Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/022—Quinonediazides
  • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
  • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
  • G03F7/0236—Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/022—Quinonediazides
  • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/16—Coating processes; Apparatus therefor
  • G03F7/162—Coating on a rotating support, e.g. using a whirler or a spinner
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
  • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
  • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light

Definitions

• the disclosed subject matter pertains to a positive radiation-sensitive aqueous base soluble photoresist composition used for making integrated circuit (IC), light emitting diode (LED) devices and display devices.
• IC integrated circuit
• LED light emitting diode
• Photoresist compositions are used in microlithographic processes for making miniaturized electronic components such as in the fabrication of computer chips, integrated circuits, light emitting diode (LED) devices and displays. Generally, in these processes, a film of a photoresist composition is first applied to a substrate material, such as silicon wafers used for making integrated circuits.
• the coated substrate is then baked to evaporate solvent in the photoresist composition and to fix the coating onto the substrate.
• the baked, coated surface of the substrate is next subjected to an image-wise exposure to imaging radiation.
• This radiation exposure causes a chemical transformation in the exposed areas of the coated surface. Visible light, ultraviolet (UV) light, electron beam and X-ray radiant energy are imaging radiation types commonly used today in microlithographic processes.
• the coated substrate is treated with a developer solution to dissolve and remove either the radiation-exposed or the unexposed areas of the coated surface of the substrate.
• photoresist compositions negative-working and positive-working.
• compositions are either chemically amplified photoresists based on either phenolic or (meth)acrylate resin or non-chemically amplified photoresists based on Novolak/diazonaphthoquinone (DNQ).
• Novolak/DNQ photoresist a positive image is formed through the photodecomposition of the diazonaphthoquinone compound (PAC) which in resist areas exposed leads to a faster dissolution of the Novolak resin in aqueous base, these types of photoresists are employed at longer UV wavelengths such with i-line (365 nm) and were for many years workhorse photoresists in the manufacturing of integrated circuits (IC).
• DNQ-based photoresist is advantageous in its cheaper price, better environmental stability, and post-exposure-bake (PEB) free, which are beneficial for OSAT companies.
• PEB post-exposure-bake
• DNQ-based photoresists show pronounced top-loss (rounding) and footing due to the bleaching of i-line (365 nm) exposure by diazonaphthoquinone (DNQ) photoactive compound (PAC).
• DNQ diazonaphthoquinone
• PAC diazonaphthoquinone
• process modification is the commonly used strategy, such as hard baking photoresist lines (after development) with a temperature higher than its glass transition temperature (Tg) that thermal reflow photoresist structures to achieve the desired profile.
• Tg glass transition temperature
• this method decreases wafer throughput due to additional process steps.
• Novel Novolak/DNQ-based photoresist formulations comprise two Novolak resins, one DNQ PAC, and one speed enhancer (dissolution enhancer), which unexpectedly show high resolution and vertical profile down to 0.9 ⁇ m line/space at 5.0 ⁇ m film thickness.
• Novel Novolak/DNQ-based photoresist formulations unexpectedly also have significant less top-loss and also have greatly improved depth-of-focus (DOF) without any further process modifications.
• compositions are ones consisting essentially of components a), b), c), d) and e) or components a), b), c), d), e) and f) as follows:
• Component a) is a blend of two Novolak polymers having structures (I) and (II); wherein R 1 to R 9 are individually selected from a C-1 to C-4 alkyl and x, y and z represent the mole % based on total moles of repeat units in the polymer of structure (I); k, l and m represent the mole % based on total moles of repeat units in the polymer of structure (II) and further wherein x ranges from about 10 to about 20 mole %, y ranges from about 50 to about 60 mole %, z ranges from about 30 to about 40 mole %, k ranges from about 10 to about 20 mole %, l ranges from about 40 to about 50 mole %,
• Component c) is a dissolution enhancer component comprising a polyphenolic compound which is a single compound or a mixture of at least two compounds selected from the group consisting of an oligomeric fractionated Novolak, a compounds having general structure (VI) and a compound having general structure (VII), wherein R de1 , R de2 , R de3 , R de4 and R de5 are individually selected from a C-1 to C-4 alkyl; [0012]
• Component d) is a surfactant and ranges from about 0 wt. % to about 0.2 wt. % solids.
• Component e) is an organic spin casting solvent.
• Component f) is a heterocyclic thiol [0015] Further, wherein the wt. % solids ranges of components a), b), c) and d), or a components a), b), c), d) and f) using a wt. % solids calculated from the total weight of components a), b), c) and d), or a), b), c), d) and f) which combined add up to 100 wt. % solids are as follows: . component a) is one wherein the wt. % solid of, said Novolak polymers of structure (I) and (II), each independently range from about 23 wt.
• composition is free hexamethyl melamine crosslinkers and photoacid generators.
• the disclosed subject matter also pertains to the method of coating the resist compositions on a substrate as part of a lithographic process.
• FIG.1 Depth-of-Focus (DOF) Curves of Example 2 and Comparative Example 1.
• FIG.2 SEM study of depth of Focus (DOF) of Example 2 @ 5 ⁇ m film thickness (FT).
• FIG.3 Linearity of Linearity for Example 2 @ 5 ⁇ m FT DETAILED DESCRIPTION
• linking point when referring to any of the inventive polymers refers to a branching point to another polymer chain and/or a crosslinking point to another polymer chain, where the extent of branching and/or crosslinking is such that the resultant branched and/or crosslinked polymer still has a molecular weight sufficiently low so as to avoid reaching the gel point where the polymer would become insoluble in solvents such as spin-casting solvents.
• alkyl refers to hydrocarbon groups which 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 multicyclic (e.g., norbornyl, adamantly and the like).
• alkyl moieties may be substituted or unsubstituted as described below.
• alkyl refers to such moieties with C-1 to C-20 carbons.
• Alkoxy refers to an alkyl group on which is 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.
• Halo or halide refers to a halogen, F, Cl, Br or I which is linked by one bond to an organic moiety.
• Haloalkyl refers to a linear, cyclic or branched saturated alkyl group such as defined above in which at least one of the hydrogens has been replaced by a halide selected from the group of F, Cl, Br, I or mixture of these if more than one halo moiety is present. Fluoroalkyls are a specific subgroup of these moieties.
• Fluoroalkyl refers to a linear, cyclic or branched saturated alkyl group as defined above in which the hydrogens have been replaced by fluorine either partially or fully (e.g., trifluoromethyl, pefluoroethyl, 2,2,2- trifluoroethyl, prefluoroisopropyl, perfluorocyclohexyl and the like). These fluoroalkyl moieties, if not perfluorinated, may be substituted or unsubstituted as described below.
• Fluoroalkyloxy refers to a fluoroalkyl group as defined above on which is attached through an oxy (- O-) moiety it may be completed fluorinated (a.k.a. perfluorinated) or alternatively partially fluorinated (e.g., trifluoromethyloxy, perfluoroethyloxy, 2,2,2-trifluoroethoxy, perfluorocyclohexyloxy and the like). These fluoroalkyl moieties, if not pefluorinated may, be substituted or unsubstituted as described below.
• alkyl, alkyloxy, fluoroalkyl, fluoroalkyloxy moieties with a possible range of carbon atoms which starts with C-1 such as for instance “C-1 to C-20 alkyl,” or “C-1 to C-20 fluoroalkyl,” as non-limiting examples, this range encompasses linear alkyls, alkyloxy, fluoroalkyl and fluoroalkyloxy starting with C-1 but only designated branched alkyls, branched alkyloxy, cycloalkyl, cycloalkyloxy, branched fluoroalkyl, and cyclic fluoroalkyl starting with C-3.
• alkylene refers to hydrocarbon groups which can be a linear, branched or cyclic which has two or more attachment points (e.g., of two attachment points: methylene, ethylene, 1,2-isopropylene, a 1,4- cyclohexylene and the like; of three attachment points 1,1,1-subsituted methane,1,1,2-subsituted ethane, 1,2,4- subsituted cyclohexane and the like).
• solid component refers to components which are not the solvent component e), namely in one embodiment components a), b), c), and d) and in another embodiment which includes an optional heterocylic component f), components a), b), c), d) and f).
• alkyleneoxyalkylene encompasses both simple alkyleneoxyalkylene moiety such as ethyleneoxyethylene (-CH 2 -CH 2 -O-CH 2 -CH 2 -), propyleneoxypropylene (-CH 2 -CH 2 -CH 2 -O-CH 2 -CH 2 -), and the like, and also oligomeric materials such as tri(ethyleneoxyethylene) (-CH 2 -CH 2 -O-CH 2 -CH 2 -O-CH 2 -CH 2 -), tri(propyleneoxypropylen), (-CH 2 -CH 2 -CH 2 -O-CH 2 -CH 2 -CH 2 -O CH 2 - CH 2 -CH 2 -), and the like.
• aryl or “aromatic groups” refers to such groups which contain 6 to 24 carbon atoms including phenyl, tolyl, xylyl, naphthyl, anthracyl, biphenyls, bis-phenyls, tris-phenyls and the like. These aryl groups may further be substituted with any of the appropriate substituents, e.g., alkyl, alkoxy, acyl or aryl groups mentioned hereinabove.
• Novolak if used herein without any other modifier of structure, refers to Novolak resins which are soluble in aqueous bases such as tetramethylammonium hydroxide and the like.
• arylene refers to a aromatic hydrocarbon moiety which has two or more attachment points (e.g., 2-5), this moiety may be a single benzene moiety (e.g., two attachment points 1,4-phenylene, 1,3-phenylene and 1,2-phenylene; three attachment points 1,2,4-subsituted benzene, 1,3,5-substituted benzene and the like), a polycyclic aromatic moiety with two attachment points such derived from naphthalene, anthracene, pyrene and the like, or a multiple benzene rings in a chain which have two attachment point (e.g., biphenylene).
• this moiety may be a single benzene moiety (e.g., two attachment points 1,4-phenylene, 1,3-phenylene and 1,2-phenylene; three attachment points 1,2,4-subsituted benzene, 1,3,5-substituted benzene and the like), a poly
• fused ring arylenes In those instances where the aromatic moiety is a fused aromatic ring, these may be called fused ring arylenes, and more specifically named, for instance, naphthalenylene, anthracenylene, pyrenylene, and the like. Fused ring arylenes may be substituted or unsubstituted as described below, additionally these fused ring arylenes may also contain a hydrocarbon substituent which has two attachment sites on the fused ring forming an additional aliphatic or unsaturated ring forming by attachment to the fused ring a ring having 5 to 10 carbon atoms.
• PAG refers to a photoacid generator that can generate acid (a.k.a.
• the acid may be a sulfonic acid, HCl, HBr, HAsF 6 , and the like.
• onium salt and other photosensitive compounds as known in the art that can photochemically generate c strong acids such as alkylsulfonic acid, arylsulfonic acid, HAsF 6 ", HSbF 6 ", HBF4 “, HPF6 “, CF3SO 3 H, HC(SO2CF3) 2 ", HC(SO 2 CF 3 ) 3 , HN(SO 2 CF 3 ) 2 ", HB(C 6 H 5 ) 4 , HB(C 6 F 5 ) 4 , bistrifluoromethylphenyl)borate acid, p-toluenesulfonic acid, HB(CF 3 )4trihalomethyl and also photosensitive derivative of trihalomethyl heterocylic compounds which can generate a hydrogen halide such as HBr or HCl.
• c strong acids such as alkylsulfonic acid, arylsulfonic acid, HAsF 6 ", HSbF 6 ", HBF4 “, HP
• arene encompasses aromatic hydrocarbon moieties comprising 1 ring or 2 to 8 carbon based aromatic rings fused together.
• heteroene refers to an arene which contains 1 or more trivalent or divalent heteroatoms respectively in such a way as to retain its aromaticity. Examples of such heteroatoms are N, O, P, and S. As non- limiting examples, such heteroarenes may contain from 1 to 3 such hetero atoms.
• substituted aryl and substituted aryl ethenyl substituent are as follows where represents the point of attachment: [0041]
• substituted aryl, and substituted ethenyls refers to these moieties in which the substituents is selected from any of the substituents described herein.
• unsubstituted refers to these same moieties, wherein no substituents apart from hydrogen is present.
• this invention relates to a composition consisting essentially of components a), b), c), d) and e) or consist essentially of components a), b), c), d), e) and f) wherein: Component a) is a blend of two Novolak polymers having structures (I) and (II); wherein R 1 to R 9 are individually selected from a C-1 to C-4 alkyl and x, y and z represent the mole % based on total moles of repeat units in the polymer of structure (I); k, l and m represent the mole % based on total moles of repeat units in the polymer of structure (II) and further wherein x ranges from about 10 to about 20 mole %, y ranges from about 50 to about 60 mole %, z ranges from about 30 to about 40 mole%, k ranges from about 10 to about 20 mole %, l ranges from about 40 to about 50 mo
• wt. % solid of, said Novolak polymers of structure (I) and (II), each independently range from about 23 wt.% to about 70 wt. %, preferably from about 25 wt. % to about 60 wt. % solids based upon the total weight of solid components a), b), c) and d), where the sum of the individually wt% solids values for these components is 100%.
• Component b) is a diazo-naphthoquinone sulfonate (DNQ-PAC) component which is a single material or a mixture of materials having general formula having structure (III) or having general formula (III-1); wherein D 1c , D 2c , D 3c , D 4c and D 5c are individually selected from H or a moiety having structures (IV) or (V), and further wherein in structure (III) at least one of D 1c , D 2c , D 3c or D 4c is a moiety having structure (IV) or (V) and in structure (III-1) at least one of D 1c , D 2c , D 3c , D 4c , D 5c is a moiety having structure (IV) or (V).
• DNQ-PAC diazo-naphthoquinone sulfonate
• Component c) is a dissolution enhancer component comprising a polyphenolic compound which is a single compound or a mixture of at least two compounds selected from the group consisting of an oligomeric fractionated Novolak, a compounds having general structure (VI) and a compound having general structure (VII), wherein R de1 , R de2 , R de3 , R de4 and R de5 are individually selected from a C-1 to C-4 alkyl; and further where this component ranges from about 4 wt. % to about 15 wt.
• a dissolution enhancer component comprising a polyphenolic compound which is a single compound or a mixture of at least two compounds selected from the group consisting of an oligomeric fractionated Novolak, a compounds having general structure (VI) and a compound having general structure (VII), wherein R de1 , R de2 , R de3 , R de4 and R de5 are individually selected from a C-1 to C-4 alkyl; and further where this component ranges from about
• Component d) is a surfactant which ranges from about 0 wt. % to about 0.2 wt. % solids.
• Component e) is an organic spin casting solvent.
• Component f) is a heterocyclic thiol [0049] Further, this composition consisting essentially of components a), b), c), d) and e) or of component a), b), c), d), e) and f) is one which is free of hexamethyl melamine type crosslinkers materials and photoacid generator. [0050] In one embodiment said composition is one which consist essentially of components a), b), c), d) and e).
• said composition is one which consist essentially of components a), b), c), d), e) and f). [0052] In one embodiment said composition is one consisting of component a), b), c), d) and e). [0053] In one embodiment said composition is one consisting of components of a), b), c), d), e) and f). [0054] In one embodiment of the inventive composition component a) is one wherein R 1 to R 9 are methyl.
• x ranges from about 15 to about 20 mole % y ranges from about 50 to about 55 mole %, and z ranges from about 30 to about 35 mole %.
• the repeat unit of structure (Ia), whose mole % x ranges from about 10 to about 25 mole %, is comprised of a mixture of isomeric repeat units having structures (Iax1), (Iax2), (Iax3) (Iax4), (Iax5), and (Iax6), which respectively have mole % values of x1, x2, x3, x4, x5 and x6, based on the total amount of the repeat unit of structure (Ia) wherein; x1, the mole % values of the repeat unit of structure (Iax1), ranges from 0 to about 5 mole %, x2, the mole % values of the repeat unit of structure (Iax2), ranges from 0 to about 5 mole %, x3, the mole % values of the repeat unit of structure (Iax3), ranges from about 20 to about 25 mole %,
• the polymer of structure (II), the repeat unit of structure (IIa), whose mole % k ranges from about 10 mole% to about 20 mole% is comprised of a mixture of isomeric repeat units having structures (IIax1), (IIax2), (IIax3) (IIax4), (IIax5), and (IIax6), which respectively have mole % values of k1, k2, k3, k4, k5 and k6, where the total of these mole % values ranges from about 10 mole % to about 20 mole %, wherein; k1, the mole % values of the repeat unit of structure (IIak1), ranges from about 10 to about 20 mole %, k2, the mole % values of the repeat unit of structure (IIak2), ranges from 0 to about 5 mole %, k3, the mole % values of the repeat unit of
• inventive composition in another embodiment, described herein, it is one wherein for the polymer of structure (II), k ranges from about 15 to about 20 mole %, l ranges from about 40 to about 50 mole %, and m ranges from about 35 to about 40 mole %.
• inventive component a) is one wherein the wt. % solid of, said Novolak polymers of structures (I) ranges from about 23 wt. % to about 55 wt. % total solids, and the Novolak polymer of structure (II) ranges from about 25 wt. % to about 56 wt.
• said Novolak polymers of structures (I) ranges from about 23.5 wt. % to about 52 wt. % total solids and said Novolak polymer of structure (II) ranges from about 28 wt. % to about 55.5 wt. % total solids.
• said DNQ PAC is one wherein D 1c , D 2c , D 3c and D 4c are individually selected from H or a moiety having structures (IV), and further wherein at least one of D 1c , D 2c , D 3c or D 4c is a moiety having structure (IV).
• component b) said DNQ PAC is one wherein D 1c , D 2c , D 3c and D 4c are individually selected from H or a moiety having structures (V), and further wherein at least one of D 1c , D 2c , D 3c or D 4c is a moiety having structure (V).
• said speed enhancer ranges from about 5 wt. % to about 15 wt. %. In another aspect of this embodiment, it ranges from about 6 wt.% to about 14 wt. %. In another aspect of this embodiment is ranges from about 6.5 wt.
• said speed enhancer is an oligomeric fractionated Novolak. In one aspect of this embodiment said speed enhancer ranges from about 5 wt. % to about 14 wt. %. In another aspect of this embodiment, it ranges from about 5 wt.% to about 13 wt. %. In another aspect of this embodiment is ranges from about 6..0 wt. % to about 12 wt. %. In another aspect of this embodiment, it ranges from about 6.5 wt.
• % to about 11 wt. % In another aspect of this embodiment, it ranges from about 6.5 wt. % to about 10 wt. %. In another aspect of this embodiment, it ranges from about 6.5 wt. % to about 10 wt. %. In another aspect of this embodiment, it ranges from about 6.5 wt. % to about 9 wt. %. In another aspect of this embodiment, it ranges from about 6.5 wt. % to about 8 wt. %. In one aspect of this embodiment, it is about 7 wt. %.
• said speed enhancer is a compound of structure (VI), a compound of structure (VII) or a mixture of these.
• R de1 , R de2 , and R de3 are all selected from the same C-1 to C-4 alkyl.
• said speed enhancer has structure (VI). In one aspect of this embodiment said speed enhancer ranges from about 5 wt. % to about 14 wt. %. In another aspect of this embodiment, it ranges from about 5 wt.% to about 13 wt. %.
• In another aspect of this embodiment is ranges from about 6.0 wt. % to about 12 wt. %. In another aspect of this embodiment, it ranges from about 6.5 wt. % to about 11 wt. %. In another aspect of this embodiment, it ranges from about 6.5 wt. % to about 10 wt. %. In another aspect of this embodiment, it ranges from about 6.5 wt. % to about 10 wt. %. In another aspect of this embodiment, it ranges from about 6.5 wt. % to about 9 wt. %. In another aspect of this embodiment, it ranges from about 6.5 wt. % to about 8 wt. %.
• said speed enhancer is a mixture of different compounds which have structure (VI).
• said speed enhancer ranges from about 5 wt. % to about 14 wt. %. In another aspect of this embodiment, it ranges from about 5 wt.% to about 13 wt. %. In another aspect of this embodiment is ranges from about 6.0 wt. % to about 12 wt. %. In another aspect of this embodiment, it ranges from about 6.5 wt. % to about 11 wt. %. In another aspect of this embodiment, it ranges from about 6.5 wt.
• component c) said speed enhancer has structure (VII). In one aspect of this embodiment, said speed enhancer ranges from about 5 wt. % to about 15 wt. %.
• it ranges from about 6 wt.% to about 14 wt. %. In another aspect of this embodiment is ranges from about 7 wt. % to about 13 wt. %. In another aspect of this embodiment, it ranges from about 8 wt. % to about 12.5 wt. %.%. In another aspect of this embodiment, it ranges from about 8 wt. % to about 12.5 wt. %. In another aspect of this embodiment, it ranges from about 9 wt. % to about 12.5 wt. %. In another aspect of this embodiment, it ranges from about 10 wt. % to about 12.5 wt. %.
• component c) said speed enhancer, is a mixture of different compounds which have structure (VII). In another aspect of this embodiment, it ranges from about 6 wt.% to about 14 wt. %. In another aspect of this embodiment is ranges from about 7 wt. % to about 13 wt. %. In another aspect of this embodiment, it ranges from about 8 wt. % to about 12.5 wt. %.%. In another aspect of this embodiment, it ranges from about 8 wt.
• component c) is a mixture of speed enhancers of structures (VI) and (VII).
• component c), said speed enhancer is either selected from one having structure (VIa), or structure (VIIa) or is a mixture of the speed enhancers of structures (VIa) and (VIIa). In another aspect of this embodiment, it has structure (VIa). In another aspect of this embodiment said speed enhancer has structure (VIIa). In another aspect of this embodiment said speed enhancer is a mixture of structures (VIa) and (VIIa). [0072] In another embodiment of the inventive composition, described herein, component c), said speed enhancer, has structure (VIa) and it ranges from about 5 wt. % to about 14 wt. %.
• it ranges from about 5 wt.% to about 13 wt. %. In another aspect of this embodiment is ranges from about 6.0 wt. % to about 12 wt. %. In another aspect of this embodiment, it ranges from about 6.5 wt. % to about 11 wt. %. In another aspect of this embodiment, it ranges from about 6.5 wt. % to about 10 wt. %. In another aspect of this embodiment, it ranges from about 6.5 wt. % to about 10 wt. %. In another aspect of this embodiment, it ranges from about 6.5 wt. % to about 9 wt. %.
• component c) said speed enhancer, has structure (VIIa) and it ranges from about 6 wt.% to about 14 wt. %. In another aspect of this embodiment is ranges from about 7 wt. % to about 13 wt. %. In another aspect of this embodiment, it ranges from about 8 wt. % to about 12.5 wt. %.%. In another aspect of this embodiment, it ranges from about 8 wt. % to about 12.5 wt. %.
• it ranges from about 9 wt. % to about 12.5 wt. %. In another aspect of this embodiment, it ranges from about 10 wt. % to about 12.5 wt. %. In another aspect of this embodiment, it ranges from about 11 wt. % to about 12.5 wt. %. In another aspect of this embodiment, it is about 12 wt. %.
• component d) for said surfactant there is no particular restriction with regard to the surfactant, and the examples of it include a polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene olein ether; a polyoxyethylene alkylaryl ether such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; a polyoxyethylene polyoxypropylene block copolymer; a sorbitane fatty acid ester such as sorbitane monolaurate, sorbitane monovalmitate, and sorbitane monostearate; a nonionic surfactant of a polyoxyethylene sorbitane fatty acid ester such as polyoxyethylene sorbitane monolaurate, polyoxyethylene sorbitane monopalmitate, polyoxyethylene
• the total weight of components a), b), c) and d), or a), b), c), d) and f), when combined with the solvent component e), results in a wt% of total of these solid components in the solvent which ranges from about 30% to about 40 %.
• component e) organic spin casting solvent, comprises one or more of butyl acetate, amyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, cyclopentanone, ethyl-3-ethoxy propanoate, methyl-3-ethoxy propanoate, methyl-3-methoxy propanoate, 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, ethylene glycol monoethyl ether, diethylene
• the solvent component comprises propylene glycol monomethyl ether (PGME). In another aspect of this embodiment the solvent component comprises propylene glycol monomethyl ether acetate (PGMEA).
• Component f) Heterocyclic thiols [0076] In one embodiment of the above-described inventive compositions it further comprises at least one optional heterocyclic thiol component.
• said heterocyclic thiol component is at least one heterocyclic thiol compound comprising a ring structure chosen from the general structures (H1), (H2) or (H3), or tautomers thereof; and said ring structure is a single ring structure having from 4 to 8 atoms, or a multi ring structure having from 5 to 20 atoms; and wherein the single ring structure, or the multi ring structure comprises an aromatic, non-aromatic, or heteroaromatic ring.
• Xt is selected from the group consisting of N(Rt3), C(Rt 1 )(Rt 2 ), O, S, Se, and Te.
• Rt 1 , Rt 2 , and Rt 3 are independently selected from the group consisting of H, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkenyl group having 2 to 8 carbon atoms, unsubstituted alkenyl group having 2 to 8 carbon atoms, a substituted alkynyl group having 2 to 8 carbon atoms, unsubstituted alkynyl group having 2 to 8 carbon atoms, a substituted aromatic group having 6 to 20 carbon atoms, a substituted heteroaromatic group having 3 to 20 carbon atoms, unsubstituted aromatic group having 6 to 20 carbon atoms and unsubstituted heteroaro
• said heterocyclic thiol compound is present from about 0.5 wt. % to about 1.5 wt,% total solids.
• said inventive composition comprises at least one heterocyclic thiol chosen from the above general structures (H1), (H2) or (H3), or tautomers thereof these may be chosen without limitation from substituted or unsubstituted triazole thiols, substituted or unsubstituted imidazole thiols, substituted or unsubstituted triazine thiols, substituted or unsubstituted mercapto pyrimidines, substituted or unsubstituted thiadiazole-thiols, substituted or unsubstituted indazole thiols, tautomers thereof or combinations thereof.
• Substituents may include, without limitation, saturated or unsaturated hydrocarbon groups, substituted or unsubstituted aromatic rings, aliphatic, aromatic or heteroaromatic alcohols, amines, amides, imides carboxylic acids, esters, ethers, halides, and the like. Such substituents may be used in concert with the heterocyclic thiol to improve solubility, to modify interaction with the substrate, to enhance exposure to light or to act as an antihalation dye.
• said inventive composition comprises at least one heterocyclic thiol chosen from the above general structures (H1), (H2) or (H3), or tautomers thereof such heterocyclic thiols may be chosen, without limitation from the following compounds (H4) to (H23) in unsubstituted or substituted form: [0079] In another aspect of the embodiment wherein said inventive composition comprises at least one heterocyclic thiol having general structures (H1), (H2) or (H3), or tautomers thereof, such heterocyclic thiols may be chosen from thiouracil derivatives such as 2-thiouracil.
• said inventive composition comprises at least one heterocyclic thiol chosen from the above general structures (H1), (H2) or (H3), or tautomers thereof
• heterocyclic thiols may be selected from the group consisting of unsubstituted triazole thiol, substituted triazole thiol, unsubstituted imidazole thiol, substituted imidazole thiol, substituted triazine thiol, unsubstituted triazine thiol, a substituted mercapto pyrimidine, unsubstituted mercapto pyrimidine, a substituted thiadiazole-thiol, unsubstituted thiadiazole-thiol, substituted indazole thiol, unsubstituted indazole thiol, tautomers thereof, and combinations thereof.
• said heterocyclic thiol this is at least one heterocyclic thiol chosen from the above general structures (H1), (H2) or (H3), or tautomers thereof such heterocyclic thiols may be selected from the group consisting of 1,3,5-triazine-2,4,6- trithiol, 2-mercapto-6-methylpyrimidin-4-ol, 3-mercapto-6-methyl-1,2,4-triazin-5-ol, 2-mercaptopyrimidine- 4,6-diol, 1H-1,2,4-triazole-3-thiol, 1H-1,2,4-triazole-5-thiol, 1H-imidazole-2-thiol, 1H-imidazole-5-thiol, 1H- imidazole-4-thiol, 2-azabicyclo[3.2.1]oct-2-ene-3-thiol, 2-azabicyclo[2.2.1]hept-2-
• this composition where it comprises at least one heterocyclic thiol chosen from the above general structures (H1), (H2) or (H3) as described herein, said heterocyclic thiol is present at a loading ranging from about 0.001 wt. % to about 1.5 wt. % of total solids. In another aspect of this embodiment, this heterocyclic thiol ranges from about 0.010 wt. % to about 1.5 wt. % of total solids. In another aspect of this embodiment this heterocyclic thiol ranges from about 0.1 wt. % to about 1.5 wt. % of total solids. In another aspect of this embodiment this heterocyclic thiol ranges from about 0.2 wt.
• this heterocyclic thiol ranges from about 0.3 wt. % to about 1.5 wt. % of total solids. In another aspect of this embodiment this heterocyclic thiol compound ranges from about 0.4 wt. % to about 1.5 wt. % of total solids. In another aspect of this embodiment this heterocyclic thiol ranges from about 0.6 wt. % to about 1.4 wt. % of total solids. In another aspect of this embodiment this heterocyclic thiol ranges from about 0.7 wt. % to about 1.3 wt. % of total solids.
• said heterocyclic thiol compound ranges from about 0.8 wt. % to about 1.2 wt. % of total solids. In another aspect of this embodiment said heterocyclic thiol compound ranges from about 0.9 wt. % to about 1.1 wt. % of total solids. In another aspect of this embodiment said heterocyclic thiol compound is about 1 wt. % of total solids. [0083] In another aspect of this composition where it comprises at least one heterocyclic thiol chosen from the above general structures (H1), (H2) or (H3) as described herein, this heterocyclic thiol compound, as described herein, ranges from about 0.01 wt.
• this heterocyclic thiol compound ranges from about 0.04 wt. % to about 0.49 wt. % of total solids. In another aspect of this embodiment this heterocyclic thiol compound ranges from about 0.08 wt. % to about 0.49 wt. % of total solids. In another aspect of this embodiment this heterocyclic this thiol compound ranges from about 0.09 wt. % to about 0.49 wt. % of total solids. In another aspect of this embodiment this heterocyclic thiol compound ranges from about 0.10 wt. % to about 0.49 wt. % of total solids.
• this heterocyclic thiol compound ranges from about 0.15 wt. % to about 0.49 wt. % of total solids. In another aspect of this embodiment this heterocyclic thiol compound ranges from 0.20 wt. % to about 0.49 wt. % of total solids. In another aspect of this embodiment this heterocyclic thiol compound ranges from 0.25 wt. % to about 0.48 wt. % of total solids. In another aspect of this embodiment this heterocyclic thiol compound ranges from 0.30 wt. % to about 0.47 wt. % of total solids. In another aspect of this embodiment this heterocyclic thiol compound ranges from 0.30 wt.
• this heterocyclic thiol compound ranges from 0.30 wt. % to about 0.47 wt. % of total solids. In another aspect of this embodiment this heterocyclic thiol compound ranges from 0.30 wt. % to about 0.49 wt. % of total solids. In another aspect of this embodiment this heterocyclic thiol compound ranges from 0.30 wt. % to about 0.45 wt. % of total solids. In another aspect of this embodiment this heterocyclic thiol compound ranges from 0.30 wt. % to about 0.45 wt. % of total solids. In another aspect of this embodiment this heterocyclic thiol compound ranges from 0.30 wt. % to about 0.45 wt. % of total solids.
• this heterocyclic thiol compound ranges from 0.30 wt. % to about 0.44 wt. % of total solids. In another aspect of this embodiment this heterocyclic thiol compound ranges from 0.30 wt. % to about 0.43 wt. % of total solids. In another aspect of this embodiment this heterocyclic thiol compound ranges from 0.30 wt. % to about 0.42 wt. % of total solids. In another aspect of this embodiment this heterocyclic thiol compound ranges from 0.30 wt. % to about 0.41 wt. % of total solids. In another aspect of this embodiment this heterocyclic thiol compound ranges from 0.30 wt.
• composition disclosed herein may be dissolved in an organic solvent.
• Suitable organic solvents include, without limitation, butyl acetate, amyl acetate, cyclohexyl acetate, 3- methoxybutyl acetate, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, cyclopentanone, ethyl-3- ethoxy propanoate, methyl-3-ethoxy propanoate, methyl-3-methoxy propanoate, methyl acetoacetate, ethyl acetoacetate, diacetone alcohol, methyl pivalate, ethyl pivalate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether propanoate, propylene glycol monoethyl ether propanoate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl
• the above-described inventive compositions it further comprises at least one optional surface leveling agents may include surfactants.
• the surfactant include a polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene olein ether; a polyoxyethylene alkylaryl ether such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; a polyoxyethylene polyoxypropylene block copolymer; a sorbitane fatty acid ester such as sorbitane monolaurate, sorbitane monovalmitate, and sorbitane monostearate; a nonionic surfactant of a polyoxyethylene sorbitane fatty acid ester such as polyoxyethylene
• Another aspect of this invention is a process of coating any one of the compositions described herein on a substrate.
• Another aspect of this invention is a process of imaging a resist comprising the steps; i) coating any one of the compositions described herein on 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 positively imaged resist film over the substrate.
• Another aspect of this invention is a process of imaging a resist comprising the steps; ia) coating any one of the compositions described herein on 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 baked selectively exposed resist film; iva) developing the selectively exposed and baked resist film to form a positively imaged resist film over the substrate.
• Another aspect of this invention is the use of the compositions described herein for coating a substrate or for preparing an imaged resist film on a substrate.
• the Si wafers were rehydration baked and vapor primed with hexamethyldisilazane (HMDS).
• HMDS hexamethyldisilazane
• the Cu wafers were silicon wafers coated with 5,000 Angstroms of silicon dioxide, 250 Angstroms of tantalum nitride, and 3,500 Angstroms of Cu (PVD deposited).
• the resist coatings were prepared by spin coating the resist samples and applying a soft bake for 120 seconds at 110°C on standard wafer track hot plate in contact mode. The spin speed was adjusted to obtain 5 to 10-microns thick resist films. All film thickness measurements were conducted on Si wafers using optical measurements. Imaging: [0093] The wafers were exposed on SUSS MA200 CC Mask Aligner or on ASML 250 i-line stepper.
• the dissolution rate of the Novolak is 63 ⁇ /S in 0.26N aqueous TMAH developer.
• MIPHOTO NOVOL T106S is a m-cresol/p-cresol/trimethylphenol/formaldehyde Novolak polymer, sold under the name of MIPHOTO NOVOL T106S, supplied by Miwon Commercial Co., Ltd.
• the dissolution rate of the Novolak is 309 ⁇ /S in 0.26N aqueous TMAH developer.
• MIPHOTO PAC BP524 is a DNQ PAC sold under this name by Miwon Commercial Co., Ltd.
• BI26X-SA is Bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, a dissolution enhancer sold under this name by Asahi Yukizai Co., Ltd.
• TPPA 4,4'-(1-(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl)ethane-1,1-diyl)diphenol
• APS-437 (a.k.a. KF-353A) is a surfactant from Shinetsu, (Tokyo, Japan).
• PGMEA (1-Methoxy-2-propanyl acetate), the solvent used for photoresist formulation examples was obtained from Sigma-Aldrich a subsidiary of Merck KGaA (Darmstadt, Germany).
• AZ 300MIF developer was obtained from EMD Performance Materials Corp, a subsidiary of Merck KGaA (Darmstadt, Germany) (a.k.a.2.38% Tetramethylammonium hydroxide (TMAH)).
• TMAH Tetramethylammonium hydroxide
• Molecular weights of polymers were measured with Gel Permeation Chromatography (GPC).
• the Novolak/DNQ photoresist composition comprises two Novolak resins, one DNQ photoactive compound, one dissolution enhancer, one surfactant, and one solvent.
• the two Novolak resins utilized in the photoresist composition consist of different monomers and composition ratios.
• Photoresists were spin-coated on silicon wafers, and soft-baked on a hot plate and then exposed by the gh-line or i-line stepper. The exposed wafers were then developed to remove the exposed areas using AZ® 300MIF developer. Finally, the wafers were rinsed with DI water and then spin dried to obtain photoresist patterns.
• the photoresist composition was spin-coated on a silicon wafer substrate, soft-baked at 110°C/120sec to obtain a film with 5.0 ⁇ m thickness.
• a Novolak/DNQ photoresist composition was made by mixing Comparative Example 1 (32.53 grams) and Comparative Example 2 (17.37 grams). Thus, a positive photoresist composition with a solid content of 34.50% by weight was prepared. This composition was evaluated as the same manner as in Comparative Example 1. The 1.0 ⁇ m L/S (line/space) resolved at 240 mJ/cm 2 showed a top CD of 0.725 ⁇ m and bottom CD of 1.180 ⁇ m.
• a Novolak/DNQ photoresist composition was made by mixing Comparative Example 1 (16.60 grams) and Comparative Example 2 (33.40 grams). Thus, a positive photoresist composition with a solid content of 34.18% by weight was prepared. This composition was evaluated as the same manner as in Comparative Example 1. The 1.0 ⁇ m L/S (line/space) resolved at 140 mJ/cm 2 showed a top CD of 0.861 ⁇ m and bottom CD of 1.151 ⁇ m.
• Novolak/DNQ photoresist composition was made by mixing 42.7% PGMEA solution of Novolak resin SPN400 Slow (21.15 grams), 30.01% PGMEA solution of Novolak resin MIPHOTO NOVOL T106S (66.21 grams), 3.71 grams of MIPHOTO PAC BP524, 4.47 grams of dissolution enhancer TPPA, 0.375 grams of adhesion additive PMT, 10.0% PGMEA solution of surfactant APS-437 (also called KF-353A, 0.446 grams) and 3.636 grams of PGMEA.
• FIG. 2 shows a scanning electron micrograph (SEM) study demonstrating the good dept of focus of (DOF) of Example 2 when coated as a 5 ⁇ m film thickness and imaged.
• FIG.3 shows a scanning electron micrograph (SEM) study demonstrating the good linearity of Example 2 when coated as a 5 ⁇ m film thickness and imaged.
• FIG.4 shows Table 1, which gives a summary of the lithographic performance of Examples 1, 2 and 3 compared to Comparative Examples 1, which again highlights the unexpected improvement of our new formulations as described herein.

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