CN115933316A - Positive photoresist composition, positive photoresist and MEMS stressed element - Google Patents
Positive photoresist composition, positive photoresist and MEMS stressed element Download PDFInfo
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- CN115933316A CN115933316A CN202211709653.8A CN202211709653A CN115933316A CN 115933316 A CN115933316 A CN 115933316A CN 202211709653 A CN202211709653 A CN 202211709653A CN 115933316 A CN115933316 A CN 115933316A
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Abstract
The invention discloses a positive photoresist composition, a positive photoresist and an MEMS stressed element, belonging to the technical field of electronic chemicals. The positive photoresist composition comprises a first phenolic resin and a second phenolic resin; the first phenolic resin is a polycondensate of formaldehyde, xylenol and methyl phenol, the second phenolic resin is a polycondensate of formaldehyde and methyl phenol, the weight average molecular weights of the first phenolic resin and the second phenolic resin are 30000-60000g/mol and 5000-7000g/mol respectively, the melting points are 155-185 ℃ and 140-160 ℃, and the alkali dissolution rates are 80-120 angstroms/second and 250-350 angstroms/second. The composition has the advantages of excellent etching resistance, high resolution, high sensitivity and good heat resistance. The thick photoresist prepared from the positive photoresist composition can be used for manufacturing MEMS stressed elements with high depth-to-width ratio, fine structure, steep side wall and smooth surface.
Description
Technical Field
The invention relates to the technical field of electronic chemicals, in particular to a positive photoresist composition, a positive photoresist and an MEMS stressed element.
Background
In integrated circuit fabrication, a photoresist is typically used as a sacrificial layer to fabricate components. Firstly, making a pattern to be made on the photoresist by using a photoetching method, then removing the exposed basal layer by using a wet etching method or a dry etching method, and then removing the photoresist by using a photoresist removing liquid to obtain the required pattern.
The sacrificial layer used in wet etching, especially in deep etching, generally requires a photoresist to have good etching resistance and adhesion, so that the protective layer can be prevented from being corroded.
Microelectromechanical Systems (MEMS), also called microelectromechanical systems, microsystems, micromachines, etc., refer to high-technology devices having dimensions of a few millimeters or even smaller. The internal structure of the micro-electro-mechanical system is generally in the micron or even nanometer scale, and the micro-electro-mechanical system is an independent intelligent system.
An important step in the LIGA Technology is the UV-LIGA Technology, which is formed by using a thick photoresist to make a primary template and combining the ultraviolet thick photoresist lithography Technology and the LIGA Technology, and is a key process of the High-aspect-ratio micro machining Technology (High-aspect-ratio) HARMST. The primary template made of the photoresist can be used for manufacturing three-dimensional micromechanical devices with high depth-to-width ratio, fine structure, steep side wall and smooth surface, such as MEMS accelerometers, MEMS microphones, micromotors, micropumps, micro vibrators, MEMS optical sensors, MEMS pressure sensors, MEMS gyroscopes, MEMS humidity sensors, MEMS gas sensors and the like.
The biggest advantage of the photoetching technology is that the photoetching glue can be directly used to make some MEMS stress elements, and the photoetching glue is used to directly make the MEMS structure, so that the structure with higher depth-width ratio can be realized, and the positioning precision can be improved.
The thickness of the film layer of the photoresist is generally 5-100 μm, and the residual solvent amount in the photoresist film is higher due to the thicker film thickness, so that the etching resistance and the adhesive force of the photoresist are poorer.
In view of this, the invention is particularly proposed.
Disclosure of Invention
One of the objects of the present invention is to provide a positive photoresist composition which is advantageous for improving the etching resistance, sensitivity and adhesion of the photoresist.
The second purpose of the invention is to provide a positive photoresist prepared by the combination of the positive photoresist.
The invention also aims to provide an MEMS stressed element manufactured by the photoresist.
The application can be realized as follows:
in a first aspect, the present application provides a positive photoresist composition comprising a phenolic resin;
the phenolic resin comprises a first phenolic resin and a second phenolic resin;
wherein the first phenolic resin is a polycondensate of formaldehyde, xylenol and methylphenol, the weight average molecular weight of the first phenolic resin is 30000-60000g/mol, the melting point is 155-185 ℃, and the alkali dissolution rate is 80-120 angstroms/second;
the second phenolic resin is polycondensate of formaldehyde and methyl phenol, and has weight average molecular weight of 5000-7000g/mol, melting point of 140-160 deg.c and alkali dissolution rate of 250-350 angstrom/sec.
In an alternative embodiment, the mass ratio of the first phenolic resin to the second phenolic resin is 1 to 9.
In an alternative embodiment, the positive photoresist composition further comprises a photosensitizer.
In an alternative embodiment, the photosensitizer is a non-ionic sulfonate photosensitizer.
In an alternative embodiment, the photosensitizer is a diazonaphthoquinone sulfonate photosensitizer of the following structural formula:
In an alternative embodiment, the positive photoresist composition further comprises a solvent.
In an alternative embodiment, the solvent comprises at least one of propylene glycol methyl ether acetate, ethylene glycol methyl ether acetate, ethyl acetate, butyl acetate, ethyl lactate, ethyl alcohol-3-ethoxypropionate, propylene glycol monomethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol ethyl ether, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, and dimethylacetamide.
In an alternative embodiment, the positive photoresist composition further comprises an adhesion promoter.
In an alternative embodiment, the adhesion promoter comprises gamma-glycidoxypropyltrimethoxysilane, 3- (2, 3-glycidoxypropyl) propylmethyldimethoxysilane, gamma-glycidoxypropyltriethoxysilane, beta- (3, 4-epoxycyclohexyl) -ethyltriethoxysilane, beta- (3, 4-epoxycyclohexyl) -ethyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propylmethyldiethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma-aminopropylmethyldimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N, N-diethyl-3-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, gamma-divinyltriaminopropyltrimethoxysilane, gamma-diethylaminomethyltriethoxysilane, N-phenylaminomethyltriethoxysilane, bis- (gamma-trimethoxysilylpropyl) amine, bis- (3-triethoxysilylpropyl) amine, 4-amino-3, 3-dimethylbutyltrimethoxysilane, 3- (2-aminoethyl) -aminopropyltriethoxysilane, 3- (N, N-dimethylaminopropyl) -aminopropylmethyldimethoxysilane, at least one of (N, N-dimethyl-3-aminopropyl) trimethoxysilane, N- (N-butyl) -gamma-aminopropyltrimethoxysilane, vinylbenzylaminoethylaminopropyltrimethoxysilane, N-cyclohexyl-gamma-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane and gamma-piperazinylpropylmethyldimethoxysilane.
In an alternative embodiment, the positive photoresist composition further comprises a sensitizer.
In an alternative embodiment, the sensitizer comprises at least one of benzophenone, 4-hydroxybenzophenone, 5- (4-diphenylaminophenylvinyl) -phenethyloxazolidine-2, 4-dione, benzoin dimethyl ether, 9-phenylacridine, and 4,4' - [1- [4- [1- (4-hydroxyphenyl) -1-methylethyl ] phenyl ] ethylene ] diphenol.
In an alternative embodiment, the positive photoresist composition further comprises a leveling agent.
In an alternative embodiment, the leveling agent comprises at least one of BYK-300, BYK-307, BYK-320, BYK-323, BYK-325, BYK-330, BYK-333, BYK-354, TEGO-432, TEGO-450, TEGO-2300, EFKA-3034, EFKA-3600, EFKA-3776, EFKA-3777, EFKA-3883, UL-5132, UL-5135, UL-5157, and UL-5165.
In an alternative embodiment, the positive photoresist composition further comprises an antifoaming agent.
In an alternative embodiment, the defoamer includes at least one of TEGO-920, EFKA-2022, EFKA-2720, EFKA-2722, EFKA-2770, and F-136.
In an alternative embodiment, the positive photoresist composition comprises 20-50 parts by weight of phenolic resin, 1-10 parts by weight of photosensitizer, 0-1 part by weight of sensitizer, 0-1 part by weight of adhesion promoter, 0-1 part by weight of leveling agent, 0-1 part by weight of defoamer and 40-70 parts by weight of solvent.
In a second aspect, the present application provides a positive photoresist thick film prepared from the components of the positive photoresist thick film composition of any one of the previous embodiments.
In an alternative embodiment, the positive photoresist has a thickness of 50-100 μm.
In a third aspect, the present application provides a MEMS stressed element made of a material including the positive photoresist of the previous embodiments.
In alternative embodiments, the MEMS force-receiving element comprises a MEMS accelerometer, a MEMS microphone, a micro-motor, a micro-pump, a micro-vibrator, a MEMS optical sensor, a MEMS pressure sensor, a MEMS gyroscope, a MEMS humidity sensor, or a MEMS gas sensor.
The beneficial effect of this application includes:
the positive photoresist composition has the advantages of excellent performance, high resolution, high sensitivity and good heat resistance by compounding two phenolic resins with specific molecular weight, melting point and alkali dissolution rate according to a specific proportion. The corresponding positive photoresist can have good sensitivity and etching resistance.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The positive photoresist composition, the positive photoresist and the MEMS stressed element provided by the present application are specifically described below.
The present application provides a first aspect of a positive photoresist composition comprising a phenolic resin; the phenolic resin comprises a first phenolic resin and a second phenolic resin.
Wherein the first phenolic resin is a polycondensate of formaldehyde, xylenol and methyl phenol, and the second phenolic resin is a polycondensate of formaldehyde and methyl phenol.
The weight average molecular weight of the first phenolic resin is 30000-60000g/mol, such as 30000g/mol, 32000g/mol, 35000g/mol, 38000g/mol, 40000g/mol, 42000g/mol, 45000g/mol, 48000g/mol, 50000g/mol, 52000g/mol, 55000g/mol, 58000g/mol or 60000g/mol, and the like, and can be any value within 30000-60000 g/mol.
The melting point can be 155-185 deg.C, such as 155 deg.C, 160 deg.C, 165 deg.C, 170 deg.C, 175 deg.C, 180 deg.C or 185 deg.C, or any other value within the range of 155-185 deg.C.
The rate of alkaline dissolution may be 80-120 a/s, such as 80 a/s, 85 a/s, 90 a/s, 95 a/s, 100 a/s, 105 a/s, 110 a/s, 115 a/s, 120 a/s, etc., or any other value within the range of 80-120 a/s.
The second phenolic resin has a weight average molecular weight of 5000-7000g/mol, such as 5000g/mol, 5200g/mol, 5500g/mol, 5800g/mol, 6000g/mol, 6200g/mol, 6500g/mol, 6800g/mol or 7000g/mol, etc., and may have any other value within the range of 5000-7000 g/mol.
The melting point may be 140-160 deg.C, such as 140 deg.C, 145 deg.C, 150 deg.C, 155 deg.C or 160 deg.C, or may be any other value within the range of 140-160 deg.C.
The rate of alkaline dissolution may be 250-350 angstroms/second, such as 250 angstroms/second, 280 angstroms/second, 300 angstroms/second, 320 angstroms/second, 350 angstroms/second, etc., or any other value within the range of 250-350 angstroms/second.
The first phenolic resin has a relatively large molecular weight and the second phenolic resin has a relatively small molecular weight. The molecular weight mainly affects the etching resistance of the photoresist, and the etching resistance of the photoresist obtained by adopting the phenolic resin with different molecular weights is different.
The melting point of the phenolic resin mainly influences the heat resistance of the photoresist, and further influences the etching resistance.
The alkali dissolution rate of the phenolic resin mainly affects the photosensitivity and the developing rate of the photoresist. The alkali dissolution rate mentioned herein specifically refers to the dissolution rate in a 2.38% aqueous solution of tetramethylammonium hydroxide at 25 ℃.
For reference, in the present application, the mass ratio of the first phenolic resin to the second phenolic resin is 1 to 9, such as 1.
In the method, two phenolic resins with specific molecular weight, melting point and alkali dissolution rate are compounded according to the specific proportion, so that the correspondingly obtained positive photoresist has good sensitivity and etching resistance.
It should be noted that, in the solution protected by the present application, it is not excluded to combine other phenolic resins on the basis of using the first phenolic resin and the second phenolic resin.
The positive photoresist thick composition provided herein also includes a photosensitizer.
Preferably, the photosensitizer used in this application is a non-ionic sulfonate photosensitizer.
More preferably, the photosensitizer used herein is a diazonaphthoquinone sulfonate photosensitizer of the following structural formula:
The photosensitizer can enable the obtained photoresist to have better photosensitivity and developing effect under the condition of the phenolic resin used in the application.
The positive photoresist composition provided herein also includes a solvent.
Among them, the solvent may exemplarily include at least one of propylene glycol methyl ether acetate, ethylene glycol methyl ether acetate, ethyl acetate, butyl acetate, ethyl lactate, ethanol-3-ethoxypropionate, propylene glycol monomethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol ethyl ether, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, and dimethylacetamide.
In an alternative embodiment, the positive photoresist composition further comprises an auxiliary agent, such as at least one of an adhesion promoter, a sensitizer, a leveling agent, and a defoaming agent.
The adhesion promoter may improve the adhesion capability of the system, and may illustratively include gamma-glycidoxypropyltrimethoxysilane, 3- (2, 3-glycidoxypropyl) propylmethyldimethoxysilane, gamma-glycidoxypropyltriethoxysilane, beta- (3, 4-epoxycyclohexyl) -ethyltriethoxysilane, beta- (3, 4-epoxycyclohexyl) -ethyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propylmethyldiethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma-aminopropylmethyldimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N, N-diethyl-3-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, gamma-divinyltriaminopropyltrimethoxysilane, gamma-diethylaminomethyltriethoxysilane, N-phenylaminomethyltriethoxysilane, bis- (gamma-trimethoxysilylpropyl) amine, bis- (3-triethoxysilylpropyl) amine, 4-amino-3, 3-dimethylbutyltrimethoxysilane, 3- (2-aminoethyl) -aminopropyltriethoxysilane, 3- (N, N-dimethylaminopropyl) -aminopropylmethyldimethoxysilane, at least one of (N, N-dimethyl-3-aminopropyl) trimethoxysilane, N- (N-butyl) -gamma-aminopropyltrimethoxysilane, vinylbenzylaminoethylaminopropyltrimethoxysilane, N-cyclohexyl-gamma-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane and gamma-piperazinylpropylmethyldimethoxysilane.
The sensitizer illustratively may include at least one of benzophenone, 4-hydroxybenzophenone, 5- (4-diphenylaminophenylvinyl) -phenethyloxazolidine-2, 4-dione, benzoin dimethyl ether, 9-phenylacridine, and 4,4' - [1- [4- [1- (4-hydroxyphenyl) -1-methylethyl ] phenyl ] ethylene ] diphenol.
The leveling agent may illustratively include at least one of BYK-300, BYK-307, BYK-320, BYK-323, BYK-325, BYK-330, BYK-333, BYK-354, TEGO-432, TEGO-450, TEGO-2300, EFKA-3034, EFKA-3600, EFKA-3776, EFKA-3777, EFKA-3883, UL-5132, UL-5135, UL-5157, and UL-5165.
Defoaming agents may illustratively include at least one of TEGO-920, EFKA-2022, EFKA-2720, EFKA-2722, EFKA-2770, and F-136.
It should be noted that other materials commonly used in the art for the adhesion promoter, sensitizer, leveling agent and defoaming agent can be used. In addition, the auxiliaries used in the photoresist of the present application may also adopt other conventional auxiliaries in the art, and are not described herein in any more detail.
The positive photoresist composition comprises, by weight, 20-50 parts of phenolic resin, 1-10 parts of photosensitizer, 0-1 part of sensitizer, 0-1 part of adhesion promoter, 0-1 part of leveling agent, 0-1 part of defoamer and 40-70 parts of solvent.
The phenolic resin may be used, by reference, in amounts of 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts or 50 parts, but also any other value in the range of 20-50 parts.
The amount of the photosensitizer used may be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, or the like, and may be any other value within the range of 1 to 10 parts.
The amount of the sensitizer to be used may be 0 part, 0.01 part, 0.05 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part or the like, and may be any other value within the range of 0 to 1 part.
The adhesion promoter may be used in an amount of 0 part, 0.01 part, 0.05 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, or the like, or may be used in any other amount within the range of 0 to 1 part.
The leveling agent may be used in an amount of 0 part, 0.01 part, 0.05 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, or the like, and may be any other value within the range of 0 to 1 part.
The amount of the defoaming agent may be 0 part, 0.01 part, 0.05 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1 part, and may be any other value within the range of 0 to 1 part.
The amount of the solvent may be 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, or the like, or may be any other value within the range of 40 to 70 parts.
That is, the auxiliary agents such as a sensitizer, an adhesion promoter, a leveling agent, and a defoaming agent may be selectively added according to actual needs.
The positive photoresist composition provided by the application has the advantages of excellent etching resistance, high resolution, high sensitivity and good heat resistance.
In addition, the present application provides a positive photoresist which is prepared from the components of the positive photoresist composition.
The corresponding preparation process and conditions can refer to the prior art, and are not described in detail herein.
For reference, the thickness of the positive photoresist provided herein is 50-100 μm.
The corresponding positive photoresist has better etching resistance, adhesive force and sensitivity.
In addition, the application also provides an MEMS stressed element, and the manufacturing material of the MEMS stressed element comprises the positive photoresist.
In alternative embodiments, the MEMS force-receiving element comprises a MEMS accelerometer, a MEMS microphone, a micro-motor, a micro-pump, a micro-vibrator, a MEMS optical sensor, a MEMS pressure sensor, a MEMS gyroscope, a MEMS humidity sensor, or a MEMS gas sensor.
The MEMS stressed element manufactured by the positive photoresist provided by the application can meet the requirement of high depth-to-width ratio and improve the positioning precision. The corresponding MEMS stress element has the characteristics of high depth-width ratio, fine structure, steep side wall and smooth surface.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a positive photoresist composition with excellent etching resistance, wherein 100 parts by mass of the positive photoresist composition comprises 25.0 parts of a first phenolic resin, 10.0 parts of a second phenolic resin, 6.3 parts of a photosensitizer, 0.5 part of a sensitizer, 0.7 part of an adhesion promoter, 0.2 part of a leveling agent, 0.5 part of an antifoaming agent, and the balance of a solvent.
Wherein the first phenolic resin is a polycondensate of formaldehyde, xylenol and methyl phenol, the weight-average molecular weight of the polycondensate is 55346g/mol, the melting point of the polycondensate is 175 ℃, and the alkali dissolution rate of the polycondensate is 92 angstrom/second. The second phenolic resin was a polycondensate of formaldehyde and methyl phenol with a weight average molecular weight of 5865g/mol, a melting point of 146 ℃ and an alkali dissolution rate of 306A/s.
The photosensitizer is PAC-520, the sensitizer is 4,4' - [1- [4- [1- (4-hydroxyphenyl) -1-methylethyl ] phenyl ] ethylidene ] diphenol, the adhesion promoter is gamma-glycidyl ether oxypropyl trimethoxy silane, the leveling agent is BYK-307, the defoaming agent is TEGO-920, and the solvent is PGMEA (propylene glycol methyl ether acetate).
Example 2
The embodiment provides a positive photoresist composition with excellent etching resistance, wherein 100 parts by mass of the positive photoresist composition comprises 26.0 parts of first phenolic resin, 8.0 parts of second phenolic resin, 6.3 parts of photosensitizer, 0.5 part of sensitizer, 0.6 part of adhesion promoter, 0.2 part of leveling agent, 0.6 part of defoaming agent, and the balance of solvent.
Wherein the first phenolic resin is a polycondensate of formaldehyde, xylenol and methyl phenol, the weight-average molecular weight of the polycondensate is 55346g/mol, the melting point of the polycondensate is 175 ℃, and the alkali dissolution rate of the polycondensate is 92 angstrom/second. The second phenolic resin was a polycondensate of formaldehyde and methyl phenol with a weight average molecular weight of 5865g/mol, a melting point of 146 ℃ and an alkali dissolution rate of 306A/s.
The photosensitizer is PAC-520, the sensitizer is 4,4' - [1- [4- [1- (4-hydroxyphenyl) -1-methylethyl ] phenyl ] ethylidene ] diphenol, the adhesion promoter is gamma-glycidyl ether oxypropyl trimethoxy silane, the flatting agent is BYK-307, the defoamer is TEGO-920, and the solvent is PGMEA.
Example 3
The embodiment provides a positive photoresist composition with excellent etching resistance, wherein 100 parts by mass of the positive photoresist composition comprises 27.0 parts of first phenolic resin, 6.0 parts of second phenolic resin, 6.3 parts of photosensitizer, 0.5 part of sensitizer, 0.5 part of adhesion promoter, 0.2 part of leveling agent, 0.7 part of defoaming agent, and the balance of solvent.
Wherein the first phenolic resin is a polycondensate of formaldehyde, xylenol and methyl phenol, the weight-average molecular weight of the polycondensate is 55346g/mol, the melting point of the polycondensate is 175 ℃, and the alkali dissolution rate of the polycondensate is 92 angstrom/second. The second phenolic resin was a polycondensate of formaldehyde and methyl phenol with a weight average molecular weight of 5865g/mol, a melting point of 146 ℃ and an alkali dissolution rate of 306A/s.
The photosensitizer is PAC-520, the sensitizer is 4,4' - [1- [4- [1- (4-hydroxyphenyl) -1-methylethyl ] phenyl ] ethylidene ] diphenol, the adhesion promoter is gamma-glycidyl ether oxypropyl trimethoxy silane, the leveling agent is BYK-307, the defoaming agent is TEGO-920, and the solvent is PGMEA.
Example 4
This example differs from example 1 in that: the first phenolic resin had a weight average molecular weight of 31352g/mol, a melting point of 158 ℃ and an alkali dissolution rate of 100A/s.
Example 5
This example differs from example 1 in that: the weight average molecular weight of the first phenolic resin is 58845g/mol, the melting point is 178 ℃, and the alkali dissolution rate is 88 angstrom/second.
Example 6
This example differs from example 1 in that: the second phenolic resin had a weight average molecular weight of 5122g/mol, a melting point of 142 ℃ and a base dissolution rate of 336A/s.
Example 7
This example differs from example 1 in that: the second phenolic resin had a weight average molecular weight of 6878g/mol, a melting point of 155 ℃ and an alkali dissolution rate of 265. ANG./sec.
Example 8
This example differs from example 1 in that: the phenolic resin contained in the positive photoresist composition included 25 parts of the first phenolic resin, 7 parts of the second phenolic resin and 3 parts of the third phenolic resin.
The third phenolic resin has a weight average molecular weight of 3984g/mol, a melting point of 144 ℃ and an alkali dissolution rate of 630 angstrom/sec.
Example 9
This example differs from example 1 in that: the phenolic resin contained in the positive photoresist composition includes 25 parts of a first phenolic resin, 7 parts of a second phenolic resin, and 3 parts of a fourth phenolic resin.
The weight average molecular weight of the fourth phenolic resin is 3550g/mol, the melting point is 138 ℃, and the alkali dissolution rate is 809 angstrom/second.
Example 10
The present example differs from example 1 in that: the photosensitizer is PAC-5320, the sensitizer is 4-hydroxybenzophenone, the adhesion promoter is gamma-aminopropyltriethoxysilane, the leveling agent is EFKA-3777, the defoaming agent is F-136, and the solvent is ethyl lactate.
Comparative example 1
The comparative example provides a positive photoresist composition, wherein 100 parts by mass of the positive photoresist composition comprises 20.0 parts of fifth phenolic resin, 6.3 parts of photosensitizer, 0.5 part of sensitizer, 0.5 part of adhesion promoter, 0.2 part of leveling agent, 0.5 part of defoaming agent, and the balance of solvent.
Wherein the weight average molecular weight of the fifth phenolic resin is 86412g/mol, the melting point is 185 ℃, and the alkali dissolution rate is 58 angstrom/second.
The photosensitizer is PAC-520, the sensitizer is 4,4' - [1- [4- [1- (4-hydroxyphenyl) -1-methylethyl ] phenyl ] ethylidene ] diphenol, the adhesion promoter is gamma-glycidyl ether oxypropyl trimethoxy silane, the leveling agent is BYK-307, the defoaming agent is TEGO-920, and the solvent is PGMEA.
Comparative example 2
The comparative example provides a positive photoresist composition, wherein 100 parts by mass of the positive photoresist composition comprises 40.0 parts of sixth phenolic resin, 6.3 parts of photosensitizer, 0.5 part of sensitizer, 0.5 part of adhesion promoter, 0.2 part of leveling agent, 0.5 part of defoaming agent, and the balance of solvent.
Wherein the weight average molecular weight of the sixth phenolic resin is 4558g/mol, the melting point is 140 ℃, and the alkali dissolution rate is 394 angstrom/second. The photosensitizer is PAC-520, the sensitizer is 4,4' - [1- [4- [1- (4-hydroxyphenyl) -1-methylethyl ] phenyl ] ethylidene ] diphenol, the adhesion promoter is gamma-glycidyl ether oxypropyl trimethoxy silane, the flatting agent is BYK-307, the defoamer is TEG-O920, and the solvent is PGMEA.
Comparative example 3
The comparative example provides a positive photoresist composition, and 100 parts of the positive photoresist composition comprise, by mass, 15 parts of fifth phenolic resin, 10 parts of sixth phenolic resin, 6.3 parts of photosensitizer, 0.5 part of sensitizer, 0.5 part of adhesion promoter, 0.2 part of leveling agent, 0.5 part of defoamer, and the balance solvent.
The fifth phenolic resin is the same as comparative example 1, and the sixth phenolic resin is the same as comparative example 2.
The photosensitizer is PAC-520, the sensitizer is 4,4' - [1- [4- [1- (4-hydroxyphenyl) -1-methylethyl ] phenyl ] ethylidene ] diphenol, the adhesion promoter is gamma-glycidyl ether oxypropyl trimethoxy silane, the leveling agent is BYK-307, the defoaming agent is TEGO-920, and the solvent is PGMEA.
Comparative example 4
The comparative example provides a positive photoresist composition, wherein 100 parts by mass of the positive photoresist composition comprises 25.0 parts of first phenolic resin, 10 parts of second phenolic resin, 6.3 parts of photosensitizer, 0.5 part of sensitizer, 0.2 part of leveling agent, 0.5 part of defoaming agent, and the balance of solvent.
That is, no adhesion promoter was used in this comparative example.
Comparative example 5
The comparative example differs from example 1 in that: the total amount of the first phenol resin and the second phenol resin contained in 100 parts of the positive photoresist composition was 60 parts by mass, and the mass ratio of the two resins was the same as that of example 1.
Comparative example 6
This comparative example differs from example 1 in that: the total amount of the first phenol resin and the second phenol resin contained in 100 parts of the positive photoresist composition was 10 parts by mass, and the mass ratio of the two resins was the same as that of example 1.
Comparative example 7
The comparative example differs from example 1 in that: the fifth phenolic resin is used for replacing the first phenolic resin, the weight-average molecular weight of the fifth phenolic resin is 86412g/mol, the melting point is 185 ℃, and the alkali dissolution rate is 58 angstrom/second.
Comparative example 8
The comparative example differs from example 1 in that: the sixth phenolic resin is used for replacing the second phenolic resin, the weight-average molecular weight of the sixth phenolic resin is 4558g/mol, the melting point is 140 ℃, and the alkali dissolution rate is 394 angstrom/second.
Comparative example 9
This comparative example differs from example 1 in that: the photosensitizer is esterification product of pyrogallol acetone resin and 2, 1-diazonaphthoquinone-5-sulfonyl chloride.
Test examples
The photoresist compositions obtained in examples 1 to 10 and comparative examples 1 to 9 were prepared into photoresists according to the same methods and conditions, respectively.
After the photoresist is dissolved, filtering the photoresist by using a 0.2 mu m micropore filtering membrane, and then gluing, pre-baking, exposing, developing and post-baking the photoresist.
The process conditions are as follows:
1. gluing: 500rpm × 5s +5000rpm × 30s;
2. pre-baking: hot plate at 110 ℃ for 180s;
3. exposure: URE-2000/35 ultraviolet lithography machine;
4. and (3) developing: 2.38wt% TMAH solution (25 ℃);
5. post-baking: hot plate 120 deg.C x 120s;
performance tests were then performed and the results are shown in table 1.
Wherein, the photosensitivity test is expressed by exposure, and the energy meter adopts Sup>A UV-A type ultraviolet radiation meter of an optical instrument factory of Beijing university; the adhesion test refers to GB/T9286-1988; the etching resistance test is expressed by a film remaining rate, wherein the film remaining rate is the percentage of the thickness of the developed film layer of the unexposed part of the photoresist to the thickness of the film layer before development.
The test results are shown in table 1.
Table 1 results of performance testing
As can be seen from the above table, the solutions provided in examples 1 to 10 of the present application can have better photosensitivity, adhesion and etching resistance than those of comparative examples 1 to 9, which indicates that the positive photoresist obtained from the components and the formulation provided in the present application can have better performance than that obtained from the components or the formulation. The results of examples 8 and 9 are worse than those of the other examples, which shows that the combination of the first phenolic resin and the second phenolic resin with other phenolic resins is not necessarily beneficial to improving the performance of the positive photoresist.
In summary, the positive photoresist composition provided by the application has the advantages of excellent etching resistance, high resolution, high sensitivity and good heat resistance. The correspondingly obtained positive photoresist can have good sensitivity and etching resistance, and can be used for manufacturing MEMS (micro-electromechanical systems) stressed elements with high depth-to-width ratio, fine structure, steep side wall and smooth surface.
The present invention has been described in terms of the preferred embodiment, and it is not intended to be limited to the embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A positive photoresist composition, wherein the positive photoresist composition comprises a phenolic resin;
the phenolic resin comprises a first phenolic resin and a second phenolic resin;
wherein the first phenolic resin is a polycondensate of formaldehyde, xylenol and methylphenol, the weight average molecular weight of the first phenolic resin is 30000-60000g/mol, the melting point is 155-185 ℃, and the alkali dissolution rate is 80-120 angstroms/second;
the second phenolic resin is a polycondensate of formaldehyde and methyl phenol, the weight average molecular weight of the second phenolic resin is 5000-7000g/mol, the melting point is 140-160 ℃, and the alkali dissolution rate is 250-350 angstrom/second;
preferably, the mass ratio of the first phenolic resin to the second phenolic resin is 1-9.
2. A positive photoresist thick composition according to claim 1, wherein the positive photoresist thick composition further comprises a photosensitizer;
preferably, the photosensitizer is a non-ionic sulfonate photosensitizer;
preferably, the photosensitizer is a diazonaphthoquinone sulfonate photosensitizer of the following structural formula:
3. The positive photoresist thick composition according to claim 1, wherein the positive photoresist thick composition further comprises a solvent;
preferably, the solvent includes at least one of propylene glycol methyl ether acetate, ethylene glycol methyl ether acetate, ethyl acetate, butyl acetate, ethyl lactate, ethanol-3-ethoxypropionate, propylene glycol monomethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol ethyl ether, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, and dimethylacetamide.
4. A positive photoresist thick composition according to any one of claims 1 to 3, characterized in that it further comprises an adhesion promoter;
preferably, the adhesion promoter includes gamma-glycidoxypropyltrimethoxysilane, 3- (2, 3-glycidoxypropyl) propylmethyldimethoxysilane, gamma-glycidoxypropyltriethoxysilane, beta- (3, 4-epoxycyclohexyl) -ethyltriethoxysilane, beta- (3, 4-epoxycyclohexyl) -ethyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propylmethyldiethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma-aminopropylmethyldimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N, N-diethyl-3-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, gamma-divinyltriaminopropyltrimethoxysilane, gamma-diethylaminomethyltriethoxysilane, N-phenylaminomethyltriethoxysilane, bis- (gamma-trimethoxysilylpropyl) amine, bis- (3-triethoxysilylpropyl) amine, 4-amino-3, 3-dimethylbutyltrimethoxysilane, 3- (2-aminoethyl) -aminopropyltriethoxysilane, 3- (N, N-dimethylaminopropyl) -aminopropylmethyldimethoxysilane, at least one of (N, N-dimethyl-3-aminopropyl) trimethoxysilane, N- (N-butyl) -gamma-aminopropyltrimethoxysilane, vinylbenzylaminoethylaminopropyltrimethoxysilane, N-cyclohexyl-gamma-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane and gamma-piperazinylpropylmethyldimethoxysilane.
5. The positive photoresist composition according to claim 4, wherein the positive photoresist composition further comprises a sensitizer;
preferably, the sensitizer comprises at least one of benzophenone, 4-hydroxybenzophenone, 5- (4-diphenylanilinovinyl) -phenethyloxazolidine-2, 4-dione, benzoin dimethyl ether, 9-phenylacridine and 4,4' - [1- [4- [1- (4-hydroxyphenyl) -1-methylethyl ] phenyl ] ethylene ] diphenol.
6. The positive photoresist composition according to claim 4, wherein the positive photoresist composition further comprises a leveling agent;
preferably, the leveling agent comprises at least one of BYK-300, BYK-307, BYK-320, BYK-323, BYK-325, BYK-330, BYK-333, BYK-354, TEGO-432, TEGO-450, TEGO-2300, EFKA-3034, EFKA-3600, EFKA-3776, EFKA-3777, EFKA-3883, UL-5132, UL-5135, UL-5157 and UL-5165.
7. A positive photoresist composition according to claim 5, wherein the positive photoresist composition further comprises an antifoaming agent;
preferably, the defoamer comprises at least one of TEGO-920, EFKA-2022, EFKA-2720, EFKA-2722, EFKA-2770, and F-136.
8. The positive photoresist composition according to claim 1, wherein the positive photoresist composition comprises, by weight, 20 to 50 parts of phenolic resin, 1 to 10 parts of photosensitizer, 0 to 1 part of sensitizer, 0 to 1 part of adhesion promoter, 0 to 1 part of leveling agent, 0 to 1 part of defoaming agent, and 40 to 70 parts of solvent.
9. A positive photoresist thick resist prepared from the components of the positive photoresist thick resist composition according to any one of claims 1 to 8;
preferably, the thickness of the positive photoresist is 50-100 μm.
10. A MEMS stressed element, wherein the MEMS stressed element is made of a material comprising the positive photoresist of claim 9;
preferably, the MEMS force-receiving element comprises a MEMS accelerometer, a MEMS microphone, a micro-motor, a micro-pump, a micro-vibrator, a MEMS optical sensor, a MEMS pressure sensor, a MEMS gyroscope, a MEMS humidity sensor, or a MEMS gas sensor.
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