CN114957575A - Modified phenolic resin, preparation method thereof and positive photoresist - Google Patents

Modified phenolic resin, preparation method thereof and positive photoresist Download PDF

Info

Publication number
CN114957575A
CN114957575A CN202210425589.4A CN202210425589A CN114957575A CN 114957575 A CN114957575 A CN 114957575A CN 202210425589 A CN202210425589 A CN 202210425589A CN 114957575 A CN114957575 A CN 114957575A
Authority
CN
China
Prior art keywords
phenolic resin
tert
modified phenolic
mixture
photoresist
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210425589.4A
Other languages
Chinese (zh)
Inventor
不公告发明人
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Jizi Technology Co ltd
Original Assignee
Shanghai Jizi Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Jizi Technology Co ltd filed Critical Shanghai Jizi Technology Co ltd
Priority to CN202210425589.4A priority Critical patent/CN114957575A/en
Publication of CN114957575A publication Critical patent/CN114957575A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/008—Azides
    • G03F7/0085—Azides characterised by the non-macromolecular additives
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

The present disclosure relates to a modified phenolic resin obtained by reacting formaldehyde and biphenol in the presence of a catalyst to obtain a phenolic resin; and converting the hydroxyl groups in the phenolic resin into groups that can be cleaved by an acid. The disclosure also relates to positive photoresist prepared from the modified phenolic resin.

Description

Modified phenolic resin, preparation method thereof and positive photoresist
Technical Field
The disclosure relates to the technical field of polymers, in particular to a modified phenolic resin, a preparation method thereof and a positive photoresist prepared from the modified phenolic resin.
Background
1930s later, chemists of Kalle of Germany began to use diazonaphthoquinone to make printing materials. In order to improve the film forming property of the material, they added phenolic resin to prepare an o-diazonaphthoquinone sulfonate-phenolic resin printing material (PAC/Novolac) with the trade name Ozatec and marketed in about 1950, at which time Kalle company has become a subsidiary of Hoechst AG and Azoplate, another US subsidiary, is responsible for Ozatec sales in the United states. Bell laboratories, in one unexpected attempt, found that diazonaphthoquinone-phenolic resins had excellent etch resistance, thereby opening up the large-scale application of orthodiazonaphthoquinone sulfonate-phenolic resin photoresist systems in the semiconductor industry.
In order to further improve the resolution of phenolic photoresists, researchers developed a 248nm (krf) positive chemical amplification system using deep ultraviolet as a light source, which mainly uses p-hydroxystyrene Polymer (PHS) as a resin main body, phenolic hydroxyl of the resin uses tert-butoxy (t-BOC) as a protective group, and photoacid generator (PAG) as a photoactive component, PAG is decomposed to generate acid under the action of ultraviolet light, and under the further action of medium baking temperature (PEB), the pendant protective group t-BOC on the side chain of the acid-catalyzed polymer is decomposed into CO2 and tert-butyl cation, and the tert-butyl cation continues to undergo beta-proton elimination reaction to produce gas isobutylene. The acid is not consumed in the reaction, and the catalytic deprotection reaction can be continued. The dephosphatation reaction converts the lipophilic polymer into a hydrophilic polymer, which is dissolved in an alkaline aqueous solution for development. The resolution limit of positive chemical amplification type photoresist with PHS resin as the main body is reduced to 0.18 um.
The photoresist of the two systems is developed by adopting an alkaline aqueous solution, is environment-friendly and convenient, and has large-scale application in the fields of IC, storage and display. However, the synthesis of phenolic resins is not easy to control, the molecular weight distribution is wide, the branching degree is high, and the proportion of linear parts is difficult to guarantee. Researchers design tubular reactors; improving the catalyst; the Novolac type phenolic resin has a high linear structure by adopting metal salt or enzyme as a catalyst, and has good etching resistance when used as a photoresist.
Higher sensitivity, resolution and better etching resistance have become the industry's requirement for phenolic resin-based positive photoresists, and thus more and more photoresist companies are continuously working on the synthesis of phenolic resins and the improvement of phenolic photoresist formulations, wherein the megahead company is represented by merck chemistry. Most of reported patents in the industry mainly adopt improved formulas, and some patents start from novel phenolic resin structures, and patents CN201980057768.3, CN110582727A and CN201980034950.7 respectively report the synthesis of phenolic resins with highly linear structures, the improvement of resin structures and the improvement of formulas, but the synthesis of phenolic resins reported in the above patents is relatively complex, which can greatly improve the difficulty of industrial mass production, and make the manufacturing steps of the photoresist more complex, and is not suitable for the technical route of the new photoresist enterprises.
Therefore, there is a need to develop a new positive photoresist to obtain a positive chemically amplified photoresist, which can be applied in the field of Integrated Circuits (ICs), Organic Light Emitting Diode (OLED) devices, and especially OLED arrays.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present disclosure provides a modified phenolic resin having a chemical structure of formula I below:
Figure BDA0003609471230000031
wherein X is more than or equal to 0 and less than or equal to 1, Y is more than or equal to 0 and less than or equal to 1, Z is more than or equal to 0 and less than or equal to 1, and X + Y + Z is equal to 1; n is 5. ltoreq. n.ltoreq.300, preferably 5. ltoreq. n.ltoreq.200; substituent R 1 、R 2 、R 3 、R 4 、R 5 、R 6 Each independently is a tert-hydroxy group or a butoxyacyloxy group or a tert-butoxy group, but not simultaneously a hydroxy group.
In a preferred embodiment, the substituent R 1 、R 2 、R 3 、R 4 、R 5 、R 6 In (b), the number of hydroxyl groups is 5% to 70%, preferably 5% to 50%.
In a preferred embodiment, wherein X ═ 1, Y ═ 0, Z ═ 0; or X ═ 0, Y ═ 1, Z ═ 0; or X ═ 0, Y ═ 0, and Z ═ 1.
A second aspect of the present disclosure provides a process for preparing a modified phenolic resin comprising:
a) reacting formaldehyde and biphenol in the presence of a catalyst to obtain a phenolic resin;
wherein the diphenol is selected from one or more of the following groups: 5,5 ' -dimethyl-2, 2 ' -biphenol, 2,6,2 ', 6 ' -tetramethyl-3, 3 ' -biphenol and 3,3 ' -dimethyl-4, 4 ' -biphenol; and
b) converting hydroxyl groups in the phenolic resin into groups that can be cleaved by an acid to obtain the modified phenolic resin.
In a preferred embodiment, the acid-cleavable group in step b) is a tert-butoxyacyloxy group and/or a tert-butoxy group.
In a preferred embodiment, 30% to 95% of the hydroxyl groups in the phenolic resin are converted to acid cleavable groups, preferably 50% to 95%.
In a preferred embodiment, said step b) comprises reacting di-tert-butyl dicarbonate and/or tert-butyl bromide with hydroxyl groups in the phenolic resin obtained in said step a) to obtain said modified phenolic resin.
In a preferred embodiment, the molar ratio of the di-tert-butyl dicarbonate and/or the tert-butyl bromide to the hydroxyl groups in the phenolic resin obtained in step a) is (0.3 to 0.95): 1, preferably (0.5 to 0.95): 1.
a third aspect of the present disclosure provides a positive photoresist comprising:
100 parts by weight of a solvent;
5 to 150 parts by weight, preferably 5 to 100 parts by weight, of a modified phenolic resin as described in the above first aspect or a modified phenolic resin prepared by a process as described in the above second aspect; and
0.05 to 90 parts by weight, preferably 0.5 to 45 parts by weight, of an acid generator.
In a preferred embodiment, the use of a modified phenolic resin as described in the above first aspect or a modified phenolic resin prepared by a process as described in the above second aspect for the preparation of a positive photoresist.
The invention has the beneficial effects that:
firstly, a biphenyl diphenol monomer with a novel structure and formaldehyde are used as reaction raw materials and condensed under the catalytic action of oxalic acid to obtain novel phenolic resin with a high linear structure; secondly, the protection group of the 248nm photoresist resin PHS, namely t-BOC or tert-butoxy, is connected to the phenolic hydroxyl group of the phenolic resin through chemical reaction by superposing and combining the photosensitive principle of the 248nm chemical amplification type photoresist to obtain the phenolic resin main body related to the invention. The resin main body is matched with a photoacid generator (PAG) and photoactive o-azido naphthoquinone sulfonate (PAC), the cracking reaction of photoacid-catalyzed tert-butoxy acyloxy (t-BOC) or tert-butoxy can also occur under the action of 365nm illumination, and the heating process of intermediate baking (PEB) after exposure can lead the catalyst of the reaction to be photo-acid proliferated, thereby being a chain reaction with extremely high reaction efficiency, so the 248nm (KrF) photoresist is also called as a chemical amplification type photoresist. The chain reaction not only greatly improves the sensitivity of the phenolic resin photoresist, but also greatly improves the resolution of the photoresist, so the phenolic resin positive photoresist can be applied to the field of Integrated Circuits (IC) and Organic Light Emitting Diodes (OLED) devices, in particular to the manufacture of OLED arrays.
Drawings
FIG. 1 is an infrared spectrum of a modified phenol resin according to one to eight examples of the present invention.
FIG. 2 is a photoresist pattern of a positive photoresist according to a first embodiment of the invention.
Fig. 3 is a photoresist pattern of a positive photoresist according to a second embodiment of the invention.
FIG. 4 is a photoresist pattern of a positive photoresist of example three of the present invention.
FIG. 5 is a photoresist pattern of a positive photoresist of example four of the present invention.
Fig. 6 a photoresist pattern of a positive photoresist of example five of the present invention.
Figure 7 is a photoresist pattern of a positive photoresist of example six of the present invention.
Fig. 8 is a photolithography pattern of a positive photoresist according to a seventh embodiment of the present invention.
Fig. 9 a photoresist pattern of a positive photoresist of example eight of the present invention.
Detailed Description
Embodiments of the present application will be described in more detail below. However, it should be understood that the present application may be embodied in various forms and should not be construed as limited to the embodiments set forth herein, but rather these embodiments are provided for a more thorough and complete understanding of the present application. It should also be understood that the drawings and embodiments of the present application are for illustration purposes only and are not intended to limit the scope of the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. In case of conflict, the present specification, including definitions, will control.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range defined by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4," "1 to 3," "1-2 and 4-5," "1-3 and 5," and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In addition, the indefinite articles "a" and "an" preceding an element or component herein are used without limitation to the number requirement (i.e., the number of occurrences) of the element or component.
In order to realize the technical route, the invention adopts the following three structures of diphenols (5,5 ' -dimethyl-2, 2 ' -diphenol, 2,6,2 ', 6 ' -tetramethyl-3, 3 ' -diphenol and 3,3 ' -dimethyl-4, 4 ' -diphenol) which are prepared by condensing formaldehyde and any one, two or three diphenols in an acidic environment with oxalic acid as a catalyst. The specific method comprises the following steps:
the first step is as follows: synthesis of unprotected phenolic hydroxyl phenolic resin: the method comprises the steps of dissolving the diphenol in methanol, putting the diphenol into a three-mouth bottle with a mechanical stirring, temperature control thermocouple and a PH meter, then putting aqueous solution of formaldehyde with the concentration of 37% and the mole number of the formaldehyde of 90-98% of the molar number of the diphenol, heating and refluxing, then adding aqueous solution of oxalic acid dihydrate with the total mass of 3-10% of the mass of the diphenol, controlling the PH value of a system to be 6-6.8, carrying out condensation polymerization for 3-5 hours to obtain viscous linear phenolic resin, soaking and washing with high-purity water, drying and pulverizing, and using for the next reaction. The phenolic resin obtained by adopting the condensation method of the invention has a highly linear structure.
The second step is that: synthesis of phenolic resin for protecting phenolic hydroxyl group:
protection with tert-butoxy (t-BOC): continuously dissolving the unprotected phenolic resin in a tetrahydrofuran solvent, putting the mixture into a dry nitrogen-protected three-neck flask, then quickly adding potassium tert-butoxide with the same mole number as that of phenolic hydroxyl groups for several times, stirring the mixture for twenty minutes at room temperature, then adding di-tert-butyl dicarbonate into the three-neck flask, wherein the mole number of the di-tert-butyl dicarbonate is 0.5 to 0.95 times of that of the phenolic hydroxyl groups, stirring the mixture strongly at room temperature for 1 to 3 hours, pouring the mixture into ice pure water after the reaction is finished, extracting the mixture with ethyl acetate, adding a drying agent, and drying the mixture to obtain the phenolic resin protected by tert-butoxy groups by evaporation; or
Protection with tert-butoxy: or dissolving unprotected phenolic resin in tetrahydrofuran solvent, putting the mixture into a dry nitrogen-protected three-neck flask, then quickly adding potassium hydroxide with the mole number 1.5-2 times that of phenolic hydroxyl groups for several times, stirring the mixture for twenty minutes at room temperature, heating the mixture to reflux, slowly dripping tert-butyl bromide into the three-neck flask, wherein the mole number of the tert-butyl bromide is 0.5-0.95 times that of the phenolic hydroxyl groups, carrying out reflux reaction for 3-5 hours, pouring the mixture into ice pure water after the reaction is finished, extracting the mixture with ethyl acetate, adding a drying agent, drying the mixture, and evaporating the low-boiling solvent to dryness to obtain the tert-butoxy-protected phenolic resin.
The phenolic resin for the positive photoresist with the structure can be matched with a photoacid generator component (PAG) and a photoactive o-azidonaphthoquinone component (PAC) to prepare a chemical amplification type photoresist, and can be widely applied to the fields of Integrated Circuits (IC) and Organic Light Emitting Diode (OLED) devices, in particular to the manufacture of OLED arrays.
The photoacid generator component (PAG) refers primarily to: chemical substances that generate acids under 365nm or broadband radiation, including iodonium salts, sulfonium salts, imidosulfonate derivatives, dicarboximidosulfonate, oxime sulfonate, diazo (sulfomethyl) compounds, disulfonylmethylenehydrazine compounds, nitrobenzyl sulfonate, bisimidazole compounds, diazomethane derivatives, glyoxime derivatives, β -ketosulfone derivatives, triazine derivatives, and combinations thereof; the acids produced include: hydrogen halides, sulfonic acids, alkylsulfonic acids, arylsulfonic acids, fluoroalkylsulfonic acids, mineral acids HAsF6, HSbF6, HPF6, and combinations thereof. The above photoacid generator (PAG) is preferably selected from the salts of triphenylsulfonium and trifluoromethanesulfonic acid synthesized in Toyo of Japan (TPS-TF), triphenylsulfonium perfluorobutylsulfonate (TPS-PFBS), D (L) -camphor-10-triphenylsulfonium sulfonate (TPS-CS), nonionic N-hydroxyphthalimide p-toluenesulfonate, N-trifluoromethane xanthyloxy-1, 8-naphthylimine (NHNI-TF), TME-triazine of Japan and chemistry, PIW-501((Z) -4-methoxy-N- (toluenesulfonyloxy) iminophenylacetonitrile of Hesley, Germany BASF, Irgacure103, Irgacure121, Irgacure203, Irgacure250, Irgacure290, Irgacure169, the photoacid generator may be used alone or in combination, the content of the photoresist in the phenolic resin is 1 to 50 percent, preferably 3 to 40 percent.
The photoactive ortho-azidonaphthoquinone (PAC) component is: the o-azido naphthoquinone compound connected to the benzene ring carbon skeleton through a sulfonate group can be converted into ketene and further converted into indene acid under the irradiation of ultraviolet light. The PAC of the present invention is preferably a framework structure of 1 to 18, but is not limited to the following structures, and the PACs of these structures may be used alone or in combination. The mass of the photoactive ortho-azidonaphthoquinone (PAC) component in the photoresist is 1% to 50%, preferably 3% to 40%, of the mass of the phenolic resin.
Figure BDA0003609471230000081
Figure BDA0003609471230000091
The components mentioned above, including the novel tert-butoxy acyloxy (t-BOC) or tert-butoxy protected linear modified phenolic resin, the photo-acid generator (PAG) and the photo-active ortho-azidonaphthoquinone (PAC) related to the present invention are dissolved in the solvent uniformly in sequence to prepare the positive chemical amplification type photoresist, under the action of light, the cracking reaction of the tert-butoxy (t-BOC) or tert-butoxy catalyzed by the photo-acid can occur, and the medium baking (PEB) heating process after exposure can lead the catalyst of the reaction to be photo-acid proliferated, so that the sensitivity and resolution of the photoresist are high. Wherein the optional solvents include, but are not limited to, the following solvents, including: ethyl acetate, butyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, methyl ethyl ketone, cyclohexanone, cyclopentanone, ethyl-3-ethoxy propionate, methyl-3-methoxy propionate, methyl acetoacetate, ethyl acetoacetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylacetamide, N-dimethylformamide, gamma-butyrolactone, propylene glycol methyl ether acetate, methyl ethyl propionate, methyl ethyl acetate, methyl ethyl ketone, cyclohexanone, methyl acetoacetate, methyl ethyl propionate, methyl propionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methyl-3-methylbutanol, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide, gamma-butyrolactone, propylene glycol methyl ether acetate, methyl ethyl acetate, methyl acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, methyl lactate, ethyl lactate, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol dimethyl ether, or diethylene glycol dimethyl ether. These solvents may be used alone or in combination of two or more.
The formula for protecting the phenolic resin positive chemical amplification photoresist can also be added with a leveling agent and an acid quenching agent. The leveling agent is not particularly limited, and commercially available ionic and nonionic surfactants can be used. Acid quenchers mainly include amines and quaternary ammonium bases, exemplified by, but not limited to, the following, including: (2- (2-heptadecyl-4, 5-dihydro-1H-imidazol-1-yl) ethan-1-ol), hydroxyethylimidazole (AI), 2-ethylimidazole (2EI), Triphenylamine (TPA), 2- (2-methoxyethoxy) -N, N-bis [2- (2-methoxyethoxy) ethyl ] -ethylamine (MNNE), N-methyldipropylamine, N-methyldiethanolamine (2EI), N, N-diisopropylethylamine, triisobutylamine, Diisopropylaniline (DIPA), and the above quenchers may be used alone or in combination.
The usage steps of the phenolic positive chemical amplification photoresist related by the invention are as follows: firstly, the coating is uniformly coated on a silicon wafer by spin coating, and the coating is baked for 40-200 seconds (pre-baking) within the temperature range of 80-150 ℃; a uniform film with a thickness of 0.5-15 microns is formed. Under the coverage of a specific mask, exposing the coating by radiation with the exposure wavelength of 365-. At this time, the uncovered exposed part of the pattern can be more easily washed away by the alkaline aqueous solution, the alkaline aqueous solution generally used for development is 2.38 wt% of TMAH aqueous solution, and the pattern with better appearance can be obtained by developing for 30-300s under the constant temperature condition of 25 ℃.
Embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While certain embodiments of the present disclosure are shown in the drawings, it is to be understood that the present disclosure may be embodied in various forms and should not be construed as limited to the embodiments set forth herein, but rather are provided for a more thorough and complete understanding of the present disclosure. It should be understood that the drawings and embodiments of the disclosure are for illustration purposes only and are not intended to limit the scope of the disclosure.
The first embodiment is as follows:
synthesis of unprotected phenolic resin: in a 500ml three-necked flask with a mechanical stirring, temperature-controlled thermocouple and pH meter, 4.28g (20mmol) of 5,5 '-dimethyl-2, 2' -biphenol is dissolved in 200ml of methanol, then 1.54g (19mmol) of 37% formaldehyde aqueous solution is added, the mixture is heated to 60 ℃ for reflux, 3.42g of 10% oxalic acid aqueous solution is slowly dropped, the pH value of the system is maintained to be 6.5, condensation reaction is carried out for 3.5 hours, viscous linear phenolic resin is obtained, after the reaction is finished, the reaction is reduced to room temperature, methanol is concentrated, the reaction is repeatedly washed by pure water, dried and pulverized for later use.
Synthesizing phenolic resin (namely modified phenolic resin) protected by tert-butoxy acyloxy: 4.85g of the unprotected phenolic resin is continuously dissolved in 120ml of tetrahydrofuran solvent, the mixture is put into a dry and nitrogen-protected three-neck flask, 4.488g (40mmol) of potassium tert-butoxide (112.2) is rapidly added in several times, the mixture is stirred for twenty minutes at room temperature, 6.104g (28mmol) of 40ml of tetrahydrofuran solution of di-tert-butyl dicarbonate (218) is slowly dropped into the three-neck flask, the mixture is vigorously stirred for 2 hours at room temperature, after the reaction is finished, the mixture is poured into ice pure water, ethyl acetate is used for extraction, a drying agent is added, and the low-boiling solvent is evaporated to dryness to obtain the phenolic resin protected by tert-butoxy group.
After 2g of the above-obtained protected novolak resin was dissolved in 6g of propylene glycol monomethyl ether acetate solvent, 0.4g of acid generator (PAG) Irgacure169 and 0.2g of photoactive o-azidonaphthoquinone (PAC) with carbon number 3 were added and uniformly dissolved, and the resultant was used as a positive chemically amplified resist.
Example two:
synthesis of unprotected phenolic resin: dissolving 4.84g (20mmol) of 2,6,2 ', 6 ' -tetramethyl-3, 3 ' -biphenyl diphenol in 220ml of methanol in a 500ml three-necked bottle with a mechanical stirring, temperature control thermocouple and pH meter, then adding 1.46g (18mmol) of formaldehyde aqueous solution with the concentration of 37%, heating to 60 ℃ for reflux, slowly dropwise adding 4.28g of oxalic acid aqueous solution with the concentration of 10%, maintaining the pH value of the system at 6.8, carrying out condensation reaction for 4 hours to obtain viscous linear phenolic resin, reducing the reaction temperature to room temperature, concentrating the methanol, repeatedly washing with pure water, drying, and pulverizing for later use.
Synthesizing phenolic resin (namely modified phenolic resin) protected by tert-butoxy acyloxy: continuously dissolving 5.38g of the unprotected phenolic resin in 150ml of tetrahydrofuran solvent, putting the mixture into a dry and nitrogen-protected three-neck flask, then rapidly adding 4.488g (40mmol) of potassium tert-butoxide (112.2) in several times, stirring for fifteen minutes at room temperature, slowly dropwise adding 4.36g (20mmol) of 30ml of tetrahydrofuran solution of di-tert-butyl dicarbonate (218) into the three-neck flask, strongly stirring for 1.5 hours at room temperature, pouring the mixture into ice pure water after the reaction is finished, extracting the mixture with ethyl acetate, adding a drying agent, drying, and evaporating the low-boiling solvent to obtain the tert-butoxyacyloxy protected phenolic resin.
After 2g of the obtained protective linear phenolic resin is dissolved in 5g of propylene glycol monomethyl ether acetate solvent, 0.5g of acid generator (PAG) N-trifluoromethane xanthyloxy-1, 8-naphthalimide (NHNI-TF) and 0.5g of photoactive o-azidonaphthoquinone (PAC) with No. 17 carbon skeleton are added, and 0.01g of acid quencher 2-ethylimidazole (2EI) is uniformly dissolved to be used as a positive chemical amplification type photoresist for standby.
Example three:
synthesis of unprotected phenolic resin: dissolving 4.28g (20mmol) of 3,3 '-dimethyl-4, 4' -biphenol in 200ml of methanol in a 500ml three-necked bottle with a mechanical stirring, temperature-controlled thermocouple and a pH meter, then adding 1.46g (18mmol) of 37% formaldehyde aqueous solution, heating to 55 ℃, slowly dropwise adding 3.00g of oxalic acid aqueous solution at the temperature of 10% of oxalic acid concentration, maintaining the pH value of the system at 6.3, carrying out condensation reaction for 4 hours to obtain viscous linear phenolic resin, reducing the temperature to room temperature after the reaction is finished, concentrating the methanol, repeatedly washing with pure water, drying and pulverizing for later use.
Synthesizing phenolic resin protected by tert-butoxy acyloxy (namely modified phenolic resin): 4.82g of the unprotected phenolic resin is continuously dissolved in 120ml of tetrahydrofuran solvent, the mixture is put into a dry and nitrogen-protected three-neck flask, 4.488g (40mmol) of potassium tert-butoxide (112.2) is rapidly added in several times, the mixture is stirred for twenty minutes at room temperature, 6.976g (32mmol) of 60ml of tetrahydrofuran solution of di-tert-butyl dicarbonate (218) is slowly dropped into the three-neck flask, the mixture is vigorously stirred for 3 hours at room temperature, after the reaction is finished, the mixture is poured into ice pure water, ethyl acetate is used for extraction, a drying agent is added, and the low-boiling solvent is evaporated to dryness to obtain the phenolic resin protected by tert-butoxy group.
After 2g of the obtained protective linear phenolic resin is dissolved in 6g of propylene glycol monomethyl ether propionate solvent, 0.6g of acid generator (PAG) N-hydroxyphthalimide p-toluenesulfonate and 0.3g of photoactive o-azidonaphthoquinone (PAC) with No. 1 carbon skeleton are added, and the protective linear phenolic resin is uniformly dissolved and used as a positive chemical amplification type photoresist for standby.
Example four:
synthesis of unprotected phenolic resin: in a 500ml three-necked flask with a mechanical stirring, temperature-controlled thermocouple and a pH meter, 4.28g (20mmol) of 5,5 '-dimethyl-2, 2' -biphenol is dissolved in 200ml of methanol, 1.54g (19mmol) of 37% aqueous formaldehyde solution is added, the mixture is heated to 60 ℃ for reflux, 3.42g of aqueous oxalic acid solution is slowly added dropwise, the concentration of oxalic acid is 10%, the pH value of the system is maintained at 6.5, condensation reaction is carried out for 3.5 hours, viscous linear phenolic resin is obtained, after the reaction is finished and is reduced to the room temperature, methanol is concentrated, washing is carried out repeatedly by pure water, and pulverization is carried out after drying for standby.
Synthesis of tert-butoxy-protected phenolic resin (i.e., modified phenolic resin): 4.85g of the unprotected phenolic resin is further dissolved in 120ml of tetrahydrofuran solvent, the mixture is put into a dry and nitrogen-protected three-neck flask, then 3.36g (60mmol) of ground potassium hydroxide (56) is added, the mixture is stirred for twenty minutes at room temperature and heated to reflux, 3.808g (28mmol) of tert-butyl bromide (136) in 20ml of tetrahydrofuran solution is slowly dropped into the three-neck flask, the mixture is stirred strongly at room temperature for 8 hours, after the reaction is finished, the mixture is poured into ice pure water, the mixture is repeatedly washed to be neutral and dried, and the tert-butoxy protected phenolic resin is obtained.
After 2g of the protected phenolic novolac resin obtained above was dissolved in 6g of propylene glycol monomethyl ether acetate solvent, 0.4g of acid generator (PAG) PIW-501 and 0.3g of photoactive o-azidonaphthoquinone (PAC) with carbon number 2 were added and dissolved uniformly to prepare a positive chemically amplified photoresist for use.
Example five:
synthesis of unprotected phenolic resin: dissolving 4.84g (20mmol) of 2,6,2 ', 6 ' -tetramethyl-3, 3 ' -biphenyl diphenol in 220ml of methanol in a 500ml three-necked bottle with a mechanical stirring, temperature-controlled thermocouple and a pH meter, then adding 1.46g (18mmol) of 37% formaldehyde aqueous solution, heating to 60 ℃ for reflux, slowly dropwise adding 4.28g of oxalic acid aqueous solution, keeping the pH value of the system at 10%, carrying out condensation reaction for 4 hours to obtain viscous linear phenolic resin, reducing the temperature to room temperature after the reaction is finished, concentrating the methanol, repeatedly washing with pure water, drying, and pulverizing for later use.
Synthesis of tert-butoxy-protected phenolic resin (i.e., modified phenolic resin): and continuously dissolving 5.38g of the unprotected phenolic resin in 150ml of tetrahydrofuran solvent, putting the mixture into a dry and nitrogen-protected three-neck flask, then adding 4.48g (80mmol) of ground potassium hydroxide (56), stirring the mixture for twenty minutes at room temperature, heating the mixture to reflux, slowly and dropwise adding 2.72g (20mmol) of tert-butyl bromide (136) into 20ml of tetrahydrofuran solution at room temperature, reacting the mixture for 8 hours at room temperature, after the reaction is finished, pouring the mixture into ice pure water, repeatedly washing the mixture to be neutral, and drying the mixture to obtain the tert-butoxy protected phenolic resin.
After 2g of the obtained protective linear phenolic resin is dissolved in 6g of propylene glycol monomethyl ether acetate solvent, 0.2g of acid generator (PAG) N-trifluoromethyl xanthyloxy-1, 8-naphthalimide (NHNI-TF) and 0.4g of photoactive o-azidonaphthoquinone (PAC) with No. 10 carbon skeleton are added, and the protective linear phenolic resin is uniformly dissolved to be used as a positive chemical amplification type photoresist for standby.
Example six:
synthesis of unprotected phenolic resin: in a 500ml three-necked flask with a mechanical stirring, temperature-controlled thermocouple and pH meter, 4.28g (20mmol) of 3,3 '-dimethyl-4, 4' -biphenol is dissolved in 200ml of methanol, then 1.46g (18mmol) of 37% formaldehyde aqueous solution is added, the mixture is heated to 55 ℃, 3.00g of 10% oxalic acid aqueous solution is slowly dropped at the temperature, the pH value of the system is maintained at 6.3, condensation reaction is carried out for 4 hours, viscous linear phenolic resin is obtained, after the reaction is finished and is reduced to the room temperature, methanol is concentrated, the mixture is repeatedly washed by pure water, dried and pulverized for later use.
Synthesis of tert-butoxy protected phenolic resin (i.e. modified phenolic resin): 4.82g of the unprotected phenolic resin is further dissolved in 150ml of tetrahydrofuran solvent, the obtained solution is put into a dry and nitrogen-protected three-neck flask, 4.2g (75mmol) of ground potassium hydroxide (56) is added, the mixture is stirred at room temperature for twenty minutes, heating reflux is carried out, 5.17g (38mmol) of tert-butyl bromide (136) 50ml of tetrahydrofuran solution is slowly dropped into the three-neck flask, the obtained solution is reacted at room temperature for 8 hours, after the reaction is finished, the obtained solution is poured into ice pure water, the obtained solution is repeatedly washed to be neutral and dried, and the tert-butoxy protected phenolic resin is obtained.
After 2g of the above-obtained protected novolak resin was dissolved in 6g of propylene glycol monomethyl ether acetate solvent, 0.3g of acid generator (PAG) Irgacure169 and 0.1g of photoactive o-azidonaphthoquinone (PAC) having a carbon skeleton No. 16 were added thereto and uniformly dissolved, thereby obtaining a positive chemically amplified resist for use.
EXAMPLE seven
Synthesis of unprotected phenolic resin: in a 500ml three-necked flask with a mechanical stirring, temperature-controlled thermocouple and pH meter, 2.14g (10mmol) of 5,5 '-dimethyl-2, 2' -biphenol and 2.14g (10mmol) of 3,3 '-dimethyl-4, 4' -biphenol are dissolved in 200ml of methanol, then 1.54g (19mmol) of 37% aqueous formaldehyde solution is added, the mixture is heated to 55 ℃ for reflux, 3.42g of 10% aqueous oxalic acid solution is slowly dropped, the pH value of the system is maintained at 6.8, condensation reaction is carried out for 3.5 hours, viscous linear phenolic resin is obtained, after the reaction is finished and the temperature is reduced to room temperature, the methanol is concentrated, the linear phenolic resin is repeatedly washed by pure water, dried and pulverized for later use.
Synthesizing phenolic resin (namely modified phenolic resin) protected by tert-butoxy acyloxy: 4.85g of the unprotected phenolic resin is continuously dissolved in 120ml of tetrahydrofuran solvent, the mixture is put into a dry and nitrogen-protected three-neck flask, 4.488g (40mmol) of potassium tert-butoxide (112.2) is rapidly added in several times, the mixture is stirred for twenty minutes at room temperature, 6.104g (28mmol) of di-tert-butyl dicarbonate (218) 40ml of tetrahydrofuran solution is slowly dropped into the three-neck flask, the mixture is strongly stirred for 2 hours at room temperature, after the reaction is finished, the mixture is poured into ice pure water, the mixture is extracted by ethyl acetate, a drying agent is added, and the solvent with low boiling point is evaporated to dryness to obtain the phenolic resin protected by tert-butoxy group.
After 2g of the above-obtained protected novolak resin was dissolved in 6g of propylene glycol monomethyl ether acetate solvent, 0.4g of acid generator (PAG) Irgacure169 and 0.2g of photoactive o-azidonaphthoquinone (PAC) with carbon number 3 were added and uniformly dissolved, and the resultant was used as a positive chemically amplified resist.
Example eight
Synthesis of unprotected phenolic resin: in a 500ml three-necked flask with a mechanical stirring, temperature-controlled thermocouple and pH meter, 2.14g (10mmol) of 5,5 '-dimethyl-2, 2' -biphenol and 2.14g (10mmol) of 3,3 '-dimethyl-4, 4' -biphenol are dissolved in 200ml of methanol, then 1.54g (19mmol) of 37% aqueous formaldehyde solution is added, the mixture is heated to 55 ℃ for reflux, 3.42g of 10% aqueous oxalic acid solution is slowly dropped, the pH value of the system is maintained at 6.8, condensation reaction is carried out for 3.5 hours, viscous linear phenolic resin is obtained, after the reaction is finished and the temperature is reduced to room temperature, the methanol is concentrated, the linear phenolic resin is repeatedly washed by pure water, dried and pulverized for later use.
Synthesis of tert-butoxy protected phenolic resin (i.e. modified phenolic resin): 4.85g of the unprotected phenolic resin is further dissolved in 150ml of tetrahydrofuran solvent, the obtained solution is put into a dry and nitrogen-protected three-neck flask, 4.2g (75mmol) of ground potassium hydroxide (56) is added, the mixture is stirred at room temperature for twenty minutes, heating reflux is carried out, 5.17g (38mmol) of tert-butyl bromide (136) 50ml of tetrahydrofuran solution is slowly dropped into the three-neck flask, the obtained solution is reacted at room temperature for 8 hours, after the reaction is finished, the obtained solution is poured into ice pure water, the obtained solution is repeatedly washed to be neutral and dried, and the tert-butoxy protected phenolic resin is obtained.
After 2g of the above-obtained protected novolak resin was dissolved in 6g of propylene glycol monomethyl ether acetate solvent, 0.3g of acid generator (PAG) Irgacure169 and 0.1g of photoactive o-azidonaphthoquinone (PAC) having a carbon skeleton No. 16 were added thereto and uniformly dissolved, thereby obtaining a positive chemically amplified resist for use.
Comparative example 1
2g of commercially available Novolac phenolic resin (structure shown below) is dissolved in 6g of propylene glycol monomethyl ether acetate solvent, and 0.45g of optically active o-azidonaphthoquinone (PAC) with a carbon skeleton number 18 is added and uniformly dissolved to be used as a common positive-working phenolic photoresist for later use.
Comparative example No. two
After 2g of commercially available Novolac phenolic resin (structure shown below) was dissolved in 6g of propylene glycol monomethyl ether propionate solvent, 0.35g of acid generator (PAG) Irgacure169 was added and uniformly dissolved, and the obtained product was used as a general positive-working phenolic resist for future use.
Figure BDA0003609471230000171
Test method
1. The polymer was tested for infrared spectroscopy (FT-IR) using a Perkin-Elmer Paragon 1000 Fourier transform infrared spectrophotometer to verify its chemical structure.
2. And (3) testing molecular weight: waters 2414 gel permeation chromatograph, solvent and mobile phase are THF.
3. Thickness, photosensitivity and resolution test: coating the photoresist on a 6-inch silicon wafer in a rotating way under the condition of 800-; baking at 110 deg.C for 40-200 s to obtain 2 μm thick film. The exposure intensity of an i-line stepping exposure machine is 200mJ/cm 2 5% -60% of gray mask plate; drying under baking (PEB) at 120 deg.C for 60-90 s; developing in TMAH aqueous solution with the concentration of 2.38 wt% at 25 ℃ for 60-130s, and fixing in ultrapure water for 30s to obtain a photoetching pattern; thickness, sensitivity and resolution were observed under an olympus metallographic microscope.
Test results
Table one example structural analysis of protective phenolic resin for positive working chemical amplification resist
Number of Number n of repeating units of modified phenolic resin
Example one n＝75
Example two n＝20
EXAMPLE III n＝80
Example four n＝45
EXAMPLE five n＝30
EXAMPLE six n＝65
EXAMPLE seven n＝25
Example eight n＝40
Comparative example 1 n＝80
Comparative example No. two n＝150
The value of n is calculated by dividing the average molecular weight in GPC measurement by the molecular weight of the structural unit.
TABLE two comparison of thickness, sensitivity and resolution after Exposure of examples 1-8 and comparative example 1
Figure BDA0003609471230000181
Figure BDA0003609471230000191
The foregoing examples are merely illustrative and are intended to illustrate some of the features of the present disclosure. The appended claims are intended to claim as broad a scope as can be conceived and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the application. As used in the claims, the term "comprising" and its grammatical variants are also logically inclusive of different and varying phrases, such as, but not limited to, "consisting essentially of" or "consisting of. Where desired, numerical ranges are provided and sub-ranges therebetween are included. Variations in these ranges are also self-explanatory to those skilled in the art and should not be considered to be dedicated to the public, but rather should be construed to be covered by the appended claims where possible. And that advances in science and technology will result in possible equivalents or sub-substitutes not currently contemplated for reasons of inaccuracy in language representation, and such changes should also be construed where possible to be covered by the appended claims.

Claims (10)

1. A modified phenolic resin having the chemical structure of formula I:
Figure FDA0003609471220000011
wherein X is more than or equal to 0 and less than or equal to 1, Y is more than or equal to 0 and less than or equal to 1, Z is more than or equal to 0 and less than or equal to 1, and X + Y + Z is equal to 1; n is 5. ltoreq. n.ltoreq.300, preferably 5. ltoreq. n.ltoreq.200; substituent R 1 、R 2 、R 3 、R 4 、R 5 、R 6 Each independently is a tert-hydroxy group or a butoxyacyloxy group or a tert-butoxy group, but not simultaneously a hydroxy group.
2. The modified phenolic resin of claim 1, wherein:
substituent R 1 、R 2 、R 3 、R 4 、R 5 、R 6 In (b), the number of hydroxyl groups is 5% to 70%, preferably 5% to 50%.
3. The modified phenolic resin of claim 1 or 2, wherein X-1, Y-0, Z-0; or X ═ 0, Y ═ 1, and Z ═ 0; or X ═ 0, Y ═ 0, and Z ═ 1.
4. A process for preparing a modified phenolic resin comprising:
a) reacting formaldehyde and biphenol in the presence of a catalyst to obtain a phenolic resin;
wherein the diphenol is selected from one or more of the following groups: 5,5 ' -dimethyl-2, 2 ' -biphenol, 2,6,2 ', 6 ' -tetramethyl-3, 3 ' -biphenol and 3,3 ' -dimethyl-4, 4 ' -biphenol; and
b) converting hydroxyl groups in the phenolic resin into groups that can be cleaved by an acid to obtain the modified phenolic resin.
5. The process according to claim 4, wherein the acid-cleavable group in step b) is a tert-butoxyacyloxy group and/or a tert-butoxy group.
6. A process according to claim 4 or 5, wherein 30-95% of the hydroxyl groups in the phenolic resin are converted to acid cleavable groups, preferably 50-95%.
7. The process of claim 4, wherein said step b) comprises reacting di-tert-butyl dicarbonate and/or tert-butyl bromide with hydroxyl groups in the phenolic resin obtained in said step a) to obtain the modified phenolic resin.
8. The process according to claim 7, wherein the molar ratio of di-tert-butyl dicarbonate and/or tert-butyl bromide to hydroxyl groups in the phenolic resin obtained in step a) is (0.3-0.95): 1, preferably (0.5-0.95): 1.
9. a positive photoresist comprising:
100 parts by weight of a solvent;
5 to 150 parts by weight, preferably 5 to 100 parts by weight, of a modified phenolic resin as defined in any one of claims 1 to 3 or a modified phenolic resin prepared by a process as defined in any one of claims 4 to 8; and
0.05 to 90 parts by weight, preferably 0.5 to 45 parts by weight of an acid generator.
10. Use of a modified phenolic resin as claimed in any one of claims 1 to 8 or prepared by a process as claimed in any one of claims 4 to 8 in the preparation of a positive photoresist.
CN202210425589.4A 2022-04-22 2022-04-22 Modified phenolic resin, preparation method thereof and positive photoresist Pending CN114957575A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210425589.4A CN114957575A (en) 2022-04-22 2022-04-22 Modified phenolic resin, preparation method thereof and positive photoresist

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210425589.4A CN114957575A (en) 2022-04-22 2022-04-22 Modified phenolic resin, preparation method thereof and positive photoresist

Publications (1)

Publication Number Publication Date
CN114957575A true CN114957575A (en) 2022-08-30

Family

ID=82980279

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210425589.4A Pending CN114957575A (en) 2022-04-22 2022-04-22 Modified phenolic resin, preparation method thereof and positive photoresist

Country Status (1)

Country Link
CN (1) CN114957575A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115785361A (en) * 2022-12-08 2023-03-14 山东大学 Photoresist material containing acrylate side chain and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004115724A (en) * 2002-09-27 2004-04-15 Sumitomo Bakelite Co Ltd Resin for photoresist and photoresist composition
JP2004231858A (en) * 2003-01-31 2004-08-19 Sumitomo Bakelite Co Ltd Resin for photoresist and photoresist composition
JP2006208658A (en) * 2005-01-27 2006-08-10 Sumitomo Bakelite Co Ltd Photoresist composition
CN109791356A (en) * 2016-11-11 2019-05-21 住友电木株式会社 Photosensitive polymer combination, resin film, cured film, the manufacturing method of semiconductor device and semiconductor device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004115724A (en) * 2002-09-27 2004-04-15 Sumitomo Bakelite Co Ltd Resin for photoresist and photoresist composition
JP2004231858A (en) * 2003-01-31 2004-08-19 Sumitomo Bakelite Co Ltd Resin for photoresist and photoresist composition
JP2006208658A (en) * 2005-01-27 2006-08-10 Sumitomo Bakelite Co Ltd Photoresist composition
CN109791356A (en) * 2016-11-11 2019-05-21 住友电木株式会社 Photosensitive polymer combination, resin film, cured film, the manufacturing method of semiconductor device and semiconductor device

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
曹维孝 等: "《非银盐感光材料 在印刷、照相、医疗中的应用》", vol. 1, 30 September 1994, 化学工业出版社, pages: 101 - 102 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115785361A (en) * 2022-12-08 2023-03-14 山东大学 Photoresist material containing acrylate side chain and preparation method and application thereof
CN115785361B (en) * 2022-12-08 2024-01-05 山东大学 Photoresist material containing acrylic ester side chain and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN100410808C (en) Negative photoresists for short wavelength imaging
TWI451198B (en) Positive resist composition and patterning process
TWI454847B (en) Positive resist composition and patterning process
US8911932B2 (en) Photo-imageable hardmask with positive tone for microphotolithography
JP6641879B2 (en) Composition for forming resist underlayer film, method for producing resist underlayer film and patterned substrate
CN1443315A (en) Photoresist composition for deep UV and process thereof
TW201233666A (en) Lactone photoacid generators and resins and photoresists comprising same
TWI263861B (en) Resist material and pattern forming method
EP1766474A2 (en) Photoactive compounds
TWI541606B (en) Method of forming resist pattern, and agent for pattern miniaturization treatment
KR20190011303A (en) Surface reforming material, resist pattern formation method, and pattern formation method
JP2005504329A (en) Thiophene-containing photoacid generator for photolithography
CN114957575A (en) Modified phenolic resin, preparation method thereof and positive photoresist
JPWO2020110793A1 (en) Photosensitive resin composition, method for producing cured fluororesin, fluororesin, fluororesin film, bank and display element
EP4066059B1 (en) Chemically amplified photoresist
KR101464789B1 (en) Composition for forming planarization insulating film for liquid crystal display element and method for producing planarization insulating film for liquid crystal display element
JP5264404B2 (en) Resist composition, resist pattern forming method, compound, acid generator
KR100536540B1 (en) Chemical Amplification, Positive Resist Compositions
JPWO2018052028A1 (en) Compound, resin, composition and pattern forming method
JP7369146B2 (en) Novolac/DNQ-based chemically amplified photoresist
JP5678747B2 (en) Resist composition for EUV light exposure and resist pattern forming method using the same
JP5658941B2 (en) Resist pattern forming method
WO2019194018A1 (en) Resist pattern formation method and chemically amplified resist material
CN111630111A (en) Composition, method for forming resist pattern, and method for forming insulating film
TWI843729B (en) Novolak/dnq based, chemically amplified photoresist

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination