CN115903376B - Photoresist, photoresist combination product and photoresist patterning method - Google Patents
Photoresist, photoresist combination product and photoresist patterning method Download PDFInfo
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- CN115903376B CN115903376B CN202110987312.6A CN202110987312A CN115903376B CN 115903376 B CN115903376 B CN 115903376B CN 202110987312 A CN202110987312 A CN 202110987312A CN 115903376 B CN115903376 B CN 115903376B
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Abstract
The invention relates to the technical field of photoresist, in particular to photoresist, a photoresist combination product and a photoresist patterning method. The photoresist comprises an organic solvent, a photoacid generator and a zirconia nanoparticle film-forming resin, wherein the zirconia nanoparticle film-forming resin is prepared by mixing zirconium propoxide and unsaturated organic carboxylic acid and heating. The photoacid generator is capable of inducing agglomeration of the zirconia nanoparticle film-forming resin and has a structure represented by formula I and/or formula II, wherein R 1～R8 is independently selected from-H, -CH 3, methoxy, ethoxy or hydroxyethoxy. The photoresist has high photoetching forming speed and the characteristic dimension of the processed pattern can reach the nanometer level. The invention also provides a photoresist combination product comprising the photoresist and a photoresist patterning method.。
Description
Technical Field
The invention relates to the technical field of photoresist, in particular to photoresist, a photoresist combination product and a photoresist patterning method.
Background
Photoresists are core materials in the micro-nano processing field, and the development level of the photoresists determines the prospect and application of micro-nano processing technology to a certain extent.
Two-photon photoresist is a special type of photoresist, and can absorb two or more photons with low energy in a photoetching beam so as to trigger chemical reaction, thereby achieving the purposes of pattern transfer and imaging. The two-photon photoresist commonly used at present is mostly organic polymer with poor mechanical property, so that the polymer structure graph after two-photon exposure is extremely easy to collapse, deform and peel off from a substrate in the developing process, and the quality of the finally obtained exposure structure is affected. The feature sizes of the patterns currently processed using two-photon lithography are substantially on the micrometer or sub-micrometer scale. In addition, the biggest disadvantage of the currently commercialized two-photon photoresist is that the lithography forming speed (namely, the lithography scanning speed) is slow (the lithography scanning speed actually applied at the present stage is mostly in the grade of mu m s -1), so that the time cost required by lithography forming is high.
In addition to two-photon photoresists, ultraviolet or violet photoresists are also commonly used photoresists. But short wavelength ultraviolet light (e.g., 193nm or 248nm ultraviolet light sources) can permanently damage polymeric material substrates such as plastics and rubber. To avoid this problem, photolithography is typically performed using ultraviolet light in the long wavelength band (e.g., 365nm ultraviolet light source) or violet light at 405nm in combination with photoresist. However, most of commercial photoresists suitable for long-wave ultraviolet light or purple light are pure organic photoresists, single in variety, poor in etching resistance and difficult to meet the special requirements of the micro-nano processing field.
Disclosure of Invention
Based on the above, the invention provides a photoresist, a photoresist combination product and a photoresist patterning method, wherein the photoetching forming speed is high, and the feature size of a processed pattern can reach the nanometer level.
In one aspect of the invention, a photoresist is provided, comprising an organic solvent, a photoacid generator and a zirconia nanoparticle film-forming resin, wherein zirconium propoxide and an unsaturated organic carboxylic acid are mixed and heated to prepare the zirconia nanoparticle film-forming resin;
The photoacid generator can trigger the agglomeration of the zirconia nanoparticle film-forming resin and has a structure shown in a formula I and/or a formula II:
Wherein R 1～R8 is independently selected from-H, -CH 3, methoxy, ethoxy, or hydroxyethoxy.
In one aspect of the present invention, a photoresist composition product is provided, including the photoresist and the developer described above.
In another aspect of the present invention, there is further provided a method of patterning a photoresist, comprising the steps of:
placing the photoresist on a substrate, and drying to form a photoresist film;
And (3) carrying out photoetching exposure on the photoresist film, and then placing the photoresist film in the developer for development to form a photoetching pattern.
According to the invention, the photoacid generator can generate acid after exposure, so that the zirconium oxide nano-particle film-forming resin can be initiated to generate an agglomeration reaction. Therefore, when the photoresist is subjected to photoetching exposure, the zirconia nanoparticle film-forming resin in the photoresist subjected to the illumination part is aggregated and is difficult to dissolve in the developer, and the photoresist not subjected to the illumination part is not aggregated and is easy to dissolve in the developer. There is a large difference in solubility of the photoresist exposed areas and the non-exposed areas in the developer, and thus a photolithographic pattern can be formed.
In addition, the photoresist has higher light sensitivity and excellent mechanical property, can be applied to the field of two-photon lithography (such as 780nm near infrared light source), has high lithography forming speed, can reach m s -1 levels, has small feature size of a processed pattern, can reach nano-level and even can reach below 50nm, thereby greatly improving the processing precision of the two-photon photoresist, shortening the processing time, reducing the cost and widening the practical application of the two-photon lithography technology. The photoresist can also be applied to the field of ultraviolet lithography (such as 405nm ultraviolet light source), and provides a novel photoresist for ultraviolet light or ultraviolet lithography in a long wave band. In addition, the zirconia nano particles ensure excellent mechanical properties of the photoresist, ensure that the photoetching pattern cannot collapse and deform in the developing process, cannot be peeled off from the substrate, and have high fidelity.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of a two-photon photoresist pattern in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of a two-photon photoresist pattern in example 2 of the present invention;
FIG. 3 is a scanning electron microscope image of a two-photon photoresist pattern in example 3 of the present invention;
FIG. 4 is a scanning electron microscope image of the two-photon resist pattern in embodiment 4 of the present invention;
FIG. 5 is a scanning electron microscope image of the two-photon resist pattern in embodiment 5 of the present invention;
FIG. 6 is a scanning electron microscope image of the two-photon resist pattern in example 6 of the present invention;
FIG. 7 is a scanning electron microscope image of the two-photon resist pattern in example 7 of the present invention;
FIG. 8 is a scanning electron microscope image of the two-photon resist pattern in embodiment 8 of the present invention;
FIG. 9 is a scanning electron microscope image of the two-photon resist pattern in embodiment 9 of the present invention;
FIG. 10 is a scanning electron microscope image of the two-photon resist pattern in embodiment 10 of the present invention;
FIG. 11 is a metallographic microscope image of a violet photoresist pattern in example 11 of the present invention;
FIG. 12 is a scanning electron microscope image of the two-photon resist pattern in comparative example 1 of the present invention;
fig. 13 is a scanning electron microscope image of the two-photon resist pattern in comparative example 2 of the present invention.
Detailed Description
Reference now will be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. Indeed, it will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the scope or spirit of the invention. For example, features illustrated or described as part of one embodiment can be used on another embodiment to yield still a further embodiment.
Accordingly, it is intended that the present invention cover such modifications and variations as fall within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention will be disclosed in or be apparent from the following detailed description. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Terms and definitions
The purple light is purple visible light, belongs to visible light, and has a wavelength of 450-400 nm.
"Purple photoresist" refers to a photoresist that is lithographically exposed using purple light as a light source.
In one aspect of the invention, a photoresist is provided, comprising an organic solvent, a photoacid generator and a zirconia nanoparticle film-forming resin, wherein zirconium propoxide and an unsaturated organic carboxylic acid are mixed and heated to prepare the zirconia nanoparticle film-forming resin;
Wherein the photoacid generator is capable of initiating agglomeration of the zirconia nanoparticle film-forming resin and has a structure represented by formula I and/or formula II:
Wherein R 1～R8 is independently selected from-H, -CH 3, methoxy, ethoxy, or hydroxyethoxy.
In some embodiments, the photoacid generator is one or more of 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine, 2- (3, 4-dimethoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (2, 4-dimethoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- [4- (2-hydroxyethoxy) styryl ] -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- [2- (furan-2-yl) vinyl ] -4, 6-bis (trichloromethyl) -1,3, 5-triazine, and 2- [2- (5-methylfuran-2-yl) vinyl ] -4, 6-bis (trichloromethyl) -1,3, 5-triazine.
The structural formula is as follows in turn:
In some embodiments, the unsaturated organic carboxylic acid may be acrylic acid, methacrylic acid, or 3, 3-dimethacrylate.
In some embodiments, the zirconium propoxide can be zirconium isopropoxide or zirconium n-propoxide.
In some embodiments, the zirconia nanoparticle film-forming resin may comprise 1% -20% by mass, and may comprise 3%, 5%, 10%, 15% by mass, and the like. The weight percentage of the photoacid generator is 0.005% -3%, and the photoacid generator can also be 0.02%, 0.05%, 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5% and the like.
In some embodiments, the volume average particle size of the zirconia nanoparticle film-forming resin is 1nm to 3nm. The volume average particle size of the zirconia nanoparticle film-forming resin is small, and thus the lithographic pattern can have a small feature size.
In some embodiments, the organic solvent is selected from solvents having a strong solubility for the photoacid generator and the zirconia nanoparticle film-forming resin, so that the photoacid generator and the zirconia nanoparticle film-forming resin are well dissolved and uniformly dispersed in the organic solvent. After the photoresist is placed on a substrate and dried to form a photoresist film, the photoacid generator and the zirconia nanoparticle film-forming resin can be ensured to be uniformly dispersed in the photoresist film. After lithographic exposure, the photoresist exposed areas are difficult to dissolve in the developer, while the photoresist non-exposed areas can dissolve accurately and quickly. Preferably, the organic solvent comprises at least one of propylene glycol monomethyl ether acetate, acetone, methanol, ethanol, n-propanol, isopropanol, butyl acetate and ethyl lactate.
In one aspect of the present invention, a photoresist composition product is provided, including the photoresist and the developer described above.
The developer has adaptability with the photoresist and is used for dissolving the photoresist in the non-exposure area. In some embodiments, the developer includes, but is not limited to, at least one of 1, 2-diacetoxy propane, propylene glycol monomethyl ether acetate, para-xylene, meta-xylene, ortho-xylene, toluene, isopropoxyethanol, ethylene glycol propyl ether, isopropanol, propylene glycol butyl ether, propylene glycol diethyl ether, ethyl acetate, and acetone.
In another aspect of the present invention, there is further provided a method of patterning a photoresist, comprising the steps of:
placing the photoresist on a substrate, and drying to form a photoresist film;
and (3) carrying out photoetching exposure on the photoresist film, and then placing the photoresist film in the developer for development to form a photoetching pattern.
In some embodiments, placing the photoresist on the substrate may be performed using methods and apparatus commonly used in the art, such as a spin coater. And controlling the rotating speed of the spin coater to be 500-5000 rpm, and coating photoresist on the substrate at the acceleration of 100rpm s -1～1000rpm s-1. Examples of substrates used include, but are not limited to, glass substrates, quartz substrates, silicon wafer substrates, and the like.
In some embodiments, the photoresist is further included before being placed on the substrate, by filtering the photoresist using a filter membrane having a pore size of about 0.22 μm, which is preferably a conventional small pore size.
In some embodiments, drying to form the photoresist film may be performed using conventional methods and apparatus, such as a photoresist dryer. And (3) controlling the temperature of the photoresist dryer to be 60-100 ℃ to dry photoresist, so that the photoresist is formed into a film.
In some embodiments, the method of photolithographic exposure is violet lithography or two-photon lithography. The light source of the purple light photoetching method is purple light with the wavelength of 405nm, the light source of the two-photon photoetching method is near infrared femtosecond pulse laser with the wavelength of 780nm, and the laser power is 5-80 mW. The photoresist of the invention is particularly suitable for two-photon lithography.
The photoresist, the photoresist combination product, and the photoresist patterning method of the present invention are described in further detail with reference to specific examples and comparative examples.
Example 1
The preparation method of the zirconium oxide nanoparticle film-forming resin in the embodiment comprises the following steps of adding 1g of zirconium isopropoxide and 12mL of methacrylic acid into a 50mL flask, and heating and stirring for 15min at 65 ℃. Subsequently, 2mL of a mixture of methacrylic acid and water (volume ratio 9:1) was added dropwise to the flask, and stirring was continued with heating at 65℃for 18h. 2mL of a methacrylic acid/water mixture (9:1 by volume) was then added dropwise to the flask and stirring was continued with heating at 65℃for 3h. The mixed solution was then poured into 60mL of deionized water, and after precipitation of the precipitate, the solid precipitate was centrifuged off and washed twice with 80mL of deionized water. The obtained precipitate is dissolved in 20mL of acetone, diluted with 20mL of deionized water, after white solid is precipitated, the white solid is washed twice with 40mL of a mixture of acetone and water (volume ratio is 1:3), and dried for 4 hours under a vacuum environment at 65 ℃ to obtain white solid powder, namely the zirconia nanoparticle film-forming resin.
0.02G of 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine and 0.5g of zirconia nano particle film-forming resin are taken and dissolved in 9.5g of propylene glycol monomethyl ether acetate solvent, and the mixture is stirred to be completely dissolved. The photoresist solution was then filtered twice using a filter membrane having a pore size of 0.22 μm.
The prepared photoresist solution is dripped on the surface of a clean glass sheet substrate, and is placed in a spin coater, and spin coating is carried out for 1min under the conditions that the rotating speed is 2000rpm and the acceleration is 1000rpm s -1. The substrate was then removed and placed into a glue dryer and dried at 100 ℃ for 1min. Then placing the substrate in a two-photon photoetching machine, and carrying out photoetching exposure under the laser power of 22.5mW and the photoetching scanning rate of 0.9m s -1 by using near infrared femtosecond pulse laser with the wavelength of 780nm as a light source. After the photoetching exposure is finished, the substrate is placed in 1, 2-diacetoxy propane for development for 15 seconds, and a nitrogen gun is used for blowing and drying the residual developer on the surface of the substrate material. Finally, a high-resolution scanning electron microscope is used for shooting a photo of the pattern obtained by photoetching exposure, wherein the scanning electron microscope shooting parameters are that the accelerating voltage is 0.800kV, the working distance is 3.7mm and the magnification is 29.74k. As shown in FIG. 1, the feature size of the resulting pattern was measured to be 48.81nm, rounded to 49nm.
Example 2
The preparation method of this example is basically the same as that of example 1, except that the laser power and the lithographic scanning rate of the lithographic exposure are different. The method comprises the following specific steps:
0.02g of 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine and 0.5g of zirconia nano particle film-forming resin are taken and dissolved in 9.5g of propylene glycol monomethyl ether acetate solvent, and the mixture is stirred to be completely dissolved. The photoresist solution was then filtered twice using a filter membrane having a pore size of 0.22 μm.
The prepared photoresist solution is dripped on the surface of a clean glass sheet substrate, and is placed in a spin coater, and spin coating is carried out for 1min under the conditions that the rotating speed is 2000rpm and the acceleration is 1000rpm s -1. The substrate was then removed and placed into a glue dryer and dried at 100 ℃ for 1min. Then placing the substrate in a two-photon photoetching machine, and carrying out photoetching exposure by using near infrared femtosecond pulse laser with the wavelength of 780nm as a light source under the laser power of 20mW and the photoetching scanning rate of 0.5m s -1. After the photoetching exposure is finished, the substrate is placed in 1, 2-diacetoxy propane for development for 15 seconds, and a nitrogen gun is used for blowing and drying the residual developer on the surface of the substrate material. Finally, a high-resolution scanning electron microscope is used for shooting a photo of the pattern obtained by photoetching exposure, wherein the scanning electron microscope shooting parameters are that the accelerating voltage is 0.800kV, the working distance is 3.7mm and the magnification is 19.64k. As shown in FIG. 2, the feature size of the resulting pattern was measured to be 56.85nm, rounded to 57nm.
Example 3
The preparation method of this example is basically the same as that of example 1, except that the lithographic scanning rate is different. The method comprises the following specific steps:
0.02g of 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine and 0.5g of zirconia nano particle film-forming resin are taken and dissolved in 9.5g of propylene glycol monomethyl ether acetate solvent, and the mixture is stirred to be completely dissolved. The photoresist solution was then filtered twice using a filter membrane having a pore size of 0.22 μm.
The prepared photoresist solution is dripped on the surface of a clean glass sheet substrate, and is placed in a spin coater, and spin coating is carried out for 1min under the conditions that the rotating speed is 2000rpm and the acceleration is 1000rpm s -1. The substrate was then removed and placed into a glue dryer and dried at 100 ℃ for 1min. Then placing the substrate in a two-photon photoetching machine, and carrying out photoetching exposure under the laser power of 22.5mW and the photoetching scanning rate of 0.7m s -1 by using near infrared femtosecond pulse laser with the wavelength of 780nm as a light source. After the photoetching exposure is finished, the substrate is placed in 1, 2-diacetoxy propane for development for 15 seconds, and a nitrogen gun is used for blowing and drying the residual developer on the surface of the substrate material. Finally, a high-resolution scanning electron microscope is used for shooting a photo of the pattern obtained by photoetching exposure, wherein the scanning electron microscope shooting parameters are that the accelerating voltage is 0.800kV, the working distance is 3.7mm and the magnification is 20.45k. As shown in FIG. 3, the feature size of the resulting pattern was measured to be 76.43nm, rounded to 76nm.
Example 4
The preparation method of this example is basically the same as that of example 1, except that the laser power and the lithographic scanning rate of the lithographic exposure are different. The method comprises the following specific steps:
0.02g of 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine and 0.5g of zirconia nano particle film-forming resin are taken and dissolved in 9.5g of propylene glycol monomethyl ether acetate solvent, and the mixture is stirred to be completely dissolved. The photoresist solution was then filtered twice using a filter membrane having a pore size of 0.22 μm.
The prepared photoresist solution is dripped on the surface of a clean glass sheet substrate, and is placed in a spin coater, and spin coating is carried out for 1min under the conditions that the rotating speed is 2000rpm and the acceleration is 1000rpm s -1. The substrate was then removed and placed into a glue dryer and dried at 100 ℃ for 1min. Then placing the substrate in a two-photon photoetching machine, and carrying out photoetching exposure under the laser power of 17.5mW and the photoetching scanning rate of 0.3m s -1 by using near infrared femtosecond pulse laser with the wavelength of 780nm as a light source. After the photoetching exposure is finished, the substrate is placed in 1, 2-diacetoxy propane for development for 15 seconds, and a nitrogen gun is used for blowing and drying the residual developer on the surface of the substrate material. Finally, a high-resolution scanning electron microscope is used for shooting a photo of the pattern obtained by photoetching exposure, wherein the scanning electron microscope shooting parameters are that the accelerating voltage is 0.800kV, the working distance is 3.7mm and the magnification is 20.03k. As shown in FIG. 4, the feature size of the resulting pattern was measured to be 117.1nm, rounded to 117nm.
Example 5
The preparation method of this example is basically the same as that of example 1, except that the laser power and the lithographic scanning rate of the lithographic exposure are different. The method comprises the following specific steps:
0.02g of 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine and 0.5g of zirconia nano particle film-forming resin are taken and dissolved in 9.5g of propylene glycol monomethyl ether acetate solvent, and the mixture is stirred to be completely dissolved. The photoresist solution was then filtered twice using a filter membrane having a pore size of 0.22 μm.
The prepared photoresist solution is dripped on the surface of a clean glass sheet substrate, and is placed in a spin coater, and spin coating is carried out for 1min under the conditions that the rotating speed is 2000rpm and the acceleration is 1000rpm s -1. The substrate was then removed and placed into a glue dryer and dried at 100 ℃ for 1min. Then placing the substrate in a two-photon photoetching machine, and carrying out photoetching exposure by using near infrared femtosecond pulse laser with the wavelength of 780nm as a light source under the laser power of 25mW and the photoetching scanning rate of 0.3m s -1. After the photoetching exposure is finished, the substrate is placed in 1, 2-diacetoxy propane for development for 15 seconds, and a nitrogen gun is used for blowing and drying the residual developer on the surface of the substrate material. Finally, a high-resolution scanning electron microscope is used for shooting a photo of the pattern obtained by photoetching exposure, wherein the scanning electron microscope shooting parameters are that the accelerating voltage is 0.800kV, the working distance is 4.0mm and the magnification is 15.00k. As shown in FIG. 5, the feature size of the resulting pattern was measured to be 201.0nm, rounded to 201nm.
Example 6
This example is essentially the same as the preparation method of example 1, except that the amount of 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine used, the laser power of the photolithographic exposure and the photolithographic scan rate are different. The method comprises the following specific steps:
0.05g of 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine and 0.5g of zirconia nano particle film-forming resin are taken and dissolved in 9.5g of propylene glycol monomethyl ether acetate solvent, and the mixture is stirred to be completely dissolved. The photoresist solution was then filtered twice using a filter membrane having a pore size of 0.22 μm.
The prepared photoresist solution is dripped on the surface of a clean glass sheet substrate, and is placed in a spin coater, and spin coating is carried out for 1min under the conditions that the rotating speed is 2000rpm and the acceleration is 1000rpm s -1. The substrate was then removed and placed into a glue dryer and dried at 100 ℃ for 1min. Then placing the substrate in a two-photon photoetching machine, and carrying out photoetching exposure under the laser power of 37.5mW and the photoetching scanning rate of 2m s -1 by using near infrared femtosecond pulse laser with the wavelength of 780nm as a light source. After the photoetching exposure is finished, the substrate is placed in 1, 2-diacetoxy propane for development for 15 seconds, and a nitrogen gun is used for blowing and drying the residual developer on the surface of the substrate material. Finally, a high-resolution scanning electron microscope is used for shooting a photo of the pattern obtained by photoetching exposure, wherein the scanning electron microscope shooting parameters are that the accelerating voltage is 0.500kV, the working distance is 4.6mm, and the magnification is 12.51k. As shown in fig. 6, the feature size of the resulting pattern was measured to be 220nm.
Example 7
The preparation method of this example is basically the same as that of example 6, except that the laser power of the photolithographic exposure is different. The method comprises the following specific steps:
0.05g of 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine and 0.5g of zirconia nano particle film-forming resin are taken and dissolved in 9.5g of propylene glycol monomethyl ether acetate solvent, and the mixture is stirred to be completely dissolved. The photoresist solution was then filtered twice using a filter membrane having a pore size of 0.22 μm.
The prepared photoresist solution is dripped on the surface of a clean glass sheet substrate, and is placed in a spin coater, and spin coating is carried out for 1min under the conditions that the rotating speed is 2000rpm and the acceleration is 1000rpm s -1. The substrate was then removed and placed into a glue dryer and dried at 100 ℃ for 1min. Then placing the substrate in a two-photon photoetching machine, and carrying out photoetching exposure by using near infrared femtosecond pulse laser with the wavelength of 780nm as a light source under the laser power of 45mW and the photoetching scanning rate of 2m s -1. After the photoetching exposure is finished, the substrate is placed in 1, 2-diacetoxy propane for development for 15 seconds, and a nitrogen gun is used for blowing and drying the residual developer on the surface of the substrate material. Finally, a high-resolution scanning electron microscope is used for shooting a photo of the pattern obtained by photoetching exposure, wherein the scanning electron microscope shooting parameters are that the accelerating voltage is 0.500kV, the working distance is 4.6mm, and the magnification is 10.70k. As shown in fig. 7, the feature size of the resulting pattern was measured to be 293nm.
Example 8
This example is essentially the same as the preparation method of example 1, except that the amount of 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine used, the laser power of the photolithographic exposure and the photolithographic scan rate are different. The method comprises the following specific steps:
0.04g of 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine and 0.5g of zirconia nano particle film-forming resin are taken and dissolved in 9.5g of propylene glycol monomethyl ether acetate solvent, and the mixture is stirred to be completely dissolved. The photoresist solution was then filtered twice using a filter membrane having a pore size of 0.22 μm.
The prepared photoresist solution is dripped on the surface of a clean glass sheet substrate, and is placed in a spin coater, and spin coating is carried out for 1min under the conditions that the rotating speed is 2000rpm and the acceleration is 1000rpm s -1. The substrate was then removed and placed into a glue dryer and dried at 100 ℃ for 1min. Then placing the substrate in a two-photon photoetching machine, and carrying out photoetching exposure by using near infrared femtosecond pulse laser with the wavelength of 780nm as a light source under the laser power of 50mW and the photoetching scanning rate of 1.5m s -1. After the photoetching exposure is finished, the substrate is placed in 1, 2-diacetoxy propane for development for 15 seconds, and a nitrogen gun is used for blowing and drying the residual developer on the surface of the substrate material. Finally, a high-resolution scanning electron microscope is used for shooting a photo of the pattern obtained by photoetching exposure, wherein the scanning electron microscope shooting parameters are that the accelerating voltage is 0.500kV, the working distance is 5.1mm and the magnification is 7.83k. As shown in FIG. 8, the feature size of the resulting pattern was measured to be 299.3nm, rounded to 299nm.
Example 9
This example is essentially the same as the preparation method of example 1, except that the photoacid generator is 2- (3, 4-dimethoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, and the laser power and lithographic scanning rate of the lithographic exposure are different. The method comprises the following specific steps:
0.02g of 2- (3, 4-dimethoxy styryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine and 0.5g of zirconia nano particle film-forming resin are dissolved in 9.5g of propylene glycol monomethyl ether acetate solvent, and the mixture is stirred to be completely dissolved. The photoresist solution was then filtered twice using a filter membrane having a pore size of 0.22 μm.
The prepared photoresist solution is dripped on the surface of a clean glass sheet substrate, and is placed in a spin coater, and spin coating is carried out for 1min under the conditions that the rotating speed is 2000rpm and the acceleration is 1000rpm s -1. The substrate was then removed and placed into a glue dryer and dried at 100 ℃ for 1min. Then placing the substrate in a two-photon photoetching machine, and carrying out photoetching exposure by using near infrared femtosecond pulse laser with the wavelength of 780nm as a light source under the laser power of 25mW and the photoetching scanning rate of 0.1m s -1. After the photoetching exposure is finished, the substrate is placed in 1, 2-diacetoxy propane for development for 15 seconds, and a nitrogen gun is used for blowing and drying the residual developer on the surface of the substrate material. Finally, a high-resolution scanning electron microscope is used for shooting a photo of the pattern obtained by photoetching exposure, wherein the scanning electron microscope shooting parameters are that the accelerating voltage is 0.800kV, the working distance is 4.0mm and the magnification is 49.08k. As shown in FIG. 9, the feature size of the resulting pattern was measured to be 147.9nm, rounded to 148nm.
Example 10
This example is essentially the same as the preparation method of example 1, except that the photoacid generator is 2- [2- (furan-2-yl) vinyl ] -4, 6-bis (trichloromethyl) -1,3, 5-triazine, the laser power of the photolithographic exposure and the photolithographic scan rate are different. The method comprises the following specific steps:
0.02g of 2- [2- (furan-2-yl) vinyl ] -4, 6-bis (trichloromethyl) -1,3, 5-triazine and 0.5g of zirconia nanoparticle film-forming resin are taken and dissolved in 9.5g of propylene glycol monomethyl ether acetate solvent, and the mixture is stirred to be completely dissolved. The photoresist solution was then filtered twice using a filter membrane having a pore size of 0.22 μm.
The prepared photoresist solution is dripped on the surface of a clean glass sheet substrate, and is placed in a spin coater, and spin coating is carried out for 1min under the conditions that the rotating speed is 2000rpm and the acceleration is 1000rpm s -1. The substrate was then removed and placed into a glue dryer and dried at 100 ℃ for 1min. Then placing the substrate in a two-photon photoetching machine, and carrying out photoetching exposure by using near infrared femtosecond pulse laser with the wavelength of 780nm as a light source under the laser power of 30mW and the photoetching scanning rate of 0.01m s -1. After the photoetching exposure is finished, the substrate is placed in 1, 2-diacetoxy propane for development for 15 seconds, and a nitrogen gun is used for blowing and drying the residual developer on the surface of the substrate material. Finally, a high-resolution scanning electron microscope is used for shooting a photo of the pattern obtained by photoetching exposure, wherein the scanning electron microscope shooting parameters are that the accelerating voltage is 0.800kV, the working distance is 4.2mm and the magnification is 10.00k. As shown in FIG. 10, the feature size of the resulting pattern was measured to be 390.8nm, rounded to 391nm.
Example 11
The preparation method of the embodiment is basically the same as that of the embodiment 1, except that the lithography method is ultraviolet lithography, and the laser power and the lithography scanning rate of the lithography exposure are different. The method comprises the following specific steps:
0.02g of 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine and 0.5g of zirconia nano particle film-forming resin are taken and dissolved in 9.5g of propylene glycol monomethyl ether acetate solvent, and the mixture is stirred to be completely dissolved. The photoresist solution was then filtered twice using a filter membrane having a pore size of 0.22 μm.
The prepared photoresist solution is dripped on the surface of a clean glass sheet substrate, and is placed in a spin coater, and spin coating is carried out for 1min under the conditions that the rotating speed is 2000rpm and the acceleration is 1000rpm s -1. The substrate was then removed and placed into a glue dryer and dried at 100 ℃ for 1min. Then placing the substrate in a purple light photoetching machine, and carrying out photoetching exposure by using 405nm wavelength purple light as a light source under the laser power of 20mW and the photoetching scanning rate of 3m s -1. After the photoetching exposure is finished, the substrate is placed in 1, 2-diacetoxy propane for development for 15 seconds, and a nitrogen gun is used for blowing and drying the residual developer on the surface of the substrate material. Finally, a photograph of the pattern obtained by the photolithographic exposure was taken using a metallographic microscope. As shown in FIG. 11, the feature size of the pattern was measured to be 6.8. Mu.m, which indicates that the photoresist prepared in this example is suitable for use in the field of ultraviolet lithography.
Comparative example 1
This comparative example was prepared in substantially the same manner as in example 1 except that the photoacid generator was 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -S-triazine, and the laser power and the lithographic scanning rate of the lithographic exposure were different. The method comprises the following specific steps:
0.02g of 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -S-triazine and 0.5g of zirconia nano particle film-forming resin are taken and dissolved in 9.5g of propylene glycol monomethyl ether acetate solvent, and the mixture is stirred to be completely dissolved. The photoresist solution was then filtered twice using a filter membrane having a pore size of 0.22 μm.
The prepared photoresist solution is dripped on the surface of a clean glass sheet substrate, and is placed in a spin coater, and spin coating is carried out for 1min under the conditions that the rotating speed is 2000rpm and the acceleration is 1000rpm s -1. The substrate was then removed and placed into a glue dryer and dried at 100 ℃ for 1min. Then placing the substrate in a two-photon photoetching machine, and carrying out photoetching exposure by using near infrared femtosecond pulse laser with the wavelength of 780nm as a light source under the laser power of 30mW and the photoetching scanning rate of 0.01m s -1. After the photoetching exposure is finished, the substrate is placed in 1, 2-diacetoxy propane for development for 15 seconds, and a nitrogen gun is used for blowing and drying the residual developer on the surface of the substrate material. Finally, a high-resolution scanning electron microscope is used for shooting a photo of the pattern obtained by photoetching exposure, wherein the scanning electron microscope shooting parameters are that the accelerating voltage is 0.800kV, the working distance is 4.2mm and the magnification is 1.00k. As shown in fig. 12, the resulting pattern of exposure was not observed, indicating that the photoacid generator 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -S-triazine was not suitable for two-photon lithography as described in the present invention.
Comparative example 2
This comparative example was prepared essentially the same as example 1 except that the photoacid generator was 2- (1, 3-benzodioxol-5-yl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, and the laser power and lithographic scanning rate of the lithographic exposure were different. The method comprises the following specific steps:
0.02g of 2- (1, 3-benzodioxol-5-yl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine and 0.5g of zirconia nanoparticle film-forming resin are taken and dissolved in 9.5g of propylene glycol monomethyl ether acetate solvent, and the mixture is stirred to be completely dissolved. The photoresist solution was then filtered twice using a filter membrane having a pore size of 0.22 μm.
The prepared photoresist solution is dripped on the surface of a clean glass sheet substrate, and is placed in a spin coater, and spin coating is carried out for 1min under the conditions that the rotating speed is 2000rpm and the acceleration is 1000rpm s -1. The substrate was then removed and placed into a glue dryer and dried at 100 ℃ for 1min. Then placing the substrate in a two-photon photoetching machine, and carrying out photoetching exposure by using near infrared femtosecond pulse laser with the wavelength of 780nm as a light source under the laser power of 30mW and the photoetching scanning rate of 0.01m s -1. After the photoetching exposure is finished, the substrate is placed in 1, 2-diacetoxy propane for development for 15 seconds, and a nitrogen gun is used for blowing and drying the residual developer on the surface of the substrate material. Finally, a high-resolution scanning electron microscope is used for shooting a photo of the pattern obtained by photoetching exposure, wherein the scanning electron microscope shooting parameters are that the accelerating voltage is 0.800kV, the working distance is 4.2mm and the magnification is 1.00k. As shown in FIG. 13, the resulting pattern of exposure was not observed, indicating that the photoacid generator 2- (1, 3-benzodioxol-5-yl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine was not suitable for use in the two-photon lithography described herein.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
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