CN114609863A - Full water-based silk photoresist based on bivoltine and diversified silkworm varieties and preparation method thereof - Google Patents
Full water-based silk photoresist based on bivoltine and diversified silkworm varieties and preparation method thereof Download PDFInfo
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- C07K14/43563—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from invertebrates from insects
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Abstract
The invention provides a full water-based silk photoresist based on two or more varieties of silkworms and a preparation method thereof, wherein the photoresist comprises silkworm silk fibroin and an aqueous solvent of the two varieties of silkworms, namely autumn white, summer aromatic or more varieties of silkworms 305; the preparation method is suitable for various kinds of two-striped and diversified silkworm varieties, the 3 kinds of silkworm varieties (autumn white, summer fragrant and 305) selected by the invention have the characteristics of being beneficial to feeding, large in silk output, high in silk quality and the like, the fibroin is easy to extract and efficient, and the conformation of the fibroin can be converted through radiation, so that the two purposes of electron beams and ion beams and the dual purposes of positive and negative are realized. In addition, the photoresist only takes water as a developing solution and a solvent, is environment-friendly and harmless to human bodies, meets the requirement of green micro-nano processing to the greatest extent, and has important value for the development and application of the mulberry industry.
Description
Technical Field
The invention belongs to the technical field of biological information, and particularly relates to a fully water-based silk photoresist based on bivoltine and diversified silkworm varieties and a preparation method thereof.
Background
The rapid development of the micro-nano processing technology brings strong development power to the technical field of current electronic information, and the maximum requirement of the microelectronic technology is to construct more independent circuit elements on a semiconductor material in equipment, so that the reduction of the characteristic size becomes the key of the current microelectronic processing technology. The technique of patterning a circuit involves patterning with photoresist and transferring the pattern with an appropriate etch, which plays a decisive role in improving resolution. The photoresist becomes an important factor in pattern transfer, and currently, many materials have good characteristics and are suitable for corresponding processes, but the raw materials often use various resins and organic solvents and are not environment-friendly.
The silk is a natural high molecular protein, has excellent biocompatibility and degradability, is green and nontoxic, is beneficial to large-scale production, and has been utilized by human for thousands of years. The natural materials are more and more widely used, and the fibroin is currently applied to a plurality of fields such as medicine, cosmetology, war industry, photoelectricity and the like, and has very good development prospect.
Some researchers apply the silkworm silk protein as the photoresist to the photoetching process, but the technical problems of low resolution and low etching resistance exist, and besides the need of searching for a proper preparation process, the selection of the silk with more excellent performance as a raw material is particularly important. Therefore, at present, there is an urgent need to find suitable high-performance silk as a photo-etching collagen material, and at the same time, there is a need to develop a corresponding preparation process with a wide application range.
Disclosure of Invention
Based on the technical problems in the prior art, the invention provides a full water-based silk photoresist based on bivoltine and diversified silkworm varieties and a preparation method thereof.
According to the first aspect of the technical scheme of the invention, the invention provides a fully water-based silk photoresist based on the two-part and multi-variety silkworm varieties, which comprises silkworm silk fibroin and a water solvent of the two-part silkworm varieties autumn white, summer aromatic or multi-variety silkworm variety 305.
Preferably, the bombyx mori silk fibroin has a molecular weight of about 25 kDa. The silkworm silk fibroin is in the form of liquid or solid powder, and the aqueous solvent adopts ultrapure water. The silkworm silk fibroin component comprises a silk fibroin heavy chain, a silk fibroin light chain and P25 glycoprotein. More preferably, the bombyx mori silk protein can be used as both negative and positive glue.
According to the second aspect of the technical scheme of the invention, the preparation method of the all-water-based silk photoresist based on the two-striped and diversified silkworm varieties comprises the following steps:
step S1, extracting silk fibroin from two or more silkworm varieties;
in step S2, a photoresist pattern is prepared by exposure to a focused ion beam and an electron beam.
Wherein, the step of extracting silk fibroin by utilizing two or more silkworm varieties further comprises the step of S1-1, selecting 3 silkworm varieties cocoon shells 305, autumn white and summer fragrant for degumming, wherein the silkworm variety 305 is a multifarious variety, the silkworm variety autumn white and the silkworm variety summer fragrant are the stock seeds in the two varieties, boiling 0.5% (M/V) (g/ml) sodium carbonate solution, and then mixing the 3 silkworm varieties cocoon shells 305, autumn white and summer fragrant with 1: 100-1: a bath ratio of 200 was placed in a 0.5% (M/V) (g/ml) sodium carbonate solution and boiled for 30min-90min (min) to remove sericin.
Further, the step of extracting silk protein by utilizing the two-piece and multi-variety silkworm varieties further comprises the step S1-2 of washing the boiled silkworm silk in flowing water, then soaking in deionized water for 30min, then changing the deionized water once, repeatedly soaking for three times, and then placing the silkworm silk in a 60 ℃ oven for 6h-12h (h) to be dried for standby, thus obtaining the silkworm silk fiber.
Furthermore, the step of extracting silk fibroin by utilizing the two-grain and multi-grain silkworm varieties further comprises the step of S1-3, wherein the anhydrous calcium chloride, the anhydrous ethanol and the water solution are prepared into silk fibroin dissolving solution according to the molar ratio of 1:2:8, and the weight ratio of the anhydrous calcium chloride to the anhydrous ethanol to the water solution is 1: and (3) putting a certain amount of the silkworm silk fibers into the silk fibroin dissolving solution at a bath ratio of 10, and keeping the temperature at 70 ℃ until the silk fibroin dissolving solution is completely dissolved, wherein no obvious silk insoluble substances exist in the dissolving solution.
Compared with the prior art, the all-water-based silk photoresist based on the two-striped and diversified silkworm varieties and the preparation method and the application technical scheme thereof have the advantages that:
1. the raw materials used by the photoresist are selected from silkworm varieties with the characteristics of easy feeding, large silk output, high silk quality and the like, and silk protein of the silkworm varieties is easy to extract, efficient, environment-friendly and wide in applicability;
2. the photoresist prepared by the invention has dual purposes of electron beam and ion beam, and positive and negative dual purposes, and most importantly, the photoresist only uses water as developing solution and solvent in use, is environment-friendly and harmless to human body, and has important application value.
Drawings
Fig. 1 shows autumn white cocoon shells based on a variety of bivoltine silkworms in the first embodiment of the present invention.
Fig. 2 is a diagram of an autumn white light photoresist sample based on a variety of the two silkworms in the first embodiment of the invention.
FIG. 3 is a chart of molecular detection of a photoresist sample prepared based on autumn white cocoon of a Chilo silkworm variety according to a first embodiment of the present invention
Fig. 4 is a structural diagram of development of an ion beam exposure 5s based on a negative glue of autumn white silk protein of a variety of two-cultivated silkworms in the first embodiment of the invention.
Fig. 5 is a structural diagram of ion beam exposure 4s development based on positive ion beam exposure of autumn white silk fibroin of a bivoltine silkworm variety in the first embodiment of the present invention.
FIG. 6 is a diagram of a kind of summer cocoon shells based on the cultivated silkworm in two varieties of the present invention.
Fig. 7 is a diagram of a summer aromatic photoresist sample based on a bivolvulus variety in the second embodiment of the present invention.
Fig. 8 is a molecular detection diagram of a photoresist sample prepared based on the summer aromatic cocoons of the bivoltine silkworm variety in the second embodiment of the present invention.
FIG. 9 is a characterization diagram of electron beam exposure optical microscope based on Chiense silk protein negative glue of Chiense silk variety II (electron beam dose 20C cm)-2)。
FIG. 10 is a characterization diagram of an electron beam exposure optical microscope based on Xiafan silk protein positive glue of a variety of Chiense silkworms in the second embodiment of the present invention (dose of electron beam dose is 10 Ccm)-2)。
FIG. 11 is a diagram of a silkworm cocoon 305 based on a diversified silkworm variety in the third embodiment of the present invention.
FIG. 12 is a diagram of a photoresist sample based on a diversified silkworm variety 305 in the third embodiment of the present invention.
Fig. 13 is a molecular detection diagram of a photoresist sample prepared based on a diversified silkworm variety 305 cocoon in the third example of the present invention.
Fig. 14 is a structural view of negative film ion beam exposure 1s development based on silk fibroin of a polytropic silkworm variety 305 in the third embodiment of the present invention.
Fig. 15 is a structural diagram of positive glue ion beam exposure for 1s development based on silkprotein of a multifarious silkworm variety 305 in the third embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments, not all embodiments, of the technical solutions. All other embodiments obtained by a person skilled in the art based on the embodiments of the present technical solution without creative efforts shall fall within the protection scope of the present invention. In addition, the scope of the present invention should not be limited to the particular structures or components or the specific parameters set forth below.
The invention provides a fully water-based silk photoresist based on a plurality of kinds of chilies and multifarious silkworm varieties and a preparation method thereof. The invention selects 3 silkworm varieties (autumn white, summer fragrant, 305), which are characterized by easy feeding, large silk output, high silk quality and the like, the fibroin is easy to extract and highly efficient, and the conformation of the fibroin can be changed by radiation, so that the silkworm silks have dual purposes of electron beams and ion beams and dual purposes of positive and negative. In addition, the photoresist only takes water as a developing solution and a solvent, is environment-friendly and harmless to human bodies, meets the requirement of green micro-nano processing to the greatest extent, and has important value for the development and application of the mulberry industry.
The invention discloses a full water-based silk photoresist based on two or more varieties of silkworms, which comprises silkworm silk fibroin and an aqueous solvent of the two varieties of silkworms, namely autumn white, summer fragrant or more varieties of silkworms 305.
The silkworm silk fibroin has a molecular weight of about 25kDa, is in a liquid or solid powder form, and adopts ultrapure water as a water solvent. The silkworm silk fibroin component mainly comprises a silk fibroin heavy chain (FibH), a silk fibroin light chain (FibL) and P25 glycoprotein.
The domestic silkworm fibroin can be used as a negative glue and a positive glue. After the negative photoresist is exposed, the exposed part becomes not easy to dissolve, a pattern is left, and the unexposed part is developed; after the positive photoresist is exposed, the unexposed part leaves a pattern, and the exposed part becomes easy to dissolve and is developed.
When the film is used as the negative glue, the thin film formed by spin-coating and curing the silkworm fibroin is the negative glue thin film without carrying out crosslinking treatment on the fibroin thin film.
When the silk fibroin film is used as a positive glue, the silk fibroin film needs to be subjected to crosslinking treatment, the crosslinking method is to soak the silk fibroin film for 5 s-7200 s by using a methanol reagent, and preferably, the treatment time of the methanol reagent is 30 min. After methanol treatment, the secondary conformation is beta-sheet, and after exposure, the short soluble polypeptide is obtained.
A method for preparing a full water-based silk photoresist based on bivoltine and diversified silkworm varieties comprises the following steps:
step S1, extracting silk fibroin from two or more silkworm varieties;
in step S2, a photoresist pattern is prepared by exposure to a focused ion beam and an electron beam.
Wherein the step S1 of extracting silk fibroin by utilizing the variety of the bivoltine and polytropic silkworms further comprises the following steps:
step S1-1, selecting cocoon shells (305, autumn white and summer fragrant) of 3 silkworm varieties for degumming, wherein the silkworm variety 305 is a diversified variety, and the autumn white and summer fragrant of the silkworm variety are breeds in two varieties, and the silkworm variety has the characteristics of being beneficial to feeding, large in silk output, high in silk quality and the like, and the fibroin of the silkworm variety is easy to extract and efficient. After boiling in 0.5% (M/V) (g/ml) sodium carbonate solution, the cocoon shells of 3 silkworm varieties (305, autumn white and summer fragrant) were mixed at a ratio of 1: the bath ratio of 100 is put into 0.5% (M/V) (g/ml) sodium carbonate solution to be boiled for 30-90min (min) to remove sericin.
And step S1-2, washing the boiled silkworm silk in flowing water, soaking in deionized water for 30min, changing the deionized water once, repeatedly soaking for three times, and then placing the silkworm silk in a 60 ℃ oven for 6-12h (h) to be dried for later use to prepare the silkworm silk fiber.
Step S1-3, preparing the fibroin dissolving solution from anhydrous calcium chloride, anhydrous ethanol and water solution according to the molar ratio of 1:2:8, and mixing the raw materials in a proportion of 1: and (3) putting a certain amount of the silkworm silk fibers into the silk fibroin dissolving solution at a bath ratio of 10, and keeping the temperature at 70 ℃ until the silk fibroin dissolving solution is completely dissolved, wherein no obvious silk insoluble substances exist in the dissolving solution.
And step S1-4, filtering the dissolved silk fibroin liquid, putting the filtered silk fibroin liquid into a dialysis bag, dialyzing for 72 hours (h), wherein the interception of the dialysis bag is 8-14KDa, changing the dialysate every 3-5h in the dialysis process, and preferably selecting water as the dialysate.
And step S1-5, filtering and centrifuging the dialyzed domestic silkworm fibroin protein solution of the 3 silkworm varieties to remove impurities. The centrifugal speed is 5000r/min-14000r/min (r/min), and the centrifugal time is 15min-40min (min).
Step S1-6, placing the silk fibroin solution in a dialysis bag, air-drying and concentrating, wherein the photoresist concentration can be 1-30% w/w (mass percent g/g) according to the processing requirement, and the preferred photoresist concentration is 3-10% w/w (mass percent g/g). The method for measuring the concentration of the silk fibroin solution comprises the following steps: measuring the weight m of a culture dish1. Thereafter, 0.5ml of silk fibroin solution was added to the culture dish to determine the weight m thereof2And drying the mixture at 60 ℃ for 4 to 12 hours. After drying the silk fibroin, determining the weight m3And finally with (m)2-m1)/(m3-m1) And calculating the concentration of the silk fibroin.
And step S1-7, detecting the molecular weight of the silk fibroin aqueous solution by SDS-PAGE, wherein the molecular weight is above 25 kDa.
In step S2, the method for obtaining the photoresist by selecting one of the focused ion beam and the electron beam includes the following steps:
and step S2-1, spin-coating the silkworm silk fibroin aqueous solution on a silicon wafer, wherein the volume of the silkworm silk fibroin used in the spin-coating is 0.1-1 mL (milliliter), the rotation speed is 1000-5000 r/min (revolution/minute), and the spin-coating time is 10-600S. Drying and curing to form the transgenic silkworm silk fibroin film, and curing at 50-100 ℃ for 1-30 min.
Step S2-2, respectively exposing the silkworm silk fibroin film by electron beams and focused ion beams; the accelerating voltage of electron beam exposure is 30kV, and dose is 1-300C cm-2(coulomb/square centimeter); the acceleration voltage of the focused ion beam is 30kV, the beam current is 2pA, and the exposure time is 0.01 s-5 s.
Step S2-3, placing the exposed bombyx mori silk fibroin film sample in water for developing and drying to obtain a bombyx mori silk fibroin structure; ultrapure water is used for development, and the development time is 1 s-7200 s.
When the silk fibroin film is used as the positive glue, the silk fibroin film needs to be subjected to crosslinking treatment, and the crosslinking method is to soak the silk fibroin film for 5-7200 s by using a methanol reagent. The resolution of the full-water-based photoresist prepared by silk fibroin of three silkworm varieties (two chemical varieties of summer fragrant, autumn white and diversified variety 305) can reach 17.4nm optimally.
Example one
The photoresist is silk fibroin extracted from the autumn white of a bivoltine silkworm variety (the autumn white cocoon shell of the silkworm variety shown in figure 1) and has the advantages of high silk quality, high yield, easiness in feeding and the like. The method comprises the following steps of carrying out exposure processing by focusing ion beams or electron beams, and selecting one ion beam or electron beam for exposure each time, wherein the method comprises the following specific steps:
1. dissolving the autumn white silkworm cocoon of the silkworm variety, wherein the dissolving method comprises the following specific steps:
1) degumming: after boiling 0.5% (M/V) (g/ml) sodium carbonate solution, the autumn white cocoon shells of the silkworm variety were mixed at a ratio of 1: boiling in 100 bath ratio for 30-90min, preferably 30min to remove sericin;
2) and (3) washing the boiled silk in flowing water, soaking in deionized water, changing the deionized water once after soaking for 30min, repeating the steps for three times, and then placing the silk in an oven at 60 ℃ for 6-12h for drying for later use.
3) Preparing a silk fibroin dissolving solution from anhydrous calcium chloride, anhydrous ethanol and an aqueous solution according to a molar ratio of 1:2:8, and mixing the components in a ratio of 1: and (3) taking a certain amount of silk fibers according to the bath ratio of 10, putting the silk fibers into the dissolving solution, keeping the temperature at 70 ℃ until the silk fibers are completely dissolved, wherein no obvious silk insoluble substances exist in the dissolving solution.
4) Filtering the dissolved fibroin protein solution, putting into a dialysis bag (the retention amount of the dialysis bag is 8-14kDa) for dialysis for 72h, and changing water every 3h-5h in the process.
5) Filtering, centrifuging and removing impurities from the dialyzed autumn white silkworm fibroin solution. The centrifugal speed is 5000r/min-14000r/min (r/min), and the centrifugal time is 15min-40min (min).
6) Placing the silk fibroin solution in a dialysis bag, air-drying and concentrating, concentrating to 1-30% w/w (mass percent g/g) according to the requirements of the subsequent process, preferably 3-7% w/w (mass percent g/g), obtaining the full-aqueous photoresist solution of the silk fibroin of the silkworm in autumn after the concentration is finished, and storing at low temperature. The method for measuring the concentration of the silk fibroin solution comprises the following steps: measuring the weight m of a culture dish1. Thereafter, 0.5ml of silk protein solution was added to the culture dish to determine the weight m2And drying at 60 deg.C for 4-12 h. After drying the silk protein, its weight m is determined3And finally with (m)2-m1)/(m3-m1) The concentration is calculated and measured. The obtained autumn white photoresist is colorless and transparent as shown in fig. 2, mainly comprises three silk fibroin (FibH, FibL and P25), is dialyzed, only takes water as a solvent, is not added with any organic reagent, can be directly used as the photoresist, meets the green and ecological photoetching requirement, and is beneficial to large-scale production.
7) The molecular weight of the silk fibroin aqueous solution is above about 25kDa as determined by SDS-PAGE. FIG. 3 shows the detection result of the photoresist molecule prepared by cultivated silkworm variety autumn white, the specific detection method is: diluting the extracted autumn white silk protein photoresist sample by 5 times by 8M urea, adding 5 xSDS-PAGE Loading Buffer, mixing uniformly, and treating at 98 ℃ for 10min to denature the protein. And (3) carrying out electrophoretic separation on the denatured protein sample by using NuPAGE 4-12% Bis-Tris protein gel under the condition of constant pressure of 120V, dyeing for 10min by using Coomassie brilliant blue dyeing solution after the electrophoresis is finished, and decoloring by using decoloring solution until a clear protein band is shown.
2. Preparing micro-nano patterns with improved resolution, etching resistance and other performances:
1) and spin-coating the silk fibroin aqueous solution on a silicon wafer, wherein the volume of the silk fibroin aqueous solution used in the spin-coating is 0.1-1 mL, the rotating speed is 1000-5000 r/min, and the spin-coating time is 10-600 s. And then drying and curing to form a fibroin film, wherein the curing temperature is 50-100 ℃, and the curing time is 1-30 min.
2) Respectively carrying out electron beam exposure and focused ion beam exposure on the silk fibroin film; the accelerating voltage of electron beam exposure is 30kV, and dose of dose is 1-300C cm-2(coulomb/square centimeter); the acceleration voltage of the focused ion beam is 30kV, the beam current is 2pA, and the exposure dose is 0.01 s-5 s.
3) Placing the exposed silk fibroin film sample in water for developing and drying to obtain a silk fibroin structure; the developing water is ultrapure water, and the developing time is 1 s-7200 s. The secondary structure of the silk protein of the exposed part is changed into a spiral structure from random curl, so that the exposed part is not easy to dissolve and presents a convex figure after water development, and figure 4 shows that the negative photoresist scanning electron microscope photo of the silkworm autumn white silk protein after the silkworm autumn white silk protein is subjected to spin coating and curing is exposed for 5s by ion beams, and the resolution ratio is about 48 nm.
When the silk fibroin film is used as positive glue, the silk fibroin film needs to be subjected to crosslinking treatment, the crosslinking method is to soak the silk fibroin film for 5-7200 s by using a methanol reagent, the preferable methanol treatment time is 30min, at the moment, the secondary conformation of the silk fibroin is converted into beta-folding, after exposure, the exposed part is broken into short polypeptide, the short polypeptide is easy to dissolve, and a concave pattern is formed by water development. FIG. 5 shows the scanning electron micrograph of positive photoresist after silkworm autumn white silk protein is spin-coated and solidified and exposed for 4s by ion beam, and the resolution can reach 17.4 nm.
Example two
The photoresist is silk fibroin extracted from Chilo-bombyx mori of Chilo-bombyx mori variety, and the Chilo-bombyx mori variety has the characteristics of large silk spinning amount, easiness in extraction of silk fibroin, high efficiency and the like. The method comprises the following steps of carrying out exposure processing by focused ion beams or electron beams:
1. dissolving summer aromatic silkworm cocoons of silkworm varieties, wherein the dissolving method comprises the following specific steps:
1) degumming: after boiling in 0.5% (M/V) (g/ml) sodium carbonate solution, the silkworm variety xiafang cocoon shells (fig. 6 shows silkworm variety xiafang cocoon shells) were mixed at a ratio of 1: boiling in 100 bath ratio for 30-90min, preferably 45min to remove sericin;
2) and (3) washing the boiled silk in flowing water, soaking the silk in deionized water (the deionized water is changed once after soaking for 30min, and the soaking is repeated for three times), and then placing the silk in an oven at 60 ℃ for 6-12h to dry for later use.
3) Preparing a silk fibroin dissolving solution from anhydrous calcium chloride, anhydrous ethanol and an aqueous solution according to a molar ratio of 1:2:8, and mixing the components in a ratio of 1: and (3) taking a certain amount of silk fibers according to the bath ratio of 10, putting the silk fibers into the dissolving solution, keeping the temperature at 70 ℃ until the silk fibers are completely dissolved, wherein no obvious silk insoluble substances exist in the dissolving solution.
4) Filtering the dissolved fibroin protein solution, putting the filtered fibroin protein solution into a dialysis bag (with a retention amount of 8-14kDa) for dialysis for 72h, and changing water every 3h-5h in the process.
5) Filtering the dialyzed summer aromatic silkworm fibroin solution, centrifuging and removing impurities. The centrifugal speed is 5000r/min-14000r/min (r/min), and the centrifugal time is 15min-40min (min).
6) Placing the silk fibroin solution in a dialysis bag, air-drying and concentrating, concentrating to 1-30% w/w (mass percent g/g) according to the subsequent process requirements, preferably 5-10% w/w (mass percent g/g), obtaining a full water-based photoresist solution of the Xiafang family silk protein after the concentration is finished, and placing the solution in a low temperature for storage. The method for measuring the concentration of the silk protein solution comprises the following steps: measuring the weight m of a culture dish1. Thereafter, 0.5ml of silk protein solution was added to the petri dish to determine the weight m thereof2And bringing it to 60Drying at the temperature of 4-12 h. After drying the silk protein, the weight m is determined3And finally with (m)2-m1)/(m3-m1) The concentration of the Xiafang silkworm photoresist is measured by calculation, and the Xiafang silkworm photoresist sample is colorless and transparent as shown in figure 7, is not added with any organic reagent and can be directly used as photoresist for photoetching. And only water is used as a solvent after dialysis, the components mainly comprise three silk fibroin proteins (FibH, FibL and P25), and the preparation method is efficient and green and is beneficial to large-scale production. ).
6) The molecular weight of the silk protein in water solution is above 25kDa as determined by SDS-PAGE. FIG. 8 shows the molecular detection results of photoresists prepared from Xiahuang of silkworm variety, which is prepared by diluting Xiahuang silk protein photoresist 5 times with 8M urea, adding 5 xSDS-PAGE Loading Buffer, mixing, and treating at 98 deg.C for 10min to denature protein. And (3) carrying out electrophoretic separation on the denatured protein sample by using NuPAGE 4-12% Bis-Tris protein gel under the condition of constant pressure of 120V, dyeing for 10min by using Coomassie brilliant blue dyeing solution after the electrophoresis is finished, and decoloring by using decoloring solution until a clear protein band is shown.
2. Preparing micro-nano patterns with improved performances such as resolution, etching resistance and the like:
1) and spin-coating the fibroin aqueous solution on a silicon wafer, wherein the volume of the fibroin aqueous solution used in the spin-coating is 0.1-1 mL, the rotating speed is 1000-5000 r/min, and the spin-coating time is 10-600 s. And then drying and curing to form a fibroin film, wherein the curing temperature is 50-100 ℃, and the curing time is 1-30 min.
2) Respectively exposing the fibroin film by electron beams and focused ion beams; the acceleration voltage of electron beam exposure is 30 kV; the acceleration voltage of the focused ion beam is 30kV, the beam current is 2pA, and the exposure time is 0.01 s-5 s.
3) Placing the exposed fibroin film sample in water for developing and drying to obtain a fibroin structure; the developing water is ultrapure water, and the developing time is 1-7200 s. FIG. 9 is a photograph of characterization of negative photoresist optical microscope using electron beam exposure after the bombyx mori xiafangsi silk protein is spin-coated and cured by the above method (dose of electron beam dose is 20C cm)-2) With resolution of about 1 micron or so. Based on the fact that the secondary conformation of silk protein can be converted by radiation, in the negative glue, the exposed part of the negative glue is changed into a spiral structure from a random coil, and the negative glue becomes insoluble after development, so that a convex photoetching pattern is obtained.
When the silk fibroin film is used as a positive glue, crosslinking treatment needs to be carried out on the silk fibroin film, the crosslinking method is to soak the silk fibroin film for 5s to 7200s by using a methanol reagent, and the preferable methanol reagent treatment time is 30 min. The secondary conformation of the methanol-treated polypeptide is beta-sheet, and the short polypeptide becomes soluble after exposure, thus obtaining a concave lithographic pattern after development. FIG. 10 is a photograph of positive photoresist optical microscope representation (electron beam dose 10 Ccm) of silkworm summer aromatic silk fibroin exposed by electron beam after spin coating and curing by the above method-2)。
EXAMPLE III
The photoresist is silk fibroin extracted by utilizing a diversified silkworm variety 305, the variety 305 has high-quality silk and is easy to feed in a large scale, and the silk fibroin is extracted efficiently and is low in cost. The method comprises the following steps of carrying out exposure processing by focused ion beams or electron beams:
1. dissolving silkworm variety 305 silkworm cocoon, wherein the dissolving method specifically comprises the following steps:
1) degumming: after boiling a 0.5% (M/V) (g/mL) sodium carbonate solution, silkworm variety 305 cocoon shells were mixed at a ratio of 1: boiling in 100 bath ratio for 30-90min, preferably 60min to remove sericin; (FIG. 11 shows silkworm variety 305 cocoon shell)
2) And (3) washing the boiled silk in flowing water, soaking the silk in deionized water (soaking for 30min, changing the deionized water once, repeating the steps for three times), and then placing the silk in an oven at 60 ℃ for 6-12h for drying for later use.
3) Preparing a silk fibroin dissolving solution from anhydrous calcium chloride, anhydrous ethanol and an aqueous solution according to a molar ratio of 1:2:8, and mixing the components in a ratio of 1: and (3) taking a certain amount of silk fibers according to the bath ratio of 10, putting the silk fibers into the dissolving solution, keeping the temperature at 70 ℃ until the silk fibers are completely dissolved, wherein no obvious silk insoluble substances exist in the dissolving solution.
4) Filtering the dissolved fibroin protein solution, placing in a dialysis bag (with a cut-off of 8-14kDa) for dialysis for 72h, and changing water every 3-5h in the process.
5) And filtering and centrifuging the dialyzed 305 silkworm silk fibroin solution to remove impurities. The centrifugal speed is 5000r/min-14000r/min (r/min), and the centrifugal time is 15min-40min (min).
6) Placing the silk fibroin solution in a dialysis bag, air-drying and concentrating, concentrating to 1-30% w/w (mass percent g/g) according to the requirements of subsequent processes, preferably 5-7% w/w (mass percent g/g), obtaining a 305 silkworm fibroin all-water-based photoresist solution after concentration, and storing at low temperature. The method for measuring the concentration of the silk protein solution comprises the following steps: measuring the weight m of a culture dish1. Thereafter, 0.5ml of silk fibroin solution was added to the culture dish to determine the weight m thereof2And drying at 60 deg.C for 4-12 h. After drying the silk protein, its weight m is determined3And finally with (m)2-m1)/(m3-m1) The concentration is calculated and measured. FIG. 12 is a sample diagram of 305 silkworm silk protein photoresist, which is colorless and transparent, mainly contains three kinds of silk fibroin (FibH, FibL and P25), is all water-based, green and nontoxic, and can be produced continuously on a large scale.
6) The molecular weight of the silk fibroin aqueous solution is above 25kDa by SDS-PAGE detection. FIG. 13 shows the detection result of the photoresist molecule prepared from silkworm variety 305, which is specifically prepared by diluting 305 silkworm fibroin photoresist with 8M urea by 5 times, adding 5 xSDS-PAGE Loading Buffer, mixing uniformly, and treating at 98 deg.C for 10min to denature protein. And (3) carrying out electrophoretic separation on the denatured protein sample by using NuPAGE 4-12% Bis-Tris protein gel under the condition of constant pressure of 120V, dyeing for 10min by using Coomassie brilliant blue dyeing solution after the electrophoresis is finished, and decoloring by using decoloring solution until a clear protein band is shown.
2. Preparing micro-nano patterns with improved performances such as resolution, etching resistance and the like:
1) and spin-coating the silk fibroin aqueous solution on a silicon wafer, wherein the volume of the silk fibroin aqueous solution used in the spin-coating is 0.1-1 mL, the rotating speed is 1000-5000 r/min, and the spin-coating time is 10-600 s. And then drying and curing to form a fibroin film, wherein the curing temperature is 50-100 ℃, and the curing time is 1-30 min.
2) Respectively carrying out electron beam exposure and focused ion beam exposure on the silk fibroin film; the acceleration voltage of electron beam exposure is 30 kV; the acceleration voltage of the focused ion beam is 30kV, the beam current is 2pA, and the exposure time is 0.01-5 s.
3) Placing the exposed silk fibroin film sample in water for developing and drying to obtain a silk fibroin structure; the secondary conformation of the exposed part is changed from random coil to a helical structure which is not easy to dissolve, and the exposed part (developing time is 1 s-7200 s) is left after development (developing water is ultrapure water), so as to form a convex structure. FIG. 14 is a scanning electron micrograph of silkworm 305 silk protein which is spin-coated and cured by the above method and exposed for 1s by negative gel ion beam, and the pattern resolution is about 40.1 nm.
When the silk fibroin film is used as a positive glue, the silk fibroin film needs to be subjected to crosslinking treatment, the crosslinking method is to soak the silk fibroin film for 5-7200 s by using a methanol reagent, the preferable methanol treatment time is 30min, the silk fibroin conformation is beta-folding after the methanol treatment, and the silk fibroin film becomes easily-soluble short polypeptide after exposure. FIG. 15 is a scanning electron micrograph of silkworm 305 silk protein after spin coating and curing by the above method and exposing for 1s with positive glue ion beam, wherein the resolution is about 50.5 nm.
In conclusion, the selected 3 silkworm varieties (autumn white, summer fragrant and 305) have the characteristics of being beneficial to feeding, large in silk spinning amount, high in silk quality and the like, the fibroin of the silkworm varieties is easy to extract and efficient, the conformation of the fibroin of the silkworm varieties can be converted through radiation, a photoetching pattern with good resolution can be manufactured, the components of the silkworm varieties mainly comprise three silk fibroin (FibH, FibL and P25), only water is used as a solvent and a developing solution, the requirement of green micro-nano processing is met to the greatest extent, and the application of the silkworm industry is greatly expanded.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (9)
1. A full water-based silk photoresist based on two or more varieties of silkworms is characterized by comprising silkworm silk fibroin of the two varieties of silkworms with autumn white, summer fragrant or more varieties of silkworms 305 and a water solvent.
2. Fully aqueous based silk photoresist based on the use of striped and diversified silkworm varieties according to claim 1, wherein the silkworm silk fibroin has a molecular weight of about 25 kDa.
3. The fully water-based silk photoresist based on the bivoltine and diversified silkworm varieties as claimed in claim 2, wherein the form of the silkworm silk fibroin is liquid or solid powder, and the aqueous solvent is ultrapure water.
4. Fully aqueous based silk photoresist based on bihydric and polytropic silkworm varieties according to claim 3, characterized in that the silkworm silk fibroin components comprise silk fibroin heavy chains, silk fibroin light chains and P25 glycoprotein.
5. Fully water-based silk photoresist based on striped and diversified silkworm varieties according to claim 4, wherein the silkworm fibroin is used as a negative glue or as a positive glue.
6. A preparation method of a full water-based silk photoresist based on bivoltine and diversified silkworm varieties is characterized by comprising the following steps:
step S1, extracting silk fibroin from two or more silkworm varieties;
in step S2, a photoresist pattern is prepared by exposure to a focused ion beam and an electron beam.
7. The method for preparing a fully water-based silk photoresist based on two or more varieties of silkworms according to claim 6, wherein the step of extracting silk fibroin from two or more varieties of silkworms further comprises step S1-1, selecting 3 varieties of silkworm cocoon shells 305, autumn leaves and summer leaves for degumming, wherein the variety of silkworms 305 is a variety of silkworms, the variety of silkworms autumn leaves and the variety of silkworms summer leaves are the stock species in the two varieties, boiling 0.5% (M/V) (g/ml) sodium carbonate solution, and then boiling the 3 varieties of silkworm cocoon shells 305, autumn leaves and summer leaves in 1: 100-1: a bath ratio of 200 was placed in a 0.5% (M/V) (g/ml) sodium carbonate solution and boiled for 30min-90min (min) to remove sericin.
8. The method for preparing fully water-based silk photoresist based on the two-piece and multi-variety silkworm varieties according to claim 6, wherein the step of extracting silk protein by using the two-piece and multi-variety silkworm varieties further comprises the step of S1-2, the boiled silkworm silk is washed in flowing water, then soaked in deionized water, the deionized water is replaced once after soaking for 30min, the soaking is repeated for three times, and then the silkworm silk is placed in an oven at 60 ℃ for 6h-12h (h) to be dried for standby use, so as to prepare the silkworm silk fiber.
9. The method for preparing fully water-based silk photoresist based on the two-part and multi-part silkworm varieties according to claim 7, wherein the step of extracting silk fibroin by using the two-part and multi-part silkworm varieties further comprises the step of S1-3, wherein the steps of preparing silk fibroin dissolving solution from anhydrous calcium chloride, anhydrous ethanol and aqueous solution according to a molar ratio of 1:2:8 are as follows, and the steps of preparing the silk fibroin dissolving solution from the mixture of the anhydrous calcium chloride, the anhydrous ethanol and the aqueous solution are as follows, wherein the ratio of the anhydrous calcium chloride to the anhydrous ethanol to the aqueous solution is as follows, and the ratio of the anhydrous calcium chloride to the anhydrous ethanol is as 1: and (3) putting a certain amount of the silkworm silk fibers into the silk fibroin dissolving solution at a bath ratio of 10, and keeping the temperature at 70 ℃ until the silk fibroin dissolving solution is completely dissolved, wherein no obvious silk insoluble substances exist in the dissolving solution.
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