CN113848686B - Negative photoresist developer and preparation method thereof - Google Patents
Negative photoresist developer and preparation method thereof Download PDFInfo
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- CN113848686B CN113848686B CN202111134406.5A CN202111134406A CN113848686B CN 113848686 B CN113848686 B CN 113848686B CN 202111134406 A CN202111134406 A CN 202111134406A CN 113848686 B CN113848686 B CN 113848686B
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 21
- 239000000337 buffer salt Substances 0.000 claims abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 150000007529 inorganic bases Chemical class 0.000 claims description 19
- 150000007530 organic bases Chemical class 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 10
- 238000011161 development Methods 0.000 claims description 9
- 239000012024 dehydrating agents Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 5
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical group C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- 229940086542 triethylamine Drugs 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 52
- 230000000052 comparative effect Effects 0.000 description 30
- 239000012528 membrane Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 11
- 238000001000 micrograph Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 239000006260 foam Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- -1 polyoxyethylene Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/322—Aqueous alkaline compositions
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
A negative photoresist developer and a preparation method thereof. The negative photoresist developer solution comprises: without any means forThe organic alkali, the nonionic surfactant, the cationic surfactant, the buffer salt and water, wherein the nonionic surfactant is a compound shown in a formula I. The preparation method is simple in preparation and is beneficial to industrial production.
Description
Technical Field
The invention belongs to the technical field of developing solutions, and particularly relates to a negative photoresist developing solution and a preparation method thereof.
Background
The developer is a chemical solvent that dissolves the soluble areas of the photoresist resulting from the exposure, and for the negative development process, is typically an organic solvent such as xylene; for the positive development process, the developer is a strong base solution diluted with water, earlier a mixture of potassium hydroxide and water.
With the increasing progress of display technology, along with the continuous improvement of requirements on resolution, imaging definition and the like, particularly with the popularization of smart phones and tablet personal computers, the display requirements on high resolution and high image quality are rapidly increased, the line width requirements of display devices are thinner, and the requirements on electrical performance are also higher. This means more refined fabrication and a reduction in the line width of the pixel cell at the process stage. Because potassium hydroxide contains a large amount of potassium ions and sodium ions, the developer has high metal ion content and is not easy to clean, and impurities are formed on the color film substrate. In the application environment of finer-line and denser-line, the residual metal ion impurities form conductive short circuits in a smaller quantity, thereby adversely affecting the transistor control switch in the TFT pixel
Patent application CN110647018A discloses a negative photoresist developer, and specifically discloses the negative photoresist developer which is formed by mixing organic alkali, a surfactant and water in proportion, wherein the surfactant is a nonionic surfactant, and alkylphenol polyoxyethylene is selected as the nonionic surfactant. However, the research shows that the negative photoresist developer has uneven etching speed of photoresist patterns, residual surfactant is easy to generate bubbles, and the residual foam can block the contact between the developer and the photoresist, thereby affecting the integrity and fineness of wiring.
Patent application CN102063024a discloses a developer composition, which is mainly composed of an alkaline compound, a surfactant, a penetrating agent, and the like; the developing solution does not generate residues, and the developing effect is improved to a certain extent compared with carbonate; however, as development proceeds, the photoresist continuously consumes alkali in the developer, and thus the development effect is unstable and the development failure rate is high. Meanwhile, as the photoresist is continuously dissolved in the developing solution, the system of the developing solution is influenced, the service time of the developing solution is short, and the developing tank is required to be replaced to use new developing solution when the photoresist is accumulated to a certain extent, so that the operation is complicated.
Patent application CN 107942624a discloses a high-precision clean developing solution for a PCB board, wherein the main components of the developing solution are organic alkali, surfactant, cosolvent, suspension dispersant and the like. The developer also adopts organic alkali to replace carbonate, and the penetration and dissolution of the developer to photoresist are improved by the aid of a surfactant and a cosolvent. The developing solution also has the problems of unstable developing effect and short service life.
Therefore, there is still a need for a negative photoresist developer with uniform etching rate, no surfactant residue, less tendency to generate bubbles, complete and fine wiring, and long service life.
Disclosure of Invention
In order to solve the problems, the invention provides a negative photoresist developer, a preparation method and application thereof.
In a first aspect, the present invention provides a negative photoresist developer solution.
A negative photoresist developer solution, comprising: inorganic base, organic base, nonionic surfactant, cationic surfactant, buffer salt and water, wherein the nonionic surfactant is a compound shown in formula I:
wherein n is an integer of 10 to 20.
The n may be 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.
The content of the nonionic surfactant is 0.5-20wt% calculated by the total weight of the negative photoresist developer. In some embodiments, the nonionic surfactant is present in an amount of 5wt% to 20wt% based on the total weight of the negative photoresist developer solution. In some embodiments, the nonionic surfactant is present in an amount of 5wt% to 15wt% based on the total weight of the negative photoresist developer solution. In some embodiments, the nonionic surfactant is present in an amount of 5wt% to 10wt% based on the total weight of the negative photoresist developer solution.
The content of the inorganic base is 1-5 wt% calculated by the total weight of the negative photoresist developer. In some embodiments, the inorganic base is present in an amount of 2wt% to 4wt% based on the total weight of the negative photoresist developer solution. In some embodiments, the inorganic base is present in an amount of 1wt% to 3wt% based on the total weight of the negative photoresist developer solution.
The content of the organic base is 0.5-3 wt% calculated by the total weight of the negative photoresist developer. In some embodiments, the organic base is present in an amount of 1wt% to 2wt% based on the total weight of the negative photoresist developer solution.
The content of the buffer salt is 1-5 wt% calculated by the total weight of the negative photoresist developer. In some embodiments, the buffer salt is present in an amount of 2wt% to 4wt% based on the total weight of the negative photoresist developer solution. In some embodiments, the buffer salt is present in an amount of 3wt% to 4wt% based on the total weight of the negative photoresist developer solution.
The content of the cationic surfactant is 1-5 wt% calculated by the total weight of the negative photoresist developer. In some embodiments, the cationic surfactant is present in an amount of 2wt% to 4wt% based on the total weight of the negative photoresist developer solution. In some embodiments, the cationic surfactant is present in an amount of 3wt% to 4wt% based on the total weight of the negative photoresist developer solution.
The inorganic base includes at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, and potassium bicarbonate.
The organic base includes at least one selected from the group consisting of monomethyl amine, dimethyl amine, trimethyl amine, monoethyl amine, diethyl amine, triethyl amine, monoethanolamine, diethanolamine, triethanolamine, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, and monoethanol dimethyl amine.
The buffer salt comprises a salt selected from sodium citrate or potassium dihydrogen phosphate.
The cationic surfactant includes at least one selected from the group consisting of an alkyl trimethylammonium salt, a dialkyl dimethylammonium salt, an amide-based quaternary ammonium salt, and an ether-based quaternary ammonium salt.
In some embodiments, a negative photoresist developer solution, comprising: the photoresist developer comprises inorganic base, organic base, nonionic surfactant, cationic surfactant, buffer salt and water, wherein the nonionic surfactant is a compound shown in a formula I, n is an integer of 10-20, and the content of the nonionic surfactant is 0.5-20wt% calculated by the total weight of the negative photoresist developer; the content of the inorganic base is 1-5 wt%; the content of the organic alkali is 0.5-3 wt%; the content of the buffer salt is 1-5 wt%; the content of the cationic surfactant is 1-5 wt% and the balance is water.
In some embodiments, a negative photoresist developer solution, comprising: the photoresist developer comprises inorganic base, organic base, nonionic surfactant, cationic surfactant, buffer salt and water, wherein the nonionic surfactant is a compound shown in a formula I, n is an integer of 10-20, and the content of the nonionic surfactant is 10wt% calculated by the total weight of the negative photoresist developer; the content of the inorganic base is 4wt%; the content of the organic base is 2wt%; the cationic surfactant content was 3wt%; the content of the buffer salt is 5wt%; the balance being water.
The preparation method of the compound shown in the formula I comprises the following steps:
and (3) dissolving the compound shown in the formula II and the compound shown in the formula III in a solvent, reacting in the presence of a dehydrating agent, and performing post-treatment to obtain the compound shown in the formula I, wherein n is an integer of 10-20.
The solvent includes at least one selected from methanol, chloroform and tetrahydrofuran.
The dehydrating agent is dicyclohexylcarbodiimide.
The temperature of the reaction is 30-60 ℃.
The reaction time is 12-24 hours.
The post-processing includes: the solvent was removed by rotary evaporation and purified by column chromatography.
The feeding mole ratio of the compound shown in the formula II to the compound shown in the formula III is 1:1-1:5. In some embodiments, the molar ratio of the compound of formula II to the compound of formula III is from 1:1 to 1:4. In some embodiments, the molar ratio of the compound of formula II to the compound of formula III is from 1:1.5 to 1:3. In some embodiments, the molar ratio of the compound of formula II to the compound of formula III is from 1:1.5 to 1:2.
The feeding mole ratio of the compound shown in the formula II to the dehydrating agent is 1:1-1:5. In some embodiments, the molar ratio of the compound of formula II to the dehydrating agent is from 1:1 to 1:4. In some embodiments, the molar ratio of the compound of formula II to the dehydrating agent is from 1:1.5 to 1:3. In some embodiments, the molar ratio of the compound of formula II to the dehydrating agent is from 1:1.5 to 1:2.
The weight-volume ratio of the compound shown in the formula II to the solvent is 1 g/100 ml-1 g/500 ml. In some embodiments, the weight to volume ratio of the compound of formula II to the solvent is from 1 g:150 ml to 1 g:400 ml. The weight-volume ratio of the compound shown in the formula II to the solvent is 1 g/200 ml-1 g/300 ml.
The eluent for column chromatography is a mixed solution of chloroform and methanol with the volume ratio of 2:1-6:1.
In a second aspect, the present invention provides a method for preparing the negative photoresist developer of the first aspect.
A method of preparing the negative photoresist developer solution of the first aspect, comprising: dissolving inorganic base, organic base, nonionic surfactant, cationic surfactant and buffer salt in water, and filtering with 0.45 micrometer filter membrane and 0.22 micrometer filter membrane in sequence to obtain the negative photoresist developer.
In a third aspect, the present invention provides an application of the negative photoresist developer solution.
The negative photoresist developer of the first aspect or the negative photoresist developer prepared by the method of the second aspect is applied in the negative photoresist developing process.
Advantageous effects
Compared with the prior art, the invention has at least one of the following technical effects:
(1) The minimum amplitude of the fine image after the negative developer provided by the invention is small, which is beneficial to the development of finer images.
(2) The negative developing solution provided by the invention has less foam, and is more beneficial to avoiding the problems of the integrity and the fineness reduction of wiring and the like caused by the contact between the foam blocking developing solution and the photoresist due to the residual foam.
(3) The negative developer provided by the invention has no layering after being placed at high temperature and low temperature, and has excellent stability.
(4) The negative developing solution provided by the invention can ensure that the straightness of a developed pattern is good, a line is straight, and the negative developing solution has no defects such as saw teeth, unclear edges and the like, and is far more excellent than the straightness of other developing solutions.
(5) The negative developing solution provided by the invention can lead the development to have no color residue and is far more excellent than other developing solutions.
Drawings
Fig. 1 shows a scanning electron microscope image of the glon R test of example 3 in experimental example 6.
Fig. 2 shows a scanning electron microscope image of the B on R test of example 3 in experimental example 6.
Fig. 3 shows a scanning electron microscope image of the B on G test of example 3 in experimental example 6.
Fig. 4 shows a scanning electron microscope image of the glon R test of comparative example 3 in experimental example 6.
Fig. 5 shows a scanning electron microscope image of the B on R test of comparative example 3 in experimental example 6.
Fig. 6 shows a scanning electron microscope image of the B on G test of comparative example 3 in experimental example 6.
Fig. 7 shows a scanning electron microscope image of the glon R test of comparative example 4 in experimental example 6.
Fig. 8 shows a scanning electron microscope image of the B on R test of comparative example 4 in experimental example 6.
Fig. 9 shows a scanning electron microscope image of the B on G test of comparative example 4 in experimental example 6.
Definition of terms
Unless otherwise indicated, the following terms and phrases as used herein are intended to have the following meanings:
"V/V" means the volume ratio. "wt%" means the mass percentage of the component mass to the total mass of the composition.
Detailed Description
In order to better understand the technical solution of the present invention, some non-limiting examples are further disclosed below to further describe the present invention in detail.
The reagents used in the present invention are all commercially available or can be prepared by the methods described herein.
Example 1: preparation of nonionic surfactants
1.35g of the compound of formula B (5 mmol) and 2.00g of the compound of formula III (5 mmol) were dissolved in 200mL of a mixed solution of tetrahydrofuran and methanol (tetrahydrofuran: methanol=1:1 (V/V)), 2.06g of dicyclohexylcarbodiimide (10 mmol) was further added, the mixture was reacted at 50℃for 12 hours, the solvent was removed by rotary evaporation, and the mixture was purified by column chromatography (eluent: chloroform: methanol=4:1 (V/V)), and dried to give 2.07g of the compound of formula A (white solid, yield 64%). The mass spectrum and the hydrogen spectrum of the obtained compound shown in the formula A are detected, and the result is as follows:
HRMS[M+H] + : the molecular formula: c (C) 29 H 49 NO 15 Theoretical value: 651.3102; actual measurement value: 651.3099.
hydrogen spectrum: 1 H NMR(400MHz，Chloroform-d)δ5.37(d，J＝7.0Hz，1H)，5.16(d，J＝7.0Hz，1H)，4.39-4.33(m，2H)，3.98-3.71(m，5H)，3.64(q，J＝6.9Hz，1H)，3.61-3.50(m，3H)，3.47(dt，J＝8.8，7.0Hz，1H)，3.35(q，J＝7.1Hz，1H)，2.90(p，J＝7.0Hz，1H)，2.67-2.57(m，2H)，1.57(qd，J＝7.1，1.6Hz，2H)，1.48-1.34(m，2H)，1.33-1.26(m，2H)，1.29-1.18(m，14H)，0.93-0.80(m，3H).
example 2: preparation of nonionic surfactants
2.05g of the compound represented by the formula D (5 mmol) and 2.00g of the compound represented by the formula III (5 mmol) were dissolved in 300mL of a mixed solution of tetrahydrofuran and methanol (tetrahydrofuran: methanol=1:1 (V/V)), 1.03g of dicyclohexylcarbodiimide (5 mmol) was further added, the mixture was reacted at 40℃for 18 hours, the solvent was removed by rotary evaporation, and the mixture was purified by column chromatography (eluent: chloroform: methanol=4:1 (V/V)), and dried to give 2.36g of the compound represented by the formula A (white solid, yield 60%). The mass spectrum of the obtained compound represented by formula C was measured, and the results were as follows:
HRMS[M+H] + : the molecular formula: c (C) 39 H 69 NO 15 Theoretical value: 791.4667; actual measurement value: 791.4650.
hydrogen spectrum: 1 H NMR(400MHz，Chloroform-d)δ5.34(d，J＝7.0Hz，1H)，5.14(d，J＝6.8Hz，1H)，4.40-4.31(m，2H)，4.30(d，J＝12.3Hz，1H)，3.91-3.83(m，4H)，3.63(q，J＝6.9Hz，1H)，3.61-3.44(m，5H)，3.42-3.34(m，1H)，2.92(p，J＝7.0Hz，1H)，2.67-2.56(m，2H)，1.54(qd，J＝7.1，1.6Hz，2H)，1.47-1.13(m，38H)，0.95-0.80(m，3H).
example 3: preparation of negative photoresist developer
Negative photoresist developer solutions were prepared according to the recipe shown in table 1.
Table 1: negative photoresist developer
The preparation method comprises the following steps: dissolving inorganic base, organic base, nonionic surfactant, cationic surfactant and buffer salt in water, and filtering with 0.45 micrometer filter membrane and 0.22 micrometer filter membrane in sequence to obtain the negative photoresist developer.
Example 4: preparation of negative photoresist developer
Negative photoresist developer solutions were prepared according to the recipe shown in table 2.
Table 2: negative photoresist developer
The preparation method comprises the following steps: dissolving inorganic base, organic base, nonionic surfactant, cationic surfactant and buffer salt in water, and filtering with 0.45 micrometer filter membrane and 0.22 micrometer filter membrane in sequence to obtain the negative photoresist developer.
Example 5: preparation of negative photoresist developer
Negative photoresist developer solutions were prepared according to the recipe shown in table 3.
Table 3: negative photoresist developer
The preparation method comprises the following steps: dissolving inorganic base, organic base, nonionic surfactant, cationic surfactant and buffer salt in water, and filtering with 0.45 micrometer filter membrane and 0.22 micrometer filter membrane in sequence to obtain the negative photoresist developer.
Comparative example 1: preparation of negative photoresist developer with reference to CN110647018A
Negative photoresist developer solutions were prepared according to the recipe shown in table 4.
Table 4: negative photoresist developer
The preparation method comprises the following steps: the preparation method comprises the following steps:
step one, treating a nonionic surfactant: and (3) taking castor oil polyoxyethylene ether with the weight 2.5 times of that of the nonionic surfactant, feeding the castor oil polyoxyethylene ether and the nonionic surfactant into a batching kettle together, stirring, intermittently adding a proper amount of water in the stirring process, keeping the mixed solution for dilution, standing for 3 hours, filtering out the nonionic surfactant, treating with 0.1% hydrogen peroxide, and heating the nonionic surfactant to remove the hydrogen peroxide.
Step two, adding the surfactant and the organic alkali treated in the step one into a batching kettle respectively, and stirring for 30min; adding water into the mixed solution at a constant speed, and continuously stirring; the solution was filtered through a 0.05 μm filter to obtain the developer.
Comparative example 2: preparation of developer with reference to CN102063024A
Developing solutions were prepared according to the formulations shown in table 5.
Table 5: developing solution
The preparation method comprises the following steps: dissolving an alkaline compound, a nonionic surfactant, a cationic surfactant and a penetrating agent in water, and filtering by adopting a filter membrane of 0.45 microns and a filter membrane of 0.22 microns in sequence to obtain the developing solution.
Comparative example 3: preparation of negative photoresist developer
Negative photoresist developer solutions were prepared according to the recipe shown in table 6.
Table 6: negative photoresist developer
The preparation method comprises the following steps: dissolving inorganic base, organic base, nonionic surfactant, cationic surfactant and buffer salt in water, and filtering with 0.45 micrometer filter membrane and 0.22 micrometer filter membrane in sequence to obtain the negative photoresist developer.
Comparative example 4: preparation of negative photoresist developer
Negative photoresist developer solutions were prepared according to the recipe shown in table 7.
Table 7: negative photoresist developer
The preparation method comprises the following steps: dissolving inorganic base, organic base, nonionic surfactant, cationic surfactant and buffer salt in water, and filtering with 0.45 micrometer filter membrane and 0.22 micrometer filter membrane in sequence to obtain the negative photoresist developer.
Experimental example 1: degree of loss of developed resist pattern
On a glass substrate (100 mm. Times.100 mm) for an alkali-free TFT-LCD, a negative photoresist (resin black matrix, TOK5110, TOK Co.) having a film thickness of 1.2 to 1.5 μm was spin-coated, and prebaked in an oven at 100℃for 100 seconds. Then, exposure was performed using a pattern mask (79 mJ/cm) 2 ) Thereafter, the developing solutions obtained in example 3, example 4, example 5, comparative example 1, comparative example 2, comparative example 3 and comparative example 4 described above were diluted 100 times with water. After the treatment with the developer, the film was rinsed with ultrapure water for a predetermined period of time, rinsed, air-dried with nitrogen gas, and then hard baked in an oven at 220℃for 20 minutes. The patterns with the amplitude of the photoresist of 1 to 40 μm were observed by an optical microscope, and the damage and loss degree of the patterns were confirmed, and the results are shown in table 8.
Experimental example 2: confirming the bubble generation amount of the developing treatment liquid
The developing solutions obtained in example 3, example 4, example 5, comparative example 1, comparative example 2, comparative example 3 and comparative example 4 were diluted 20 times and 20mL was contained in a 100mL measuring cylinder, and the foam heights were measured after shaking at an appropriate frequency for 10 minutes with a vertical shaker and standing for 10 minutes, and the results are shown in table 8.
Experimental example 3: investigation of developer stability
The developing solutions obtained in example 3, example 4, example 5, comparative example 1, comparative example 2, comparative example 3 and comparative example 4 were placed in an incubator at 60℃for 10 hours, and then placed in a freezer at-10℃for 10 hours, taken out, and left to stand to room temperature, and the liquid state was observed. The results are shown in Table 8.
Table 8: experimental example test results
Conclusion: as can be seen from table 8:
(1) The minimum amplitude of the fine image after the negative developer provided by the invention is small, which is beneficial to the development of finer images.
(2) The negative developing solution provided by the invention has less foam, and is more beneficial to avoiding the problems of the integrity and the fineness reduction of wiring and the like caused by the contact between the foam blocking developing solution and the photoresist due to the residual foam.
(3) The negative developer provided by the invention has no layering after being placed at high temperature and low temperature, and has excellent stability.
Experimental example 5: straightness detection
The developing solutions obtained in example 3, example 4, example 5, comparative example 1, comparative example 2, comparative example 3 and comparative example 4 were taken respectively, and the straightness was examined as follows.
The operation is as follows: respectively coating red photoresist (R), green photoresist (G), blue photoresist (B), black photoresist (BM) and a film column (PS), wherein the RGB film thickness is 3 mu m, the BM film thickness is 1 mu m, the PS film thickness is 2.5 mu m, pre-baking in an oven, and baking the BM and PS at 100 ℃ for 100s; RGB was baked at 90℃for 88s. Then, exposure was performed using a pattern mask (40 mJ/cm) 2 ) Thereafter, the developer was diluted 100 times with water. After the treatment with the developer, the film was rinsed with ultrapure water for a predetermined period of time, rinsed, air-dried with nitrogen gas, and then hard baked in an oven at 220℃for 20 minutes. The straightness of the pattern was observed by an electron microscope.
Results: as shown in table 9.
Table 9: straightness detection result
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Conclusion: as is clear from table 9, the negative developer of the present invention has good linearity of the developed pattern, and the line is flat, and has no defects such as jaggies, and no edge defects, and is far more excellent than other developers.
Experimental example 6: color residue
The developing solutions obtained in example 3, example 4, example 5, comparative example 1, comparative example 2, comparative example 3 and comparative example 4 were taken respectively, and color residue was detected as follows.
The operation is as follows: verifying that the rear photoresist has no adverse effect on the front photoresist, performing three tests of G on R (red photoresist is exposed and developed, then a layer of green photoresist is coated, then the green photoresist is exposed and developed, and the pattern is observed by a scanning electron microscope), B on R (red photoresist is exposed and developed, then a layer of blue photoresist is coated, then the blue photoresist is exposed and developed, and the pattern is observed by a scanning electron microscope), B on G (green photoresist is exposed and developed, then a layer of blue photoresist is coated, then the blue photoresist is exposed and developed, and the pattern is observed by a scanning electron microscope)
Results: as shown in table 10.
Table 10: color residue detection results
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Conclusion: as can be seen from Table 10 and FIGS. 1-9, the negative developer provided by the present invention can be developed without color residue, and is far more excellent than other developers.
While the methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations and combinations of the methods and applications described herein can be made and applied within the spirit and scope of the invention. Those skilled in the art can, with the benefit of this disclosure, suitably modify the process parameters to achieve this. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included within the present invention.
Claims (9)
1. A negative photoresist developer solution, comprising: inorganic base, organic base, nonionic surfactant, cationic surfactant, buffer salt and water, wherein the nonionic surfactant is a compound shown in formula I:
wherein n is an integer of 10 to 20.
2. The negative photoresist developer solution of claim 1, wherein the nonionic surfactant is present in an amount of 0.5% wt% to 20% wt% by weight based on the total weight of the negative photoresist developer solution; and/or the inorganic base is present in an amount of 1wt% -5wt%; and/or the organic base content is 0.5-wt% -3-wt%; and/or the buffer salt is present in an amount of 1wt% -5wt%; and/or the cationic surfactant is present in an amount of 1wt% to 5wt%.
3. The negative photoresist developer of claim 1, the inorganic base comprising at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, and potassium bicarbonate.
4. The negative photoresist developer of claim 1, the organic base comprising at least one selected from the group consisting of monomethyl amine, dimethyl amine, trimethyl amine, monoethyl amine, diethyl amine, triethyl amine, monoethanolamine, diethanolamine, triethanolamine, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, and monoethanol dimethyl amine.
5. The negative photoresist developer solution of claim 1, the buffer salt comprising a compound selected from sodium citrate or potassium dihydrogen phosphate; and/or the cationic surfactant comprises at least one selected from the group consisting of alkyl trimethylammonium salt, dialkyl dimethylammonium salt, amide-based quaternary ammonium salt, and ether-based quaternary ammonium salt.
6. The negative photoresist developer solution of any one of claims 1-5, wherein the nonionic surfactant is present in an amount of 10wt% based on the total weight of the negative photoresist developer solution; the content of the inorganic base is 4wt%; the content of the organic base is 2wt%; the cationic surfactant content was 3wt%; the content of the buffer salt is 5wt%; the balance being water.
7. A process for the preparation of a compound of formula I comprising:
and (3) dissolving the compound shown in the formula II and the compound shown in the formula III in a solvent, reacting in the presence of a dehydrating agent, and performing post-treatment to obtain the compound shown in the formula I, wherein n is an integer of 10-20.
8. The method according to claim 7, wherein the solvent comprises at least one selected from the group consisting of methanol, chloroform and tetrahydrofuran; the dehydrating agent is dicyclohexylcarbodiimide; the temperature of the reaction is 30-60 ℃; the reaction time is 12-24 hours; the post-processing includes: the solvent was removed by rotary evaporation and purified by column chromatography.
9. Use of a negative photoresist developer solution according to any one of claims 1 to 5 in a negative photoresist development process.
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| CN113253580A (en) * | 2021-05-11 | 2021-08-13 | 绵阳艾萨斯电子材料有限公司 | Negative photoresist developing solution and preparation method and application thereof |
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| DE19617939A1 (en) * | 1996-04-29 | 1997-10-30 | Inst Organische Katalyseforsch | Chiral amphiphilic compounds used as e.g. surfactants, emulsifiers or aqueous hydrogenation reaction auxiliary aids |
| CN101374551A (en) * | 2006-01-26 | 2009-02-25 | 辉瑞产品公司 | Novel glycolipid adjuvant compositions |
| WO2008011168A2 (en) * | 2006-07-21 | 2008-01-24 | Amgen Inc. | Glycosylated peptide antagonists of the bradykinin b1 receptor |
| CN111176082A (en) * | 2020-02-14 | 2020-05-19 | 福建省佑达环保材料有限公司 | High-concentration CF developer composition for display panel field |
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