TW419615B - Photo crosslinkable, aqueous base developable negative photoresist composition and method for use thereof - Google Patents

Abstract

An aqueous base developable, high resolution photoresist composition for use in deep UV and i-line is discolsed. The composition of the present invention comprises of a phenolic polymer resin a crosslinker selected from glycoluril derivatives capable of reacting with there resins under acid catalysis, a photoacid generator and an organic solvent. The composition of the present incention is particularly useful for production of negative tone images of high resolution (less than 0.25 micrometer).

Description

4 19 615 a ?, B7 V. Description of the invention (1) Scope of the invention The present invention relates to a water-soluble alkali-developed photoresist composition, and a process for forming a lithographic etching pattern therefrom. Previous techniques have achieved higher circuits in electronic components. Density is one of the continuing efforts of the electronics industry. In order to obtain a more comprehensive accumulation of degrees, the industry has developed new and improved lithographic relief tools and technologies, which in turn require new photoresists that can improve the resolution of lithographic money engraved patterns. Water-soluble alkali-developed photoresist compositions formed by crosslinking have been disclosed in Reck et al.} SPIE regional Technical Conference on Photopolymers, Ellenville, N.Y., 63 (1988) and US Patent Nos. 5,034,304 and 5,204,225 issued to Feely. Such formulations are characterized by having aromatic components such as poly (based on phenylphenylene) or acid varnishes, which are sensitive to substitution of electrophilic aromatic groups; one can form an anionic cation during acid treatment A combination agent; and a photoacid generator. Printed by the Central Bureau of Standards of the Ministry of Economic Affairs of the Ministry of Economic Affairs, ^ Please read the note on the back of the item, and then fill out this page) US Patent No. 4,810,601 issued to Allen and others is related to negative modulation The photoresist pattern is formed by cross-linking an aromatic compound with a monomer or polymer source of anions. In this way, diethyloxymethyl formaldehyde, diethylfluorenyloxy 1,3,5-trimethylbenzene and triphenylphosphloorionate are simultaneously used to crosslink a poly (hydroxystyrene) matrix. US Patent No. 5,296,332 to Sachdev and Japanese Patent Nos. 2-1 5270 and 1-293339 to Kokai describe water-soluble ageing compositions containing Styrene) or Fenjun varnish -4-This paper size applies to Chinese National Standards (CNS) (210x 297 ^^,) 41 961 5 A7 _____ — B7 ______ 5. Description of the invention (2) Cross-linking fluorene of anions and cations during acid treatment, and-photoacid generator. SUMMARY OF THE INVENTION A broad aspect of the present invention is a water-soluble alkali-developed photoresist composition for producing a substrate on a substrate to produce a negatively modulated photoresist image of less than 1/4 micron. Another aspect of the present invention is a photoresist composition which does not generate micro bridges between photoresist images on a substrate. This photoresist composition comprises (a) a film-forming polymer resin having a phenolic functional group, and (b) an acid-catalysable crosslinking agent, selected from the aminoplast coating family, and more specifically, selected from glycoluril. Derivatives' (c) — a radiation-degradable acid generator to assist the cross-linking between the film-forming agent and the cross-linking agent, and (d) — an organic base selected as needed to improve the storage stability of the formulation. The polymer resin of the present invention is selected from the group consisting of poly (Ethylene) and partially protected 2 (Hydroxybenzyl ethylene) or poly (Hydroxystyrene-co-ethenylcyclohexanol). 'Please read the notes on the back before filling in the following page.

419615

Or novolac (phenol formaldehyde) resin as shown in the following general chemical formula:

OH 0H

At ---- f, please read the back ^-Note?-And then fill in the hundred) The cross-linking agent of this composition is selected from the glycoluril derivative represented by the following chemical formula: 〇CH3〇CH2 \ N Jk n ^ CH2〇CH3 Rr ^ ~ (-R2 _ talk / Ya, ⑽CH3 〇 Wherein R is an alkoxy radical 'is preferably CH2OCH3, and 1 ^ and 112 may be selected from hydrogen, alkyl or aryl. The composition of the present invention may also include a radiation-degradable acid generator. Another broad aspect of the present invention is the synthesis of a novel glycoluril derivative which can be used as a cross-linking agent of the composition. Industrial Consumer Cooperative Press " The invention also provides a method that uses a novel photoresist composition to produce a negative modulation photoresist image on a substrate. The method includes a) coating a Tang film on the substrate, including a Functional film-forming polymer resin, an acid-catalyzed cross-linking agent selected from the derivatives of Ganmai, and a radiation-degradable acid generator; -6-This paper is applicable to China ’s national ladder (CNS ) 枋 （2 [〇X2 < 37 public 尨） Ministry of Economic Affairs Central Standard 4'-Industrial Cooperation and Consumer Cooperatives India Gas 4 19615 A / ___... " B7 five Explanation of the invention (4) b) Exposing the film by ultraviolet imaging to cause cross-linking of the exposed portions of the film: C) Baking the substrate at elevated temperature, and d) Developing the film in an aqueous alkali developer. This composition is quite sensitive to deep ultraviolet rays. The photoresist speed can be adjusted by adjusting the ratio of the cross-linking agent to the polymer resin, adding an organic base, and / or selecting a portion of the protected poly (severe styrene) or phenolic resin. Brief description of the figures Figures 1 to 3 are photomicrographs showing images made using different compositions of the invention. Detailed Description of the Invention The present invention relates to a high-resolution, water-soluble alkali-developed photoresist composition for forming a negatively modulated image on a substrate. These compositions include a) a film-forming polymer resin having various functional groups; b) a glycoluril derivative cross-linking agent that can react with a phenol functional group and form a cross-link under the action of an acid catalyst; c) Photodegradable acid generator, which forms the acid catalyst required for crosslinking when exposed to ultraviolet light; and d)-tertiary amines of organic bases, which are specially added to increase the life of this formulation and adjust the exposure speed a polymer with phenol functional group

The resin is selected from the group consisting of poly (hydroxystyrene), partially protected poly (_Wu Q ethylene) or poly (hydroxystyrene-co-ethylene cyclohexanol), as shown by the chemical formula: (Read the Behind-the-scenes ¾ refill this page)

.-IIP

419615 V. Description of the invention (5 A7 B7

Wherein R can be Cl-4, base, CH3COCH2CH2- (the base, and y is any number between 0 and ^, and n >!, Preferably n is greater than 20, with 2 〇 > η > ι〇〇 is the best. The preferred cross-linking agent of the composition of the present invention is Gan Shef, its general chemical formula is a group, hydroxyalkyl, ethoxyalkyl

R 'FV

〇 A

.R -R2 R.

X Ν, ί'Ι Central Ministry of Economic Affairs standard for poverty alleviation, which is printed by Rif, where R is a oxy group, preferably CH2Och: an alkyl group having 1 to 6 carbon atoms, an example is U)- Methoxymethyl-3a, 6a-diethylglycoluril is 1oxymethyl-3a 'methyl such as; Giganton' and (c) 4-methoxymethyl-3a_methyl. It is shown that butyl glycoluril, if the following chemical formula 坼 and R | and R_2 can be selected respectively 8- wood paper standard applicable to the National Standard (CNS) (210 x291-: ·) ·)-f Please read first (Note on the back-fill in this page again)

4 19615, A 7 B7 V. Description of the invention (60 〇, CH3CH2-

N .'N -ch2ch3

N. Ya 〇 (a) person ν ’eh person — (— (CH2) 2CH3 ch3 r / Ν '' Ν '

.R (CH2) 3CH3, R c, please read the note on the back before filling out this page) i " 〇 (b) 〇⑹ * π in the Ministry of Economic Affairs 挲 扃 printed by staff consumer cooperatives] and R 〖Can also be selected from ytyl and aryl or qi and aryl, such as (d) methylmethoxymethyl-3a-phenylglycourea, and (e) methylmethylmethoxy-3a-methyl -6a-phenylglycol urea, as shown in the following chemical formula ...

R and N IT ~ (-C6H5 / γ% 〇⑹

'M f \ T ch3- c6h5 〇 (e) -9- The paper scale is applicable to the Chinese National Standard (CNS) Λ4Μί 格 (210x297 * i? · ^ 1 9 61 5 A7 B7 Five' Description of the invention (1 ^ and ruler 2 can be aryl groups such as phenyl, difurfuryl, or alkylphenyl, and halogenated aryl groups or substituted diphenyl ether groups, as illustrated by the following chemical formulas (f) to (h): 〇ch3och2 'Ν 'CH3OCH2 /, Ν- 〇.CH ^ OCHg t'Bu 、 CH2〇CH3 (f) 〇 (Please read the precautions on the back before filling in {: ii 本 石; 〇

, 1T CH3〇CH2 ^

NT 'N' xh2〇ch3 CH3〇CH2 ^ n ^ n.CH2OCH3 CH3 ~ (〇) ~~) ~ CH3 CH3〇CH, ~ Ah N'ChbOCHs o -Ό. +. (N ^ 0 ^ 〇

F

F (g) Anyway: Ministry of AiT ^ i; Jh Industry and Consumers " 卬 4 · '; ϊ: (h) The composition of the present invention preferably also includes a photoacid generator (referred to as PAG), which may be selected from the phosphonium salts of Group IV elements, such as those disclosed in US Patent No. 4,175,972, which is incorporated herein by reference, and the aromatic phosphonium salts of Group 5a elements In the US patent incorporated by reference -10-this paper if, size of the national valve standard (CNS) A4 (210X297 mm) 419615 A7 B7 V. Description of the invention (8) No doubt disclosed in No. 4, 〇69, 〇55. Aromatic sixth & group phosphonium salts include those represented by the following formulas: [⑻a (Rl) b (R2) cx] d + [MQe]-(ef) where R is a monovalent aromatic organic radical and r1 is A monovalent organic radical selected from the group consisting of alkyl 'cycloalkyl and substituted dry radicals. R2 is a polyvalent organic radical forming a hetero5 or a ring-melting structure, and X is a sixth & Group elements or metalloids' Q series—halogen radicals, a is an integer including 0 to 3, b is an integer including 0 to 2, and c is an integer equal to 0 or 1. The radicals included in 11 are aromatic hydrocarbon radicals such as (C6-C), such as phenol, tolyl, xylyl, fluorenyl, anthracenyl, and via! To 4 ~ For example, C0-s) alkyl, C (1-s) alkoxy, nitro, gas group, fluoro group and radicals substituted by monofluorene radicals; Aromatic heterocyclic radicals such as pyridyl and furyl: R1 radicals include Cd-8) alkyl groups, such as -c2h4och3 '-CH2-COCH3 and the like, substituted amido groups; R2 radicals Including the following structure: (Please read the notes on the back before filling in this f) D, y- °

^ 'M · " 十 Α "ί;) ,, η1_; ή " 合 竹. ^-印 1! Ί From the above formulae MQe- (BF4 ·, PF6 ·, SbF6-, FeCI4. GaCl4_, InF4 · Etc. The compound anion system included in the above-mentioned chemical formula 6_f)-for example, 'SnCl6 ·, SbCl6 ·, BiCl5', A1F6 · 3, family phosphonium salt systems, such as -11-this k Zhang m m Which The material (CNS) is as specified (2IGx: 297 cm)

X

N-〇-s〇

V 961 5

Non-metallic radiation-degradable acid generators suitable for use in the composition of the present invention are N-continuyloxyphosphonium imines in the following form:

2 ~~ R where r is selected from toluene, benzyl, CF3, CF2CF3, _ (CF2) nmn to 4 and z is hydrogen or aryl or aryl, and wherein hydrazone is formed with or without heteroatoms The material ring, or fluorene, forms a fused aromatic ring, or ⑶ is hydrogen, fluorenyl, or aryl, respectively, and Cw2 can form a 12-paper & ruler / JlM using 中 围 囡 家 # 准 （CNS） 210X297 ^ 7 ^-(Please read the notes on the back before copying this page)

419615 Α7 Β7 5. Description of the invention (ΊΟ) Single or double bond. The composition of the present invention may also contain a small amount of a basic compound selected from organic amines, especially a tertiary amine. The composition of the present invention is preferably a solvent or a solvent system e to carry the solvents or solvents used for these compositions. The system is preferably to meet the need to provide a uniform coating on the substrate that is completely shielded with photoresist components. This solvent is preferably one which does not affect the photoactivation of the photoresist during the drying step, and does not evaporate at a temperature at which the photoresist operation (without reaction with the resin and / or the crosslinking agent) is added. Typical of these solvents are propyleneglycol monomethyl ether acetate (PGMEA for short), ethyl-3-ethoxypropionate (EEP), methoxypropanol, and ethoxylate. Propanol, butoxypropanol, and ethyl lactate. ill / f ·: Ministry Zhong Rong K.iv-XJm_T.l.i / I Yu Heyue ;;. 卬 S-; (Please read the ji meaning on the back 呗 5 >?

、 ST for forming a negative modulation image is applying the composition of the present invention (for example, by rotating coating) on a substrate, and heating the substrate at a temperature of about 70 to 130 degrees Celsius by a heating plate 1 To 3 minutes to evaporate the residual solvent. This film is then imagewise exposed to UV radiation having a wavelength of 20 to 37 nm to degrade the radiation-degradable components in the composition and form a catalytic amount of acid. The crosslinking reaction between the phenol resin and the crosslinking agent is accelerated by heating the substrate at 70 to 130 degrees Celsius, preferably for 1 to 3 minutes. This will make the image less soluble or insoluble in aqueous alkali and in the development stage, the unexposed areas can be removed by aqueous alkali such as tetramethylammonium hydroxide (TMAH) diluted solution. In another specific embodiment of the present invention, the glycoluril-13- paper used as a cross-linking agent mi: the standard (CNS) Λ4 size (210X297) while the ~ ~ --- 41 9 B1 〇A7 B7 V. Description of the invention (11 Derivatives are synthesized from the corresponding dicarbonyl compounds shown in the following path: * CO (f ^ b) 2 〇 * Ηζ〇〇

HD

Human Ch ^ OH R 'R-

-B κ ^ γ% 0 HD O o

(Please read the ": i" on the back before filling in "i: s" on this page.) '11 The glycoluril derivatives of the present invention are highly selected from the organic compounds selected. Compared with unsubstituted glycoluril, it will be lower. The dissolution rate of the final composition was apparent. The general procedure for replacing the light-weight group with the light-weight group is as follows: ^ The synthesis of the light-emitting group with the light-emitting group is illustrated by the synthesis of 3a-methyl such as propyl group as described below. Add 2,3-dioxane (1.0 mole) and urea (3.0 mole) to 20 liters of 2% gas acid, and stir the solution at room temperature for 24 hours (or, Reflux for 2-3 hours). The precipitate was "washed with water and then ethanol and then dried. This off-white powder was crystallized in acetic acid to complete the analytically pure title compound at a 45% yield. 14- This paper is suitable for Shizhou Zhongyuan® Home Standard 萆 (CNS) Μ specifications (2! 0 · χ 297 male I) 419615 A7 B7 ί: ΐ: 才 — 部 欠-Tm T. Consumer cooperation printing 5. Description of the invention (12 'silk aryl substituted for the general Cheng Wei will apply the appropriate diphenylethylenedione derivative (path 1, feet, and 112 are aryl or a combination of alkyl and aryl) (10 mole) and urea (03 mole). 0 ml of toluene was suspended 'and 50 ml of trifluoroacetic acid was added. The resulting solution was refluxed for 8 hours' during which the water was removed via a Dean-Stark trap. This solution was removed Cool down at room temperature, leave the deposited crystalline material, rinse with toluene ', then hexane, and dry. _ Glycolurium Hydrogen Membrane i Suspend glycoluril in a 37% aqueous formic acid solution (05 mol). Derivatives (〇. 〖Mole) 'and the pH was adjusted to 10 to 11 by adding 10% sodium hydroxide. The resulting mixture was mixed The contents were heated at 50 degrees Celsius for 24 hours to dissolve all the solids in the solution. This solution was cooled to room temperature and the permanent parts were removed under reduced pressure. Residues (either solids or sticky materials) It will be used in the next step without further purification. The acidification of the wind-based plastic compound will convert the methylol glycoluril into its corresponding tetramethoxymethyl derivative, which is borrowed from too much 2 Suspended in 2,2-dimethoxypropane, and then added a few drops of concentrated hydrogen acid, and the mixture was stirred at room temperature for 24 hours. The solvent was removed under reduced pressure, and the residue was not crystallized with a suitable solvent (Such as in the case of -aryl or aryl aryl substituted for Ganmai) 'is the distillation of the oily residue (such as in methylpropyl or methylbutane and other conditions) at high altitude and two temperatures to The desired methoxymethyl derivative of glycoluril is produced. The following examples describe in detail the preparation method and the use of the process of the present invention. The detailed preparation is within the scope of the more general detailed method described above and -15- Paper Scale (CNS) (2I0x " 29T ^ ~) '' '~~~ ---- (锖 Please read the notes on the back before filling out this page) Order Printed by the Ministry of Economic Affairs, Bureau of Standardization, Shellfisher Consumer Cooperative

The second reward example is only for the purpose of illustration, and the patent of 13 9 615 No. 87U2044_ petition for the amendment to the Chinese specification (June 88) 5. The description of the invention (for the purpose of illustration.丨 服 # ^ It is not intended to limit the scope of the present invention. Example I 'and (4-hydroxystyrene_co_vinylcyclohexanol) (wherein hydroxyphenylethylene to ethylene 5 Mohs ratio of ethylene 9: 1) (10 g) and > Methyl. 6a_, methyl-methyl-methoxymethyl glycoluril (10 g), and (trifluoromethylsulfonyloxy) all [2_2 .1] Hepta-5_ene_2,3_dicarboximide octa [00 mg] was dissolved in 50 ¾ liters of propylene glycol monoethyl ether acetate (pGMEA). Filtered by a micron filter and spin-coated on a substrate. After baking at 110 ° C for 1 minute, '248 μm UV at approximately 20 mJ / cm², using a step of 0 να I-line Enter and repeat the tool for exposure. After hard roasting at 11 ° C to minutes, develop the photoresist at 026 aqueous tetramethylphosphonium ammonium oxide. Therefore, a well-defined high-resolution image of 220 nm lines is formed. Like (Figure 丨) d Example II. Poly (4-hydroxystyrene) (10 g) and 4-tetramethoxymethyl-3 du, 6 & -bis- [4- (4-third -Butylphenoxy) phenyl] glycol urea (45 g) and methoxymethylglycol urea (Powderini) (0.8 g) and MDT (1.20 g) were dissolved in 50 ml PGMEA. This solution was spin-coated on a silicon wafer to form a dry thickness of 0.5 micron, and was exposed through a photomask with about 20 millijoules per square centimeter of ultraviolet light at 248 nanometers. Then the substrate was exposed. Bake at 110 ° C for one minute, then develop in 0 26 N aqueous tetramethylammonium hydroxide solution and rinse with water. A high-resolution image with a maximum of 0.22 microns is formed, as shown in the SEM photograph (Figure 2). Example III. Dissolve poly (4-hydroxystyrene) (0 g), methyl-methoxymethyl-3a-methyl-6a-butylglycol urea (1.1 g), and MDT (1.20 g) in 50 ml -16- This paper size applies to China National Standard (CNS) A4 specification (210 × 297 mm) --------- 1 ------ IT ------ ii. (Please (Please read the notes on the back before filling out this page) 61 5 A7 B7 V. Invention (14) in PGMEA and filtered through a 0.2 micron filter. The resulting solution was spin-coated on a silicon wafer to form a dry thickness of about 0.6 micron. This wafer was at 95 ° C Bake to remove excess solvent and expose it with approximately 20 耄 Joules / cm 248 nm UV using a step and repeat tool of 0.28. After exposure, it was baked at 95 ° C for 1 minute, and then developed in a 0.14 N aqueous tetramethylammonium hydroxide solution. Form a high-resolution image of 200 nm (Figure '(read the precautions on the back before filling in this education) 4 \ If. Nishi f: Aίι ίΐ- 印 -17- standard of this paper 迠 川 屮 家 标彳 (rNS grid (2l0x 297 mm)

Claims (1)

4 1 9 61 5 Supplementary Chinese Patent No. 8Ή12044 (5 1989, Preparation Example 1-foxymethyl-3a-formamidine (methyl_benzium powfWT; 1-benzene synthesized in η -I, 2.propanedione (1000 g) was added dropwise to a solution of urea (0.0 g of 2% hydrogen acid in hydrogen) solution which was mechanically disturbed. After the addition was completed, the solution was Stir for 24 hours at room temperature. Filter the precipitate, wash with plenty of water, and then dry again. Suspend the product in 1_0 liters of 4: 1 water-acetic acid, heat gently to boiling, and stir at this temperature The solution was cooled to room temperature for one hour, the solid was filtered, washed with deionized water and then with methanol, and dried in a vacuum oven at 50 ° C. overnight to obtain 92.0 g of fluorenyl-phenylglandular white powder. A three-necked flask equipped with a mechanical stirrer's condenser and a powder funnel was fed with 400 liters of a 37% aqueous solution of formaldehyde and heated to 40.0 in a water bath. 40 g of 25% tetramethyl was added Ammonium hydroxide (TMAH) was adjusted to a pH of about 90, and 90.0 g of the above glycoluril product was added in portions. The mixture is allowed to stir at this temperature. After half an hour ', add an additional 2.0 grams of 25% TMAH and continue stirring at 40-45DC for 3 hours (after one hour, all solids become a solution). The solution is cooled and suspended at 55 ° C. Remove the water from the heat transfer device (remove about 80% of the water). Dissolve the remaining viscous material in 150.0 ml of methanol and maintain it at room temperature overnight. Filter and isolate the white crystalline compound with cold methanol (5 (0 ml) was washed and dried to obtain 780 g of the tetrahydroxyfluorenyl derivative. A second batch of 14.0 g was recovered from the mother liquor, with a total recovered amount of 920 g, melting point = 72-75 t. -Hydroxymethyl-3a- Methyl-6a-phenylglycol urea (90 g) was suspended in a mixture of 150 ml of anhydrous 419615 methanol and 150 ml of 2,2-dimethoxypropane. One ml of concentrated hydrochloric acid was added, and the mixture was stirred at room temperature. After one hour, all solids were dissolved in the solution. The solution was maintained at room temperature overnight and the isolated white crystalline compound was filtered and washed with cold methanol and dried to obtain 69 g of the final product (methyl_ Phenyl powcjerLink). From the mother liquid, separated from the second batch of 17.0 G, total recovery is .0 g of methyl-phenyl PowderLmk, melting point = 133- 〖36 ° C. Pure sample was obtained from methanol recrystallization (30.35% solids), melting point = 135-137 ° C. Elemental analysis: % C% H% N Calculated value for C16H30N4O6: 55.88 6.86 13.72 Found: 55.68 6.88 13.75 Proton (1H) NMR spectrum: (CDC13, delta ppm): 0.95 (t 3H7, 1, j / 3Η), 1.25 (m , 2H), 1.69 (s, 3H), 2.05 (t, j = 8Hz, 2H), 3.25 (s 6H) ^ 9 «{< " ,, n,, ⑽λ j.28 (s, 6H), 4.8 (s, 4H), 4,78 (q, j = 11Hz, 4H). Preparation Example 2 A 3-liter three-necked flask equipped with a mechanical beaker and a dropping funnel was used to prepare wounds of methylphenidylmethyl, and 10 liters of deionized water, 25 ml of concentrated hydrochloric acid, and Coke_Mole were fed. ) Urea. Na mixture until the urea forms a solution, and here, the solution is stirred, and irg gram mole is added dropwise) • 2-419615, 2,3-hexane-burned dipyrene 'for 30 minutes. After adding the excess, the mixture was further stirred at room temperature for 5.0 hours. The precipitate was filtered, washed with two liters of deionized water, then washed with two 500 ml portions of acetone, and then dried in the air. The white powder was suspended in 900 ml. 2: 1 acetic acid and water, stir and heat to 85-90t for half an hour at the same time, the mixture is cooled to room temperature, and maintained at room temperature for two hours 'filter the mixture' with one liter of deionized water and then with one It was washed with 1 liter of copper and dried in a vacuum oven at 50 ° C. overnight to obtain a white crystalline powder (white point, measured by DSC) (91 g; yield 46%). In a two-liter flask equipped with a mechanical stirrer and a thermometer, put 400.0 ml of a 37% aqueous formaldehyde solution and 300 ml of methanol, and heat gently to 40 t, at this temperature * by adding 10% Tetramethyl was adjusted to a pH of 9-9.5 'with an aqueous hydroxide solution (DMAA, 5.0 ml), and then the above product (90 g in total) was divided into several portions and added with stirring. After raising the temperature to 50 ° C, the pH was adjusted to 9.5 by adding TMAH. The reaction mixture was stirred at this temperature for another hour (after 30 minutes, all solids formed a solution) 'slowly cooled to room temperature, and dilute hydrochloric acid was added to adjust the pH to 7.5. The solvent was evaporated on a reduced pressure rotary evaporator at 55 C or lower, and the oily residue was pumped under high vacuum (0-2 mm Hg) to remove most of the water. To this glassy compound, 0 ml of anhydrous methanol and 500 ml of dimethoxypropane were added, then 3,0 ml of concentrated hydrochloric acid was added, and the mixture was stirred at room temperature overnight. The pH was raised to 6-7 by adding 25% TMAH, and the solvent was removed on a reduced pressure rotary evaporator. Then add 450.0 liters of 2.1 methyl sulfonium dibutyl with hexane, and heat the mixture with • 3- 4 1 S 61 5 to reflux until everything is dissolved (a small amount of tetramethylammonium gaseous salt is still floating on Solution). The reflux was continued for 15 minutes, filtered through filter paper, and the solution was cooled to room temperature and maintained at room temperature overnight. The crystalline material was separated by filtration, washed with cold methyl tert-butyl ether (50 ml portions), and dried to obtain 92.0 g of a methyl-propyl compound. The second batch of product can be isolated from the filtrate to obtain a total of 114 g of product. Although the purity of this material (melting point = 90 ° C, measured by Dsc) is sufficient, it can still be recrystallized from methyl 2: butyl methyl ether · hexane (25% solids) at 2: 1. Pure compounds for analysis. Elemental analysis:% C% H% N Calculated value for C19H28N406: 51.47 8.07 14.97 Found: 51.22 8.39 14.89 Proton (1H) NMR spectrum: (CDC13, delta ppm);] 05 (c Sichuan, Ί ^ is, iH), 3.3 (s, 6H), 3.35 (s, 6H), 4.7 (dd, 1.6Hz), and 7.3 (m, 5H). 19615, 1 No. 87112044 Chinese Patent Application and Patent Application Scope Revision (89: ~-^-\ A8-Month) Zhen-VI-Patent Application-)-1-A method of forming a photoresist pattern, It comprises: forming an unhardened film on a substrate, the film system comprising 90% by weight of soil and 60% by weight of an acid resin or polymer, 5% to 20% by weight of a glycoluril derivative, and 2 % To 20% by weight of the photoacid generator, ° Because it is coated with a solution of the phenolic resin or polymer, the gall bile derivative and the photoacid generator, the solution is in an organic solvent ' And evaporating the solvent from the generated coating; exposing the film in a pattern with ultraviolet imaging having a wavelength of 250 to 370 nm, so that the pattern causes the generation of an acid catalyst; and exposing the exposed film to Celsius Bake at 90 to 130 ° C for 1 to 2 minutes; and develop the photoresist in an aqueous alkaline solution; wherein the phenolic resin is a poly (hydroxybenzylacetamidine), and the Copolymer, as shown in the following chemical formula: f Please read the Precautions to fill out this page) The Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs printed 1 of them, and 0 ^ X ^ 1, some of the protected poly (hydroxybenzyl ethylene), as shown in the following chemical formulas. The translation standards on this paper apply Chinese National Standard (CMS) A4 specifications (210X297 Mm) 4 13 615 A8 B8 C8 D8 Patent Application Scope Where X is a number from 0.5 to 1.0, wherein R is an organic radical, or a phenol-formaldehyde (phenol novolac) resin; wherein the glycoluril derivative has the following general formula CK, o H ^ OCHa c ^ och / ^ n \ ^ n'n > ^ oc ^ C 1 ο (Please read the notes on the back before filling in the unpaged pages) / λ Printed by the Ministry of Economic Affairs and the Bureau ’s Consumer Cooperatives Among them, h and R2 can be selected from alkyl, alkenyl, alkoxy, aryl, phenyl, furyl, 4-phenyl, alkylaryl, tolyl, tolyl, and 1 to 6 carbons, respectively. Group, 2,4,6-trimethylphenyl group, CnH2n + lC6H4 ·, where n may be 3 to 6, aryl, diphenyl ether, and diphenylsulfide; and the photoacid generator has the following structure: Sulfonate: -2- This paper size applies to China National Standards (CNS), 8 and 4 cases (210 × 297 mm) Λ 19615 Scope of application for patents, printed by employees of the Shenyang Standards Bureau of the Ministry of Economic Affairs, Consumers Cooperatives, where R is selected from toluene, benzene, CP, ^,, CF2CF3 'and (CF2) nZ (where n * ~ l to 4, Z is Z or Xuanji 丄 rentu 4 is not a group), and X and Y may be fluorene, alkyl, or aryl, m soil, Banyi &, or may contain heteroatoms I or more Ring, or form a condensed aroma, ^ licorice or osmic acid generators are selected! Bursting salt. 2. According to the method of item 1 of the scope of patent application, ', Zhongyou Photoacid Generator is a tweezer salt selected from Group IV elements. According to the method of "Patent No. 丨", wherein the disproportionating agent is selected from a sulfonium salt of a group sa element. 4. The method according to item 丨 of the patent application scope, wherein the unhardened film additionally contains 0.02% to 0.5% organic base. 5 .: A photo-crosslinkable water-based testable negative light-limiting composition, which is a solution type and contains the following components in an organic solvent: 40% to 80% by weight of a phenolic resin or polymer, 5 weight. /. to. % By weight of a glycoluril derivative, and 2% by weight to 20% by weight of a photoacid generator; wherein the phenolic resin is a poly (4-hydroxyphenylethylfluorene), a copolymer of hydroxybenzylethylene and hydroxycyclohexylethynyl , As shown in the following chemical formula: -3 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) Order trI. Δ 6 9 n 5 ABCD VI. Patent application scope where η > 1 And OSXS 1, partially protected poly (hydroxystyrene), as shown in the following chemical formula: The Consumer Cooperatives of the China Standards Bureau of the Ministry of Economic Affairs printed X where the number is 0.5 to 1.0, where R is an organic radical, or a phenol-formaldehyde (phenol novolac) resin; and the general chemical formula of the glycoluril derivative is: 〇 t R1 ~)-^ R2CH3〇CH / NYN, OCh3〇π wherein R, and and 2 may be selected from the group consisting of alkyl, alkenyl, alkoxy, aryl, and benzene, each having 1 to 6 carbons. -"Furanyl, phen · yl ... fluorenylaryl, tolyl, tolylmethyl, 2,4,6-tritolyl, CnH2n + lC6H, 'where n can be 3 to 6, halogenated aromatic Diphenyl ether, diphenyl ether, and diphenyl sulfide; and -4- (Please read the notes on the back before filling this page) This paper size is applicable to China Garden Standard (CNS) A4 (210X 297 mm) 4 1 9 61 5 B8 C8 D8 6. Scope of patent application Where the photoacid generator is a sulfonate with the following structure: Wherein R is selected from the group consisting of toluene, benzene, CF3, CF2CF3, and (CF2) nZ (where η = 1 to 4, Z is fluorene or alkyl or aryl), and X and Y may be Η, Alkyl, or aryl, or form a polycyclic ring that may or may not contain heteroatoms, or form a fused aromatic ring, or the acid generator is selected from Ionium salts. 6. The composition according to item 5 of the application, wherein the photoacid generator is a phosphonium salt selected from Group IV elements. 7. The composition according to item 5 of the scope of patent application, wherein the photoacid generator is a tweezer salt selected from Group 6a elements. 8. The composition according to item 5 of the patent application scope, further comprising 0.01% to 0.5% of an organic base. (Please read the notes on the back before filling this page) Order Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs -5- This paper size applies to the Chinese National Standard (CNS)