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CN-122018234-A - Negative micron-sized photoresist and preparation method thereof

CN122018234ACN 122018234 ACN122018234 ACN 122018234ACN-122018234-A

Abstract

The invention provides a negative micron-sized photoresist and a preparation method thereof, wherein the preparation method comprises the steps of adding sulfur-containing acrylic ester polymer into a double-boiling point organic solvent, fully dissolving the sulfur-containing acrylic ester polymer under the condition of stirring to form sulfur-rich polymer matrix solution, adding functional components containing a silica skeleton structure into the sulfur-rich polymer matrix solution to obtain prefabricated mixed solution, adding surface-treated nano shading particles into the prefabricated mixed solution, stirring and vacuum defoaming in sequence to obtain a precursor solution, and adding a photoinitiation component and a crosslinking promotion component into the precursor solution to obtain the negative micron-sized photoresist. Through the cooperation of the steps, the invention realizes the integral regulation and control of the light energy transmission and crosslinking behavior under the condition of not depending on additional process means, thereby overcoming the problems of uneven thick film crosslinking and structural defects which are easy to generate in the traditional single organic polymer photoresist system.

Inventors

  • YANG ZHONGPING
  • YANG RENHONG

Assignees

  • 广东诚展科技股份有限公司

Dates

Publication Date
20260512
Application Date
20260306

Claims (10)

  1. 1. The preparation method of the negative micron-sized photoresist is characterized by comprising the following steps: S1, adding sulfur-containing acrylic ester polymer into a double-boiling point organic solvent, and fully dissolving the sulfur-containing acrylic ester polymer under the stirring condition to form a sulfur-rich polymer matrix solution; S2, adding a functional component containing a silica skeleton structure into the sulfur-rich polymer matrix solution to obtain a prefabricated mixed solution; s3, adding the surface-treated nano shading particles into the prefabricated mixed solution, and sequentially stirring and vacuum defoaming to obtain a precursor solution; s4, adding a photoinitiation component and a crosslinking promotion component into the precursor liquid to obtain the negative micron-sized photoresist.
  2. 2. The method for preparing negative-tone micron-sized photoresist according to claim 1, wherein step S1 comprises: S1.1, placing a sulfur-containing acrylic ester polymer in a vacuum oven, drying for 4-12 hours at 40-60 ℃ and-0.08 to-0.095 MPa, and simultaneously, dehydrating a double-boiling point organic solvent in advance and placing the organic solvent in a closed brown bottle for later use; s1.2, adding a double-boiling point organic solvent into a jacketed glass liquid preparation kettle, adding deionized water, starting mechanical stirring, adjusting the stirring rotation speed to 300-800 rpm, and stabilizing the temperature to 25-35 ℃ through a constant-temperature water bath; s1.3, adding the acrylic polymer containing the sulfur structural unit into a glass liquid preparation kettle for multiple times in a segmented manner, maintaining stirring for 10-20 min after each addition, then heating to 45-55 ℃ and continuously stirring for 30-90 min to obtain a sulfur-rich polymer matrix solution.
  3. 3. The method according to claim 1 or 2, wherein in the step S1, the sulfur-containing acrylate polymer comprises at least one of poly (2- (phenylthio) ethyl acrylate), poly (2, 2' -thiodiethyl acrylate) and poly (thiodiethanol diacrylate), and the double-boiling organic solvent comprises at least one of propylene glycol methyl ether acetate/cyclohexanone compound solvent, gamma-butyrolactone/methyl isobutyl ketone compound solvent, N-methylpyrrolidone/propylene glycol methyl ether compound solvent and dimethyl sulfoxide/cyclopentanone compound solvent.
  4. 4. The method for preparing negative-tone micron-sized photoresist according to claim 1, wherein step S2 comprises: S2.1, adding a mixed solvent of absolute ethyl alcohol and toluene into a three-neck flask, introducing nitrogen for protection, controlling the temperature of a system to be 0-10 ℃, then adding a silane precursor into the three-neck flask, and adding deionized water and an acid catalyst under the condition of stirring speed of 300-600 rpm to enable the silane precursor to undergo controlled hydrolysis and condensation reaction to form silica-structured sol; S2.2, continuously stirring and reacting the silica structure sol for 1-4 hours under the protection of nitrogen, slowly raising the temperature to 20-30 ℃, adding an organosilane modifier containing unsaturated bonds into the silica structure sol, continuously stirring and reacting for 2-6 hours, and performing reduced pressure distillation or rotary evaporation treatment after the reaction is finished to obtain a silica skeleton structure functional component solution; S2.3, dehydrating and stabilizing the functional component solution of the silica skeleton structure, transferring the functional component solution to a closed brown container for light-shielding preservation, taking part of the sulfur-rich polymer matrix solution as a prefabricated mother solution, adding the functional component solution of the silica skeleton structure into the prefabricated mother solution at 25-35 ℃, performing dispersion treatment for 10-30 min, adding the prefabricated mother solution back into the residual sulfur-rich polymer matrix solution in a dropwise manner, controlling the stirring speed at 400-900 rpm in the back adding process, maintaining the temperature of the system at 25-35 ℃, slowly raising the temperature to 40-50 ℃ after the back adding is completed, and continuously stirring for 30-60 min to obtain the prefabricated mixed solution.
  5. 5. The method according to claim 4, wherein in the step S2, the silane precursor comprises at least one of methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, hydrogen triethoxysilane, and phenyltriethoxysilane, the organosilane modifier comprises at least one of methacryloxypropyl trimethoxysilane, acryloxypropyl triethoxysilane, vinyltriethoxysilane, and allyltrimethoxysilane, and the acidic catalyst comprises at least one of glacial acetic acid, dilute hydrochloric acid, dilute nitric acid, oxalic acid, and p-toluenesulfonic acid.
  6. 6. The method for preparing negative-tone micron-sized photoresist according to claim 1, wherein step S3 comprises: S3.1, placing the nano shading particles in a vacuum oven, drying for 2-6 hours at 60-90 ℃ and-0.08 to-0.095 MPa, adding the dried nano shading particles into absolute ethyl alcohol, and dispersing for 5-15 min by adopting ultrasonic; S3.2, adding a surface compatilizer into the nano shading particles under the condition of continuous stirring, reacting for 1-4 hours at the temperature of 40-70 ℃, after the reaction is finished, centrifugally separating the nano shading particles subjected to surface treatment, and washing and redispersing by using a double-boiling point organic solvent to obtain nano shading particle dispersion liquid; S3.3, adding the nano shading particle dispersion liquid into part of the prefabricated mixed liquid at the temperature of 25-35 ℃, shearing and dispersing for 10-30 min, adding the nano shading particle dispersion liquid back into the rest prefabricated mixed liquid, controlling the stirring speed at 400-900 rpm in the back adding process, maintaining the system temperature at 25-35 ℃, and continuously stirring for 30-60 min after the back adding is completed to obtain dispersed mother liquid; s3.4, carrying out vacuum defoaming treatment on the dispersion mother solution, wherein the defoaming temperature is controlled to be 25-35 ℃, the vacuum degree is-0.08 to-0.095 MPa, the defoaming time is 10-30 min, and then filtering through a solvent-resistant filter membrane with the thickness of 0.45 mu m or 0.2 mu m, wherein the filtering process is carried out in a dark place under a closed condition, so as to obtain the precursor solution containing the surface-treated nano shading particles.
  7. 7. The method according to claim 6, wherein in the step S3, the surface compatilizer comprises at least one of methacryloxypropyl trimethoxysilane, acryloxypropyl triethoxysilane, vinyl triethoxysilane, and allyl trimethoxysilane, the double boiling point organic solvent comprises at least one of propylene glycol methyl ether acetate/cyclohexanone complex solvent, γ -butyrolactone/methyl isobutyl ketone complex solvent, N-methylpyrrolidone/propylene glycol methyl ether complex solvent, dimethyl sulfoxide/cyclopentanone complex solvent, and the nano light shielding particles comprise at least one of nano titanium dioxide particles, nano zinc oxide particles, and nano cerium oxide particles.
  8. 8. The method for preparing negative-tone micron-sized photoresist according to claim 1, wherein step S4 comprises: s4.1, transferring the precursor liquid into a sealed brown liquid preparation bottle, stirring for 10-20 min at 25-30 ℃, adding a photoinitiating component into the precursor liquid at a light-shielding condition, stirring for 20-40 min at a rotating speed of 300-600 rpm at 25-35 ℃, adding a crosslinking promoting component under a continuous stirring condition, regulating the stirring rotating speed to 400-800 rpm, and continuously stirring for 30-60 min at 30-45 ℃; S4.2, carrying out vacuum defoaming treatment at 25-35 ℃, controlling the vacuum degree to be minus 0.08-minus 0.095MPa, and the defoaming time to be 10-30 min, filtering by adopting a solvent-resistant filter membrane with the thickness of 0.45 mu m or 0.2 mu m after defoaming, wherein the filtering process is carried out under the conditions of light shielding and sealing, and collecting filtrate after the filtering is completed, thus obtaining the negative micron-sized photoresist.
  9. 9. The method of preparing negative-type micro-scale photoresist according to claim 1 or 8, wherein in step S4, the photoinitiating component is at least one selected from the group consisting of 2-hydroxy-2-methyl-1-phenyl-1-propanone, diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide, 1-hydroxycyclohexylphenyl ketone, benzophenone, and isopropylthioanthrone, and the crosslinking promoting component is at least one selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and ethoxylated trimethylolpropane triacrylate.
  10. 10. A negative-tone micron-sized photoresist, characterized by being produced by a method for producing a negative-tone micron-sized photoresist as claimed in any one of claims 1 to 9.

Description

Negative micron-sized photoresist and preparation method thereof Technical Field The invention belongs to the technical field of ink materials, and particularly relates to negative micron-sized photoresist and a preparation method thereof. Background The negative micron-sized photoresist is a photosensitive polymer material for processing a micron-sized structure, and under the illumination condition, a polymer chain segment in an exposure area is subjected to crosslinking reaction under the action of photoinitiation components to form a compact and difficultly-dissolved three-dimensional network structure, and an unexposed area is removed in the development process, so that the construction of a micron-sized pattern is realized. The negative micron-sized photoresist is mainly applied to the micro-machining field which needs to prepare a micron-sized structure and has high requirements on film thickness, mechanical strength and structural stability. The method can be used for preparing dielectric isolation structures, buffer layers and sacrificial layers in the manufacture of microelectronics and integrated circuits, and can also be applied to processing micron-sized support structures, through holes and three-dimensional configurations in micro-electromechanical systems. The traditional photoetching colloid generally takes a single organic polymer as a main body, the molecular structure and the optical characteristic of the photoetching colloid are relatively single, and under the condition of micron-level thick films, incident light is easy to excessively penetrate or scatter for multiple times when propagating along the thickness direction in the material, so that the light energy is obviously unevenly distributed in the film layer. On the one hand, the area close to the incident light is easy to obtain too high exposure energy, so that the crosslinking reaction is too fast and the crosslinking density is too high, and on the other hand, the area far from the incident light is possibly insufficiently crosslinked due to insufficient light energy, so that a remarkable crosslinking gradient is formed inside the same film layer. The crosslinking gradient can be further amplified in the subsequent development and curing processes, and the stress concentration phenomenon is easy to be caused due to the difference of volume shrinkage degree and mechanical property of different areas, so that film forming defects such as warping, cracking, interface debonding or local collapse are generated. Disclosure of Invention The invention aims to solve the technical problem of providing a negative micron-sized photoresist and a preparation method thereof, and aims to solve the problems that the negative micron-sized photoresist is easy to generate uneven exposure and defects. In order to solve the above problems, the present invention provides a method for preparing negative micron-sized photoresist, comprising the steps of: S1, adding sulfur-containing acrylic ester polymer into a double-boiling point organic solvent, and fully dissolving the sulfur-containing acrylic ester polymer under the stirring condition to form a sulfur-rich polymer matrix solution; S2, adding a functional component containing a silica skeleton structure into the sulfur-rich polymer matrix solution to obtain a prefabricated mixed solution; s3, adding the surface-treated nano shading particles into the prefabricated mixed solution, and sequentially stirring and vacuum defoaming to obtain a precursor solution; s4, adding a photoinitiation component and a crosslinking promotion component into the precursor liquid to obtain the negative micron-sized photoresist. In some embodiments, step S1 comprises: S1.1, placing a sulfur-containing acrylic ester polymer in a vacuum oven, drying for 4-12 hours at 40-60 ℃ and-0.08 to-0.095 MPa, and simultaneously, dehydrating a double-boiling point organic solvent in advance and placing the organic solvent in a closed brown bottle for later use; s1.2, adding a double-boiling point organic solvent into a jacketed glass liquid preparation kettle, adding deionized water, starting mechanical stirring, adjusting the stirring rotation speed to 300-800 rpm, and stabilizing the temperature to 25-35 ℃ through a constant-temperature water bath; s1.3, adding the acrylic polymer containing the sulfur structural unit into a glass liquid preparation kettle for multiple times in a segmented manner, maintaining stirring for 10-20 min after each addition, then heating to 45-55 ℃ and continuously stirring for 30-90 min to obtain a sulfur-rich polymer matrix solution. In some embodiments, in step S1, the sulfur-containing acrylate polymer comprises at least one of poly (2- (phenylthio) ethyl acrylate), poly (2, 2' -thiodiethyl acrylate), poly (thiodiethanol diacrylate), and the dual boiling point organic solvent comprises at least one of propylene glycol methyl ether acetate/cyclohexanone complex solvent, gamma-butyrolactone/methyl iso