Chemically Amplified Photoresist

Abstract

The present invention relates to a resist composition comprising a polymer component (A), a photoacid generator component (B), a photoactive diazonaphthoquinone component (C), and a solvent (D). The polymer component comprises a mixture of a novolak derivative and a polymer containing a hydroxystyrene unit. The polymer component comprises repeating units having a free phenolic hydroxy moiety and a phenolic hydroxy moiety protected with an acid-cleavable acetal moiety. The positive photoresist composition is suitable for the manufacture of electronic devices.

Description

[Technical field]

[0001] The present invention relates to positive-working, radiation-sensitive, aqueous base-soluble photoresist compositions used to manufacture integrated circuits (ICs), light-emitting diode (LED) devices, and display devices. [Background technology]

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

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

[0004] The use of positive-working photosensitive photoresist compositions that can be developed with aqueous base is known in the prior art. For example, US 5,069,997 describes a radiation-sensitive mixture based on an acid-cleavable group, which comprises a polymeric binder and an organic compound that forms a strong acid upon irradiation, and whose solubility in an aqueous alkaline developer is increased by the action of acid.

[0005] US2002 / 0001769A1 (Patent Document 2) discloses a positive photoresist composition containing an alkali-soluble resin in which a portion of phenolic hydroxy groups is protected with an acid-decomposable group, a quinone diazide ester, and a compound that generates an acid when irradiated with light.

[0006] Japanese Patent Application Laid-Open No. 2008-046594A2 (Patent Document 3) discloses a positive photoresist composition containing a resin that is a reaction product of a novolak resin and a polyhydroxystyrene in which some of the phenolic hydroxy groups are protected with acid-cleavable groups, and an acid generator.

[0007] Most of the known techniques concern either chemically amplified photoresists based on phenolic or (meth)acrylate resins, or non-chemically amplified photoresists based on novolak / diazonaphthoquinone (DNQ). In chemically amplified positive photoresists, base-soluble resins, usually phenolic or (meth)acrylate resins, are released into the resist in areas exposed to radiation by acid-catalyzed cleavage of protecting groups on these resins that originally masked the base-soluble moieties, rendering it aqueous base-developable. In these chemically amplified photoresists, the catalytic acid is formed by photolysis of a photoacid generator (PAG) component. These types of resists are typically used at shorter wavelengths for higher resolution in IC manufacturing.

[0008] Conventional novolac / DNQ resist platforms produce sloped profiles due to their high radiation film absorption, especially in relatively thick films. On the other hand, positive chemically amplified platforms can provide adequate performance at film thicknesses below 10 μm, but the polymers used in these resists are significantly more expensive than conventional novolac resins. Also, some designs of positive chemically amplified resists that require a post-exposure bake have a negative impact on device throughput. Cost and device throughput are also issues in applications related to display manufacturing. A potential impact on device throughput issues occurs in certain chemically amplified resists where the protecting groups that mask base-soluble moieties have high activation energies for their cleavage to unmask the base-soluble moieties. These high activation energy groups can be removed by catalysis with acid, but this removal requires a time-consuming post-exposure bake step. Furthermore, process temperatures for manufacturing display devices are increasing. For example, substrate temperatures are elevated during boron or phosphorus implantation into low-temperature polysilicon used in thin film transistors. Photoresist patterns are required to maintain their shape at process temperatures. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] US5,069,997 [Patent Document 2] US2002 / 0001769A1 [Patent Document 3] Patent Publication 2008-046594A2 [Non-patent literature]

[0010] [Non-Patent Document 1] “Diazonapthoquinone-based Resist”,Ralph Dammel,SPIE,Optical Engineering Press,Volume TT11,Chapters 2 and 3 Summary of the Invention [Problem to be solved by the invention]

[0011] It is an object of the present invention to provide a cost-competitive chemically amplified system that can be used in display manufacturing.

[0012] The present invention aims to provide a chemically amplified photoresist composition, the film derived therefrom has high thermal stability, high resolution, contrast, and can form resist patterns without a post-exposure bake (PEB). The elimination of PEB can increase manufacturing throughput, reduce process time, and reduce the risk of formation of features with harmful post-exposure delay effects, such as extensive T-topping. Without being bound by theory, PEB is not required due to the low activation energy protecting groups that ensure that the resist film is fully deprotected during the exposure step in the exposed areas. Because the protecting groups are deprotected during exposure, there is no time lag between the generation of photoacid from the photoacid generator (PAG) and the reaction of this photoacid to deprotect the protecting groups. This deprotection during exposure can reduce the opportunity for air contaminants to consume photoacid at the exposed resist surface, thus avoiding the post-exposure delay effects that lead to severe T-topping of the imaged resist features. Since severe T-topping of the imaged resist features can affect device yield, it is an important problem to solve. [Means for solving the problem]

[0013] One aspect of the present invention is (A) a polymer component, (B) a photoacid generator (PAG), (C) photoactive diazonaphthoquinone compounds (PACs), and (D) Solvent The present invention provides a chemically amplified resist composition comprising:

[0014] Another aspect of the present invention is i) coating the composition on a substrate to form a resist film; ii) selectively exposing the resist film to light using a mask to form a selectively exposed resist film; iii) developing the selectively exposed film to form a positive imaged resist film on the substrate; The present invention provides a method for imaging a resist comprising the steps of:

[0015] A further aspect of the present invention provides a method for manufacturing a device comprising the above-described manufacturing method for imaging a resist on a substrate.A further aspect of the present invention provides the use of the above-described chemically amplified resist composition for coating a substrate.

[0016] The accompanying drawings provide a further understanding of the disclosed invention, and are incorporated in and constitute a part of this specification, illustrating embodiments of the disclosed invention and, together with the detailed description of the invention, serve to explain the principles of the disclosed invention. [Brief description of the drawings]

[0017] [Figure 1] FIG. 1 shows non-limiting examples of DNQ PAC compounds that can be used as free PACs. [Diagram 2] FIG. 2 shows non-limiting examples of photoacid generators that generate sulfonic acids and other strong acids. [Diagram 3] FIG. 3 shows non-limiting examples of photoacid generators that generate either HCl or HBr. [Figure 4] FIG. 4 shows the SEM image obtained in Example 1. [Diagram 5] FIG. 5 shows an SEM image obtained in Comparative Example 1.

[0018] definition Unless otherwise stated, the following terms used in the specification and claims have the following meanings in this application.

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

[0020] In this specification, when numerical ranges are described using "from", "-" or "to", they are inclusive of both limits and have the same units. For example, 5 to 25 mol % means 5 mol % or more and 25 mol % or less.

[0021] The section headings used herein are for organizational purposes only and should not be construed as limiting the subject matter described. All references or portions 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.

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

[0023] In this specification, unless otherwise stated, "hydrocarbon" means carbon and hydrogen, and optionally oxygen or nitrogen. "Hydrocarbyl group" means monovalent or divalent or higher hydrocarbon. In this specification, "aliphatic hydrocarbon group" means linear, branched or cyclic aliphatic hydrocarbon, and "aliphatic hydrocarbon group" means monovalent or divalent or higher aliphatic hydrocarbon. "Aromatic hydrocarbon" means a hydrocarbon containing an aromatic ring, which may be fused with a cyclic aliphatic, as well as optionally containing an aliphatic hydrocarbon group as a substituent. "Aromatic hydrocarbon group" means a monovalent or divalent or higher aromatic hydrocarbon. These aliphatic and aromatic hydrocarbon groups optionally contain fluorine, oxy, hydroxy, amino, carbonyl, or silyl. Furthermore, "aromatic ring" means a hydrocarbon containing a conjugated unsaturated ring structure, and cyclic aliphatic means a hydrocarbon containing a ring structure but not a conjugated unsaturated ring structure.

[0024] "Alkyl" means a group obtained by removing one hydrogen from a linear or branched saturated hydrocarbon, and includes linear and branched alkyl, and cycloalkyl means a group obtained by removing one hydrogen from a saturated hydrocarbon that contains a cyclic structure, and optionally includes a linear or branched alkyl in the cyclic structure as a side chain.

[0025] "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.

[0026] "Halo" or "halide" refers to the halogens F, Cl, Br, and I attached to an organic moiety by a single bond.

[0027] "Haloalkyl" refers to a saturated linear, cyclic or branched alkyl group, such as those defined 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.

[0028] "Fluoroalkyl" refers to linear, cyclic or branched saturated alkyl groups as defined above in which hydrogens have 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 unsubstituted or substituted as described below.

[0029] "Fluoroalkyloxy" refers to a fluoroalkyl group, as defined above, attached through an oxy (-O-) moiety, which may be fully fluorinated (also known as perfluorinated) or alternatively partially fluorinated (e.g., trifluoromethyloxy, perfluoroethyloxy, 2,2,2-trifluoroethoxy, perfluorocyclohexyloxy, and the like). These fluoroalkyl moieties, if not fully fluorinated, may be substituted or unsubstituted as described below.

[0030] In this specification, "C x~y ", "C x ~C y " and "C x " refers to the number of carbon atoms in a molecule or substituent. For example, "C 1-6 "Alkyl" refers to an alkyl having 1 to 6 carbons (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl). Furthermore, as used herein, fluoroalkyl refers to an alkyl in which one or more hydrogens are replaced with fluorine, and fluoroaryl refers to an aryl in which one or more hydrogens are replaced with fluorine.

[0031] As used herein, the term "alkylene" refers to a group obtained by removing two or more hydrogens from a linear, branched, or cyclic saturated hydrocarbon group having two or more points of attachment (e.g., those having two points of attachment include methylene, ethylene, 1,2-isopropylene, 1,4-cyclohexylene, and the like; those having three points of attachment include 1,1,1-substituted methanes, 1,1,2-substituted ethanes, 1,2,4-substituted cyclohexanes, and the like). Again, non-limiting examples include C1-C 20 When specifying the possible ranges of alkylene, the range includes linear alkylene starting from C1, but only branched alkylene or cycloalkylene starting from C3. These alkylene moieties may be substituted or unsubstituted as follows:

[0032] The terms "monoalkyleneoxyalkylene" and "oligomeric alkyleneoxyalkylene" include both simple alkyleneoxyalkylene moieties, such as ethyleneoxyethylene (-CH-CH-O-CH-CH-), propyleneoxypropylene (-CH-CH-CH-O-CH-CH-CH-), and the like, and oligomeric materials, such as 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.

[0033] As used herein, the term "aryl group" or "aromatic group" refers to any group having a C6 to C 24 It means a group obtained by removing one hydrogen from an aromatic hydrocarbon containing, for example, phenyl, tolyl, xylyl, naphthyl, anthracyl, biphenyls, bisphenyls, tolylphenyls, and the like. These aryls may be further substituted with any of the suitable substituents as described above, for example, alkyl, alkoxy, acyl, or aryl groups.

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

[0035] As used herein, the term "arylene" refers to a hydrocarbon group obtained by removing two or more hydrogens from an aromatic hydrocarbon 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 those having two attachment points; 1,2,4-substituted benzenes, 1,3,5-substituted benzenes, and the like for those having three attachment points), a polycyclic aromatic moiety having two attachment points, such as moieties derived from naphthalene, anthracene, pyrene, and the like, or multiple linked benzene rings having two attachment points (e.g., biphenylene). In instances where the aromatic moieties are fused aromatic rings, these are referred to as fused ring arylenes, more specifically named, 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 may form a ring having C5-10 upon bonding to the fused ring.

[0036] Here, the term "PAG" refers to a photoacid generator capable of generating an acid (also called a photoacid) under deep UV or UV radiation, e.g., 200-300 nm, i-line, h-line, g-line and / or broadband radiation, unless otherwise stated. The acid may be sulfonic acids, HCl, HBr, HAsF6, and the like.

[0037] As used herein, the term "PAC" refers to a diazonaphthoquinone moiety, which is further substituted with a sulfonyl moiety (-SO2-) bonded to a phenolic compound via 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, such that the PAC may be such a phenolic compound in which more than one 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.

[0038] The term "free PAC" refers to a compound that is not bound to a polymer in the photoresist formulation.

[0039] As used herein, the term "fused aromatic rings" refers to C 6~8 This refers to carbon-based polycyclic aromatic compounds (e.g., naphthalene, anthracene, and the like) that contain fused aromatic rings. These fused aromatic rings can have a single point of attachment to the organic moiety as part of an aryl moiety, such as the pendant fused aromatic ring aryl groups on a photoacid generator (PAG), or they can have two points of attachment as part of an arylene moiety, such as in the case of a spacer in a substituent attached to a PAG. In PAGs, such substituents, along with other substituents that may interact by resonant delocalization, give stronger absorption and / or broadband emission at 365 nm and are more effective at these wavelengths.

[0040] As used herein, the term "arene" refers to a ring or rings of C 6~8 The aromatic hydrocarbon moiety includes an aromatic ring.

[0041] As used herein, the term "heteroarene" refers to an arene that contains one or more trivalent or divalent heteroatoms, respectively, to the extent that its aromaticity is maintained. Examples of such heteroatoms are N, O, P, and S. As a non-limiting example, such a heteroarene may contain 1 to 3 such heteroatoms.

[0042] Unless otherwise indicated in the specification, the term "substituted" when referring to aryl, alkyl, alkyloxy, fluoroalkyl, fluoroalkyloxy, fused aromatic rings, arenes, and heleroarenes includes unsubstituted alkyl, substituted alkyl, unsubstituted aryl, alkyloxyaryl (alkyl-O-aryl), dialkyloxyaryl ((alkyl-O-)2-aryl), haloaryl, alkyloxy, alkylaryl, haloalkyl, halide, hydroxyl, cyano, nitro, acetyl, alkylcarbonyl, formyl, ethenyl (CH2=CH-), phenylethenyl (Ph-CH=CH-), arylethenyl (aryl-CH=CH-), and ethenylenearylene moieties (e.g., Ar(-CH=CH-Ar-)). z (z is 1-3)) refers to one of these moieties which also contain one or more substituents selected from the group consisting of. Non-limiting illustrative examples of substituted aryl and substituted arylethenyl substituents are the following, where

[0043] [ka] represents a bond.

[0044] [ka] Others are substituted aryls, and substituted ethenyls, in which the substituents are selected from any of the above substituents. Similarly, the term "unsubstituted" refers to the same moiety having no substituents other than hydrogen.

[0045] The term "quencher system" refers to a collection of basic components, such as amines, that can act in a resist formulation to scavenge acid generated by a photoacid generator upon exposure to i-line or broadband radiation.

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

[0047] As used herein, when a polymer contains multiple types of repeat units, these repeat units are copolymerized, which can be either alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a combination thereof.

[0048] In this specification, "%" refers to mass % and "ratio" refers to mass ratio.

[0049] As used herein, the abbreviation "mol %" stands for mole percent.

[0050] In this specification, °C is used as the temperature unit. For example, "20 degrees" means "20°C." DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0051] Aspects of the invention are described in detail below.

[0052] Chemically amplified resist composition The chemically amplified resist composition according to the present invention comprises (A) a polymer component, (B) a photoacid generator (PAG), (C) photoactive diazonaphthoquinone compounds (PACs), and (D) Solvent Includes.

[0053] Each of these components is described below. (A) Polymer component In a first aspect, the present invention relates to a chemically amplified resist composition comprising a polymer component (A) selected from the group consisting of a mixture of a novolak derivative (A-1) and a polymer (A-2) containing a hydroxystyrene repeat unit, an acetal group crosslinked copolymer of a novolak derivative (A-1) and a polymer (A-2) containing a hydroxystyrene unit, and a mixture thereof.

[0054] The mixture of polymers comprises a novolak derivative (A-1) and a polymer (A-2) containing hydroxystyrene units, The novolak derivative (A-1) comprises a novolak repeat unit having a free phenolic hydroxy moiety and a phenolic hydroxy moiety protected with an acid-cleavable acetal moiety; and The polymer (A-2) containing a hydroxystyrene repeating unit has a free phenolic hydroxy moiety and a phenolic hydroxy moiety protected with an acid-cleavable acetal moiety.

[0055] The crosslinked copolymer has an acetal group linker between the novolak derivative (A-1) and the polymer (A-2) containing hydroxystyrene repeat units, The novolak derivative (A-1) comprises a novolak repeat unit having a free hydroxyl moiety and a phenolic hydroxyl moiety protected with an acid-cleavable acetal moiety; and The polymer (A-2) containing a hydroxystyrene repeating unit has a free phenolic hydroxy moiety and a phenolic hydroxy moiety protected with an acid-cleavable acetal moiety.

[0056] The acid cleavable acetal moiety of the present invention is preferably a group of formula (I):

[0057] [ka] In the formula, R 1 and R 2 are each independently 1~4 Represents alkyl.

[0058] In the present invention, the polymer component in which a part of the phenolic hydroxyl groups is protected with an acid-cleavable acetal moiety can be produced by any conventional method without particular limitation, and can be produced, for example, by the following method. The polymer component is dissolved in an organic solvent, and an acid catalyst and an alkyl vinyl ether corresponding to the acid-cleavable acetal moiety are added to the resulting solution; the mixture is reacted at a temperature of about 20°C to about 40°C for about 24 hours; and the reaction is stopped with a basic compound. After purification, a polymer component in which a part of the phenolic hydroxyl groups is protected with an acid-cleavable acetal moiety is obtained.

[0059] Typically, 20 mol % to 31 mol %, preferably 23 mol % to 28 mol %, of the total phenolic hydroxy moieties of the polymer component are protected with acid-cleavable acetal moieties.

[0060] (A-1) Novolak derivatives Novolac resins are obtained by condensing phenolic compounds and aldehydes in the presence of an acid catalyst. Examples of phenolic compounds used in the preparation of novolac resins include, but are not limited to, phenol, o-cresol, m-cresol or p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol or 3,5-xylenol, 2,3,5-trimethylphenol, 2-tert-butylphenol, 3-tert-butylphenol or 4-tert-butylphenol, 2-tert-butyl-4-methylphenol or 2-tert-butyl-5-methylphenol, 2-ethylphenol, 3-ethylphenol or 4-ethylphenol, 2,5-diethylphenol or 3,5-diethylphenol, 2,3,5-triethylphenol, 2,2-bis(4-hydroxyphenyl)propane, 4,4'-dihydroxydiphenylether, bis(4-hydroxyphenyl)sulfone, and the like. These phenolic compounds may be used alone or in combination of two or more.

[0061] Examples of aldehydes used in the preparation of novolac resins include, but are not limited to, aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, acrolein or crotonaldehyde; alicyclic aldehydes such as cyclohexanealdehyde, cyclopentanaldehyde, furfural or furyl acrolein; aromatic aldehydes such as benzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde or p-methylbenzaldehyde, p-ethylbenzaldehyde, 2,4-dimethylbenzaldehyde, 2,5-dimethylbenzaldehyde, 3,4-dimethylbenzaldehyde or 3,5-dimethylbenzaldehyde; aromatic aliphatic aldehydes such as phenylacetaldehyde or cinnamaldehyde; and the like. These aldehydes can be used alone or in combination of two or more kinds. Among these aldehydes, formaldehyde is preferably used.

[0062] A preferred novolak resin is a phenol-formaldehyde novolak, a cresol-formaldehyde novolak or a xylenol-formaldehyde novolak, and has a mass average molecular weight of 800 to 5,000.

[0063] The acid-cleavable acetal moiety for protecting a portion of the phenolic hydroxyl group in the novolac resin can be any group that is decomposed or dissociated by the reaction of the acid generated from the components (B) and (C) described below. The acid-cleavable acetal moiety includes, but is not limited to, 1-ethoxymethyl, 1-ethoxyethyl, 1-propoxymethyl, 1-propoxyethyl, 1-n-butoxymethyl, 1-iso-butoxymethyl, 1-tert-butoxymethyl, and other alkoxyalkyls. Among them, 1-ethoxyethyl is preferred.

[0064] Novolak derivatives in which some of the phenolic hydroxyl groups are protected with acid cleavable acetal moieties contain repeat units represented by formulae (II) and (III):

[0065] [ka] In the formula, R a , R c , R e and R f is independently C 1~4 R is alkyl; b and R d are independently -X-phenol, where X is -O-, -C(CH3)2-, -(C=O)-, or -SO2-; a and n c are independently 0 to 3, and n b and n d are independently 0 or 1, provided that n a +n b and n d +n c each not exceed 3.

[0066] (A-2) Hydroxystyrene-containing polymer Hydroxystyrene-containing polymers include, but are not limited to, polymers containing units selected from the group consisting of 4-hydroxystyrene units, 3-hydroxystyrene units, 2-hydroxystyrene units, and mixtures thereof, such as 2-vinylphenol (2-hydroxystyrene) homopolymer, 3-vinylphenol (3-hydroxystyrene) homopolymer, 4-vinylphenol (4-hydroxystyrene) homopolymer, 4-isopropenylphenol homopolymer, and copolymers of vinylphenol with copolymerizable comonomers, such as, for example, acrylic acid derivatives, methacrylic acid derivatives, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, and other styrene derivatives.

[0067] Hydroxystyrene containing polymers can be prepared by standard methods, typically involving radical polymerization. The copolymerization of two or more monomers produces random copolymers.

[0068] Preferred polymers containing hydroxystyrene are poly(4-hydroxystyrene), poly(3-hydroxystyrene), poly(2-hydroxystyrene), poly(α-methyl-4-hydroxystyrene) or poly(4-hydroxystyrene-co-t-butyl acrylate), and have a mass average molecular weight of 2,000 to 25,000.

[0069] The acid-cleavable acetal moiety for protecting a portion of the phenolic hydroxyl group in the polymer containing hydroxystyrene can be any group that is decomposed or dissociated by the reaction of the acid generated from the components (B) and (C) described below. The acid-cleavable acetal moiety includes, but is not limited to, 1-ethoxymethyl, 1-ethoxyethyl, 1-propoxymethyl, 1-propoxyethyl, 1-n-butoxymethyl, 1-iso-butoxymethyl, 1-tert-butoxymethyl, and other alkoxyalkyls. Among them, 1-ethoxyethyl is preferred.

[0070] Polymers containing hydroxystyrene in which some of the phenolic hydroxyl groups are protected with acid cleavable acetal moieties include repeat units represented by formulae (IV) and (V):

[0071] [ka] In the formula, R g , R h , R i , R j , R k , R l , R m , R n , R o , and R p are each independently hydrogen or C 1~4 is alkyl, R q and R r are each independently C 1~4 It is an alkyl.

[0072] Novolak derivatives and polymers containing hydroxystyrene can be crosslinked during the reaction of the phenolic hydroxyl groups with alkyl vinyl ethers. Preferably, a crosslinking agent such as bis(vinyloxy)methane, 1,2-bis(vinyloxy)ethane, 1,4-bis(ethenyloxy)cyclohexane, 1,4-bis[(vinyloxy)methyl]cyclohexane, and the like is added to the reaction mixture.

[0073] The mass ratio of the novolak derivative to the polymer containing hydroxystyrene is about 76:24 to about 64:36, and preferably about 73:27 to about 67:33.

[0074] The mass ratio of the polymer component (A) to the total mass of the composition is typically about 15 to about 22 mass %.

[0075] (B) PAG In another embodiment of the composition of the present invention, this is any of the above compositions, wherein the PAG is selected from the group consisting of at least an aromatic imide N-oxysulfonate derivative of an organic sulfonic acid, an aromatic sulfonium salt of an organic sulfonic acid, and a trihalotriazine derivative, and the diazonaphthoquinone sulfonate compound provided is not included in the PAG.

[0076] For example, more specifically, the PAG can be one that upon 365 nm and / or broadband irradiation generates a photoacid, such as a sulfonic acid, such as an alkylsulfonic acid, arylsulfonic acid, or fluoroalkylsulfonic acid, a perfluorosulfonic acid, an inorganic acid, such as HAsF6, HSbF6, HPF6, or an acid derived from tetra(perfluorophenyl)borate [H(perf-Ph)4B], or the analogous tetra(perfluoroaryl)borate [H(perf-Aryl)4B]. Non-limiting examples of such PAGs include a variety of photoacid generators, such as onium salts, dicarboxyimidyl sulfonate esters, oxime sulfonate esters, diazo(sulfonylmethyl) compounds, disulfonylmethylene hydrazine 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 with appropriate substitutions known in the art. More specifically, these may be, for example, as non-limiting examples, substituted or unsubstituted triarylsulfonium salts of organic sulfonic acids, where the triarylsulfonium moiety or its corresponding acid anion comprises at least one aryl moiety having conjugated aryls, 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 alternatively a substituted or unsubstituted fused aromatic ring moiety containing 2 to 4 rings.Such substituents include difunctional moieties capable of undergoing resonance delocalization, such as arylenes, including those derived from fused aromatics, or such as ethenylene (-C=C-), ethenyl (CH=CH-), phenyleneethenyl (Ph-CH=CH-), arylethenyl (aryl-CH=CH-), and ethenylenearylene moieties (e.g., Ar(-CH=CH-Ar-). z , z=1 to 3).

[0077] Illustrative, non-limiting examples of substituted aryl and substituted arylethenyl substituents are the following, wherein:

[0078] [ka] represents a bond.

[0079] [ka] Other examples of 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 2 shows non-limiting examples of such PAGs. These PAGs may have substituents as described above.

[0080] In another aspect of the novel compositions, the PAG may be a photoacid generator that is not itself directly sensitive to i-line or broadband radiation, but is sensitized to this radiation by a sensitizer that broadens 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.

[0081] In another embodiment of the invention, the PAG may be a trihalomethyl derivative, which may contain from 1 to 3 trihalomethyl substituents. In another embodiment of this aspect of the invention, the trihalomethyl derivative is an arene or substituted arene containing from 1 to 3 trihalomethyl substituents. In another embodiment of this embodiment, the trihalomethyl derivative may contain from 1 to 3 trihalomethyl substituents attached to the arene or substituted arene moiety via a sulfone spacer (-SO2-).

[0082] FIG. 3 shows non-limiting examples of i-line (broadband) trihalo photoacid generators that generate either HCl or HBr.

[0083] In another embodiment of the invention where the PAG is trihalomethyl, it may be a heteroarene or a substituted heteroarene containing 1 to 3 trihalomethyl moieties.

[0084] In another embodiment of the invention where the PAG is trihalomethyl, it may be a derivative of a heteroarene or substituted heteroarene that contains 1 to 3 trihalomethyl substituents attached to the heteroarene or substituted heteroarene via a sulfone spacer (-SO2-).

[0085] In another embodiment of the composition of the present invention, this is any of the above compositions wherein the PAG is selected from the group consisting of compounds having at least Structure (VIa), Structure (VIb), and Structure (VIc), wherein R 1p is a fluoroalkyl moiety, and R 2p is H, an alkyl, oxyalkyl, thioalkyl, or aryl moiety; R 3p is a fluoroalkyl, alkyl, or aryl moiety, and R 4p is H, an alkyl, oxyalkyl, thioalkyl, or aryl moiety; and further, X is Cl or Br, R 5p is an aryl or alkyl moiety and n is 0 or 1:

[0086] [ka] In another aspect of the composition of the invention, the PAG may be a trihalomethyl derivative having the structure (VId), where R 6p is a substituted or unsubstituted alkenyl, or a substituted or unsubstituted aryl group, or a substituted or unsubstituted fused aromatic ring containing 2 to 4 rings, and Y is oxygen or nitrogen, and X is Cl or Br:

[0087] [ka] In another embodiment of the composition of the present invention, the PAG may be a trihalomethyl derivative, which may be an oxazole or substituted oxazone having the structure (VIe), where R 7p is a substituted or unsubstituted alkenyl, or a substituted or unsubstituted aryl group, and X is Cl or Br:

[0088] [ka] In another embodiment of the composition of the present invention, the PAG may be a trihalomethyl derivative, a derivative of a substituted triazine containing one or two trihalomethyl moieties.

[0089] In another embodiment of the composition of the present invention, the PAG may be a trihalomethyl derivative having the structure (VIf), where X is Br or Cl, and R 8p is an unsubstituted or substituted alkenyl, an unsubstituted aryl or a substituted aryl moiety, or a substituted or unsubstituted fused aromatic ring moiety containing 2 to 4 rings:

[0090] [ka] In another aspect of the composition of the invention, the PAG may be a trihalomethyl derivative, which may be a derivative having the structure (VIg), and R 9p is an unsubstituted or substituted alkenyl or an unsubstituted aryl or substituted aryl moiety:

[0091] [ka] The mass ratio of the photoacid generator (B) to the total mass of the solid components in the composition is typically about 1.1 to about 1.6 mass %.

[0092] (C)PAC In other embodiments of the compositions of the invention described above that include a free PAC component, the PAC component can be derived from a 1,2-diazonaphthoquinone-5-sulfonate compound or a 1,2-diazonaphthoquinone-4-sulfonate compound. Figure 1 shows non-limiting examples of these types of DNQ PACs that can be used as the free PAC component, in which the moiety D is H or a moiety selected from VIIa and VIIb, and in each compound shown in Figure 1, at least one D is either a moiety of structure VIIa or VIIb:

[0093] [ka] In another embodiment of the above compositions of the invention that include a free PAC, the PAC is either a single PAC compound or a mixture of multiple PAC compounds having the structure (VIII), where D 1c , D 2c , D 3c and D. 4c is independently selected from H or a moiety having the structure (VIIa), and further 1c , D 2c , D 3c Or D 4c At least one of is a moiety having the structure (VIIa):

[0094] [ka] In another embodiment of the above compositions of the invention that include a free PAC, the PAC is either a single PAC compound or a mixture of multiple PAC compounds having the structure (VIII), where D 1c , D 2c , D 3c and D. 4c is independently selected from H or a moiety having the structure (VIIb), and further 1c , D 2c , D 3c Or D 4c At least one of is a moiety having the structure (VIIb):

[0095] [ka] In another embodiment of the above compositions of the invention that include a free PAC, the PAC is either a single PAC compound or a mixture of PAC compounds having the structure (VIIIa), where D 1d , D 2d , D 3d and D. 4d is independently selected from H or a moiety having the structure (VIIa), and further 1d , D 2d , D 3d Or D 4d At least one of is a moiety having the structure (VIIa):

[0096] [ka] In another embodiment of the above compositions of the invention that include a free PAC, the PAC is either a single PAC compound or a mixture of PAC compounds having the structure (VIIIa), where D 1d , D 2d , D 3d and D. 4d is independently selected from H or a moiety having the structure (VIIb), and further 1d , D 2d , D 3d Or D 4d At least one of is a moiety having the structure (VIIb):

[0097] [ka] In another embodiment of the above-described compositions of the invention that include a free PAC component, the PAC component is either a single PAC compound or a mixture of multiple PAC compounds having the structure (VIIIb), where D 1e , D 2e and D. 3e is independently selected from H or a moiety having the structure (VIIa), and further 1e , D 2eOr D 3e At least one of is a moiety having the structure (VIIa):

[0098] [ka] In another embodiment of the above compositions of the invention that include a free PAC, the PAC is either a single PAC compound or a mixture of multiple PAC compounds having the structure (VIIIb), where D 1e , D 2e and D. 3e are individually selected from H or a moiety having the structure (VIIb), and further, D 1e , D 2e Or D 3e At least one of the is a moiety having the structure (VIIb):

[0099] [ka] The mass ratio of the PAC (C) to the total mass of the solid components in the composition is typically about 12 to about 18% by mass.

[0100] (D) Solvent In the above composition of the present invention, the solvent is an organic solvent. Examples of suitable organic solvents include, but are not limited to, butyl acetate, amyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, cyclopentanone, ethyl-3-ethoxypropanoate, methyl-3-ethoxypropanoate, methyl-3-methoxypropanoate, methyl acetoacetate, ethyl acetoacetate, diacetone alcohol, methyl pivalate, ethyl pivalate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether propanoate, propylene glycol monoethyl ether propanoate, ethylene glycol monomethyl ether ... Examples of suitable solvents include ethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, N-methylpyrrolidone, dimethyl sulfoxide, gamma-butyrolactone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, methyl lactate, ethyl lactate, propyl lactate, tetramethylene sulfone, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether. These solvents may be used alone or as a mixture of two or more. Particularly preferred is glycol methyl ether acetate (1-methoxy-2-propanyl acetate).

[0101] Optional ingredients Heterocyclic thiol compounds In any of the above compositions of the invention, in another embodiment, a heterocyclic thiol compound is present and is selected from a mono- or di-thiol derivative of an unsaturated heterocyclic compound containing nitrogen, sulfur, or a combination of these two atoms as the heteroatom in the heterocyclic compound. In another aspect of this embodiment, the mono- or di-thiol derivative is a derivative of a triazole, thiazole, imidazole, or thiadiazole heterocyclic compound. In another aspect of this embodiment, the mono- or di-thiol derivative is a derivative of a triazine heterocyclic compound. In another aspect of this embodiment, the mono- or di-thiol derivative is selected from the group consisting of those having structures (IXa), (IXb), (IXc), (IXd), and (IXe).

[0102] [ka] The mass ratio of the heterocyclic thiol compound to the total mass of the solid components in the composition is 0.11 to 0.16% by mass.

[0103] Base component In another embodiment of any of the compositions of the invention described above, it comprises a base compound. Exemplary base components include those having a boiling point of greater than 100° C. at atmospheric pressure and a pK a or a mixture of a plurality of amine compounds having the formula:

[0104] In another embodiment of the composition of the present invention described above, the base component is selected from the group consisting of compounds having at least the structures (Xa), (Xb), (Xc), (Xd), (Xe), (Xf), (Xg), (Xh), (Xi), (Xj), and (Xk), where R b1 is C 1~20 Saturated alkyl chain or C 2~20 is an unsaturated alkyl chain, R b2 , R b3 , R b4 , R b5 , R b6 , R b7 , Rb8 , R b9 , R b10 , R b11 , R b12 , and R b13 are independently H and C 1~20 alkyl.

[0105] [ka] The mass ratio of the base component to the total mass of the solid components in the composition is approximately 0.11 to approximately 0.16% by mass.

[0106] Other optional ingredients Other optional components that are compatible with and can be added to the photoresist compositions of the present invention as disclosed and claimed herein, if desired, include auxiliary resins, plasticizers, surface leveling agents, and stabilizers to improve the properties of the photoresist layer, etc. Surface leveling agents can include surfactants, etc. Generally, the amount of the other components is up to 3% by weight, preferably up to 1% by weight, based on the total weight of the composition.The surfactant is not particularly limited, and examples thereof include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene olein ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, and sorbitan monostearate; nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorinated surfactants such as F-Top EF301, EF303, and EF352 (manufactured by Gemco), Megafac F171, F172, F173, R08, R30, R90 and R94 (manufactured by Dainippon Ink and Chemicals), Florad FC-430, FC-431, FC-4430 and FC-4432 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-381, S-382, S-386, SC101, SC102, SC103, SC104, SC105, SC106, Surfinol E1004, KH-10, KH-20, KH-30 and KH-40 (manufactured by Asahi Glass Co., Ltd.); organosiloxane polymers such as KP-341, X-70-092 and X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd.); and acrylic or methacrylic acid polymers such as Polyflow No. 75 and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

[0107] Resist imaging method Another aspect of the present invention is i) coating the composition on a substrate to form a resist film; ii) selectively exposing the resist film to light using a mask to form a selectively exposed resist film; iii) developing the selectively exposed film to form a positive imaged resist film on the substrate; The present invention provides a method for imaging a resist, comprising:

[0108] The method for coating the composition on the substrate surface can be freely selected from known methods, such as spin coating, spray coating, roll coating, bar coating, doctor coating, slit coating, slit and spin coating, and similar methods. Silicon substrates, metal substrates, glass substrates, and resist films can be used. Glass substrates with a silicon layer are suitable for display applications.

[0109] After forming the coating film of the composition according to the present invention, it is preferable to pre-bake the coating film in order to dry the coating film and reduce the residual amount of the solvent. This pre-bake method can be carried out at a temperature of about 80°C to about 120°C for about 30 seconds to about 300 seconds to form a resist film. When there is a space between the hot plate and the substrate, proximity baking is preferable.

[0110] The resist film is then selectively exposed to light through a mask. The irradiation light preferably contains at least a wavelength of about 350 to about 440 nm.

[0111] The selectively exposed resist film is developed with an alkaline aqueous solution to form a positive imaged resist film on the substrate. The alkaline aqueous solution can be freely selected from known compound solutions, such as aqueous tetramethylammonium hydroxide solution, aqueous trimethylammonium hydroxide solution, aqueous potassium hydroxide solution, and the like. An aqueous tetramethylammonium hydroxide solution is preferred. The positive imaged resist film is then washed with deionized water, washing solution, and the like to remove residual developer.

[0112] PEB is not essential in resist films derived from compositions according to the present invention.

[0113] Device fabrication The substrate with the imaged resist of the above-mentioned manufacturing method is further processed to fabricate a device. Such further processing can be carried out using known methods. Preferably, the device is a display device, a solar cell device, an organic light emitting diode device and an inorganic light emitting diode device. One preferred embodiment of the device of the present invention is a display device. EXAMPLES

[0114] More specific embodiments of the present disclosure and experimental results supporting such embodiments are described below, but it should be noted that the following disclosure is for illustrative purposes only and is therefore not intended to limit the scope of the invention as defined in the claims in any manner.

[0115] The molecular weight of the polymer relative to polystyrene is determined by gel permeation chromatography (GPC) using monodispersed polystyrene standards.

[0116] Polymer synthesis example 1 A 250 mL round bottom flask is charged with 11.8 g of poly-4-hydroxystyrene (Maruka lyncur M2VPM, Mw 12,000, Mw / Mn=3, 30.0 wt% in PGMEA), 11.8 g of novolac resin (Asahi Organic Chemicals, CL16F90G, Mw 917, Mw 2930, Mw / Mn 3.19, cresol, xylenol novolac) and an additional 23.76 g of PGMEA, which is then stirred to form a clear solution. 3.54 g (0.25 equivalents based on the total amount of poly-4-hydroxystyrene / novolac resin) of ethyl vinyl ether is then added to the solution with stirring, followed by the addition of 20 mg of p-toluenesulfonic acid monohydrate as a catalyst. The reaction is carried out at room temperature in a closed system for 24 hours. The reaction is quenched by adding 36.5 mg of tris[2-(2-methoxyethoxy)ethyl]amine (TMEEA, 10.0 wt % in PGMEA, 1.1 equivalents relative to p-toluenesulfonic acid monohydrate) all at once. The resulting solution contains approximately 35.0 wt % ethoxyethyl-protected poly-4-hydroxystyrene / novolac resin. The resulting resin has a number average molecular weight (M n ) and a mass average molecular weight (M w The as-prepared product is directly used to prepare photoresist formulations.

[0117] Example 1 A positive photoresist composition is prepared by dissolving 3.3151 g of 25% ethoxyethyl protected poly-4-hydroxystyrene / novolac resin synthesized according to Polymer Synthesis Example 1, 0.5850 g of 2,3,4-trihydroxybenzophenone-2,1,5-diazonaphthoquinone sulfonate (PW1093), 0.0544 g of 2-methyl-alpha-[2-[[(propylsulfonyl)oxy]imino]-3(2H)-thienylidene]-(CI103), 0.0055 g of trioctylamine (TOA), 0.0090 g of monazoline C (Mona C), and 0.0090 g of megface (R-2011) in 14.0275 g of propylene glycol monomethyl ether acetate (PGMEA). The resulting solution is filtered through a 0.2 μm PTFE (polytetrafluoroethylene) filter.

[0118] Comparative Example 1 A positive photoresist composition is prepared by dissolving 3.3151 g of 30% ethoxyethyl-protected novolac resin, 0.5850 g of 2,3,4-trihydroxybenzophenone-2,1,5-diazonaphthoquinone sulfonate (PW1093), 0.0544 g of 2-methyl-alpha-[2-[[(propylsulfonyl)oxy]imino]-3(2H)-thienylidene]-(CI103), 0.0055 g of trioctylamine (TOA), 0.0036 g of monazoline C (Mona C), and 0.0090 g of megface (R-2011) in 14.0275 g of propylene glycol monomethyl ether acetate (PGMEA). The resulting solution is filtered through a 0.2 μm PTFE filter.

[0119] Lithography evaluation The photoresist composition is spin-coated onto a 6-inch diameter Si wafer at an appropriate spin speed (1,000-2,000 rpm) to produce the desired film thickness. The composition coating film is pre-baked on a contact hotplate at 90°C for 90 seconds. The resist film is then exposed to a masked pattern using an Ultratech g,h line stepper. The exposed resist film is paddle developed with standard AZ® 300 MIF developer (2.38% tetramethylammonium hydroxide in water) for 60 seconds. The developed resist film is then thoroughly washed with deionized water.

[0120] The resist pattern profile cross-section is examined using a scanning electron microscope. A Hitachi SU8030 SEM is used to evaluate the resist profile.

[0121] The resist pattern is heat treated at 135° C. for 200 seconds to evaluate the thermal stability.

[0122] The pattern profile cross section and the thermal stability of the prepared positive photoresist composition are shown in Table 1. Figure 4 shows the SEM image obtained in Example 1. Figure 5 shows the SEM image obtained in Comparative Example 1.

[0123] [Table 1]

[0124] Although the invention has been described and illustrated with a certain degree of detail, it will be understood that this disclosure is made by way of example only, and that numerous variations in the conditions and order of the steps can be restored by those skilled in the art without departing from the spirit and scope of the invention. While this application is directed to the invention set forth in the claims, the disclosure of this application also includes: 1. A chemically amplified photoresist composition comprising a polymer component (A), a photoacid generator (B), a photoactive diazonaphthoquinone compound (C), and a solvent (D), The polymer component (A) is a mixture of a novolak derivative (A-1) and a polymer (A-2) containing hydroxystyrene repeat units; The novolak derivative (A-1) comprises a novolak repeat unit having a free phenolic hydroxy moiety and a phenolic hydroxy moiety protected with an acid-cleavable acetal moiety; and The polymer (A-2) containing a hydroxystyrene repeating unit contains a free phenolic hydroxy moiety and a phenolic hydroxy moiety protected with an acid-cleavable acetal moiety. Chemically amplified photoresist compositions. 2. The composition described in 1 above, wherein the acid-cleavable acetal moiety is a group represented by formula (1).

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Claims

1. A chemically amplified photoresist composition comprising a polymer component (A), a photoacid generator (B), a photoactive diazonaphthoquinone compound (C), and a solvent (D), The polymer component (A) is a mixture of a novolak derivative (A-1) and a polymer (A-2) containing a hydroxystyrene repeat unit; The novolak derivative (A-1) comprises a novolak repeat unit having a free phenolic hydroxy moiety and a phenolic hydroxy moiety protected with an acid-cleavable acetal moiety; and The polymer (A-2) containing a hydroxystyrene repeating unit contains a free phenolic hydroxy moiety and a phenolic hydroxy moiety protected with an acid-cleavable acetal moiety. Chemically amplified photoresist compositions.

2. The composition according to claim 1, wherein the acid-cleavable acetal moiety of the novolak derivative (A-1) and the polymer (A-2) containing a hydroxystyrene repeating unit is a group represented by formula (1). 【Chemistry 1】 In the formula, R １ and R ２ are each independently １～４ Represents alkyl.

3. 3. The composition according to claim 1, wherein the weight ratio of the novolak derivative to the polymer containing hydroxystyrene repeating units is from 76:24 to 64:

36.

4. 3. The composition according to claim 1, wherein the weight ratio of the novolak derivative to the polymer containing hydroxystyrene repeating units is from 73:27 to 67:

33.

5. The composition according to any one of claims 1 to 4, wherein the molar ratio of the phenolic hydroxy moieties protected with acid-cleavable acetal moieties to the total phenolic hydroxy moieties contained in the polymer component (A) is from 20 to 31 mol %.

6. The composition according to any one of claims 1 to 4, wherein the molar ratio of phenolic hydroxy moieties protected with acid-cleavable acetal moieties to the total phenolic hydroxy moieties contained in the polymer component (A) is from 23 to 28 mol %.

7. The composition according to any one of claims 1 to 6, wherein the novolak derivative is selected from the group consisting of phenol-formaldehyde novolak derivatives, cresol-formaldehyde novolak derivatives, and xylenol-formaldehyde novolak derivatives.

8. 8. The composition of claim 1, wherein the polymer containing hydroxystyrene repeat units comprises units selected from the group consisting of 4-hydroxystyrene units, 3-hydroxystyrene units, 2-hydroxystyrene units, and mixtures thereof.

9. The composition according to any one of claims 1 to 8, wherein the weight ratio of polymer component (A) to the total weight of the composition is from 15 to 22% by weight.

10. The composition according to any one of claims 1 to 9, wherein the photoacid generator (B) is selected from the group consisting of at least an aromatic imide N-oxysulfonate derivative of an organic sulfonic acid, an aromatic sulfonium salt of an organic sulfonic acid, and a trihalotriazine derivative.

11. 11. The composition according to claim 1, wherein the mass ratio of the photoacid generator (B) to the total mass of the solid components in the composition is from 1.1 to 1.6 mass %.

12. The composition according to any one of claims 1 to 11, wherein the photoactive diazonaphthoquinone compound (C) is derived from a 1,2-diazonaphthoquinone-5-sulfonate compound or a 1,2-diazonaphthoquinone-4-sulfonate compound or a mixture thereof.

13. The photoactive diazonaphthoquinone compound (C) is either a single photoactive diazonaphthoquinone compound or a mixture of multiple photoactive diazonaphthoquinone compounds having the structure (2), １ｅ , D ２ｅ , and D ３ｅ are independently selected from H or a moiety having the structure (3), and D １ｅ , D ２ｅ , or D ３ｅ The composition of any one of claims 1 to 12, wherein at least one of the is a moiety having the structure (3). 【Chemistry 2】

14. The composition according to any one of claims 1 to 13, wherein the weight ratio of the photoactive diazonaphthoquinone compound (C) to the total weight of the solid components in the composition is from 12 to 18% by weight.

15. The composition according to any one of claims 1 to 14, further comprising a base compound.

16. The base component has a boiling point of more than 100° C. at atmospheric pressure and a pK ａ 16. The composition of claim 15, wherein the amine compound or mixture of amine compounds has the formula:

17. 17. The composition according to claim 15 or 16, wherein the weight ratio of the base component to the total weight of the solid components in the composition is from 0.11 to 0.16% by weight.

18. The composition according to any one of claims 1 to 17, further comprising a heterocyclic thiol compound.

19. 19. The composition of claim 18, wherein the heterocyclic thiol compound is present and is selected from mono- or di-thiol derivatives of unsaturated heterocyclic compounds containing nitrogen, sulfur or a combination of these two atoms as the heteroatom in the heterocyclic compound.

20. The polymer component (A) further comprises an acetal group crosslinked copolymer of a novolak derivative (A-1) and a polymer (A-2) containing a hydroxystyrene repeating unit, The novolak derivative (A-1) comprises a novolak repeat unit having a free phenolic hydroxy moiety and a phenolic hydroxy moiety protected with an acid-cleavable acetal moiety; and The polymer (A-2) containing a hydroxystyrene repeating unit contains a free phenolic hydroxy moiety and a phenolic hydroxy moiety protected with an acid-cleavable acetal moiety. The composition according to any one of claims 1 to 19.

21. 1. A method of imaging a resist comprising the steps of: i) coating the composition according to any one of claims 1 to 20 onto a substrate to form a resist film; ii) selectively exposing the resist film to light using a mask to form a selectively exposed resist film; iii) developing the selectively exposed film to form a positive imaged resist film on the substrate; A method of imaging a resist comprising:

22. 22. A method for manufacturing a device comprising the steps of imaging a resist on a substrate according to claim 21.

23. Use of a composition according to any one of claims 1 to 20 for coating a substrate.

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