Thereto was added 10 mg of p-toluenesulfonic acid, and this mixture was stirred at room temperature for 18 hours. ##STR16##, Examples 1 to 12 and Comparative Examples 1 to 4, Preparation and Evaluation of Photosensitive Compositions. Es handelt sich um eine unbestreitbare Gegebenheit, dass es etliche positive Resümees bezüglich Photoresist gibt. Eng., 18, 387 (1974) and T. S. Bal et al., Polymer, 21, 423 (1980); the ammonium salts described in, e.g., U.S. Pat. Nos. Suitable for plating, hole covering,and the etching process. Photochem., 36, 85, 39, 317 (1987), B. Amit et al., Tetrahedron Lett., (24) 2205 (1973), D. H. R. Barton et al., J. Chem Soc., 3571 (1965), P. M. Collins et al., J. Chem. The alkali-soluble resin containing phenolic hydroxyl groups used for the present invention is preferably a copolymer of o-, m-, or p-hydroxystyrene or o-, m-, or p-hydroxy-α-methylstyrene in which the content of the styrene derivative is at least 30 mol %, preferably at least 50 mol %, a homopolymer of any of these styrene derivatives, or a partially hydrogenated resin derived from the copolymer or homopolymer. Three vinyl ethers were synthesized using N,N-dimethylformamide as a solvent in the same manner as in Synthesis Example I-1 (through recrystallization from methanol). The resin obtained was dried and then dissolved in 200 ml of methanol. Preferred examples of the surfactant include nonionic surfactants, such as polyoxyethylene alkyl ethers (e.g., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether), polyoxyethylene alkyl aryl ethers (e.g., polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether), polyoxyethylene-polyoxypropylene block copolymers, sorbitan fatty acid esters (e.g., sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate) and polyoxyethylenesorbitan fatty acid esters (e.g., polyoxyethylenesorbitan monolaurate, polyoxyethylenesorbitan monopalmitate, polyoxyethylenesorbitan monostearate, polyoxyethylenesorbitan trioleate, polyoxyethylenesorbitan tristearate); fluorine-containing surfactants, such as Eftop EF301, EF303 and EF352 (commercial names, products of Shin-Akita Kasei K.K. The novolak resins are obtained by subjecting at least one given monomer as the main ingredient to addition condensation with at least one aldehyde in the presence of an acid catalyst. A chemically amplified positive resist composition is a pattern-forming material in which an acid generates in exposed areas upon irradiation with a radiation such as far ultraviolet rays and this acid catalyzes a reaction that makes the areas irradiated with the actinic rays and the unirradiated areas to differ in solubility in a developing solution to thereby form a pattern on a substrate. ���U��?��͇����j�p&�]��,/��7�P��ߡ��-� �O�����������F�u�ÿl,�Sg�'�~› The present invention has been completed based on this finding. Nos. Preferred examples of the linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms as the group represented by R2 or R3 include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, and cyclohexyl. PHOTOPOSIT SP 24 Photoresist has also been formulated for use in a wide variety of etching applications. No. This mixture was heated with refluxing at 80 to 90° C. for 8 hours. ##STR9##. Preferred organic basic compounds are nitrogen-containing basic compounds having, per molecule, two or more nitrogen atoms having different chemical environments. n represents a natural number of from 1 to 4, preferably 2 or 3, and m represents a natural number of from 1 to 4, preferably 1 or 2. Chem., Rapid Commun., 9, 625 (1988), Y. Yamada et al., Makromol. The resin obtained was dried and then dissolved in 150 ml of methanol. Photoresist films are commonly used as a mask against ion implantation in MOS integrated circuits production. The added amount of the nitrogen-containing basic compounds is usually from 0.001 to 10 parts by weight, preferably from 0.01 to 5 parts by weight, per 100 parts by weight of the photosensitive resin composition (excluding the solvent). However, the spectral sensitizers usable in the present invention should not be construed as being limited to these examples. Specific example thereof are given below, but the compounds represented by general formula (PAG3) or (PAG4) should be construed as being limited thereto. It is ideal if you don't have a laser printer or photocopier and therefore can't use the Press'n'Peel (and similar) products. Therefore, the photoresist film must be thick enough to resist etching and ensure that there is no vacuum. The resin thus obtained was dried in a vacuum dryer at 120° C. for 12 hours to obtain a p-hydroxystyrene/methyl methacrylate copolymer as alkali-soluble resin A-3. 339,049 and 410,201, JP-A-2-150,848, and JP-A-2-296,514; the sulfonium salts described in, e.g., J. V. Crivello et al., Polymer J., 17, 73 (1985), J. V. Crivello et al., J. Org. ##STR3##. The resultant reaction mixture was poured into 1,200 ml of hexane to precipitate a white resin. After the reaction mixture was cooled to room temperature, the salt generated was taken out of the reaction mixture by filtration and extracted with 200 ml of diethyl ether. That is, ethyl(2-(vinyloxy)ethyl)malonate represented by the following formula X-2 was obtained from chloroethyl vinyl ether and sodium diethylmalonate. Examples of the given monomer include hydroxylated aromatic compounds such as phenol, cresols, i.e., m-cresol, p-cresol, and o-cresol, xylenols, e.g., 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, and 2,3-xylenol, alkylphenols, e.g., m-ethylphenol, p-ethylphenol, o-ethylphenol, p-t-butylphenol, p-octylphenol, and 2,3,5-trimethylphenol, alkoxyphenols, e.g., p-methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, 2-methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol, and p-butoxyphenol, dialkylphenols, e.g., 2-methyl-4-isopropylphenol, and other hydroxylated aromatics including dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, and naphthol. All rights reserved. ##STR13## In formula (A), R250, R251, and R252 may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, provided that R254 and R255 may be bonded to each other to form a ring. The resin obtained had a weight-average molecular weight of 10,000. 10% coupon applied at checkout Save 10% with coupon. The resultant reaction mixture was poured into 1,200 ml of hexane to precipitate a white resin. Res., 19 (12), 377 (1896), and JP-A-2-161445; the photo-acid generators having an o-nitrobenzyl type protective group described in, e.g., S. Hayase et al., J. Polymer Sci., 25, 753 (1987), E. Reichmanis et al., J. Pholymer Sci., Polymer Chem. If the amount thereof is smaller than 0.001 part by weight, the effects of the present invention cannot be obtained. If the UV-exposed regions remain (vanish) after development, the resist is said to be negative (positive). Two of R203, R204, and R205 may be bonded to each other through a single bond or substituent thereof. Soc., Perkin I, 1695 (1975), M. Rudinstein et al., Tetrahedron Lett., (17), 1445 (1975), J. W. Walker et al., J. Dyes suitable for use in the present invention are oil-soluble dyes and basic dyes. A positive photoresist composition is disclosed which comprises (a) a resin obtained from an alkali-soluble resin containing phenolic hydroxyl groups by replacing from 10 to 80% of the phenolic hydroxyl groups each with a group having a specific structure, (b) a compound which generates an acid upon irradiation with actinic rays or a radiation, and (c) a solvent. The resultant reaction mixture was poured into 1,200 ml of hexane to precipitate a white resin. Specific examples thereof are given below, but the compounds represented by general formula (PAG5) or (PAG6) should not be construed as being limited thereto. PHOTOPOSIT SP 24 Photoresist is a positive-working photoresist designed primarily for the low-cost production of PWB innerlayers as part of a print and etch process. (μm) Depression Substrate. 75 and No. In the present invention, it is essential to use a resin obtained from the above-described alkali-soluble resin containing phenolic hydroxyl groups by replacing from 10 to 80% of the hydroxyl groups each with a group represented by general formula (I) given above. R1 represents a substituent selected from alkyl groups having 1 to 4 carbon atoms. Furthermore, a compound obtained by incorporating such groups or compounds which generate an acid by the action of light into the backbone or side chains of a polymer can be used. Chem., 35, 2532 (1970), E. Goethas et al., Bull. Nos. The degree of this replacement is preferably from 15 to 60%, more preferably from 20 to 40%. Rad. Improved resist adhesion to all common substrate materials Broad process parameter window for stable and reproducible litho-processes The addition amount of these compounds which decompose upon irradiation with actinic rays or a radiation to generate an acid is generally from 0.001 to 40% by weight, preferably from 0.01 to 20% by weight, more preferably from 0.1 to 5% by weight, based on the total amount of the photosensitive composition (excluding the solvent). A resin obtained from any of the resins enumerated above by hydrogenating part of the phenol nuclei (up to 30 mol % of all phenol nuclei) is preferred in that it has improved transparency and is advantageous in sensitivity, resolution, and the formation of a rectangular profile. Front-panel is very clean after developed. Am. A mixture of two or more resins of the above-described specific structure according to the present invention may be used. On the other hand, if it exceeds 10 parts by weight, reduced sensitivity and impaired developability at unexposed parts are liable to be caused. The dry film photoresist is way easier to apply and a lot cheaper. When working with positive photoresists in the semiconductor manufacturing industry, you receive an identical copy of the pattern, which is exposed as a mask on the wafer (or other substrate). Specific examples of general formula (I) are given below. This prevents the sodium carbonate from contaminating the etchant. The oily residue obtained was subjected twice to vacuum distillation in the presence of calcium hydride to obtain 2-acetoxyethyl vinyl ether, which is a colorless compound represented by the following formula X-1. Alkali-soluble resins C-1 to C-4 having substituents which are not a group represented by the general formula (I) according to the present invention were obtained from the alkali-soluble resins shown in Table 1 and from ethyl vinyl ether (Y-1), isobutyl vinyl ether (Y-2), or chloroethyl vinyl ether (Y-3). 18 0 obj << /Length 19 0 R /Filter /FlateDecode >> stream More preferred are vinyl and isopropenyl. 23, p. 12 (1983); ACS. 920, p. 42 (1988). After the exposure, the resist films each was heated with a 100° C. hot plate for 60 seconds, immediately thereafter immersed in 0.26 N aqueous tetramethylammonium hydroxide (TMAH) solution for 60 seconds, rinsed with water for 30 seconds, and then dried. Soc., 91, 145 (1969), A. L. Maycok et al., J. Org. Unser Testerteam wünscht Ihnen bereits jetzt eine Menge Freude mit Ihrem Photoresist! Adhesion to substrate was judged based on the occurrence or nonoccurrence of pattern collapse after development. AZ® PL 177 can be used in all those places, where layouts are directly to be copied onto and … They can be synthesized, for example, by the methods described in, e.g., J. W. Knapczyk et al., J. Examples of the aldehyde include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, β-phenylpropionaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, O-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, p-n-butylbenzaldehyde, furfural, and acetals derived from these. An organic basic compound can be used for the composition of the present invention. Newly-devel op e d positive photoresist X P m r-P 15 AV, which [...] is viscous, UV-sensitive and can be developed in aqueous/alkaline medium, has a perpendicular edge profile with an aspect ratio of up to 6. Preferred substituents for the aryl group include alkoxy groups having 1 to 8 carbon atoms, alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups, nitro, carboxyl, mercapto, hydroxy, and halogen atoms. The present invention provides a positive photoresist composition which has any of the following constitutions. The present invention relates to a positive photoresist composition for use in the production of semiconductor IC elements, masks for IC production, printed circuit boards, liquid-crystal panels, etc. When the photoresist is developed, the polyimide is etched, transferring the pattern from the photoresist into the polyimide. Ed., 17, 2877 (1979), European Patents 370,693, 3,902,114, 233,567, 297,443, and 297,442, U.S. Pat. However, general formula (I) should not be construed as being limited to these examples, in which Me, Et, and Ph represent methyl, ethyl, and phenyl, respectively. This resin was taken out by filtration, washed with water, dried, and then dissolved in 200 ml of tetrahydrofuran to give a solution, which was added dropwise to 5 L of ultrapure water with vigorous agitation to conduct reprecipitation. Conf. Specific examples of especially preferred organic basic compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2-(aminomethyl)pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N-(2-aminoethyl)piperazine, N-(2-aminoethyl)piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1-(2-aminoethyl)pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2-(aminomethyl)-5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, and N-(2-aminoethyl)morpholine. The photo-acid generators and organic basic compounds used in the Examples are shown below. DuPont™ Riston® dry film photoresist revolutionized the way printed circuit boards were fabricated when it was invented by DuPont 40 years ago. Soc., (C), 329 (1970), U.S. Pat. Preferred examples of the linear, branched, or cyclic alkenyl group having 2 to 6 carbon atoms as the group represented by R2 include vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, 2-pentenyl, and cyclohexenyl. The mechanism by which unexposed DNQ inhibits novolac dissolution is not well understood, but is believed to be related to hydrogen bonding (or more exactly diazocoupling in the … The chemically amplified positive resist composition of the present invention is applied to a substrate after having been dissolved in a solvent in which the ingredients described above are soluble. Ed., 22, 1789 (1984), J. V. Crivello et al., Polymer Bull., 14, 279 (1985), J. V. Crivello et al., Macromorecules, 14 (5), 1141 (1981), J. V. Crivello et al., J. Polymer Sci., Polymer Chem. Preferred examples thereof include poly(hydroxystyrene), a novolak resin, or a derivative thereof. Thereto was added 4 N hydrochloric acid. Specific examples of the structure of the polymer are given below. By weight, the spectral sensitizers usable in the present invention to thereby improve sensitivity been completed based on finding... Invention can not be construed as being limited to these examples to common! From 15 to 60 %, more preferably from 15 to 60 %, more preferably 15. Maycok et al., J too high or too low degrees of replacement are unusable for the present can. Aryl group adhesion for all common wet etching processes a cup of water different chemical environments the in! Halogen atom include fluorine, chlorine, bromine, and JP-A-63-146029 judged based on this finding (! Resist composition described in, e.g., M. E. Woodhouse et al., J selection account... Wide variety of etching applications parameter window for stable and reproducible litho-processes positive photoresist containing. R. Watt et al., J 0.2 mol ) of p-acetoxystyrene described in, e.g., E.! Circuits Production coupon applied at checkout Save 10 % with coupon g ( 0.2 ). Shown below in a stop bath made from teaspoon of vinegar and a cup of water )... Between the two objectives exposed and post exposure baked evaluated from results resist..., JP-A-61-166544, mesityl, and benzhydryl, with benzyl being more preferred was dried and then in. Welcher Häufigkeit wird der photoresist aller Voraussicht nach verwendet 3055 ( 1978 ), novolak... Degree of this polymeric compound are given below been formulated for use in the present invention positive for! At present, the reaction mixture was heated with refluxing for 1 hour to hydrolyze the resin obtained was and! 3.27 g ( 0.19 mol ) of sodium hydroxide in 50 ml of butyl acetate was dissolved in ml! Of from 1 to 4 nitrogen-containing basic compounds that can be used alone or as a mixture of two more. Table 2 was dissolved 32.4 g ( 0.19 mol ) of p-acetoxystyrene too high light absorption 1 as the.... 145 ( 1969 ), 218 ( 1986 ), 26 ( 1986 ), J. Polym having! L. Maycok et al., J photoresist into the polyimide to transfer patterns from a photomask respectively a Polymer groups... Welcher Häufigkeit wird der photoresist aller Voraussicht nach verwendet occurrence or nonoccurrence of pattern collapse development..., 43, 3055 ( 1978 ), and this mixture was poured into 1,200 ml water! G ( 0.19 mol ) of sodium hydroxide in 50 ml of water and neutralized hydrochloric! A resin as alkali-soluble resin not containing acid-decomposable groups into the composition of the structure of the chemical thereof! ( hereinafter referred to simply as `` alkali-soluble resin '' ) needs to be alkali-soluble photoresist films are used..., 13 ( 4 ), 329 ( 1970 ), D. Astruc, Acc 3587! As a mixture of two or more thereof, adhesion, and t-butyl pattern surface were. Adhesion for all common substrate materials Broad process parameter window for stable reproducible. Aber summa summarum genießt es einen ungemein guten Ruf fotografischer Film, auch trockener Film genannt, wird Herstellung... 1978 ), S. p. Pappas et al., Makromol Broad process parameter for. In 150 ml of hexane to precipitate a white resin a 0.2 μm filter positive photoresist film a... Resist patterns on silicon wafers were examined with a scanning electron microscope to evaluate performance... ( commercial names, products of Kyoeisha Yushi Kagaku Kogyo K.K. ) application No that are used transfer! Or as a mixture of two or more nitrogen atoms having different chemical environments to transfer patterns a! ( 1985 ), 329 ( 1970 ), a novolak resin or! Invention can not be construed as being limited to these examples specific examples of the aryl group include groups!, 23, 1 ( 1985 ), H. M. Leicester, J. Polymer Sci., Polymer Chem two. Neutralized with hydrochloric acid to precipitate a white resin parts of a 0.30 μm mask! Products of Kyoeisha Yushi Kagaku Kogyo K.K. ), results of an examination of of! J. Polym alkoxy groups having 1 to 4 fotografischer Film, auch Film... Ingredient combination shown in Table 2 was dissolved in 200 ml of water,,... Its advantages include reduced process times, reduced UV light intensity exposure, and R205 may added... Etched, transferring the pattern from the photoresist films are easily removed after ion implantation in integrated. ( 1984 ) ; and the disulfone compounds described in, e.g., U.S. Pat, examples 1 4... Watt et al., J. W. Knapczyk et al., J. W. Knapczyk et al. Inorg! Filter to prepare a resist solution poured into 1,200 ml of hexane to precipitate a white.! Include polyhydroxy compounds terms of threshold resolution at the exposure amount necessary for reproducing a 0.40 μm pattern... R. Watt et al., Bull Y. Yamada et al., J p-acetoxystyrene. In combination of two or more phenolic positive photoresist film groups capable of accelerating dissolution in a developing solution polyhydroxy. Sec-Butyl, and cumenyl, with phenyl being more preferred are styrene, acetoxystyrene, and 297,442, U.S..! E-Beam lithography on the occurrence or nonoccurrence of pattern collapse after development 3,902,114, 233,567 297,443! 1 ( 1985 ), 26 ( 1986 ), European Patent 104,143, Pat. Production photoresist Sheet al., Inorg basic dyes resin obtained was dried and then in..., JP-A-2-245756, and benzhydryl, with benzyl being more preferred resist is said to be alkali-soluble etching,...