Positive photosensitive materials

Abstract

Disclosed herein are photosensitive compositions comprising DNQ-PAC, a heterocyclic thiol compound or a tautomeric form thereof, an acrylate polymer, a novolac, and a PAG, and methods of using the same on substrates that may include thiophilic substrates.

Description

Field of the Invention

[0001] This patent application is in the field of photoresist imaging. More specifically, this patent application discloses and claims positive photosensitive materials applicable to (but not limited to) chalcophile or reflective substrates.

[0002] background

[0003] In the field of electronic device manufacturing, imaging materials must be made to function on a variety of substrates. It is known in the art that different substrates may present different challenges. For example, reflective, highly conductive substrates may impose optical conditions within the imageable film, which can lead to phenomena such as scum, footing, standing wave artifacts (e.g., "scalloping", etc.). In addition, interfacial problems may arise from poor adhesion. Poor adhesion may lead to undercutting or delamination of the film during development. On the other hand, the film may exhibit strong adhesion to certain types of substrates, which may lead to footing formation or scum.

[0004] Several attempts have been made to manage the above optical and interfacial phenomena. In order to improve adhesion, substrate treatments have been described. For example, U.S. Patent No. 4,956,035 discloses "a composition for promoting the adhesion of an organic compound to a metal surface, the composition comprising an etching solution, an effective amount of a quaternary ammonium cationic surfactant, and a solubilizing amount of a second surfactant or solvent." This composition is said to be useful for improving the adhesion of photoresists to copper-clad circuit boards, and improving the adhesion of solder masks to printed circuits. However, while this treatment may be effective on substrates such as copper-clad circuit boards, its practicality on semiconductor substrates that require greater precision may be problematic, particularly where etching chemicals may be involved.

[0005] As another example, U.S. Patent Application No. 2011 / 0214994 discloses "a pretreatment agent for electroplating belonging to the present invention, characterized in that it comprises an aqueous solution containing: (A) an anti-adsorption agent selected from at least one of triazole compounds, pyrazole compounds, imidazole compounds, cationic surfactants and amphoteric surfactants; and (B) chloride ions as a basic component." The pretreatment agent may also contain a nonionic surfactant, a solvent selected from at least one of water-soluble ethers, amines, alcohols, glycol ethers, ketones, esters and fatty acids, and an acid and an oxidant. Although this formulation contains an ingredient that can be said to have an anti-adsorption function, its use may be incompatible with semiconductor processing because it adds an extra step and requires a separate feed stream.

[0006] Thus, there remains a need for positive tone photosensitive materials having compositions suitable for imaging on reflective and thiophilic substrates that produce images with low defects at high resolution. As will become apparent, the subject matter disclosed herein addresses the above needs.

[0007] Overview

[0008] In one aspect, the present invention relates to a composition comprising components a), b), c), d) and e):

[0009] a) at least one diazonaphthoquinone sulfonate photosensitizing compound (DNQ-PAC),

[0010] b) at least one heterocyclic thiol having the structures (7), (8) and / or (9),

[0011] c) at least one photoacid generator;

[0012] d) at least one acrylic polymer comprising repeating units selected from the group consisting of those having structures (1), (2), (3), (4), (5) and (6),

[0013] e) at least one novolac polymer having a dissolution rate in 0.26N tetramethylammonium hydroxide at 23°C of at least 50 angstroms per second, wherein

[0014] The repeating units are present in the acrylic polymer in the following mole % ranges, based on the total moles of all different repeating units present, and wherein the sum of the individual mole % values ​​of all repeating units present in the polymer must equal 100 mole %, and

[0015] (1) is in the range of about 0 to about 35 mol %

[0016] (2) is in the range of about 5 to about 55 mol %

[0017] (3) is in the range of about 0 to about 30 mol%

[0018] (4) is in the range of about 15 to about 55 mol %

[0019] (5) is in the range of about 10 to about 40 mol %.

[0020] (6) is in the range of about 0 to about 25 mol %, and

[0021] R1, R2, R3, R4, R5 and R6 are independently selected from H, F, C-1 to C-4 fluoroalkyl or C-1 to C-4 alkyl

[0022] R7 is selected from H, C-1 to C-4 alkyl, C-1 to C-4 alkoxyalkyl and halogen,

[0023] R8 is a C-3 to C-8 cyclic alkyl group, or a C-7 to C-14 alicyclic alkyl group,

[0024] R9 is a C-2 to C-8 (hydroxy) alkylene group,

[0025] R 10 is an acid cleavable group,

[0026] R 11 is a C-3 to C-12, (alkoxy)alkylene group; and

[0027] In the heterocyclic thiol, for structure (7), Xt is selected from C(Rt1)(Rt2), O, S, Se and Te; for structure (8), Y is selected from C(Rt3) and N; for structure (9), Z is selected from C(Rt3) and N; and

[0028] Rt1, Rt2 and Rt3 are independently selected from H, substituted alkyl having 1 to 8 carbon atoms, unsubstituted alkyl having 1 to 8 carbon atoms, substituted alkenyl having 2 to 8 carbon atoms, unsubstituted alkenyl having 2 to 8 carbon atoms, substituted alkynyl having 2 to 8 carbon atoms, unsubstituted alkynyl having 2 to 8 carbon atoms, substituted aryl having 6 to 20 carbon atoms, substituted heteroaryl having 3 to 20 carbon atoms, unsubstituted aryl having 6 to 20 carbon atoms, and unsubstituted heteroaryl having 3 to 20 carbon atoms;

[0029]

[0030] Another aspect of the invention is a method of forming a positive relief image using the composition of the invention.A further aspect of the invention is the use of a composition according to the invention for forming a positive relief image on a substrate.

[0031] Details

[0032] As used herein, the conjunction "or" is not intended to be exclusive unless otherwise indicated or required by the context. For example, the phrase "or alternatively" is intended to be exclusive. As another example, when describing a chemical substitution at a particular site, "or" can be exclusive.

[0033] As used herein, the term "thiophilic" refers to an element that has an affinity for the chalcogen elements sulfur, selenium, and tellurium. In addition to the chalcogen elements themselves, these elements may also include copper, zinc, gallium, germanium, arsenic, silver, cadmium, lanthanum, tin, antimony, gold, mercury, thallium, lead, and bismuth. Without limitation, these elements may form bonds with one or more of the chalcogen elements, which are primarily covalent in character. A thiophilic substrate comprises one or more of the above-listed thiophilic species.

[0034] As used herein, it is understood that a repeating unit within a polymer may be referred to by its corresponding monomer. For example, acrylate monomer (I) corresponds to its polymer repeating unit (II).

[0035]

[0036] As used herein, the name "(meth)acrylate repeating unit" may refer to an acrylate repeating unit or, alternatively, a methacrylate repeating unit. Thus, "acrylic acid" and "methacrylic acid" are collectively referred to as "(meth)acrylic acid," "acrylic acid derivatives" and "methacrylic acid derivatives" are collectively referred to as "(meth)acrylic acid derivatives," and "acrylate (acrylic)" and "methacrylate (methacrylic)" are collectively referred to as "(meth)acrylate ((meth)acrylic)."

[0037] Herein, unless otherwise indicated, "alkyl" refers to a hydrocarbon group that can be straight chain, branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, etc.), or cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, etc.), polycyclic (e.g., norbornyl, adamantyl, etc.). These alkyl groups may be substituted or unsubstituted as described below. The term alkyl refers to such groups having C-1 to C-20 carbons. It should be understood that for structural reasons, straight chain alkyls start with C-1, while branched and cyclic alkyls start with C-3 and polycyclic alkyls start with C-5. In addition, it should be further understood that, unless otherwise indicated, groups derived from alkyls such as alkoxy, haloalkoxy described below have the same carbon number range. If the alkyl length is specified to be different from that described above, the alkyl definition described above still holds true relative to its coverage of all types of alkyl groups as described above, and structural considerations regarding the minimum carbon number of a given type of alkyl still apply. Here, the specific designation of C-3 to C-8 cyclic alkyl or C-7 to C-14 alicyclic alkyl in R8 refers only to structural groups which, as carboxylate, have a carboxylate bond which does not form a carboxylate bond with the oxygen of the (meth)acrylate repeating unit of structure (3), and which carboxylate bond is easily cleaved by acidolysis with a photoacid generator during the usual photolithography process of a photoresist film. Therefore, this designation excludes tertiary attachment points having β hydrogen available for elimination of carboxylate, which can be eliminated by acidolysis (also referred to as only H + The tertiary carbocation can be easily formed and regenerated by eliminating olefin, (meth)acrylic acid group and H + ).

[0038] "Alkyloxy" (also referred to as Alkoxy) refers to an alkyl group as defined above attached via an oxy (-O-) group (e.g., methoxy, ethoxy, propoxy, butoxy, 1,2-isopropoxy, cyclopentyloxy, cyclohexyloxy, etc.). These alkoxy groups may be substituted or unsubstituted as described below.

[0039] "Halo" or "halo" refers to a halogen, F, Cl, Br, I, attached to an organic group by a bond.

[0040] "Haloalkyl" refers to a straight chain, cyclic or branched saturated alkyl group such as defined above, wherein if more than one halo group is present, at least one of the hydrogens has been replaced by a halo selected from the group consisting of F, Cl, Br, I or mixtures thereof. Fluoroalkyl is a specific subset of these groups.

[0041] "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.). These fluoroalkyl groups, if not perfluorinated, may be substituted or unsubstituted as described below.

[0042] "Fluoroalkyloxy" refers to a fluoroalkyl group as defined above attached through an oxy (-O-) group which may be fully fluorinated (also referred to as perfluorinated) or alternatively partially fluorinated (e.g., trifluoromethoxy, perfluoroethoxy, 2,2,2-trifluoroethoxy, perfluorocyclohexyloxy, etc.). These fluoroalkyl groups, if not perfluorinated, may be substituted or unsubstituted as described below.

[0043] Herein, when referring to alkyl, alkyloxy, fluoroalkyl, fluoroalkyloxy groups having a possible range of carbon atoms starting with C-1 (such as "C-1 to C-20 alkyl" or "C-1 to C-20 fluoroalkyl") as a non-limiting example, this range encompasses straight chain alkyl, alkyloxy, fluoroalkyl and fluoroalkyloxy groups starting with C-1, but only branched alkyl, branched alkyloxy, cycloalkyl, cycloalkyloxy, branched fluoroalkyl and cyclic fluoroalkyl groups starting with C-3 are represented. Similarly, the terms "C-1 to C-4 alkyl" and "C-1 to C-4 alkoxy" represent a group that includes C-1 to C-4 straight chain alkyl groups but also includes C-3 branched alkyl or C-3 cyclic alkyl groups.

[0044] As used herein, the term "alkylene" refers to a hydrocarbon group having two or more points of attachment (e.g., with two points of attachment: methylene, ethylene, 1,2-isopropylene, 1,4-cyclohexylene, etc.; with three points of attachment: 1,1,1-substituted methane, 1,1,2-substituted ethane, 1,2,4-substituted cyclohexane, etc.) that may be linear, branched, or cyclic. Also herein, when a possible range of carbons (such as C-1 to C-20) is indicated, as a non-limiting example, this range encompasses linear alkylene starting with C-1, but only branched alkylene or cycloalkylene starting with C-3 is indicated. These alkylene groups may be substituted or unsubstituted as described below.

[0045] The terms "monoalkyleneoxyalkylene" and "oligoalkyleneoxyalkylene" encompass simple alkyleneoxyalkylene groups such as ethyleneoxyethylene (-CH2-CH2-O-CH2-CH2-), propyleneoxypropylene (-CH2-CH2-CH2-O-CH2-CH2-CH2-), and the like, and oligomeric materials such as tris(ethyleneoxyethylene) (-CH2-CH2-O-CH2-CH2-O-CH2-CH2-), tris(propyleneoxypropylene) (-CH2-CH2-CH2-O-CH2-CH2-O CH2-CH2-), and the like.

[0046] Herein, the term "aryl" or "aromatic group" refers to such groups containing 6 to 24 carbon atoms, including phenyl, tolyl, xylyl, naphthyl, anthracenyl, biphenyl, biphenyl, triphenyl, etc. These aryl groups may be further substituted with any appropriate substituent (for example, the alkyl, alkoxy, acyl or aryl groups mentioned above).

[0047] If the term "novolac" is used herein without any other structure modifier, it refers to a novolac that is soluble in an aqueous base, such as tetramethylammonium hydroxide and the like.

[0048] 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 200-300 nm, i-line, h-line, g-line and / or broadband irradiation. The acid may be sulfonic acid, HCl, HBr, HAsF6, etc.

[0049] Herein, the term "PAC" refers to a diazonapthoquinone moiety, wherein this group is further substituted with a sulfonyl group (-SO2-) bonded to a phenolic compound through a sulfonate (-SO2-O-) bond. The phenolic compound forming this sulfonate bond may be a phenolic compound substituted with more than one phenolic OH group, and thus, the PAC may be a phenolic compound wherein more than one of the phenolic OH groups forms the 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.

[0050] The term "substituted aryl" encompasses substituents selected from any of the substituents described above. Similarly, the term "unsubstituted aryl" refers to a group in which no substituents other than hydrogen are present.

[0051] The term "quencher" refers to an assembly of basic components, such as an amine or other Lewis base (e.g., a basic anion, such as a carboxylate anion in a carboxylate salt, e.g., a tetraalkylammonium), which can be used in a resist formulation to capture the acid generated by a photoacid generator during exposure to i-line or broadband radiation.

[0052] The term "wt % solids" refers to the wt % of each non-solvent component based on the total weight of the non-solvent components in the photoresist formulation. The non-solvent components may be solid or liquid.

[0053] In one aspect, the present invention relates to a composition comprising components a), b), c), d) and e):

[0054] a) at least one diazonaphthoquinone sulfonate photosensitizing compound (DNQ-PAC),

[0055] b) at least one heterocyclic thiol having the structures (7), (8) and / or (9),

[0056] c) at least one photoacid generator,

[0057] d) at least one acrylic polymer comprising repeating units selected from the group consisting of those having structures (1), (2), (3), (4), (5) and (6),

[0058] e) at least one novolac polymer having a dissolution rate in 0.26N tetramethylammonium hydroxide at 23°C of at least 50 angstroms per second, wherein

[0059] The repeating units are present in the acrylic polymer in the following mole % ranges based on the total moles of all different repeating units present, and further wherein the sum of the individual mole % values ​​of all repeating units present in the polymer must equal 100 mole %, and

[0060] (1) is in the range of about 0 to about 35 mol %,

[0061] (2) is in the range of about 5 to about 55 mol %.

[0062] (3) is in the range of about 0 to about 30 mol %,

[0063] (4) is in the range of about 15 to about 55 mol %.

[0064] (5) is in the range of about 10 to about 40 mol %.

[0065] (6) is in the range of about 0 to about 25 mol %, and

[0066] R1, R2, R3, R4, R5 and R6 are independently selected from H, F, C-1 to C-4 fluoroalkyl or C-1 to C-4 alkyl,

[0067] R7 is selected from H, C-1 to C-4 alkyl, C-1 to C-4 alkoxyalkyl and halogen,

[0068] R8 is a C-3 to C-8 cyclic alkyl group, or a C-7 to C-14 alicyclic alkyl group,

[0069] R9 is a C-2 to C-8 (hydroxy) alkylene group,

[0070] R 10 is an acid cleavable group,

[0071] R 11 is a C-3 to C-12, (alkoxy)alkylene group; and

[0072] In the heterocyclic thiol, for structure (7), Xt is selected from C(Rt1)(Rt2), O, S, Se and Te; for structure (8), Y is selected from C(Rt3) and N; for structure (9), Z is selected from C(Rt3) and N; and

[0073] Rt1, Rt2 and Rt3 are independently selected from H, substituted alkyl having 1 to 8 carbon atoms, unsubstituted alkyl having 1 to 8 carbon atoms, substituted alkenyl having 2 to 8 carbon atoms, unsubstituted alkenyl having 2 to 8 carbon atoms, substituted alkynyl having 2 to 8 carbon atoms, unsubstituted alkynyl having 2 to 8 carbon atoms, substituted aryl having 6 to 20 carbon atoms, substituted heteroaryl having 3 to 20 carbon atoms, unsubstituted aryl having 6 to 20 carbon atoms, and unsubstituted heteroaryl having 3 to 20 carbon atoms;

[0074]

[0075] Diazonaphthoquinone sulfonate photosensitizer compound (DNQ-PAC)

[0076] In one aspect of the inventive compositions described herein, the DNQ-PAC is a single material or a mixture of materials, wherein the 2,1,5-diazonaphthoquinone sulfonate group having structure (10) forms at least one sulfonate ester with a phenolic compound.

[0077]

[0078] In one aspect of the compositions of the invention described herein, the DNQ PAC is a single material or a mixture of materials having the general formula (11), wherein D 1c , D 2c , D 3c and D 4c are selected from H or a group having structure (10), and further, wherein D 1c , D 2c , D 3c or D 4c At least one of the groups is a group having structure (10).

[0079]

[0080]

[0081] In one aspect of the compositions of the invention described herein, the DNQ PAC is a single compound or a mixture of PAC compounds having structure (12a), wherein D 1e , D 2e and D 3e are selected from H or a group having structure (10), and further, wherein D 1e , D 2e or D 3e At least one of the groups is a group having structure (10).

[0082]

[0083] In one aspect of the compositions of the invention described herein, the DNQ PAC is a single compound or a mixture of PAC compounds having structure (12b), wherein D 1e , D 2e , D 3e and D 4e are selected from H or a group having structure (10), and further, wherein D 1e , D 2e , D 3e or D 4e At least one of the groups is a group having structure (10).

[0084]

[0085] In one aspect of the compositions of the invention described herein, the DNQ PAC is a single compound or a mixture of compounds having structure (13), wherein D 1f , D 2f , D 3f and D 4f are selected from H or a group having structure (10), and further, wherein D 1f , D 2f , D 3f or D 4f At least one of the groups is a group having structure (10),

[0086]

[0087] Photoacid generator

[0088] The photosensitive composition disclosed herein may include a variety of photoacid generators, such as but not limited to onium salts, dicarboximidyl sulfonate esters, oxime sulfonate esters, diazo(sulfonylmethyl) compounds, disulfonylmethylenehydrazine compounds, nitrobenzyl sulfonate esters, biimidazole compounds, diazomethane derivatives, ethylenedioxime derivatives, β-ketosulfone derivatives, disulfone derivatives, sulfonate derivatives, sulfonic acid imide ester derivatives and halogenated triazine compounds, or combinations thereof.

[0089] The onium salt photoacid generator may include, but is not limited to, alkyl sulfonate anions, substituted and unsubstituted aryl sulfonate anions, fluoroalkyl sulfonate anions, fluoroaryl alkyl sulfonate anions, fluorinated aryl alkyl sulfonate anions, hexafluorophosphate anions, hexafluoroarsenate anions, hexafluoroantimonate anions, tetrafluoroborate anions, equivalents thereof, or combinations thereof.

[0090] Specifically but not limited to, suitable photoacid generators may include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, and triphenylsulfonium 2-(bicyclo[2.2.1]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate. , 4-cyclohexylphenyl diphenylsulfonium perfluoro-n-octanesulfonate, 4-cyclohexylphenyl diphenylsulfonium 2-(bicyclo[2.2.1]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 4-methylsulfonylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-methylsulfonylphenyl diphenylsulfonium nonafluoro-n-butanesulfonate, 4-methylsulfonylphenyl diphenylsulfonium perfluoro-n-octanesulfonate and 2-( 4-Methanesulfonylphenyldiphenylsulfonium bicyclo[2.2.1]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonic acid, diphenyl iodine trifluoromethanesulfonate, diphenyl iodine nonafluoro-n-butanesulfonate, diphenyl iodine perfluoro-n-butanesulfonate, 2-(bicyclo[2.2.1]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonic acid, diphenyl iodine trifluoromethanesulfonate, bis(4-tert-butyl) bis(4-tert-butylphenyl)iodine, bis(4-tert-butylphenyl)iodine nonafluoro-n-butanesulfonate, bis(4-tert-butylphenyl)iodine perfluoro-n-octanesulfonate, bis(4-tert-butylphenyl)iodine 2-(bicyclo[2.2.1]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium trifluoromethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium nonafluoro-n-butanesulfonate 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium perfluoro-n-octanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium 2-(bicyclo[2.2.1]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophenium trifluoromethanesulfonate, nonafluoro -1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophenium-n-butanesulfonate, 1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophenium-n-perfluoro-n-octanesulfonate, 1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophenium-n-perfluoro-n-octanesulfonate, 2-(bicyclo[2.2.1]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophenium-n-trifluoromethanesulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophenium perfluoro-n-octanesulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophenium 2-([bicyclo 2.2.1]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(nonafluoro-n-butylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(perfluoro-n-octanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-[2-(bicyclo[2.2.1]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonyloxy]bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, trifluoromethanesulfonic acid 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl ester (naphthalene trifluoromethanesulfonic acid dicarboximide ester), N-[2-(tetracyclo[4.4.0.1. 2,5 .1 7,10 ] dodecan-3-yl)-1,1-difluoroethanesulfonyloxy]bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, 1,3-dioxoisoindolin-2-yl trifluoromethanesulfonate, 1,3-dioxoisoindolin-2-yl nonafluoro-n-butanesulfonate, 1,3-dioxoisoindolin-2-yl perfluoro-n-octanesulfonate, 3-dioxoisoindolin-2-yl 2-(bicyclo[2.2.1]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, N-[2-(tetracyclo[4.4.0.1 2,5 .1 7,10 ] dodecan-3-yl)-1,1-difluoroethanesulfonic acid 3-dioxoisoindolin-2-yl ester, trifluoromethanesulfonic acid 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl ester, nonafluoro-n-butanesulfonic acid 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl ester, perfluoro-n-octanesulfonic acid 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl ester, 2-(bicyclo[2.2.1]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonic acid 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl ester, or N-[2-(tetracyclo[4.4.0.1 2,5 .1 7,10 ] dodecan-3-yl)-1,1-difluoroethanesulfonic acid 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl ester, (E)-2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(methoxyphenyl)-4,6-bis-(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)vinyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, or equivalents thereof or combinations thereof. Suitable photoacid generators may also include onium salts comprising anions and cations in combination, not shown above.

[0091] The photosensitive composition disclosed herein may also include 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, acridone chlorpromazine, equivalents thereof, or any combination of the foregoing.

[0092] Heterocyclic Thiols

[0093] It should be understood that for the heterocyclic thiols selected from the above structures (7), (8) and (9), these structures represent one of several potential tautomeric forms. For example, but not limited to, structures (7), (8) and (9) can appear as their prototropic tautomers, whether in equilibrium or not, as follows:

[0094]

[0095] In addition, interactions with surfaces (such as thiophilic surfaces) or other components in solution may affect the relative concentrations of ring structures (7), (8) and (9) and their respective tautomers. Thus, it should be understood that prototropic tautomers (including cyclic tautomers) and valence tautomers may be referred to interchangeably by naming any of their tautomeric forms.

[0096] In another embodiment, the composition of the present invention comprises at least one heterocyclic thiol, the heterocyclic thiol is selected from the above general formula (7), (8) or (9) or its tautomer, for example, it can be selected from but not limited to substituted or unsubstituted triazole thiols, substituted or unsubstituted imidazole thiols, substituted or unsubstituted triazinethiols, substituted or unsubstituted mercapto pyrimidines, substituted or unsubstituted thiadiazole thiols, substituted or unsubstituted indazole thiols, their tautomers or their combinations. The substituents may include but are not limited to saturated or unsaturated hydrocarbon groups, substituted or unsubstituted aromatic rings, aliphatic, aromatic or heteroaromatic alcohols, amines, amides, imides, carboxylic acids, esters, ethers, halides, etc. Such substituents can be used with heterocyclic thiols to improve solubility, change the interaction with the substrate, enhance exposure to light or be used as anti-halation dyes.

[0097] In another embodiment, the composition of the present invention comprises at least one heterocyclic thiol selected from the above general structure (7), (8) or (9) or its tautomer, such heterocyclic thiol can be selected from but not limited to the following compounds (1t) to (17t) in unsubstituted or substituted form:

[0098]

[0099]

[0100] In another embodiment, wherein the composition of the present invention comprises at least one heterocyclic thiol selected from the above general structure (7), (8) or (9) or its tautomer, such heterocyclic thiol can be selected from thiouracil derivatives, such as 2-thiouracil.These include, but are not limited to, 5-methyl-2-thiouracil, 5,6-dimethyl-2-thiouracil, 6-ethyl-5-methyl-2-thiouracil, 6-methyl-5-n-propyl-2-thiouracil, 5-ethyl-2-thiouracil, 5-n-propyl-2-thiouracil, 5-n-butyl-2-thiouracil, 5-n-hexyl-2-thiouracil, 5-n-butyl-6-ethyl-2-thiouracil, 5-hydroxy-2-thiouracil, 5,6-dihydroxy-2-thiouracil, 5-hydroxy-6-n-propyl-2-thiouracil, 5-methoxy-2-thiouracil, 5-n-butoxy-2-thiouracil, 5-methoxy-6-n-propyl-2-thiouracil , 5-bromo-2-thiouracil, 5-chloro-2-thiouracil, 5-fluoro-2-thiouracil, 5-amino-2-thiouracil, 5-amino-6-methyl-2-thiouracil, 5-amino-6-phenyl-2-thiouracil, 5,6-diamino-2-thiouracil, 5-allyl-2-thiouracil, 5-allyl-3-ethyl-2-thiouracil, 5-allyl-6-phenyl-2-thiouracil, 5-benzyl-2-thiouracil, 5-benzyl-6-methyl-2-thiouracil, 5-acetylamino-2-thiouracil, 6-methyl-5-nitro-2-thiouracil, 6-amino-2-thiouracil, 6-amino-5-methyl-2- Thiouracil, 6-amino-5-n-propyl-2-thiouracil, 6-bromo-2-thiouracil, 6-chloro-2-thiouracil, 6-fluoro-2-thiouracil, 6-bromo-5-methyl-2-thiouracil, 6-hydroxy-2-thiouracil, 6-acetylamino-2-thiouracil, 6-n-octyl-2-thiouracil, 6-dodecyl-2-thiouracil, 6-tetra-dodecyl-2-thiouracil, 6-hexadecyl-2-thiouracil, 6-(2-hydroxyethyl)-2-thiouracil, 6-(3-isopropyloctyl)-5-methyl-2-thiouracil, 6-(m-nitrophenyl)-2-thiouracil, 6-(m-nitrophenyl)-5-n-propyl-2-thiouracil pyrimidine, 6-α-naphthyl-2-thiouracil, 6-α-naphthyl-5-tert-butyl-2-thiouracil, 6-(p-chlorophenyl)-2-thiouracil, 6-(p-chlorophenyl)-2-ethyl-2-thiouracil, 5-ethyl-6-eicosyl-2-thiouracil, 6-acetylamino-5-ethyl-2-thiouracil, 6-eicosyl-5-allyl-2-thiouracil, 5-amino-6-phenyl-2-thiouracil, 5-amino-6-(p-chlorophenyl)-2-thiouracil, 5-methoxy-6-phenyl-2-thiouracil, 5-ethyl-6-(3,3-dimethyloctyl)-2-thiouracil, 6-(2-bromoethyl)-2-thiouracil.

[0101] In another embodiment, the composition of the present invention comprises at least one heterocyclic thiol selected from the above-mentioned general structure (7), (8) or (9) or its tautomer, such heterocyclic thiol can be selected from the group consisting of unsubstituted triazole thiol, substituted triazole thiol, unsubstituted imidazole thiol, substituted imidazole thiol, substituted triazine thiol, unsubstituted triazine thiol, substituted mercapto pyrimidine, unsubstituted mercapto pyrimidine, substituted thiadiazole-thiol, unsubstituted thiadiazole-thiol, substituted indazole thiol, unsubstituted indazole thiol, their tautomers and combinations thereof.

[0102] In another embodiment, the composition of the present invention comprises at least one heterocyclic thiol selected from the above general structure (7), (8) or (9) or its tautomer, such heterocyclic thiol is selected from the group consisting of: 1,3,5-triazine-2,4,6-trithiol, 2-mercapto-6-methylpyrimidine-4-ol, 3-mercapto-6-methyl-1,2,4-triazine-5-ol, 2-mercaptopyrimidine-4,6-diol, 1H-1,2,4-triazole-3-thiol, 1H-1,2,4-triazole-5-thiol. , 1H-imidazole-2-thiol, 1H-imidazole-5-thiol, 1H-imidazole-4-thiol, 2-azabicyclo[3.2.1]oct-2-ene-3-thiol, 2-azabicyclo[2.2.1]hept-2-ene-3-thiol, 1H-benzo[d]imidazole-2-thiol, 2-mercapto-6-methylpyrimidin-4-ol, 2-mercaptopyrimidin-4-ol, 1-methyl-1H-imidazole-2-thiol, 1,3,4-thiadiazole-2,5-dithiol, 1H-indazole-3-thiol, tautomers thereof, and combinations thereof.

[0103] Further disclosed herein is a method of forming a positive relief image, comprising: forming a photosensitive layer by applying a positive photosensitive composition as described herein to a substrate; exposing the photosensitive layer to actinic radiation in an image-wise manner to form a latent image; and developing the latent image in a developer. Optionally, the image-wise exposed photosensitive layer may be thermally treated, depending on the chemistry of the deprotection. Preferably, the substrate is thiophilic. More preferably, the substrate is copper.

[0104] The heterocyclic thiol in the photosensitive composition disclosed herein may include, but is not limited to, substituted or unsubstituted triazole thiol, substituted or unsubstituted imidazole thiol, substituted or unsubstituted triazinethiol, substituted or unsubstituted mercapto pyrimidine, substituted or unsubstituted thiadiazole thiol, substituted or unsubstituted indazole thiol, their tautomers or combinations thereof. The substituent may include, but is not limited to, saturated or unsaturated hydrocarbon groups, substituted or unsubstituted aromatic rings, aliphatic, aromatic or heteroaromatic alcohols, amines, amides, imide carboxylic acids, esters, ethers, halides, etc. Such substituents may be used together with heterocyclic thiols to improve solubility, change the interaction with the substrate, enhance exposure to light, or be used as an antihalation dye.

[0105] Such heterocyclic thiols may include, but are not limited to, unsubstituted or substituted forms of the following compounds:

[0106]

[0107]

[0108]

[0109] Thiouracil derivatives, such as 2-thiouracil are further examples. These include, but are not limited to, 5-methyl-2-thiouracil, 5,6-dimethyl-2-thiouracil, 6-ethyl-5-methyl-2-thiouracil, 6-methyl-5-n-propyl-2-thiouracil, 5-ethyl-2-thiouracil, 5-n-propyl-2-thiouracil, 5-n-butyl-2-thiouracil, 5-n-hexyl-2-thiouracil, 5-n-butyl-6-ethyl-2-thiouracil, 5-hydroxy-2-thiouracil, 5,6-dihydroxy-2-thiouracil, 5-hydroxy-6-n-propyl-2-thiouracil, 5-methoxy-2-thiouracil, 5-n-butoxy-2-thiouracil, 5-methoxy-6-n-propyl-2-thiouracil , 5-bromo-2-thiouracil, 5-chloro-2-thiouracil, 5-fluoro-2-thiouracil, 5-amino-2-thiouracil, 5-amino-6-methyl-2-thiouracil, 5-amino-6-phenyl-2-thiouracil, 5,6-diamino-2-thiouracil, 5-allyl-2-thiouracil, 5-allyl-3-ethyl-2-thiouracil, 5-allyl-6-phenyl-2-thiouracil, 5-benzyl-2-thiouracil, 5-benzyl-6-methyl-2-thiouracil, 5-acetylamino-2-thiouracil, 6-methyl-5-nitro-2-thiouracil, 6-amino-2-thiouracil, 6-amino-5-methyl-2- Thiouracil, 6-amino-5-n-propyl-2-thiouracil, 6-bromo-2-thiouracil, 6-chloro-2-thiouracil, 6-fluoro-2-thiouracil, 6-bromo-5-methyl-2-thiouracil, 6-hydroxy-2-thiouracil, 6-acetylamino-2-thiouracil, 6-n-octyl-2-thiouracil, 6-dodecyl-2-thiouracil, 6-tetra-dodecyl-2-thiouracil, 6-hexadecyl-2-thiouracil, 6-(2-hydroxyethyl)-2-thiouracil, 6-(3-isopropyloctyl)-5-methyl-2-thiouracil, 6-(m-nitrophenyl)-2-thiouracil, 6-(m-nitrophenyl)-5-n-propyl-2-thiouracil pyrimidine, 6-α-naphthyl-2-thiouracil, 6-α-naphthyl-5-tert-butyl-2-thiouracil, 6-(p-chlorophenyl)-2-thiouracil, 6-(p-chlorophenyl)-2-ethyl-2-thiouracil, 5-ethyl-6-eicosyl-2-thiouracil, 6-acetylamino-5-ethyl-2-thiouracil, 6-eicosyl-5-allyl-2-thiouracil, 5-amino-6-phenyl-2-thiouracil, 5-amino-6-(p-chlorophenyl)-2-thiouracil, 5-methoxy-6-phenyl-2-thiouracil, 5-ethyl-6-(3,3-dimethyloctyl)-2-thiouracil, 6-(2-bromoethyl)-2-thiouracil.

[0110] Acrylate (acrylic acid) polymer

[0111] In one aspect of the inventive compositions described herein, the repeating units of the acrylate polymer are selected from repeating units having structures (1), (2), (3), (4), (5) and (6).

[0112] In another aspect of the composition of the present invention, the repeating unit of the acrylate polymer is selected from repeating units having structures (1), (2), (4), (5) and (6).

[0113] In any aspect of the inventive composition described herein, the acrylate polymer is an acrylate polymer wherein

[0114] The range of structure (1) is from about 0 to about 35 mol%.

[0115] Structure (2) ranges from about 5 to about 55 mol %.

[0116] The range of structure (3) is from about 0 to about 30 mol%.

[0117] The range of structure (4) is from about 15 to about 55 mol%.

[0118] Structure (5) ranges from about 10 to about 40 mol %, and

[0119] Structure (6) ranges from about 0 to about 25 mol %;

[0120] In a preferred embodiment, the acrylate polymer is an acrylate polymer wherein

[0121] The range of structure (1) is from about 5 to about 20 mol%.

[0122] Structure (2) ranges from about 5 to about 25 mol %.

[0123] The range of structure (3) is from about 0 to about 30 mol%.

[0124] The range of structure (4) is from about 15 to about 55 mol%.

[0125] Structure (5) ranges from about 20 to about 40 mol %, and

[0126] The range of structure (6) is from about 5 to about 25 mol%.

[0127] In another aspect of the composition of the present invention, the acrylate polymer is a polymer whose repeating units are those having structures (1), (2a), (4a), (5) and (6a), wherein n and n' are the number of methylene spacer groups and independently range from 1 to 4, R1, R2, R4, R5 and R7 are independently selected from C-1 to C-4 alkyl, R 9'and R 11' are each selected from H or C-1 to C-4 alkyl, and R 11” is a C-1 to C-4 alkyl. In one aspect of this embodiment, the range of structure (1) is about 5 to about 20 mol%, the range of structure (2a) is about 5 to about 25 mol%, the range of structure (4a) is about 15 to about 55 mol%, the range of structure (5) is about 20 to about 40 mol%, and the range of structure (6a) is about 5 to about 25 mol%.

[0128]

[0129] In any of the inventive compositions described herein, in the acrylate polymer component, for the repeating units of structure (5), R 10 is an acid-cleavable group selected from tert-butyl, tetrahydropyran-2-yl, tetrahydrofuran-2-yl, 4-methoxytetrahydropyran-4-yl, 1-ethoxyethyl, 1-butoxyethyl, 1-propoxyethyl, 3-oxocyclohexyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, 8-methyl-8-tricyclo[5.2.1.0 2,6]decyl, 1,2,7,7-tetramethyl-2-norbornyl, 2-acetoxymenthyl, 2-hydroxymethyl, 1-methyl-1-cyclohexylethyl, 4-methyl-2-oxotetrahydro-2H-pyran-4-yl, 2,3-dimethylbutan-2-yl, 2,3,3-trimethylbutan-2-yl, 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 1,2,3,3-tetramethylbicyclo[2.2.1]hept-2-yl, 2-ethyl-1,3,3-trimethylbicyclo[2.2.1]hept-2-yl, 2,6,6-trimethylbicyclo[3.1.1]hept-2-yl, 2,3-dimethylpentan-3-yl or 3-ethyl-2-methylpentan-3-yl.

[0130] In one aspect of the inventive compositions described herein, the acrylate polymer is a polymer whose repeating units are those having structures (1), (2b), (4b), (5a), and (6b). In another aspect of this embodiment, structure (1a) ranges from about 5 to about 20 mole percent, structure (2b) ranges from about 5 to about 25 mole percent, structure (4b) ranges from about 15 to about 55 mole percent, structure (5a) ranges from about 20 to about 40 mole percent, and (6b) ranges from about 5 to about 25 mole percent.

[0131]

[0132] In an embodiment of the composition of the present invention described herein, the acrylic polymer is a polymer comprising repeating units selected from the group consisting of structures (1), (2), (3), (4), (5), and (6), wherein (1) ranges from about 0 to about 35 mol%, (2) ranges from about 5 to about 55 mol%, (3) ranges from about 0 to about 30 mol%, (4) ranges from about 15 to about 55 mol%, (5) ranges from about 10 to about 40 mol%, and (6) ranges from about 0 to about 25 mol%, and other types of (meth)acrylic repeating units and / or styrene repeating units may also be present. In this embodiment, the acrylic polymer may comprise at least one styrene repeating unit selected from the group consisting of structures (14), wherein R 14 is selected from H or CH3, and R 14' and R 14” may be the same or different and are selected from H, OH, OR p , O-(C=O)-OR p O-(C=O)-(C=O)-OR p , where R p is an acid-labile group R 10 Preferably, in this embodiment, the polymer comprises at least one styrene repeating unit selected from the group consisting of styrene repeating units having structure (14), wherein R 14 is selected from H or CH3, and R 14' and R 14” can be the same or different and are selected from H, OH, OCOOC(CH3)3 or OCOCOO(CH3)3. Specific non-limiting R p is a tertiary alkyl group having at least one β-hydrogen group that can be eliminated upon cleavage by H+ acidolysis to form an olefin (e.g., tert-butyl group). In addition, in this embodiment, the acrylic polymer may contain at least one (meth)acrylate of a lactone group, which is a single cyclic lactone or a lactone group contained in an alicyclic alkyl group. The lactone group may be a single cyclic lactone or a lactone group contained in an alicyclic alkyl group. A more specific example of such a (meth)acrylate of a lactone group is shown in structure (15), wherein R 15 is selected from H or CH3 and m is 1 or 2. In one aspect of this embodiment, the acrylic polymer further comprises styrenic repeating units of structure (1) and (meth)acrylate repeating units of structure (15).

[0133]

[0134] For the inventive compositions described herein, component d) of the acrylate polymer may have, but is not limited to, a weight average molecular weight in the range of 800 Daltons to 30,000 Daltons. Other exemplary weight average molecular weights of the structure may be, but are not limited to, in the range of 1,500 Daltons to 20,000 Daltons. Still further exemplary weight average molecular weights of the structure may be, but are not limited to, in the range of 2,500 Daltons to 20,000 Daltons. Molecular weights may be determined by gel permeation chromatography using a universal calibration method, calibrated to polystyrene standards.

[0135] Novolac polymer

[0136] The novolac polymer used in the compositions of the present invention described herein may comprise repeating units having a bridge and a phenolic compound. Suitable phenolic compounds include, but are not limited to, phenol, cresol, substituted and unsubstituted resorcinol, xylenol, substituted and unsubstituted pyrogallol, and combinations thereof. Novolac polymers are typically prepared by condensation polymerization of a phenolic compound with an aldehyde (such as formaldehyde, acetaldehyde, or substituted or unsubstituted benzaldehyde) using an acid catalyst or are condensation products of a phenolic compound with a substituted or unsubstituted methylol compound. The bridge described above may comprise a methylene group or a methine group. Novolac polymers may also be prepared as condensation products of ketones (such as acetone, methyl ethyl ketone, acetophenone, etc.). The catalyst may comprise a Lewis acid, a Bronsted acid, or a methylol group. acid), dicationic metal ions and tricationic metal ions, etc. For example (but not limited to), aluminum chloride, calcium chloride, manganese chloride, oxalic acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid or a combination thereof can be used.

[0137] Examples of suitable novolac polymers for use in the compositions of the present invention described herein include those obtained by the condensation reaction of phenolic compounds (such as phenol, o-cresol, m-cresol, p-cresol, 2-5-xylenol, etc.) with aldehyde compounds (such as formaldehyde) in the presence of an acid or a multivalent metal ion catalyst. Exemplary weight average molecular weights of alkali-soluble novolac polymers may range from 1,000 to 30,000 Daltons. Other exemplary weight average molecular weights may be from 1,000 to 20,000 Daltons. Yet other exemplary weight average molecular weights may be from 1,500 Daltons to 10,000 Daltons. An exemplary volume dissolution rate of novolac polymers in 2.38% tetramethylammonium hydroxide aqueous solution is / second (angstrom unit / second) to / sec. Other exemplary bulk dissolution rates are / second to / sec. Yet another exemplary volume dissolution rate is / second to / sec. Yet another exemplary volume dissolution rate / sec can be obtained from a single novolac polymer or a blend of novolac polymers, each of which contains m-cresol repeating units.

[0138] Exemplary cresol novolac polymers may comprise, in terms of cresol mole percentages, 0%-60% p-cresol, 0%-20% o-cresol, and 0%-80% m-cresol. Other exemplary cresol novolac polymers may comprise 0%-50% p-cresol, 0%-20% o-cresol, and 50%-100% m-cresol. The repeating units in the novolac polymers are determined by the composition of the polymer, such that, for example, p-cresol may be introduced by polymerization with an aldehyde or by dimethylol-p-cresol. In addition, the cresol novolac polymers may contain other phenolic compounds, such as phenol, xylenol, resorcinol, pyrogallol, and the like. Additionally, the novolac polymers may be branched or linear and may be blended to achieve a selected mole percentage of repeating units or dissolution rate. The bulk dissolution rate may be measured by the following procedure:

[0139] (1) A 1-3 μm (micrometer) film of novolac was spin-coated from solution onto a silicon wafer and soft-baked on a contact hotplate at about 110° C. for about 120 seconds.

[0140] (2) Measuring film thickness using optical methods such as interferometry or ellipsometry or mechanical profilometry.

[0141] (3) Immerse the coated wafer in a tetramethylammonium hydroxide (TMAH) developer solution, and measure the time (t) for complete dissolution of the novolac film visually or by optical interferometry (e.g., a dissolution rate monitor). c ). Divide the film thickness by t c Calculate the ex vivo dissolution rate.

[0142] In embodiments of the inventive compositions described herein, the novolac polymer may be a novolac polymer comprising repeating units of structure (16), wherein Ra and Rb are independently C-1 to C-4 alkyl, na is 0 to 3, and nb is 0 or 1.

[0143]

[0144] In an embodiment of the composition of the present invention described herein, the novolac polymer may be a novolac polymer comprising repeating units of structure (17), wherein Rc is a C-1 to C-4 alkyl group, Rd is a C-1 to C-4 alkyl group, X is -O-, C(CH3)2-, -(C=O)- or -SO2-, nc is 0 to 3, and nd is 0 or 1.

[0145]

[0146] In the embodiments of the composition of the present invention described herein, the novolac polymer may be a novolac polymer comprising the novolac resin containing the repeating units (16) and (17).

[0147] In the embodiments of the composition of the present invention described herein, the novolac polymer may be a novolac polymer comprising the novolac resin containing the repeating units (16) and (17).

[0148] In particular embodiments of the compositions of the invention described herein, the novolac polymer is a m-cresol and formaldehyde novolac resin.

[0149] In any embodiment of the present composition described herein, the novolac polymer comprises from about 10 to about 90 wt% solids. In another aspect of this embodiment, from about 30 to about 75 wt% solids. As yet another example and not limited thereto, the novolac polymer may comprise from 40 wt% solids to about 65 wt% solids.

[0150] In yet another embodiment, the compositions of the present invention may have a total wt% solids content of about 30 wt% solids to about 65 wt% solids, and may be used to form coatings of 5-200 μm.

[0151] Solvent components

[0152] The photosensitive composition disclosed herein can be dissolved in 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 ... 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, sulfolane, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol dimethyl ether or diethylene glycol dimethyl ether, gamma-butyrolactone. These solvents can be used alone or in the form of a mixture of two or more.

[0153] Optional components

[0154] Other optional additives (which are compatible with the compositions disclosed and claimed herein and may be added to the compositions disclosed and claimed herein as needed) include auxiliary resins, plasticizers, surface levelers and stabilizers (to improve the properties of the resist layer), colorants that improve the visibility of the patterned resist layer formed by development, antihalation dyes, and quenchers.

[0155] Quencher

[0156] In one embodiment of the inventive composition described herein, it further comprises a quencher, which may be selected from tetraalkylammonium salts, or amine-based quenchers having a boiling point of at least 100°C.

[0157] Examples of suitable tetraalkylammonium salts are those of carboxylic acids and alkylsulfonic acids. More specifically, tetraalkylammonium salts of alkyldicarboxylic acids may be employed, such as the non-limiting example of tetrabutylammonium oxalate and the like.

[0158] In another embodiment of any of the above aspects of the invention, the amine-based quencher having only compounds containing structure (18) or a mixture of compounds containing structure (18) having a boiling point of at least 100° C. at 1 atmosphere pressure is an amine-based quencher wherein R am1 is a C-15 to C-20 alkyl group, and R am1a -(CH2) n OH, wherein n is an integer in the range of 2 to 4, and further wherein positions 3 and 2 are connected by a single bond. In another aspect of this embodiment, the amine-based quencher has a boiling point of at least 150°C, at least 200°C in another aspect, at least 250°C in another aspect, and at least 300°C in yet another aspect.

[0159] In another embodiment of any of the above aspects of the invention, the amine-based quencher has a boiling point of at least 100° C. at 1 atmosphere pressure and consists of only compounds having structure (18) or a mixture of only compounds having structure (18), i.e., a compound having one structure (18) wherein R am1a -(CH2) n OH, and wherein n is 2 or 3, and further wherein positions 3 and 2 are connected by a single bond. In another aspect of this embodiment, the quencher has a boiling point of at least 150°C, at least 200°C in another aspect, at least 250°C in another aspect, and at least 300°C in yet another embodiment.

[0160] In another embodiment of any of the above aspects of the invention, the amine-based quencher has a boiling point of at least 100° C. at 1 atmosphere pressure and consists of only compounds having structure (18) or a mixture of compounds having structure (18), wherein R am1a -(CH2) n OH, and wherein n is 2, and further wherein positions 3 and 2 are connected by a single bond. In another aspect of this embodiment, the amine-based quencher has a boiling point of at least 150°C, at least 200°C in another aspect, at least 250°C in another aspect, and at least 300°C in yet another embodiment.

[0161]

[0162] In another embodiment of any of the above aspects of the invention, the amine-based quencher consists of a compound of structure (19).

[0163]

[0164] In another embodiment of the present invention, the amine-based quencher has a boiling point of at least 100° C. at 1 atmosphere pressure and is a compound having structure (18) or a mixture of compounds having structure (18), wherein R am1 is a C-15 to C-20 alkyl group, and R am1a is a C-1 to C-5 alkyl group, and further wherein positions 3 and 2 are connected by a single bond. In another aspect of this embodiment, the boiling point of the quencher is at least 150°C, at least 200°C in another aspect, at least 250°C in another aspect, and at least 300°C in yet another embodiment.

[0165] In another embodiment of the present invention, the amine-based quencher is a compound having structure (18) or a mixture of compounds having structure (18) having a boiling point of at least 100° C. at 1 atmosphere pressure, wherein R am1 is a C-15 to C-20 alkyl group, and R am1a is a C-3 to C-5 alkyl group, and further wherein positions 3 and 2 are connected by a single bond. In another aspect of this embodiment, the boiling point of the quencher is at least 150°C, at least 200°C in another aspect, at least 250°C in another aspect, and at least 300°C in yet another embodiment.

[0166] In another embodiment of the present invention, the amine-based quencher has a boiling point of at least 100° C. at 1 atmosphere pressure and is a compound having structure (18) or a mixture of compounds having structure (18), wherein R am1 is a C15 to C-20 alkyl group, and R am1ais a C-4 to C-5 alkyl group, and further wherein positions 3 and 2 are connected by a single bond. In another aspect of this embodiment, the boiling point of the quencher is at least 150°C, in another aspect at least 200°C, in another aspect at least 250°C, and in yet another embodiment at least 300°C.

[0167] In another embodiment of any of the above aspects of the invention, the amine-based quencher has a boiling point of at least 100° C. at 1 atmosphere pressure and is a compound having structure (18) or a mixture of compounds having structure (18), wherein R am1 is a C-1 to C-5 alkyl group or H, and Ram1a -(CH2) n OH, wherein n is an integer in the range of 2 to 4, and further wherein positions 3 and 2 are connected by a double bond. In another aspect of this embodiment, the boiling point of the quencher is at least 150°C, in another aspect at least 200°C, in another aspect at least 250°C, and in yet another embodiment at least 300°C.

[0168] In another embodiment of any of the above aspects of the invention, the amine-based quencher has a boiling point of at least 100° C. at 1 atmosphere pressure and is a compound having structure (18) or a mixture of compounds having structure (18), wherein R am1 is a C-1 to C-3 alkyl group or H, and R am1a -(CH2) n OH, wherein n is an integer in the range of 2 to 4, and further wherein positions 3 and 2 are connected by a double bond. In another aspect of this embodiment, the boiling point of the quencher is at least 150°C, in another aspect at least 200°C, in another aspect at least 250°C, and in yet another embodiment at least 300°C.

[0169] In another embodiment of any of the above aspects of the invention, the amine-based quencher has a boiling point of at least 100° C. at 1 atmosphere pressure and is a compound having structure (18) or a mixture of compounds having structure (18), wherein R am1 is H, and R am1a -(CH2) n OH, wherein n is an integer in the range of 2 to 4, and further wherein positions 3 and 2 are connected by a double bond. In another aspect of this embodiment, the boiling point of the quencher is at least 150°C, in another aspect at least 200°C, in another aspect at least 250°C, and in yet another embodiment at least 300°C.

[0170] In another embodiment of any of the above aspects of the invention, the amine-based quencher is a compound of structure (20).

[0171]

[0172] In another embodiment of the above aspects of the invention, the amine-based quencher is a compound of structure (18), wherein R am1 is a C-15 to C-20 alkyl group, and R am1a is a C-3 to C-5 alkyl group, and further wherein positions 3 and 2 are connected by a double bond. In another aspect of this embodiment, the boiling point of the quencher is at least 150°C, in another aspect at least 200°C, in another aspect at least 250°C, and in yet another embodiment at least 300°C.

[0173] In another embodiment of the above aspects of the invention, the amine-based quencher is a compound of structure (18), wherein R am1 is a C-15 to C-20 alkyl group, and R am1a is a C-4 to C-5 alkyl group, and further wherein positions 3 and 2 are connected by a double bond. In another aspect of this embodiment, the boiling point of the quencher is at least 150°C, in another aspect at least 200°C, in another aspect at least 250°C, and in yet another embodiment at least 300°C.

[0174] In another embodiment of any of the above aspects of the invention, the amine-based quencher is a compound having structure (21) or a mixture of compounds having structure (21) having a boiling point of at least 100°C at 1 atmosphere pressure, wherein n and n' are independently integers ranging from 2 to 4, and R' is C-1-C-4 alkyl or H. In another aspect of this embodiment, the boiling point of the quencher is at least 150°C, at least 200°C in another aspect, at least 250°C in another aspect, and at least 300°C in yet another embodiment.

[0175]

[0176] In another embodiment of any of the above aspects of the invention, the amine-based quencher is a compound having structure (21) or a mixture of compounds having structure (21), wherein n and n' are 2, and R' is C-1-C-4 alkyl or H. In another aspect of this embodiment, the boiling point of the quencher is at least 150°C, in another aspect at least 200°C, in another aspect at least 250°C, and in yet another embodiment at least 300°C.

[0177] In another embodiment of any of the above aspects of the invention, the amine-based quencher is a compound having structure (21) or a mixture of compounds having structure (21), wherein n and n' are 2, and R' is C-1-C-4 alkyl or H. In another aspect of this embodiment, the boiling point of the quencher is at least 150°C, in another aspect at least 200°C, in another aspect at least 250°C, and in yet another embodiment at least 300°C.

[0178] In another embodiment of any of the above aspects of the invention, the amine-based quencher is solely a compound having structure (22).

[0179]

[0180] In another embodiment of any of the above aspects of the invention, the amine-based quencher is a compound having structure (23) or a mixture of compounds having structure (22) having a boiling point of at least 100°C at 1 atmosphere pressure, wherein n and n' are independently 2 to 4.

[0181]

[0182] In another embodiment of any of the above aspects of the invention, the amine-based quencher is a compound having structure (24).

[0183]

[0184] In another embodiment of any of the above aspects of the invention, the amine-based quencher is a compound having structure (25) or a mixture of compounds having structure (25) having a boiling point of at least 100° C. at 1 atmosphere pressure, wherein R am3 and R am3a are independently selected from H or C-2 to C-25 alkyl, and further wherein R am3 or R am3a At least one of them is a C-2 to C-25 alkyl group.

[0185]

[0186] In another embodiment of any of the above aspects of the invention, the amine-based quencher consists solely of a compound having structure (26) or a mixture of compounds having structure (26) having a boiling point of at least 100° C. at 1 atmosphere pressure, wherein R am4 It is a C-2 to C-25 alkyl group.

[0187]

[0188] In another embodiment of the above aspects of the invention, the amine-based quencher is a compound of structure (18), wherein R am1 is a C2 to C20 alkyl group, and R am1a is C-1 to C-5 alkyl, and further wherein positions 3 and 2 are connected by a double bond.

[0189] In another embodiment of any of the above aspects of the invention, the amine-based quencher consists of a compound having structure (27).

[0190]

[0191] Surfactants and surface levelers

[0192] The surface leveling agent may include a surfactant. There is no specific limitation on the surfactant, and examples thereof include: polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene octadecyl 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 monovalmitate, 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 Inc.), 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 Yushikagaku Kogyo KK).

[0193] method

[0194] The process for preparing a patterned photoresist layer by using the photosensitive composition disclosed herein can be conventional. For example, the photosensitive composition in the form of a solution is uniformly applied to a substrate (such as a semiconductor silicon wafer or a substrate having a metal coating as previously described) by using a suitable coating machine (such as a spin coater), followed by baking in a convection oven or on a hot plate to form a photoresist layer, which is then exposed to actinic radiation (such as deep ultraviolet light, near ultraviolet light, or visible light, which is emitted from low-pressure, high-pressure and ultra-high-pressure mercury lamps, arc lamps, xenon lamps, ArF, KrF and F2 excimer lasers, electron beams, X-rays, extreme UV sources, etc. (through a photomask) or from a reflective mask with a desired pattern on an exposure device and an electron beam scanned according to the desired pattern) to accumulate a latent image of the pattern in the resist layer. The actinic radiation can be in the range of 250nm to 436nm. Thereafter, the latent image in the photoresist layer can be optionally baked in a convection oven or on a hot plate and developed using an alkaline developer solution having a concentration of 1 to 10% w / w, such as an aqueous solution of tetra(C1-C4 alkyl)ammonium hydroxide, choline hydroxide, lithium hydroxide, sodium hydroxide or potassium hydroxide (e.g., tetramethylammonium hydroxide) to obtain a patterned photoresist layer with good fidelity to the photomask pattern.

[0195] The thickness can be in the range of 20nm to 100 microns. In order to achieve these thicknesses, a combination of different rotation speeds and total solid concentrations can be used. Depending on the substrate size, a rotation speed of 500rpm to 10,000rpm can be used. Concentration can be expressed as the wt% of the total solid component in the total weight of the formulation including solids and solvents. Non-limitingly, an exemplary wt% is a solid component of about 0.05wt% to about 65wt% in the formulation. Non-limitingly, the wt% of the solid component in the total formulation can be in the range of about 20wt% to about 60wt%. Non-limitingly, a further example of the wt% range of the formulation is about 40wt% to about 60wt% solid.

[0196] The photosensitive composition comprises one or more polymers as shown above, one or more photoacid generators, one or more solvents and one or more heterocyclic thiol additives. The photosensitive composition may further contain a solvent and optional components such as a quencher and a surfactant.

[0197] As noted above, given as wt% solids, for example, the polymer (novolac + acrylate polymer) can be present at 30 wt% solids to 99 wt% solids, or the polymer can be present at about 40 wt% solids to about 99 wt% solids. More specifically, when maintaining the total solids wt% of the polymer as described above, the novolac polymer can be present at about 30 wt% solids to about 99 wt% solids, while the acrylate polymer can be present at about 5 wt% solids to about 50 wt% solids. In a more specific aspect, the novolac polymer can be in the range of about 55 wt% solids to about 99 wt% solids, while the acrylate polymer can be in the range of about 10 wt% solids to about 40 wt% solids.

[0198] The DNQ-PAC may be present at about 0.2 wt % solids to about 20 wt % solids, or this component may be present at about 0.5 wt % solids to about 10 wt % solids.

[0199] The photoacid generator (PAG) may be present at about 0.2 wt % solids to 2 wt % solids, or about 0.55 wt % solids to about 2 wt % solids.

[0200] The heterocyclic thiol additive may be present at about 0.01 wt % solids to about 1 wt % solids.

[0201] If present, the optional quencher component may be present at about 0.01 to 0.1 wt % solids.

[0202] If present, the optional surfactant component may be present at about 0.01 to 0.1 wt % solids.

[0203] For all purposes, each of the above-mentioned documents is incorporated herein by reference in its entirety. The following specific examples will provide a detailed description of the methods for producing and utilizing the compositions of the present invention. However, these examples are not intended to limit or restrict the scope of the present invention in any way, and should not be construed as providing conditions, parameters or values ​​that must be exclusively utilized in order to implement the present invention.

[0204] experiment

[0205] Chemicals

[0206] NIT PAG, N-hydroxynaphthalimide trifluoromethanesulfonate is sold by Heraeus PM NA Daychem LLC under the name (NIT PAG, 100%, Tech, pdr). APS-437 is a surfactant: from Shin-Etsu (Tokyo, Japan).

[0207] MTA: additive, (1H-1,2,4-triazole-3-thiol); TEA: (triethylamine); PGME (1-methoxy-2-propanol); PGMEA (1-methoxy-2-propyl acetate), and unless otherwise noted, any other chemicals were purchased from Sigma Aldrich, a subsidiary of Merck KGaA (Darmstadt, Germany).

[0208] Tetrabutylammonium oxalate was obtained by neutralizing oxalic acid with a 25 wt % TMAH aqueous solution and removing the water by evaporation.

[0209] Novolac polymer

[0210] For the following formulation examples, three novolac polymers were used: Novolak-1 is a meta-cresol and formaldehyde novolac and is marketed under the name “ALNOVOL TM SPN 560 / 47 MPAC slow" Mw 24010, D: 7.3 was obtained from Allnex (Alpharetta, Ga) and has Novolak-2 is a meta-cresol and formaldehyde phenolic varnish and is marketed under the name "ALNOVOL TM SPN 560 / 47 MPAC fast" Mw 7,245, D: 4.8 was obtained from allnex (Alpharetta, GA) and has Novolak-3 is a 1 / 1wt / wt blend of Novolak-1 and Novolak-2, with a dissolution rate of 1.5% in 0.26N aqueous TMAH developer. Novolak CL23 is a novolac polymer (sold by Asahi Yukizai Corporation under the name CL23F10G) comprising 50% m-cresol, 20% p-cresol and 30% 2,5-xylenol, formaldehyde, and Mw=4,000 and having a dissolution rate of 1.3 % in 0.26 N aqueous TMAH. / Second.

[0211] DNQ-PAC

[0212] PW-898 (CAS 107761-81-9) is 2,2'-4,4-tetrahydroxy-DNQ PAC (6-diazo-5,6-dihydro-5-oxo-1-naphthalene-sulfonate with (4-hydroxyphenyl)-(2,3,4-trihydroxyphenyl), ketone) obtained from Accel Pharmtech LLC (East Brunswick, NJ). It is a mixture of materials having the general formula (12) wherein D 1e , D 2e , D 3e or D 4e are each selected from H or a group having structure (10), and wherein D 1e , D 2e , D 3e or D 4e At least one of them is a group having structure (10).

[0213]

[0214] NK-280 is a DNQ-PAC sold under this name by Toyo Gosei Co., Ltd. It is a mixture of materials having the general formula (11), wherein D 1c , D 2c , D 3c and D 4c are each selected from H or a group having structure (10), wherein D 1c , D 2c , D 3c or D 4c At least one of the groups is a group having structure (10), and an average of about 2.8 phenolic positions D 1c , D 2c , D 3c and D 4c The group is esterified via (10).

[0215]

[0216] Acrylic polymer synthesis example 1

[0217]

[0218] Monomer repeat unit percentages are given as molar percentages. In this example, 6.46 g of methacrylic acid, 35.24 g of benzyl methacrylate, 43.25 g of hydroxypropyl methacrylate, 54.47 g of tert-butyl acrylate were mixed in 209.1 g of PGME solvent. The polymerization was carried out at 90 ° C under nitrogen for 18 hours in the presence of 2.3 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The polymer solids were washed and dried at 45 ° C under vacuum to obtain 137.1 g (98% yield) with a weight average molecular weight of 15,072 Daltons.

[0219] Acrylic polymer synthesis example 2:

[0220]

[0221] 1.8 g acrylic acid, 6.5 g methoxyethyl acylate, 22.0 g benzyl methacrylate, 21.6 g hydroxypropyl methacrylate, 21.3 g tert-butyl methacrylate were mixed in 179.6 g PGME solvent. The polymerization was carried out at 80° C. under nitrogen for 18 hours in the presence of 3.3 g AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 45° C. to obtain 73.5 g (>99% yield) with a weight average molecular weight of 11,868 Daltons.

[0222] Acrylic polymer synthesis example 3:

[0223]

[0224] 1.8 g acrylic acid, 6.5 g methoxyethyl acylate, 17.6 g benzyl methacrylate, 21.6 g hydroxypropyl methacrylate, 24.9 g tert-butyl methacrylate were mixed in 172.9 g PGME solvent. The polymerization reaction was carried out at 90 ° C under nitrogen for 18 hours in the presence of 1.6 g AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried at 45 ° C under vacuum to obtain 71.6 g (99% yield) with a weight average molecular weight of 17,205 Daltons.

[0225] Acrylic polymer synthesis example 4:

[0226]

[0227] 2.7 g acrylic acid, 6.5 g methoxyethyl acylate, 15.4 g benzyl methacrylate, 21.6 g hydroxypropyl methacrylate, 24.9 g tert-butyl methacrylate were mixed in 135.2 g PGME solvent. The polymerization reaction was carried out at 90 ° C under nitrogen for 18 hours in the presence of 1.6 g AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried at 45 ° C under vacuum to obtain 70.3 g (99% yield) with a weight average molecular weight of 17,153 Daltons.

[0228] Acrylic polymer synthesis example 5:

[0229]

[0230] 3.6 g acrylic acid, 6.5 g methoxyethyl acylate, 13.2 g benzyl methacrylate, 21.6 g hydroxypropyl methacrylate, 24.9 g tert-butyl methacrylate were mixed in 135.8 g PGME solvent. The polymerization was carried out at 90 ° C. under nitrogen for 18 hours in the presence of 3.3 g AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried at 45 ° C. under vacuum to obtain 70.8 g (> 99% yield) with a weight average molecular weight of 11,913 Daltons.

[0231] Acrylic polymer synthesis example 6:

[0232]

[0233] 1.8 g acrylic acid, 3.3 g methoxyethyl acylate, 17.6 g benzyl methacrylate, 21.6 g hydroxypropyl methacrylate, 28.4 g tert-butyl methacrylate were mixed in 138.2 g PGME solvent. The polymerization reaction was carried out at 90 ° C under nitrogen for 18 hours in the presence of 1.6 g AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried at 45 ° C under vacuum to obtain 71.9 g (99% yield) with a weight average molecular weight of 15,843 Daltons.

[0234] Acrylic polymer synthesis example 7:

[0235]

[0236] 6.5 g of methoxyethyl acylate, 15.4 g of benzyl methacrylate, 21.6 g of hydroxypropyl methacrylate, 30.2 g of tert-butyl methacrylate were mixed in 140.0 g of PGME solvent. The polymerization reaction was carried out at 90 ° C. under nitrogen for 18 hours in the presence of 1.6 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried at 45 ° C. under vacuum to obtain 72.45 g (98% yield) with a weight average molecular weight of 17,525 Daltons.

[0237] Acrylic polymer synthesis example 8:

[0238]

[0239] The monomer repeat unit percentage is given as molar percentage. In this example, 7.16g of methoxyethyl acylate, 15.86g of benzyl methacrylate, 25.23g of hydroxypropyl methacrylate, 32.78g of 1-ethylcyclopentyl methacrylate were mixed in 152.6g of PGME solvent. The polymerization reaction was carried out for 18 hours at 90°C under nitrogen in the presence of 1.2g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The polymer solid was washed and dried at 45°C under vacuum to obtain 79.3g (98% yield) with a weight average molecular weight of 17,888 Daltons.

[0240] Acrylic polymer synthesis example 9:

[0241]

[0242] 4.32 g acrylic acid, 14.32 g methoxyethyl acylate, 22.91 g benzyl methacrylate, 50.46 g hydroxypropyl methacrylate, 63.75 g 1-ethylcyclopentyl methacrylate were mixed in 158.5 g PGME solvent. The polymerization reaction was carried out at 90 ° C under nitrogen for 18 hours in the presence of 2.71 g AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The polymer solid was washed and dried at 45 ° C under vacuum to obtain 153.45 g (98.5% yield) with a weight average molecular weight of 17,103 Daltons.

[0243] Acrylic polymer synthesis example 10:

[0244]

[0245] 5.76 g acrylic acid, 14.32 g methoxyethyl acylate, 19.38 g benzyl methacrylate, 50.46 g hydroxypropyl methacrylate, 63.75 g 1-ethylcyclopentyl methacrylate were mixed in 156.4 g PGME solvent. The polymerization reaction was carried out at 90 ° C under nitrogen for 18 hours in the presence of 2.71 g AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The polymer solid was washed and dried at 45 ° C under vacuum to obtain 150.2 g (97.7% yield) with a weight average molecular weight of 15,557 Daltons.

[0246] Acrylic polymer synthesis example 11

[0247]

[0248] 8.61 g of methacrylic acid, 22.23 g of isobornyl methacrylate, 26.43 g of benzyl methacrylate, 43.25 g of hydroxypropyl methacrylate, 44.36 g of tert-butyl acrylate were mixed in 156.4 g of PGME solvent. The polymerization was carried out at 90° C. under nitrogen for 18 hours in the presence of 2.46 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The polymer solids were washed and dried under vacuum at 45° C. to give 142.5 g (98.3% yield) with a weight average molecular weight of 25,535 Daltons.

[0249] Formulation Examples

[0250] Formulation Example 1

[0251] 16.1 g of the acrylic polymer resin of Acrylic Polymer Synthesis Example 11, 25.1 g of Novolak-3, 0.42 g of 1,3-dioxo-1H-benzo[de]isoquinoline-2(3H)-trifluoromethanesulfonate [also known as naphthalene diimide trifluoromethanesulfonate, NIT] (NIT PAG), 0.03 g of 1H-1,2,4-triazole-3-thiol, 0.03 g of tetrabutylammonium oxalate, 0.050 g of APS-437, and 0.42 g of NK-280 were dissolved in 57.85 g of PGMEA solvent to obtain a resist solution having a solid content of 42.15%. This solution was filtered for use.

[0252] Formulation Example 2

[0253] 16.1 g of the acrylic polymer resin of Acrylic Polymer Synthesis Example 11, 25.1 g of Novolak-3, 0.42 g of 1,3-dioxo-1H-benzo[de]isoquinoline-2(3H)-trifluoromethanesulfonate [also known as naphthalene dicarboxylic acid imidoyl ester, NIT] (NIT PAG), 0.03 g of 1H-1,2,4-triazole-3-thiol, 0.03 g of tetrabutylammonium oxalate, 0.050 g of APS-437, and 0.42 g of PW-898 were dissolved in 57.85 g of PGMEA solvent to obtain a resist solution having a solid content of 42.15%. This solution was filtered for use.

[0254] Formulation Example 3

[0255] 12.3 g of the acrylic polymer resin of Acrylic Polymer Synthesis Example 11, 28.8 g of Novolak-3, 0.32 g of 1,3-dioxo-1H-benzo[de]isoquinoline-2(3H)-trifluoromethanesulfonate [also known as naphthalene dicarboxylic acid trifluoromethanesulfonate, NIT] (NIT PAG), 0.03 g of 1H-1,2,4-triazole-3-thiol, 0.03 g of tetrabutylammonium oxalate, 0.050 g of APS-43, and 0.85 g of NK-280 were dissolved in 57.62 g of PGMEA solvent to obtain a resist solution having a solid content of 42.38%. This solution was filtered for use.

[0256] Formulation Example 4

[0257] 9.95 g of the acrylic polymer resin of Acrylic Polymer Synthesis Example 11, 29.8 g of Novolak-3, 0.32 g of 1,3-dioxo-1H-benzo[de]isoquinoline-2(3H)-trifluoromethanesulfonate [also known as naphthalene dicarboxylic acid imidoyl ester, NIT] (NIT PAG), 0.03 g of 1H-1,2,4-triazole-3-thiol, 0.03 g of tetrabutylammonium oxalate, 0.050 g of APS-437, and 2.24 g of NK-280 were dissolved in 57.58 g of PGMEA solvent to obtain a resist solution having a solid content of 42.4%. This solution was filtered for use.

[0258] Formulation Example 5

[0259] 7.08 g of the acrylic polymer resin of Acrylic Polymer Synthesis Example 11, 32.66 g of Novolak-3, 0.20 g of 1,3-dioxo-1H-benzo[de]isoquinoline-2(3H)-trifluoromethanesulfonate [also known as naphthalene dicarboxylic acid imidoyl ester, NIT] (NIT PAG), 0.03 g of 1H-1,2,4-triazole-3-thiol, 0.03 g of tetrabutylammonium oxalate, 0.050 g of APS-437, and 2.17 g of NK-280 were dissolved in 57.78 g of PGMEA solvent to obtain a resist solution having a solid content of 42.2%. This solution was filtered for use.

[0260] Formulation Example 6

[0261] 4.2 g of the acrylic polymer resin of Acrylic Polymer Synthesis Example 11, 35.49 g of Novolak-3, 0.11 g of 1,3-dioxo-1H-benzo[de]isoquinoline-2(3H)-trifluoromethanesulfonate [also known as naphthalene dicarboxylic acid imidoyl ester, NIT] (NIT PAG), 0.03 g of 1H-1,2,4-triazole-3-thiol, 0.03 g of tetrabutylammonium oxalate, 0.050 g of APS-437, and 2.10 g of NK-280 were dissolved in 57.99 g of PGMEA solvent to obtain a resist solution having a solid content of 42.0%. This solution was filtered for use.

[0262] Formulation Examples 7, 8, 9, 10, 11, 12, 13, 14, 15 and 16

[0263] These formulations were prepared in the same manner as Formulation Example 1, but with acrylic polymer synthesis examples 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 replacing acrylic polymer synthesis example 11, respectively. These additional resist formulations were tested under the same processing conditions mentioned below. All of these resist formulations showed better PED performance than the formulation without diazonaphthoquinone sulfonate (Formulation Example 17, see below).

[0264] Formulation Example 17 (Comparative Example)

[0265] 16.5 g of the acrylic polymer resin of Acrylic Polymer Synthesis Example 11, 25.1 g of Novolak-3, 0.42 g of NIT PAG, 0.03 g of 1H-1,2,4-triazole-3-thiol, 0.03 g of tetrabutylammonium oxalate, and 0.050 g of APS-437 were dissolved in 57.8 g of PGMEA solvent to obtain a resist solution of 42.2% solids. This solution was filtered for use. This example is used for comparison with Examples 1 to 16 to show the significant effect of the diazonaphthoquinone sulfonate additive on the post-exposure delay in the presence of amines.

[0266] Photolithography Photoresist Process

[0267] Coating

[0268] All formulations were tested on 8" diameter Si and Cu wafers. The Si wafers were dehydration baked and primed with hexamethyldisilazane (HMDS) vapor. The Cu wafers were silicon wafers coated with 5,000 angstroms of silicon dioxide, 250 angstroms of tantalum nitride, and 3,500 angstroms of Cu (PVD deposited).

[0269] The photoresist coating was prepared by spin coating the photoresist sample and applying a soft bake on a standard wafer track hotplate in contact mode at 130° C. for 300 seconds. The spin speed was adjusted to obtain a 40 micron thick photoresist film. All film thickness measurements were performed on Si wafers using optical measurements.

[0270] Imaging:

[0271] The wafers were exposed on a SUSS MA200 CC mask aligner. The photoresist was post-exposed and baked at 100°C for 100 seconds and developed in AZ 300 MIF (0.26N tetramethylammonium hydroxide = TMAH aqueous solution) at 23°C for 240 seconds by immersion (spin-up immersion) (puddle). The developed photoresist images were studied using a Hitachi S4700 or AMRAY 4200L electron microscope.

[0272] Wafer handling

[0273] Wafers were exposed on an ASML 250 i-line stepper. The resist was post-exposed and baked at 90°C for 60 seconds and developed in an AZ 300 MIF (0.26N tetramethylammonium hydroxide = TMAH aqueous solution) (EMD Performance Materials, AZ Products, Somerville, NJ) at 23°C for 120 seconds by immersion (spin-on immersion). The developed resist images were examined using a Hitachi S4700 or AMRAY 4200L electron microscope.

[0274] All formulations were tested on 6" diameter Si and Cu wafers. The Si wafers were dehydration baked and primed with hexamethyldisilazane (HMDS) vapor. The Cu wafers were silicon wafers coated with 5,000 angstroms of silicon dioxide, 250 angstroms of tantalum nitride, and 3,500 angstroms of Cu (PVD deposited).

[0275] Resist coatings were prepared by spin coating the resist samples and applying a soft bake on a standard wafer track hotplate in contact mode at 120° C. for 180 seconds. The spin speed was adjusted to obtain a 10 micron thick resist film. All film thickness measurements were performed on Si wafers using optical measurements.

[0276] Post-Exposure Delay (PED) Testing

[0277] During the PED test, the coated wafers were delayed for 24 hours after UV exposure before development. The wafers were then developed according to the same conditions as the wafers without delay. SEM was used to examine the effect of PED on the 10 to 2 μm L / S feature morphology with a spacing of 1 / 1. Table 1 summarizes these PED results. All formulations containing DNQ PAC showed excellent PED tolerance up to 24 hours. Formulations 5 and 6 also showed good PED tolerance but lower L / S resolution (only as low as 4.5 μm L / S for formulation 5, and 6.5 μm for formulation 6), and it is believed that it can be attributed to the lower wt% of PAG (0.47 and 0.26 wt% solids). This shows that these formulations still show excellent PED delay tolerance for distinguishable features, thereby confirming the unexpected results of the improved PED tolerance imparted by adding DNQ PAC to these formulations.

[0278] Table 1

[0279]

[0280]

[0281] O: For "Lithographic Performance", this indicates that the resist is able to resolve at least 2.2 μm L / S at 1 / 1 pitch, O: For PED delay, at least 24 hours delay without any significant change in morphology. X: For PED delay, this indicates that all L / S morphologies show poor features from 10-2.2 μm.

Claims

1. A composition comprising components a), b), c), d) and e): a) at least one diazonaphthoquinone sulfonate photosensitizing compound (DNQ-PAC), b) at least one heterocyclic thiol having the structures (7), (8) and / or (9), c) at least one photoacid generator; d) at least one acrylic polymer comprising repeating units selected from repeating units having structures (1), (2), (3), (4), (5) and (6), e) at least one novolac polymer having a dissolution rate in 0.26 N tetramethylammonium hydroxide at 23° C. of at least 50 angstroms per second, wherein The repeating units are present in the acrylic polymer in the following mole % ranges based on the total moles of all different repeating units present, and further wherein the sum of the individual mole % values ​​of all repeating units present in the polymer must equal 100 mole %, and (1) is in the range of 0 to 35 mol %. (2) is in the range of 5 to 55 mol%. (3) is in the range of 0 to 30 mol%. (4) is in the range of 15 to 55 mol%, (5) is in the range of 10 to 40 mol%. (6) is in the range of 0 to 25 mol%, and R1, R2, R3, R4, R5 and R6 are independently selected from H, F, C-1 to C-4 fluoroalkyl or C-1 to C-4 alkyl, R7 is selected from H, C-1 to C-4 alkyl, C-1 to C-4 alkoxyalkyl and halogen, R8 is a C-3 to C-8 cyclic alkyl group, or a C-7 to C-14 alicyclic alkyl group, R9 is a C-2 to C-8 (hydroxy)alkylene group, R 10 is an acid cleavable group, R 11 is a C-3 to C-12, (alkoxy)alkylene group; and In the structure (7), Xt is selected from C(Rt1)(Rt2), O, S, Se and Te; In the structure (8), Y is selected from C(Rt3) and N; In the structure (9), Z is selected from C(Rt3) and N; and Rt1, Rt2 and Rt3 are independently selected from H, substituted alkyl having 1 to 8 carbon atoms, unsubstituted alkyl having 1 to 8 carbon atoms, substituted alkenyl having 2 to 8 carbon atoms, unsubstituted alkenyl having 2 to 8 carbon atoms, substituted alkynyl having 2 to 8 carbon atoms, unsubstituted alkynyl having 2 to 8 carbon atoms, substituted aryl having 6 to 20 carbon atoms, substituted heteroaryl having 3 to 20 carbon atoms, unsubstituted aryl having 6 to 20 carbon atoms, and unsubstituted heteroaryl having 3 to 20 carbon atoms; 2. The composition of claim 1, wherein the DNQ-PAC is a single material or a mixture of materials, wherein the 2,1,5-diazonaphthoquinone sulfonate group having structure (10) forms at least one sulfonate ester with a phenolic compound, 3. The composition according to claim 1 or 2, wherein the DNQ PAC is a single material having the general formula (11) or a mixture of materials having the general formula (11), wherein D 1c , D 2c , D 3c and D 4c are selected from H or a group having structure (10), and further, wherein D 1c , D 2c , D 3c or D 4c At least one of the groups is a group having structure (10), 4. The composition of claim 1 or 2, wherein the DNQ PAC is a single compound or a mixture of PAC compounds having structure (12a), wherein D 1e , D 2e and D 3e are selected from H or a group having structure (10), and further, wherein D 1e , D 2e or D 3e At least one of the groups is a group having structure (10), 5. The composition of claim 1 or 2, wherein the DNQ PAC is a single compound or a mixture of PAC compounds having structure (12b), wherein D 1e , D 2e , D 3e and D 4e are selected from H or a group having structure (10), and further, wherein D 1e , D 2e , D 3e or D 4e At least one of the groups is a group having structure (10), 6. The composition of claim 1 or 2, wherein the DNQ PAC is a single compound having structure (13) or a mixture of compounds having structure (13), wherein D 1f , D 2f , D 3f and D 4f are selected from H or a group having structure (10), and further, wherein D 1f , D 2f , D 3f or D 4f At least one of the groups is a group having structure (10), 7. The composition of claim 1 or 2, wherein the heterocyclic thiol is selected from unsubstituted triazole thiols, substituted triazole thiols, unsubstituted imidazole thiols, substituted imidazole thiols, substituted triazinethiols, unsubstituted triazinethiols, substituted mercaptopyrimidines, unsubstituted mercaptopyrimidines, substituted thiadiazole-thiols, unsubstituted thiadiazole-thiols, substituted indazole thiols, unsubstituted indazole thiols, tautomers thereof, and combinations thereof.

8. The composition according to claim 1 or 2, wherein the heterocyclic thiol is selected from 1,3,5-triazine-2,4,6-trithiol, 2-mercapto-6-methylpyrimidine-4-ol, 3-mercapto-6-methyl-1,2,4-triazine-5-ol, 2-mercaptopyrimidine-4,6-diol, 1H-1,2,4-triazole-3-thiol, 1H-1,2,4-triazole-5-thiol, 1H-imidazole-2-thiol, 1H-imidazole-5-thiol, 1H-imidazole-2-thiol, 1H-imidazole-5-thiol, 1H-imidazole-5-thiol, 1H-imidazole-5-thiol, 1H-imidazole-6 ... -imidazole-4-thiol, 2-azabicyclo[3.2.1]oct-2-ene-3-thiol, 2-azabicyclo[2.2.1]hept-2-ene-3-thiol, 1H-benzo[d]imidazole-2-thiol, 2-mercapto-6-methylpyrimidin-4-ol, 2-mercaptopyrimidin-4-ol, 1-methyl-1H-imidazole-2-thiol, 1,3,4-thiadiazole-2,5-dithiol, 1H-indazole-3-thiol, tautomers thereof, and combinations thereof.

9. The composition of claim 1 or 2, wherein at least one photoacid generator is selected from onium salts, dicarboximidosulfonates, oximesulfonates, diazo(sulfonylmethyl) compounds, disulfonylmethylenehydrazine compounds, nitrobenzylsulfonates, biimidazole compounds, diazomethane derivatives, ethylenedioxime derivatives, β-ketosulfone derivatives, disulfone derivatives, sulfonate derivatives, sulfonic acid imide ester derivatives and halogenated triazine compounds, or a combination thereof.

10. The composition according to claim 1 or 2, wherein the acrylic polymer is one whose repeating units are selected from repeating units having structures (1), (2), (3), (4), (5) and (6).

11. The composition according to claim 1 or 2, wherein the acrylic polymer is one whose repeating units are selected from repeating units having structures (1), (2), (4), (5) and (6).

12. The composition according to claim 1 or 2, wherein in the acrylic polymer, (1) is in the range of 5 to 20 mol%. (2) is in the range of 5 to 25 mol%. (3) is in the range of 0 to 30 mol%. (4) is in the range of 15 to 55 mol%, (5) is in the range of 20 to 40 mol%, and (6) is in the range of 5 to 25 mol %.

13. The composition of claim 1 or 2, wherein the acrylic polymer is a polymer whose repeating units are those having structures (1), (2a), (4a), (5) and (6a), wherein n and n' are the number of methylene spacer groups and independently range from 1 to 4, R1, R2, R4, R5 and R7 are independently selected from C-1 to C-4 alkyl, R 9' and R 11' are each selected from H or C-1 to C-4 alkyl, and R 11'' is a C-1 to C-4 alkyl group, 14. The composition according to claim 13, wherein (1) is in the range of 5 to 20 mol%. (2a) is in the range of 5 to 25 mol%, (4a) is in the range of 15 to 55 mol%, (5) is in the range of 20 to 40 mol%, and (6a) is in the range of 5 to 25 mol%.

15. The composition according to claim 1 or 2, wherein in the repeating unit of structure (5), the R 10 The acid cleavable group is selected from tert-butyl, tetrahydropyran-2-yl, tetrahydrofuran-2-yl, 4-methoxytetrahydropyran-4-yl, 1-ethoxyethyl, 1-butoxyethyl, 1-propoxyethyl, 3-oxocyclohexyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, 8-methyl-8-tricyclo[5.2.1.0 2,6]decyl, 1,2,7,7-tetramethyl-2-norbornyl, 2-acetoxymenthyl, 2-hydroxymethyl, 1-methyl-1-cyclohexylethyl, 4-methyl-2-oxotetrahydro-2H-pyran-4-yl, 2,3-dimethylbutan-2-yl, 2,3,3-trimethylbutan-2-yl, 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 1,2,3,3-tetramethylbicyclo[2.2.1]hept-2-yl, 2-ethyl-1,3,3-trimethylbicyclo[2.2.1]hept-2-yl, 2,6,6-trimethylbicyclo[3.1.1]hept-2-yl, 2,3-dimethylpentan-3-yl or 3-ethyl-2-methylpentan-3-yl.

16. The composition according to claim 1 or 2, wherein the acrylic polymer is a polymer whose repeating units are those having structures (1), (2b), (4b), (5a) and (6b), (6b)。 17. The composition according to claim 16, wherein (1a) is in the range of 5 to 20 mol %. (2b) is in the range of 5 to 25 mol%, (4b) is in the range of 15 to 55 mol%, (5a) is in the range of 20 to 40 mol%, and (6b) is in the range of 5 to 25 mol%.

18. The composition of claim 1 or 2, wherein the polymer further comprises at least one styrenic repeating unit selected from repeating units having structure (14), wherein R 14 is selected from H or CH3, and R 14' and R 14'' may be the same or different and are selected from H, OH, OCOOC(CH3)3 or OCOCOO(CH3)3, 19. The composition according to claim 1 or 2, wherein the polymer further comprises a (meth)acrylate having a lactone group, the lactone group being a single cyclic lactone or a lactone group contained in an alicyclic alkyl group.

20. The composition according to claim 1 or 2, wherein the polymer further comprises at least one repeating unit of structure (15) comprising a lactone group, wherein R 15 is selected from H or CH3 and m is 1 or 2, 21. The composition of claim 1 or 2, wherein the novolac polymer comprises repeating units of structure (16), wherein Ra and Rb are independently C-1 to C-4 alkyl, na is 0 to 3, nb is 0 or 1, 22. The composition of claim 1 or 2, wherein the novolac polymer comprises repeating units of structure (17), wherein Rc is a C-1 to C-4 alkyl group, Rd is a C-1 to C-4 alkyl group, X is -O-, -C(CH3)2-, -(C=O)-, or -SO2-, nc is 0 to 3, nd is 0 or 1, 23. The composition of claim 1 or 2, wherein the novolac polymer comprises repeating units (16) and (17), wherein Ra and Rb are independently C-1 to C-4 alkyl, na is 0 to 3, and nb is 0 or 1 and Rc is C-1 to C-4 alkyl, Rd is C-1 to C-4 alkyl, X is -O-, -C(CH3)2-, -(C=O)- or -SO2-, nc is 0 to 3, and nd is 0 or 1 24. The composition of claim 1 or 2, wherein the novolac polymer is a novolac polymer of m-cresol and formaldehyde.

25. The composition of claim 1 or 2, wherein the novolac polymer comprises 10 to 90 wt% solids.

26. A method of forming a positive relief image, comprising: Forming a photosensitive layer by applying the positive photosensitive composition according to any one of claims 1 to 25 to a substrate; imagewise exposing the photosensitive layer to actinic radiation to form a latent image; Develop the latent image in the developer, The image-wise exposed photosensitive layer is optionally subjected to a thermal treatment.

27. The method of claim 26, wherein the substrate is thiophilic.

28. The method of claim 26, wherein the substrate is copper.

29. Use of a composition according to any one of claims 1 to 25 for forming a positive relief image on a substrate.

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