CN114967341A - Positive photosensitive resin composition for low-temperature process and method for producing resist film - Google Patents
Positive photosensitive resin composition for low-temperature process and method for producing resist film Download PDFInfo
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- CN114967341A CN114967341A CN202110214390.2A CN202110214390A CN114967341A CN 114967341 A CN114967341 A CN 114967341A CN 202110214390 A CN202110214390 A CN 202110214390A CN 114967341 A CN114967341 A CN 114967341A
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- 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
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Abstract
A positive photosensitive resin composition for low temperature processing comprises an alkali-soluble phenolic resin, a compound with quinonediazide groups, a mixed solvent and at least one additive. The mixed solvent comprises a first solvent and a second solvent, wherein the volatilization speed of the first solvent relative to the volatilization speed of the n-butyl acetate 100 is more than 50, and the boiling point of the second solvent is between 150 ℃ and 200 ℃. At least one additive has a molecular weight of 500-5000 and a structural unit shown in formula (I), wherein R1 is selected from the group consisting of hydrogen, hydroxyl, C1-C5 alkyl, phenyl, halogen atoms and cyano, R2 is selected from the group consisting of hydrogen, acid radicals, benzene and derivatives thereof, phenols, benzoic acid and derivatives thereof and aromatic heterocycles, and n is 10-80. The present disclosure also provides a method for manufacturing a photoresist film,
Description
Technical Field
The present invention relates to a positive photosensitive resin composition and a method for manufacturing a photoresist film, and more particularly to a positive photosensitive resin composition for a low temperature process.
Background
In the current preparation of photosensitive resin compositions and photoresist films, after the photosensitive resin composition is coated, reduced pressure or vacuum drying is carried out to evacuate most of the solvent, so that the composition is formed into a film. Then, pre-baking is performed to bake the remaining solvent and increase the adhesion of the film. And then exposing, developing and post-baking to obtain the photoresist film with the semi-cone-shaped pattern.
The pressure value during vacuum drying or vacuum drying and the baking temperature affect the formation and quality of the photoresist film, for example, too low pressure value will cause the solvent to boil suddenly, resulting in uneven film surface, and too high pressure will cause the solvent not to dry, resulting in too soft film surface and failure of film formation. The current photosensitive resin compositions are not suitable for low temperature processes under the requirements for adhesion and resist patterns. The implementation of the low temperature process therefore leaves open the development of new photosensitive resin compositions, which also contribute to the development of the low temperature process.
Disclosure of Invention
One embodiment of the present invention provides a photosensitive resin for low temperature processing.
Another embodiment of the present invention provides a photoresist film prepared by a low temperature process, which has proper sensitivity and residual film ratio, good adhesion, and satisfactory photoresist pattern.
Another embodiment of the present invention provides a method for manufacturing a photoresist film, which eliminates the need for high temperature baking and reduces the threshold for pressure reduction.
The positive photosensitive resin composition for low temperature processing provided by one embodiment of the present invention includes (a) an alkali-soluble phenolic resin, (B) a compound having a quinonediazido group, (C) a mixed solvent, and (D) at least one additive. (C) The mixed solvent comprises (C-1) a first solvent and (C-2) a second solvent, wherein the volatilization rate of the first solvent relative to the volatilization rate of the n-butyl acetate 100 is more than 50, and the boiling point of the second solvent is between 150 and 200 ℃. (D) At least one additive has a molecular weight of 500-5000 and a structural unit shown in formula (I), wherein R1 is selected from the group consisting of hydrogen, hydroxyl, C1-C5 alkyl, phenyl, halogen atom and cyano, R2 is selected from the group consisting of hydrogen, acid radical, benzene and its derivatives, phenols, benzoic acid and its derivatives, and aromatic heterocycles, and n is 10-80,
in an embodiment of the invention, the alkali-soluble phenolic resin (a) is 100 parts by weight, the mixed solvent (C) is 400 to 1500 parts by weight, and the weight ratio of the first solvent (C-1) to the second solvent (C-2) is between 90: 10-50: between 50.
In an embodiment of the present invention, the alkali-soluble phenol resin (a) is 100 parts by weight, and the quinonediazide group-containing compound (B) is 20 to 40 parts by weight.
In an embodiment of the invention, the alkali-soluble phenolic resin (a) is 100 parts by weight, and the additive (D) is 20 to 40 parts by weight.
In an embodiment of the present invention, the (C-1) first solvent is selected from the group consisting of n-butyl acetate, Propylene Glycol Monomethyl Ether (PGME), n-propyl propionate (NPP), isobutyl alcohol (IBA), isopropyl alcohol (IPA), isobutyl acetate (IBAC), and methyl isobutyl ketone (MIBK), and the (C-2) second solvent is selected from the group consisting of ethyl 3-ethoxypropionate, propylene glycol monobutyl ether (PnB), diethylene glycol methyl ether (DM), cyclohexanone (ANONE), Propylene Glycol Diacetate (PGDA), Dimethylformamide (DMF), methoxybutyl acetate (MBA), and Ethyl Lactate (EL).
In an embodiment of the invention, the (C-1) first solvent is n-butyl acetate, and the (C-2) second solvent is ethyl 3-ethoxypropionate.
In an embodiment of the invention, the mixed solvent (C) accounts for 70 to 90 wt% of the composition.
In an embodiment of the present invention, the at least one additive (D) has a structural unit represented by formula (II), wherein m is 10-30,
in an embodiment of the invention, the positive photosensitive resin composition for low temperature processing further includes a surfactant, a contrast enhancer, an adhesion promoter, or a combination thereof.
An embodiment of the present invention further provides a method for manufacturing a photoresist film, including the steps of: a coating step of coating the positive photosensitive resin composition on a substrate; a baking step of baking the positive photosensitive resin composition at a low temperature; an exposure step of exposing the positive photosensitive resin composition; and a developing step of performing development.
In an embodiment of the present invention, the baking step further includes a pre-baking step of pre-baking at a temperature not exceeding 90 ℃ before the exposure step, and; a post-baking step of performing post-baking after the developing step at a temperature not exceeding 90 ℃.
In one embodiment of the present invention, wherein the pre-baking step uses a 80 ℃ hot plate for pre-baking, and; the post-baking step uses a hot plate at 85 ℃ for post-baking.
In an embodiment of the invention, the manufacturing method further includes a reduced pressure drying step, wherein the reduced pressure drying of the positive photosensitive resin composition is performed before the baking step, and a pressure of the reduced pressure drying is greater than 20 Pa.
In an embodiment of the invention, in the manufacturing method, a pressure of the reduced pressure drying in the reduced pressure drying step is 1500 Pa.
The composition of some embodiments of the invention uses the mixed solvent and at least one additive, the first solvent of the mixed solvent has a volatilization speed of more than 50 relative to the volatilization speed of 100 n-butyl acetate, the second solvent has a boiling point between 150 ℃ and 200 ℃, and the at least one additive has a molecular weight of 500 to 5000 and a structural unit shown in formula (I), so the composition is suitable for low-temperature processing, and the formed photoresist film has proper sensitivity and residual film rate, good adhesion and photoresist pattern meeting the requirement. The method of several embodiments of the invention can omit high-temperature baking and is beneficial to avoid the step of greatly reducing pressure because of using the composition.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the content of the description, and in order to make the above and other objects, features, and advantages of the present invention more clearly understood, the following preferred embodiments are described in detail with reference to the accompanying drawings.
Drawings
FIG. 1A is a schematic diagram of a photoresist pattern according to an embodiment of the invention.
FIG. 1B is a schematic diagram of a photoresist pattern according to another embodiment of the present invention.
FIG. 1C is a schematic diagram of a photoresist pattern according to yet another embodiment of the present invention.
Detailed Description
Unless otherwise defined, the low temperature mentioned in the present disclosure is not particularly limited, but preferably may be less than or equal to 150 ℃, less than or equal to 100 ℃, and most preferably may be less than or equal to 90 ℃.
Positive photosensitive resin composition
One embodiment of the present invention provides a positive photosensitive resin composition, which can be used in a low temperature process. The positive photosensitive resin composition of some embodiments of the invention includes (a) an alkali-soluble phenolic resin, (B) a quinonediazido compound as a photosensitizer, (C) a mixed solvent, and (D) at least one additive.
(A) Alkali soluble phenolic resin
The alkali-soluble phenol resin (a) in some embodiments of the present invention is not particularly limited, but in some embodiments, the alkali-soluble phenol resin (a) is obtained by polycondensing a phenol and an aldehyde using a catalyst such as an inorganic or organic acid.
In several embodiments of the present invention, (A) the phenol used in the alkali-soluble phenol-formaldehyde resin may comprise a cresol (e.g., o-cresol, m-cresol, p-cresol), a xylenol (e.g., 3, 5-xylenol, 2, 3-xylenol, 3, 4-xylenol, etc.), a trimethylphenol (e.g., 2,3, 4-trimethylphenol, 2,3, 5-trimethylphenol, 2,4, 5-trimethylphenol, 3,4, 5-trimethylphenol, etc.), a tributylphenol (e.g., 2-tributylphenol, 3-tributylphenol, 4-tributylphenol, etc.), a methoxyphenol (e.g., 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, etc.), a phenol, 2, 3-dimethoxyphenol, 2, 5-dimethoxyphenol, 3, 5-dimethoxyphenol, etc.), ethylphenols (e.g., 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2, 3-diethylphenol, 3, 5-diethylphenol, 2,3, 5-triethylphenol, 3,4, 5-triethylphenol, etc.), chlorophenols (e.g., o-chlorophenol, m-chlorophenol, p-chlorophenol, 2, 3-dichlorophenol, etc.), resorcinols (e.g., resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, etc.), catechols (e.g., 5-methylcatechol, etc.), gallphenols (e.g., 5-methylgallphenol, etc.), bisphenols (e.g., bisphenol A, bisphenol B, etc.), B. C, D, E, F, etc.), methylolated cresols (e.g., 2, 6-dimethylol-p-cresol, etc.), naphthols (e.g., α -naphthol, β -naphthol, etc.), etc., and the like, and they may be used alone or in combination of a plurality thereof.
In some embodiments of the present invention, the aldehyde used in the (a) alkali-soluble phenolic resin may include formaldehyde, salicylaldehyde, p-formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloromaldehyde, etc., which may be used alone or in combination of a plurality thereof.
In some embodiments of the present invention, the weight average molecular weight (Mw) of the alkali-soluble phenolic resin (a) is 4,000 to 20,000, and preferably 6,000 to 10,000. In several embodiments of the present disclosure, the weight average molecular weight of (a) the alkali-soluble phenolic resin may be determined by colloid permeation chromatography (GPC). When the weight average molecular weight is less than 4,000, high-speed coating at a coating speed of 200 mm/sec or more cannot be performed, and a uniform film thickness cannot be formed. On the other hand, when the weight average molecular weight is more than 20,000, since the viscosity of the resin is too high, there is a great difference in the weight average molecular weight between the polymer withdrawn from the beginning and the polymer withdrawn at the end of the reaction tank, possibly resulting in failure to stabilize the synthesis.
In some embodiments of the present invention, (a) the alkali-soluble phenolic resin may also be a novolac resin. In several embodiments of the present invention, (a) the alkali-soluble phenol resin may be used singly or in combination of two or more.
(B) Compounds having quinonediazido group
In some embodiments of the present invention, (B) the compound having a quinonediazido group is not particularly limited, but is mainly used as a photosensitizer. (B) The compound having a quinonediazide group is generally a quinonediazide compound obtained by reacting a low-molecular compound or a high-molecular compound having a functional group capable of undergoing a condensation reaction with a quinonediazide compound containing an acid chloride, such as naphthoquinonediazide sulfonyl chloride (for example, 1, 2-naphthoquinonediazide-5-sulfonyl chloride, 1, 2-naphthoquinonediazide-4-sulfonyl chloride) or benzoquinonediazide sulfonyl chloride. Here, the functional group capable of undergoing a condensation reaction with the acid chloride-containing quinonediazide compound is mainly a hydroxyl group. Hydroxyl compounds capable of undergoing a condensation reaction with an acid chloride-containing quinonediazide include hydroxybenzylalkanes such as hydroquinone, resorcinol, 2, 4-dihydroxydiphenylone, 2,3, 4-trihydroxydiphenylone, 2,4, 6-trihydroxydiphenylone, 2,4,4 ' -trihydroxydiphenylone, 2,3,4,4 ' -tetrahydroxydiphenylone, 2 ', 3,4,6 ' -pentahydroxydiphenylone, and the like, hydroxybenzylalkanes such as bis (2, 4-dihydroxyphenyl) methane, bis (2,3, 4-trihydroxyphenyl) methane, bis (2, 4-dihydroxyphenyl) propane, and the like, hydroxybenzymethanes such as 4,4 ' -3 ", 4 "-tetrahydroxy-3, 5,3 ', 5 ' -tetramethyltriphenylmethane, 4 ', 2", 3 ", 4" -pentahydroxy-3, 5,3 ', 5 ' -tetramethyltriphenylmethane, etc.), which may be used alone or in admixture of a plurality thereof.
In still another embodiment of the present invention, the (B) quinonediazide-containing compound may be a compound obtained by reacting a naphthoquinonediazide-containing compound with a phenol-group-containing compound, such as a compound obtained by reacting TrisP-PA with naphthoquinone-1, 2-diazide-5-sulfonyl chloride, for example. The amount of the alkali-soluble phenol resin (A) is 20 to 40 parts by weight based on 100 parts by weight of the alkali-soluble phenol resin (B) having a quinonediazide group.
(C) Mixed solvent
The (C) mixed solvent in several embodiments of the present invention is not particularly limited. In some embodiments, the (C) mixed solvent may include (C-1) a first solvent and (C-2) a second solvent, and is 70-90 wt% of the composition. In some embodiments, when the alkali-soluble phenolic resin (A) is 100 parts by weight, the mixed solvent (C) is 400-1500 parts by weight. In several embodiments, (C-1) the first solvent has a volatilization rate of 50 or more (i.e., relative volatilization rate with butyl acetate volatilization rate of 100), such as n-butyl acetate, Propylene Glycol Monomethyl Ether (PGME), n-propyl propionate (NPP), Isobutanol (IBA), Isopropanol (IPA), isobutyl acetate (IBAC), methyl isobutyl ketone (MIBK), and the like. In several embodiments, the (C-2) second solvent has a boiling point between 150 ℃ and 200 ℃, such as ethyl 3-ethoxypropionate, propylene glycol monobutyl ether (PnB), diethylene glycol methyl ether (DM), diethylene glycol methyl ethyl ether (DEME), cyclohexanone (ANONE), Propylene Glycol Diacetate (PGDA), Dimethylformamide (DMF), methoxybutyl acetate (MBA), Ethyl Lactate (EL), and the like. In several embodiments, the weight ratio of (C-1) the first solvent to (C-2) the second solvent is between 90: 10-50: between 50.
(D) At least one additive
The (D) at least one additive in several embodiments of the present invention is not particularly limited. In some embodiments, (D) at least one additive has a molecular weight of 500-5000 and a structural unit represented by formula (I), wherein R1 is selected from the group consisting of hydrogen, hydroxyl, C1-C5 alkyl, phenyl, halogen atom, and cyano, R2 is selected from the group consisting of hydrogen, acid radical, benzene and its derivatives, phenols, benzoic acid and its derivatives, and aromatic heterocycles, and n is 10-80, wherein the benzene derivatives are compounds of benzene substituted with one or more halogens, cyano, alkyl, alkoxy, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, hydroxyl, nitro, amino, etc., the phenols include compounds of phenol and its derivatives of phenol substituted with one or more halogens, cyano, alkyl, alkoxy, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, hydroxyl, nitro, amino, etc., and the benzoic acid derivatives of benzoic acid substituted with one or more halogens, cyano, alkyl, alkoxy, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, hydroxyl, nitro, amino, etc, Cyano group, alkyl group, alkoxy group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, hydroxyl group, nitro group, amino group, and the like, wherein the hetero atom of the heterocycle is selected from N, O, S, and the like, and is, for example, a compound represented by the following formulae (i), (ii), (iii), and (iv). When the alkali-soluble phenolic resin accounts for 100 parts by weight, at least one additive accounts for 20-40 parts by weight. In some embodiments of the present invention, the composition may further comprise a plurality of additives, and may further comprise a surfactant, a contrast-enhancing agent, an adhesion promoter or a combination thereof in addition to the compound having the structural unit represented by formula (I),
in some embodiments of the present invention, (D) at least one additive has a structural unit represented by formula (II), wherein m is 10 to 30,
examples 1 to 2 below illustrate (A) an alkali-soluble phenol resin and (B) a compound having a quinonediazido group in some examples of the present invention, and examples 3 to 7 illustrate a positive photosensitive resin composition in some examples of the present invention.
Example 1: (A) alkali soluble phenolic resin and preparation thereof
A four-port split reaction tank having a capacity of 10 liters was provided with a nitrogen inlet, a stirrer, a heater and a condenser. After introducing nitrogen gas for 30 minutes, 1 mol of cresols, 0.5 mol of dihydroxybenzaldehydes and 0.015 mol of oxalic acid were added. Stirring was carried out slowly for 6 hours and the temperature was raised to 90 ℃ at which the condensation reaction proceeded. Then, the solution was heated to 170 ℃ and dried under reduced pressure of 10mmHg, and the solvent was volatilized to obtain (A) an alkali-soluble phenol resin.
Example 2: (B) compound having quinonediazido group and preparation thereof
0.5 mol of TrisP-PA and 1.5 mol of naphthoquinone-1, 2-diazide-5-sulfonyl chloride were dissolved in dimethylacetamide, the reaction solution was cooled with ice cubes, and triethylamine as an alkaline catalyst was added thereto to allow a reaction for 2 hours. Triethylamine was filtered off, the filtrate was poured into water to produce a precipitate, the precipitate was collected and washed with water 2 times, and then the temperature was raised to 50 ℃ and the reduced pressure of 10mmHg was applied for drying to obtain (B) a quinonediazido group-containing compound.
Example 3: preparation of Positive photosensitive resin composition
Taking 100 parts by weight of (A) alkali-soluble phenolic resin, adding 30 parts by weight of (B) compound with quinonediazide group, adding 20 parts by weight of (D) additive containing trisstyrylphenol ethoxylated (II) structure, adding 80 parts by weight of n-butyl acetate (NBAc) and 3-Ethyl Ethoxypropionate (EEP): 20 (C) mixed solvent. After mixing and stirring, the mixture was filtered through a 0.45 μm filter to prepare composition 1 having a solvent content of 80 wt%. The (A) alkali-soluble phenol resin used may be, for example, the (A) alkali-soluble phenol resin of example 1, the (B) compound having a quinonediazido group used may be, for example, the (B) compound having a quinonediazido group of example 2,
examples 4 to 7: preparing positive photosensitive resin compositions 4-7
Example 4 is different from example 3 in that the additive having the structure represented by formula (II) was added in an amount of 30 parts by weight, and the rest was the same. Example 5 is different from example 3 in that the additive having the structure represented by formula (II) was added in an amount of 40 parts by weight. Example 6 differs from example 3 in that the weight ratio of n-butyl acetate to ethyl 3-ethoxypropionate was changed to 90: 10. example 7 differs from example 3 in that the weight ratio of n-butyl acetate to ethyl 3-ethoxypropionate was changed to 70: 30 and the rest parts are the same.
In the present disclosure, further disclosed are comparative examples 1 to 6, wherein the ratio of n-butyl acetate to ethyl 3-ethoxypropionate is changed in comparative examples 1 to 2, the kind of the second solvent is changed in comparative examples 3 to 5, and the amount of the additive having the structure shown in formula (II) is changed in comparative example 6, which is described in detail below.
In comparison to example 3, comparative example 1 uses a weight ratio of 95: 5 of n-butyl acetate and ethyl 3-ethoxypropionate, and comparative example 2 used a mixture of 45: 55 of n-butyl acetate and 3-ethoxy ethyl propionate to obtain a positive photosensitive resin composition b. Comparative example 3 using a weight ratio of n-butyl acetate to dipropylene glycol methyl ether acetate (DPMA, bp. 209 ℃ C.) of 95: 5 to obtain a positive photosensitive resin composition c. Comparative example 4 Using a weight ratio of n-butyl acetate to propylene glycol monomethyl ether acetate (PGMEA, boiling point: 146 ℃ C.) of 80: 20 to obtain a positive photosensitive resin composition d. Comparative example 5 using a 50 weight ratio of n-butyl acetate to Propylene Glycol Monomethyl Ether Acetate (PGMEA): 50 to obtain a positive photosensitive resin composition e. Comparative example 6A positive photosensitive resin composition f was prepared without using an additive having a structure represented by formula (II). The differences between the compositions 1 to 5 of examples 3 to 7 and the compositions a to f of comparative examples 1 to 6 are summarized in Table 1 below.
Table 1:
in some embodiments of the present invention, there is also provided a method for manufacturing a photoresist film, including the steps of: a coating step of coating the positive photosensitive resin composition on a substrate; a baking step of baking the positive photosensitive resin composition at a low temperature; an exposure step of exposing the positive photosensitive resin composition; and a developing step of performing development. The method for manufacturing a resist film according to some embodiments of the present invention is suitable for manufacturing a resist film from the positive photosensitive resin composition. The positive photosensitive resin composition is also suitable for the manufacturing method disclosed in the present disclosure. In an embodiment of the invention, the baking step further includes a pre-baking step and a post-baking step, respectively performing the pre-baking before the exposure step and performing the post-baking after the developing step at a temperature not higher than 90 ℃. Specifically, the pre-baking further comprises pre-baking using a 80 ℃ hot plate, and the post-baking comprises post-baking using an 85 ℃ hot plate. In some embodiments of the present invention, preferably, the positive photosensitive resin composition is dried under reduced pressure before being baked at a low temperature. In a more preferred embodiment of the present invention, the pressure of the reduced pressure drying is greater than 20Pa, and the reduced pressure is also allowed to be much greater than 20Pa, such as 1500 Pa. The following example 8 illustrates a method of manufacturing a photoresist film in several embodiments of the present invention.
Example 8: method for manufacturing photoresist film
The compositions 1 to 5 and a to f are applied to a substrate by spin coating. Vacuuming/reducing the pressure to 1500Pa, and baking at 80 deg.C for 180 s to obtain 1.5 μm film, wherein the vacuuming/reducing pressure can be adjusted according to the photoresist pattern to be formed. The resist films were exposed, developed with 2.38% TMAH for 60 seconds, and baked on a hot plate at 85 ℃ for 180 seconds to obtain resist films.
The resist films obtained by the above-mentioned methods were further evaluated for compositions 1 to 5 and a to f. The evaluation content includes: whether the photoresist pattern is a desired pattern, the film sensitivity, and the residual film rate. The following example 9 exemplifies the method of evaluation, and presents the evaluation results of each resist film.
Example 9: evaluation method and evaluation result thereof
And (3) evaluating the graph: the pattern after post bake was confirmed using a Field Emission Scanning Electron Microscope (FESEM) U-8010, in which the pattern conforms to a half cone as illustrated in FIG. 1A, and evaluated as O for the expected results. The graph portion fits into a half cone as exemplified in fig. 1B, and is rated by Δ. Those whose pattern does not conform to a half cone are rated gamma as illustrated in FIG. 1C.
Evaluation of sensitivity: the exposure was carried out using a Nikon Stepper FX-601, and the exposure pattern was observed using an optical microscope, and the line width and the line pitch were 4 μm, and the amount of exposure energy (Eop, unit: mJ) required was confirmed by the three-dimensional structure of the line width and the line pitch. Those with 20mJ < Eop ≦ 50mJ rated O, 50mJ < Eop ≦ 60mJ rated Δ, and those with Eop ≦ 20 or 60mJ < Eop rated gamma.
Evaluation of residual film: the film thickness before and after development was measured by a film thickness meter F50, and the percentage of the thickness after development to the thickness before development (unit:%) was calculated, in which the residual film Rate (RFT) was rated as ≈ 90% or more, Δ was rated for 70% or more but not more than 90%, and gamma was rated for not more than 70%. The evaluation results of the resist films are shown in table 2 below. A greater residual film rate reflects a higher resistance to chemicals.
Table 2:
the evaluation results in table 2 confirm that the positive photosensitive resin composition of several embodiments of the present invention (1) has good sensitivity and (2) is suitable for low temperature processes, which can meet the requirements for adhesion and resist pattern, and has good film forming property, and thus is suitable for, for example, continuous micro-nano imprinting (Roll-to-Roll, R2R), slit coating method for preparing resist film, and other processes with temperature not exceeding 90 ℃. The method in some embodiments of the invention reduces the temperature required for manufacturing the photoresist film, eliminates the step of baking at high temperature (over 90 ℃), and further reduces the pressure drop threshold of decompression/vacuum drying, so that the photoresist film meeting the requirements can be completed without rapid and large decompression.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (14)
1. A positive photosensitive resin composition for low temperature processing, comprising:
a (A) alkali-soluble phenolic resin;
a (B) a compound having a quinonediazido group;
a (C) mixed solvent comprising a (C-1) first solvent and a (C-2) second solvent, wherein the (C-1) first solvent has a volatilization rate of more than 50 relative to the volatilization rate of the n-butyl acetate 100, and the (C-2) second solvent has a boiling point of between 150 and 200 ℃; and
one (D) at least one additive, wherein the at least one additive has a molecular weight of 500-5000 and a structural unit shown in a formula (I), wherein R1 is selected from a group consisting of hydrogen, hydroxyl, C1-C5 alkyl, phenyl, halogen atoms and cyano, R2 is selected from a group consisting of hydrogen, acid radicals, benzene and derivatives thereof, phenols, benzoic acid and derivatives thereof and aromatic heterocycles, and n is 10-80;
2. the positive photosensitive resin composition for low temperature processing as claimed in claim 1, wherein the alkali-soluble phenolic resin (a) is 100 parts by weight, the mixed solvent (C) is 400 to 1500 parts by weight, and the weight ratio of the first solvent (C-1) to the second solvent (C-2) is 90: 10-50: between 50.
3. The positive photosensitive resin composition for low-temperature processing according to claim 1, wherein the alkali-soluble phenol resin (A) is 100 parts by weight, and the quinonediazide-containing compound (B) is 20 to 40 parts by weight.
4. The positive photosensitive resin composition for low temperature processing as claimed in claim 1, wherein the alkali-soluble phenolic resin (A) is 100 parts by weight, and the additive (D) is 20 to 40 parts by weight.
5. The positive photosensitive resin composition of claim 1, wherein the (C-1) first solvent is selected from the group consisting of n-butyl acetate, Propylene Glycol Monomethyl Ether (PGME), n-propyl propionate (NPP), isobutyl alcohol (IBA), isopropyl alcohol (IPA), isobutyl acetate (IBAC), and methyl isobutyl ketone (MIBK), and the (C-2) second solvent is selected from the group consisting of ethyl 3-ethoxypropionate, propylene glycol monobutyl ether (PnB), diethylene glycol methyl ether (DM), cyclohexanone (ANONE), Propylene Glycol Diacetate (PGDA), Dimethylformamide (DMF), methoxybutyl acetate (MBA), and Ethyl Lactate (EL).
6. The positive photosensitive resin composition for low temperature processing as claimed in claim 1, wherein the (C-1) first solvent is n-butyl acetate, and the (C-2) second solvent is ethyl 3-ethoxypropionate.
7. The positive photosensitive resin composition for low temperature processing as claimed in claim 1, wherein the mixed solvent (C) is 70 to 90 wt% of the composition.
9. the positive photosensitive resin composition for low temperature processing as claimed in claim 1, wherein the positive photosensitive resin composition further comprises a surfactant, a contrast enhancer, an adhesion promoter or a combination thereof.
10. A method for manufacturing a resist film, comprising the steps of:
a coating step of coating the positive photosensitive resin composition according to any one of claims 1 to 9 on a substrate;
a baking step of baking the positive photosensitive resin composition at a low temperature;
an exposure step of exposing the positive photosensitive resin composition; and
and a developing step of performing development.
11. The method of manufacturing a resist film according to claim 10, wherein the baking step further comprises a pre-baking step of pre-baking at a temperature not exceeding 90 ℃ before the exposure step, and; a post-baking step of performing post-baking after the developing step at a temperature not exceeding 90 ℃.
12. The method for manufacturing a resist film according to claim 11, wherein the pre-baking step is performed using a hot plate of 80 ℃, and; the post-baking step is post-baked using a 85 ℃ hot plate.
13. The method of manufacturing a resist film according to claim 10, further comprising a reduced pressure drying step of performing reduced pressure drying of the positive photosensitive resin composition before the baking step, wherein a pressure of the reduced pressure drying is greater than 20 Pa.
14. The method of manufacturing a resist film according to claim 13, wherein the pressure of the reduced pressure drying in the reduced pressure drying step is 1500 Pa.
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