Chemically Amplified Photoresist

Abstract

The present invention relates to a resist composition comprising (A) a polymer component, (B) a photoacid generator component, (C) a photoactive naphthoquinone diazo component and (D) a solvent. The polymer component comprises a mixture of a novolac derivative and a polymer comprising hydroxystyrene repeating units. The polymer component comprises repeating units having free phenolic hydroxyl moieties and repeating units having phenolic hydroxyl moieties protected by acid-cleavable acetal moieties. The positive photoresist composition is suitable for manufacturing electronic devices.

Description

Field of the Invention

[0001] The present invention relates to a positive radiation sensitive aqueous alkali soluble photoresist composition for use in manufacturing integrated circuits (ICs), light emitting diode (LED) devices and display equipment.

[0002] background

[0003] Photoresist compositions are used in microlithography processes to manufacture miniaturized electronic components such as for manufacturing computer chips, integrated circuits, light emitting diode (LED) devices and displays. Generally speaking, in these methods, a film of a photoresist composition is first applied to a substrate material, such as a silicon wafer for manufacturing integrated circuits. The coated substrate is then baked to evaporate the solvent in the photoresist composition and to fix the coating to the substrate. Next, the baked coated surface of the substrate is subjected to imagewise exposure to imaging radiation.

[0004] This radiation exposure causes a chemical transformation in the exposed areas of the coated surface. Visible light, ultraviolet (UV) light, electron beam and X-ray radiant energy are the types of imaging radiation commonly used today in microlithography. After this imaging exposure, the coated substrate is treated with a developer solution to dissolve and remove the radiation exposed or unexposed areas of the coated surface of the substrate.

[0005] The use of positive-working, sensitive photoresist compositions that can be developed by aqueous alkaline is known in the prior art. For example, U.S. Pat. No. 5,069,997 describes radiation-sensitive mixtures based on polymer binders containing acid-cleavable groups and organic compounds that form strong acids upon irradiation and whose solubility in aqueous alkaline developers increases with the action of the acid.

[0006] US2002 / 0001769 A1 discloses a positive photoresist composition containing an alkali-soluble resin (in which a part of the phenolic hydroxyl groups are protected by acid-decomposable groups), a quinone diazide and a compound that generates an acid upon irradiation with light.

[0007] Japanese Patent Publication No. 2008-046594 A2 discloses a positive photoresist composition containing a resin and an acid generator, wherein the resin is a reaction product of a novolac resin and polyhydroxystyrene, and a part of the phenolic hydroxyl groups of the polyhydroxystyrene is protected by an acid-cleavable group.

[0008] Most of the known techniques involve chemically amplified photoresists based on phenolic or (meth)acrylate resins, or non-chemically amplified photoresists based on novolac / diazonaphthoquinone (DNQ). In chemically amplified positive photoresists, alkali-soluble resins (usually phenolic or (meth)acrylate resins) are released in areas of the resist exposed to radiation, rendering them aqueous-base developable, by acid-catalyzed cleavage of protecting groups on these resins, initially masking the alkali-soluble portions. In these chemically amplified photoresists, the catalytic acid is formed by photolysis of a photoacid generator (PAG) component. These types of resists are typically employed at shorter wavelengths in pursuit of higher resolution in IC manufacturing.

[0009] Conventional novolac / DNQ resist platforms produce tilted profiles due to their high film absorption of irradiated light, especially at thicker films. On the other hand, positive chemically amplified platforms can provide adequate performance for film thicknesses below 10 μm, however, the polymers used for these resists are much more expensive than conventional novolac resins. Similarly, certain designs for positive chemically amplified resists that require post-exposure baking have a deleterious effect on device throughput. Cost and device throughput are also problematic for applications related to the manufacture of displays. Potential impacts on device throughput issues occur in certain chemically amplified resists where the protective groups that shield the alkali-solubilizing portion have high activation energy for their cleavage to remove the shielding of the alkali-solubilizing portion. Although these high activation energy groups can be removed by acid catalysis, this removal requires a time-consuming post-exposure baking step. In addition, process temperatures for manufacturing display devices have been increasing. For example, substrate temperatures increase during the implantation of boron or phosphorus into low-temperature polysilicon for thin-film transistors. The photoresist pattern needs to maintain its shape at process temperatures.

[0010] Needs addressed by the present invention and problems solved

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

[0012] The present invention is directed to a chemically amplified photoresist composition, the derived films of which have high thermal stability, high resolution, contrast, and are capable of forming resist patterns without the need for a post-exposure bake (PEB). Eliminating the PEB can increase manufacturing throughput, reduce processing time, and reduce the likelihood of the formation of deleterious post-exposure delay effects such as features with a large degree of T-topping. While not being bound by theory, no PEB is required because the low activation energy protecting groups ensure that the resist film in the exposed area is fully deprotected during the exposure stage. Because the protecting groups undergo deprotection during exposure, there is no time lag between the generation of photoacid by a photoacid generator (PAG) and the reaction of this photoacid to deprotect the protecting groups. This deprotection during exposure can reduce the chance of airborne contaminants consuming photoacid on the exposed resist surface, avoiding post-exposure delay effects that result in severe T-topping of imaged resist features. This is an important problem to be solved because severe T-topping of imaged resist features can affect device yield.

[0013] Summary of the Invention

[0014] One embodiment of the present invention provides a chemically amplified resist composition comprising:

[0015] (A) polymer components,

[0016] (B) Photoacid generator (PAG),

[0017] (C) Photoactive naphthoquinone diazide compounds (PACs) and

[0018] (D) Solvent.

[0019] Another embodiment of the present invention provides a process for imaging a resist comprising the steps of:

[0020] i) coating the composition on a substrate to form a resist film;

[0021] ii) selectively exposing the resist film to light using a mask to form a selectively exposed resist film;

[0022] iii) developing the selectively exposed film to form a positive-image resist film on the substrate.

[0023] Yet another embodiment of the present invention provides a method for manufacturing a device, comprising the above manufacturing method of imaging a resist on a substrate. Yet another embodiment of the present invention provides the use of the above chemically amplified resist composition in coating a substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] The accompanying drawings are included herein to provide a further understanding of the subject matter disclosed herein and are incorporated in and constitute a part of this specification, illustrating embodiments of the subject matter disclosed herein and together with the description serve to explain the principles of the subject matter disclosed herein. In the drawings:

[0026] Figure 1 Set forth non-limiting examples of DNQ PAC compounds that can be used as free PACs;

[0027] Figure 2 Non-limiting examples of photoacid generators that generate sulfonic acids and other strong acids are described;

[0028] Figure 3 Describing non-limiting examples of photoacid generators that produce HCl or HBr;

[0029] Figure 4 Describe the SEM image obtained in Example 1; and

[0030] Figure 5 The SEM image obtained in Comparative Example 1 is illustrated.

[0031] definition

[0032] Unless otherwise specified, the following terms used in the specification and claims shall have the following meanings for this application.

[0033] It should be understood that both the foregoing general description and the following detailed description are illustrative and explanatory and do not limit the subject matter as claimed herein. In this application, unless otherwise expressly provided, the use of the singular includes the plural, the wording "one" or "an" means "at least one", and the use of "or" means "and / or". In addition, the use of the term "including" and other forms (such as "includes" and "included") is non-restrictive. Similarly, unless otherwise expressly provided, terms such as "element" or "component" include elements and components comprising one unit and elements or components comprising more than one unit. As used herein, unless otherwise indicated, the conjunction "and" is intended to be inclusive and the conjunction "or" is not intended to be exclusive. For example, the phrase "or, or" is intended to be exclusive. As used herein, the term "and / or" refers to any combination of the aforementioned elements (including the use of a single element).

[0034] In this specification, when "to", "-" or "~" is used to indicate a numerical range, it includes both endpoints and its unit is universal. For example, 5 to 25 mol% means 5 mol% or more and 25 mol% or less.

[0035] The section headings used herein are for organizational purposes and should not be construed as limiting the subject matter described herein. All documents or portions of documents cited in this application, including but not limited to patents, patent applications, articles, books, and papers, are expressly incorporated herein by reference in their entirety for any purpose. If one or more of the documents and similar materials incorporated herein define a term in a manner that contradicts the definition of the term in this application, the present application shall prevail.

[0036] As used herein, the term "point of attachment" when referring to any of the polymers of the present invention refers to a branch point to another polymer chain and / or a cross-link point to another polymer chain, wherein the extent of branching and / or cross-linking is such that the resulting branched and / or cross-linked polymer still has a molecular weight low enough to avoid reaching a gel point, where the polymer would become insoluble in a solvent (such as a spin casting solvent).

[0037] Herein, unless otherwise indicated, "hydrocarbon" means including carbon and hydrogen, and optionally includes oxygen or nitrogen. "Hydrocarbon group" means monovalent or divalent or higher valent hydrocarbon. In this specification, "aliphatic hydrocarbon group" means straight chain, branched or cyclic aliphatic hydrocarbon, and "aliphatic hydrocarbon group" means monovalent or divalent or higher valent aliphatic hydrocarbon. "Aromatic hydrocarbon group" means a hydrocarbon containing an aromatic ring, which aromatic ring may optionally not only contain an aliphatic hydrocarbon group as a substituent but also be fused with an alicyclic ring. "Aromatic hydrocarbon group" means monovalent or divalent or higher valent aromatic hydrocarbon. These aliphatic hydrocarbon groups and aromatic hydrocarbon groups optionally contain fluorine, oxy, hydroxyl, amino, carbonyl or silyl, etc. In addition, "aromatic ring" means a hydrocarbon containing a conjugated unsaturated ring structure, and alicyclic ring means a hydrocarbon containing a ring structure but a non-conjugated unsaturated ring structure.

[0038] The “alkyl group” means a group obtained by removing any one hydrogen from a straight or branched, saturated hydrocarbon and includes a straight chain alkyl group and a branched chain alkyl group, and a cycloalkyl group means a group obtained by removing one hydrogen from a saturated hydrocarbon including a cyclic structure and, if necessary, including a straight chain or branched chain alkyl group as a side chain in the cyclic structure.

[0039] "Alkyloxy" (also known as alkoxy) refers to an alkyl group as defined above (e.g., methoxy, ethoxy, propoxy, butoxy, 1,2-isopropoxy, cyclopentyloxy, cyclohexyloxy, etc.) to which is attached an oxy (-O-) moiety. These alkoxy moieties may be substituted or unsubstituted as described below.

[0040] "Halo" or "halo group" refers to halogen, F, Cl, Br, I, attached to an organic moiety by a bond.

[0041] "Haloalkyl" refers to a straight chain, cyclic or branched saturated alkyl group such as defined above wherein at least one hydrogen has been replaced by a halo group selected from the group consisting of F, Cl, Br, I or a mixture of these if more than one halo moiety is present. Fluoroalkyl is a specific subgroup of these moieties.

[0042] "Fluoroalkyl" refers to a linear, cyclic or branched saturated alkyl group as defined above in which hydrogen has been partially or fully replaced by fluorine (e.g., trifluoromethyl, perfluoroethyl, 2,2,2-trifluoroethyl, perfluoroisopropyl, perfluorocyclohexyl, etc.). If not perfluorinated, these fluoroalkyl moieties may be substituted or unsubstituted as described below.

[0043] "Fluoroalkyloxy" refers to a fluoroalkyl group as defined above, bonded via an oxy (-O-) moiety, which may be fully fluorinated (also known as perfluorinated) or partially fluorinated (e.g., trifluoromethoxy, perfluoroethoxy, 2,2,2-trifluoroethoxy, perfluorocyclohexyloxy, etc.). If not perfluorinated, these fluoroalkyl moieties may be substituted or unsubstituted as described below.

[0044] In this article, “C x-y ”, “C x -C y ” and “C x ” refers to the number of carbons in a molecule or substituent. For example, “C 1-6 The term "alkyl" means an alkyl group having 1 to 6 carbon atoms (such as methyl, ethyl, propyl, butyl, pentyl and hexyl). In addition, a fluoroalkyl group as used in the present specification refers to a fluoroalkyl group in which one or more hydrogens in the alkyl group are replaced by fluorine, and a fluoroaryl group is a fluoroaryl group in which one or more hydrogens in the aryl group are replaced by fluorine.

[0045] The term "alkylene" herein means a group obtained by removing any two or more hydrogens from a straight-chain, branched-chain or cyclic saturated hydrocarbon, which has two or more attachment points (e.g., having two attachment points: methylene, ethylene, 1,2-isopropylene, 1,4-cyclohexylene, etc.; having three attachment points: 1,1,1-substituted methane, 1,1,2-substituted ethane, 1,2,4-substituted cyclohexane, etc.). Also herein, as a non-limiting example, when specifying C1 to C 20 When the possible range is specified, this range includes straight chain alkylene groups starting with C1 but only specifying branched alkylene groups, or cycloalkylene groups starting with C3. These alkylene moieties may be substituted or unsubstituted as described below.

[0046] The terms "monoalkyleneoxyalkylene" and "oligoalkyleneoxyalkylene" include simple alkyleneoxyalkylene moieties such as ethyleneoxyethylene (-CH2-CH2-O-CH2-CH2-), propyleneoxypropylene (-CH2-CH2-CH2-O-CH2-CH2-CH2-), and the like, as well as oligomeric materials such as tris(ethyleneoxyethylene) (-CH2-CH2-O-CH2-CH2-O-CH2-CH2-), tris(propyleneoxypropylene) (-CH2-CH2-CH2-O-CH2-CH2-CH2-O CH2-CH2-), and the like.

[0047] The term "aryl" or "aromatic group" herein means a group obtained by removing any one hydrogen from an aromatic hydrocarbon, containing C6 to C 24 , including phenyl, tolyl, xylyl, naphthyl, anthracenyl, biphenyl, biphenyl, phenyl, etc. These aryl groups may be further substituted by any one of the appropriate substituents (for example, the alkyl, alkoxy, acyl or aryl groups mentioned above).

[0048] If the term "novolac" is used herein without any other structural modifier, it refers to a novolac resin, which is soluble in an aqueous base such as tetramethylammonium hydroxide and the like.

[0049] The term "arylene" herein means a hydrocarbon group obtained by removing any two or more hydrogens from an aromatic hydrocarbon, which has two or more (e.g., 2 to 5) attachment points, such moiety may be a single benzene moiety (e.g., two attachment points 1,4-phenylene, 1,3-phenylene, and 1,2-phenylene; three attachment points 1,2,4-substituted benzene, 1,3,5-substituted benzene, etc.), a polycyclic aromatic moiety with two attachment points, such as derived from naphthalene, anthracene, pyrene, etc., or multiple benzene rings in a chain with two attachment points (e.g., biphenylene). In these examples, where the aromatic moiety is a fused aromatic ring, these may be referred to as fused ring arylene, and more specifically as, for example, naphthalenylene, anthracene, pyrenylene, etc. The fused ring arylene groups may be substituted or unsubstituted as described below, and may also contain hydrocarbon substituents having two bonding sites on the fused ring that are bonded to the fused ring (having C 5-10 ) to form an additional aliphatic or unsaturated ring.

[0050] Herein, unless otherwise described, the term "PAG" refers to a photoacid generator that can generate an acid (also referred to as a photoacid) under deep UV or UV irradiation (such as 200 to 300 nm, i-line, h-line, g-line and / or broadband irradiation). The acid can be sulfonic acid, HCl, HBr, HAsF6, etc.

[0051] Herein, the term "PAC" refers to a diazonapthoquinone component, wherein this moiety is further substituted with a sulfonyl moiety (-SO2-) bonded to a phenolic compound through a sulfonate (-SO2-O-) bond. The phenolic compound forming this sulfonate bond may have a phenolic compound substituted with more than one phenolic OH moiety, and thus, the PAC may be a phenolic compound in which more than one of the phenolic OHs forms this sulfonate bond. Non-limiting examples of these free PAC materials are described in "Diazonapthoquinone-based Resist, Ralph Dammel, SPIE, Optical Engineering Press, Vol. TT 11, Chapters 2 and 3".

[0052] The term "free PAC" refers to compounds in a photoresist formulation that are not bound to a polymer.

[0053] The term "fused aromatic ring" as used herein refers to a carbon-based polycyclic aromatic compound comprising carbon-based polycyclic aromatic rings fused together. 6-8 The fused aromatic rings may have a single point of attachment to the organic moiety as part of the aryl portion, such as a pendant fused aromatic ring aryl group on a photoacid generator (PAG), or have two points of attachment as part of the arylene portion, such as, for example, in a spacer group of a substituent bound to a PAG. In PAGs, such substituents, along with other substituents that may interact through resonance delocalization, give greater absorbance at 365 nm and / or broadband radiation and result in greater efficiency at these wavelengths.

[0054] The term "aromatic hydrocarbon" as used herein includes aromatic hydrocarbon moieties comprising one ring or fused together C-based 6-8 Aromatic rings.

[0055] The term "heteroaromatic hydrocarbon" herein refers to an aromatic hydrocarbon containing one or more trivalent or divalent heteroatoms, respectively, in a manner that retains its aromaticity. Examples of such heteroatoms are N, O, P and S. As non-limiting examples, these heteroaromatic hydrocarbons may contain 1 to 3 such heteroatoms.

[0056] Unless otherwise indicated in the context, the term "substituted" when referring to aryl, alkyl, alkoxy, fluoroalkyl, fluoroalkoxy, fused aromatic ring, arene, heteroarene refers to one of these moieties that also contains one or more substituents selected from the group consisting of unsubstituted alkyl, substituted alkyl, unsubstituted aryl, alkoxyaryl (alkyl-O-aryl), dialkoxyaryl ((alkyl-O-)2-aryl), haloaryl, alkoxy, alkylaryl, haloalkyl, halo, hydroxy, cyano, nitro, acetyl, alkylcarbonyl, formyl, vinyl (CH2=CH-), phenylvinyl (Ph-CH=CH-), arylvinyl (aryl-CH=CH-), and substituents comprising vinylenearylene moieties (e.g., Ar (-CH=CH-Ar-) z , wherein z is 1 to 3. Specifically, non-limiting examples of substituted aryl and substituted arylvinyl substituents are as follows, wherein Indicates the junction point:

[0057]

[0058] Additionally, substituted aryl and substituted vinyl, wherein the substituent is selected from any one of the above substituents. Likewise, the term "unsubstituted" refers to these same moieties, wherein no substituents are present except for hydrogen.

[0059] The term "quencher system" refers to a combination of basic components, such as amines, which in a resist formulation can function to trap the acid generated by the photoacid generator during exposure to i-line or broadband radiation.

[0060] The term "solid component" refers to a component of a photoresist formulation that is not a solvent. Such a component may be solid or liquid.

[0061] In the present specification, when a polymer contains a plurality of types of repeating units, these repeating units are copolymerized. These copolymerizations may be any one of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization or any mixture thereof.

[0062] In this specification, "%" means mass % and "ratio" means mass ratio.

[0063] In the present specification, the abbreviation "mol%" means mole %.

[0064] In this specification, Celsius is used as a temperature unit. For example, "20 degrees" means "20 degrees Celsius".

[0065] Detailed description

[0066] Embodiments of the present invention are described in detail below.

[0067] Chemically amplified resist composition

[0068] The chemically amplified resist composition according to the present invention comprises:

[0069] (A) polymer components,

[0070] (B) Photoacid generator (PAG),

[0071] (C) Photoactive naphthoquinone diazide compounds (PACs) and

[0072] (D) Solvent.

[0073] These components are described separately below.

[0074] (A) Polymer component

[0075] In a first embodiment, the present invention relates to a chemically amplified resist composition comprising (A) a polymer component selected from the group consisting of a mixture of (A-1) a novolac derivative and (A-2) a polymer comprising hydroxystyrene repeating units, an acetal group-crosslinked copolymer of (A-1) a novolac derivative and (A-2) a polymer comprising hydroxystyrene repeating units, and a mixture thereof.

[0076] The polymer mixture comprises (A-1) a novolac derivative and (A-2) a polymer comprising hydroxystyrene repeating units; wherein:

[0077] (A-1) a novolac derivative comprising a novolac repeating unit having a free phenolic hydroxyl moiety and a phenolic hydroxyl moiety protected by an acid-cleavable acetal moiety; and

[0078] (A-2) A polymer comprising hydroxystyrene repeating units having a free phenolic hydroxyl moiety and a phenolic hydroxyl moiety protected by an acid-cleavable acetal moiety.

[0079] The cross-linked copolymer has an acetal group linking group between (A-1) a novolac derivative and (A-2) a polymer comprising hydroxystyrene repeating units; wherein:

[0080] (A-1) a novolac derivative comprising a novolac repeating unit having a free phenolic hydroxyl moiety and a phenolic hydroxyl moiety protected by an acid-cleavable acetal moiety; and

[0081] (A-2) A polymer comprising hydroxystyrene repeating units having a free phenolic hydroxyl moiety and a phenolic hydroxyl moiety protected by an acid-cleavable acetal moiety.

[0082] The acid-cleavable acetal moiety of the present invention is preferably a group represented by formula (I):

[0083]

[0084] Among them, R 1 and R 2 Each independently represents C 1-4 alkyl.

[0085] In the present invention, the polymer component in which a part of the phenolic hydroxyl groups is protected by the acid-cleavable acetal moiety can be prepared by any conventional process without specific limitation, and, for example, can be prepared by the following process. 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 quenched with a basic compound. After purification, the polymer component in which a part of the phenolic hydroxyl groups is protected by the acid-cleavable acetal moiety is obtained.

[0086] Typically, 20 mol% to 31 mol%, preferably 23 mol% to 28 mol% of the total phenolic hydroxyl moieties of the polymer component are protected with acid-cleavable acetal moieties.

[0087] (A-1) Novolac derivatives

[0088] Novolac resin is obtained by fusing phenolic compounds and aldehydes in the presence of an acid catalyst. Examples of phenol-based compounds for producing the novolac resin 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'-dihydroxydiphenyl ether, bis(4-hydroxyphenyl)sulfone etc. These phenolic compounds can be used alone or in combination of two or more.

[0089] Examples of aldehydes used to prepare 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 cyclohexanal, cyclopentanal, furfural, or furanyl 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; etc. These aldehydes can also be used individually or in combination of two or more. Among these aldehydes, formaldehyde is preferably used.

[0090] A preferred novolac resin is phenol-formaldehyde novolac, cresol-formaldehyde novolac, or xylenol-formaldehyde novolac having a mass average molecular weight of 800 to 5,000.

[0091] The acid-cleavable acetal moiety used to protect a part of the phenolic hydroxyl groups in the novolac resin may be any group that is decomposed or dissociated by the reaction of the acid generated by 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-isobutoxymethyl, 1-tert-butoxymethyl and other alkoxyalkyl groups. Among these, 1-ethoxyethyl is preferred.

[0092] The novolac derivative in which a portion of the phenolic hydroxyl groups are protected by an acid-cleavable acetal moiety comprises repeating units represented by formula (II) and (III):

[0093]

[0094] Where R a , R c , R e and R f Independently C 1-4 Alkyl; R b and R d is independently -X-phenol, wherein X is -O-, -C(CH3)2-, -(C=O)- or -SO2-, n a and n c independently 0 to 3, n b and n d is independently 0 or 1, conditional on n a +n b and n d +n c No more than 3 respectively.

[0095] (A-2) Polymer containing hydroxystyrene

[0096] The polymer containing hydroxystyrene includes, but is not limited to, a polymer containing a unit selected from the group consisting of 4-hydroxystyrene units, 3-hydroxystyrene units, 2-hydroxystyrene units, and any mixture 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 and copolymerizable comonomers. Such comonomers include, for example, acrylic acid derivatives, methacrylic acid derivatives, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene and other styrene derivatives.

[0097] Polymers containing hydroxystyrene can be prepared by standard procedures, which generally involve free radical polymerisation.Copolymerisation of two or more monomers produces random copolymers.

[0098] A preferred polymer containing hydroxystyrene is poly(4-hydroxystyrene), poly(3-hydroxystyrene), poly(2-hydroxystyrene), poly(α-methyl-4-hydroxystyrene) or poly(4-hydroxystyrene-co-tert-butyl acrylate) having a mass average molecular weight of 2,000 to 25,000.

[0099] The acid-cleavable acetal moiety used to protect a portion of the phenolic hydroxyl groups in the polymer containing hydroxystyrene may be any group that is decomposed or dissociated by the reaction of the acid generated by 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-isobutoxymethyl, 1-tert-butoxymethyl and other alkoxyalkyl groups. Among these, 1-ethoxyethyl is preferred.

[0100] The polymer comprising hydroxystyrene wherein a portion of the phenolic hydroxyl groups are protected with an acid-cleavable acetal moiety comprises repeating units represented by formula (IV) and (V):

[0101]

[0102] Where 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 Alkyl, R q and R r Each independently is C 1-4 alkyl.

[0103] Novolac derivatives and polymers containing hydroxystyrene can be crosslinked during the reaction of the phenolic hydroxyl groups with the alkyl vinyl ether. Preferably, a crosslinking agent is added to the reaction mixture, such as bis(vinyloxy)methane, 1,2-bis(vinyloxy)ethane, 1,4-bis(vinyloxy)cyclohexane, 1,4-bis[(vinyloxy)methyl]cyclohexane, and the like.

[0104] The mass ratio of the novolac derivative to the polymer comprising hydroxystyrene repeating units is about 76:24 to about 64:36, preferably about 73:27 to about 67:33.

[0105] The mass ratio of the (A) polymer component to the total mass of the composition is generally about 15 to about 22 mass %.

[0106] (B)PAG

[0107] In another embodiment of the composition of the present invention, it is any one of the above compositions, wherein the PAG is at least selected from the group consisting of: aromatic imide N-oxysulfonate derivatives of organic sulfonic acids, aromatic sulfonium salts of organic sulfonic acids, and trihalotriazine derivatives, provided that the diazonaphthoquinone sulfonate compound is not included in the PAG.

[0108] For example, more specifically, the PAG may be a photoacid such as a sulfonic acid (such as an alkylsulfonic acid, an arylsulfonic acid or a fluoroalkylsulfonic acid, a perfluorosulfonic acid), an inorganic acid (such as HAsF6, HSbF6, HPF6), or an acid derived from tetrakis(perfluorophenyl)borate (H(perf-Ph)4B) or a similar tetrakis(perfluoroaryl)borate (H(perf-aryl)4B) upon 365 nm and / or broadband irradiation. Non-limiting examples of such PAGs include various photoacid generators such as onium salts, dicarboximidosulfonates, oximesulfonates, diazo(sulfonylmethyl) compounds, disulfonylmethylenehydrazine compounds, nitrobenzylsulfonates, biimidazole compounds, diazomethane derivatives, oxime derivatives, β-ketosulfone derivatives, disulfone derivatives, sulfonate derivatives, imidosulfonate derivatives, diazonaphthoquinonesulfonates, or a combination thereof. Such photoacid generators may be inherently sensitive to 365 nm and / or broadband radiation by appropriate substitution as known in the art. More specifically, as non-limiting examples, these may be, for example, substituted or unsubstituted triarylsulfonium salts of organic sulfonic acids, wherein the triarylsulfonium moiety or its corresponding acid anion contains at least one aryl moiety having a conjugated aryl group, wherein the conjugated aryl moiety is selected from a benzene ring having at least one substituent selected from the following: aryloxy, alkoxy, nitro, cyano, acetyl, aryl, alkenyl, alkoxyaryl (alkyl-O-aryl-), dialkoxyaryl ((alkyl-O-)2-aryl), or wherein the conjugated aryl moiety is or is a substituted or unsubstituted fused aromatic ring moiety comprising 2 to 4 rings. Such substituents may be bonded via a bifunctional moiety capable of undergoing resonance delocalization, such as an arylene group, including an arylene group derived from a fused aromatic, or, for example, a vinylene (-C=C-) moiety. Vinyl (CH2=CH-), phenylvinyl (Ph-CH=CH-), arylvinyl (aryl-CH=CH-), and vinylene arylene moieties (e.g., Ar (-CH=CH-Ar-) z , wherein z is a 1 to 3 substituent.

[0109] Specifically, non-limiting examples of substituted aryl and substituted arylvinyl substituents are as follows, wherein Indicates the junction point:

[0110]

[0111] Other examples of common PAGs that are sensitive to 365 nm and / or broadband radiation are substituted or unsubstituted 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl ester organosulfonic acids. Figure 2 Non-limiting examples of the above-mentioned PAGs are shown. These PAGs may also have substituents as described above.

[0112] In another aspect of this novel composition, the PAG may be one in which the photoacid generator itself is not directly sensitive to i-line or broadband radiation, but has been made sensitive to such radiation using a photosensitizer that extends the effective wavelength and / or energy range. Such photosensitizers 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 benzophenones and thioxanthones, fluorenes, carbazoles, indoles, benzocarbazoles, acridones, chlorpromazine, equivalents thereof, or combinations of any of the foregoing.

[0113] In another embodiment of the present invention, the PAG may be a trihalomethyl derivative, and it may be a trihalomethyl derivative containing 1 to 3 trihalomethyl substituents. In another embodiment of this aspect of the present invention, the trihalomethyl derivative is a substituted aromatic hydrocarbon or aromatic hydrocarbon containing 1 to 3 trihalomethyl substituents. In another aspect of this embodiment, the trihalomethyl derivative may be a trihalomethyl derivative containing 1 to 3 trihalomethyl substituents, which are bonded to the aromatic hydrocarbon or substituted aromatic hydrocarbon portion through a sulfone spacer (-SO2-).

[0114] Figure 3 Non-limiting examples of i-line (broadband) trihalo photoacid generators that produce HCl or HBr are described.

[0115] In another embodiment of the present invention, wherein the PAG is a trihalomethyl, it may be one of a heteroarene or a substituted heteroarene comprising 1 to 3 trihalomethyl moieties.

[0116] In another embodiment of the present invention, wherein the PAG is a trihalomethyl group, it may be a derivative of a heteroarene or substituted heteroarene comprising 1 to 3 trihalomethyl substituents, which are bonded to the heteroarene or substituted heteroarene via a sulfone spacer group (-SO2-).

[0117] In another embodiment of the composition of the present invention, it is any one of the above compositions, wherein the PAG is at least selected from the group consisting of: a compound having structure (VIa), structure (VIb) and structure (VIc); wherein R 1p is a fluoroalkyl moiety, and R 2p is H, alkyl, oxyalkyl, sulfanyl or aryl moiety; wherein R 3p is a fluoroalkyl, alkyl or aryl moiety, and R 4p is H, alkyl, oxyalkyl, sulfanyl or aryl moiety; and further wherein X is Cl or Br, R 5p is an aryl or alkyl moiety, and n is 0 or 1:

[0118]

[0119] In another embodiment of the composition of the present invention, the PAG may be a trihalomethyl derivative having structure (VId), wherein R 6p is a substituted or unsubstituted alkenyl or a substituted or unsubstituted aryl or a substituted or unsubstituted fused aromatic ring moiety comprising 2 to 4 rings and Y is oxygen or nitrogen and X is Cl or Br:

[0120]

[0121] In another embodiment of the composition of the present invention, the PAG may be a trihalomethyl derivative, which may be an oxazole or a substituted oxazone having structure (VIe), wherein R 7p is a substituted or unsubstituted alkenyl or a substituted or unsubstituted aryl, and X is Cl or Br:

[0122]

[0123] In another embodiment of the composition of the present invention, the PAG may be a trihalomethyl derivative, a derivative of a substituted triazine comprising 1 or 2 trihalomethyl moieties.

[0124] In another embodiment of the composition of the present invention, the PAG may be a trihalomethyl derivative, which may be a trihalomethyl derivative having structure (VIf), wherein X is Br or Cl and R 8p is an unsubstituted or substituted alkenyl, an unsubstituted aryl or substituted aryl moiety or a substituted or unsubstituted fused aromatic ring moiety comprising 2 to 4 rings:

[0125]

[0126] In another embodiment of the composition of the present invention, the PAG may be a trihalomethyl derivative, which may be a derivative having structure (VIg), and R 9p is an unsubstituted or substituted alkenyl or an unsubstituted aryl or substituted aryl moiety:

[0127]

[0128] The mass ratio of the (B) photoacid generator to the total mass of the solid components in the composition is generally about 1.1 to about 1.6 mass %.

[0129] (C)PAC

[0130] In other embodiments of the compositions of the present invention hereinabove, wherein they comprise a free PAC component, such a PAC component may be derived from a 1,2-diazonaphthoquinone-5-sulfonate compound or a 1,2-diazonaphthoquinone-4-sulfonate compound. Figure 1 Non-limiting examples of these types of DNQ PACs that can be used as free PAC components are set forth; wherein Figure 1 , the moiety D is H or a moiety selected from VIIa and VIIb, wherein Figure 1 In each of the compounds depicted, at least one D is part of structure VIIa or VIIb:

[0131]

[0132] In other embodiments of the compositions of the present invention above, wherein the compositions comprise free PAC, the PAC is a single PAC compound or a mixture of PAC compounds having structure (VIII), wherein D 1c , D 2c , D 3c and D 4c are individually selected from H or a moiety having structure (VIIa), and further wherein D 1c , D 2c , D 3c or D 4c At least one of is a moiety having structure (VIIa):

[0133] In other embodiments of the compositions of the present invention above, wherein the compositions comprise free PAC, the PAC is a single PAC compound or a mixture of PAC compounds having structure (VIII), wherein D 1c , D 2c , D 3c and D 4c are individually selected from H or a moiety having structure (VIIb), and further wherein D 1c , D 2c , D3c or D 4c At least one of is a moiety having structure (VIIb):

[0134] In other embodiments of the compositions of the present invention as above, wherein they comprise free PAC, the PAC is a single PAC compound or a mixture of PAC compounds having structure (VIIIa), wherein D 1d , D 2d , D 3d and D 4d are individually selected from H or a moiety having structure (VIIa), and further wherein D 1d , D 2d , D 3d or D 4d At least one of is a moiety having structure (VIIa):

[0135] In other embodiments of the compositions of the present invention as above, wherein they comprise free PAC, the PAC is a single PAC compound or a mixture of PAC compounds having structure (VIIIa), wherein D 1d , D 2d , D 3d and D 4d are individually selected from H or a moiety having structure (VIIb), and further wherein D 1d , D 2d , D 3d or D 4d At least one of is a moiety having structure (VIIb):

[0136] In other embodiments of the compositions of the present invention as above, wherein they comprise a free PAC component, the PAC component is a single PAC compound or a mixture of PAC compounds having structure (VIIIb), wherein D 1e , D 2e and D 3e are individually selected from H or a moiety having structure (VIIa), and further wherein D 1e , D 2e or D 3e At least one of is a moiety having structure (VIIa):

[0137] In other embodiments of the compositions of the present invention as above, wherein they comprise free PAC, the PAC is a single PAC compound or a mixture of PAC compounds having structure (VIIIb), wherein D1e , D 2e and D 3e are individually selected from H or a moiety having structure (VIIb), and further wherein D 1e , D 2e or D 3e At least one of is a moiety having structure (VIIb):

[0138]

[0139] (C) The mass ratio of PAC to the total mass of solid components in the composition is generally about 12 to about 18 mass %.

[0140] (D) Solvent

[0141] In the above-mentioned 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-ethoxypropionate, methyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl acetoacetate, ethyl acetoacetate, diacetone alcohol, methyl pivalate, ethyl pivalate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether propionate ...ethyl ether, cyclohexanone, cyclopentanone, ethyl 3-ethoxypropionate The solvents include propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, N-methyl pyrrolidone, 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 or diethylene glycol dimethyl ether. These solvents can be used alone or in a mixture of two or more. Propylene glycol methyl ether acetate (acetic acid 1-methoxy-2-propanol ester) is particularly preferred.

[0142] Optional components

[0143] Heterocyclic thiol compounds

[0144] In another embodiment of any of the above compositions of the present invention, a heterocyclic thiol compound is present and is selected from mono- or di-thiol derivatives of unsaturated heterocyclic compounds comprising nitrogen, sulfur or a combination of these two atoms as heteroatoms in the heterocyclic compound. In another aspect of this embodiment, the mono- or di-thiol derivatives are derivatives of triazole, diazole, imidazole and thiadiazole heterocycles. In another aspect of this embodiment, the mono- or di-thiol derivatives are derivatives of triazine heterocycles. In another aspect of this embodiment, the mono- or di-thiol derivatives are selected from the group consisting of those having structures (IXa), (IXb), (IXc), (IXd) and (IXe).

[0145]

[0146] 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 mass %.

[0147] Alkali component

[0148] In another embodiment of any of the above compositions of the present invention, it contains a base compound. Exemplary base components are selected from amine compounds or mixtures of amine compounds having a boiling point above 100° C. at atmospheric pressure and a pKa of at least 1.

[0149] In another embodiment of any of the above compositions of the present invention, the base component is at least selected from the group consisting of: compounds having structures (Xa), (Xb), (Xc), (Xd), (Xe), (Xf), (Xg), (Xh), (Xi), (Xj) and (Xk); wherein R b1 It is C 1-20 Saturated alkyl chain or C 2-20 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 Independently selected from the group consisting of: H and C 1-20 alkyl.

[0150]

[0151]

[0152] The mass ratio of the alkali component to the total mass of the solid components in the composition is about 0.11 to about 0.16 mass %.

[0153] Other optional components

[0154] Other optional components that are compatible with the photoresist composition of the present invention disclosed and claimed herein as required and that can be added thereto include auxiliary resins, plasticizers, surface levelers and stabilizers to improve the properties of the resist layer, etc. The surface leveler may include a surfactant. Generally speaking, the amount of the other components is up to 3% by mass, preferably 1% by mass, based on the total mass of the composition. 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 alkyl aryl 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 Jemco Inc.), Megafac F171, F172, F173, R08, R30, R90 and R94 (manufactured by Dainippon Ink & Chemicals, Inc.), Florad FC-430, FC-431, FC-4430 and FC-4432 (manufactured by Sumitomo 3M Ltd.), 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 polymers such as Polyflow No. 75 and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

[0155] Process for imaging the resist

[0156] Another embodiment of the present invention provides a process for imaging a resist comprising the steps of:

[0157] i) coating the composition on a substrate to form a resist film;

[0158] ii) selectively exposing the resist film to light using a mask to form a selectively exposed resist film; and

[0159] iii) developing the selectively exposed film to form a positive-image resist film on the substrate.

[0160] The method for coating the composition on the substrate surface can be freely selected from known methods, such as spin coating, spray coating, roller coating, rod coating, knife coating, slot coating, slot and spin coating, etc. Silicon substrates, metal substrates, glass substrates, resin films can be used. Glass substrates with silicon layers are suitable for display applications.

[0161] After forming the coating film of the composition according to the present invention, it is preferred to pre-bake the coating film to dry the coating film and reduce the residual amount of the solvent. The pre-bake method can be performed to form a resist film, pre-baking at a temperature of about 80 to about 120° C. for about 30 to about 300 seconds. Proximity baking is preferred because there is a space between the hot plate and the substrate.

[0162] Next, the resist film is selectively exposed to light through a mask. The irradiation light preferably includes a wavelength of at least about 350 to about 440 nm.

[0163] The selectively exposed resist film is developed with an alkaline aqueous solution to form a positive image resist film on the substrate. The alkaline aqueous solution can be freely selected from known compound solutions, such as tetramethylammonium hydroxide aqueous solution, trimethylammonium hydroxide aqueous solution, potassium hydroxide aqueous solution, etc. Tetramethylammonium hydroxide aqueous solution is preferred. Then, the positive image resist film is rinsed with deionized water, a cleaning solution, etc. to remove residual developer.

[0164] PEB is not essential for the resist film derived from the composition according to the present invention.

[0165] Manufacturing equipment

[0166] The substrate with the imaged resist of the above-described manufacturing method is further processed to produce a device. Such further processing can be performed by 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. A preferred embodiment of the device of the present invention is a display device. Example

[0167] Reference will now be made to more specific embodiments of the invention and experimental results providing support for such embodiments.Applicants note, however, that the following disclosure is for illustrative purposes only and is not intended to limit the scope of the subject matter claimed herein in any way.

[0168] The molecular weight of polystyrene according to the polymer is measured by gel permeation chromatography (GPC) using monodisperse polystyrene standards.

[0169] Polymer Synthesis Example 1

[0170] A 250 mL round-bottom flask was charged with 11.8 g of poly-4-hydroxystyrene (Maruzen Petrochemical, Maruka lyncur M2VPM, Mw 12,000, Mw / Mn=3, 30.0 mass% in PGMEA), 11.8 g of novolac resin (Asahi Yukizai CL16F90G, Mw 917, Mw 2930, Mw / Mn 3.19, cresol, xylenol novolac) and further 23.76 g of PGMEA, followed by stirring to form a clear solution. Then 3.54 g (0.25 equivalents based on the total amount of poly-4-hydroxystyrene / novolac resin) of ethyl vinyl ether was added to the solution under stirring, followed by addition of 20 mg of p-toluenesulfonic acid monohydrate as a catalyst. The reaction was carried out in a closed system at room temperature for 24 hours. The reaction was quenched by adding 36.5 mg of tris[2-(2-methoxyethoxy)ethyl]amine (TMEEA, 10.0 mass % in PGMEA, 1.1 equivalents to p-toluenesulfonic acid monohydrate) all at once. The resulting solution was a solution containing about 35.0 mass % of ethoxyethyl-protected poly-4-hydroxystyrene / phenolic novolac resin. The resulting resin had a number average molecular weight (Mn) of 1,654 and a mass average molecular weight (Mw) of 7,332. The photoresist formulation was prepared by directly using the product as prepared.

[0171] Example 1

[0172] The positive photoresist composition is prepared by dissolving 3.3151 g of 25% ethoxyethyl protected poly-4-hydroxystyrene / phenolic varnish resin (synthesized by Polymer Synthesis Example 1), 0.5850 g of 2,3,4-trihydroxybenzophenone-2,1,5-diazonaphthoquinone sulfonate (PW1093), 0.0544 g of benzyl cyanide, 0.0544 g of 2-methyl-.α.-[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 was filtered through a 0.2 μm PTFE (polytetrafluoroethylene) filter.

[0173] Comparative Example 1

[0174] The positive photoresist composition was prepared by dissolving 30% ethoxyethyl protected novolac resin 3.3151 g, 2,3,4-trihydroxybenzophenone-2,1,5-diazonaphthoquinone sulfonate (PW1093) 0.5850 g, benzyl cyanide, 2-methyl-.α.-[2-[[(propylsulfonyl)oxy]imino]-3(2H)-thienylene]-(CI103) 0.0544 g, trioctylamine (TOA) 0.0055 g, monazoline C (Mona C) 0.0036 g and megface (R-2011) 0.0090 g in propylene glycol monomethyl ether acetate (PGMEA) 14.0275 g. The resulting solution was filtered through a 0.2 μm PTFE filter.

[0175] Lithography Evaluation

[0176] The photoresist composition was spin coated on a 6" diameter Si wafer at an appropriate spin speed (1,000 to 2,000 rpm) to produce the desired film thickness. The coating film of the composition was pre-baked on a contact hot plate at 90°C for 90 seconds. The resist film was then exposed to a mask pattern by using an Ultratech g, h line stepper. Standard The exposed resist film was developed for 60 seconds by puddle with 300 MIF developer (2.38% tetramethylammonium hydroxide aqueous solution) and then the developed resist film was thoroughly rinsed with deionized water.

[0177] The cross section of the resist pattern profile was examined by scanning electron microscopy. A Hitatchi SU8030 SEM was used to evaluate the resist profile.

[0178] The resist pattern was heat-treated at 135° C. for 200 seconds to evaluate thermal stability.

[0179] The pattern profile cross-section and thermal stability of the positive photoresist composition prepared above are shown in Table 1. Figure 4 The SEM image obtained in Example 1 is described. Figure 5 The SEM image obtained in Comparative Example 1 is illustrated.

[0180] Table 1

[0181]

[0182] Although the present invention has been described and illustrated with a certain degree of particularity, it should be understood that the disclosure has been made by way of example only and that those skilled in the art may employ numerous variations in conditions and sequence of steps without departing from the spirit and scope of the present invention.

Claims

1. A chemically amplified photoresist composition comprising (A) a polymer component, (B) a photoacid generator, (C) a photoactive diazonaphthoquinone compound, and (D) a solvent, in: (A) the polymer component is a mixture of (A-1) a novolac derivative and (A-2) a polymer containing hydroxystyrene repeating units; (A-1) a novolac derivative comprising a novolac repeating unit having a free phenolic hydroxyl moiety and a phenolic hydroxyl moiety protected by an acid-cleavable acetal moiety; and (A-2) A polymer comprising hydroxystyrene repeating units having a free phenolic hydroxyl moiety and a phenolic hydroxyl moiety protected by an acid-cleavable acetal moiety.

2. The composition according to claim 1, wherein the acid-cleavable acetal moiety is a group represented by formula (1): in, R 1 and R 2 Each independently represents C 1-4 alkyl.

3. The composition according to claim 1 or 2, wherein the mass ratio of the novolac derivative to the polymer comprising hydroxystyrene repeating units is 76:24 to 64:

36.

4. The composition according to claim 1 or 2, wherein the mass ratio of the novolac derivative to the polymer comprising hydroxystyrene repeating units is 73:27 to 67:

33.

5. The composition according to claim 1 or 2, wherein the molar ratio of the phenolic hydroxyl moieties protected by the acid-cleavable acetal moieties to the total phenolic hydroxyl moieties constituting the (A) polymer component is 20 to 31 mol%.

6. The composition according to claim 1 or 2, wherein the molar ratio of the phenolic hydroxyl moieties protected by the acid-cleavable acetal moieties to the total phenolic hydroxyl moieties constituting the (A) polymer component is 23 to 28 mol%.

7. The composition according to claim 1 or 2, wherein the novolac derivative is selected from the group consisting of phenol-formaldehyde novolac derivatives, cresol-formaldehyde novolac derivatives and xylenol-formaldehyde novolac derivatives.

8. The composition according to claim 1 or 2, wherein the polymer comprising hydroxystyrene repeating units comprises units selected from the group consisting of 4-hydroxystyrene units, 3-hydroxystyrene units, 2-hydroxystyrene units and any mixture thereof.

9. The composition according to claim 1 or 2, wherein the mass ratio of (A) the polymer component to the total mass of the composition is 15 to 22% by mass.

10. The composition according to claim 1 or 2, wherein (B) the photoacid generator is at least selected from the group consisting of aromatic imide N-oxysulfonate derivatives of organic sulfonic acids, aromatic sulfonium salts of organic sulfonic acids, and trihalotriazine derivatives.

11. The composition according to claim 1 or 2, wherein the mass ratio of (B) the photoacid generator to the total mass of solid components in the composition is 1.1 to 1.6% by mass.

12. The composition according to claim 1 or 2, wherein (C) the photoactive naphthoquinone diazide compound is derived from a 1,2-naphthoquinone diazide-5-sulfonate compound or a 1,2-naphthoquinone diazide-4-sulfonate compound or a mixture thereof.

13. The composition according to claim 1 or 2, wherein (C) the photoactive naphthoquinone diazide compound is a single photoactive naphthoquinone diazide compound or a mixture of photoactive naphthoquinone diazide compounds having structure (2), wherein D 1e , D 2e and D 3e are individually selected from H or a moiety having structure (3), and further wherein D 1e , D 2e or D 3e is a moiety having structure (3), 14. The composition according to claim 1 or 2, wherein the mass ratio of (C) the photoactive naphthoquinonediazide compound to the total mass of solid components in the composition is 12 to 18% by mass.

15. The composition according to claim 1 or 2, further comprising an alkali component.

16. The composition according to claim 15, wherein the base component is selected from an amine compound or a mixture of amine compounds having a boiling point above 100°C at atmospheric pressure and a pKa of at least 1.

17. The composition according to claim 15, wherein the mass ratio of the alkali component to the total mass of solid components in the composition is 0.11 to 0.16 mass%.

18. The composition according to claim 16, wherein the mass ratio of the alkali component to the total mass of solid components in the composition is 0.11 to 0.16 mass%.

19. The composition according to claim 1 or 2, further comprising a heterocyclic thiol compound.

20. The composition according to claim 19, 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 heteroatoms in the heterocyclic compound.

21. The composition according to claim 1 or 2, wherein the polymer component (A) further comprises a copolymer cross-linked by acetal groups of (A-1) a novolac derivative and (A-2) a polymer comprising hydroxystyrene repeating units; wherein: (A-1) a novolac derivative comprising a novolac repeating unit having a free phenolic hydroxyl moiety and a phenolic hydroxyl moiety protected by an acid-cleavable acetal moiety; and (A-2) A polymer comprising hydroxystyrene repeating units having a free phenolic hydroxyl moiety and a phenolic hydroxyl moiety protected by an acid-cleavable acetal moiety.

22. A process for imaging a resist comprising the steps of: i) coating the composition according to any one of claims 1 to 21 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-image resist film on the substrate.

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

Images