CN107145037B - Photoresist composition and preparation method thereof - Google Patents
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- CN107145037B CN107145037B CN201710552426.1A CN201710552426A CN107145037B CN 107145037 B CN107145037 B CN 107145037B CN 201710552426 A CN201710552426 A CN 201710552426A CN 107145037 B CN107145037 B CN 107145037B
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- 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
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
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- 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
- G03F7/016—Diazonium salts or compounds
- G03F7/021—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders
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Abstract
The invention relates to the technical field of macromolecules, in particular to a photoresist composition and a preparation method thereof. The photoresist composition according to the present invention comprises: 30-45 parts of resin, 0.02-0.2 part of background dye and 55-70 parts of organic solvent; the resin comprises photosensitive resin and film-forming resin, and the photosensitive resin comprises diazonaphthoquinone resin and diphenylamine diazo resin.
Description
Technical Field
The invention relates to the technical field of macromolecules, in particular to a photoresist composition and a preparation method thereof.
Background
Photoresists are key functional materials for lithographic processes in the large scale integrated circuit industry. After the photoresist is irradiated by ultraviolet light, a series of chemical reactions occur, so that the dissolution rate of the photoresist in a developing solution is changed before and after exposure, and a specific high-precision pattern can be transferred to the surface of a substrate to be processed through the processes of developing, hardening, etching, removing a film and the like.
In the conventional method, SiNx is generally used as a passivation layer of a TFT, and due to the high dielectric constant k and low transparency, the capacitance-resistance delay (RC delay) becomes a bottleneck of high aperture ratio; at present, materials with low dielectric constant are often used to replace or match SiNx as passivation layers, and diazonaphthoquinone resin materials are often used at present.
However, at present, there is no resin material or resin composition capable of performing two exposures to achieve more fine pattern preparation.
Disclosure of Invention
The invention aims to provide a photoresist composition capable of carrying out double exposure and a preparation method thereof, and the specific technical scheme is as follows.
According to an aspect of the present invention, there is provided a photoresist composition comprising: 30-45 parts of resin, 0.02-0.2 part of background dye and 55-70 parts of organic solvent; the resin comprises photosensitive resin and film-forming resin, and the photosensitive resin comprises diazonaphthoquinone resin and diphenylamine diazo resin.
The two photosensitive resins have different photosensitive spectrums, the main photosensitive wavelength of the diazonaphthoquinone resin is 365nm (i line), and the main photosensitive wavelength of the diphenylamine diazoresin is 420nm (g line); thus enabling two exposures.
According to one embodiment of the present invention, the mass ratio of the film-forming resin to the photosensitive resin is (4-6): 1.
according to one embodiment of the invention, the mass ratio of the diphenylamine diazo resin to the diazonaphthoquinone resin is (2-4): 1.
according to one embodiment of the invention, the film-forming resin is a water-insoluble polymer selected from any one or a combination of more of epoxy resins, polyvinyl acetal resins and polyurethane resins.
According to an embodiment of the present invention, the organic solvent is selected from any one or more of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, methyl ethyl ketone, butyl acetate, dioxane, N-methyl pyrrolidone, methanol and tetrahydrofuran.
According to one embodiment of the invention, the background dye is selected from any one or a combination of more of basic brilliant blue, crystal violet, victoria pure blue, indigo, methyl violet, malachite green and oil soluble blue.
According to one embodiment of the present invention, the diphenylamine diazo resin has the following structure:
wherein n is an integer from 2 to 1000; w is methylene, X is selected from hydrogen, methoxy or methyl, Y is nitro, Z is selected from methyl or ethyl, R is methyl-Selected from hexafluorophosphate, dodecylbenzene sulfonate, dodecylsulfonate, p-toluenesulfonate, mesitylene sulfonate or naphthalenesulfonate anions.
According to one embodiment of the invention, wherein n is 6, R-Is mesitylene sulfonate anion, X is H, Z is methyl.
According to one embodiment of the present invention, the diazonaphthoquinone resin has the following structure:
according to another aspect of the present invention, there is also provided a method for preparing a photoresist composition according to the present invention, comprising the steps of: dissolving the background dye in an organic solvent, then adding the film-forming resin, the diazonaphthoquinone resin and the diphenylamine diazo resin, dissolving and filtering to obtain the photoresist composition.
The invention has the beneficial effects that: the invention provides a photoresist composition capable of realizing double exposure, which can realize the preparation of a hyperfine graph by using a double Mask plate (Mask) to carry out double exposure.
Drawings
FIG. 1 is a photosensitive spectrum of a diazonaphthoquinone resin.
FIG. 2 is a photosensitive spectrum of diphenylamine-diazo resin. Wherein numerals 1 to 7 sequentially represent absorbance values after irradiation of ultraviolet light (g-line) having a wavelength of 420nm for 0s, 10s, 20s, 30s, 40s, 50s, 60 s.
FIG. 3 shows the results of the molecular weight distribution test of the diphenylamine diazonium resin according to the present invention.
FIG. 4 is a schematic cross-linking diagram of diphenylamine diazo resin, film-forming resin and passivation layer.
FIG. 5 is a schematic view of two exposures using dual masks; the mask comprises a first mask plate A, a second mask plate B, a PR III, a film containing photoresist, a PR I, a first photoresist film pattern and a PR II, wherein the PR II is a second photoresist film pattern.
Detailed Description
The present invention will now be described with reference to the following detailed description, which is to be construed as illustrative only and not limiting in any way.
The invention aims to provide a photoresist composition capable of realizing double exposure, which can realize the preparation of a hyperfine pattern by using a double Mask plate (Mask) to carry out double exposure.
According to an aspect of the present invention, there is provided a photoresist composition comprising: 30-45 parts of resin, 0.02-0.2 part of background dye and 55-70 parts of organic solvent; the resin comprises photosensitive resin and film-forming resin, and the photosensitive resin comprises diazonaphthoquinone resin and diphenylamine diazo resin.
The two photosensitive resins according to the invention have different photosensitive spectrums, the main photosensitive wavelength of the diazonaphthoquinone resin is 365nm (i line), and the main photosensitive wavelength of the diazonaphthoquinone resin is 420nm (g line); thus enabling two exposures.
According to one embodiment of the present invention, the mass ratio of the film-forming resin to the photosensitive resin is (4-6): 1. for example, the mass ratio of film-forming resin to photosensitive resin can be 4:1, 4.2:1, 4.5:1, 5:1, 5.5:1, 6:1, and the like.
According to one embodiment of the invention, the mass ratio of the diphenylamine diazo resin to the diazonaphthoquinone resin is (2-4): 1. for example, the mass ratio of diphenylamine diazo resin to diazonaphthoquinone resin may be 2:1, 2.2:1, 2.5:1, 3:1, 3.5:1, 3.8:1, 4:1, or the like.
According to one embodiment of the invention, the film-forming resin is a water-insoluble polymer selected from any one or a combination of more of epoxy resins, polyvinyl acetal resins and polyurethane resins.
According to an embodiment of the present invention, the organic solvent is selected from any one or more of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, methyl ethyl ketone, butyl acetate, dioxane, N-methyl pyrrolidone, methanol and tetrahydrofuran.
According to one embodiment of the invention, the background dye is selected from any one or a combination of more of basic brilliant blue, crystal violet, victoria pure blue, indigo, methyl violet, malachite green and oil soluble blue.
According to one embodiment of the present invention, the diphenylamine diazo resin has the following structure:
wherein n is an integer from 2 to 1000; preferably 2-100, more preferablySelected from 2 to 10, for example selected from 2,4, 6, 8 or 10, W is methylene, X is selected from hydrogen, methoxy or methyl, Y is nitro, Z is selected from methyl or ethyl, R is methyl or ethyl-Selected from hexafluorophosphate, dodecylbenzene sulfonate, dodecylsulfonate, p-toluenesulfonate, mesitylene sulfonate or naphthalenesulfonate anions.
According to one embodiment of the invention, wherein n is 6, R-Is mesitylene sulfonate anion, X is H, Z is methyl.
Preparation method of diphenylamine diazo resin
The synthetic route of the N-ethyl 2-nitrodiphenylamine 4-diazonium salt is as follows:
1) 300g (1.49mol) of 2, 4-dinitrochlorobenzene was added to 1485mL of anhydrous ethanol, heated to dissolve, and 173g (1.63mol) of anhydrous Na was added2CO3. Heating and refluxing, dripping 196.9g (1.63mol) of N-ethyl aniline, reacting for 6h, cooling and standing for 12h to obtain the compound A which is a deep red prism type single crystal with the yield of 299g and the yield of 70 percent.
2) 180g (0.63mol) of Compound A was dissolved in 1000mL of 95% ethanol, and 66.5g (0.63mol) of anhydrous Na was added2CO3Heating and refluxing, and slowly dropwise adding 301g (1.25mol) of Na2S·9H2O is dissolved in 500mL of water, and the solution is dripped off for about 2h, refluxed for 4h and cooled. And pouring the reaction mixed solution into 2000mL of water, standing for a period of time, layering, pouring out the upper layer of water, and then adding a small amount of water for washing to obtain brown oily aniline B, wherein aniline is easy to oxidize and unstable in the air and needs to be converted into a sulfate form.
1000mL of 10% H was added to Aniline B2SO4Heating to 65 deg.C to dissolve the oil, filtering while hot, cooling to crystallize, and recrystallizing the remaining oil with the saturated solution for multiple times until no crystals precipitate to obtain the sulfate of compound B as golden plate-like crystals in 249g yield and 69% yield.
3) 100g (0.28mol) of the sulfate salt of the compound B are added to 360mL 5％H2SO4Adding 600g crushed ice, keeping the temperature of ice-water bath at 0-5 ℃, and slowly dripping NaNO while stirring2Solution (NaNO)2The solution was prepared by mixing 23g (0.33mol) of NaNO2Dissolved in 110mL of water), and stirring is continued for 2h after the dropwise addition is finished, so as to obtain the diazonium salt C.
The mixture after the reaction was filtered, and 151g of ZnCl was added to the filtrate2Precipitating a large amount of yellow solid in the saturated solution, filtering, washing with ethanol for 2 times, and air-drying in a fume hood to obtain 1/2ZnCl of the diazonium salt C2Double salt D, yield 72.9g, 60% yield.
IR(cm-1):ν＝2981.4cm-1(w,H2C-H),2224.0cm-1(s,C-N2 +),1601cm-1,1581cm-1,1537cm-1(vs,Ar)；
1H NMR(400MHz,D2O,δ):8.67(d,1H,H Ar-NO2),8.19(t,1H,H Ar-N2 +),7.54,7.30,7.23,7.14(m,6H,H Ar),4.05(q,2H,CH2),1.12(t,3H,CH3)。
Anal.calcd for C14H13N4O2 +·HSO4 -(％):C 45.90,H 3.85,N 15.39；found(％):C44.42,H 3.46,N 14.73。
1/2ZnCl of the above diazonium salt C2Condensing the double salt D and paraformaldehyde to prepare diazo resin, wherein the polymerization method comprises the following steps: 1/2ZnCl of diazonium salt C2The double salt D (0.039mol) was added portionwise with stirring to 52mL of 98% sulfuric acid and, after complete dissolution, finely divided paraformaldehyde (1.4g, 0.047mol) was added portionwise at 0-5 ℃ and the temperature was maintained for 5 h. Slowly pouring the reaction mixture into 230mL of frozen ethanol, stirring, dissolving with enough water, and adding enough ZnCl2And (3) precipitating a large amount of solid in the saturated solution, carrying out suction filtration, washing for 2 times by using ethanol, and airing in a fume hood to obtain the corresponding water-soluble formaldehyde diazo resin E.
The water-soluble formaldehyde diazo resin (0.04mol) is dissolved in 200mL of water, and impurities are filtered off. While stirring, a saturated aqueous solution of sodium mesitylenesulfonate (9.99g, 0.045mol) was added dropwise to the filtrateAnion exchange started when H was 2.5 and 10% NaCO was added3The solution was adjusted to pH 7 and the resulting precipitate was filtered off with suction, washed 3 times with water and dried under vacuum at 27 ℃ overnight to give formaldehyde-condensed N-ethyl-2-nitrodiphenylamine 4-diazomesitylene sulfonic acid resin F (77% yield).
The formaldehyde N-ethyl-2-nitrodiphenylamine 4-diazomesitylene sulfonic acid resin is identified, and the data is as follows:
IR(cm-1):ν＝2971.8cm-1(w,H2C-H),2200.0cm-1(s,C-N2 +),1588.2cm-1,1543.4cm-1(vs,Ar)；
1H NMR(400MHz,D2O,δ):8.67(d,1H,H-Ar-NO2),8.19(t,1H,H-Ar-N2 +),7.54,7.30,7.23,7.14(m,6H,H-Ar),4.05(q,2H,CH2),1.12(t,3H,CH3)。
the molecular weight distribution of the resin is determined by gel chromatography, and the result calculated by the software of the system is shown in figure 3.
Similarly, diphenylamine diazo resins with other different substituents can be prepared by similar synthetic methods by using the corresponding starting materials.
According to one embodiment of the present invention, the diazonaphthoquinone resin has the following structure:
According to another aspect of the present invention, there is also provided a method for preparing a photoresist composition according to the present invention, comprising the steps of: dissolving the background dye in an organic solvent, then adding the film-forming resin, the diazonaphthoquinone resin and the diphenylamine diazo resin, dissolving and filtering to obtain the photoresist composition. The filtration may be performed using, for example, filter paper.
The order of adding the film-forming resin, the diazonaphthoquinone resin, and the diphenylamine diazo resin is arbitrary, for example, the three resins may be added simultaneously, the film-forming resin, the diazonaphthoquinone resin, and the diphenylamine diazo resin may be sequentially added, the film-forming resin, the diphenylamine diazo resin, and the diazonaphthoquinone resin may be sequentially added, the diazonaphthoquinone resin, the diphenylamine diazo resin, and the film-forming resin may be sequentially added, the diphenylamine diazo resin, the diazonaphthoquinone resin, and the film-forming resin may be sequentially added, and the diphenylamine diazo resin, the film-forming resin.
Photoresist composition and preparation method thereof
Example 1
A photoresist composition comprising: 0.02 part by weight of basic brilliant blue, 30 parts by weight of epoxy resin, 2071.5 parts by weight of diazonaphthoquinone resin BP, and diphenylamine diazo resin (wherein n is 2, and W is CH2、R-Dodecyl sulfonate anion, X is methoxyl, Y is nitryl, Z is methyl) 5.5 weight portions, and ethylene glycol monomethyl ether 62.8 weight portions.
The preparation method of the photoresist composition comprises the following steps: 0.02g of basic brilliant blue was dissolved in 62.8g of ethylene glycol monomethyl ether, and then 1.5 parts by weight of diazonaphthoquinone resin, 5.5g of diphenylamine diazo resin, and 30g of epoxy resin were added in this order, dissolved and filtered with filter paper to obtain the resist composition of example 1.
Example 2
A photoresist composition comprising: 2 parts of crystal violet, 25 parts of polyurethane resin, 25 parts of diazonaphthoquinone resin BP2101 parts, and diphenylamine diazo resin (wherein n is 6, and W is CH2、R-Mesitylene sulfonate anion, X is hydrogen, Y is nitro, Z is methyl) 4 weight portions, and propylene glycol monoethyl ether 68 weight portions.
The preparation method of the photoresist composition comprises the following steps: 2g of crystal violet was dissolved in 68g of propylene glycol monoethyl ether, and then 4g of diphenylamine diazo resin, 1g of diazonaphthoquinone resin, and 25g of polyurethane resin were sequentially added, dissolved and filtered with filter paper to obtain the photoresist composition of example 2.
Example 3
A photoresist composition comprising: 0.2 part of Victoria pure blue, 27 parts of polyvinyl acetal resin, 2091.2 parts of diazonaphthoquinone resin BP, and diphenylamine diazo resin (wherein n is 1000, and W is CH)2、R-Hexafluorophosphate anion, X is methyl, Y is nitro, Z is ethyl) 3.6 parts by weight, and dioxane 68 parts by weight.
The preparation method of the photoresist composition comprises the following steps: 0.2g of Victoria pure blue was dissolved in 68g of dioxane, and then 1.2g of diazonaphthoquinone resin, 27g of polyvinyl acetal resin, and 3.6g of diphenylamine diazo resin were sequentially added, dissolved and filtered with filter paper to obtain the photoresist composition of example 3.
Example 4
A photoresist composition comprising: 1 part by weight of oil-soluble blue, 33 parts by weight of polyurethane resin, 33 parts by weight of diazonaphthoquinone resin BP2112, and diphenylamine diazo resin (wherein n is 10, and W is CH)2、R-Naphthalene sulfonate anion, X is methyl, Y is nitro, Z is methyl) 6 weight portions, and methanol 58 weight portions.
The preparation method of the photoresist composition comprises the following steps: 1g of oil-soluble blue was dissolved in 58g of methanol, and then 6g of diphenylamine diazo resin, 33g of polyurethane resin, and 2g of diazonaphthoquinone resin were sequentially added, dissolved and filtered with filter paper, to obtain the photoresist composition of example 4.
Example 5
A photoresist composition comprising: 0.5 part by weight of methyl violet, 36 parts by weight of polyvinyl acetal resin, 3 parts by weight of diazonaphthoquinone resin BP 2123, and diphenylamine diazo resin (wherein n is 8, and W is CH2、R-P-toluenesulfonate anion, X is hydrogen, Y is nitro, Z is ethyl) 6 parts by weight, and tetrahydrofuran 54.5 parts by weight.
The preparation method of the photoresist composition comprises the following steps: 0.5g of methyl violet was dissolved in 54.5g of tetrahydrofuran, and then 36g of polyvinyl acetal resin, 3g of diazonaphthoquinone resin, and 6g of diphenylamine diazo resin were sequentially added, dissolved and filtered with filter paper to obtain the photoresist composition of example 5.
Example 6
A photoresist composition comprising: 1.5 parts of indigo, 32 parts of epoxy resin, 2082.5 parts of diazonaphthoquinone resin BP, and diphenylamine diazo resin (wherein n is 100, and W is CH)2、R-Dodecyl benzene sulfonate anion, X is methyl, Y is nitro, Z is ethyl) 5 weight parts, methyl ethyl ketone 59 weight parts.
The preparation method of the photoresist composition comprises the following steps: 1.5g of indigo was dissolved in 59g of methyl ethyl ketone, and then 32g of epoxy resin, 5g of diphenylamine diazo resin, and 2.5g of diazonaphthoquinone resin were sequentially added, dissolved and filtered with filter paper to obtain the photoresist composition of example 6.
Example 7
A photoresist composition comprising: 1.7 parts of malachite green, 28 parts of polyvinyl acetal resin, 1.8 parts of diazonaphthoquinone resin 703 normal glue, and diphenylamine diazo resin (wherein n is 500, and W is CH)2、R-Mesitylene sulfonate anion, X is methoxyl, Y is nitryl, Z is methyl) 4.5 weight portions, and N-methyl pyrrolidone 64 weight portions.
The preparation method of the photoresist composition comprises the following steps: 1.7g of malachite green was dissolved in 64g N-methylpyrrolidone, and then 1.8g of diazonaphthoquinone resin, 4.5g of diphenylamine diazo resin, 28g of polyvinyl acetal resin were added in this order, dissolved and filtered with filter paper to obtain the photoresist composition of example 7.
Double exposure
The double exposure according to the present invention may be performed by a step in which a diazonaphthoquinone resin is used as a positive photoresist and a diphenylamine diazo resin is used as a negative photoresist. FIG. 1 is a photosensitive spectrum of a diazonaphthoquinone resin. FIG. 2 is a photosensitive spectrum of diphenylamine-diazo resin. As can be seen from FIG. 1, the main photosensitive wavelength of the diazonaphthoquinone resin is in the vicinity of 365 nm. As can be seen from FIG. 2, the main photosensitive wavelength of the diphenylamine diazonium resin is around 420nm, and furthermore, the absorbance value is continuously decreased as the exposure time is prolonged, that is, the content of the diphenylamine diazonium resin is continuously decreased, and the diphenylamine diazonium resin is completely decomposed after being irradiated at the 420nm wavelength for 60 s.
(1) First exposure
The photoresist composition of the invention is coated on the SiO deposited by the plasma enhanced chemical vapor deposition at the rotating speed of 2000-6000 r/min2(thickness of
) The glass substrate is prebaked for 2-10 minutes at 100 ℃ to form a photoresist-containing thin film PRIIII, and then is subjected to first exposure by an exposure machine at a wavelength of 365nm (i rays) and an exposure intensity of 30-180mJ/cm2。
Since the main photosensitive wavelength of the diazonaphthoquinone resin is near 365nm (i-line) (as shown in fig. 1), photodecomposition occurs upon irradiation with 365nm ultraviolet light. After developing with the developer for 20 seconds, the photosensitive portion was dissolved in the developer and removed, and the non-photosensitive portion was developed into an image. Meanwhile, since the main photosensitive wavelength of the diphenylamine diazo resin is 420nm (g line) (as shown in fig. 2), no reaction occurs upon irradiation with 365nm ultraviolet light, and neither a photosensitive portion nor an unexposed portion is dissolved in the developer and left. Thus, the first photoresist film pattern PR I identical to the image of the first mask plate a is obtained.
(2) Second exposure
Exposing the photoresist composition with ultraviolet light (g rays) having a wavelength of 420nm at an intensity of 30-180mJ/cm2。
Since the main photosensitive wavelength of the diphenylamine diazo resin is around 420nm (g line), the diphenylamine diazo resin is crosslinked with the film-forming resin upon the second exposure. After developing with the developer for 20 seconds, the photosensitive portion was developed into an image, and the non-photosensitive portion was dissolved in the developer and removed. Meanwhile, since the main photosensitive wavelength of the diazonaphthoquinone resin is 365nm (i-line), no photodecomposition occurs upon irradiation with ultraviolet light of 420nm, and neither a photosensitive portion nor an unexposed portion is dissolved in the developer and left. Thereby obtaining a second photoresist film pattern PRII.
Through the mode of double-mask plate twice exposure, the preparation of a finer line width graph under the limitation of the line width of the mask plate can be realized. As shown in fig. 5, the minimum line width or line distance for the first mask plate a and the second mask plate B is 1 μm, and the exposure of the pattern with a line width of 0.5 μm can be realized by shifting the two mask plates by 0.5 μm (i.e. the line width of the first photoresist film pattern I is 1 μm, and the line width of the second photoresist film pattern II is 0.5 μm).
FIG. 4 is a schematic cross-linking diagram of diphenylamine diazo resin, film-forming resin and passivation layer. During exposure, diazo phenyl is mainly heterocleaved due to the electron withdrawing action of the nitro group, so that a large amount of diphenylamine cations are generated to react with-OH nucleophilic reagents on the film-forming resin. In addition, diphenylamine cations can also react with SiO2The hydrogen bond formed between the surface of the film and water molecules is crosslinked, and the result is the exposed photoresist and SiO2The surfaces are bonded together by hydrogen bonds and do not detach during development, while the unexposed portions of the photoresist do not have such bonding and are removed after development.
In the invention, the same developing solution is used for the two times of development, and the developing solution is prepared by mixing 1-5 parts by mass of Na2SiO38-10 parts by mass of benzyl alcohol and 4-8 parts by mass of sodium dodecyl sulfate are dissolved in 80-120 parts by mass of water.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (6)
1. A photoresist composition, comprising: 30-45 parts of resin, 0.02-0.2 part of background dye and 55-70 parts of organic solvent; the resin comprises photosensitive resin and film-forming resin, and the photosensitive resin comprises diazonaphthoquinone resin and diphenylamine diazo resin; the mass ratio of the diphenylamine diazo resin to the diazonaphthoquinone resin is (2-4): 1;
wherein the diazonaphthoquinone resin is selected from BP207, BP208, BP209, BP210, BP211, BP212, 702 normal glue and 703 normal glue;
the diphenylamine diazo resin has the following structure:
wherein n is 2 and W is CH2、R-Dodecyl sulfonate anion, X is methoxyl, Y is nitryl, and Z is methyl; n is 6 and W is CH2、R-Is mesitylene sulfonate anion, X is hydrogen, Y is nitro, Z is methyl; n is 1000 and W is CH2、R-Is hexafluorophosphate radical anion, X is methyl, Y is nitro, Z is ethyl; n is 10 and W is CH2、R-Is naphthalenesulfonate anion, X is methyl, Y is nitro and Z is methyl; n is 8 and W is CH2、R-Is p-toluenesulfonate anion, X is hydrogen, Y is nitro, Z is ethyl; n is 100 and W is CH2、R-Dodecyl benzene sulfonate anion, X is methyl, Y is nitro, and Z is ethyl; n is 500 and W is CH2、R-Is mesitylene sulfonate anion, X is methoxyl, Y is nitryl, and Z is methyl.
2. The photoresist composition of claim 1, wherein the mass ratio of the film-forming resin to the photosensitive resin is (4-6): 1.
3. the photoresist composition of claim 1, wherein the film-forming resin is selected from any one or more of epoxy resin, polyvinyl acetal resin and polyurethane resin.
4. The photoresist composition of claim 1, wherein the organic solvent is selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, methyl ethyl ketone, butyl acetate, dioxane, N-methyl pyrrolidone, methanol and tetrahydrofuran.
5. The photoresist composition of claim 1, wherein the background dye is selected from the group consisting of basic brilliant blue, crystal violet, victoria pure blue, indigo, methyl violet, malachite green and oil soluble blue.
6. The method of any one of claims 1 to 5, comprising the steps of: dissolving the background dye in an organic solvent, then adding the film-forming resin, the diazonaphthoquinone resin and the diphenylamine diazo resin, dissolving and filtering to obtain the photoresist composition.
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| CN105807563A (en) * | 2016-05-16 | 2016-07-27 | 京东方科技集团股份有限公司 | Photoresist composition and preparation method and composition method thereof |
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2017
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| CN102971391A (en) * | 2010-07-02 | 2013-03-13 | Dic株式会社 | Fluorine-based surfactant, and coating composition and resist composition each using same |
| CN105319845A (en) * | 2014-06-27 | 2016-02-10 | 奇美实业股份有限公司 | Photosensitive resin composition, protective film and element with protective film |
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