Positive-working photosensitive material

Abstract

To provide a positive working photosensitive material and additive thereof which may be useful on copper, chalcophile element, silicon, or reflective substrates.SOLUTION: Disclosed herein is a photosensitive composition comprising a) at least one photoacid generator; b) at least one Novolak polymer; c) at least one acrylate polymer, comprising a component having structure (I); d) at least one glycidyl hydroxy benzoic acid condensate material comprising one or more compounds having structure (II); e) at least one heterocyclic thiol compound comprising a ring structure chosen from the general structures (III), (IIIa) or (IIIb); and f) at least one solvent. Disclose herein are also the methods of using this composition to form a resist pattern and the methods of using these resist patterns to produce metal lines. Disclosed herein are also compounds having structure (II) and mixtures of such compounds.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] This patent application is in the field of photoresist imaging. More specifically, this patent application discloses and claims positive-working photosensitive materials and additives thereto that may be useful, but are not limited to, on copper, cuprophilic, silicon or reflective substrates. [Background technology]

[0002] Photoresist compositions are used in microlithography processes for the manufacture of miniaturized electronic components, such as the manufacture of integrated circuit devices.In these processes, a coated film of a photoresist composition is generally applied to a substrate, such as a silicon wafer used to manufacture integrated circuits, circuit boards, and flat panel display substrates.The coated substrate is then baked to evaporate the solvent in the photoresist composition and to fix the coating on the substrate.The coated and baked surface of the substrate is then subjected to imagewise exposure to actinic radiation.

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

[0004] After this development operation, the now partially unprotected substrate may be treated with a substrate etching solution, plasma gases or reactive ions, or a metal or metal composite may be deposited by sputtering or chemical vapor deposition, or a metal may be electroplated, in the spaces of the substrate where the photoresist coating was removed during development. The areas of the substrate where the photoresist coating still remains are protected. The remaining areas of the photoresist coating may then be removed during a stripping operation, leaving a patterned substrate surface. Optionally, it is desirable to heat treat the remaining photoresist layer after the development step and before the etching step to improve its adhesion to the underlying substrate.

[0005] In the manufacture of patterned structures, e.g., in wafer-level packaging, display, light-emitting diode applications or in the manufacture of microelectromechanical systems, electrochemical deposition of electrical interconnects has been used as the density of interconnects increases. See, e.g., Solomon, Electrochemically Deposited Solder Bumps for Wafer-Level Packaging, Packaging / Assembly, Solid State Technology, pages 84-88, April 2001. Gold bumps, copper or other metal posts and copper traces for rewiring in wafer-level packaging require photoresist molds that can be subsequently electroplated to form the final metal structures in modern interconnect technologies. The photoresist layers are very thick compared to the photoresists used in IC manufacturing for critical layers. Both feature sizes and photoresist thicknesses are typically in the range of 2 μm to 100 μm (micrometers), so high aspect ratios (thickness of photoresist to line size) need to be patterned in the photoresist.

[0006] Positive-working photoresists containing novolac polymers and quinone diazide compounds as photoactive compounds are well known in the art. Novolac polymers may be reacted with quinone diazide to combine with polymers. Photoresists based solely on novolac / diazide have been found to not have the photosensitivity or sidewall slope required for certain types of processes, especially for very thick films. Furthermore, significant dark-film loss in the developer is often observed.

[0007] Known chemically amplified photoresists, such as blocked poly-4-hydroxystyrene (PHOST), blocked copolymers containing hydroxystyrene and blocked (meth)acrylic acid repeat units, such as tert-butyl (meth)acrylate, or photoresists based on (meth)acrylic materials containing alicyclic groups, acid cleavable groups and dissolution improving groups, such as acid anhydrides or lactones, exhibit the necessary photosensitivity and also have additives to compensate for substrate reflection problems, acid diffusion problems or film loss, but unfortunately may also exhibit adhesion failure during certain subsequent unit operations, such as electroplating or etching. In particular, for example, during electroplating of metal lines using a patterned film of such resist as a mask barrier, even resists that otherwise produce smooth lines at the substrate interface tend to produce metal line patterns that lose adhesion during or after the metal electroplating process. It is also important to electroplate metal lines with a large contact area with the substrate to avoid electrical and thermal conduction problems that arise when the electroplated lines have a small contact area with the substrate.

[0008] Therefore, there is a need for a positive photoresist material that produces a patterned photoresist that can be used to form metal lines with good adhesion during metal electroplating operations, has high photosensitivity even in thick film applications, even on reflective substrates, has a suitable development time for processing, has low film loss in developers and basic electroplating solutions, and can withstand wet electroplating and etching operations to allow for the electroplating of metal lines without loss of adhesion of those lines, and also allows for the electroplating of metal lines that maintain a large contact area with the substrate, thereby avoiding the conductivity and heat problems that arise in metal lines from small contact areas. This specification and the accompanying claims address these needs. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] US6,042,988 [Patent Document 2] US6783912 [Patent Document 3] US6908722 [Non-patent literature]

[0010] [Non-Patent Document 1] Solomon, Electrochemically Deposited Solder Bumps for Wafer-Level Packaging, Packaging / Assembly, Solid State Technology, pages 84-88, April 2001 [Non-Patent Document 2] “Diazonapthoquinone-based Resist”,Ralph Dammel,SPIE,Optical Engineering Press,Volume TT11,Chapters 2 and 3 [Non-Patent Document 3] “Evaluation of the standard addition method to determine rate constants for acid generation in chemically amplified photoresist at 157 nm”Adam R.Pawloski;Charles R.Szmanda;Paul F.Nealey,Proc.SPIE 4345,Advances in Resist Technology and Processing XVIII,Santa Clara CA,February 25,2001,Editor Francis Houlihan p1056,August 24,2001 [Non-Patent Document 4] “Chemically Amplification Resists for Microlithography” Hiroshi Ito,Adv.Polym.Sci.172 p37,2005 [Non-Patent Document 5] “Chemical Amplification Mechanisms for Microlithography”E.Reichmanis et al.,Chem.Mater.13,2305,2001 [Non-Patent Document 6] “i-Line sensitive Photoacid Generators for UV curring”Masumitsu Shirai et al,Progress in Organic coatings,64,175,2009 [Non-Patent Document 7] “The plating Forecast and Assurance,Larry G Yeon,Larry King Corporation,Chapter 1,pages 5 to 56,2004” Summary of the Invention

[0011] The present invention relates to a) at least one photoacid generator; b) at least one novolac polymer; c) at least one acrylate polymer comprising a component having the following structure (I):

[0012] [ka] [In the formula, R1 to R6 are independently -H or -CH3, and A is a linear or branched C2-C 10 An alkylene group, B is C1-C 12 A primary or secondary unsubstituted linear, branched, cyclic or aliphatic alkyl group, where C is C1-C 12 a primary or secondary unsubstituted linear, branched, cyclic or aliphatic alkyl group; and D is a linking group, which is a direct valence bond or a linear or branched C1-C 10 , preferably C2 to C 10 Ar is a substituted or unsubstituted aromatic or heteroaromatic group; E is a linear or branched C-C 10 is an alkylene group, G is an acid cleavable group, t is from 0 mol % to about 40 mol %, v is from 0 mol % to about 15 mol %, w is from 0 mol % to about 45 mol %, x is from 0 mol % to about 80 mol %, y is from about 20 mol % to about 50 mol %, and z is from about 20 mol % to about 50 mol %, and further wherein the sum of t, v, w, x, y, and z is equal to 100 mol. d) at least one glycidyl hydroxybenzoic acid condensate material comprising one or more compounds having the following structure (II):

[0013] [ka] [In the formula, W is an organic moiety having a molecular weight of 600 or less, where W forms an ether bond with the oxygen to which it is attached; m is an integer from 1 to 3, and n is an integer from 1 to 4, when m is 1, n is 3 or 4; and when m is 2 or 3, n is an integer from 1 to 4; n' is 0 or 1. e) at least one heterocyclic thiol compound comprising a ring structure selected from the general structural formulas (III), (IIIa) or (IIIb), or tautomers thereof;

[0014] [ka] [In the formula, the ring structure is a monocyclic structure having 4 to 8 atoms or a polycyclic structure having 5 to 20 atoms; wherein the monocyclic structure or the polycyclic structure includes an aromatic, non-aromatic or heteroaromatic ring; and In the structure (III), X is selected from the group consisting of C(Rt1)(Rt2), O, S, Se, and Te; In the structure (IIIa), Y is selected from the group consisting of C(Rt3) and N; In the structure (IIIb), Z is selected from the group consisting of C(Rt3) and N; and Rt1, Rt2, and Rt3 are independently selected from H, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkenyl group having 2 to 8 carbon atoms, an unsubstituted alkenyl group having 2 to 8 carbon atoms, a substituted alkynyl group having 2 to 8 carbon atoms, an unsubstituted alkynyl group having 2 to 8 carbon atoms, a substituted aromatic group having 6 to 20 carbon atoms, a substituted heteroaromatic group having 3 to 20 carbon atoms, an unsubstituted aromatic group having 6 to 20 carbon atoms, and an unsubstituted heteroaromatic group having 3 to 20 carbon atoms. f) at least one solvent; The present invention relates to a positive-working photosensitive composition comprising:

[0015] The present invention also relates to a process for applying the positive-working photosensitive composition described herein onto a substrate; imagewise exposing the photosensitive layer to actinic radiation to form a latent image; baking the latent image; and developing the baked latent image in a developer.

[0016] The present invention also relates to compounds having at least one glycidyl hydroxybenzoic acid condensate material, which comprises one or more compounds having the structure (II).

[0017] [ka] [In the formula, W is an organic moiety having a molecular weight of 600 or less, where W forms an ether bond with the oxygen to which it is attached; m is an integer from 1 to 3, and n is an integer from 1 to 4, when m is 1, n is 3 or 4; and when m is 2 or 3, n is an integer from 1 to 4; n' is 0 or 1. [Brief description of the drawings]

[0018] [Figure 1] A photoresist having an undercut profile. [Diagram 2] Plated Cu wire with foot. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] As used herein, the conjunction "or" is not intended to be exclusive unless otherwise indicated or required by context. For example, the phrase "or alternatively" is intended to be exclusive. As a further example, "or" can be exclusive when describing chemical substitutions at a particular location.

[0020] As used herein, the term "cupophilic elements" refers to elements that have an affinity for the chalcogen elements sulfur, selenium, and tellurium. In addition to the chalcogens themselves, these elements may also include copper, zinc, gallium, germanium, arsenic, silver, cadmium, lanthanum, tin, antimony, gold, mercury, thallium, lead, and bismuth. Without being limited thereto, these elements may form primarily covalent bonds with one or more of the chalcogen elements. Cuprophilic substrates include one or more of the cupophilic elements listed above.

[0021] As used herein, it is understood that a repeat unit within a polymer may also be referred to by its corresponding monomer, for example, acrylate monomer (1) corresponds to the polymer repeat unit (2).

[0022] [ka] As used herein, the designation "(meth)acrylate repeat unit" may refer to an acrylate repeat unit or, alternatively, a methacrylate repeat unit. Thus, "acrylic acid" and "methacrylic acid" are collectively referred to as "(meth)acrylic acid", "acrylic acid derivatives" and "methacrylic acid derivatives" are collectively referred to as "(meth)acrylic acid derivatives", and "acrylates" and "methacrylates" are collectively referred to as "(meth)acrylates".

[0023] It is to be understood that both the general description above and the detailed description below are exemplary and explanatory, and are not intended to restrict the invention as claimed. In this application, unless specifically stated otherwise, the use of the singular includes the plural, the singular means "at least one," and the use of "or" means "and / or." Furthermore, the use of the term "comprises" and other verb forms such as "comprises" is not limiting. Also, the use of terms such as "element" or "component" includes both elements and components that contain one unit, and elements or components that contain more than one unit, unless specifically stated otherwise. Unless otherwise indicated, the conjunction "and" as used herein is intended to be inclusive, and the conjunction "or" is not intended to be exclusive. For example, the phrase "or instead of" is intended to be exclusive. As used herein, the conjunction "and / or" refers to any combination of the aforementioned elements, including the use of a single element.

[0024] The section headings used herein are for organizational purposes only and should not be construed as limiting the subject matter described. All references or portions of references cited herein, including but not limited to patents, patent applications, papers, books, and treatises, are incorporated herein in their entirety for all purposes. In the event that the definition of a term in one or more of the references and similar materials incorporated herein conflicts with that herein, the definition in the present application shall control.

[0025] Here, unless otherwise stated, alkyl refers to a hydrocarbon group that can be linear, branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, and the like), or cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, and the like) polycyclic (e.g., norbornyl, adamantyl, and the like). These alkyl moieties can be substituted or unsubstituted as described below. The term alkyl refers to such moieties having C1-C20 carbons. For structural reasons, linear alkyls start at C1, while branched alkyls start at C3 and polycyclic alkyls start at C5. Furthermore, moieties derived from alkyl as described below, such as alkyloxy, haloalkyloxy, and the like, are understood to have the same carbon number range unless otherwise stated. In the event that a different alkyl group length is specified above, the above definition of alkyl is still valid in that it encompasses all types of alkyl moieties as described above, and the above structural discussion regarding the minimum carbon number of a given type of alkyl group still applies.

[0026] Alkyloxy (also known as alkoxy) refers to an alkyl group as defined above 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.

[0027] Halo or halide refers to a halogen, i.e., F, Cl, Br, I, attached to an organic moiety by a single bond.

[0028] Haloalkyl refers to a saturated linear, cyclic or branched alkyl group, such as those described above, in which at least one of the hydrogens is replaced by a halide selected from the group consisting of F, Cl, Br, I, or mixtures thereof when more than one halo moiety is present. Fluoroalkyl is a specific subgroup of these moieties.

[0029] Fluoroalkyl refers to linear, cyclic or branched saturated alkyl groups as defined above in which hydrogen has been partially or fully replaced by fluorine (e.g., trifluoromethyl, perfluoroethyl, 2,2,2-trifluoroethyl, perfluoroisopropyl, perfluorocyclohexyl, and the like). These fluoroalkyl moieties, if not fully fluorinated, may be substituted or unsubstituted as described below.

[0030] Fluoroalkyloxy refers to a fluoroalkyl group, as defined above, attached through an oxy (-O-) moiety, which may be fully fluorinated (also known as perfluoro) 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.

[0031] When referring herein to alkyl, alkyloxy, fluoroalkyl, fluoroalkyloxy moieties having a range of possible carbon atoms starting from C1, such as, as non-limiting examples, "C1-C20 alkyl" or "C1-C20 fluoroalkyl," this range includes linear alkyl, alkyloxy, fluoroalkyl, and fluoroalkyloxy starting from C1, but specifies only branched alkyl, branched alkyloxy, cycloalkyl, cycloalkyloxy, branched fluoroalkyl, and cyclic fluoroalkyl starting from C3.

[0032] The term alkylene herein refers to a hydrocarbon group that may be linear, branched or cyclic and has two or more points of attachment (two points of attachment include, for example, methylene, ethylene, 1,2-isopropylene, 1,4-cyclohexylene, and the like, and three points of attachment include, for example, 1,1,1-substituted methanes, 1,1,2-substituted ethanes, 1,2,4-substituted cyclohexanes, and the like). Again, when specifying possible carbon ranges, such as, for example, C1-C20 as a non-limiting example, this range includes linear alkylenes beginning at C1, but specifies only branched alkylenes or cycloalkylenes beginning at C3. These alkylene moieties may be substituted or unsubstituted as described below.

[0033] The terms mono- and oligoalkyleneoxyalkylene include both simple alkyleneoxyalkylene moieties, such as ethyleneoxyethylene (-CH-CH-O-CH-CH-), propyleneoxypropylene (-CH-CH-CH-O-CH-CH-CH-CH-), and the like, as well as oligomeric materials, such as tri(ethyleneoxyethylene) (-CH-CH-O-CH-CH-O-CH-CH-), tri(propyleneoxypropylene) (-CH-CH-CH-O-CH-CH-CH-OCH-CH-CH-), and the like.

[0034] As used herein, the term aryl or aromatic group refers to such groups containing 6 to 24 carbon atoms, such as phenyl, tolyl, xylyl, naphthyl, anthracyl, biphenyls, bis-phenyls, tris-phenyls, and the like. These aryl groups may be further substituted with any of the appropriate substituents described above, such as alkyl, alkoxy, acyl, or aryl groups described above.

[0035] When the term novolak is used herein without other modification of the structure, it refers to novolak resins that are soluble in aqueous bases such as tetramethylammonium hydroxide and the like.

[0036] The term arylene refers to an aromatic hydrocarbon moiety having two or more attachment points (e.g., 2-5), which may be a single benzene moiety (e.g., 1,4-phenylene, 1,3-phenylene, and 1,2-phenylene for two attachment points; 1,2,4-substituted benzenes, 1,3,5-substituted benzenes, and the like for three attachment points), a polycyclic aromatic moiety having two attachment points, such as moieties derived from naphthalene, anthracene, pyrene, and the like, or a plurality of linked benzene rings having two attachment points (e.g., biphenylene).When the aromatic moieties are fused aromatic rings, they are also called fused ring arylenes, and may be more specifically referred to as, for example, naphthalenylene, anthracenylene, pyrenylene, and the like. The fused ring arylenes may be substituted or unsubstituted as described below, and may additionally contain a hydrocarbon substituent on the fused ring having two bonding sites, thus forming an additional aliphatic or unsaturated ring, which upon bonding to the fused ring may form a ring having from 5 to 10 carbon atoms.

[0037] Herein, the term "PAG" refers to a photoacid generator capable of generating an acid (also called a photoacid) under deep UV or UV irradiation, such as 200-300 nm, i-line, h-line, g-line and / or broadband irradiation, unless otherwise stated. The acid may be sulfonic acids, HCl, HBr, HAsF6, and the like.

[0038] Here, the term PAC refers to a diazonaphthoquinone moiety, which is further substituted with a sulfonyl moiety (-SO2-), which is bonded to a phenolic compound through a sulfonate ester (-SO2-O-) bond. The phenolic compound forming the sulfonate ester bond may be a phenolic compound substituted with more than one phenolic OH moiety, and thus a PAC may be such a phenolic compound in which more than one of the phenolic OH forms the sulfonate bond. Non-limiting examples of these free PAC materials are described in "Diazonapthoquinone-based Resist", Ralph Dammel, SPIE, Optical Engineering Press, Volume TT11, Chapters 2 and 3.

[0039] Here, the term fused aromatic ring refers to carbon-based polycyclic aromatic compounds containing 2-8 carbon-based aromatic rings fused together (e.g., naphthalene, anthracene, and the like), which may have a single point of attachment to an organic moiety as part of an aryl moiety, such as a pendant fused aromatic ring aryl group on a photoacid generator (PAG), or may have two points of attachment as part of an arylene moiety, such as a spacer in a substituent attached to a PAG. In PAGs, such substituents, along with other substituents that may interact by resonant delocalization, provide stronger absorption and / or broadband emission at 365 nm and are more effective at these wavelengths.

[0040] As used herein, the term "arene" includes aromatic hydrocarbon moieties containing one ring or two to eight carbon-based aromatic rings fused together.

[0041] Unless otherwise stated herein, the term "substituted" or "substituted" when referring to aryl, alkyl, alkyloxy, fluoroalkyl, fluoroalkyloxy, fused aromatic rings, and arenes includes substituents including unsubstituted alkyl, substituted alkyl, unsubstituted aryl, alkyloxyaryl (alkyl-O-aryl-), dialkyloxyaryl ((alkyl-O-)2-aryl), haloaryl, alkyloxy, alkylaryl, haloalkyl, halide, hydroxyl, cyano, nitro, acetyl, alkylcarbonyl, formyl, ethenyl (CH2=CH-), phenylethenyl (Ph-CH=CH-), arylethenyl (aryl-CH=CH-), and ethenylenearylene moieties (e.g., Ar(-CH=CH-Ar-)). z (z is 1-3). Non-limiting examples of substituted aryl and substituted arylethenyl substituents are the following, where:

[0042] [ka] represents a bond in structures (3), (4) and (5).

[0043] [ka] Others are substituted aryl, in which the substituents are selected from any of the above substituents, and substituted ethenyl. Similarly, the terms "unsubstituted" or "unsubstituted" refer to the same moiety in which there are no substituents other than hydrogen.

[0044] The term "quencher" refers to a basic component or collection of basic components, such as amines, or tetraalkylammonium carboxylate salts, that can act in a resist formulation to capture the acid generated by a photoacid generator during exposure to i-line or broadband radiation.

[0045] As used herein, the terms bis[tetraalkylammonium] and tetraalkylammonium include moieties in which different types of alkyl groups may be present as defined above, and also include moieties in which one or more of the alkyl groups is an alkyl having an aryl substituent, such as benzyl (-CH-Ph), 2-phenylethyl (-CH-CH-Ph), and the like.

[0046] The term "solid components" refers to components other than the solvent in a photoresist formulation. Such components may be solids or liquids.

[0047] For the heterocyclic thiols described herein, it is understood that these thiol forms potentially represent one of several tautomeric forms, for example, but not by way of limitation, (6) can appear as its prototropic tautomer (7), either in equilibrium or disequilibrium.

[0048] [ka] Additionally, interactions with surfaces, such as cuprophilic surfaces, or other components in solution can affect the relative concentrations of ring structures 3 and 4 and their respective tautomers. Accordingly, it is understood that prototropic tautomers (including annular tautomers) and valence tautomers can be referred to interchangeably by listing any of their tautomeric forms.

[0049] The composition of the present invention comprises a) at least one photoacid generator; b) at least one novolac polymer; c) at least one acrylate polymer comprising a component having the following structure (I):

[0050] [ka] [In the formula, R1 to R6 are independently -H or -CH3, and A is a linear or branched C2-C 10An alkylene group, B is C1-C 12 A primary or secondary unsubstituted linear, branched, cyclic or aliphatic alkyl group, where C is C1-C 12 a primary or secondary unsubstituted linear, branched, cyclic or aliphatic alkyl group; and D is a linking group, which is a direct valence bond or a linear or branched C1-C 10 , preferably C2 to C 10 Ar is a substituted or unsubstituted aromatic or heteroaromatic group; E is a linear or branched C-C 10 is an alkylene group, G is an acid cleavable group, t is from 0 mol % to about 40 mol %, v is from 0 mol % to about 15 mol %, w is from 0 mol % to about 45 mol %, x is from 0 mol % to about 80 mol %, y is from about 20 mol % to about 50 mol %, and z is from about 20 mol % to about 50 mol %, and further wherein the sum of t, v, w, x, y, and z is equal to 100 mol %. d) at least one glycidyl hydroxybenzoic acid condensate material comprising one or more compounds having the following structure (II):

[0051] [ka] [In the formula, W is an organic moiety having a molecular weight of 600 or less, where W forms an ether bond with the oxygen to which it is attached; m is an integer from 1 to 3, and n is an integer from 1 to 4, when m is 1, n is 3 or 4; and when m is 2 or 3, n is an integer from 1 to 4; n' is 0 or 1. e) at least one heterocyclic thiol compound comprising a ring structure selected from the general structural formulas (III), (IIIa) or (IIIb), or tautomers thereof;

[0052] [ka] [In the formula, the ring structure is a monocyclic structure having 4 to 8 atoms or a polycyclic structure having 5 to 20 atoms; wherein the monocyclic structure or the polycyclic structure includes an aromatic, non-aromatic or heteroaromatic ring; and In the structure (III), X is selected from the group consisting of C(Rt1)(Rt2), O, S, Se, and Te; In the structure (IIIa), Y is selected from the group consisting of C(Rt3) and N; In the structure (IIIb), Z is selected from the group consisting of C(Rt3) and N; and Rt1, Rt2, and Rt3 are independently selected from the group consisting of H, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkenyl group having 2 to 8 carbon atoms, an unsubstituted alkenyl group having 2 to 8 carbon atoms, a substituted alkynyl group having 2 to 8 carbon atoms, an unsubstituted alkynyl group having 2 to 8 carbon atoms, a substituted aromatic group having 6 to 20 carbon atoms, a substituted heteroaromatic group having 3 to 20 carbon atoms, an unsubstituted aromatic group having 6 to 20 carbon atoms, and an unsubstituted heteroaromatic group having 3 to 20 carbon atoms. f) at least one solvent; The present invention relates to a positive-working photosensitive composition comprising:

[0053] In one preferred embodiment, the glycidyl hydroxybenzoic acid condensate material having structure (II) is one in which the moiety W is an aliphatic moiety selected from the group consisting of aliphatic hydrocarbons, aliphatic alkyl ethers, bis(alkyl)sulfones, and bis(alkyl)ketones. In another preferred embodiment, the glycidyl hydroxybenzoic acid condensate material having structure (II) is one in which the moiety W is an aromatic moiety selected from arenes, polycyclic arenes, bis(aryl)ethers, biphenyls, bis(aryl)sulfones, bis(phenyl)alkylenes, (alkyl)(aryl)ketones, bis(aryl)ketones, bis(aryl)sulfones, and (alkyl)(aryl)sulfones.

[0054] The glycidyl hydroxybenzoic acid condensate material containing one or more compounds having structure (II) as component d) may be a single compound or a mixture of compounds resulting from the reaction of selected glycidyl ether derivatives of the organic moiety W with selected hydroxybenzoic acid derivatives. Unexpectedly, only certain specific glycidyl hydroxybenzoic acid condensate materials outlined by structure (II) and its attendant descriptive limitations endow the photoresist compositions described above with the ability to produce patterned photoresist films that can be used to form metallic lines with good adhesion during metal electroplating operations. These positive photoresist compositions also have high photosensitivity in thick film applications and on reflective substrates, and have valuable development times in terms of process. Additionally, the novel photoresist compositions also have low unexposed film loss in the developer. The adhesion defect resistance of the metallization allows for electroplated metal lines without loss of adhesion and loss of adhesion during the subsequent lithographic etching process.

[0055] As outlined above, the descriptive requirement described in the embodiment of the glycidyl hydroxybenzoic acid condensate material is that W is an organic moiety having a molecular weight less than 600, where the organic moiety W forms an ether bond with the oxygen to which it is attached. Another limitation is that m, the number of hydroxy moieties on the benzoic acid moiety of structure (II), is an integer between 1 and 3, and n, the number of glycidyl-derived moieties on the organic moiety, is an integer between 1 and 4. Further limitations on these parameters are that when m is 1, n must be 3 or 4, and when m is 2 or 3, n ranges from 1 to 4. The n' term defines how many of the glycidyl-derived moieties on W have reacted with the hydroxyphenol moiety of a given hydroxybenzoic acid derivative instead of reacting with the carboxylic acid. The n' term can be 0 or 1.

[0056] In another embodiment of the above positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material is one in which m is 1. In yet another embodiment, m is 2. In yet another, m is 3.

[0057] In any of the above positive-working photosensitive compositions, in another aspect, the glycidyl hydroxybenzoic acid condensate material is one where n is 1. In yet another aspect, n is 2. In yet another aspect, n is 3. In yet another aspect, n is 4.

[0058] In any of the above positive-working photosensitive compositions, in another aspect, the glycidyl hydroxybenzoic acid condensate material has n′=0. In yet another aspect, n′=1.

[0059] In another embodiment of the positive-working photosensitive composition, component d), the glycidyl hydroxybenzoic acid condensate material, comprises at least one compound having the structure (IVa-1), where n is 3 to 4 and Rw is OH or the moiety (IVb-1),

[0060] [ka] represents the point of attachment in moiety (IVb-1) to the compound of structure (IVa-1).

[0061] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having a structure (IV-1) in which n is 3-4.

[0062] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (IVa-2). Further, in this embodiment, n is 1 to 4, Rw1 is OH or the moiety (IVb-2), and

[0063] [ka] represents the point of attachment in moiety (IV-2) to the above compound of structure (IVa-2).

[0064] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material contains at least one compound having the structure (IV-2) in which n is 1-4.

[0065] [ka] In another embodiment of the positive-working photosensitive composition described above, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (IVa-3), where n is 1 to 4, and Rw2 is OH or a moiety (IVa), with the proviso that at most one Rw2 is a moiety (IVb-3), and

[0066] [ka] represents the point of attachment of moiety (IVb-3) to said compound of structure (IVa-3).

[0067] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having a structure (IV-3) in which n is 1-4.

[0068] [ka] In another embodiment of the positive-working photosensitive composition, the organic moiety W is selected from the group consisting of the moieties of structures (Wa), (Wb), (Wc), (Wd), (We) and (Wf).

[0069] [ka] represents a point of attachment within each of these organic moieties, where it forms an ether bond with the oxygen in said glycidyl hydroxybenzoic acid condensate material of structure (II). Further, in this embodiment, Xa is a moiety selected from the group consisting of a direct valence bond, alkylene, -SO2-, -C(=O)-, and -O-; Ra1, Rb1, and Rc are independently selected from C1-C5 alkyl or C2-C5 alkyleneoxyalkyl; Ra2 is selected from C1-C5 alkyl, C2-C5 alkyleneoxyalkyl, C1-C5 alkyloxy, halide, C1-C5 alkylsulfonyl, C1-C5 alkylcarbonyl, and C1-C5 alkylcarbonyloxy, and n'' ranges from 0 to 12.

[0070] [ka] In another embodiment of the positive-working photosensitive composition, the organic moiety W is selected from the group consisting of moieties of structures (Wa1), (Wb1), (Wc1), (Wd1) and (We1).

[0071] [ka] represents the point of attachment within each of these organic moieties where it forms an ether bond with the oxygen in said glycidyl hydroxybenzoic acid condensate material of structure (II).

[0072] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (Va-1), where Rw3 is OH or a moiety of the structure (Vb-1),

[0073] [ka] represents the point of attachment in the moiety. Also in this embodiment, m is 2-3, n' is 0 or 1, and Xa is selected from the group consisting of a direct valence bond, alkylene, -SO2-, -C(=O)-, and -O-. In another aspect of this embodiment, m is 2. In yet another aspect of this embodiment, m is 3.

[0074] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having structure (V-1), where m is 2-3 and Xa is selected from the group consisting of a direct valence bond, alkylene, -SO2-, -C(=O)-, and -O-. In another aspect of this embodiment, m is 2. In yet another aspect of this embodiment, m is 3.

[0075] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (Va-2), where Rw4 is OH or a moiety of the structure (Vb-2),

[0076] [ka] represents the point of attachment in this moiety. Further, in this embodiment, Xa is selected from the group consisting of a direct valence bond, alkylene, -SO2-, -C(=O)-, and -O-.

[0077] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (V-2), where Xa is selected from the group consisting of a direct valence bond, an alkylene, -SO2-, -C(=O)-, and -O-.

[0078] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (Va-3), wherein Rw5 is OH or a moiety of the structure (Vb-3),

[0079] [ka] represents the point of attachment in this moiety.

[0080] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxyl benzoic acid condensate material comprises at least one compound having the structure (V-3). Preferably, in this embodiment, the glycidyl hydroxyl benzoic acid condensate material is compound (V-3).

[0081] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (Va-4), wherein Rw6 is OH or a moiety of the structure (Vb-4),

[0082] [ka] represents the point of attachment in this moiety.

[0083] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (V-4). Preferably, in this embodiment, the glycidyl hydroxybenzoic acid condensate material is a compound having the structure (V-4).

[0084] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (Va-5), wherein Rw7 is OH or a moiety of the structure (Vb-5),

[0085] [ka] represents the point of attachment in this moiety.

[0086] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (V-5). Preferably, in this embodiment, the glycidyl hydroxybenzoic acid condensate material is a compound having the structure (V-5).

[0087] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (Va-6), wherein Rw8 is OH or a moiety of the structure (Vb-6),

[0088] [ka] represents the point of attachment in this moiety.

[0089] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (V-6).

[0090] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (Va-7), wherein Rw9 is OH or a moiety of the structure (Vb-7),

[0091] [ka] represents the point of attachment in this moiety, further where Xa is an alkylene moiety.

[0092] [ka] In another embodiment of the above positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (V-7), where Xa is an alkylene moiety.

[0093] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (Va-8), wherein Ra and Rb are independently a C1-C5 alkyl moiety or a C2-C5-alkylene-O-alkyl moiety, and Rw10 is OH or a moiety of the structure (Vb-8),

[0094] [ka] represents the point of attachment in this moiety.

[0095] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (V-8), where Ra and Rb are independently a C1-C5 alkyl moiety or a C2-C5-alkylene-O-alkyl moiety.

[0096] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (Va-9), wherein Rw11 is OH or a moiety of the structure (Vb-9),

[0097] [ka] represents the point of attachment in this moiety.

[0098] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (V-9). Preferably, in this embodiment, the glycidyl hydroxybenzoic acid condensate material is a compound having the structure (V-9).

[0099] [ka] In another embodiment of the positive-working photosensitive composition described above, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (Va-10), where Rw12 is OH or the moiety (Vb-10),

[0100] [ka] represents a point of attachment in this moiety with the proviso that at most one Rw12 is a moiety (Vb-10), and further wherein Xa is selected from the group consisting of a direct valence bond, alkylene, -SO2-, -C(=O)-, and -O-.

[0101] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (Va-11), where Rw13 is OH or the moiety (Vb-11),

[0102] [ka] represents the point of attachment in this moiety, with the proviso that at most one Rw13 is (Vb-11).

[0103] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (V-11).

[0104] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (Va-12), where Rw14 is OH or a moiety (Vb-12),

[0105] [ka] represents the point of attachment in this moiety, with the proviso that at most one Rw14 is (Vb-12).

[0106] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (V-12).

[0107] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (Va-13), where Rw15 is OH or the moiety (Vb-13),

[0108] [ka] represents the point of attachment in this moiety, with the proviso that at most one Rw15 is (Vb-13).

[0109] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (V-13). Preferably, in this embodiment, the glycidyl hydroxybenzoic acid condensate material is a compound having the structure (V-13).

[0110] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (Va-14), where Rw16 is OH or the moiety (Vb-14),

[0111] [ka] represents the point of attachment in this moiety, with the proviso that at most one Rw16 is (Vb-14).

[0112] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (V-14). Preferably, in this embodiment, the glycidyl hydroxybenzoic acid condensate material is a compound having the structure (V-14).

[0113] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (Va-15), where Rw17 is OH or a moiety (Vb-15),

[0114] [ka] represents a point of attachment in this moiety, with the proviso that at most one Rw17 is a moiety (Vb-15), and further wherein Xa is an alkylene moiety.

[0115] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (V-15), where Xa is an alkylene moiety.Preferably, in this embodiment, the glycidyl hydroxybenzoic acid condensate material is a compound having the structure (V-15).

[0116] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (Va-16), where Rw18 is OH or a moiety (Vb-16),

[0117] [ka] represents a point of attachment in this moiety, with the proviso that at most one Rw18 is a moiety (Vb-16), and further wherein Ra and Rb are independently a C1-C5 alkyl moiety, or a C2-C5 alkylene-O-alkyl moiety.

[0118] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having structure (V-16), where Ra and Rb are independently a C1-C5 alkyl moiety or a C2-C5-alkylene-O-alkyl moiety. Preferably, in this embodiment, the glycidyl hydroxybenzoic acid condensate material is a compound having structure (V-16).

[0119] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (Va-17), where Rw19 is OH or the moiety (Vb-17),

[0120] [ka] represents the points of attachment in these moieties, with the proviso that at most one Rw19 is the moiety (Vb-17).

[0121] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (V-17). Preferably, in this embodiment, the glycidyl hydroxybenzoic acid condensate material is a compound having the structure (V-17).

[0122] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (VIa-1), wherein Rw20 is OH or a moiety of the structure (VIb-1),

[0123] [ka] represents the point of attachment in the moiety. In this embodiment, m is 2 to 3, and n' is 0 or 1. Also in this embodiment, Ra1 and Rb1 are independently selected from C1 to C5 alkyl or C2 to C5 alkylene-O-alkyl moieties.

[0124] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having structure (VI-1), where Ra1 and Rb1 are independently selected from C1-C5 alkyl or C2-C5-alkylene-O-alkyl moieties, and m is 2 or 3. In another aspect of this embodiment, m is 3. In yet another aspect of this embodiment, m is 2.

[0125] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (VIa-2), wherein Rw21 is OH or a moiety of the structure (VIb-2),

[0126] [ka] represents the point of attachment in the moiety, further wherein Ra1 and Rb1 are independently selected from a C1-C5 alkyl, or a C2-C5-alkylene-O-alkyl moiety.

[0127] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (VI-2), wherein Ra1 and Rb1 are independently selected from C1-C5 alkyl or C2-C5-alkylene-O-alkyl moieties.

[0128] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (VIa-3), wherein Rw22 is OH or a moiety (VIb-3),

[0129] [ka] represents the point of attachment in this moiety, with the proviso that at most one Rw22 is a moiety (VIb-3). In this embodiment, Ra1 and Rb1 are independently selected from a C1-C5 alkyl or C2-C5-alkylene-O-alkyl moiety.

[0130] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having structure (VI-3), wherein Ra1 and Rb1 are independently selected from C1-C5 alkyl or C2-C5-alkylene-O-alkyl moieties.

[0131] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (VIIa-1), wherein Rw23 is OH or a moiety of the structure (VIIb-1),

[0132] [ka] represents the point of attachment in the moiety. In this embodiment, m is 1, 2 or 3, and n' is 0 or 1, and also, Ra2 is selected from a C1-C5 alkyl or a C2-C5-alkylene-O-alkyl moiety, and m is 1, 2 or 3. In another aspect of this embodiment, m is 3. In yet another aspect of this embodiment, m is 2. In yet another aspect of this embodiment, m is 1.

[0133] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having structure (VII-1), where Ra2 is selected from a C1-C5 alkyl or a C2-C5-alkylene-O-alkyl moiety, and m is 1, 2, or 3. In another aspect of this embodiment, m is 3. In yet another aspect of this embodiment, m is 2. In yet another aspect of this embodiment, m is 1.

[0134] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (VIIa-2), wherein Rw24 is OH or a moiety (VIIb-2),

[0135] [ka] represents the point of attachment in this moiety, with the proviso that at most one Rw24 is a moiety (VIIb-2). In this embodiment, Ra2 is a C1-C5 alkyl or C2-C5-alkylene-O-alkyl moiety.

[0136] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (VII-2), where Ra2 is a C1-C5 alkyl or C2-C5-alkylene-O-alkyl moiety.

[0137] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (VIIa-3), wherein Rw25 is OH or a moiety (VIIb-3),

[0138] [ka] represents the point of attachment in this moiety, with the proviso that at most one Rw25 is a moiety (VIIb-3). In this embodiment, Ra2 is a C1-C5 alkyl or C2-C5-alkylene-O-alkyl moiety.

[0139] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound having the structure (VIIa-4), wherein Rw26 is OH or the moiety (VIIb-4),

[0140] [ka] represents the point of attachment in this moiety, with the proviso that at most one Rw26 is a moiety (VIIb-4). In this embodiment, Ra2 is a C1-C5 alkyl or C2-C5-alkylene-O-alkyl moiety.

[0141] [ka] In another embodiment of the positive-working photosensitive composition, the glycidyl hydroxybenzoic acid condensate material comprises at least one compound selected from the group consisting of (VIII), (VIIIa), (VIIIb), (VIIIc), (VIIId) and (VIIIe).

[0142] [ka] In any case, in another embodiment of the positive-working photosensitive composition, the "at least one photoacid generator" of component a) may be any of a variety of photoacid generators, such as onium salts, dicarboxyimidyl sulfonate esters (also known as dicarboxyimide sulfonate esters or N-hydroxyimide sulfonates), oxime sulfonate esters, diazo(sulfonylmethyl) compounds (also known as α,α-bis(arylsulfonyl)diazomethanes, e.g., Ph-(SO2)-C(=N2)-(SO2)-Ph), disulfonylmethylene compounds (also known as α,α-methylene disulfone; e.g., Ph-(SO2)-CH2-(SO2)-Ph), and disulfonylhydrazine compounds (also known as disulfonehydrazine PAGs, e.g., Ph-(SO2)-NH-NH-(SO2)-Ph)), nitrobenzyl sulfonate esters (e.g., For example, the aryl group may be selected from 2-nitrobenzyl sulfonate ester derivatives, biimidazole compounds, diazomethane derivatives, glyoxime derivatives (e.g., CH3-(C=NO-SO2-Ph)-(C=NO-SO2-Ph)-CH3), β-ketosulfone derivatives (e.g., Ph-(C=O)-CH2-SO2-Ph), disulfone derivatives (e.g., Ph-SO2-SO2-Ph), sulfonic acid ester derivatives, imidoyl sulfonate derivatives (e.g., phthalimidoyl triflate, phthalimidoyl tosylate, 5-norbornene-2,3-dicarboximidoyl triflate, 5-norbornene-2,3-dicarboximidoyl tosylate, and 5-norbornene-2,3-dicarboxylimidoyl n-butylsulfonate), diazonaphthoquinone sulfonate esters, halogenated triazine compounds, or combinations thereof. The following publications give various examples of these different types of photoacid generators.

[0143] US6,042,988 (Patent Document 1); US6783912 (Patent Document 2); US6908722 (Patent Document 3); “Evaluation of the standard addition method to determine rate constants for acid generation in chemically amplified photoresist at 157 nm” Adam R. Pawloski; Charles R. Szmanda; Paul F. Nealey, Proc. SPIE 4345, Advances in Resist Technology and Processing XVIII, Santa Clara CA, February 25, 2001, Editor Francis Houlihan p1056, August 24, 2001 (Non-Patent Document 3); “Chemically Amplification Resists for Microlithography” Hiroshi Ito, Adv. Polym. Sci. 172 p37, 2005 (Non-Patent Document 4); “Chemical Amplification Mechanisms for Microlithography” E. Reichmanis et al. al., Chem. Mater. 13, 2305, 2001 (non-patent document 5); “i-Line sensitive Photoacid Generators for UV curring” Masumitsu Shirai et al., Progress in Organic coatings, 64, 175, 2009 (non-patent document 6).

[0144] Onium salt photoacid generators may include, but are not limited to, alkylsulfonate anions, substituted and unsubstituted arylsulfonate anions, fluoroalkylsulfonate anions, fluoroarylalkylsulfonate anions, fluorinated arylalkylsulfonate anions, hexafluorophosphate anions, hexafluoroarsenate anions, hexafluoroantimonate anions, tetrafluoroborate anions, equivalents thereof, or combinations thereof.

[0145] Specifically, suitable photoacid generators include, but are not limited to, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, and triphenylsulfonium 2-(bicyclo[2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-cyclohexylphenyldiphenylsulfonium 2-(bicyclo[2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium trifluorom ... sulfonium nonafluoro-n-butanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, and 4-methanesulfonylphenyldiphenylsulfonium 2-(bicyclo[2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n- octanesulfonate, diphenyliodonium 2-(bicyclo[2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesulfonate, bis(4-t-butylphenyl)iodonium perfluoro-n-octanesulfonate, bis(4-t-butylphenyl)iodonium 2-(bicyclo[2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium trifluoromethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium perfluoro-n-octanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium 2-(bicyclo[ 2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophenium trifluoromethanesulfonate, 1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophenium perfluoro-n-octanesulfonate, 1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophenium 2-(bis( chloro[2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophenium trifluoromethanesulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophenium perfluoro-n-octanesulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophenium Ophenium 2-(bicyclo[2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonate N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(nonafluoro-n-butanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(perfluoro-n-octanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-[2-(bicyclo[2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonyloxy]bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl trifluoromethanesulfonate (naphthalenedicarboxyimidyl triflate), N-[2-(tetracyclo[4.4.0.1. 2,5 .1 7,10 ]dodecan-3-yl)-1,1-difluoroethanesulfonyloxy]bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, 1,3-dioxoisoindolin-2-yl trifluoromethanesulfonate, 1,3-dioxoisoindolin-2-yl nonafluoro-n-butanesulfonate, 1,3-dioxoisoindolin-2-yl perfluoro-n-octanesulfonate, 3-dioxoisoindolin-2-yl 2-(bicyclo[2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 3-dioxoisoindolin-2-yl N-[2-(tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodecan-3-yl)-1,1-difluoroethanesulfonate, 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl trifluoromethanesulfonate, 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl nonafluoro-n-butanesulfonate, 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl perfluoro-n-octanesulfonate, 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl 2-(bicyclo[2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, or 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl N-[2-(tetracyclo[4.4.0.1 2,5 .1 7,10]dodecan-3-yl)-1,1-difluoroethanesulfonate, (E)-2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(methoxyphenyl)-4,6-bis-(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, equivalents thereof or combinations thereof, etc. Suitable photoacid generators may include onium salts containing anions and cations in combinations not mentioned above.

[0146] In one embodiment of the photoresist composition, the photoacid generator is selected from those that upon 365 nm and / or broadband irradiation generate sulfonic acids such as alkyl, aryl or fluoroalkylsulfonic acids, perfluorosulfonic acids, inorganic acids such as HAsF6, HSbF6, HPF6, or acids derived from tetraphenylborate H(Ph)4B or similar tetraarylborate H(aryl)4B. Non-limiting examples of such PAGs include various photoacid generators such as onium salts, dicarboxyimidyl sulfonate esters, oxime sulfonate esters, diazo(sulfonylmethyl) compounds, disulfonylmethylenehydrazine compounds, nitrobenzyl sulfonate esters, biimidazole compounds, diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, disulfone derivatives, sulfonate ester derivatives, imidoyl sulfonate derivatives, diazonaphthoquinone sulfonate esters, or combinations thereof. Such photoacid generators may inherently exhibit sensitivity to 365 nm and / or broadband radiation by appropriate substitutions known in the art. More specifically, they may be, for example, as a non-limiting example, substituted or unsubstituted triarylsulfonium salts of organic sulfonic acids, where the triarylsulfonium moiety or its corresponding acid anion contains at least one aryl moiety having a conjugated aryl, said conjugated aryl moiety being selected from phenyl rings having at least one substituent selected from aryloxy, alkyloxy, nitro, cyano, acetyl, aryl, alkenyl, alkyloxyaryl (alkyl-O-aryl-), dialkyloxyaryl ((alkyl-O-)2-aryl), or said conjugated aryl moiety is instead a substituted or unsubstituted fused aromatic ring moiety containing 2 to 4 rings.Such substituents may be attached via a difunctional moiety capable of undergoing resonance delocalization, such as arylene, including arylene derived from fused aromatics, or substituents containing, for example, an ethenylene (-C=C-) moiety, ethenyl (CH2=CH-), phenyleneethenyl (Ph-CH=CH-), arylethenyl (aryl-CH=CH-), and ethenylenearylene moieties (e.g., Ar(-CH=CH-Ar-)z, z=1-3). Non-limiting examples of substituted aryl and substituted arylethenyl substituents are (3), (4), and (5) as follows:

[0147] [ka] Other common PAGs sensitive to 365 nm and / or broadband radiation are the substituted or unsubstituted 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl ester organic sulfonic acids. Figure 1 shows non-limiting examples of the above PAGs. These PAGs may have the substituents described above.

[0148] In another embodiment of the photoresist composition, the photoacid generator is not directly sensitive to i-line or broadband radiation, but may be sensitized to this radiation by a sensitizer that extends the effective wavelength and / or energy range. Such sensitizers may be, but are not limited to, substituted and unsubstituted anthracenes, substituted and unsubstituted phenothiazines, substituted and unsubstituted perylenes, substituted and unsubstituted pyrenes, and aromatic carbonyl compounds such as benzophenone and thioxanthone, fluorene, carbazole, indole, benzocarbazole, acridone chlorpromazine, equivalents thereof, or combinations of any of the foregoing.

[0149] In any of the above positive-working photosensitive compositions, in another embodiment, the "at least one novolac polymer" of component b) is selected from novolac polymers containing repeating units having a bridge and a phenolic compound. Suitable phenolic compounds include, but are not limited to, phenols, cresols, substituted and unsubstituted resorcinols, 2,5-xylenols, substituted and unsubstituted benzenetriols, and combinations thereof. Novolac polymers are usually prepared by condensation polymerization of a phenolic compound with an aldehyde, such as formaldehyde, acetaldehyde, or substituted or unsubstituted benzaldehyde, or a substituted or unsubstituted methylol compound, using an acid catalyst. The bridge can include a methylene group or a methine group. Novolac polymers can also be prepared as condensation products of ketones, such as acetone, methyl ethyl ketone, acetophenone, and the like. Catalysts may include Lewis acids, Bronsted acids, dicationic and tricationic metal ions, and the like. For example, but not limited to, aluminum chloride, calcium chloride, magnesium chloride, oxalic acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, or combinations including any of these may be used.

[0150] Examples of suitable novolac polymers include those obtained by the condensation reaction of phenolic compounds, such as phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, and the like, with aldehydes, such as formaldehyde, in the presence of an acid or polyvalent metal ion catalyst. Exemplary weight average molecular weights of alkali-soluble novolac polymers can range from 1,000 to 30,000 Daltons. Other exemplary weight average molecular weights can be from 1,000 to 20,000 Daltons. Still other exemplary weight average molecular weights can be from 1,500 to 10,000 Daltons. Exemplary bulk dissolution rates of novolac polymers in 2.38% aqueous tetramethylammonium hydroxide are from 10 Å / sec (angstroms per second) to 15,000 Å / sec. Other exemplary bulk dissolution rates are from 100 Å / sec to 10,000 Å / sec. Yet other exemplary bulk dissolution rates are between 200 A / sec and 5,000 A / sec. Yet another exemplary dissolution rate of 1,000 A / sec can be obtained from a single novolac polymer or a blend of multiple novolac polymers, each containing m-cresol repeat units.

[0151] Exemplary cresol-based novolac polymers may include cresol mole percentages of 0% to 60% p-cresol, 0% to 20% o-cresol, and 0% to 80% m-cresol. Other exemplary cresol-based novolac polymers may include 0% to 50% p-cresol, 0% to 20% o-cresol, and 50% to 100% m-cresol. The repeat units in the novolac polymer are defined by the composition of the polymer, so, for example, p-cresol may be introduced by polymerization with an aldehyde or by dimethylol-p-cresol. Additionally, cresol-based novolac polymers may include other phenolic compounds, such as phenol, 2,5-xylenols, resorcinols, benzenetriols, and the like. Additionally, novolac polymers may be branched or linear and may be blended to achieve a selected repeat unit mole percentage or dissolution rate. The bulk dissolution rate may be measured by the following procedure: (1) A 1-3 μm (micrometer) film of the novolac resin is spin-coated from solution onto a silicon wafer and soft-baked at 110° C. for 120 seconds on a contact hotplate. (2) The film thickness is measured using optical methods such as interferometry or ellipsometry or a mechanical profilometer. (3) The coated wafer is immersed in a solution of tetramethylammonium hydroxide (TMAH) developer and the time to completely dissolve the novolac film (t c ) is detected visually or using optical interferometry (e.g., a dissolution rate monitor). The bulk dissolution rate is determined by multiplying the film thickness by t c It is calculated by dividing by .

[0152] In any of the above positive-working photosensitive compositions, in another embodiment, the "at least one novolac polymer" of component b) is selected from novolac polymers containing one or more cresol-based repeat units selected from o-cresol, p-cresol, or m-cresol.

[0153] In any of the above positive-working photosensitive compositions, in another embodiment, the "at least one novolak polymer" of component b) is a cresol-based novolak that contains at least 80 mole % m-cresol.

[0154] In any of the above positive-working photosensitive compositions, in another embodiment, the composition contains only one novolac polymer as part of component b) above.

[0155] In another embodiment of any of the above positive-working photosensitive compositions, the composition comprises two or more of the above novolak polymers in component b).

[0156] As described above, the acrylate polymer of component c) has structure (I), where R1 to R6 are independently -H or -CH3, and A is a linear or branched C2-C 10 An alkylene group, B is C1-C 12 A primary or secondary unsubstituted linear, branched, cyclic or aliphatic alkyl group, where C is C1-C 12 a primary or secondary unsubstituted linear, branched, cyclic or aliphatic alkyl group; and D is a linking group, which is a direct valence bond or a linear or branched C1-C 10 , preferably C2 to C 10 Ar is a substituted or unsubstituted aromatic or heteroaromatic group, and E is a linear or branched C-C 10 is an alkylene group, G is an acid cleavable group, t is 0 mol % to about 40 mol %, v is 0 mol % to about 15 mol %, w is 0 mol % to about 45 mol %, x is 0 mol % to about 80 mol %, y is about 20 mol % to about 50 mol %, and z is about 20 mol % to about 50 mol %, and further wherein the sum of t, v, w, x, y, and z is equal to 100 moles.

[0157] [ka] In any of the above positive-working photosensitive compositions, in another embodiment, the structure (I) may optionally include other types of optional styrenic repeat units having the structure (Ia).

[0158] [ka] In structure (Ia), Rs1 is selected from H, Cl or CH3, and Rs2 and Rs3 can be the same or different and are selected from H, OH, OCOORs4, or OCOCOORs4 (O-(C=O)-(C=O)-O-Rs4), and Rs4 is an acid cleavable group. The polymer of the present invention may contain only (meth)acrylate units or may contain a mixture of (meth)acrylate units and styrenic units. Acid labile groups may be present in the polymer. The polymer may contain acid cleavable groups that can be esterified to (meth)acrylate repeat units through a carboxylate group, or to carbonate or oxylate groups, where the carbonate or oxylate groups are esterified to phenols or alcohols. For example, one monomeric repeat unit known in the art is tert-butyl 4-vinylphenyl carbonate, where tert-butyl carbonate is esterified to 4-hydroxystyrene.Acid cleavable groups include, but are not limited to, t-butyl, tetrahydropyran-2-yl, tetrahydrofuran-2-yl, 4-methoxytetrahydropyran-4-yl, 1-ethoxyethyl, 1-butoxyethyl, 1-propoxyethyl, 3-oxocyclohexyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, 8-methyl-8-tricyclo[5.2.1.0] 2,6]decyl group, 1,2,7,7-tetramethyl-2-norbornyl group, 2-acetoxymenthyl group, 2-hydroxymethyl group, 1-methyl-1-cyclohexylethyl group, 4-methyl-2-oxotetrahydro-2H-pyran-4-yl group, 2,3-dimethylbutan-2-yl group, 2,3,3-trimethylbutan-2-yl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-methylcyclo Examples of suitable acid-cleavable groups include hexyl, 1-ethylcyclohexyl, 1,2,3,3-tetramethylbicyclo[2.2.1]heptan-2-yl, 2-ethyl-1,3,3-trimethylbicyclo[2.2.1]heptan-2-yl, 2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl, 2,3-dimethylpentan-3-yl, and 3-ethyl-2-methylpentan-3-yl groups. Monomer repeat units having an acid-cleavable group are said to be protected. The polymer may be fully protected, partially protected, partially deprotected, or fully deprotected. Deprotection may occur, for example, in the presence of acid generated by the action of light during or after exposure of the photosensitive composition.

[0159] In any of the above positive-working photosensitive compositions, in another embodiment, the structure (I) may optionally include other types of optional (meth)acrylate derived repeat units that provide additional etch resistance, modify the solubility properties of the polymer in the protected, partially protected, partially deprotected or fully deprotected form, modify the photosensitivity, modify the adhesion, provide an attached photoacid generator, or provide other useful properties. Such (meth)acrylate derived repeat units may include, but are not limited to, certain chemical functional groups contained within pendant groups on the (meth)acrylate derived repeat units, such as lactones, acid anhydrides, phenols, alcohols, carboxylic acids, substituted and unsubstituted benzyl groups, ethers, alicyclic esters, ester alcohols, ester ethers, aliphatic ethers, aromatic esters, and the like.

[0160] In another embodiment of the above positive-working photosensitive composition, the acrylate polymer of component c) consists solely of repeat units as set forth in Structure (I).

[0161] Additionally, the optional styrenic unit is one having the structure (Ia).

[0162] Optionally, structure (I) may include other types of optional styrenic repeat units.

[0163] A non-limiting example of these optional styrenic units is one having the structure (Ia).

[0164] According to the above embodiment, at least one acrylate polymer comprising a component having structure (I) can be synthesized using one or more feeds of the described monomers. At least some of the monomers may be introduced, in whole or in part, at the beginning of the polymerization reaction. Furthermore, the monomer feeds may be carried out at selected feed rates during the reaction to adjust the co-reactivity of different monomers or to control other polymer properties such as molecular weight or solubility. The polymerization may be initiated by a free radical initiator, a cationic polymerization initiator, an anionic polymerization initiator, or a chelating catalyst.

[0165] In any of the above positive-working photosensitive compositions, in another embodiment, the acrylate polymer of component c) is selected from the group consisting of the linear or branched C2-C 10 The alkylene group is selected from, but is not limited to, ethylene, 1,2-propylene, 1,3-propylene, or the like. Exemplary groups for B may include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, or the like. Exemplary groups for E may include, but are not limited to, ethylene, 1,2-propylene, 1,3-propylene, or the like.

[0166] In any of the above positive-working photosensitive compositions, in another embodiment, the acrylate polymer of the component c) is selected from the group consisting of C1 to C2, 12 The primary or secondary unsubstituted linear, branched, cyclic or alicyclic alkyl groups are selected from methyl, ethyl, propyl, butyl, isopropyl, isobutyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, tetrahydrodicyclopentadienyl, adamantyl and the like.

[0167] In any of the above positive-working photosensitive compositions, in another embodiment, the acrylate polymer of component c) is C1-C 12The primary or secondary unsubstituted linear, branched, cyclic or alicyclic alkyl groups are selected from methyl, ethyl, propyl, butyl, isopropyl, isobutyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, tetrahydrodicyclopentadienyl, and the like.

[0168] In any of the above positive-working photosensitive compositions, in another embodiment, the acrylate polymer of component c) is C1-C 12 The primary or secondary unsubstituted linear, branched, cyclic or alicyclic alkyl groups are those selected from methyl, ethyl, propyl, butyl, isopropyl, isobutyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, tetrahydrodicyclopentadienyl, and the like.

[0169] In any of the above positive-working photosensitive compositions, in another embodiment, the component c) acrylate polymer is selected from the group consisting of linear or branched C2-C 10 The alkylene groups are selected from ethylene, 1,2-propylene, 1,3-propylene, and the like.

[0170] In another embodiment of any of the above positive-working photosensitive compositions, component c) is the acrylate polymer, wherein A is a methylene, ethylene, or 1,2-propylene group, B is a methyl, ethyl, propyl, or butyl group, C is a methyl, ethyl, propyl, butyl, cyclohexyl, isobornyl, or tetrahydrodicyclopentadienyl group, D is a direct valence bond, a methylene group, or an ethylene group, and E is a methylene group, an ethylene group, or a 1,2-propylene group.

[0171] In any of the above positive-working photosensitive compositions, in another embodiment the acrylate polymer of component c) is one in which G is a high activation energy acid labile group selected from a tertiary alkyl having at least one adjacent hydrogen at the tertiary attachment point of the carboxylate oxygen in the repeat unit designated by z forming a tertiary ester, or a low activation energy protecting group selected from an acetal or ketal formed with the carboxylate oxygen in the repeat unit designated by z.

[0172] In another embodiment of any of the above positive-working photosensitive compositions, the acrylate polymer of component c) is one in which G is t-butyl, tetrahydropyran-2-yl, tetrahydrofuran-2-yl, 4-methoxytetrahydropyran-4-yl, 1-ethoxyethyl, 1-butoxyethyl, 1-propoxyethyl, 3-oxocyclohexyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, 8-methyl-8-tricyclo[5.2.1.0], 1-methyl-2-propanyl ... 2,6]decyl group, 1,2,7,7-tetramethyl-2-norbornyl group, 2-acetoxymenthyl group, 2-hydroxymenthyl group, 1-methyl-1-cyclohexylethyl group, 4-methyl-2-oxotetrahydro-2H-pyran-4-yl group, 2,3-dimethylbutan-2-yl group, 2,3,3-trimethylbutan-2-yl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-methylcyclohexyl and wherein the acid cleavable group is selected from the group consisting of a 1-ethylcyclohexyl group, a 1,2,3,3-tetramethylbicyclo[2.2.1]heptan-2-yl group, a 2-ethyl-1,3,3-trimethylbicyclo[2.2.1]heptan-2-yl group, a 2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl group, a 2,3-dimethylpentan-3-yl group, and a 3-ethyl-2-methylpentan-3-yl group.

[0173] In any of the above positive-working photosensitive compositions, in another embodiment, the acrylate polymer of component c) is one in which t is 0 mol %, v is about 2 mol % to about 15 mol %, w is 0 mol %, x is about 5 mol % to about 30 mol %, y is about 20 mol % to about 45 mol %, z is about 20 mol % to about 45 mol %, R2 is methyl, R4 and R5 are methyl, and R6 is H.

[0174] In another embodiment of any of the above positive-working photosensitive compositions, component c), the acrylate polymer, is one in which D is methylene, Ar is phenyl, E is a -CH2-CH(CH3)- group, where the -CH2- portion of the group is attached to the carboxylate oxygen of the repeat unit designated y, and G is a tert-butyl group.

[0175] In any of the above positive-working photosensitive compositions, in another embodiment, the acrylate polymer of component c) is one in which t is 0 mol %, v is about 2 mol % to about 15 mol %, w is about 5 mol % to about 20 mol %, x is about 5 mol % to about 50 mol %, y is about 20 mol % to about 45 mol %, z is about 20 mol % to about 45 mol %, R2 and R3 are H, and R3, R4, and R6 are methyl.

[0176] In another embodiment of any of the above positive-working photosensitive compositions, component c), the acrylate polymer, is one in which A is an ethylene group, B is methyl, D is methylene, Ar is phenyl, E is a -CH2-CH(CH3)- group, where the -CH2- portion of the group is attached to the carboxylate oxygen of the repeat unit designated by y, and G is a tert-butyl group or a 1-ethylcyclopentyl group.

[0177] In any of the above positive-working photosensitive compositions, in another embodiment, the acrylate polymer of component c) is one in which t is about 5 mol % to about 30 mol %, v is about 2 mol % to about 15 mol %, w is 0 mol %, x is 0 mol %, y is about 20 mol % to about 45 mol %, z is about 20 mol % to about 45 mol %, R1 is methyl, R2 is H, and R5 and R6 are methyl.

[0178] In another embodiment of any of the above positive-working photosensitive compositions, component c), the acrylate polymer, is one in which C is methyl, E is a -CH2-CH(CH3)- group, where the -CH2- portion of the group is attached to the carboxylate oxygen of the repeat unit designated y, and G is a tert-butyl group or a 1-ethylcyclopentyl group.

[0179] In any of the above positive-working photosensitive compositions, in another embodiment, the acrylate polymer of component c) is one in which t is about 5 mol % to about 30 mol %, v is about 2 mol % to about 15 mol %, w is 0 mol %, x is about 10 mol % to about 30 mol %, y is about 20 mol % to about 45 mol %, z is about 20 mol % to about 45 mol %, R1, R2, R4 and R5 are methyl, and R6 is H.

[0180] In another embodiment of any of the above positive-working photosensitive compositions, component c), the acrylate polymer, is one in which C is isobornyl or tetrahydrodicyclopentadienyl, E is a -CH2-CH(CH3)- group, where the -CH2- portion of this group is attached to the carboxylate oxygen of the repeat unit designated by y, and G is a tert-butyl group or a 1-ethylcyclopentyl group.

[0181] In any of the above positive-working photosensitive compositions, in another embodiment, the acrylate polymer of component c) is one in which t is 0 mol %, v is 0 mol %, w is about 5 mol % to about 20 mol %, x is about 5 mol % to about 30 mol %, y is about 20 mol % to about 45 mol %, z is about 20 mol % to about 45 mol %, R3 is H, and R4, R5, and R6 are methyl.

[0182] In another embodiment of any of the above positive-working photosensitive compositions, component c), the acrylate polymer, is one in which A is an ethylene group, B is methyl, D is methylene, Ar is phenyl, E is a -CH2-CH(CH3)- group, where the -CH2- portion of the group is attached to the carboxylate oxygen of the repeat unit designated by y, and G is a tert-butyl group or a 1-ethylcyclopentyl group.

[0183] In any of the above positive-working photosensitive compositions, in another embodiment, the component c) comprises the acrylate polymer comprising structure (I) having a Mw, as measured by GPC (using polystyrene standards), which may range, but is not limited to, from 800 Daltons to 30,000 Daltons. Other exemplary weight average molecular weights of structure (I) may range, but are not limited to, from 1,500 Daltons to 20,000 Daltons. Still other exemplary weight average molecular weights of structure (I) may range, but are not limited to, from 2,500 Daltons to 20,000 Daltons.

[0184] In another embodiment of any of the above positive-working photosensitive compositions, component c) comprises the acrylate polymer comprising structure (I) having a polydispersity (Mw / Mn) in the range of between 1 and about 2.5 as measured by GPC (using polystyrene standards). In another aspect of this embodiment, the polydispersity can be in the range of about 1.3 to about 2.5. In another aspect of this embodiment, the polydispersity can be in the range of about 1.5 to about 2.3.

[0185] In any of the above positive-working photosensitive compositions, in another embodiment, the component e) comprising at least one heterocyclic thiol compound comprising a ring structure selected from the structure (III), (IIIa) or (IIIb) or tautomers thereof may include, but is not limited to, substituted or unsubstituted triazolethiols, substituted or unsubstituted imidazolethiols, substituted or unsubstituted triazinethiols, substituted or unsubstituted mercaptopyrimidines, substituted or unsubstituted thiadiazole-thiols, substituted or unsubstituted indazolethiols, tautomers thereof or combinations thereof. The substituents may include, but are not limited to, saturated or unsaturated hydrocarbon groups, substituted or unsubstituted aromatic rings, aliphatic, aromatic or heteroaromatic alcohols, amines, amides, imides, carboxylic acids, esters, ethers, halides, and the like. Such substituents may be used in concert with heterocyclic thiols to enhance solubility, improve interaction with substrates, enhance exposure, or function as antihalation dyes.

[0186] In any of the above positive-working photosensitive compositions, in another embodiment, such heterocyclic thiols of component e) can include, but are not limited to, the following compounds (VIV to VIVp) in unsubstituted or substituted form:

[0187] [ka] In any of the above positive-working photosensitive compositions, in another embodiment, such heterocyclic thiols as component e) may include, for example, thiouracil derivatives such as 2-thiouracil, including, but not limited to, 5-methyl-2-thiouracil, 5,6-dimethyl-2-thiouracil, 6-ethyl-5-methyl-2-thiouracil, 6-methyl-5-n-propyl-2-thiouracil, 5-ethyl-2-thiouracil, 5-n-propyl-2-thiouracil, 5-n-butyl-2-thiouracil, 5 -n-hexyl-2-thiouracil, 5-n-butyl-6-ethyl-2-thiouracil, 5-hydroxy-2-thiouracil, 5,6-dihydroxy-2-thiouracil, 5-hydroxy-6-n-propyl-2-thiouracil, 5-methoxy-2-thiouracil, 5-n-butoxy-2-thiouracil, 5-methoxy-6-n-propyl-2-thiouracil, 5-bromo-2-thiouracil, 5-chloro-2-thiouracil, 5-fluoro-2-thiouracil, 5-amino-2-thiouracil, 5-amino-6-methyl-2-thiouracil, 5-amino-6-phenyl-2-thiouracil, 5,6-diamino-2-thiouracil, 5-allyl-2-thiouracil, 5-allyl-3-ethyl-2-thiouracil, 5-allyl-6-phenyl-2-thiouracil, 5-benzyl-2-thiouracil, 5-benzyl-6-methyl-2-thiouracil, 5-acetamido-2-thiouracil, 6-methyl-5-nitro-2-thiouracil, 6-amino-2-thiouracil, 6-amino-5-methyl-2-thiouracil, 6-amino-5-n-propionate Pyr-2-thiouracil, 6-bromo-2-thiouracil, 6-chloro-2-thiouracil, 6-fluoro-2-thiouracil, 6-bromo-5-methyl-2-thiouracil, 6-hydroxy-2-thiouracil, 6-acetamido-2-thiouracil, 6-n-octyl-2-thiouracil, 6-dodecyl-2-thiouracil, 6-tetradodecyl-2-thiouracil, 6-hexadecyl-2-thiouracil, 6-(2-hydroxyethyl) -2-thiouracil, 6-(3-isopropyloctyl)-5-methyl-2-thiouracil, 6-(m-nitrophenyl)-2-thiouracil, 6-(m-nitrophenyl)-5-n-propyl-2-thiouracil, 6-α-naphthyl-2-thiouracil, 6-α-naphthyl-5-t-butyl-2-thiouracil, 6-(p-chlorophenyl)-2-thiouracil, 6-(p-chlorophenyl)-2-ethyl-2-thiouracil, 5-ethyl- Examples of such thiouracil include 6-eicosyl-2-thiouracil, 6-acetamido-5-ethyl-2-thiouracil, 6-eicosyl-5-allyl-2-thiouracil, 5-amino-6-phenyl-2-thiouracil, 5-amino-6-(p-chlorophenyl)-2-thiouracil, 5-methoxy-6-phenyl-2-thiouracil, 5-ethyl-6-(3,3-dimethyloctyl)-2-thiouracil, and 6-(2-bromoethyl)-2-thiouracil.

[0188] In another embodiment of the positive-working photosensitive composition, the heterocyclic thiol component of component e) is selected from the group consisting of unsubstituted triazole thiols, substituted triazole thiols, unsubstituted imidazole thiols, substituted imidazole thiols, substituted triazine thiols, unsubstituted triazine thiols, substituted mercaptopyrimidines, unsubstituted mercaptopyrimidines, substituted thiadiazole-thiols, unsubstituted thiadiazole-thiols, substituted indazole thiols, unsubstituted indazole thiols, tautomers thereof, and combinations thereof.

[0189] In another embodiment of the positive-working photosensitive composition, the heterocyclic thiol of component e) is 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-triazine-5-ol, 2-mercapto-pyrimidin-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-5-thiol, 1H-imidazole-6-thiol, 1H-imidazole-5 ... and tautomers thereof and combinations thereof.

[0190] In any of the above positive-working photosensitive compositions, in another aspect, an optional basic quencher may be present. In one aspect of this aspect, the basic quencher may be selected from amines or tetraalkylammonium carboxylate salts. In another aspect of this aspect, the basic quencher is selected from amines. In another aspect of this aspect, the basic quencher is a tetraalkylammonium carboxylate salt.

[0191] In one embodiment of the positive-working photosensitive composition, when the optional basic quencher is present and is an amine, the amine has a boiling point above 100° C. at atmospheric pressure and a pK a In another aspect of this embodiment, the amine quencher is selected from the group consisting of compounds or mixtures of compounds having the structures (Xa), (Xb), (Xc), (Xd), (Xe), (Xf), (Xg), (Xh), (Xi), and (Xj), or a mixture 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 consisting of H and C1-C1-C20 alkyl.

[0192] [ka] In one embodiment of the positive-working photosensitive composition, when the optional basic quencher is present and is a tetraalkylammonium carboxylate salt, the salt can be a salt of a monofunctional aliphatic carboxylic acid or a bis[tetraalkylammonium] salt of an aliphatic dicarboxylic acid. In one aspect of this embodiment, the basic quencher is a carboxylate salt of a monofunctional aliphatic carboxylic acid. In one aspect of this embodiment, the basic quencher is a bis[tetraalkylammonium] salt of an aliphatic dicarboxylic acid.

[0193] In one embodiment of the positive-working photosensitive composition, when the optional basic quencher is present and is a tetraalkylammonium salt of an aliphatic monofunctional carboxylic acid, it may be selected from salts in which the tetraalkylammonium moiety is selected from tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, tetraheptylammonium, tetraoctylammonium, benzyltrimethylammonium, benzyltriethylammonium, benzyltripropylammonium, benzyltributylammonium, and the carboxylate moiety may be selected from formate, acetate, propionate, butyrate, pentanoate, hexanoate, heptanoate, octanoate, cyclohexanecarboxylate, and the like. In one aspect of this embodiment, the tetraalkylammonium salt of an aliphatic carboxylic acid is selected from salts in which the tetraalkylammonium moiety is selected from tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrapentylammonium, and benzyltrimethylammonium, and the aliphatic carboxylate is selected from acetate, propionate, butyrate, pentanoate, and cyclohexylcarboxylate.

[0194] In one embodiment of the above positive-working photosensitive composition, when the optional basic quencher is present and is a bis[tetraalkylammonium] salt of an aliphatic dicarboxylic acid, non-limiting examples of such salts are those in which the bis[tetraalkylammonium] moiety is selected from bis[tetramethylammonium], bis[tetraethylammonium], bis[tetrapropylammonium], bis[tetrabutylammonium], bis[tetrapentylammonium], bis[tetrahexylammonium], bis[tetraheptylammonium], bis[tetraoctylammonium], bis[benzyltrimethylammonium], bis[benzyltripropylammonium], bis[benzyltributylammonium], and the like, and the aliphatic dicarboxylate moiety may be selected from oxalate, malonate, succinate, adipate, heptanedionate, octanedioate, nonanedioate, fumarate, maleate, glutaconate, itaconate, and the like. In one aspect of this embodiment, the bis[tetraalkylammonium] salt of an aliphatic dicarboxylic acid is selected from salts in which the bis[tetraalkylammonium] moiety is selected from bis[tetramethylammonium], bis[tetraethylammonium], bis[tetrapropylammonium], bis[tetrabutylammonium], bis[tetrapentylammonium], and bis[benzyltrimethylammonium], and the aliphatic carboxylate is selected from oxalate, malonate, succinate, adipate, and heptadioate.

[0195] In one embodiment of the above positive-working photosensitive composition, an optional basic quencher is present and is a bis[tetraalkylammonium]oxalate.

[0196] In one embodiment of the positive-working photosensitive composition, the optional basic quencher, when present, is a bis[tetraalkylammonium] salt of an aliphatic dicarboxylic acid, where the bis[tetraalkylammonium] moiety is selected from bis[tetramethylammonium], bis[tetraethylammonium], bis[tetrapropylammonium], bis[tetrabutylammonium], bis[tetrapentylammonium], and bis[benzyltrimethylammonium], and the dicarboxylate is an oxalate.

[0197] In any of the above positive-working photosensitive compositions, in another embodiment, the solvent component f) may be selected from the following non-limiting examples of suitable organic solvents: butyl acetate, amyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate (MBA), 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 (also known as 1-methoxypropan-2-ol (PGME)), propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propanyl acetate), propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propanyl acetate), propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propanyl acetate), propylene glycol monoethyl ... ether), propylene glycol propyl ether acetate, propylene glycol monoethyl ether propanoate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, N-methyl-2-pyrrolidone, anisole, dimethylsulfoxide, gamma-butyrolactone, 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, gamma-butyrolactone. These solvents may be used alone or as a mixture of two or more of them.In another aspect of this embodiment, the solvent component f) is selected from butyl acetate, amyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, ethyl 3-ethoxypropanoate, methyl 3-ethoxypropanoate, methyl 3-methoxypropanoate, propylene glycol monomethyl ether (also known as 1-methoxypropan-2-ol) (PGME), propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propanyl acetate) (PGMEA), propylene glycol monoethyl ether propanoate, methyl lactate, ethyl lactate, and propylene glycol dimethyl ether. In another aspect of this embodiment, the solvent component f) is propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propanyl acetate) (PGMEA) or a mixture of propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate.

[0198] Other optional additives that are compatible with and can be added to the compositions disclosed and claimed herein, if desired, include auxiliary resins, plasticizers, surface leveling agents and stabilizers to improve the properties of the resist layer, colorants to enhance the visibility of the patterned resist layer formed by development; antihalation dyes, tetraalkylammonium salts, such as tetrabutylammonium oxalate, and the like.

[0199] The surface leveling agent may include surfactants. There is no particular limitation on the surfactant, 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 Limited), Asahi Guard AG710, Surflon S-381, S-382, S-386, SC101, SC102, SC103, SC104, SC105, SC106, Surfinol E1004, KH-10, KH-20, KH-30 and KH-40 (manufactured by Asahi Glass Co., Ltd.); organosiloxane polymers such as KP-341, X-70-092 and X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd.); and acrylic or methacrylic acid polymers such as Polyflow No. 75 and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

[0200] In any of the above positive-working photosensitive compositions, in another embodiment, the combined amount of the two polymer components, i.e., the novolac of component b) and the acrylate polymer containing structure (I) of component c), is such that the novolac polymer component b) may comprise from about 20% to about 80% by weight of the combined weight of the novolac polymer component and the acrylate polymer component. In another aspect of this embodiment, the novolac polymer of component b) may comprise from about 30% to about 75% by weight of the combined weight of the novolac polymer component and the acrylate polymer component. As yet another example and without limitation, the novolac polymer may comprise from about 40% to about 65% w / w of the combined weight of the novolac polymer component and the acrylate polymer component.

[0201] In all embodiments described herein for said positive-working photosensitive composition, the weight percent of each solid component as a portion of the total mass of the solid components must total 100 weight percent; this includes the essential solid components a), b), c), d) and e) as well as optional components such as basic quenchers or any impurities that may be present. Furthermore, as used herein, the term "solid components" refers to any component in said positive-working photosensitive composition, other than the solvent component f), regardless of the actual physical state of these "solid components," which may be either solid or liquid.

[0202] In all embodiments described herein for the positive-working photosensitive composition, the weight percent of component a), the photoacid generator, as a fraction of the total mass of solid components, may range from about 0.1 weight percent to about 6 weight percent. In one aspect of this embodiment, this may range from about 0.1 weight percent to about 4 weight percent. In yet another aspect of this embodiment, this may range from about 0.2 weight percent to about 2 weight percent.

[0203] In all embodiments described herein for the positive-working photosensitive composition, the weight percent of component b), the novolac polymer, as a fraction of the total mass of solid components, may range from about 14% to about 80% by weight. In one aspect of this embodiment, it may range from about 30% to about 60% by weight. In yet another aspect of this embodiment, it may range from about 40% to about 60% by weight.

[0204] In all embodiments described herein for the positive-working photosensitive composition, the weight percent of component c) the acrylate polymer(s) as a fraction of the total weight of the solid components may range from about 14% to about 80% by weight. In one aspect of this embodiment, it may range from about 25% to about 60% by weight. In yet another aspect of this embodiment, it may range from about 25% to about 50% by weight.

[0205] In all embodiments described herein for the positive-working photosensitive composition, the weight percent of the glycidyl hydroxybenzoic acid condensate material(s), component d), as a fraction of the total weight of the solid components, can range from about 1% to about 30% by weight. In one aspect of this embodiment, it can range from about 3% to about 20% by weight. In yet another aspect of this embodiment, it can range from about 5% to about 15% by weight.

[0206] In all embodiments described herein for the positive-working photosensitive composition, the weight percent of the heterocyclic thiol compound(s), component e), as a fraction of the total weight of the solid components, may range from about 0.01% to about 0.5% by weight. In one aspect of this embodiment, it may range from about 0.02% to about 0.4% by weight. In yet another aspect of this embodiment, it may range from about 0.05% to about 0.25% by weight.

[0207] In all embodiments described herein for the positive-working photosensitive compositions, the weight percent of the optional basic quencher component(s), when present, as a fraction of the total weight of the solid components may range from about 0.01% to about 0.5% by weight. In one aspect of this embodiment, it may range from about 0.02% to about 0.3% by weight. In yet another aspect of this embodiment, it may range from about 0.05% to about 0.2% by weight.

[0208] In all embodiments described herein for the positive-working photosensitive composition, the weight percent of the optional surfactant component(s) as a fraction of the total weight of the solid components, if present, may range from about 0.001% to about 1% by weight. In one aspect of this embodiment, it may range from about 0.001% to about 0.2% by weight. In yet another aspect of this embodiment, it may range from about 0.005% to about 0.15% by weight. In yet another aspect of this embodiment, it may range from about 0.005% to about 0.30% by weight.

[0209] In all embodiments described herein for the positive-working photosensitive composition, the weight percent of the solids of the total composition, including solvent, may range from about 0.05% to about 65% by weight. In one aspect of this embodiment, this may range from about 20% to about 60% by weight. In yet another aspect of this embodiment, this may range from about 35% to about 60% by weight.

[0210] In all the above embodiments, the total weight % of each component as a part of the total mass of all components in the composition, including essential components a), b), c), d), e) and f) (also known as solvent), as well as any optional components or impurities present, must be 100 weight %.

[0211] As used herein, the term "solid components" refers to any components in said positive-working photosensitive composition, other than the solvent component, regardless of the actual physical state of these "solid components," which may be either a solid or a liquid.

[0212] Also disclosed herein is a method of forming a positive relief image, which method includes applying a positive-working photosensitive composition described herein to a substrate to form a film, which is then baked to form a photosensitive layer; imagewise exposing the photosensitive layer to actinic radiation to form a latent image; and developing the latent image with a developer. Optionally, the imagewise exposed photosensitive layer may be thermally treated, depending on the deprotection chemistry.

[0213] The procedure for producing a patterned photoresist layer by using the photosensitive composition disclosed herein can be conventional. For example, a substrate such as a semiconductor silicon wafer or a substrate with a metal coating as described above is uniformly coated with the photosensitive composition in the form of a solution by using a suitable coating machine such as a spin coater, and then baked in a convection oven or hot plate to form a photoresist layer, and then the photoresist layer is imagewise exposed to actinic radiation such as deep ultraviolet, near ultraviolet or visible light emitted from low pressure, high pressure and ultra-high pressure mercury lamps, arc lamps, xenon lamps, ArF, KrF and F2 excimer lasers, electron beams, X-rays, extreme UV sources and the like through a photomask in an exposure device or from a reflective mask with a desired pattern, and electron beam scanning according to a desired pattern to form a latent image of the pattern in the resist layer. The actinic radiation can be in the range of 250 nm to 450 nm, or can be broadband radiation. The latent image in the photoresist layer can then be optionally baked in a convection oven or hot plate and developed with an alkaline developer such as tetra(C1-C4 alkyl)ammonium hydroxide, choline hydroxide, lithium hydroxide, sodium hydroxide or potassium hydroxide, e.g., tetramethylammonium hydroxide (TMAH), at a concentration of 1-10% weight / weight in water, to form a patterned photoresist layer with high fidelity to the pattern of the photomask. Thicknesses can range from 20 nm to 200 microns. To achieve these thicknesses, various combinations of spin speeds and total solids concentrations can be used as described above. Depending on the size of the substrate, spin speeds of 500 rpm to 10,000 rpm can be used. In some cases, a double spin coat can be used to achieve a thicker coating thickness of about 100 to about 200 microns.

[0214] Deposition of metal onto the patterned resist on a substrate formed by the photosensitive composition disclosed herein may be carried out using metal electrolytic plating (also known as electrodeposition or electrolytic plating).

[0215] In general, methodologies for electroplating various metals using different processes and metals are described in "The plating Forecast and Assurance, Larry G Yeon, Larry King Corporation, Chapter 1, pages 5 to 56, 2004". The metal electroplating may be performed by static plating, barrel plating, brush plating, continuous plating, electroforming, pulse current plating, and other electroplating methods.

[0216] As applied to the present invention, metal electroplating onto the patterned resist on a substrate formed by the photosensitive composition according to the present invention disclosed herein may be performed with a variety of metals, non-limiting examples of which are gold, copper, silver, tungsten, cadmium, chromium, indium, iron, lead, nickel, palladium, platinum, rhodium, ruthenium, tin, zinc, aluminum, tantalum, and niobium. In one aspect of this, electroplating may be performed with gold, copper, silver, tungsten, chromium, indium, nickel, palladium, rhodium, tantalum, niobium, and electrolytically deposited tin / silver alloys. In one aspect of this embodiment, electroplating may be performed with gold, copper, silver, tungsten, chromium, indium, nickel, palladium, rhodium, tantalum, and niobium. In one aspect of this, electroplating may be performed with copper, tungsten, chromium, nickel, tantalum, niobium, and electrolytically deposited tin / silver alloys. In one particular aspect of this, electroplating may be performed with copper.

[0217] After metal is selectively electrolytically plated onto the patterned photoresist on the substrate, the resist can be removed to leave the metal pattern on the substrate. The resist pattern is removed using a chemical stripper (also called remover) or solvent. Suitable strippers for removing the resist pattern include, but are not limited to, materials such as AZ® 400T Remover or AZ® Kwik Strip, or other strippers based on polar aprotic solvents such as N-methyl-2-pyrrolidone (NMP), dimethylsulfoxide (DMSO) and the like, used alone or in combination with other components selected from other solvents, water, and bases (e.g., TMAH).

[0218] Suitable solvents for removing the resist pattern are any organic solvent that dissolves the unpatterned resist, examples of such solvents are alkyl ketones, such as acetone, as well as any of the solvents previously described as suitable solvents for the compositions of the present invention, a non-limiting example being PGMEA.

[0219] Another aspect of the present invention is a method of forming a relief image (or, alternatively, a resist pattern on a substrate), comprising the steps of: a) forming a photosensitive layer by applying any of the positive-working photosensitive compositions described herein onto a substrate to form a film and then baking the film; b) imagewise exposing the photosensitive layer to actinic radiation to form a latent image; c) developing said latent image in a developer.

[0220] Another aspect of the present invention is a method of forming a relief image comprising the steps of: a') forming a photosensitive layer by applying any of the positive-working photosensitive compositions described herein onto a substrate to form a film and then baking the film; b') imagewise exposing the photosensitive layer to actinic radiation to form a latent image; c') thermally treating the imagewise exposed photosensitive layer to form a baked latent image; d') developing said baked latent image in a developer.

[0221] In another aspect of the invention, this includes a method of forming a relief image that is subsequently used as a mask in metal deposition to form a metal pattern, the method comprising the steps of: a'') forming a photosensitive layer by applying any of the positive-working photosensitive compositions described herein onto a substrate to form a film and then baking the film; b'') imagewise exposing the photosensitive layer to actinic radiation to form a latent image; c'') developing the latent image in a developer to form a resist pattern on the substrate; d'') selectively electroplating on a substrate using the resist pattern as a barrier; e'') stripping the resist pattern leaving behind the selectively electrolytically plated metal, thereby forming a metal pattern on the substrate.

[0222] In another aspect of the invention, this involves the following steps as a method for forming a relief image which is subsequently used as a mask in metal deposition to form a metal pattern. a''') forming a photosensitive layer by applying any of the positive-working photosensitive compositions described herein onto a substrate to form a film and then baking the film; b''') imagewise exposing the photosensitive layer to actinic radiation to form a latent image; c''') thermally treating the imagewise exposed photosensitive layer to form a baked latent image; d''') developing the baked latent image in a developer to form a resist pattern on the substrate; e'') selectively electroplating on a substrate using the resist pattern as a barrier; f''') stripping the resist pattern leaving behind the selectively electrolytically plated metal, thereby forming a metal pattern on the substrate.

[0223] Another aspect of the present invention is a glycidyl hydroxybenzoic acid condensate material comprising one or more compounds having the structure (II).

[0224] [ka] wherein W is an organic moiety having a molecular weight of 600 or less; wherein W forms an ether bond with the oxygen to which it is attached; m is an integer from 1 to 3, and n is an integer from 1 to 4, when m is 1, n is 3 or 4; and when m is 2 or 3, n is an integer from 1 to 4; n' is 0 or 1. In another embodiment of the glycidyl hydroxybenzoic acid condensate material, it is any one of the variations of component d) described above for the positive-working photosensitive composition.

[0225] Another aspect of the present invention is the use of a glycidyl hydroxybenzoic acid condensate material comprising one or more compounds having structure (II) as previously described, or of the positive-working photosensitive composition of the present invention as previously described, to form a positive relief image on a substrate.

[0226] Each of the documents mentioned above is incorporated herein in its entirety for all purposes. The following specific examples provide detailed illustrations of how to make and use the compositions of the present invention. However, these examples are not intended to limit or restrict the scope of the present invention in any way, and should not be construed as teaching the conditions, parameters or values ​​that must be exclusively utilized to carry out the present invention. EXAMPLES

[0227] Additive synthesis example 1:

[0228] [ka] 61.6 g of 3,5-dihydroxybenzoic acid, 68.08 g of bisphenol A diglycidyl ether, and 0.45 g of benzyltriethylammonium chloride were mixed in 130 g of propylene glycol methyl ether (PGME) solvent. The reaction was allowed to proceed for 15 hours at 110° C. under nitrogen. After cooling to room temperature, the reaction mixture was precipitated in DI water. The solid glycidyl hydroxybenzoic acid condensate material was washed and dried under vacuum at 50° C. to produce 130.0 g (100% yield) with a gel permeation chromatography (GPC) (using polystyrene standards) weight average molecular weight of Mw=1151 and a number average molecular weight of Mn=1090. Thus, a glycidyl hydroxybenzoic acid condensate material was obtained having a dissolution rate of 5400 Å / sec in AZ® 300 MIF developer. Proton NMR analysis indicates that the compound is about 95% pure with about 5% by-product where one of the hydroxyphenols has also condensed with a glycidyl moiety. This was confirmed by analysis by proton NMR, which was performed in acetone-d6. In this spectrum, two of the aromatic hydrogens of the dihydroxybenzoic acid unit that are ortho to the carbonyl are observed at 7.06 ppm, while the eight aromatic protons in the bisphenol A derived unit are observed at 7.173 and 7.152, 6.901 and 6.879 ppm. If the purity were 100%, this compound would give a 2 / 1 proton ratio for the aromatic protons in the bisphenol A derivative:the two ortho hydroxybenzoic acid aromatic protons. The observed ratio was 2.036, indicating a purity of at least 94.6%. The presence of this small amount of impurity is also confirmed by GPC and HPLC data. GPC and high pressure liquid chromatography (HPLC) data also confirmed the absence of residual starting materials. The slight impurities represent some side reactions of the phenolic hydroxyl and epoxide moieties during the synthesis.

[0229] Additive synthesis example 2:

[0230] [ka] 15.4g of 3,5-dihydroxybenzoic acid, 10.81g of neopentyl glycol diglycidyl ether, 0.01g of benzyltriethylammonium chloride were mixed in 26g of 1-methoxy-2-propanyl acetate (PGMEA) solvent. The reaction was allowed to proceed for 8 hours at 110°C under nitrogen. After cooling to room temperature, the reaction mixture was transferred into a bottle for use. GPC (using polystyrene standards) shows that it has a weight average molecular weight of Mw=736 and a number average molecular weight of Mn=505. The dissolution rate in AZ® 300 MIF developer is 5500 Å / sec. GPC data also confirmed the absence of residual raw materials.

[0231] Additive synthesis example 3:

[0232] [ka] 46.2g of 3,5-dihydroxybenzoic acid, 30.2g of trimethylolpropane triglycidyl ether, 0.45g of benzyltriethylammonium chloride were mixed in 76.4g of propylene glycol monomethyl ether acetate (PGMEA) solvent. The reaction was allowed to proceed for 12 hours at 110°C under nitrogen. After cooling to room temperature, the reaction mixture was transferred into a bottle for use. GPC (using polystyrene standards) shows that it has a weight average molecular weight of Mw=1084 and a number average molecular weight of Mn=794. The dissolution rate in AZ® 300MIF developer is 7400 Å / sec. GPC data also confirmed the absence of residual raw materials.

[0233] Additive synthesis example 4:

[0234] [ka] 41.4g of 4-hydroxybenzoic acid, 30.2g of trimethylolpropane triglycidyl ether, 0.14g of benzyltriethylammonium chloride were mixed in 107.5g of propylene glycol monomethyl ether acetate (PGMEA) solvent. The reaction was allowed to proceed for 17 hours at 140°C under nitrogen. After cooling to room temperature, the reaction mixture was transferred into a bottle for use. GPC (using polystyrene standards) shows that it has a weight average molecular weight of Mw=1409 and a number average molecular weight of Mn=1181. The dissolution rate in AZ® 300 MIF developer is 6700 Å / sec.

[0235] Additive synthesis example 5: (comparative material)

[0236] [ka] 26.24g (0.19 moles) of 4-hydroxybenzoic acid, 34.04g (0.1 moles) of bisphenol A diglycidyl ether, 0.1g of benzyltriethylammonium chloride were mixed in 60.28g of propylene glycol monomethyl ether acetate (PGMEA) solvent. The reaction was allowed to proceed for 15 hours at 110°C under nitrogen. After cooling to room temperature, the reaction mixture was transferred into a bottle for use. GPC (using polystyrene standards) shows that it has a weight average molecular weight of Mw=1538, a number average molecular weight of Mn=1098. The dissolution rate in AZ® 300 MIF developer is 5 Å / sec.

[0237] Additive synthesis example 6: (comparative material) 15.4 g (0.1 mole) of 3,5-dihydroxybenzoic acid, 53.75 g of (glycidyl end-capped) poly(bisphenol A-co-epichlorohydrin) (average Mn=about 1075), 0.1 g of benzyltriethylammonium chloride were mixed in 104 g of propylene glycol methyl ether (PGME) solvent. The reaction was allowed to proceed for 10 hours at 110° C. under nitrogen. After cooling to room temperature, the reaction mixture was precipitated in DI water. The solid glycidyl hydroxybenzoic acid condensate material was washed and dried under vacuum at 50° C. to yield 69.0 g (99.8% yield) with a GPC (using polystyrene standard) weight average molecular weight of Mw=3829 and a number average molecular weight of Mn=1895. A glycidyl hydroxybenzoic acid condensate material was obtained. The dissolution rate in AZ® 300MIF developer is 6 Å / sec.

[0238] Additive synthesis example 7:

[0239] [ka] 25.0g (0.147 moles) of gallic acid, 23.76g (0.0698 moles) of bisphenol A diglycidyl ether, and 0.18g of benzyltriethylammonium chloride were mixed in 114g of a mixed solvent of propylene glycol monomethyl ether acetate and propylene glycol methyl ether (PGMEA / PGME: 1.85 / 1). The reaction was allowed to proceed at 110°C for 15 hours under nitrogen. After cooling to room temperature, the reaction mixture was transferred into a bottle for use. GPC (using polystyrene standards) shows that it has a weight average molecular weight of Mw=1867 and a number average molecular weight of Mn=1024. The dissolution rate in AZ® 300 MIF developer is 10500 Å / sec.

[0240] Additive synthesis example 8:

[0241] [ka] 30.8g of 3,5-dihydroxybenzoic acid, 23.23g of glycidyl isopropyl ether, 0.13g of benzyltriethylammonium chloride were mixed in 81g of 1-methoxy-2-propanyl acetate (PGMEA) solvent. The reaction was allowed to proceed for 18 hours at 135°C under nitrogen. The solvent was then evaporated under vacuum at 50°C. GPC (using polystyrene standards) shows that it has a weight average molecular weight of Mw=429 and a number average molecular weight of Mn=407. The dissolution rate in AZ® 300 MIF developer is 10645 Å / sec.

[0242] Dissolution rate test of phenolic additives: All glycidyl hydroxybenzoic acid condensate materials were dissolved in PGMEA to prepare 50% solutions. Coatings were then formed by spin-coating resist samples and applying a soft bake at 110°C for 180 seconds using a standard wafer track hotplate in contact mode. The spin speed was adjusted to obtain a resist film with a thickness of 10 microns. All film thickness measurements were made on Si wafers using optical metrology. The films were immersed in AZ® 300 MIF developer (a 0.26N aqueous solution of tetramethylammonium hydroxide = TMAH) (EMD Performance Materials, AZ Products, Somerville, NJ) at 23°C. Dissolution rates were determined by measuring the film loss at a specified time.

[0243] Acrylic polymer synthesis example 1:

[0244] [ka] The proportions of monomer repeat units are reported as mole percentages. In this example, 6.46 g of methacrylic acid, 35.24 g of benzyl methacrylate, 43.25 g of hydroxypropyl methacrylate, and 54.47 g of tert-butyl acrylate were mixed in 209.1 g of PGME solvent. The polymerization reaction proceeds for 18 hours at 90° C. under nitrogen in the presence of 2.3 g of AIBN. After cooling to room temperature, the reaction mixture is precipitated in DI water. The polymer solids are washed and dried under vacuum at 45° C. to yield 137.1 g (98% yield) with a GPC (with polystyrene standards) weight average molecular weight of 15,072 Daltons and a number average molecular weight of 7345 Daltons.

[0245] Acrylic polymer synthesis example 2:

[0246] [ka] 1.8 g acrylic acid, 6.5 g methoxyethyl acrylate, 22.0 g benzyl methacrylate, 21.6 g hydroxypropyl methacrylate, and 21.3 g tert-butyl methacrylate were mixed in 179.6 g PGME solvent. The polymerization reaction proceeded for 18 hours at 80° C. under nitrogen in the presence of 3.3 g AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 45° C. to yield 73.5 g (>99% yield) with a GPC (with polystyrene standard) weight average molecular weight of 11,868 Daltons and a number average molecular weight of 5382.

[0247] Acrylic polymer synthesis example 3:

[0248] [ka] 1.8 g of acrylic acid, 6.5 g of methoxyethyl acrylate, 17.6 g of benzyl methacrylate, 21.6 g of hydroxypropyl methacrylate, and 24.9 g of tert-butyl methacrylate were mixed in 172.9 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 DI water. The white polymer solid was washed and dried under vacuum at 45° C. to yield 71.6 g (99% yield) with a GPC (with polystyrene standard) weight average molecular weight of 17,205 Daltons and a number average molecular weight of 8407.

[0249] Acrylic polymer synthesis example 4:

[0250] [ka] 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 DI water. The white polymer solid was washed and dried under vacuum at 45° C. to yield 70.3 g (99% yield) with a GPC (with polystyrene standard) weight average molecular weight of 17,153 Daltons and a number average molecular weight of 9424.

[0251] Acrylic polymer synthesis example 5:

[0252] [ka] 3.6 g acrylic acid, 6.5 g methoxyethyl acrylate, 13.2 g benzyl methacrylate, 21.6 g hydroxypropyl methacrylate, 24.9 g tert-butyl methacrylate were mixed in 135.8 g PGME solvent. The polymerization reaction proceeded for 18 hours at 90° C. under nitrogen in the presence of 3.3 g AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 45° C. to yield 70.8 g (>99% yield) with a GPC (with polystyrene standard) weight average molecular weight of 11,913 Daltons and a number average molecular weight of 5564.

[0253] Acrylic polymer synthesis example 6:

[0254] [ka] 1.8 g of acrylic acid, 10.0 g of methyl methacrylate, 28.8 g of hydroxypropyl methacrylate, and 24.9 g of tert-butyl methacrylate were mixed in 124.7 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 DI water. The white polymer solid was washed and dried under vacuum at 45° C. to yield 64.4 g (98% yield) with a GPC (with polystyrene standard) weight average molecular weight of 16,650 Daltons and a number average molecular weight of 7919.

[0255] Acrylic Polymer Synthesis Example 7:

[0256] [ka] 1.8 g of acrylic acid, 3.3 g of methoxyethyl acrylate, 17.6 g of benzyl methacrylate, 21.6 g of hydroxypropyl methacrylate, and 28.4 g of tert-butyl methacrylate were mixed in 138.2 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 DI water. The white polymer solid was washed and dried under vacuum at 45° C. to yield 71.9 g (99% yield) with a weight average molecular weight of 15,843 Daltons and a number average molecular weight of 7642 Daltons.

[0257] Acrylic polymer synthesis example 8:

[0258] [ka] 6.5 g of methoxyethyl acrylate, 15.4 g of benzyl methacrylate, 21.6 g of hydroxypropyl methacrylate, and 30.2 g of tert-butyl methacrylate were mixed in 140.0 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 DI water. The white polymer solid was washed and dried under vacuum at 45° C. to yield 72.45 g (98% yield) with a GPC (with polystyrene standard) weight average molecular weight of 17,525 Daltons and a number average molecular weight of 8695 Daltons.

[0259] Acrylic Polymer Synthesis Example 9:

[0260] [ka] The proportions of monomer repeat units are reported as mole percentages. 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 were mixed in 152.6 g of PGME solvent. The polymerization reaction proceeds 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 is precipitated in DI water. The polymer solids are washed and dried under vacuum at 45° C. to yield 79.3 g (98% yield) with a GPC (with polystyrene standards) weight average molecular weight of 17,888 Daltons and a number average molecular weight of 9502.

[0261] Acrylic Polymer Synthesis Example 10:

[0262] [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 DI water. The polymer solids were washed and dried under vacuum at 45° C. to yield 153.45 g (98.5% yield) with a GPC (with polystyrene standard) weight average molecular weight of 17,103 Daltons and a number average molecular weight of 8316.

[0263] Acrylic Polymer Synthesis Example 11:

[0264] [ka] 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 DI water. The polymer solids were washed and dried under vacuum at 45° C. to yield 150.2 g (97.7% yield) with a GPC (with polystyrene standard) weight average molecular weight of 15,557 Daltons and a number average molecular weight of 7795.

[0265] Acrylic Polymer Synthesis Example 12:

[0266] [ka] 8.61 g of methacrylic acid, 22.23 g of isobornyl methacrylate, 26.43 g of benzyl methacrylate, 43.25 g of hydroxypropyl methacrylate, and 44.36 g of tert-butyl acrylate 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 2.46 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The polymer solids were washed and dried under vacuum at 45° C. to yield 142.5 g (98.3% yield) with a GPC (with polystyrene standard) weight average molecular weight of 25,535 Daltons and a number average molecular weight of 12,215.

[0267] Novolac Polymers: Three novolac polymers were used in the following formulation examples. Novolac-1 (SPN-560S) was synthesized from m-cresol and formaldehyde and had a bulk dissolution rate of 700 Å / sec in 2.38% aqueous TMAH developer. Novolac-2 (SPN560F) was synthesized from m-cresol and formaldehyde and had a bulk dissolution rate of 1,600 Å / sec in 2.38% aqueous TMAH developer. Novolac-3 is a 1 / 1 blend of novolac-1 and novolac-2 and has a bulk dissolution rate of 1,000 Å / sec in 2.38% aqueous TMAH developer.

[0268] Prescription Examples chemicals α,α-Bis(4-hydroxyphenyl)-4-(4-hydroxy-α,α-dimethylbenzyl)ethylbenzene (TPPA) was obtained from Honshu Chemical Industry Co., Ltd., Yaesu Daimaru Building, 1-1-1 Kyobashi, Chuo-ku, Tokyo, Japan, 104-0031, Japan.

[0269] N-hydroxy-naphthylimide triflate (NIT) was obtained from Heraues Daychem (Vandalia, Ohio).

[0270] 3-Mercapto-1,2,4-triazole (also referred to as 1H-1,2,3-triazole-3-thiol) (MTA) was obtained from Sigma-Aldrich Corp. (St. Louis, MO, USA).

[0271] The surfactant APS-437 was obtained from Shin-Etsu Chemical Co., Ltd., Tokyo, Japan.

[0272] The novolac components were m-cresol / formaldehyde novolacs (SPN-560F and SPN-560S) supplied by Allnex, Brussels, Belgium.

[0273] Tetrabutylammonium oxalate was obtained from Merck Performance Materials, Wiesbaden, Germany.

[0274] NK-280 is a diazonaphthoquinone photoactive compound (DNQ-PC) sold under this name by Toyo Gosei Co., Ltd. and has the following general structural formula:

[0275] [ka] Formulation example 1: 4.2 g of glycidyl hydroxybenzoic acid condensate material from Additive Synthesis Example 1, 16.5 g of acrylic polymer resin from Acrylic Polymer Synthesis Example 12, 20.9 g of Novolac-3, 0.42 g of 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl trifluoromethanesulfonate [naphthalenedicarboxyimidyl triflate, NIT] (NIT PAG), 0.075 g of 1H-1,2,4-triazole-3-thiol, 0.055 g of tetrabutylammonium oxalate, and 0.050 g of APS-437 were dissolved in 57.8 g of PGMEA solvent to obtain a resist solution with 42.2% solids. The solution was coated onto a copper wafer and the resulting 10 μm film was dried at 110° C. for 180 seconds. The resist was processed to form a patterned image, which was post-exposure baked at 90° C. for 60 seconds and developed for 120 seconds.

[0276] Prescription examples 2-8: In these formulations, Additive Synthesis Example 1 in Formulation Example 1 was replaced with Additive Synthesis Examples 2, 3, 4, 5, 6, 7 and 8, respectively.

[0277] Formulation Example 9 (Comparative Example): Acrylic Polymer Synthesis 16.5 g of acrylic polymer resin from Example 12, 25.1 g of Novolac-3, 0.42 g of NIT PAG, 0.075 g of 1H-1,2,4-triazole-3-thiol, 0.055 g of tetrabutylammonium oxalate, and 0.050 g of APS-437 were dissolved in 57.8 g of PGMEA solvent to obtain a resist solution with 42.2% solids. The solution was coated onto a copper wafer and the resulting 10 μm film was dried at 110° C. for 180 seconds. The resist was processed to form a patterned image, which was post-exposure baked at 90° C. for 60 seconds and developed for 120 seconds. The resulting resist pattern profile shows no undercutting. This example is used for comparison with Examples 1-8 to show the significant effect of the additive of the condensate of a multifunctional glycidyl compound with 4-hydroxybenzoic acid or 3,5-dihydroxybenzoic acid or gallic acid on the resist undercut profile on copper substrates.

[0278] Formulation Examples 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20: In these formulations, the acrylic synthetic polymer 12 used in formulation example 1 was replaced with acrylic synthetic examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and 11, respectively, to obtain resist solutions. These resists were tested under the same processing conditions as described above.

[0279] [Table 1]

[0280] [Table 2]

[0281] [Table 3]

[0282] Structure of thiol additives

[0283] [ka]

[0284] [Table 4]

[0285] [ka]

[0286] Formulation Example 27: (as a comparative example in DNQ type resist): 4.2g of glycidyl hydroxybenzoic acid condensate material from Additive Synthesis Example 1, 30.575g of novolac SPN560 resin, 7.3g of diazonaphthoquinone sulfonic acid ester (also called NK280), 0.075g of 1H-1,2,4-triazole-3-thiol (also called 3-mercapto-1,2,4-triazole), and 0.050g of APS-437 were dissolved in 57.8g of PGMEA solvent to prepare a solution. The solution was filtered for testing.

[0287] Coating Procedure Formulations 1-27 were tested on 6 inch diameter Si and Cu wafers. The Si wafers were dehydration baked and vapor primed with hexamethyldisilazane (HMDS). The Cu wafers were silicon wafers coated with 5,000 Angstroms of silicon dioxide, 250 Angstroms of tantalum nitride, and 3,500 Angstroms of Cu (PVD electrolytic plating).

[0288] Resist coatings were formed by spin-coating the resist samples and applying a soft bake at 110 °C for 180 seconds using a standard wafer track hotplate in contact mode. The spin speed was adjusted to obtain a 10 micron thick resist film. All film thickness measurements were performed on Si wafers using optical metrology.

[0289] Imaging Procedure: The wafers were exposed on an ASML 250i line stepper. The resist was post-exposure baked at 90° C. for 60 seconds and puddle developed in AZ® 300MIF developer (a 0.26N aqueous solution of tetramethylammonium hydroxide=TMAH) (EMD Performance Materials, AZ Products, Somerville, NJ) for 120 seconds at 23° C. The developed resist images were examined using a Hitachi S4700 or AMRAY 4200L electron microscope.

[0290] Cu electroplating Cu electroplating was carried out in a cup using Enthone GSW Copper Plating Solution. The current density was controlled at 1 ASD; the plating temperature was 25°C; and the plating time was 12 min. After plating, the resist was removed by acetone. The copper wire images were examined using a Hitachi S4700 or AMRAY4200L electron microscope.

[0291] Formulation 1 gives a resist pattern profile with an undercut of about 1.0-2.5 μm. Resist formulations 2, 3, 4, 7 and 8 show the same undercut as formulation example 1. Resist formulations 5 and 6 show scum and cannot be developed. Therefore, the glycidyl hydroxybenzoic acid condensate material as additive examples 5 and 6 with slow dissolution rate cannot be used in the resist formulation. Resist formulations 10-20 in Table 2 show undercut, suggesting that the glycidyl hydroxybenzoic acid condensate material additive can also produce undercut profiles with various acrylic polymer resins. The formulations are not limited to those listed in Tables 1 and 2 that were tested. Additive synthesis example 1 in Table 2 was also replaced with additive synthesis examples 2, 3, 4, 7 and 8. The combination of additive synthesis resin examples 2, 3, 4, 7 and 8 with various acrylic polymer resin examples 2-11 also show undercut profiles.

[0292] The formulations in Table 3 were also tested. The profile shows undercut. The thiol additive does not affect the undercut profile.

[0293] The formulations in Table 4 were also tested. Commercially available phenolic resins show no or slight undercut of <0.05 μm at limited doses.

[0294] Comparative Example Formulation 27 was tested on an ASML stepper. The DNQ type photoresist using Additive Synthesis Example 1 exhibited an undercut profile.

[0295] After copper plating with the patterned undercut resist, it was confirmed that the copper wires had footings, which is beneficial for the conductivity of any devices made with these metal lines with footings, as the copper wires with footings stabilize the wires (in other words, are less likely to peel off) and have a larger contact area onto the substrate.

[0296] Figure 1 shows resist images made using Formulation Example 20, which shows 10 micron lines in a 12 micron thick resist film exhibiting a 0.98 micron undercut profile. In Figure 1, the SEM image on the left shows the resist lines, while the SEM image on the right shows an extension of one of the lines exhibiting a 0.98 micron undercut. Figure 2 shows copper metal lines produced by electrolytic plating copper onto a substrate having these undercut profiles after stripping the resist. This shows the beneficial footing produced on the metal lines, providing resistance to adhesion loss and improving conductivity.

[0297] Additionally, Table 5 shows examples of novel compositions for thicker films above 50 microns.

[0298] [Table 5]

[0299] Coatings: Formulations 28-34 were tested on 8 inch diameter Si and Cu wafers. The Si wafers were dehydration baked and vapor primed with hexamethyldisilazane (HMDS). The Cu wafers were silicon wafers coated with 5,000 Angstroms of silicon dioxide, 250 Angstroms of tantalum nitride, and 3,500 Angstroms of Cu (PVD electrolytic plating).

[0300] Resist samples were spin-coated and a soft bake of 300 seconds at 130 °C was applied using a standard wafer track hotplate in contact mode to form resist coatings. The spin speed was adjusted to obtain a 50 micron thick resist film. Film thickness measurements were performed on Si wafers using optical metrology.

[0301] Imaging: Wafers were exposed with a SUSS MA200CC mask aligner. The resist was post-exposure baked at 100° C. for 100 seconds and puddle developed in AZ® 300MIF developer (a 0.26N aqueous solution of tetramethylammonium hydroxide=TMAH) at 23° C. for 240 seconds. The developed resist images were examined using a Hitachi S4700 or AMRAY 4200L electron microscope.

[0302] The undercut size was measured by magnified SEM images. Formulations 28-32 were 500-1000 mJ / cm 2 The formula shows an undercut of 2.1 to 2.5 over an exposure dose range of 100 nm. In comparison, formulas 33 and 34 showed no undercut. TPPA and B126X-SA are not efficient at producing undercut in this formula. While this application is directed to the invention set forth in the claims, the disclosure of this application also includes: 1. A positive-working photosensitive composition comprising: a) at least one photoacid generator; b) at least one novolac polymer; c) at least one acrylate polymer comprising a component having the following structure (I):

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Claims

1. The following structure (II): 【Chemistry 1】 [In the formula, W is an organic moiety having a molecular weight of 600 or less, where W forms an ether bond with the oxygen to which it is attached; m is an integer from 1 to 3, and n is an integer from 1 to 4, when m is 1, n is 3 or 4; and when m is 2 or 3, n is an integer from 1 to 4; n′ is 0 or 1. wherein the organic moiety W is selected from the group consisting of moieties of the structures (Wa), (Wb), (Wc), (Wd), and (We), 【Chemistry 2】 represents the point of attachment within each of these organic moieties, where it forms an ether bond with the oxygen in said glycidyl hydroxybenzoic acid condensate material of structure (II); Xa is a moiety selected from the group consisting of a direct valence bond, alkylene, -SO 2 -, -C(=O)-, and -O-; Ra1, Rb1 and Rc are independently selected from C 1 -C 5 alkyl or C 2 -C 5 alkyleneoxyalkyl; A glycidyl hydroxybenzoic acid condensate material, wherein Ra2 is selected from C 1 -C 5 alkyl, C 2 -C 5 alkyleneoxyalkyl, C 1 -C 5 alkyloxy, halide, C 1 -C 5 alkylsulfonyl, C 1 -C 5 alkylcarbonyl, and C 1 -C 5 alkylcarbonyloxy, and n'' ranges from 0 to 12. 【Chemistry 3】

2. 2. The glycidyl hydroxybenzoic acid condensate material of claim 1, wherein in structure (II), the hydroxy group(s) on the benzene ring(s) are located meta- and / or para to the carboxyl group(s).

3. The glycidyl hydroxybenzoic acid condensate material according to claim 1 or 2, wherein m is 2 to 3.

4. It comprises at least one compound having the structure (IVa-1), where n is 3 to 4 and Rw is OH or a moiety (IVb-1), 【Chemistry 4】 3. The glycidyl hydroxybenzoic acid condensate material according to claim 1 or 2, wherein represents a point of attachment in said moiety. 【Chemistry 5】

5. It comprises at least one compound having the structure (IVa-2), where n is 1 to 4 and Rw1 is OH or a moiety (IVb-2), 【Chemistry 6】 The glycidyl hydroxybenzoic acid condensate material according to any one of claims 1 to 3, wherein represents a point of attachment in said moiety. 【Chemistry 7】

6. at least one compound having the structure (IVa-3), where n is 1 to 4 and Rw2 is OH or a moiety (IVa), with the proviso that at most one Rw2 is a moiety (IVb-3), 【Chemistry 8】 The glycidyl hydroxybenzoic acid condensate material according to any one of claims 1 to 3, wherein represents a point of attachment in said moiety. 【Chemistry 9】

7. At least one compound having the structure (Va-1), where Rw3 is OH or a moiety of the structure (Vb-1), 【Chemistry 10】 represents the point of attachment in this moiety, where: m is 2 to 3; n' is 1 or 0; and Xa is a direct valence bond, alkylene, -SO ２ The glycidyl hydroxybenzoic acid condensate material according to any one of claims 1 to 3, wherein the glycidyl hydroxybenzoic acid condensate material is selected from the group consisting of -, -C(=O)- and -O-. 【Chemistry 11】

8. At least one compound having the structure (VIa-1), wherein Rw20 is OH or a moiety of the structure (VIb-1), 【Chemistry 12】 represents the point of attachment in this moiety, where: m is 2 to 3; n' is 0 or 1; Ra1 and Rb1 are independently C １ ~C ５ Alkyl or C ２ ~C ５ 4. The glycidyl hydroxybenzoic acid condensate material according to claim 1, wherein the glycidyl hydroxybenzoic acid condensate material is selected from the group consisting of -alkylene-O-alkylene moieties. 【Chemistry 13】

9. At least one compound of structure (VIIa-1), wherein Rw23 is OH or a moiety of structure (VIIb-1), 【Chemistry 14】 represents the point of attachment in this moiety, where: m is 1, 2 or 3, and n' is 0 or 1; Ra2 is C １ ~C ５ Alkyl or C ２ ~C ５ 3. The glycidyl hydroxybenzoic acid condensate material of claim 1 or 2, wherein the glycidyl hydroxybenzoic acid condensate material is selected from the group consisting of -alkylene-O-alkylene moieties. 【Chemistry 15】

10. At least one compound of structure (VIIa-2), in which Rw24 is OH or a moiety (VIIb-2), 【Chemistry 16】 represents a point of attachment in this moiety, with the proviso that at most one Rw24 is a moiety (VIIb-2), Ra2 is C １ ~C ５ Alkyl or C ２ ~C ５ 4. The glycidyl hydroxybenzoic acid condensate material according to claim 1, wherein the moiety is an -alkylene-O-alkylene. 【Chemistry 17】

11. At least one compound of structure (VIIa-3), wherein Rw25 is OH or a moiety (VIIb-3), 【Chemistry 18】 represents a point of attachment in this moiety, with the proviso that at most one Rw25 is a moiety (VIIb-3), and further where Ra2 is C １ ~C ５ Alkyl or C ２ ~C ５ 3. The glycidyl hydroxybenzoic acid condensate material of claim 1 or 2, wherein the -alkylene-O-alkyl moiety is 【Chemistry 19】

12. At least one compound of structure (VIIa-4), wherein Rw26 is OH or a moiety (VIIb-4), 【Chemistry 20】 represents a point of attachment in this moiety, with the proviso that at most one Rw26 is a moiety (VIIb-4), and further wherein Ra2 is C １ ~C ５ Alkyl or C ２ ~C ５ 3. The glycidyl hydroxybenzoic acid condensate material of claim 1 or 2, wherein the -alkylene-O-alkyl moiety is 【Chemistry 21】

13. The following structure (II): 【Chemical 22】 [In the formula, W is an organic moiety having a molecular weight of 600 or less, where W forms an ether bond with the oxygen to which it is attached; m is an integer from 1 to 3, and n is an integer from 1 to 4, when m is 1, n is 3 or 4; and when m is 2 or 3, n is an integer from 1 to 4; n′ is 0 or 1. wherein the organic moiety W is an aromatic moiety selected from polycyclic arenes, bis(aryl)ethers, biphenyls, bis(aryl)sulfones, bis(phenyl)alkylenes, (alkyl)(aryl)ketones, bis(aryl)ketones, bis(aryl)sulfones, and (alkyl)(aryl)sulfones.

14. The structure (II): 【Chemistry 23】 [In the formula, W is an organic moiety having a molecular weight of 600 or less, where W forms an ether bond with the oxygen to which it is attached; m is an integer from 1 to 3, and n is an integer from 1 to 4, when m is 1, n is 3 or 4; and when m is 2 or 3, n is an integer from 1 to 4; n′ is 0 or 1. A glycidyl hydroxybenzoic acid condensate material comprising one or more compounds having the formula: In structure (II), the hydroxy group(s) on the benzene ring(s) are located meta- and / or para to the carboxyl group(s), and / or m is 2 to 3, and / or - at least one compound having the structure (IVa-2), where n is 1 to 4 and Rw1 is OH or the moiety (IVb-2), 【Chemistry 24】 represents the attachment point in this moiety, 【Chemistry 25】 or - at least one compound having structure (IVa-3), in which n is 1 to 4 and Rw2 is OH or a moiety (IVa), with the proviso that at most one Rw2 is a moiety (IVb-3), in which 【Chemistry 26】 represents the attachment point in this moiety, 【Chemical 27】 with the proviso that said organic moiety W is selected from the group consisting of moieties of the structures (Wa), (Wb), (Wc), (Wd), (We) and (Wf), 【Chemistry 28】 represents the point of attachment within each of these organic moieties, where it forms an ether bond with the oxygen in said glycidyl hydroxybenzoic acid condensate material of structure (II); Xa is a moiety selected from the group consisting of a direct valence bond, alkylene, -SO 2 -, -C(=O)-, and -O-; Ra1, Rb1 and Rc are independently selected from C 1 -C 5 alkyl or C 2 -C 5 alkyleneoxyalkyl; Ra2 is selected from C 1 -C 5 alkyl, C 2 -C 5 alkyleneoxyalkyl, C 1 -C 5 alkyloxy, halide, C 1 -C 5 alkylsulfonyl, C 1 -C 5 alkylcarbonyl, and C 1 -C 5 alkylcarbonyloxy, and n″ ranges from 0 to 12; Glycidyl hydroxybenzoic acid condensate material. 【Chemical Formula 29】 15. The structure (II): 【Chemistry 30】 [In the formula, W is an organic moiety having a molecular weight of 600 or less, where W forms an ether bond with the oxygen to which it is attached; m is an integer from 1 to 3, and n is an integer from 1 to 4, when m is 1, n is 3 or 4; and when m is 2 or 3, n is an integer from 1 to 4; n′ is 0 or 1. A glycidyl hydroxybenzoic acid condensate material comprising one or more compounds having the formula: - at least one compound having the structure (IVa-1), where n is 3 to 4 and Rw is OH or the moiety (IVb-1), 【Chemistry 31】 represents the attachment point in this moiety, 【Chemistry 32】 or - at least one compound having structure (Va-1), where Rw3 is OH or a moiety of structure (Vb-1), 【Chemical 33】 represents the point of attachment in this moiety, where: m is 2 to 3; n' is 1 or 0; and Xa is selected from the group consisting of a direct valence bond, alkylene, -SO 2 -, -C(=O)-, and -O-; 【Chemical 34】 or - at least one compound having structure (VIa-1), where Rw20 is OH or a moiety of structure (VIb-1), 【Chemistry 35】 represents the point of attachment in this moiety, where: m is 2 to 3; n' is 0 or 1; Ra1 and Rb1 are independently selected from C 1 -C 5 alkyl or C 2 -C 5 -alkylene-O-alkyl moieties; 【Chemical 36】 or - at least one compound of structure (VIIa-1), in which Rw23 is OH or a moiety of structure (VIIb-1), 【Chemical 37】 represents the point of attachment in this moiety, where: m is 1, 2 or 3, and n' is 0 or 1; Ra2 is selected from C 1 -C 5 alkyl or C 2 -C 5 -alkylene-O-alkyl moieties; 【Chemical Formula 38】 or - at least one compound of structure (VIIa-2), in which Rw24 is OH or the moiety (VIIb-2), 【Chemical Formula 39】 represents a point of attachment in this moiety, with the proviso that at most one Rw24 is a moiety (VIIb-2), Ra2 is a C 1 -C 5 alkyl or C 2 -C 5 -alkylene-O-alkyl moiety; 【Chemistry 40】 or - at least one compound of structure (VIIa-3), in which Rw25 is OH or the moiety (VIIb-3), 【Chemistry 41】 represents the point of attachment in this moiety with the proviso that at most one Rw25 is a moiety (VIIb-3) and further wherein Ra2 is a C 1 -C 5 alkyl or C 2 -C 5 -alkylene-O-alkyl moiety; 【Chemistry 42】 or - at least one compound of structure (VIIa-4), in which Rw26 is OH or is the moiety (VIIb-4), 【Chemistry 43】 represents the point of attachment in this moiety, with the proviso that at most one Rw26 is a moiety (VIIb-4) and further wherein Ra2 is a C 1 -C 5 alkyl or C 2 -C 5 -alkylene-O-alkyl moiety; 【Chemistry 44】 Glycidyl hydroxybenzoic acid condensate material.

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