50 mol%. In one aspect of this embodiment, the repeat units of structure (Ia) are about 20 mole % and the repeat units of structure (IIa) are about 45 mole %. Further, in all of these embodiments having structure (A-5), the mole % values ​​of the repeat units having structures (Ia), (IIIa), and (IVa) are selected within those ranges such that the sum of the mole % values ​​equals but does not exceed 100 mole %.

[0052] [ka] In another aspect of the compositions of the present invention, component a) described herein ranges from about 10% to about 25% by weight of total solids. In another aspect of this embodiment, it ranges from about 15% to about 22% by weight of total solids. In yet another aspect, it ranges from about 17% to about 22% by weight of total solids. In yet another aspect, it ranges from about 18% to about 21% by weight of total solids. In yet another aspect, it ranges from about 19% to about 21% by weight. In yet another aspect, it is about 20% by weight.

[0053] Another aspect of the compositions of the present invention is when component a) described herein is one of these copolymers.

[0054] Another aspect of the compositions of the present invention is where component a) described herein is a mixture of at least two different of these copolymers.

[0055] component b) In another aspect of the compositions of the present invention, component b) described herein ranges from about 20% to about 65% by weight of total solids. In another aspect of this embodiment, this ranges from about 25% to about 60% by weight of total solids. In another aspect of this embodiment, this ranges from about 30% to about 55% by weight of total solids. In another aspect of this embodiment, this ranges from about 30% to about 50% by weight of total solids. In another aspect of this embodiment, this ranges from about 30% to about 45% by weight of total solids. In another aspect of this embodiment, this ranges from about 30% to about 40% by weight of total solids. In another aspect of this embodiment, this ranges from about 32% to about 38% by weight of total solids. In another aspect of this embodiment, this ranges from about 33% to about 37% by weight of total solids. In another aspect of this embodiment, this ranges from about 34% to about 36% by weight of total solids, and in another aspect of this embodiment, this is about 35% by weight of total solids.

[0056] Another aspect of the compositions of the present invention is where component b) described herein is a single copolymer of structure (B).

[0057] Another aspect of the compositions of the present invention is where component b) described herein is at least two different copolymers of structure (B).

[0058] Another aspect of the compositions of the present invention is where component b) described herein comprises at least one copolymer of Structure (B), which contains from about 5 mole % to about 20 mole % of repeat units of Structure (1).

[0059] Another aspect of the compositions of the present invention is where component b) described herein comprises at least one copolymer of structure (B), which contains from about 5 mole % to about 20 mole % of repeat units of structure (7).

[0060] In another aspect of the compositions of the present invention, component b) described herein comprises at least one copolymer of Structure (B), wherein the repeat units of Structure (1) range from about 5 mol % to about 20 mol % and the repeat units of Structure (7) range from about 5 mol % to about 20 mol %.

[0061] In another aspect of the compositions of the present invention, component b) described herein comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from about 5 mol% to about 10 mol% repeating units of Structure (1), from about 15 mol% to about 20 mol% repeating units of Structure (3), from about 25 mol% to about 35 mol% repeating units of Structure (5), and from about 40 mol% to about 50 mol% repeating units of Structure (6).

[0062] In another aspect of the compositions of the present invention, component b) described herein comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from about 5 mol% to about 15 mol% repeating units of Structure (1), from about 15 mol% to about 25 mol% repeating units of Structure (3), from about 35 mol% to about 45 mol% repeating units of Structure (5), and from about 25 mol% to about 35 mol% repeating units of Structure (6).

[0063] In another aspect of the compositions of the present invention, component b) described herein comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from about 5 mol% to about 10 mol% repeating units of Structure (1), from about 15 mol% to about 25 mol% repeating units of Structure (3), from about 45 mol% to about 55 mol% repeating units of Structure (5), and from about 15 mol% to about 25 mol% repeating units of Structure (6).

[0064] In another aspect of the compositions of the present invention, component b) described herein comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from about 5 mol% to about 10 mol% repeating units of Structure (1), from about 12 mol% to about 22 mol% repeating units of Structure (3), from about 20 mol% to about 35 mol% repeating units of Structure (5), from about 25 mol% to about 40 mol% repeating units of Structure (6), and from about 5 mol% to about 15 mol% repeating units of Structure (7).

[0065] In another aspect of the compositions of the present invention, component b) described herein comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from about 12 mol% to about 22 mol% repeating units of Structure (3), from about 30 mol% to about 40 mol% repeating units of Structure (5), from about 25 mol% to about 40 mol% repeating units of Structure (6), and from about 5 mol% to about 15 mol% repeating units of Structure (7).

[0066] In another aspect of the compositions of the present invention, component b) described herein comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from about 5 mol% to about 8 mol% repeating units of Structure (1), from about 10 mol% to about 17 mol% repeating units of Structure (3), from about 30 mol% to about 40 mol% repeating units of Structure (5), from about 25 mol% to about 40 mol% repeating units of Structure (6), and from about 5 mol% to about 15 mol% repeating units of Structure (7).

[0067] In another aspect of the compositions of the present invention, component b) described herein comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from about 5 mol% to about 7.5 mol% repeating units of Structure (1), from about 10 mol% to about 17 mol% repeating units of Structure (3), from about 30 mol% to about 40 mol% repeating units of Structure (5), from about 25 mol% to about 40 mol% repeating units of Structure (6), and from about 5 mol% to about 15 mol% repeating units of Structure (7).

[0068] In another aspect of the compositions of the present invention, component b) described herein comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from about 5 mol% to about 15 mol% repeating units of Structure (1), from about 5 mol% to about 15 mol% repeating units of Structure (3), from about 30 mol% to about 40 mol% repeating units of Structure (5), from about 25 mol% to about 40 mol% repeating units of Structure (6), and from about 5 mol% to about 15 mol% repeating units of Structure (7).

[0069] In another aspect of the compositions of the present invention, component b) described herein comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from about 5 mol% to about 15 mol% repeating units of Structure (1), from about 20 mol% to about 35 mol% repeating units of Structure (3), from about 30 mol% to about 40 mol% repeating units of Structure (5), from about 15 mol% to about 25 mol% repeating units of Structure (6), and from about 5 mol% to about 15 mol% repeating units of Structure (7).

[0070] In another aspect of the compositions of the present invention, component b) described herein comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from about 5 mol% to about 15 mol% repeating units of Structure (1), from about 20 mol% to about 30 mol% repeating units of Structure (3), from about 35 mol% to about 45 mol% repeating units of Structure (5), from about 15 mol% to about 25 mol% repeating units of Structure (6), and from about 5 mol% to about 15 mol% repeating units of Structure (7).

[0071] In another aspect of the compositions of the present invention, component b) described herein comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from about 7 mol% to about 18 mol% repeating units of Structure (1), from about 15 mol% to about 25 mol% repeating units of Structure (3), from about 25 mol% to about 35 mol% repeating units of Structure (5), from about 15 mol% to about 25 mol% repeating units of Structure (6), and from about 5 mol% to about 15 mol% repeating units of Structure (7). In another aspect, this comprises only one copolymer of Structure (B).

[0072] In another aspect of the compositions of the present invention, component b) described herein comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from about 7 mol% to about 15 mol% repeating units of Structure (1), from about 25 mol% to about 35 mol% repeating units of Structure (3), from about 25 mol% to about 35 mol% repeating units of Structure (5), and from about 25 mol% to about 35 mol% repeating units of Structure (6).

[0073] In another aspect of the compositions of the present invention, component b) described herein comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from about 7 mol% to about 15 mol% repeating units of Structure (1), from about 27 mol% to about 45 mol% repeating units of Structure (3), from about 30 mol% to about 40 mol% repeating units of Structure (5), and from about 15 mol% to about 25 mol% repeating units of Structure (6).

[0074] In another aspect of the compositions of the present invention, component b) described herein comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from about 7 mol% to about 15 mol% repeating units of Structure (1), from about 15 mol% to about 25 mol% repeating units of Structure (3), from about 35 mol% to about 45 mol% repeating units of Structure (5), and from about 25 mol% to about 35 mol% repeating units of Structure (6).

[0075] In another aspect of the compositions of the present invention, component b) described herein comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from about 7 mol% to about 15 mol% repeating units of Structure (1), from about 20 mol% to about 37 mol% repeating units of Structure (3), from about 30 mol% to about 45 mol% repeating units of Structure (5), and from about 20 mol% to about 30 mol% repeating units of Structure (6).

[0076] In another aspect of the compositions of the present invention, component b) described herein comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from about 7 mol% to about 15 mol% repeating units of Structure (1), from about 20 mol% to about 30 mol% repeating units of Structure (3), from about 30 mol% to about 45 mol% repeating units of Structure (5), and from about 20 mol% to about 35 mol% repeating units of Structure (6).

[0077] In another aspect of the compositions of the present invention, component b) described herein comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from about 10 mol% to about 20 mol% repeating units of Structure (1), from about 20 mol% to about 30 mol% repeating units of Structure (3), from about 30 mol% to about 45 mol% repeating units of Structure (5), and from about 20 mol% to about 35 mol% repeating units of Structure (6).

[0078] In another aspect of the compositions of the present invention, component b) described herein comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from about 15 mol% to about 20 mol% repeating units of Structure (1), from about 15 mol% to about 27 mol% repeating units of Structure (3), from about 30 mol% to about 45 mol% repeating units of Structure (5), and from about 20 mol% to about 35 mol% repeating units of Structure (6).

[0079] In another aspect of the compositions of the present invention, component b) described herein comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from about 12 mol% to about 20 mol% repeating units of Structure (1), from about 17 mol% to about 30 mol% repeating units of Structure (3), from about 30 mol% to about 45 mol% repeating units of Structure (5), and from about 20 mol% to about 35 mol% repeating units of Structure (6).

[0080] In another aspect of the compositions of the present invention, component b) described herein comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from about 12 mol% to about 20 mol% repeating units of Structure (1), from about 15 mol% to about 20 mol% repeating units of Structure (3), from about 30 mol% to about 45 mol% repeating units of Structure (5), and from about 20 mol% to about 35 mol% repeating units of Structure (6).

[0081] In another aspect of the compositions of the present invention, component b) described herein comprises a second copolymer of Structure (B), wherein at least one of said copolymers consists of from about 5 mol% to about 15 mol% repeating units of Structure (1), from about 15 mol% to about 25 mol% repeating units of Structure (3), from about 35 mol% to about 45 mol% repeating units of Structure (5), and from about 25 mol% to about 35 mol% repeating units of Structure (6).

[0082] Another aspect of the compositions of the present invention is where component b) described herein is a copolymer of only one type of structure (B).

[0083] Another aspect of the compositions of the present invention is where component b) described herein comprises a second, different copolymer of structure (B).

[0084] Another aspect of the compositions of the invention described herein is where in component b), the repeating units of structure (1), when present, have either structure (1a) or (1b).

[0085] [ka] Another aspect of the compositions of the invention described herein is that in component b), the repeating unit of structure (3) is structure (3a) or (3b):

[0086] [ka] and The repeating unit of structure (5) is structure (5a) or (5b):

[0087] [ka] and The repeating unit of structure (7), when present, may be structure (7a) or (7b):

[0088] [ka] and The repeating unit of structure (6) is structure (6a), (6b), (6c) or (6d):

[0089] [ka] This is the case when the device has either of the following:

[0090] Ingredient c) In another aspect of the composition of the present invention, the novolac polymer, component c), described herein, is present in a range of about 20% to about 65% by weight of total solids. In another aspect of this embodiment, the novolac polymer is present in a range of about 25% to about 60% by weight of total solids. In another aspect of this embodiment, the novolac polymer is present in a range of about 30% to about 55% by weight of total solids. In another aspect of this embodiment, the novolac polymer is present in a range of about 35% to about 55% by weight of total solids. In another aspect of this embodiment, the novolac polymer is present in a range of about 35% to about 50% by weight of total solids. In another aspect of this embodiment, the novolac polymer is present in a range of about 30% to about 55% by weight of total solids. In another aspect of this embodiment, the novolac polymer ranges from about 30% to about 50% by weight of total solids. In another aspect of this embodiment, the novolac polymer ranges from about 35% to about 50% by weight of total solids. In another aspect of this embodiment, the novolac polymer ranges from about 35% to about 50% by weight of total solids. In another aspect of this embodiment, the novolac polymer ranges from about 38% to about 48% by weight of total solids. In another aspect of this embodiment, the novolac polymer ranges from about 39% to about 47% by weight of total solids. In another aspect of this embodiment, the novolac polymer ranges from about 40% to about 46% by weight of total solids. In another aspect of this embodiment, the novolac polymer ranges from about 41% to about 45% by weight of total solids. In another aspect of this embodiment, the novolac polymer ranges from about 42% to about 45% by weight of total solids. In another aspect of this embodiment, the novolac polymer ranges from about 43% to about 45% by weight of total solids. In another aspect of this embodiment, the novolac polymer is about 44% by weight of total solids.

[0091] In another aspect of the compositions of the invention described herein, in component c), the novolac-based resin component comprises repeating units of structure (N), where Ra1, Ra2, and Ra3 are each independently (i) hydrogen, (ii) unsubstituted C1-C4 alkyl, (iii) 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, Ra1 and Ra2 are each hydrogen, and Ra3 is -CH3. In yet another aspect of this embodiment, repeat unit (N) has the structure (NA). In another aspect of this embodiment, the novolac-based resin component further comprises one or more repeat units of 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 one specific embodiment of this embodiment, structure (NB) has the more specific structure (NC).

[0092] [ka] ingredient d) Another aspect of the compositions of the invention described herein is where, in component d), the photoacid generator (PAG) is any compound capable of photogenerating an acid (also known as 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. These include, 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 pentasubstituted 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, e.g., HBr or HCl. In one aspect of this embodiment, the PAG can 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. 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. In another aspect of this embodiment, it has the structure (PA), where R 3p is a fluoroalkyl, alkyl, or aryl moiety, and R 4p is H, an alkyl, oxyalkyl, thioalkyl, or aryl moiety. Another aspect of the compositions of the invention described herein is where component d), the photoacid generator (PAG) component, comprises 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl trifluoromethanesulfonate (NIT PAG).

[0093] In another aspect of the compositions of the invention, the photoacid generator, component d), described herein, is present in a range of about 0.1% to about 2% by weight of total solids. In another aspect of this embodiment, the photoacid generator is present in a range of about 0.15% to about 1.8% by weight of total solids. In another aspect of this embodiment, the photoacid generator is present in a range of about 0.2% to about 1.6% by weight of total solids. In another aspect of this embodiment, the photoacid generator is present in a range of about 0.2% to about 1.5% by weight of total solids. In another aspect of this embodiment, the photoacid generator is present in a range of about 0.25% to about 1.4% by weight of total solids. In another aspect of this embodiment, the photoacid generator is present in a range of about 0.25% to about 1.3% by weight of total solids. In another aspect of this embodiment, the photoacid generator is present in a range of about 0.30% to about 1.2% by weight of total solids. In another aspect of this embodiment, the photoacid generator ranges from about 0.30% to about 1.1% by weight of total solids. In another aspect of this embodiment, the photoacid generator ranges from about 0.35% to about 1.0% by weight of total solids. In another aspect of this embodiment, the photoacid generator ranges from about 0.40% to about 0.8% by weight of total solids. In another aspect of this embodiment, the photoacid generator ranges from about 0.40% to about 0.9% by weight of total solids.

[0094] In another aspect of this embodiment, the photoacid generator ranges from about 0.40% to about 0.7% by weight of total solids. In another aspect of this embodiment, the photoacid generator ranges from about 0.40% to about 0.7% by weight of total solids. In another aspect of this embodiment, the photoacid generator ranges from about 0.40% to about 0.60% by weight of total solids. In another aspect of this embodiment, the photoacid generator ranges from about 0.45% to about 0.55% by weight of total solids. In another aspect of this embodiment, the photoacid generator is about 0.5% by weight of total solids.

[0095] [ka] Component e) Another aspect of the compositions of the invention described herein is component e), the base additive, which may include, but is not limited to, a basic material or combination of materials, such as, but not limited to, a base additive having a boiling point above 100° C. at atmospheric pressure and a pK of at least 1. a Such acid quenchers include, but are not limited to, amine compounds having structures (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj), (XIIk), and (XIl), 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.

[0096] [ka] Component e) can also be selected from a basic material or mixture of materials that is, but is not limited to, a tetraalkylammonium or trialkylammonium salt of a dicarboxylic acid, or a mixture 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 dicarboxylic acids suitable for these salts are oxalic acid, maleic acid, malonic acid, fumaric acid, phthalic acid, and the like. Structures (XIIma)-(XIImd) provide general structures of such materials, where Rqa, Rqb, Rqc, and Rqd are independently C4-C8 alkyl groups, and Rqe is a valence bond, an arylene moiety, a C1-C4 alkylene moiety, or an alkenyl moiety (-C(Rqf)=C(Rqg)-, where Rqf and Rqg are independently H or C1-C4 alkyl). Structure (XIIme) provides a specific example of such a material.

[0097] [ka] In another aspect of the compositions of the present invention, the base additive, component e), described herein, ranges from about 0.0001% to about 0.010% by weight of total solids. In another aspect of this embodiment, the base additive ranges from about 0.0015% to about 0.0090% by weight of total solids. In another aspect of this embodiment, the base additive ranges from 0.0020% to about 0.0085% by weight of total solids. In another aspect of this embodiment, the base additive ranges from 0.0025% to about 0.0080% by weight of total solids. In another aspect of this embodiment, the base additive ranges from 0.0030% to about 0.0075% by weight of total solids. In another aspect of this embodiment, the base additive ranges from 0.0035% to about 0.0070% by weight of total solids. In another aspect of this embodiment, the base additive ranges from 0.0040% to about 0.0060% by weight of total solids. In another aspect of this embodiment, the base additive ranges from 0.0045% to about 0.0055% by weight of total solids. In another aspect of this embodiment, the base additive is about 0.0050% by weight of total solids.

[0098] Component f) Another aspect of the compositions of the invention described herein is component f), a heterocyclic thiol compound selected from general formulas (H1), (H2), and (H3). 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; Rt1, Rt2, and Rt3 are independently selected from the group consisting of H, 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.

[0099] Structures (1t) through (19t) show specific examples of suitable heterocyclic thiols that may be used in the compositions of the present invention:

[0100] [ka] In another aspect of the compositions of the invention, the heterocyclic thiol compound, component f), described herein, is present in an amount ranging from about 0.01% to about 1.5% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound is present in an amount ranging from about 0.04% to about 1.2% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound is present in an amount ranging from about 0.08% to about 1.1% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound is present in an amount ranging from about 0.09% to about 1.0% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound is present in an amount ranging from about 0.10% to about 0.9% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound is present in an amount ranging from 0.15% to about 0.8% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.20% to about 0.75% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.25% to about 0.74% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.74% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.73% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.72% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.71% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.70% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.69% by weight of total solids, hi another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.68% by weight of total solids.In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.67% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.66% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.65% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.64% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.63% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.62% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.61% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.60% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.59% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.58% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.57% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.56% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.55% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.54% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.53% by weight of total solids, hi another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.52% by weight of total solids.In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.51% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.50% 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 0.48% 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 0.46% 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 ranges from 0.30% to about 0.39% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.38% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.30% to about 0.37% by weight of total solids, hi another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.31% to about 0.36% by weight of total solids.In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.32% to about 0.36% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.32% to about 0.36% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.33% to about 0.36% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound ranges from 0.34% to about 0.36% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound is about 0.35% by weight of total solids.

[0101] In another aspect of the compositions of the present invention, the heterocyclic thiol compound, component f), described herein, is present in a range of about 0.001% 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 0.010% 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 0.1% 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 0.2% 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 0.3% to about 1.5% by weight of total solids. In another aspect of this embodiment, the heterocyclic thiol compound is present in a range of 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.

[0102] Another aspect of the invention described herein is that the organic spin-casting solvent component of component g) 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 ether ... In one aspect of this embodiment, the organic spin-casting solvent comprises one or more of the following: butyl 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 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; 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 comprises PGMEA in the range of about 55% to about 80% by weight, 3-methoxybutyl acetate in the range of about 5% to about 20% by weight, and gamma-butyrolactone in the range of about 1% to about 2% by weight, wherein the sum of the weight percentages of these individual components equals 100% by weight.

[0103] Optional Ingredients In one embodiment of the composition of the present invention described above, it further comprises 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, 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.

[0104] The composition of the present invention has a weight percent in solution defined by the total weight of all solid components a), b), c), d), e), f), and optional solid components such as surfactants, relative to the sum of these solid components and the organic spin-casting solvent, component g), which in one embodiment can range from about 20% to about 60% by weight. In another embodiment, this ranges from about 30% to about 55% by weight. In another embodiment, this ranges from about 35% to about 55% by weight. In yet another embodiment, this ranges from about 40% to about 55% by weight. In another embodiment, this ranges from about 50% by weight.

[0105] Another aspect of the present invention is a method of coating a substrate with any of the inventive compositions described herein. The coating method can be any method known in the art, such as spin coating, spray coating, and blade coating. Another aspect of the present invention is the use of the inventive compositions described herein to form a photoresist.

[0106] Another aspect of the invention is a method of imaging a resist comprising the steps of: i) coating any one of the compositions of the present invention 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; The method includes:

[0107] 61. A method of imaging a resist, comprising the steps of: ia) coating any one of the compositions of the present invention 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; The method comprising: [Example]

[0108] Described below are more specific embodiments of the present disclosure and experimental results supporting such embodiments. 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.

[0109] 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.

[0110] chemicals Unless otherwise stated, all chemicals were obtained from Millipore Sigma.

[0111] Coating 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 coated with 5,000 Å of silicon dioxide, 250 Å of tantalum nitride, and 3,500 Å of Cu (PVD-deposited).

[0112] 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.

[0113] Image formation: These wafers were exposed on a SUSS MA200 CC 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 photoresist images were examined using a Hitachi S4700 or AMRAY 4200L electron microscope.

[0114] material Synthesis of random copolymer of structure (B) The following example shows the synthesis of random copolymers of structure (B) used as component b) in the formulations tested. Each associated structure indicates the proportion of repeat units in the isolated copolymer in mole percent.

[0115] Synthesis example of copolymer of structure (B) Example 1 (CPB-1)

[0116] [ka] In this example, 4.32 g of acrylic acid, 24.67 g of benzyl methacrylate, 34.60 g of hydroxypropyl methacrylate, and 46.14 g of tert-butyl acrylate were mixed in 207.1 g of PGME solvent. The polymerization reaction proceeded for 18 hours at 90°C under nitrogen in the presence of 1.84 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in deionized water. The polymer solids were washed and dried under vacuum at 45°C to yield 107.3 g (98% yield) of polymer with a weight average molecular weight of 16,138 daltons and a number average molecular weight of 8,207 daltons.

[0117] Synthesis example of copolymer of structure (B) Example 2 (CPB-2)

[0118] [ka] In this example, 7.2 g of acrylic acid, 35.24 g of benzyl methacrylate, 57.67 g of hydroxypropyl methacrylate, and 38.45 g of tert-butyl acrylate were mixed in 138.56 g of PGME solvent. The polymerization reaction proceeded for 18 hours at 90°C under nitrogen in the presence of 1.64 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in deionized water. The polymer solids were washed and dried under vacuum at 45°C to yield 135.8 g (98% yield) of polymer with a weight average molecular weight of 39,998 Daltons and a number average molecular weight of 16,987 Daltons.

[0119] Synthesis Example of Copolymer of Structure (B) Example 3 (CPB-3)

[0120] [ka] In this example, 7.2 g of acrylic acid, 35.24 g of benzyl methacrylate, 72.09 g of hydroxypropyl methacrylate, and 25.63 g of tert-butyl acrylate were mixed in 140.56 g of PGME solvent. The polymerization reaction proceeded for 18 hours at 90°C under nitrogen in the presence of 1.64 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in deionized water. The polymer solids were washed and dried under vacuum at 45°C to yield 137.4 g (98% yield) of polymer with a weight average molecular weight of 32,439 Daltons and a number average molecular weight of 13,090 Daltons.

[0121] Synthesis Example of Copolymer of Structure (B) Example 4 (CPB-4)

[0122] [ka] In this example, 2.7 g of acrylic acid, 6.5 g of methoxyethyl acrylate, 15.4 g of benzyl methacrylate, 21.6 g of hydroxypropyl methacrylate, and 24.9 g of tert-butyl methacrylate were mixed in 135.2 g of PGME solvent. The polymerization reaction proceeded for 18 hours at 90°C under nitrogen in the presence of 1.6 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in deionized water. The white polymer solid was washed and dried under vacuum at 45°C to give 70.3 g (99% yield) of polymer with a weight average molecular weight of 17,153 daltons and a number average molecular weight of 8,707 daltons.

[0123] Synthesis Example of Copolymer of Structure (B) Example 5 (CPB-5)

[0124] [ka] In this example, 7.16 g of methoxyethyl acrylate, 15.86 g of benzyl methacrylate, 25.23 g of hydroxypropyl methacrylate, and 32.78 g of 1-ethylcyclopentyl methacrylate (Osaka Organic Chemical Industry Co., Ltd., Osaka, Japan) were mixed in 152.6 g of PGME solvent. The polymerization reaction proceeded for 18 hours at 90°C under nitrogen in the presence of 1.2 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in deionized water. The polymer solids were washed and dried under vacuum at 45°C to yield 79.3 g (98% yield) of polymer with a weight-average molecular weight of 17,985 daltons and a number-average molecular weight of 10,278 daltons.

[0125] Synthesis Example of Copolymer of Structure (B) Example 6 (CPB-6)

[0126] [ka] 4.32 g of acrylic acid, 14.32 g of methoxyethyl acrylate, 22.91 g of benzyl methacrylate, 50.46 g of hydroxypropyl methacrylate, and 63.75 g of 1-ethylcyclopentyl methacrylate were mixed in 158.5 g of PGME solvent. The polymerization reaction proceeded for 18 hours at 90°C under nitrogen in the presence of 2.71 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in deionized water. The polymer solids were washed and dried under vacuum at 45°C, yielding 153.34 g (98.5% yield) of polymer with a GPC (polystyrene standard) weight average molecular weight of 17,103 daltons and a number average molecular weight of 8316 daltons.

[0127] Synthesis Example of Copolymer of Structure (B) Example 7 (CPB-7)

[0128] [ka] In this example, 5.76 g of acrylic acid, 14.32 g of methoxyethyl acrylate, 19.38 g of benzyl methacrylate, 50.46 g of hydroxypropyl methacrylate, and 63.75 g of 1-ethylcyclopentyl methacrylate were mixed in 156.4 g of PGME solvent. The polymerization reaction proceeded for 18 hours at 90°C under nitrogen in the presence of 2.71 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in deionized water. The polymer solids were washed and dried under vacuum at 45°C, yielding 150.2 g (97.7% yield) of polymer with a GPC (polystyrene standard) weight average molecular weight of 15,557 daltons and a number average molecular weight of 7795 daltons.

[0129] Synthesis Example of Copolymer of Structure (B) Example 8 (CPB-8)

[0130] [ka] In this example, 7.2 g of acrylic acid, 14.31 g of methoxyethyl acrylate, 42.29 g of benzyl methacrylate, 50.46 g of hydroxypropyl methacrylate, and 36.43 g of 1-ethylcyclopentyl methacrylate were mixed in 150.7 g of PGME solvent. The polymerization reaction proceeded for 18 hours at 90°C under nitrogen in the presence of 1.97 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in deionized water. The polymer solids were washed and dried under vacuum at 45°C, yielding 147.2 g (97.7% yield) of polymer with a GPC (polystyrene standard) weight average molecular weight of 35,913 daltons and a number average molecular weight of 16,541 daltons.

[0131] Synthesis Example of Copolymer of Structure (B) Example 9 (CPB-9)

[0132] [ka] In this example, 7.93 g of acrylic acid, 14.31 g of methoxyethyl acrylate, 40.53 g of benzyl methacrylate, 50.46 g of hydroxypropyl methacrylate, and 36.43 g of 1-ethylcyclopentyl methacrylate were mixed in 149.66 g of PGME solvent. The polymerization reaction proceeded for 18 hours at 90°C under nitrogen in the presence of 2.46 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in deionized water. The polymer solids were washed and dried under vacuum at 45°C to yield 146.7 g (98% yield) of polymer with a GPC (polystyrene standard) weight average molecular weight of 36,037 daltons and a number average molecular weight of 15,251 daltons.

[0133] Synthesis Example of Copolymer of Structure (B) Example 10 (CPB-10)

[0134] [ka] In this example, 8.65 g of acrylic acid, 14.31 g of methoxyethyl acrylate, 38.77 g of benzyl methacrylate, 50.46 g of hydroxypropyl methacrylate, and 36.43 g of 1-ethylcyclopentyl methacrylate were mixed in 148.6 g of PGME solvent. The polymerization reaction proceeded for 18 hours at 90°C under nitrogen in the presence of 2.30 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in deionized water. The polymer solids were washed and dried under vacuum at 45°C, yielding 145.6 g (98% yield) of polymer with a GPC (polystyrene standard) weight average molecular weight of 26,086 daltons and a number average molecular weight of 12,854 daltons.

[0135] Synthesis Example of Copolymer of Structure (B) Example 11 (CPB-11)

[0136] [ka] In this example, 10.09 g of acrylic acid, 14.31 g of methoxyethyl acrylate, 35.24 g of benzyl methacrylate, 50.46 g of hydroxypropyl methacrylate, and 36.43 g of 1-ethylcyclopentyl methacrylate were mixed in 146.5 g of PGME solvent. The polymerization reaction proceeded for 18 hours at 90° C. under nitrogen in the presence of 2.30 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in deionized water. The polymer solids were washed and dried under vacuum at 45° C. to yield 144.6 g (98.7% yield) of polymer with a GPC (polystyrene standard) weight average molecular weight of 30,206 daltons and a number average molecular weight of 12,269 daltons.

[0137] Synthesis Example of Copolymer of Structure (B) Example 12 (CPB-12)

[0138] [ka] In this example, 7.28 g of acrylic acid, 53.60 g of benzyl methacrylate, 43.32 g of hydroxypropyl methacrylate, and 38.83 g of tert-butyl acrylate were mixed in 141 g of PGMEA solvent. The polymerization reaction proceeded for 20 hours at 90°C under nitrogen in the presence of 2.46 g of AIBN. After cooling to room temperature, the reaction mixture was used for further use. Theoretically, this would allow the final polymer product to have a weight percent solids of 50 wt% in the spin-casting solvent PGMEA, which was used directly for the preparation of the formulation solution. A small amount (approximately 2 g) of the product was precipitated in deionized water. The polymer solids from the precipitation were washed and dried under vacuum at 50°C. The vacuum-dried product was characterized by GPC (polystyrene standard). The measured weight average molecular weight was 28,661 daltons, and the number average molecular weight was 10,293 daltons.

[0139] Synthesis Example of Copolymer of Structure (B) Example 13 (CPB-13)

[0140] [ka] In this example, 7.93 g of acrylic acid, 59.95 g of benzyl methacrylate, 50.49 g of hydroxypropyl methacrylate, and 36.45 g of 1-ethylcyclopentyl methacrylate were mixed in 158 g of PGMEA solvent. The polymerization reaction proceeded for 20 hours at 90°C under nitrogen in the presence of 2.46 g of AIBN. After cooling to room temperature, the reaction mixture was used for further use. Theoretically, this would allow the final polymer product to have a weight percent solids of 50 wt% in the spin-casting solvent PGMEA, which was used directly to prepare the formulations. A small amount (approximately 2 g) of the product was precipitated in deionized water. The polymer solids from the precipitation were washed and dried under vacuum at 50°C. The vacuum-dried product was characterized by GPC (polystyrene standard). The measured weight average molecular weight was 32,272 daltons and the number average molecular weight was 13,253 daltons.

[0141] Synthesis Example of Copolymer of Structure (B) Example 14 (CPB-14)

[0142] [ka] In this example, 7.92 g of acrylic acid, 59.99 g of benzyl methacrylate, 43.19 g of hydroxypropyl methacrylate, and 45.72 g of 1-ethylcyclopentyl methacrylate were mixed in 156 g of PGMEA solvent. The polymerization reaction proceeded for 20 hours at 90°C under nitrogen in the presence of 2.46 g of AIBN. After cooling to room temperature, the reaction mixture was used for further use. Theoretically, this would allow the final polymer product to have a weight percent solids of 50 wt% in the spin-casting solvent PGMEA, which was used directly for the preparation of the formulation solution. A small amount (approximately 2 g) of the product was precipitated in deionized water. The polymer solids from the precipitation were washed and dried under vacuum at 50°C. The vacuum-dried product was characterized by GPC (polystyrene standard). The measured weight average molecular weight was 29,183 daltons and the number average molecular weight was 11,834 daltons.

[0143] Synthesis Example of Copolymer of Structure (B) Example 15 (CPB-15)

[0144] [ka] In this example, 8.65 g of acrylic acid, 49.35 g of benzyl methacrylate, 50.46 g of hydroxypropyl methacrylate, and 45.60 g of 1-ethylcyclopentyl methacrylate were mixed in 154 g of PGMEA solvent. The polymerization reaction proceeded for 20 hours at 90°C under nitrogen in the presence of 2.46 g of AIBN. After cooling to room temperature, the reaction mixture was used for further use. Theoretically, this would allow the final polymer product to have a weight percent solids of 50 wt% in the spin-casting solvent PGMEA, which was used directly for the preparation of the formulation solution. A small amount (approximately 2 g) of the product was precipitated in deionized water. The polymer solids from the precipitation were washed and dried under vacuum at 50°C and characterized by GPC (polystyrene standard). The measured weight average molecular weight was 25,414 daltons, and the number average molecular weight was 11,894 daltons.

[0145] Synthesis Example of Copolymer of Structure (B) Example 16 (CPB-16)

[0146] [ka] In this example, 8.67 g of acrylic acid, 40.52 g of benzyl methacrylate, 50.47 g of hydroxypropyl methacrylate, and 54.68 g of 1-ethylcyclopentyl methacrylate were mixed in 158 g of PGMEA solvent. The polymerization reaction proceeded for 20 hours at 90°C under nitrogen in the presence of 2.46 g of AIBN. After cooling to room temperature, the reaction mixture was used for further use. Theoretically, this would allow the final polymer product to have a weight percent solids of 50 wt% in the spin-casting solvent PGMEA, which was used directly for the preparation of the formulation solution. A small amount (approximately 2 g) of the product was precipitated in deionized water. The polymer solids from the precipitation were washed and dried under vacuum at 50°C. The vacuum-dried product was characterized by GPC (polystyrene standard). The weight average molecular weight was 26,763 daltons and the number average molecular weight was 11,560 daltons.

[0147] Synthesis Example of Copolymer of Structure (B) Example 17 (CPB-17)

[0148] [ka] In this example, 10.80 g of acrylic acid, 44.06 g of benzyl methacrylate, 50.48 g of hydroxypropyl methacrylate, and 45.57 g of 1-ethylcyclopentyl methacrylate were mixed in 151 g of PGMEA solvent. The polymerization reaction proceeded for 20 hours at 90°C under nitrogen in the presence of 2.46 g of AIBN. After cooling to room temperature, the reaction mixture was used for further use. Theoretically, this would allow the final polymer product to have a weight percent solids of 50 wt% in the spin-casting solvent PGMEA, which was used directly for the preparation of the formulation solution. A small amount (approximately 2 g) of the product was precipitated in deionized water. The polymer solids from the precipitation were washed and dried under vacuum at 50°C. The vacuum-dried product was characterized by GPC (polystyrene standard). The weight average molecular weight was 32,591 daltons and the number average molecular weight was 14,187 daltons.

[0149] Synthesis Example of Copolymer of Structure (B) Example 18 (CPB-18)

[0150] [ka] In this example, 30.74 g of acrylic acid, 112.92 g of benzyl methacrylate, 134.72 g of hydroxypropyl methacrylate, and 121.73 g of 1-ethylcyclopentyl methacrylate were mixed in 600 g of PGME solvent. The polymerization reaction proceeded for 20 hours at 90°C under nitrogen in the presence of 7.23 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in deionized water. The polymer solids were washed and dried under vacuum at 45°C, yielding 387.7 g (98% yield). The vacuum-dried polymer was characterized by GPC (polystyrene standard). The weight average molecular weight was 20,772 daltons and the number average molecular weight was 7,795 daltons.

[0151] Synthesis Example of Copolymer of Structure (B) Example 19 (CPB-19)

[0152] [ka] In this example, 11.92 g of acrylic acid, 41.42 g of benzyl methacrylate, 50.46 g of hydroxypropyl methacrylate, and 47.81 g of 1-ethylcyclopentyl methacrylate were mixed in 150 g of PGME solvent. The polymerization reaction proceeded for 20 hours at 90°C under nitrogen in the presence of 2.70 g of AIBN. After cooling to room temperature, the reaction mixture was used for further use. Theoretically, this would allow the final polymer product to have a weight percent solids of 50 wt% in the spin-casting solvent PGMEA, which was used directly for the preparation of the formulation solution. A small amount (approximately 2 g) of the product was precipitated in deionized water. The polymer solids from the precipitation were washed and dried under vacuum at 50°C. The vacuum-dried product was characterized by GPC (polystyrene standard). The weight average molecular weight was 32,898 daltons and the number average molecular weight was 9,249 daltons.

[0153] Synthesis Example of Copolymer of Structure (B) Example 20 (CPB-20)

[0154] [ka] In this example, 13.00 g of acrylic acid, 38.78 g of benzyl methacrylate, 50.46 g of hydroxypropyl methacrylate, and 45.57 g of 1-ethylcyclopentyl methacrylate were mixed in 149 g of PGMEA solvent. The polymerization reaction proceeded for 20 hours at 90°C under nitrogen in the presence of 2.46 g of AIBN. After cooling to room temperature, the reaction mixture was used for further use. Theoretically, this would allow the final polymer product to have a weight percent solids of 50 wt% in the spin-casting solvent PGMEA, which was used directly for the preparation of the formulation solution. A small amount (approximately 2 g) of the product was precipitated in deionized water. The polymer solids from the precipitation were washed and dried under vacuum at 50°C. The vacuum-dried product was characterized by GPC (polystyrene standard). The weight average molecular weight was 27,168 daltons and the number average molecular weight was 10,081 daltons.

[0155] Synthesis of copolymers of structure (A) with high dissolution rates The following two example acrylic polymers, as copolymers of structure (A) of component a), were prepared and tested in the following formulations:

[0156] Synthesis of Copolymer of Structure (A) Example 1 (CPA-1)

[0157] [ka] In this example, 7.21 g of acrylic acid, 21.62 g of hydroxypropyl methacrylate, and 44.05 g of benzyl methacrylate were mixed in 138.4 g of PGME solvent. The polymerization reaction proceeded for 18 hours at 90°C under nitrogen in the presence of 1.6 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in deionized water. The white polymer solid was washed and dried under vacuum at 50°C to yield 71.4 g (98% yield) of polymer with a weight average molecular weight of 15,929 Daltons and a dissolution rate of 920 Å / sec in 0.26% aqueous TMAH at 23°C.

[0158] Synthesis of Polymer Class B Alkali-Soluble Resin Example 2 (CPA-2)

[0159] [ka] In this example, 9.01 g of acrylic acid, 5.21 g of styrene, 21.62 g of hydroxypropyl methacrylate, and 30.84 g of benzyl methacrylate were mixed in 126.9 g of PGME solvent. The polymerization reaction proceeded for 18 hours at 90°C under nitrogen in the presence of 1.64 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in deionized water. The white polymer solid was washed and dried under vacuum at 50°C to yield 64.9 g (97% yield) of polymer with a weight average molecular weight of 15,314 daltons, a number average molecular weight of 7,843 daltons, and a dissolution rate of 840 Å / sec in 0.26% aqueous TMAH at 23°C.

[0160] Commercially available acrylic polymers with high dissolution rates Table 1 lists commercially available carboxylic acid-containing resins that were used as random copolymers of component a) having the same structure (A) and their characteristics. These were used in Formulations 1-80. These materials have fast dissolution rates in 0.26 N TMAH aqueous developer at room temperature (23°C). For example, Joncryl 817 was measured to have a dissolution rate of 1780 Å / sec.

[0161] [Table 1]

[0162] Novolac Polymer For the following formulation examples, three novolac polymers were used. Novolac-1, Novolac-2, and Novolac-3 were used as the novolac polymers of component c). These polymers were based on commercially available novolac polymers (Allnex, Alpharetta, Ga.) derived from meta-cresol and formaldehyde. Novolac-1 was a commercially available novolac polymer known as "ALNOVOL TM SPN560 / 47MPAC SLOW”, Mw 24010, D: 7.3, with a bulk dissolution rate of 700 Å / sec in 0.26N aqueous TMAH developer; Novolak-2 is “ALNOVOL TM SPN560 / 47MPAC FAST", Mw 7,245, D: 4.8, with a bulk dissolution rate of 1,600 Å / sec in 0.26N aqueous TMAH developer. Novolac-3 was a 1 / 1 blend of Novolac-1 and Novolac-2.

[0163] Base Additives The base additive used in the following formulations was the mono-tributylammonium salt of oxalic acid (tributylammonium oxalate), which was prepared as described in Synthesis Example 1 according to US20190064662A1.

[0164] Example of a mixture Example Formulation 1: In this example, 17.325 g of the polymer of Synthesis Example 1 (CPM-1), 21.753 g of Novolak-3, 9.90 g of Joncyrl 817 (BASF), 0.248 g of 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl trifluoromethanesulfonate [naphthalenedicarboxyimidyl triflate, also known as NIT] (NIT PAG), 0.173 g of 5-mercapto-1-phenyl-1H-tetrazole (PMT) (TCI), 0.0025 g of tetrabutylammonium oxalate (Merck A solution was prepared by dissolving 0.099 g of KGaA (PM-I, Wiesbaden, Germany) and 0.099 g of APS-437 (also known as KF353A) (Shin-Etsu Chemical Co., Ltd., Tokyo, Japan) in a mixed solvent of 38.244 g of PGMEA, 10.24 g of 3-methoxybutyl acetate, and 2.016 g of γ-butyrolactone (GBL). This solution was filtered for lithography testing.

[0165] Mixture example 2 In this example, 17.325 g of the polymer from Synthesis Example 2 (CPM-2), 21.753 g of Novolac-3, 9.90 g of Joncryl 817, 0.248 g of NIT PAG, 0.173 g of 5-mercapto-1-phenyl-1H-tetrazole (PMT), 0.0025 g of tetrabutylammonium oxalate, and 0.099 g of APS-437 were dissolved in a mixed solvent of 38.244 g of PGMEA, 10.24 g of 3-methoxybutyl acetate, and 2.016 g of γ-butyrolactone (GBL). This solution was filtered for lithography testing.

[0166] Mixture Example 3 In this example, 17.325 g of the polymer from Synthesis Example 3 (CPM-3), 21.753 g of Novolac-3, 9.90 g of Joncryl 817, 0.248 g of NIT PAG, 0.173 g of 5-mercapto-1-phenyl-1H-tetrazole (PMT), 0.0025 g of tetrabutylammonium oxalate, and 0.099 g of APS-437 were dissolved in a mixed solvent of 38.244 g of PGMEA, 10.24 g of 3-methoxybutyl acetate, and 2.016 g of γ-butyrolactone (GBL). This solution was filtered for lithography testing.

[0167] Mixture Example 4 A solution was prepared by dissolving 17.325 g of the polymer (CPM-4) from Synthesis Example 4, 21.753 g of Novolac-3, 9.90 g of Joncryl 817, 0.248 g of NIT PAG, 0.173 g of 5-mercapto-1-phenyl-1H-tetrazole (PMT), 0.0025 g of tetrabutylammonium oxalate, and 0.099 g of APS-437 in a mixture of 38.244 g of PGMEA, 10.24 g of 3-methoxybutyl acetate, and 2.016 g of γ-butyrolactone (GBL). This solution was filtered for lithography testing.

[0168] Mixture Example 5 In this example, 17.325 g of the polymer from Synthesis Example 5 (CPM-5), 21.753 g of Novolac-3, 9.90 g of Joncryl 817, 0.248 g of NIT PAG, 0.173 g of 5-mercapto-1-phenyl-1H-tetrazole (PMT), 0.0025 g of tetrabutylammonium oxalate, and 0.099 g of APS-437 were dissolved in a mixed solvent of 38.244 g of PGMEA, 10.24 g of 3-methoxybutyl acetate, and 2.016 g of γ-butyrolactone (GBL). This solution was filtered for lithography testing.

[0169] Mixture Example 6 In this example, 17.325 g of the polymer from Synthesis Example 6 (CPM-6), 21.753 g of Novolac-3, 9.90 g of Joncryl 817, 0.248 g of NIT PAG, 0.173 g of 5-mercapto-1-phenyl-1H-tetrazole (PMT), 0.0025 g of tetrabutylammonium oxalate, and 0.099 g of APS-437 were dissolved in a mixture of 38.244 g of PGMEA, 10.24 g of 3-methoxybutyl acetate, and 2.016 g of γ-butyrolactone (GBL). This solution was filtered for lithography testing.

[0170] Mixture Example 7 In this example, 17.325 g of the polymer from Synthesis Example 7 (CPM-7), 21.753 g of Novolac-3, 9.90 g of Joncryl 817, 0.248 g of NIT PAG, 0.173 g of 5-mercapto-1-phenyl-1H-tetrazole (PMT), 0.0025 g of tetrabutylammonium oxalate, and 0.099 g of APS-437 were dissolved in a mixture of 38.244 g of PGMEA, 10.24 g of 3-methoxybutyl acetate, and 2.016 g of γ-butyrolactone (GBL). This solution was filtered for lithography testing.

[0171] Mixture Example 8 A solution was prepared by dissolving 17.325 g of the polymer (CPM-8) from Synthesis Example 8, 21.753 g of Novolac-3, 9.90 g of Joncryl 817, 0.248 g of NIT PAG, 0.173 g of 5-mercapto-1-phenyl-1H-tetrazole (PMT), 0.0025 g of tetrabutylammonium oxalate, and 0.099 g of APS-437 in a mixture of 38.244 g of PGMEA, 10.24 g of 3-methoxybutyl acetate, and 2.016 g of γ-butyrolactone (GBL). This solution was filtered for lithography testing.

[0172] Mixture Example 9 In this example, 17.325 g of the polymer from Synthesis Example 9 (CPM-9), 21.753 g of Novolac-3, 9.90 g of Joncryl 817, 0.248 g of NIT PAG, 0.173 g of 5-mercapto-1-phenyl-1H-tetrazole (PMT), 0.0025 g of tetrabutylammonium oxalate, and 0.099 g of APS-437 were dissolved in a mixture of 38.244 g of PGMEA, 10.24 g of 3-methoxybutyl acetate, and 2.016 g of γ-butyrolactone (GBL). This solution was filtered for lithography testing.

[0173] Mixture Example 10 In this example, 17.325 g of the polymer from Synthesis Example 10 (CPM-10), 21.753 g of Novolac-3, 9.90 g of Joncryl 817, 0.248 g of NIT PAG, 0.173 g of 5-mercapto-1-phenyl-1H-tetrazole (PMT), 0.0025 g of tetrabutylammonium oxalate, and 0.099 g of APS-437 were dissolved in a mixture of 38.244 g of PGMEA, 10.24 g of 3-methoxybutyl acetate, and 2.016 g of γ-butyrolactone (GBL). This solution was filtered for lithography testing.

[0174] Mixture Example 11 In this example, 17.325 g of the polymer from Synthesis Example 11 (CPM-11), 21.753 g of Novolac-3, 9.90 g of Joncryl 817, 0.248 g of NIT PAG, 0.173 g of 5-mercapto-1-phenyl-1H-tetrazole (PMT), 0.0025 g of tetrabutylammonium oxalate, and 0.099 g of APS-437 were dissolved in a mixture of 38.244 g of PGMEA, 10.24 g of 3-methoxybutyl acetate, and 2.016 g of γ-butyrolactone (GBL). This solution was filtered for lithography testing.

[0175] Mixture Example 12 In this example, 34.65 g of the polymer solution (CPM-12) from Synthesis Example 12, 21.753 g of Novolac-3, 9.90 g of Joncryl 817, 0.248 g of NIT PAG, 0.173 g of 5-mercapto-1-phenyl-1H-tetrazole (PMT), 0.0025 g of tetrabutylammonium oxalate, and 0.099 g of APS-437 were dissolved in a mixed solvent of 20.919 g of PGMEA, 10.24 g of 3-methoxybutyl acetate, and 2.016 g of γ-butyrolactone (GBL). This solution was filtered for lithography testing.

[0176] Mixture Example 13 In this example, 34.65 g of the polymer solution (CPM-13) from Synthesis Example 13, 21.753 g of Novolac-3, 9.90 g of Joncryl 817, 0.248 g of NIT PAG, 0.173 g of 5-mercapto-1-phenyl-1H-tetrazole (PMT), 0.0025 g of tetrabutylammonium oxalate, and 0.099 g of APS-437 were dissolved in a mixed solvent of 20.919 g of PGMEA, 10.24 g of 3-methoxybutyl acetate, and 2.016 g of γ-butyrolactone (GBL). This solution was filtered for lithography testing.

[0177] Mixture Example 14 In this example, 34.65 g of the polymer solution (CPM-14) from Synthesis Example 14, 21.753 g of Novolac-3, 9.90 g of Joncryl 817, 0.248 g of NIT PAG, 0.173 g of 5-mercapto-1-phenyl-1H-tetrazole (PMT), 0.0025 g of tetrabutylammonium oxalate, and 0.099 g of APS-437 were dissolved in a mixed solvent of 20.919 g of PGMEA, 10.24 g of 3-methoxybutyl acetate, and 2.016 g of γ-butyrolactone (GBL). This solution was filtered for lithography testing.

[0178] Mixture Example 15 In this example, 34.65 g of the polymer solution (CPM-15) from Synthesis Example 15, 21.753 g of Novolac-3, 9.90 g of Joncryl 817, 0.248 g of NIT PAG, 0.173 g of 5-mercapto-1-phenyl-1H-tetrazole (PMT), 0.0025 g of tetrabutylammonium oxalate, and 0.099 g of APS-437 were dissolved in a mixed solvent of 20.919 g of PGMEA, 10.24 g of 3-methoxybutyl acetate, and 2.016 g of γ-butyrolactone (GBL). This solution was filtered for lithography testing.

[0179] Mixture Example 16 In this example, 34.65 g of the polymer solution from Synthesis Example 16 (CPM-16), 21.753 g of Novolac-3, 9.90 g of Joncryl 817, 0.248 g of NIT PAG, 0.173 g of 5-mercapto-1-phenyl-1H-tetrazole (PMT), 0.0025 g of tetrabutylammonium oxalate, and 0.099 g of APS-437 were dissolved in a mixed solvent of 20.919 g of PGMEA, 10.24 g of 3-methoxybutyl acetate, and 2.016 g of γ-butyrolactone (GBL). This solution was filtered for lithography testing.

[0180] Mixture Example 17 In this example, 34.65 g of the polymer solution from Synthesis Example 17 (CPM-17), 21.753 g of Novolac-3, 9.90 g of Joncryl 817, 0.248 g of NIT PAG, 0.173 g of 5-mercapto-1-phenyl-1H-tetrazole (PMT), 0.0025 g of tetrabutylammonium oxalate, and 0.099 g of APS-437 were dissolved in a mixture of 20.919 g of PGMEA, 10.24 g of 3-methoxybutyl acetate, and 2.016 g of γ-butyrolactone (GBL). This solution was filtered for lithography testing.

[0181] Mixture Example 18 In this example, 17.325 g of the polymer from Synthesis Example 18 (CPM-18), 21.753 g of Novolac-3, 9.90 g of Joncryl 817, 0.248 g of NIT PAG, 0.173 g of 5-mercapto-1-phenyl-1H-tetrazole (PMT), 0.0025 g of tetrabutylammonium oxalate, and 0.099 g of APS-437 were dissolved in a mixture of 38.244 g of PGMEA, 10.24 g of 3-methoxybutyl acetate, and 2.016 g of γ-butyrolactone (GBL). This solution was filtered for lithography testing.

[0182] Mixture Example 19 In this example, 34.65 g of the polymer solution from Synthesis Example 19 (CPM-19), 21.753 g of Novolac-3, 9.90 g of Joncryl 817, 0.248 g of NIT PAG, 0.173 g of 5-mercapto-1-phenyl-1H-tetrazole (PMT), 0.0025 g of tetrabutylammonium oxalate, and 0.099 g of APS-437 were dissolved in a mixture of 20.919 g of PGMEA, 10.24 g of 3-methoxybutyl acetate, and 2.016 g of γ-butyrolactone (GBL). This solution was filtered for lithography testing.

[0183] Mixture Example 20 In this example, 34.65 g of the polymer solution (CPM-20) from Synthesis Example 18, 21.753 g of Novolac-3, 9.90 g of Joncryl 817, 0.248 g of NIT PAG, 0.173 g of 5-mercapto-1-phenyl-1H-tetrazole (PMT), 0.0025 g of tetrabutylammonium oxalate, and 0.099 g of APS-437 were dissolved in a mixture of 20.919 g of PGMEA, 10.24 g of 3-methoxybutyl acetate, and 2.016 g of γ-butyrolactone (GBL). This solution was filtered for lithography testing.

[0184] Mixture examples 21-40 Formulation Examples 20-40 used the same ingredients as Formulation Examples 1-20, except that Joncryl 822 was used instead of Joncryl 817.

[0185] Mixture examples 41-60 Formulation Examples 41-60 used the same ingredients as Formulation Examples 1-20, except that Joncryl 817 was replaced with the synthesis of copolymer (CPA-1) of structure (A) in Example 1.

[0186] Mixture examples 61-80 Formulation Examples 61-80 used the same ingredients as Formulation Examples 1-20, except that Joncryl 819 was used instead of Joncryl 817.

[0187] Comparative Formulation Examples Without Joncryl and CPA Copolymers A solution was prepared by dissolving 17.325 g of the polymer (CPB-7) from Synthesis Example 7, 31.653 g of Novolac-3, 0.248 g of NIT PAG, 0.173 g of 5-mercapto-1-phenyl-1H-tetrazole (PMT), 0.0025 g of tetrabutylammonium oxalate, and 0.099 g of APS-437 in a mixture of 38.244 g of PGMEA, 10.24 g of 3-methoxybutyl acetate, and 2.016 g of γ-butyrolactone (GBL). This solution was filtered for lithography testing.

[0188] Coating with the formulation All formulations were tested on 8-inch diameter Si and Cu wafers. The Si wafers were dehydration baked and vapor primed with hexamethyldisilazane (HMDS).

[0189] Resist coatings were prepared by spin-coating resist samples and applying a soft bake at 140°C for 360 seconds on a standard wafer track hotplate in contact mode. The spin speed was adjusted to obtain a resist film thickness of 60 microns. Dual coatings were applied to obtain a film thickness of 150-200 microns. All film thickness measurements were performed on Si wafers using optical metrology.

[0190] Imaging of coated wafers These coated wafers were exposed using a SUSS MA200CC mask aligner or an ORC i-line stepper. The wafers were baked at 100 °C for 100 seconds and then puddle developed in AZ300MIF (a 0.26 N aqueous solution of tetramethylammonium hydroxide = TMAH) at 23 °C for 120 to 360 seconds. The developed resist images were examined using a Hitachi S4700 or AMRAY 4200L electron microscope.

[0191] Table 2 shows lithography test results obtained for 60-micron film thicknesses imaged on a SUSS contact printer. At 20 wt. % loadings of Joncryl 817, Joncryl 822, CPA-1, and CPA-2 on a total solids basis, the photospeed increased by approximately 40% compared to films without these components. The copolymer of Joncryl and CPA additives acted as a photospeed enhancer and also reduced the contact angle of the film with water by 10°. When tert-butyl (tertBu) groups were used as the cleavable group, the photospeed was slower than that of 1-ethylcyclopentyl (EtCp) groups. Faster photospeeds were observed with increasing EtCP mole percent and increasing carboxylic acid mole percent. When the mole % of acrylic acid exceeded 10%, unexposed film loss was observed, but this was very small (about 1 micron) and did not interfere with imaging ability, and also had the advantage of further increasing the hydrophilicity of the film and, consequently, further improving the wetting of these formulations to the substrate.

[0192] Figures 1 and 2 show the results for 500 mJ / cm 2 2F shows SEM images of a comparative formulation imaged using a dose of 300 mJ / cm on a SUSS contact printer, and an image obtained using Formulation 7. As can be seen in Figure 1, the comparative sample gave poor imaging with a very sloped profile. In contrast, Figure 2F shows the comparative formulation imaged using a dose of 300 mJ / cm on a SUSS contact printer. 2 The results show good resolution of vertical 40 micron L / S features obtained at a dose of 1000 .mu.m.

[0193] [Table 2]

[0194] Figure 1 shows an image obtained using a comparative example with nearly the same formulation as Formulation 7 in Table 1, but excluding the Joncryl or CPA copolymer additive (alternatively, component a). The image observed in Figure 1 shows a significant slope of the L / S pattern, with a yield of only 240 mJ / cm. 2 compared to the straight wall profile shown in Figure 2 obtained with Formulation 7 at a dose of 400 mJ / cm 2 The images shown in Figures 1 and 2 were obtained under the same processing conditions on an 80 micron film after a soft bake at 140°C for 360 seconds, a post-exposure bake at 90°C for 100 seconds, and 6 x 50 second development times in 0.26N aqueous developer.

[0195] Wettability contact angle measurement Wettability, a property indirectly related to the imaging ability of these formulations, was evaluated by static water contact angle. Resist films were coated and baked at 140°C for 360 seconds, followed by a 60-second developer immersion. The contact angles of the films were determined using a Dataphysics Contact Angle System (OCA). The comparative formulation had a static water contact angle of 81°. In comparison, the introduction of either a Joncryl derivative or a CPA copolymer into the formulations resulted in a decrease in the contact angle of the example formulations by approximately 5 to 10°C, improving their wettability. For example, Formulation 7, which contained Joncryl 817, had a measured static contact angle of 75°. Formulation 47, which contained CPA-1, also had a contact angle of 75°. Similar effects were observed with formulations containing CAP-2, Joncryl 819, or Joncryl 822.

[0196] Another aspect of these formulations in which reduced contact angles and improved wetting were observed was the increased content of acrylic acid repeat units in the CPB component of these formulations. For example, Formulation 20, prepared using CPB-20, a copolymer with 18 mol% acrylic acid repeat units, had a contact angle of 70° compared to Formulation 7, which differed only in that it was prepared using CPB-7 (containing 8 mol% of this acrylic acid repeat unit) instead of CPB-20 and gave a contact angle of 75°, even though both had the same content of Joncryl 817. A similar effect was observed in formulations containing CPB copolymers with a relatively high content of acrylic acid repeat units. In all observed cases, the improved wetting resulted in better lithographic performance with straight sidewalls, as shown in Figure 2 for Formulation 7.

[0197] Some unexposed area erosion of less than 1 micron was observed in some of the wetted samples, but this slight unexposed area erosion did not adversely affect the imaging ability of these formulations.

[0198] While the disclosed and claimed invention has been described and illustrated with a certain degree of detail, it will be apparent that this disclosure is made by way of example only and that one skilled in the art may resort to numerous variations in the conditions and sequence of steps without departing from the spirit and scope of the disclosed and claimed invention.

Claims

1. 1. A positive-working chemically amplified photosensitive composition comprising: As component a), at least one random copolymer having the structure (A), the repeat units of structure (I) range from 17 mol % to 70 mol %; The repeat units of structure (II) range from 0 to 70 mole %; The repeat units of structure (III) range from 0 to 70 mole %; the sum of repeat units of structures (II) and (III) ranges from 30 mol % to 70 mol %; The repeat units of structure (IV) range from 0 mole % to 35 mole %, wherein the sum of the mole % of repeat units of structures (I), (II), (III) and (IV) does not exceed 100 mole %, or equals 100 mole % if no other type of repeat unit is present; and Ri １ , Ri ２ , Ri １４ and Ri １３ are independently selected from H or C1-C4 alkyl; ３ , Ri ４ , Ri ５ , Ri ６ , Ri ７ , Ri ８ , Ri ９ , Ri １０ , Ri １１ , and Ri １２ is independently selected from H, C1-C8 alkyl, C1-C4 alkoxy, phenyl, substituted phenyl, and mixtures thereof; Li １ is a C2-C6 alkylene moiety, ni, mi, oi, and pi are the number of repeat units of structures (I), (II), (III), and (IV), respectively, and further The copolymer of structure (A) has a minimum dissolution rate of 500 Å / sec in 0.26 N tetramethylammonium hydroxide at 23° C. and does not contain any repeat units with acid-cleavable groups; 【Chemistry 1】 Component b) at least one acrylic copolymer component of structure (B) comprising repeating units selected from those having structures (1), (2), (3), (4), (5), (6), and (7), provided that: R １ , R ２ , R ３ , R ４ , R ５ , R ６ , and R ７ are individually selected from H, F, C1-C4 perfluoroalkyl, or C1-C4 alkyl; R ８ and R ９ is independently selected from H, C1-C4 alkyl, C1-C4 alkyloxyalkyl, and halogen; R １０ is selected from the group consisting of C1-C8 primary alkyl, C3-C8 secondary alkyl, C3-C8 cyclic secondary alkyl, and C7-C14 secondary alicyclic alkyl; R １１ is a C2-C8 (hydroxy)alkylene moiety; R １２ is a tertiary alkyl acid cleavable group, and R １３ is a C3-C12 (alkyloxy) alkylene moiety; and further These repeat units collectively make up 100 mole % of the repeat units in the functionalized acrylic copolymer, wherein: the repeating units of structure (1) range from 0 mol % to 20 mol % of the acrylic copolymer; the repeating units of structure (2) range from 0 mol % to 20 mol % of the acrylic copolymer; the repeating units of structure (3) range from 5 mol % to 55 mol % of the acrylic copolymer; the repeating units of structure (4) range from 0 mol % to 30 mol % of the acrylic copolymer; the repeating units of structure (5) range from 15 mol % to 55 mol % of said acrylic copolymer; the repeating units of structure (6) range from 18 mol % to 40 mol % of said acrylic copolymer; The repeat units of structure (7) range from 0 mol % to 40 mol % of said acrylic copolymer; 【Chemistry 2】 as component c), at least one novolac polymer; As component d), at least one photoacid generator (PAG); as component e), at least one base additive; as component f), at least one heterocyclic thiol compound; As component g), organic spin-casting solvents; A positive-working chemically amplified photosensitive composition comprising:

2. 10. The composition of claim 1, wherein component a) is a copolymer consisting of repeating units of structures (I) and (II).

3. 10. The composition of claim 1, wherein component a) is a copolymer consisting of repeating units of structures (I) and (III).

4. 10. The composition of claim 1, wherein component a) is a copolymer consisting of repeating units of structures (I), (II), and (III).

5. 10. The composition of claim 1, wherein component a) is a copolymer consisting of repeating units of structures (I), (II), and (IV).

6. 10. The composition of claim 1, wherein component a) is a copolymer consisting of repeating units of structures (I), (III), and (IV).

7. 10. The composition of claim 1, wherein component a) is a copolymer consisting of repeating units of structures (I), (II), (III), and (IV).

8. The composition of any one of claims 1 to 7, wherein the repeat units of structure (I) range from 20 mole % to 65 mole % of all repeat units in the copolymer.

9. 2. The composition of claim 1, wherein component a) has a structure selected from the group consisting of Structure (A-1), Structure (A-2), Structure (A-3), Structure (A-4), Structure (A-5), Structure (A-6), Structure (A-7), Structure (A-8), and Structure (A-9). 【Transformation 3】 【Chemistry 4】 【Transformation 5】 【Transformation 6】 【Transformation 7】 【Transformation 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】

10. 10. The composition of any one of claims 1 to 7 and 9, wherein component a) is in the range of 10% to 25% by weight of the total solids.

11. 10. The composition of any one of claims 1 to 7 and 9, wherein component b) is in the range of 20% to 65% by weight of the total solids.

12. 10. The composition of any one of claims 1-7 and 9, wherein component b) comprises at least one copolymer of Structure (B) containing from 5 mole % to 20 mole % of repeat units of Structure (1).

13. 10. The composition of any one of claims 1-7 and 9, wherein component b) comprises at least one copolymer of Structure (B) containing from 5 mole % to 20 mole % of repeat units of Structure (7).

14. 10. The composition of any one of claims 1-7 and 9, wherein component b) comprises at least one copolymer of Structure (B), wherein the repeat units of Structure (1) range from 5 mol% to 20 mol% and the repeat units of Structure (7) range from 5 mol% to 20 mol%.

15. 10. The composition of any one of claims 1 to 7 and 9, wherein component b) comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from 5 mol% to 15 mol% of repeating units of Structure (1), from 15 mol% to 25 mol% of repeating units of Structure (3), from 35 mol% to 45 mol% of repeating units of Structure (5), and from 25 mol% to 35 mol% of repeating units of Structure (6).

16. 10. The composition of any one of claims 1 to 7 and 9, wherein component b) comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from 5 mol% to 10 mol% of repeating units of Structure (1), from 15 mol% to 25 mol% of repeating units of Structure (3), from 45 mol% to 55 mol% of repeating units of Structure (5), and from 15 mol% to 25 mol% of repeating units of Structure (6).

17. 10. The composition of any one of claims 1 to 7 and 9, wherein component b) comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from 5 mol% to 10 mol% of repeating units of Structure (1), from 12 mol% to 22 mol% of repeating units of Structure (3), from 20 mol% to 35 mol% of repeating units of Structure (5), from 25 mol% to 40 mol% of repeating units of Structure (6), and from 5 mol% to 15 mol% of repeating units of Structure (7).

18. 10. The composition of any one of claims 1 to 7 and 9, wherein component b) comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from 12 mol% to 22 mol% of repeating units of Structure (3), from 30 mol% to 40 mol% of repeating units of Structure (5), from 25 mol% to 40 mol% of repeating units of Structure (6), and from 5 mol% to 15 mol% of repeating units of Structure (7).

19. 10. The composition of any one of claims 1 to 7 and 9, wherein component b) comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from 5 mol% to 8 mol% of repeating units of Structure (1), from 10 mol% to 17 mol% of repeating units of Structure (3), from 30 mol% to 40 mol% of repeating units of Structure (5), from 25 mol% to 40 mol% of repeating units of Structure (6), and from 5 mol% to 15 mol% of repeating units of Structure (7).

20. 10. The composition of any one of claims 1 to 7 and 9, wherein component b) comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from 5 mol% to 7.5 mol% of repeating units of Structure (1), from 10 mol% to 17 mol% of repeating units of Structure (3), from 30 mol% to 40 mol% of repeating units of Structure (5), from 25 mol% to 40 mol% of repeating units of Structure (6), and from 5 mol% to 15 mol% of repeating units of Structure (7).

21. 10. The composition of any one of claims 1 to 7 and 9, wherein component b) comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from 5 mol% to 15 mol% of repeating units of Structure (1), from 5 mol% to 15 mol% of repeating units of Structure (3), from 30 mol% to 40 mol% of repeating units of Structure (5), from 25 mol% to 40 mol% of repeating units of Structure (6), and from 5 mol% to 15 mol% of repeating units of Structure (7).

22. 10. The composition of any one of claims 1 to 7 and 9, wherein component b) comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from 5 mol% to 15 mol% of repeating units of Structure (1), from 20 mol% to 35 mol% of repeating units of Structure (3), from 30 mol% to 40 mol% of repeating units of Structure (5), from 15 mol% to 25 mol% of repeating units of Structure (6), and from 5 mol% to 15 mol% of repeating units of Structure (7).

23. 10. The composition of any one of claims 1 to 7 and 9, wherein component b) comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from 5 mol% to 15 mol% of repeating units of Structure (1), from 20 mol% to 30 mol% of repeating units of Structure (3), from 35 mol% to 45 mol% of repeating units of Structure (5), from 15 mol% to 25 mol% of repeating units of Structure (6), and from 5 mol% to 15 mol% of repeating units of Structure (7).

24. 10. The composition of any one of claims 1 to 7 and 9, wherein component b) comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from 7 mol% to 18 mol% repeating units of Structure (1), from 15 mol% to 25 mol% repeating units of Structure (3), from 25 mol% to 35 mol% repeating units of Structure (5), from 15 mol% to 25 mol% repeating units of Structure (6), and from 5 mol% to 15 mol% repeating units of Structure (7).

25. 10. The composition of any one of claims 1 to 7 and 9, wherein component b) comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from 7 mol% to 15 mol% of repeating units of Structure (1), from 25 mol% to 35 mol% of repeating units of Structure (3), from 25 mol% to 35 mol% of repeating units of Structure (5), and from 25 mol% to 35 mol% of repeating units of Structure (6).

26. 10. The composition of any one of claims 1 to 7 and 9, wherein component b) comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from 7 mol% to 15 mol% of repeating units of Structure (1), from 27 mol% to 45 mol% of repeating units of Structure (3), from 30 mol% to 40 mol% of repeating units of Structure (5), and from 15 mol% to 25 mol% of repeating units of Structure (6).

27. 10. The composition of any one of claims 1 to 7 and 9, wherein component b) comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from 7 mol% to 15 mol% of repeating units of Structure (1), from 15 mol% to 25 mol% of repeating units of Structure (3), from 35 mol% to 45 mol% of repeating units of Structure (5), and from 25 mol% to 35 mol% of repeating units of Structure (6).

28. 10. The composition of any one of claims 1 to 7 and 9, wherein component b) comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from 7 mol% to 15 mol% of repeating units of Structure (1), from 20 mol% to 37 mol% of repeating units of Structure (3), from 30 mol% to 45 mol% of repeating units of Structure (5), and from 20 mol% to 30 mol% of repeating units of Structure (6).

29. 10. The composition of any one of claims 1 to 7 and 9, wherein component b) comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from 7 mol% to 15 mol% of repeating units of Structure (1), from 20 mol% to 30 mol% of repeating units of Structure (3), from 30 mol% to 45 mol% of repeating units of Structure (5), and from 20 mol% to 35 mol% of repeating units of Structure (6).

30. 10. The composition of any one of claims 1 to 7 and 9, wherein component b) comprises at least one copolymer of Structure (B), wherein said at least one copolymer consists of from 10 mol% to 20 mol% of repeating units of Structure (1), from 20 mol% to 30 mol% of repeating units of Structure (3), from 30 mol% to 45 mol% of repeating units of Structure (5), and from 20 mol% to 35 mol% of repeating units of Structure (6).

31. The composition according to any one of claims 1 to 7 and 9, The repeating unit of structure (1), when present, may be structure (1a) or (1b): 【Chemistry 12】 and The repeating unit of structure (3) is structure (3a) or (3b): 【Chemistry 13】 and The repeating unit of structure (5) is structure (5a) or (5b): 【Chemistry 14】 and The repeat unit of structure (7), when present, is structure (7a) or (7b): 【Chemistry 15】 and The repeating unit of structure (6) is structure (6a), (6b), (6c) or (6d): 【Chemistry 16】 The composition comprising any one of the following:

32. The composition according to any one of claims 1 to 7 and 9, wherein the photoacid generator (PAG) of component d) is 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.

33. 10. The composition of any one of claims 1 to 7 and 9, wherein the heterocyclic thiol of component f) is selected from the following general formula: 【Chemistry 23】 However, 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 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.

34. 1. A method of imaging a resist comprising the steps of: i) coating the composition according to any one of claims 1 to 7 and 9 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; The method comprising:

35. 1. A method for imaging a resist comprising the steps of: ia) coating the composition according to any one of claims 1 to 7 and 9 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; iv) developing the selectively exposed and baked resist film to form a positive imaged resist film on the substrate; The method comprising:

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