CN110673440B - Lithographically patternable graphene/native protein compositions, methods of making and patterning thereof - Google Patents
Lithographically patternable graphene/native protein compositions, methods of making and patterning thereof Download PDFInfo
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- CN110673440B CN110673440B CN201910968018.3A CN201910968018A CN110673440B CN 110673440 B CN110673440 B CN 110673440B CN 201910968018 A CN201910968018 A CN 201910968018A CN 110673440 B CN110673440 B CN 110673440B
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- 238000000059 patterning Methods 0.000 title claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 21
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- 102000002322 Egg Proteins Human genes 0.000 claims description 44
- 108010000912 Egg Proteins Proteins 0.000 claims description 44
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- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 5
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- 238000011160 research Methods 0.000 description 3
- 101710166307 Protein lines Proteins 0.000 description 2
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- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 210000003743 erythrocyte Anatomy 0.000 description 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 2
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- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
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- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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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- General Physics & Mathematics (AREA)
- Carbon And Carbon Compounds (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
The invention discloses a composition capable of being subjected to photoetching patterning, which comprises graphene, natural protein and a solvent. The composition has photosensitivity to ultraviolet, visible and near infrared light, and when the composition is used in photoetching patterning, patterning can be completed without introducing photoinitiator, and the obtained pattern has high resolution. The invention also discloses a preparation method of the composition and a photoetching patterning method using the composition.
Description
Technical Field
The present invention relates to the field of microelectronics technologies. And more particularly, to a lithographically patternable graphene/native protein composition, methods of making and patterning thereof.
Background
Graphene is a material having Sp 2 The hybridized two-dimensional carbon material with the hexagonal honeycomb lattice structure, andery-Gamer and Constant-Nuo Wo Xiao Luofu, a university of Manchester, UK, successfully separates the graphene from the graphite by a mechanical stripping method and finds excellent physical and chemical properties, thereby obtaining the Nobel physical prize of 2010 jointly, and raising the hot trend of the research on the graphene material. The research shows that the graphene has excellent optical, electrical and mechanical properties and has wide application prospects in the fields of superconductivity, energy sources, information, sea water desalination, anti-corrosion materials, stimulus response materials, biological medicines and the like.
In many research fields, how to load graphene into various matrix materials to prepare structures with different dimensions and morphologies, and simultaneously maintain unique excellent properties of the graphene is a very core problem. How to introduce graphene into a photoresist material to prepare a patterned structure containing graphene has great significance in endowing the patterned structure with more performance and higher resolution.
Disclosure of Invention
Based on the above problems, a first object of the present invention is to provide a composition which is photosensitive to light in the ultraviolet, visible and near infrared bands and which can be lithographically patterned. When the composition is used in photoetching patterning, the patterning can be completed without introducing a photoinitiator to form various needed pattern structures, the resolution of the obtained pattern is high, and the finest width of the pattern can reach 200nm or less.
A second object of the present invention is to provide a method of preparing a lithographically patternable composition.
A third object of the present invention is to provide a method of photolithographic patterning. In the method, patterning can be completed without introducing a photoinitiator, and the prepared pattern has high resolution.
In order to achieve the first object, the present invention adopts the following technical scheme:
a lithographically patternable composition comprising graphene, a native protein, and a solvent.
Further, the composition comprises 0.5-10% of graphene by weight percent. Exemplary graphene mass percentages in the composition include, but are not limited to, 1-10%, 1-8%, 1-7%, 1-6%, 2-9% by weight, 2-8%, 2-7%, 2-6%, 6-10%, 7-10%, 8-10%, 6-9%, 7-8%, and the like.
Further, the composition comprises 0.01-20% of natural proteins by weight percent. Exemplary natural proteins include, but are not limited to, 0.01 to 18%, 0.01 to 15%, 0.01 to 10%, 0.05 to 20%, 0.05 to 15%, 1.0 to 15%, 0.01 to 9%, 0.01 to 8%, 0.01 to 7%, 0.01 to 6%, 0.01 to 5%, 0.01 to 4%, 0.01 to 3%, 0.01 to 2%, 0.01 to 1%, 0.01 to 0.5%, 0.01 to 0.3%, 0.5 to 10%, 0.5 to 9%, 0.5 to 8%, 0.5 to 7%, 0.5 to 6%, 0.5 to 5%, 0.5 to 4%, 0.5 to 3%, 0.5 to 2%, 0.5 to 1%, 1 to 10%, 5 to 10%, 1 to 9%, 1 to 8%, 1 to 7%, 1 to 6%, 1 to 5%, 1 to 4%, 1 to 3%, 1 to 2% and the like by mass of the composition.
In the present invention, the solvent is used to dissolve the graphene and the natural protein. Further, exemplary solvents include, but are not limited to, water. Optionally, the composition comprises 80-99.49% by weight of solvent. Further, the mass percentage of the solvent in the composition includes, but is not limited to, 85 to 98%, 85 to 99.49%, 88 to 99.49%, 89 to 99.49%, 90 to 99.49% by weight, 91 to 99.49%, 92 to 99.49%, 93 to 97%, 94 to 97%, 95 to 97%, 96 to 97%, 85 to 92%, 86 to 91%, 87 to 90%, 88 to 89% by weight, 93 to 96%, 94 to 95%, 92 to 99.49% and the like.
Further, the natural proteins and the solvent are both derived from egg white. That is, graphene and egg white are included in the composition. That is, the solvent is the rest of the egg white except the natural protein. At this time, the content of egg white in the composition is preferably 90 to 99.5% by weight.
Further, the natural protein and a portion of the solvent are derived from egg white. That is, graphene, egg white, and another portion of solvent are included in the composition. At this time, the partial solvent is the rest of the egg white except the natural protein. Exemplary additional portions of the solvent include, but are not limited to, water. At this time, the content of egg white in the composition is preferably 80 to 89.5% by weight.
Further, the egg white is one or more selected from egg white of chicken, duck, goose, quail, pigeon, bird, tortoise, and snake.
In order to achieve the second object, the present invention adopts the following technical scheme:
a method of preparing a lithographically patternable composition comprising the steps of:
and uniformly mixing graphene, natural protein and a solvent to obtain the composition capable of being subjected to photoetching patterning.
In order to achieve the third object, the present invention adopts the following technical scheme:
a method of photolithographic patterning, comprising the steps of:
uniformly mixing graphene, natural protein and solvent in the first object to obtain a composition in the first object;
applying the composition to a substrate to obtain a substrate having a film formed of the composition on a surface thereof;
a) Exposing, developing, or otherwise developing a film formed from the composition using a light source
b) Adopts the laser direct writing and developing method,
to obtain a substrate with a pattern on the surface.
Further, the application process may be accomplished by any suitable method, preferably by coating or doctor blading. Preferably, the coating is one or more of spin coating, spray coating and dip coating. By said applying, the composition is dispensed on a substrate. The rotational speed may be up to 8000rpm, preferably about 500 to 4000rpm, and more preferably 2000 to 4000rpm, during dispensing.
Alternatively, the substrate may be of any size and shape, and is preferably a substrate useful in photolithography, such as silicon, silicon dioxide, silicon On Insulator (SOI), strained silicon, gallium arsenide, coated substrates, including substrates coated with silicon nitride, silicon oxynitride, titanium nitride, tantalum nitride, ultra-thin gate oxides (e.g., hafnium dioxide), metal or metal coated substrates, including substrates coated with titanium, tantalum, copper, aluminum, tungsten, alloys thereof, and combinations thereof.
Further, the light source is selected from one or more of ultraviolet light having a wavelength range of 250.ltoreq.λ <400nm, visible light having a wavelength range of 400.ltoreq.λ <780nm, and near infrared light having a wavelength range of 780.ltoreq.λ <2500 nm.
Optionally, the light source is provided by a laser, mercury lamp, LED lamp, tungsten halogen lamp or xenon lamp. It will be appreciated by those skilled in the art that the sources of light described herein are illustrative and not limiting, and that the scope of the invention is not limited thereto, and that the skilled artisan can choose different light sources depending on the photoresist composition used and the actual needs.
Further, the wavelength adjustment range of the laser is 250-2500 nm.
Further, the laser is selected from a femtosecond laser with a pulse width of 10 to 300 femtoseconds, a picosecond laser with a pulse width of 0.3 to 800 picoseconds, or a nanosecond laser with a pulse width of 0.8 to 80 nanoseconds.
Further, the laser is selected from a femtosecond laser with a repetition frequency of 1000 Hz-150 MHz, a picosecond laser with a repetition frequency of 25 KHz-150 MHz, or a nanosecond laser with a repetition frequency of 1 Hz-100 kHz.
Further, the developer used for the development is water. The defect that the traditional photoresist and developing solution use toxic and harmful chemical substances is overcome, and the substances involved in the whole patterning process are environment-friendly, so that the requirements of circular economy and environment friendliness are completely compounded.
Further, the water is selected from tap water, deionized water, mineral water, spring water or ultrapure water; preferably, the ultrapure water has a conductivity of 80 megaohms.
Further, the method of exposing a film formed of the composition to light using a light source includes the steps of:
providing a mask having a desired pattern;
directing the mask to an upper surface of the film;
illuminating the resulting structure;
after the illumination is finished, the mask is removed.
Unless otherwise indicated, all starting materials used in the present invention are commercially available, and any ranges recited herein include any number between the endpoints and any subrange formed by any number between the endpoints or any number between the endpoints.
The beneficial effects of the invention are as follows:
in the composition and the patterning method by photoetching provided by the invention, the interaction principle of light and substances is utilized, the photo-thermal effect of heat generated by light absorption of graphene directly causes the crosslinking and curing reaction of natural proteins, the natural proteins are further developed, the crosslinked proteins are not dissolved in water, the proteins which are not crosslinked are dissolved in water, a specific crosslinked protein/graphene pattern is finally formed, and graphene is successfully loaded in a matrix with good biocompatibility, such as the natural proteins. The invention breaks through the limitation that the traditional graphene is required to be subjected to photo-initiator patterning when loaded on the photoresist, and the graphene is used as a photo-induced heating agent and a functional substance, not only bears the function of a natural protein photo-curing agent, but also plays the photoelectric characteristic of the graphene in a final microstructure as a functional loading component, thereby providing a graphene/natural protein composition and a simple and environment-friendly patterning method thereof. Meanwhile, the method can complete patterning without introducing a photoinitiator, and the obtained pattern has high resolution, and can obtain patterns with the finest width of 200nm and below and high resolution.
The composition and the patterning method provided by the invention have important roles in the preparation of special micro devices, cell scaffolds and the like, and have wide application effects.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
FIG. 1 shows a scanning electron microscope image of a line pattern formed by exposing a graphene/natural protein composition (graphene content 0.5wt% and egg white content 99.5 wt%) on a glass substrate with an 800nm femtosecond laser in example 1 of the present invention.
FIG. 2 shows a line pattern scanning electron microscope image formed by exposing a graphene/natural protein composition (graphene content 8wt%, egg white content 92 wt%) on a glass substrate with an 800nm femtosecond laser in example 2 of the present invention.
FIG. 3 shows a line pattern scanning electron microscope image formed by exposing a graphene/natural protein composition (graphene content 10wt%, egg white content 90 wt%) on a glass substrate with an 800nm femtosecond laser in example 3 of the present invention.
FIG. 4 is a scanning electron microscope image showing a dot pattern formed by exposing a graphene/natural protein composition (graphene content 2wt%, egg white content 98 wt%) on a glass substrate with an 800nm femtosecond laser in example 4 of the present invention.
FIG. 5 shows a scanning electron micrograph of concentric ring patterns formed by exposing a graphene/natural protein composition (graphene content 4wt%, egg white content 96 wt%) on a glass substrate with a 400nm femtosecond laser in example 5 of the present invention.
FIG. 6 shows a scanning electron microscope image of a graphene/natural protein composition (6 wt% graphene content, 94wt% egg white content) on a glass substrate exposed with 355nm nanosecond laser to form a line pattern in example 6 of the present invention.
FIG. 7 shows a scanning electron microscope image of a graphene/natural protein composition (graphene content 3wt%, egg white content 97 wt%) on a glass substrate exposed with a high-pressure mercury lamp in example 7 of the present invention to form a concentric circular pattern.
FIG. 8 shows a scanning electron microscope image of a gear pattern formed by exposing a graphene/natural protein composition (graphene content 5wt%, egg white content 95 wt%) on a glass substrate with a 365nm LED lamp in example 8 of the present invention.
FIG. 9 is a scanning electron microscope image showing a three-dimensional pattern formed by exposing a graphene/natural protein composition (graphene content 2.5wt% and egg white content 97.5 wt%) on a glass substrate with an 800nm femtosecond laser in example 9 of the present invention.
FIG. 10 is a scanning electron microscope image showing a dot pattern formed by exposing a graphene/natural protein composition (graphene content 3wt%, egg white content 87%, added solvent water content 10 wt%) on a glass substrate with an 800nm femtosecond laser in example 10 of the present invention.
FIG. 11 shows a scanning electron microscope image of a line pattern formed by exposing a graphene/natural protein composition (graphene content 1wt%, quail egg white content 99 wt%) on a glass substrate with an 800nm femtosecond laser in example 11 of the present invention.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments and the accompanying drawings. Like parts in the drawings are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
Example 1
A method of patterning a graphene/native protein composition comprising the steps of:
a) A proper amount of graphene/natural protein composition is dripped on a glass substrate, wherein the content of graphene in the composition is 0.5wt% and the content of egg white serving as natural protein is 99.5wt%, so that a liquid film is spontaneously formed under the action of gravity.
B) The graphene/natural protein composition liquid film is subjected to laser direct writing exposure by using 800nm femtosecond laser, the laser power is adjusted by using an attenuator under the condition of fixed scanning speed of 10 microns/second to perform exposure, the laser power is gradually changed from 48.3 milliwatts to 31.6 milliwatts, the exposed liquid film is developed by using deionized water for 60-120 seconds, and then the cured graphene/natural protein pattern is obtained by drying at room temperature, so that the line structure shown in figure 1 is formed. As can be seen from FIG. 1, the line resolution is 180nm, the line edges are relatively rough, and the process threshold energy is relatively high, 31.6 mW.
Example 2
A method of patterning a graphene/native protein composition comprising the steps of:
a) And (3) dropwise adding a proper amount of graphene/natural protein composition on the glass substrate, wherein the content of graphene in the composition is 8wt%, the content of egg white serving as natural protein is 92wt%, and a liquid film is spontaneously formed under the action of gravity.
B) The graphene/natural protein composition liquid film is subjected to laser direct writing exposure by using 800nm femtosecond laser, the laser power is changed by using an attenuator under the condition of fixed scanning speed of 10 microns/second to perform exposure, the laser power is changed from 5.5 milliwatts to 2.5 milliwatts, the exposed liquid film is developed by using deionized water for 60-120 seconds, and then the cured graphene/natural protein pattern is obtained by drying at room temperature, so that the line structure shown in figure 2 is formed. As can be seen from fig. 2, the line resolution is 170nm, with good resolution and contrast, with low line edge roughness, and with a low processing threshold energy of 2.5 milliwatts.
Example 3
A method of patterning a graphene/native protein composition comprising the steps of:
a) And (3) dropwise adding a proper amount of graphene/natural protein composition on the glass substrate, wherein the content of graphene in the composition is 10wt%, the content of egg white serving as natural protein is 90wt%, and a liquid film is spontaneously formed under the action of gravity.
B) The graphene/natural protein composition liquid film is subjected to laser direct writing exposure by using 800nm femtosecond laser, the laser power is changed by using an attenuator under the condition of fixed scanning speed of 10 microns/second to perform exposure, the laser power is changed from 4.1 milliwatts to 2 milliwatts, the exposed liquid film is developed by using deionized water for 60-120 seconds, and then the cured graphene/natural protein pattern is obtained by drying at room temperature, so that the line structure shown in figure 3 is formed. As can be seen from fig. 3, the line resolution is 160nm, the line is complete and smooth, has good resolution and contrast, and has low line edge roughness.
Example 4
A method of patterning a graphene/native protein composition comprising the steps of:
a) And (3) dropwise adding a proper amount of graphene/natural protein composition on the glass substrate, wherein the content of graphene in the composition is 2wt%, the content of egg white serving as natural protein is 98wt%, and a liquid film is spontaneously formed under the action of gravity.
B) Performing laser direct writing exposure on the graphene/natural protein composition liquid film by using 800nm femtosecond laser, controlling the exposure time to be 50 milliseconds by a program, controlling the laser power to be 17 milliwatts by using an attenuator to obtain a micro dot array pattern, developing the exposed liquid film by using deionized water for 60-120 seconds, and drying at room temperature to obtain a cured graphene/natural protein pattern, thereby forming a dot array pattern structure shown in figure 4. As can be seen from fig. 4, the dot array pattern is composed of dots having a size of about 280nm, and has a good resolution and contrast.
Example 5
A method of patterning a graphene/native protein composition comprising the steps of:
a) And (3) dropwise adding a proper amount of graphene/natural protein composition on the glass substrate, wherein the content of graphene in the composition is 4wt%, the content of egg white serving as natural protein is 96wt%, and a liquid film is spontaneously formed under the action of gravity.
B) Performing laser direct writing exposure on the graphene/natural protein composition liquid film by using a 400nm femtosecond laser, performing exposure by using an attenuator to control laser power under the condition of fixed scanning speed of 10 microns/second, developing the exposed liquid film for 60-120 seconds by using deionized water, and drying at room temperature to obtain a solidified graphene/natural protein pattern, so as to form a concentric circle structure shown in figure 5. As can be seen from fig. 5, the minimum width of the graphene/natural protein lines obtained by 400nm femtosecond laser patterning is 180nm, and the graphene/natural protein lines have good resolution and contrast and low line edge roughness.
Example 6
A method of patterning a graphene/native protein composition comprising the steps of:
a) And (3) dropwise adding a proper amount of graphene/natural protein composition on the glass substrate, wherein the content of graphene in the composition is 6wt%, the content of egg white serving as natural protein is 94wt%, and a liquid film is spontaneously formed under the action of gravity.
B) The graphene/natural protein composition liquid film is subjected to laser direct writing exposure by utilizing 355nm nanosecond laser, the fixed scanning speed is 5 microns/second, the laser power is gradually changed from 10.7 milliwatts to 7.9 milliwatts, the exposed liquid film is developed for 60-120 seconds by using deionized water, and then the cured graphene/natural protein pattern is obtained by drying at room temperature, so that the line structure shown in figure 6 is formed. As can be seen from fig. 6, the thinnest width of the graphene/native protein pattern of the present invention is 200nm, with good resolution and contrast, while having low line edge roughness.
Example 7
A method of patterning a graphene/native protein composition comprising the steps of:
a) A proper amount of graphene/natural protein composition was dropped on the glass substrate, the content of graphene in the composition was 3wt% and the content of egg white as a natural protein was 97wt%, and a thin glass sheet was covered on the above liquid composition, thereby forming a liquid film of the graphene/natural protein composition between the supporting glass sheet and the covered glass sheet.
B) Setting a mask plate according to the required pattern shape, exposing the graphene/natural protein composition liquid film by using a high-pressure mercury lamp for 3 minutes, developing the exposed liquid film for 60-120 seconds by using deionized water, and drying at room temperature to obtain a solidified graphene/natural protein pattern, thereby forming a concentric circle pattern shown in fig. 7. As can be seen from fig. 7, the exposure of the graphene/native protein composition with the high-pressure mercury lamp forms a concentric circular structure with a mask pattern set, with better resolution and contrast.
Example 8
A method of patterning a graphene/native protein composition comprising the steps of:
a) A proper amount of graphene/natural protein composition was dropped on the glass substrate, the content of graphene in the composition was 5wt%, the content of egg white as a natural protein was 95wt%, and a thin glass sheet was covered on the above liquid composition, thereby forming a liquid film of the graphene/natural protein composition between the supporting glass sheet and the covered glass sheet.
B) Setting a mask plate according to the required pattern shape, and exposing the graphene/natural protein composition liquid film by utilizing a 365nm LED lamp, wherein the power density is 10mW/cm 2 The exposure time was 30 seconds. The exposed liquid film was developed with deionized water for 60-120 seconds and then dried at room temperature to give a cured graphene/natural protein pattern, forming a micro-gear structure as shown in fig. 8. As can be seen from fig. 8, the exposed graphene/natural protein composition such as 365nm LED forms a micro-gear structure with a mask pattern set, and has better resolution and contrast.
Example 9
A method of patterning a graphene/native protein composition comprising the steps of:
a) A proper amount of graphene/natural protein composition was dropped on the glass substrate, the content of graphene in the composition was 2.5wt%, the content of egg white as a natural protein was 97.5wt%, and a thin glass sheet was covered on the above liquid composition, thereby forming a liquid film of the graphene/natural protein composition between the supporting glass sheet and the covered glass sheet.
B) The graphene/natural protein composition liquid film is subjected to laser direct writing exposure by using 800nm femtosecond laser, laser power is adjusted by using an attenuator under the condition of fixed scanning speed of 10 microns/second to perform exposure, the laser power is fixed at 20 milliwatts, the exposed liquid film is developed for 60-120 seconds by using deionized water, and then the cured graphene/natural protein pattern is obtained by drying at room temperature, so that the three-dimensional structure in the shape of red blood cells as shown in figure 9 is formed. As can be seen in FIG. 9, the three-dimensional structure of the red blood cell shape is approximately 7 microns in size and is built up on the substrate to form a self-supporting three-dimensional micro-volume structure.
Example 10
A method of patterning a graphene/native protein composition comprising the steps of:
a) A proper amount of graphene/natural protein composition was dropped on a glass substrate, the content of graphene in the composition was 3wt%, the content of egg white as a natural protein was 87wt%, and the content of water as an additive solvent was 10wt%, and a thin glass sheet was covered on the above liquid composition, thereby forming a liquid film of the graphene/natural protein composition between the supporting glass sheet and the covered glass sheet.
B) Performing laser direct writing exposure on the graphene/natural protein composition liquid film by using 800nm femtosecond laser, performing exposure by using an attenuator to adjust laser power under the condition of fixed scanning speed of 10 microns/second, fixing the laser power at 25 milliwatts, developing the exposed liquid film by using deionized water for 60-120 seconds, and drying at room temperature to obtain a cured graphene/natural protein pattern, thereby forming a lattice pattern structure shown in figure 10. As can be seen from fig. 10, the dot array pattern is composed of dots having a size of about 300nm, with good resolution and contrast.
Example 11
A method of patterning a graphene/native protein composition comprising the steps of:
a) A proper amount of graphene/natural protein composition was dropped on the glass substrate, the content of graphene in the composition was 1wt%, the content of quail egg white as a natural protein was 99wt%, and a thin glass sheet was covered on the above liquid composition, thereby forming a liquid film of the graphene/natural protein composition between the supporting glass sheet and the covered glass sheet.
B) The graphene/natural protein composition liquid film is subjected to laser direct writing exposure by using 800nm femtosecond laser, the laser power is adjusted by using an attenuator under the condition of fixed scanning speed of 10 microns/second to perform exposure, 45.4 milliwatts is gradually changed to 33.1 milliwatts, the exposed liquid film is developed by using deionized water for 60-120 seconds, and then the cured graphene/natural protein pattern is obtained by drying at room temperature, so that the line pattern structure shown in figure 11 is formed. As can be seen from fig. 11, the line resolution is 210nm, which has better resolution and contrast, and also has a certain line edge roughness.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (17)
1. A lithographically patternable composition, wherein the composition consists of graphene, a native protein, and a solvent;
the composition comprises 0.5-10% of graphene and 0.01-20% of natural protein by weight percent.
2. The composition of claim 1, wherein the natural protein and solvent are both from egg white; the egg white content of the composition is 90-99.5% by weight.
3. The composition of claim 1, wherein the natural protein and a portion of the solvent are from egg white; the egg white content of the composition is 80-89.5% by weight.
4. A composition according to claim 2 or 3, wherein the egg white is selected from one or more of egg white, duck egg white, goose egg white, quail egg white, pigeon egg white, tortoise egg white, and snake egg white.
5. A method of preparing a composition according to any one of claims 1 to 4, comprising the steps of: and uniformly mixing the graphene, the natural protein and the solvent to obtain the composition.
6. A method of photolithographic patterning, comprising the steps of:
uniformly mixing graphene according to any one of claims 1-4, natural proteins and a solvent to obtain the composition;
applying the composition to a substrate to obtain a substrate having a film formed of the composition on a surface thereof;
exposing, developing, or otherwise developing a film formed from the composition using a light source
Adopts the laser direct writing and developing method,
to obtain a substrate with a pattern on the surface.
7. The method of claim 6, wherein the applying is by coating or doctor blading.
8. The method of claim 7, wherein the coating is one or more of spin coating, spray coating, dip coating.
9. The method of claim 7, wherein the developer used for the developing is water.
10. The method according to claim 9, wherein the developer is selected from tap water, deionized water, mineral water or ultrapure water.
11. The method of claim 10, wherein the ultrapure water has a conductivity of 80 megaohms.
12. The method of claim 6, wherein the light source is one or more of ultraviolet light, visible light, near infrared light.
13. The method of claim 12, wherein the light source is provided by a laser, mercury lamp, LED lamp, tungsten halogen lamp, or xenon lamp.
14. The method of claim 13, wherein the laser has a wavelength adjustment range of 250-2500 nm.
15. The method of claim 13, wherein the laser is selected from a femtosecond laser with a pulse width of 10-300 femtoseconds, a picosecond laser with a pulse width of 0.3-800 picoseconds, or a nanosecond laser with a pulse width of 0.8-80 nanoseconds.
16. The method of claim 13, wherein the laser is selected from a femtosecond laser with a repetition rate of 1000hz to 150MHz, a picosecond laser with a repetition rate of 25kHz to 150MHz, or a nanosecond laser with a repetition rate of 1hz to 100 kHz.
17. The method of claim 6, wherein exposing the film formed from the composition with a light source comprises the steps of:
providing a mask having a desired pattern;
directing the mask to an upper surface of the film, exposing;
after the exposure is completed, the mask is removed.
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