CN114647149A - Full-water-base multipurpose silk photoresist based on EvH-converted composite silk and preparation method thereof - Google Patents
Full-water-base multipurpose silk photoresist based on EvH-converted composite silk and preparation method thereof Download PDFInfo
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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Abstract
The invention provides a full-water-base multipurpose silk photoresist based on EvH composite silk and a preparation method thereof, wherein the full-water-base multipurpose silk photoresist is prepared from silk of silkworm strain with a transgenic bagworm repetitive motif EvH, and comprises silkworm silk fibroin of the transgenic bagworm and an aqueous solvent. The full-water-based multipurpose silk photoresist based on the converted EvH composite silk is industrially produced by using the silkworm silk, and the full-water-based photoresist is prepared by using the silkworm silk based on the good biocompatibility, biodegradability, physical stability and chemical stability of the silkworm silk, so that the environment friendliness of the processing technology is met. The photoresist provided by the invention is genetically improved by adopting natural silkworm silk protein, and high-resolution micro-nano patterns are realized based on balance control between mechanical properties and molecular weight.
Description
Technical Field
The invention belongs to the technical field of biological electronic information, and particularly relates to a full-water-base multipurpose silk photoresist based on EvH-converted composite silk and a preparation method thereof.
Background
The semiconductor chip is an important foundation of information technology, and the semiconductor industry has been developed for more than 70 years since the birth of the last 40-50 years, and the rapid development of the semiconductor industry can not leave the progress of the core process, namely the photoetching process. The photoresist is one of the key materials which are necessary in the photoetching process and have the greatest technical difficulty, plays a vital role in the development process of the semiconductor technology, is monopolized by international enterprises all the time, and is absolutely necessary to be replaced in China. At present, most commercial photoresists use artificially synthesized polymers or toxic and harmful organic reagents are added during production, so that the human health is damaged, certain harm is brought to the ecological environment, and the sustainable development of green ecology is not facilitated.
According to the report, the gene recombination spider silk protein is used as the full water-based photoresist, the water solubility of the full water-based photoresist is controlled based on the beta-folding of a secondary structure in the spider silk protein, and a multi-dimensional and scale-spanning micro-nano structure can be prepared. But the feeding cost of the spiders is high, the required feeding environment is very harsh, and the spiders are not suitable for large-area popularization and application. In the face of the rapidly growing industrial demand, there is an urgent need to find an all-water-based photoresist which is suitable for industrial needs and has little negative effect on the environment.
Disclosure of Invention
Based on the technical problems in the prior art, the invention provides a full-water-base multipurpose silk photoresist based on EvH-converted composite silk and a preparation method thereof.
According to the first aspect of the technical scheme, the invention provides a full-water-based multipurpose silk photoresist based on EvH-converted composite silk, wherein the full-water-based multipurpose silk photoresist is prepared from silk of a silkworm strain with a transgenic bagmoth repeating motif EvH, and comprises silkworm fibroin protein and an aqueous solvent of the transgenic bagmoth, and the full-water-based photoresist realizes a high-resolution micro-nano pattern.
Wherein the silkworm silk fibroin has a molecular weight of about 25 kDa. Further, 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 silk fibroin heavy chain, silk fibroin light chain and glycoprotein. Preferably, bombyx mori silk fibroin is used as a negative glue, or as a positive glue.
According to the second aspect of the technical scheme of the invention, the preparation method of the full-water-base multipurpose silk photoresist based on the EvH-converted composite silk comprises the following steps:
step S1, extracting silk fibroin from the compound silk of EvH;
in step S2, a photoresist pattern is prepared by exposure through a focused ion beam and an electron beam.
Wherein, the step S1 further comprises the step S1-1 of degumming: boiling 0.5% (M/V) sodium carbonate solution, transferring EvH compound silkworm cocoon shell, mixing them in the ratio of 1: 100 bath ratio, and steaming for 30-90 min (min), preferably 50min, to remove sericin without excessive damage to sericin.
Additionally, the step S1 further includes a step S1-2 of washing the cooked EvH compound silk in running tap water, soaking in a cleaning solution, changing the cleaning solution once after soaking in the cleaning solution for 30min, repeating three times to sufficiently clean residual sericin, and then drying the EvH compound silk in an oven at 60 ℃ for 6h-12h (hours) for standby; the cleaning solution is deionized water.
Further, the step S1 further includes a step S1-3 of preparing the fibroin solution from anhydrous calcium chloride, anhydrous ethanol and an aqueous solution at a molar ratio of 1:2:8, wherein the weight ratio of the fibroin solution is 1: 10, putting a certain amount of silk fibers into silk fibroin dissolving solution, and dissolving at a constant temperature of any one of 30-100 ℃ to completely dissolve the silk fibers, wherein no obvious silk insoluble substances exist in the dissolving solution; the dissolution temperature was 70 ℃.
Compared with the prior art, the full-water-base multipurpose silk photoresist based on the EvH-transferred composite silk and the preparation method thereof have the following beneficial effects:
1. the full-water-based multipurpose silk photoresist based on the converted EvH composite silk is industrially produced by using the silkworm silk, and the full-water-based photoresist is prepared by adopting the silkworm silk protein based on the good biocompatibility, biodegradability, physical stability and chemical stability of the silkworm silk, so that the environment friendliness of the processing technology is met.
2. The photoresist provided by the invention is genetically improved by adopting natural silkworm silk protein, and high-resolution micro-nano patterns are realized based on balance control between mechanical properties and molecular weight.
3. The invention provides a transgenic bag moth silk protein repetitive motif EvH which is transferred into silkworm silk protein to obtain silkworm silk of a transgenic strain with improved mechanical property, and the all-water-based and multipurpose photoresist with excellent performance is prepared by the silkworm silk protein repetitive motif.
4. The photoresist disclosed by the invention is simple and convenient in preparation process and low in cost, is beneficial to large-scale production of the photoresist, can meet the environment friendliness of a processing process, and can be used for directly preparing high-precision micro-nano patterns with excellent mechanical property and good anti-etching property.
5. The full-water-based multipurpose silk photoresist based on the EvH-converted composite silk and the preparation method thereof are based on the silk protein polycrystalline structure, can be used as an electron beam photoresist and an ion beam photoresist, can realize positive and negative purposes, are used for optimizing commercial photoresist, and have good application prospects in the field of integrated circuit micro-nano processing.
Drawings
FIG. 1 is a diagram of a photoresist sample expressing EvH protein using FibH promoter
FIG. 2 is a diagram showing the molecular size detection result of a photoresist sample expressing EvH protein by using FibH promoter (SDS-PAGE detection diagram of genetically modified silkworm EvH silk protein molecules);
FIG. 3 is a schematic diagram of a negative photoresist electron beam pattern for expressing EvH protein using the FibH promoter;
FIG. 4 is a schematic diagram of a negative photoresist ion beam pattern for expressing EvH protein using the FibH promoter;
FIG. 5 is a schematic diagram of a positive photoresist pattern of a photoresist ion beam for expressing EvH protein using the FibH promoter;
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 full-water-base multipurpose silk photoresist based on EvH (bageworm silk protein repeating motif) composite silk, wherein the bageworm silk has mechanical properties exceeding those of spider silk, and a bageworm silk heavy chain repeating sequence is adopted as a target protein to be transferred into the silkworm silk protein.
The full-water-based multipurpose silk photoresist comprises silk protein extracted from a silkworm strain and an aqueous solution, wherein the silkworm strain is a silkworm strain with a transgenic bagworm repetitive motif EvH. Furthermore, the positive and negative dual-purpose of the high-toughness silk full-water-based multipurpose photoresist is realized by controlling the crosslinking degree of the silkworm silk protein, and the full-water-based multipurpose silk based on the converted EvH composite silk can be used as a negative photoresist and a positive photoresist. Exposing the full-water-base multipurpose silk serving as negative glue and based on the transferred EvH composite silk, wherein the exposed part is insoluble in water, and the exposed part is developed to leave an illumination part to form a pattern; the full-water-base multipurpose silk serving as positive glue and based on the transferred EvH composite silk needs to be subjected to cross-linking treatment, the irradiated part is soluble in water, and the non-irradiated part is left after development to form a pattern.
The photoresist disclosed by the invention is simple and convenient in technology and low in cost, is suitable for large-scale production of the photoresist, can meet the environment-friendly property of a processing process, and can be used for directly preparing micro-nano patterns with excellent mechanical property, good etching resistance and high precision. The photoresist disclosed by the invention is based on a silk protein polycrystalline structure, and can be used as an electron beam photoresist and an ion beam photoresist. The method has a good application prospect in the field of integrated circuit micro-nano processing.
The invention discloses a preparation method of full-water-base multipurpose silk photoresist based on EvH-converted composite silk, which comprises the following steps:
step S1, extracting silk fibroin from the compound silk of EvH;
in step S2, a photoresist pattern is prepared by exposure to a focused ion beam and an electron beam.
Wherein the step S1 further comprises the steps of:
step S1-1, degumming: boiling 0.5% (M/V) sodium carbonate solution, mixing EvH-transferred compound silkworm cocoon shell with 1: 100 bath ratio, steaming for 30-90 min (min), preferably 50min, to remove sericin without excessive damage to sericin;
step S1-2, after washing the boiled rotor EvH compound silk in flowing tap water, soaking the silk in a cleaning solution, after soaking the silk in the cleaning solution for 30min, replacing the cleaning solution once, repeating the steps for three times, fully cleaning residual sericin, and then placing the cleaned rotor EvH compound silk in an oven at 60 ℃ for 6h-12h (h) to dry for standby; the cleaning solution is deionized water;
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: 10, putting a certain amount of silk fibers into silk fibroin dissolving solution, and dissolving at a constant temperature of any one of 30-100 ℃ to completely dissolve the silk fibers, wherein no obvious silk insoluble substances exist in the dissolving solution; . The preferred dissolution temperature is 70 ℃;
step S1-4, putting the dissolved silk fibroin solution into a dialysis bag, dialyzing for 72h to remove salt and small molecular peptide fragments, wherein the interception amount of the dialysis bag is 8-14 kDa, and water is changed every 3-5 h in the dialysis process;
step S1-5, placing the silk fibroin solution in a dialysis bag, air-drying and concentrating to obtain a silk fibroin solution with a certain concentration, concentrating to 1% -30% w/w (mass percentage g/g) according to the subsequent process requirements, preferably 3% -7% w/w (mass percentage g/g), obtaining a full water-based photoresist solution of the genetically modified silk after concentration, and storing at low temperature (4 ℃). The method for measuring the concentration of the silk fibroin solution comprises the following steps: measuring the weight m of a culture dish1Thereafter, 0.5ml of silk protein solution was added to the petri dish to determine the weight m thereof2And drying at 60 deg.C for 4-12 h(ii) a After drying of the silk protein, the weight m of the dish containing the silk protein solution was determined3And finally with (m)2-m1)/(m3-m1) And calculating and measuring the concentration of the concentrated silk protein aqueous solution. The molecular weight of the silk fibroin aqueous solution is above about 25 kDa.
Compared with the traditional photoresist, the photoresist mainly comprises three silk fibroin ((FibH, FibL, P25) and exogenous bag moth silk fibroin (EvH), water is used as a solvent, no organic reagent exists, and the development requirement of the current green lithography technology is met.
In addition, compared with the common silk photoresist, the full water-based photoresist based on the genetically modified silkworm fibroin (expressing the exogenous bag moth fibroin EvH) has a series of outstanding advantages of excellent mechanical property, good etching resistance, high resolution and the like, the resolution can reach 30nm level at most, the processing of higher-precision micro-nano patterns can be met, and the full water-based photoresist has important utilization value.
Step S2 is to obtain a photoresist by performing exposure processing with a focused ion beam/electron beam, and specifically includes the following steps:
and S2-1, rotationally coating the transgenic silkworm fibroin aqueous solution obtained in the step S1 on a silicon chip, wherein when the silk fibroin aqueous solution is rotationally coated, the volume of the used transgenic silkworm fibroin aqueous solution is 0.1-1 mL (milliliter), the rotating speed of a spin coating device is 1-5000 r/min (revolutions per minute), and the spin coating time is 10S-10 min. After spin coating, curing at 30-120 ℃ for 0.3-50 min; the curing temperature is preferably 50-100 ℃, and the curing time is 5-30 min.
And step S2-2, selecting one of focused ion beams or electron beams for exposure of the uniform genetically modified silkworm silk fibroin film formed by solidification. The accelerating voltage of electron beam exposure is 30kV, dose of dose is 0.5-300C 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 transgenic silkworm silk fibroin film in water for developing and drying to obtain a transgenic silkworm silk fibroin structure; the preferable choice for developing is ultrapure water, the developing time is 1 s-7200 s, and the negative photoresist pattern is obtained after the developing; the genetically modified silkworm fibroin can be subjected to radiation conversion based on secondary conformation, an exposed part is changed from irregular curling to spiral shape, and the exposed part is not easy to dissolve after development to form a convex structure with better definition.
If the genetically modified silkworm fibroin protein positive glue pattern is to be prepared, the genetically modified silkworm fibroin protein film needs to be subjected to crosslinking treatment, the crosslinking method is to soak the genetically modified silkworm fibroin protein film for 5-7200 s by using a methanol reagent, preferably, the genetically modified silkworm fibroin protein film is treated for 30min (min) by using methanol, so that the secondary conformation of the genetically modified silkworm fibroin protein is converted into beta folding, an exposed part is converted into short polypeptide by radiation, and the short polypeptide is easily dissolved after being developed for 1-7200 s to form a concave structure with better definition, so that the positive glue pattern is obtained. The resolution of the full-water-base multipurpose silk photoresist prepared from the converted EvH composite silk can reach 20nm level.
The invention relates to a composite silkworm silk photoresist based on gene modification, which is a full-water-based photoresist prepared by transferring a repetitive motif EvH determining excellent mechanical properties in a silk of a baggy moth into a transgenic silkworm strain in a silkworm body. The composite silk obtained by transferring the bagworms EvH into the silkworm bodies has excellent mechanical properties, and in addition, the prepared photoresist only takes water as a solvent and a developing solution, so that the green sustainable development of ecological environment is facilitated, and the composite silk has a series of outstanding advantages of good etching resistance, high resolution and the like. Based on the silk fibroin polymorphic structure, the nano-silver/nano-silver film can be used as an electron beam photoresist and an ion beam photoresist, can realize positive and negative dual purposes, can be used as a positive photoresist and a negative photoresist, can prepare high-precision biological micro-nano processing patterns on a large scale, and has better application and development prospects. The technical solution of the present invention will be further described with reference to the following specific examples.
In the first embodiment, the photoresist is silk fibroin extracted from a silkworm strain (named EvH) with a transgenic bagworm repetitive motif EvH, and the silk mechanical property of the silk fibroin is excellent, so that the photoresist plays an important role in improving the resolution of a photoetching pattern. In this embodiment, the exposure process is performed by using an electron beam, and the specific steps are as follows:
1. dissolving the EvH-transferred silkworm strain cocoons, wherein the dissolving method comprises the following specific steps:
1) degumming: after boiling in 0.5% (M/V) sodium carbonate solution, silkworm cocoon shells of transgenic bagworm repeat motif EvH were mixed at a ratio of 1: boiling in 100 bath ratio for 30-90 min, preferably 30min to remove sericin without excessive damage to fibroin;
2) washing the boiled silk in flowing water, soaking in deionized water for 30min, changing the deionized water once, repeating the steps for three times, and then placing the soaked silk in a 60 ℃ oven for 6-12 h 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: 10, putting a certain amount of silk fiber into the solution at constant temperature of 70 ℃ until the silk fiber is completely dissolved, wherein no obvious silk insoluble substances exist in the solution;
4) putting the dissolved silk fibroin solution into a dialysis bag (the interception amount of the dialysis bag is 8-14 kDa) for dialysis for 50-100 h, and changing water every 1-10 h in the process; preferably, the interception amount of the dialysis bag is 10-12 kDa, the dialysis is carried out for 72 hours, and water is changed every 3-5 hours;
5) the silk fibroin solution is placed in a dialysis bag to be air-dried and concentrated, and then is centrifuged for 30min at the rotation speed of 8000-15000rad/min, so that the silk fibroin aqueous solution with the concentration of 3-10% w/w (mass percent g/g) can be obtained according to the requirement, and the preferred concentration is 3-7% w/w. 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 drying at 60 deg.C for 4-12 h. After drying the silk protein, the weight m is determined3And finally with (m)2-m1)/(m3-m1) The concentration is calculated and measured. FIG. 1 is a diagram of a photoresist sample expressing exogenous bagworm silk protein EvH using the FibH promoter, where T7 indicates its concentration of 7% w/w (mass% g/g). The photoresist sample is colorless and transparent, mainly contains four silk proteins (FibH, FibL, P25 and EvH), takes water as a solvent after dialysis, and does not contain toxic, harmful or harmful substancesThe mechanical reagent meets the requirements of micro-nano processing biocompatibility and environmental protection to the greatest extent.
6) FIG. 2 is a diagram showing the molecular size detection result of the photoresist sample protein using FibH promoter to express exogenous bageworm silk protein EvH, and the result shows that the molecular size of the extracted genetically modified silkworm silk protein is mainly above 25 KDa. The molecular detection method comprises diluting the extracted silk fibroin aqueous solution with 8M urea 20 times, 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 excellent resolution and etching resistance:
1) and spin-coating the transgenic silkworm silk fibroin aqueous solution on a silicon wafer, wherein the volume of the transgenic silkworm silk fibroin used in the spin-coating is 0.1-1 mL, the rotation speed is 1000-5000 r/min, and the spin-coating time is 10-600 s. Drying and curing to form the transgenic silkworm silk fibroin film, and curing at 50-100 ℃ for 1-30 min.
2) Performing electron beam exposure on the silk fibroin film, wherein the acceleration voltage of the electron beam exposure is 30kV, and the dose of dose is 0.5-300C cm-2, preferably 1-3C cm-2;
3) placing the exposed transgenic silkworm silk fibroin film sample in water for developing and drying to obtain a transgenic silkworm silk fibroin structure; when the genetically modified silkworm fibroin is used as negative glue, the secondary conformation of the exposed part is changed from irregular curling to an insoluble spiral structure, ultrapure water is used for development, the development time is 1-7200 s, and the convex negative glue pattern obtained after development is preferably 30-120 s;
when the genetically modified silkworm fibroin positive glue is prepared, the genetically modified silkworm fibroin film needs to be subjected to crosslinking treatment, the crosslinking method comprises the steps of soaking the genetically modified silkworm fibroin film for 5-7200 s by using a methanol reagent, preferably soaking the genetically modified silkworm fibroin film for 30min, converting the secondary conformation of the genetically modified silkworm fibroin into beta-folding by soaking the fibroin in the methanol, converting an exposed part into short polypeptide by radiation, dissolving the short polypeptide in water easily, developing the short polypeptide by using ultrapure water for 1-7200 s, preferably 30-120 s to obtain a concave positive glue pattern, and developing the pattern by using EvH photoresist positive glue electron beam exposure (a uniform protein film is obtained after spin coating and curing by the method, and then soaking the protein film in the methanol for 30min and obtaining a photoresist pattern by using an electron beam) in a picture 3.
In the second embodiment, the silk fibroin extracted from the silkworm strain (named EvH) with transgenic bagworm repeat motif EvH as the photoresist in the second embodiment is processed by exposure with an ion beam, and the specific steps are as follows:
1. and (3) dissolving the silkworm strain cocoons transferred to EvH, wherein the specific dissolving method is consistent with the first embodiment. The difference between the second example and the first example is that the subsequent processing process is different, the first example uses electron beam exposure, and the second example uses focused ion beam exposure, and the focused ion beam exposure has better resolution and sensitivity.
2. Preparing micro-nano patterns with excellent resolution and etching resistance:
1) and spin-coating the transgenic silkworm fibroin aqueous solution on a silicon wafer, wherein the volume of the transgenic silkworm fibroin 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. Drying and curing to form the transgenic silkworm silk fibroin film, and curing at 50-100 ℃ for 1-30 min.
2) And carrying out ion beam exposure on the silk fibroin film, wherein the acceleration voltage of a focused ion beam is 30kV, the beam current is 2pA, and the exposure dose is 0.01 s-5 s.
3) The exposed transgenic silkworm silk fibroin film sample is placed in water for development and drying to obtain a transgenic silkworm silk fibroin structure; when the genetically modified silkworm silk protein is used as negative glue, the secondary conformation of the exposed part is changed from irregular curling to an insoluble spiral structure, ultrapure water is used for development, the development time is 1-7200 s, a convex negative glue pattern is obtained after development, the preferable development time is 30-120 s, and the figure 4 shows EvH photoresist negative glue ion beam exposure development pattern (a uniform protein film is obtained after spin coating and curing according to the method, and a focused ion beam is used for exposure for 1s to obtain a 20 nm-level photoetching pattern);
when the genetically modified silkworm fibroin positive glue is prepared, the genetically modified silkworm fibroin film needs to be subjected to crosslinking treatment, the crosslinking method comprises the steps of soaking the genetically modified silkworm fibroin film for 5-7200 s by using a methanol reagent, preferably soaking the genetically modified silkworm fibroin film for 40min, soaking the genetically modified silkworm fibroin film in methanol to convert the secondary conformation into beta-folding, radiating an exposed part to convert the beta-folding into short polypeptide, wherein the short polypeptide is easy to dissolve in water, developing the exposed part by using ultrapure water for 1-7200 s, preferably 30-120 s, to obtain a concave positive glue pattern, and exposing and developing the pattern by using EvH photoresist positive glue ion beam (the uniform protein film is obtained after spin coating and curing by the method, then soaking the protein film in methanol for 30min, and exposing the protein film for 0.8s by using focused ion beam to obtain a 20 nm-level photoetching pattern).
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. The full-water-based multipurpose silk photoresist is characterized by being prepared from silks of silkworm strains with transgenic bagworms with repeated motif EvH and comprising silkworm silk fibroin and an aqueous solvent of the transgenic bagworms, and realizing high-resolution micro-nano patterns.
2. Full water based multipurpose silk resist based on EvH transferred composite silk according to claim 1, wherein the bombyx mori silk fibroin has a molecular weight of about 25 kDa.
3. The full-water-based multipurpose silk photoresist based on EvH-transformed composite silk according to claim 2, wherein the form of bombyx mori silk fibroin is liquid or solid powder, and the aqueous solvent is ultrapure water.
4. Full water based multipurpose silk photoresist based on composite trans EvH silk according to claim 3, wherein bombyx mori silk fibroin components comprise silk fibroin heavy chain, silk fibroin light chain and glycoprotein.
5. Full-water based multipurpose silk photoresist based on composite converted EvH silk according to claim 4, wherein silkworm silk fibroin is used as negative glue or as positive glue.
6. A preparation method of full-water-based multipurpose silk photoresist based on EvH-converted composite silk is characterized by comprising the following steps:
step S1, extracting silk fibroin from the compound silk of EvH;
in step S2, a photoresist pattern is prepared by exposure to a focused ion beam and an electron beam.
7. The preparation method of full water-based multipurpose silk photoresist based on EvH-converted composite silk according to claim 6, wherein the step S1 further comprises the steps of S1-1, degumming: boiling 0.5% (M/V) sodium carbonate solution, transferring EvH compound silkworm cocoon shell, mixing them in the ratio of 1: 100 bath ratio, and steaming for 30-90 min (min), preferably 50min, to remove sericin without excessive damage to sericin.
8. The preparation method of the full-water-based multipurpose silk photoresist based on the converted EvH composite silk according to the claim 6, wherein the step S1 further comprises the steps of S1-2, washing the cooked converted EvH composite silk in running tap water, soaking in a cleaning solution, after soaking in the cleaning solution for 30min, replacing the cleaning solution once, repeating the step three times to fully clean residual sericin, and then drying the cleaned converted EvH composite silk in an oven at 60 ℃ for 6h-12h (h) for standby; the cleaning solution is deionized water.
9. The preparation method of the full-water-based multipurpose silk photoresist based on EvH composite silks according to claim 7, wherein the step S1 further comprises the step S1-3 of preparing a 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 solution in the ratio of 1: 10, putting a certain amount of silk fibers into the silk fibroin dissolving solution, and dissolving the silk fibers completely at a constant temperature of any one temperature of 30-100 ℃, wherein no obvious silk insoluble substances exist in the dissolving solution; the dissolution temperature was 70 ℃.
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| CN106773533A (en) * | 2017-02-09 | 2017-05-31 | 中国科学院上海微系统与信息技术研究所 | A kind of photoresist and its application process |
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| US20160033861A1 (en) * | 2013-03-15 | 2016-02-04 | Tufts University | All water-based nanopatterning |
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