CN114715837A - Method for manufacturing nano cantilever beam with recoverable deformation - Google Patents

Method for manufacturing nano cantilever beam with recoverable deformation Download PDF

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CN114715837A
CN114715837A CN202011530038.1A CN202011530038A CN114715837A CN 114715837 A CN114715837 A CN 114715837A CN 202011530038 A CN202011530038 A CN 202011530038A CN 114715837 A CN114715837 A CN 114715837A
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cantilever
cantilever beam
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substrate
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CN114715837B (en
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陶虎
秦楠
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Shanghai Institute of Microsystem and Information Technology of CAS
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Shanghai Institute of Microsystem and Information Technology of CAS
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81CPROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00015Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
    • B81C1/00134Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems comprising flexible or deformable structures
    • B81C1/0015Cantilevers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81CPROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00436Shaping materials, i.e. techniques for structuring the substrate or the layers on the substrate
    • B81C1/00523Etching material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81CPROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C2201/00Manufacture or treatment of microstructural devices or systems
    • B81C2201/01Manufacture or treatment of microstructural devices or systems in or on a substrate
    • B81C2201/0101Shaping material; Structuring the bulk substrate or layers on the substrate; Film patterning
    • B81C2201/0128Processes for removing material
    • B81C2201/0143Focussed beam, i.e. laser, ion or e-beam
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81CPROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C2201/00Manufacture or treatment of microstructural devices or systems
    • B81C2201/01Manufacture or treatment of microstructural devices or systems in or on a substrate
    • B81C2201/0101Shaping material; Structuring the bulk substrate or layers on the substrate; Film patterning
    • B81C2201/0156Lithographic techniques
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/25Process efficiency

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Abstract

The application discloses a method for manufacturing a deformation recoverable nano cantilever beam, which comprises the following steps: providing a substrate; arranging a photoetching material on the substrate to form a film corresponding to the size of a cantilever beam, wherein the cantilever beam comprises a cantilever beam body and a support upright post which are connected with each other; sequentially carrying out electron beam three-dimensional direct writing exposure on a cantilever body area and a support column area set in the film by using an electron beam based on a cantilever structure diagram input in advance to obtain a cantilever structure to be developed; and developing and fixing the cantilever beam structure to be developed to obtain a cantilever beam structure corresponding to the cantilever beam structure diagram, wherein the cantilever beam body in the cantilever beam structure can be restored by deformation under the action of electronic irradiation. The protein nano cantilever beam is prepared by direct writing of the electron beam, the pollution problem of impurity ions can not be introduced, the depth of the electron beam incident on the cantilever beam is changed by changing different accelerating voltages and exposure doses, and the bending-recovery behavior of the cantilever beam can be realized under the drive of energy minimization.

Description

Method for manufacturing nano cantilever beam with recoverable deformation
Technical Field
The invention relates to the technical field of nano cantilever beam manufacturing, in particular to a method for manufacturing a nano cantilever beam with recoverable deformation.
Background
The nano cantilever beam is a novel nano structure with one end serving as a fixed support and the other end serving as a free end, when molecules or atoms are adsorbed on the surface layer of the nano cantilever beam, and under the action of illumination, thermal stress or mechanical stress, the cantilever beam structure of the nano cantilever beam can be subjected to bending deformation or change of resonant frequency, and the nano cantilever beam can be used for detecting information such as high-sensitivity biology, chemistry, mechanics, optics and the like. The novel sensor based on the nano cantilever beam has great application requirements in the technical fields of single cell mechanical measurement, trace gas monitoring and identification, single molecule characterization, optics, mechanical metamaterials and the like. The nano cantilever technology is crossed with material science, chemistry, electronics, biology, medicine, computer science and the like, and the special requirements of various application scenes provide a plurality of new challenges for the material property, the processing precision, the functional effect and the like of the nano cantilever.
The development of silicon micromachining technology as well as MEMS (micro-electro-mechanical systems) technology has enabled the fabrication of micro-cantilevers since the 90s of the 20 th century. At present, the micro-cantilever is mainly made of silicon, silicon nitride, metal and the like, and in biomedical application, the biocompatibility of the materials is poor, inflammation or immune reaction is easily caused, and the practical use of the materials is often limited. The current common processing technology comprises photoetching, etching, film technology and the like, the period of the whole preparation process is long, the requirements of all involved links on the processing technology are high, high yield is not easy to obtain by sequential processing, the consistency of the performance of devices in different batches is ensured, and the problem of pain point which restricts the manufacturing of the micro cantilever beam is always solved. The characteristic size of the current micro-cantilever is in the micron level, and although nano-structures such as silicon nano-structures can be obtained by deep etching, wet etching and the like, the complex processing technology and the professional equipment requirement are difficult and serious. The method is limited by the precision of the current processing technology, and cannot meet the processing requirement on the nano-sized cantilever beam sensitive structure during the high-sensitivity detection of single atoms or single molecules.
Therefore, it is highly desirable to provide a method for manufacturing a deformation recoverable nano-cantilever, which can solve the current lack of a method for manufacturing a protein nano-cantilever effectively.
Disclosure of Invention
In order to solve the technical problem, the invention discloses a method for manufacturing a nanometer cantilever beam with recoverable deformation, which comprises the following steps:
providing a substrate;
arranging a photoetching material on the substrate to form a film corresponding to the size of a cantilever beam, wherein the cantilever beam comprises a cantilever beam body and a support upright post which are connected with each other;
sequentially carrying out electron beam three-dimensional direct writing exposure on a cantilever body area and a support upright post area which are set in the film by using an electron beam based on a cantilever structure diagram which is input in advance to obtain a cantilever structure to be developed;
and developing and fixing the cantilever beam structure to be developed to obtain a cantilever beam structure corresponding to the cantilever beam structure diagram, wherein the cantilever beam body in the cantilever beam structure can be restored by deformation under the action of electronic irradiation.
Further, the method for obtaining the cantilever structure to be developed by sequentially performing electron beam three-dimensional direct writing exposure on a cantilever body region and a support column region set in the film by using an electron beam based on a cantilever structure diagram input in advance includes:
setting exposure doses of different exposure layers according to the requirements of the processing line width, the structural mechanical property and the structural height of the cantilever beam structure diagram;
and dynamically adjusting the exposure focus of the electron beam by controlling the acceleration voltage and combining with the working distance to realize the three-dimensional direct writing exposure of the electron beam in the film to obtain the cantilever beam structure to be developed.
Further, the step of disposing a photolithographic material on the substrate to form a thin film corresponding to the size of the cantilever beam includes:
arranging a photoetching material on the substrate, and baking to form a single-layer film;
repeatedly executing: and arranging a photoetching material on the single-layer film, and baking until the film corresponding to the size of the cantilever beam is formed.
Furthermore, the thickness of each single-layer film is 0.1nm-1000 μm.
Further, the method includes the following steps of sequentially performing electron beam three-dimensional direct writing exposure on a cantilever body area and a support column area set in the film by using an electron beam based on a cantilever structure diagram input in advance to obtain a cantilever structure to be developed, and then:
baking the cantilever beam structure to be developed to obtain a baked three-dimensional nanostructure to be developed;
the cantilever beam structure corresponding to the cantilever beam structure diagram is obtained by developing and fixing the cantilever beam structure to be developed, and the method comprises the following steps:
and developing and fixing the baked to-be-developed three-dimensional nanostructure to obtain a cantilever beam structure corresponding to the cantilever beam structure chart.
Further, the step of developing and fixing the baked to-be-developed three-dimensional nanostructure to obtain a cantilever beam structure corresponding to the cantilever beam structure diagram comprises:
and (3) placing the substrate comprising the three-dimensional nanostructure to be developed after baking in a developing solution, keeping the temperature for 1s-1000h at-100 to 300 ℃, taking out the substrate, and keeping the temperature for 1s-1000h at-100 to 300 ℃ to obtain a cantilever beam structure corresponding to the cantilever beam structure diagram.
Further, the photolithographic material includes: the method comprises the following steps of preparing an existing polymer photoetching material, a novel protein biological photoetching material and a composite functional photoetching material loaded with one or more of gold nanoparticles, graphene, carbon nanotubes, quantum dots, drug molecules, fluorescent molecules, dye molecules, biological enzymes, blood and DNA, wherein the concentration of the photoetching material is as follows: 0.001-100 g/ml.
Further, the substrate includes: silicon base, metal, ceramic, oxide semiconductor, conductive glass, conductive polymer and plastic.
Further, the disposing a photolithographic material on the substrate to form a multilayer thin film includes:
the multilayer thin film is formed by disposing a photolithographic material on the substrate using one or more of a drop coating method, a spin coating method, a draw film forming method, a doctor blade method, a spray coating method, and a slit die coating method.
Further, the thin film is formed of at least one of the photolithographic materials.
By adopting the technical scheme, the method for manufacturing the nanometer cantilever beam with the recoverable deformation has the following beneficial effects:
in order to solve the problem of lack of a preparation method for effectively processing the protein nano cantilever beam, the invention provides a processing technology of the protein nano cantilever beam with the characteristic dimension superior to 50 nm. The protein nano cantilever beam is prepared by direct writing of electron beams, and the pollution problem of impurity ions cannot be introduced; by changing the accelerating voltage and the working distance, the exposure focus and the acting path of the electron beam in the protein film are dynamically regulated and controlled, and the nanometer precision three-dimensional direct writing is realized; the cross-linking degree (crystallization degree) and mechanical property of the support column and the cantilever beam are defined by changing the exposure dose, the exposure times and the exposure speed; the depth of an electron beam incident cantilever beam is changed by changing different accelerating voltages and exposure doses, so that the evolution of the crystallization degree of the protein cantilever beam from uniform distribution → non-uniform distribution → uniform distribution is realized, the balance and rebalance process after the stress unbalance of the cantilever beam is caused, and the bending-recovery behavior of the cantilever beam is realized under the drive of energy minimization. The protein nano cantilever beam has good corresponding relation between the deformation restorable characteristic and the electron irradiation energy, and can be used as a high-sensitivity electron irradiation sensing device.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a flow chart of an alternative method for fabricating a shape-recoverable cantilever according to an embodiment of the present disclosure;
FIG. 2 is a schematic illustration of a contrast between different accelerating voltages and the occurrence of a photoresist polymerization reaction in a photoresist material according to an embodiment of the present invention;
FIG. 3 is a schematic diagram illustrating a relationship between a protein molecular structure and lithography performance provided in an embodiment of the present disclosure;
FIG. 4 is a schematic diagram showing the degree of crystallization of the recombinant spider silk protein by an electron beam exposure dose provided in this example;
fig. 5 is a schematic view illustrating fabrication of a nano cantilever according to the present embodiment;
fig. 6 is a schematic diagram illustrating deformation recovery of a nano cantilever according to the present embodiment;
fig. 7 is a schematic view illustrating deformation recovery of another nano-cantilever according to the present embodiment;
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic may be included in at least one implementation of the invention. In the description of the present invention, it is to be understood that the terms "upper", "lower", "top", "bottom", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are only for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. Moreover, the terms "first," "second," and the like are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein.
Electron beam lithography is commonly used for direct writing of two-dimensional micro-nano patterns of photoresist, and the cantilever beam structure is prepared through processing technologies such as evaporation, deposition, etching, lift-off (stripping) and the like. The used technical process is complex, the fault tolerance rate of the processing process is low, the finally required nano structure can be obtained on the premise of ensuring the success of each processing link, and the direct writing processing of the cantilever beam structure can not be realized through single electron beam lithography.
In the traditional electron beam lithography, because the influence of a back scattering effect requires that a substrate has good conductivity, a layer of metal layers (metallization) with nanometer thickness is arranged on the substrate, otherwise, an exposure pattern is distorted and even is away from an exposure area by thousands of micrometers or even centimeters, so that the fine processing of a nanometer structure on various substrates with different conductive properties, such as silicon bases, ceramics, metals, plastics, oxides and the like, cannot be guaranteed.
In the current electron beam lithography process, the adopted exposure focus is certain, namely the penetration depth and the action position of an electron beam in a lithography material are certain, the action path of the electron beam cannot be defined in a three-dimensional space, and the electron beam is limited to two-dimensional plane structure processing. The existing conventional electron beam lithography method can not realize direct writing processing of three complex micro-nano structures such as suspension, hollowing, large depth-to-width ratio and the like on planes and even curved surfaces.
In addition, the area range of the two-photon effect is adjusted by modifying a two-photon exposure system at present, so that the processing of the nanometer scale is realized, and on one hand, a large amount of money and time are required; on the other hand, a matched photoetching material needs to be developed, and extremely high requirements are provided for the photosensitivity of the material, the molecular structure and the use of a photoinitiator. The processed three-dimensional structure is a simple nanowire obtained under extreme conditions, and cannot be popularized and used as a general and universal technology.
Proteins are important components that make up all cells and tissues of an organism. All important components of an organism require the participation of proteins, which are closely related to life phenomena. It is generally believed that protein accounts for approximately 16% to 20% of the total body mass. Fibroin, spidroin, deer antler protein, collagen, arthropod elastin and the like are widely used in the biomedical field due to their excellent biocompatibility, mechanical properties, controllable degradability and the like. The development of protein-based nano cantilever beam technology has definite scientific and application values in the high-precision and high-sensitivity sensing fields of single-cell multi-modal characterization, single-molecule or single-atom identification, photosensitive and thermosensitive measurement, new mechanism exploration for tumor treatment and the like.
To solve the above technical problem, the present invention provides a method for manufacturing a deformation-recoverable nano cantilever beam, please refer to fig. 1, where fig. 1 is a flowchart of an alternative method for manufacturing a deformation-recoverable nano cantilever beam according to an embodiment of the present application, where fig. 1 includes:
s102, providing a substrate;
in a specific implementation process, in order to increase the adhesion between the nano-cantilever support structure and the substrate and achieve a stable effect, the substrate can be subjected to surface treatment before the thin film is coated to improve the hydrophilicity and hydrophobicity of the substrate, for example, for a hydrophilic protein lithography material, the surface of the substrate can be cleaned by oxygen plasma; for hydrophobic protein photoresist materials, the substrate surface may be treated with a silylating agent. When the three-dimensional nano cantilever beam capable of freely moving is required to be obtained (the nano cantilever beam supporting upright column is not contacted with the substrate in the exposure process), the surface treatment operation of the substrate is not required.
And S104, arranging a photoetching material on the substrate to form a film corresponding to the size of a cantilever beam, wherein the cantilever beam comprises a cantilever beam body and a support upright post which are connected with each other.
In a specific implementation process, the thin film corresponding to the size of the cantilever beam structure can be set according to the length, the width and the height of the cantilever beam structure pattern. For example, when the height of the cantilever beam structure pattern is too high, the film can be formed by stacking a plurality of films.
The cantilever beam body is connected with the one end of support post, and the cross-linking degree can set up as required, and the cantilever beam body is used for snatching the volume of awaiting measuring, and the support post is used for supporting the cantilever beam body. The specific structure of the cantilever body and the support column is not specifically limited in the embodiments of the present description. The cantilever beam body can be a light and thin cuboid structure, and one end of the cantilever beam body and a preset position of the central position can be connected with one end of the cylindrical support upright post.
S106, sequentially carrying out electron beam three-dimensional direct writing exposure on a cantilever body area and a support upright post area which are set in the film by using an electron beam based on a cantilever structure diagram which is input in advance to obtain a cantilever structure to be developed;
and S108, developing and fixing the cantilever beam structure to be developed to obtain a cantilever beam structure corresponding to the cantilever beam structure diagram, wherein the cantilever beam body in the cantilever beam structure can be restored by deformation under the irradiation of electrons.
In the specific implementation process, because the manufactured cantilever beam structure is in a crystalline state, under the condition that low-energy electrons irradiate the upper plane of the cantilever beam body, the non-uniform protein crystal structure is induced to be converted into an amorphous state (namely, decrosslinking) by controlling the total action depth of the electrons on the cantilever beam, so that stress and deformation are generated, and the lower plane of the cantilever beam body is still in the crystalline state, so that the cantilever beam body can be bent upwards. Under the condition that the upper plane of the cantilever body is irradiated by high-energy electrons, the irradiated upper plane of the cantilever body is converted and recovered to a crystalline state (namely, crosslinked again) in an amorphous state, and the stress balance is achieved again, so that the cantilever body can be deformed and recovered.
On the basis of the foregoing embodiment, in an embodiment of this specification, the obtaining a cantilever structure to be developed by sequentially performing electron beam three-dimensional direct writing exposure on a cantilever body region and a support pillar region set in the thin film by using an electron beam based on a cantilever structure diagram input in advance includes:
setting exposure doses of different exposure layers according to the requirements of the processing line width, the structural mechanical property and the structural height of the cantilever beam structure diagram;
and dynamically adjusting the exposure focus of the electron beam by controlling the acceleration voltage and combining with the working distance to realize the three-dimensional direct writing exposure of the electron beam in the film to obtain the cantilever beam structure to be developed.
Specifically, a nano digital graphic file of the nano cantilever beam is introduced into an electron beam exposure system, and exposure doses of different exposure layers are defined according to requirements of processing line width (0.001nm-10 μm), structural mechanical properties (supporting upright posts are firm and stable, and the cantilever beam is thin and stiff) or cross-linking degree (crystallization degree: amorphous state, partial crystalline state, degradation state and the like), structural thickness or height (0.1nm-1000 μm) and the like: 0.001-1000000 μ c/cm 2.
FIG. 2 is a comparative schematic diagram of different accelerating voltages corresponding to the occurrence of the photoresist polymerization reaction in the photoresist material according to the embodiment of the present application, as shown in FIG. 2, by varying the accelerating voltage (0.001kV-1000kV) and the exposure dose (0.001-1000000 μ c/cm)2) The depth (0.1nm-1000 μm) of the electron beam incident on the cantilever beam is changed, and the evolution of the crystallization degree of the protein cantilever beam from uniform distribution → non-uniform distribution → uniform distribution is realized, so that the balance and rebalance process after the stress imbalance of the cantilever beam is caused, and the bending-recovery behavior of the cantilever beam is realized under the drive of energy minimization. Wherein the electron dwell probability is normalized.
The exposure times and rates are determined according to the line width and the complexity (single-layer, multi-layer, stacking, nesting, suspending, up-down size and the like) of the structure, and complex alignment operation is not required to be added among multiple exposures.
The method for manufacturing the nano cantilever beam with the recoverable deformation can change the position (1-10000nm) of an electron beam exposure focus in a photoetching material film by regulating and controlling the acceleration voltage of electron beam exposure, thereby realizing the processing of a true cantilever beam structure. And obtaining the corresponding relation of the position of the electron beam exposure focus along with the change of the electron beam acceleration voltage by Monte Carlo simulation and combining a real experiment result. Typical courses include: after the light enters from the upper surface of the film, high-energy electrons quickly penetrate through a photoetching material with a certain depth (mainly elastic collision, electron energy has no obvious loss), and a cross-linking reaction of the material cannot be caused, so that the film is called as a transparent layer; when the electron reaches the interior of the lithography material, intensive electron retention (mainly inelastic collision and large loss of electron energy) occurs, that is, the electron and the lithography material undergo an effective crosslinking reaction to form a material polymerization (lithography effect), which is called a crosslinked layer. As shown in fig. 2.
On the basis of the foregoing embodiments, in an embodiment of the present specification, the disposing a photolithographic material on the substrate to form a thin film corresponding to a cantilever beam size includes:
arranging a photoetching material on the substrate, and baking to form a single-layer film;
repeatedly executing: and arranging a photoetching material on the single-layer film, and baking until the film corresponding to the size of the cantilever beam is formed.
Specifically, in order to eliminate the interference of residual solvent in the film and retain the activity of bioactive substances, the substrate coated with the photoetching material is placed in a device such as a hot plate, a vacuum oven, a refrigerator or a vacuum freeze drying oven, and is kept for 1s-1000h at the temperature of-100 to 300 ℃ and the pressure of 1-200 kPa.
In one embodiment of the present specification, the thickness of each single-layer film is 0.1nm-1000 μm.
On the basis of the foregoing embodiment, in an embodiment of this specification, the performing, by using an electron beam based on a cantilever structure diagram input in advance, an electron beam three-dimensional direct writing exposure on a cantilever body region and a support pillar region set in the thin film in sequence to obtain a cantilever structure to be developed further includes:
baking the cantilever beam structure to be developed to obtain a baked three-dimensional nanostructure to be developed;
the cantilever beam structure corresponding to the cantilever beam structure diagram is obtained by developing and fixing the cantilever beam structure to be developed, and the method comprises the following steps:
and developing and fixing the baked three-dimensional nanostructure to be developed to obtain a cantilever beam structure corresponding to the cantilever beam structure chart.
Specifically, in order to ensure the stability of the cantilever beam structure and retain the activity of bioactive substances, the exposed substrate coated with the photoetching material is placed in a device such as a hot plate, a vacuum oven, a refrigerator or a vacuum freeze drying oven, and is kept for 1s-1000h at the temperature of-100 to 300 ℃ and the pressure of 1-200 kPa.
On the basis of the foregoing embodiment, in an embodiment of this specification, the developing and fixing the baked three-dimensional nanostructure to be developed to obtain a cantilever structure corresponding to the cantilever structure diagram includes:
and (3) placing the substrate comprising the three-dimensional nanostructure to be developed after baking in a developing solution, keeping the temperature for 1s-1000h at-100 to 300 ℃, taking out the substrate, and keeping the temperature for 1s-1000h at-100 to 300 ℃ to obtain the cantilever beam structure corresponding to the cantilever beam structure diagram.
Specifically, the substrate coated with the photoresist after exposure is placed in a developing solution of pure water, methanol, isopropanol, acetone, toluene or anisole and the like, and is kept at the temperature of-100 to 300 ℃ for 1s to 1000 h. Taking out and keeping the temperature at-100 to 300 ℃ for 1s to 1000h to obtain the required cantilever beam structure.
On the basis of the above embodiments, in an embodiment of the present specification, the lithography material includes: the method comprises the following steps of preparing an existing polymer photoetching material, a novel protein biological photoetching material and a composite functional photoetching material loaded with one or more of gold nanoparticles, graphene, carbon nanotubes, quantum dots, drug molecules, fluorescent molecules, dye molecules, biological enzymes, blood and DNA, wherein the concentration of the photoetching material is as follows: 0.001-100 g/ml.
Specifically, the existing polymer lithography materials may include: PMMA (polymethyl methacrylate), EBR-9 (polyalfa-trifluoroethyl chloroacrylate), PBS (polybutylsulfone), ZEP (alternating copolymer of alfa-methyl chloroacrylate and alfa-methylstyrene), HSQ-polyhydrosilsesquioxane); the novel protein biophotographic material may include: pure natural fibroin, deerhorn protein, collagen, gene recombinant spider silk protein, arthropod elastin and the like; and the composite functional photoetching material loaded with gold nanoparticles, graphene, carbon nanotubes, quantum dots, drug molecules, fluorescent molecules, dye molecules, biological enzymes, blood, DNA and the like. Wherein, the concentration of the photoetching material: 0.001-100 g/ml.
On the basis of the above embodiments, in one embodiment of the present specification, the substrate includes: silicon base, metal, ceramic, oxide semiconductor, conductive glass, conductive polymer and plastic.
Specifically, the silicon group may include: silicon, silicon nitride, silicon oxide, quartz, glass, or the like; the metal material may include: gold, silver, copper, aluminum, platinum, iron, tin, stainless steel, and the like; the ceramic may include: alumina, zirconia, titania, boron carbide, and the like; the oxide semiconductor may include: zinc oxide, tin oxide, iron oxide, chromium oxide, aluminum oxide, and the like; the conductive glass may include: indium tin oxide, etc.; the conductive polymer may include: polyacetylene, polypyrrole, polythiophene, polyphenylene, polyphenylacetylene, polyaniline, polyethylene, polypropylene, polystyrene, epoxy resin, phenol resin, and the like; the plastic may include: polyethylene, polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, polyvinyl chloride, general-purpose polystyrene, polystyrene foam, impact-resistant polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polymethacrylate, acryl, organic glass, ethylene-vinyl acetate copolymer, polyethylene terephthalate, polybutylene terephthalate, polyamide nylon, polycarbonate, polyoxymethylene resin, polyphenylene oxide, polyphenylene sulfide, polyurethane, polystyrene, polytetrafluoroethylene, and the like.
On the basis of the foregoing embodiments, in an embodiment of the present specification, the disposing a photolithographic material on the substrate to form a thin film corresponding to a size of the cantilever beam structure includes:
the thin film is formed by disposing a photolithographic material on the substrate using one or more of a drop coating method, a spin coating method, a draw-film forming method, a blade coating method, a spray coating method, a slit die coating method.
Specifically, Drop-casting is performed: dripping the solution on a substrate, volatilizing the solvent, and then forming a film;
spin-coating method Spin-coating: the method comprises two steps of firstly dripping solution and then spin-coating, and firstly spin-coating and then dripping solution, and volatilizing the solvent to form a film after rotation;
dip-coating method: putting the substrate dip into the solution, and forming a film by pulling;
blade coating method Blade-coating: i.e., the sector-blade method;
spraying method Spray-coating;
slot-die-coating by Slot extrusion coating: similar to the roll-to-roll approach.
On the basis of the above embodiments, in one embodiment of the present specification, the thin film is formed of at least one of the photolithographic materials.
The same protein nano cantilever beam can be made of the same material or different materials, so that the functionality of the nano structure is improved. The above operations are repeated, and the controllable preparation of the heterogeneous protein nano cantilever beam can be realized.
The preparation method of the nanometer cantilever beam with recoverable deformation is suitable for pure natural fibroin, deerhorn protein, collagen, gene recombination spider silk protein, arthropod elastin and the like, and composite functional protein photoetching materials loaded with gold nanoparticles, graphene, carbon nanotubes, quantum dots, drug molecules, fluorescent molecules, dye molecules, biological enzymes, blood, DNA and the like. Can realize the convenient and fast direct writing of the protein cantilever structure by utilizing electron beams under the resolution ratio superior to 50 nm. The selected substrate comprises silicon base, ceramics, metal, plastics, oxide semiconductor, conductive polymer and other materials.
For a better explanation of the invention, the following are specific examples of the invention:
example one: fig. 3 is a schematic diagram of a relationship between a protein molecular structure and lithography performance provided in an embodiment of the present specification, fig. 4 is a schematic diagram (near-field infrared spectrum) of an electron beam exposure dose to a crystallization degree of a gene recombination spider silk protein provided in the present embodiment, and fig. 5 is a schematic diagram of a manufacturing of a nano cantilever provided in the present embodiment, as shown in fig. 3 to 5:
(1) preparing a film: coating the gene recombinant spider silk protein photoetching material on a substrate.
In order to increase the adhesion between the nano cantilever beam supporting structure and the substrate and achieve a stable effect, the surface 900s of the silicon substrate is cleaned by oxygen plasma before the film is coated so as to ensure that the gene recombinant spider silk protein nano cantilever beam upright column is tightly adhered to the substrate.
The specific gravity of amino acid sequences (GA) n and An (A: glycine and G: alanine) which are responsible for mechanical strength in the molecular structure of the protein is increased by selecting the gene recombinant spider silk protein, so that the mechanical property and stability of the three-dimensional nano cantilever beam are enhanced. Concentration of genetic recombination spider silk protein photoetching material: 0.01-1 g/ml. Spin-coating 90s on a silicon substrate at 1000-8000 rpm to obtain the gene recombinant spider silk protein film with the thickness of 1000 nm.
(2) Pre-baking: in order to eliminate the interference of residual solvent in the film, the substrate coated with the genetic recombinant spider silk protein photoetching material is placed in a vacuum oven and kept for 300s-3h at the temperature of 60-150 ℃ and the pressure of 1-100 kPa.
(3) Electron beam direct writing:
the nano digital pattern file of the nano cantilever beam is led into an electron beam exposure system, and the electron beam exposure dose is selected to be 500-2The accelerating voltage is 0.1-5kV, the working distance is 1-5mm, the thickness of the beam body of the nanometer cantilever beam is 20-80nm, the width is 50-300nm, the length is 100-5000nm, and the crosslinking degree is a complete crystalline state; the exposure dose of the electron beam is 2000-200000 mu c/cm2The accelerating voltage is 3-50kV, the working distance is 2-20mm, the height of the supporting upright column of the nanometer cantilever beam is 50-50000nm, the diameter is 50-1000nm, and the crosslinking degree is in a complete crystalline state.
By changing different accelerating voltage (0.001kV-1000kV) and exposure dose (0.001-1000000 μ c/cm)2) The depth (0.1nm-1000 μm) of the electron beam incident on the cantilever beam is changed, and the evolution of the crystallization degree of the protein cantilever beam from uniform distribution → non-uniform distribution → uniform distribution is realized, so that the balance and rebalance process after the stress imbalance of the cantilever beam is caused, and the bending-recovery behavior of the cantilever beam is realized under the drive of energy minimization.
(4) Post-baking: in order to ensure the stability of the gene recombination spider silk protein nano cantilever structure, the substrate coated with the gene recombination spider silk protein photoetching material after exposure is placed in a vacuum oven, and is kept for 30-1200s at the temperature of 20-120 ℃ and the pressure of 1-100 kPa.
(5) And (3) developing: and (3) placing the exposed substrate coated with the genetic recombinant spider silk protein photoetching material in pure water for development, and keeping the temperature at 10-100 ℃ for 10-900 s. Taking out, and keeping the temperature at 20-120 ℃ for 300s-12h to obtain the required gene recombinant spider silk protein nano cantilever.
The same protein nano cantilever beam can be made of the same material or different materials, so that the functionality of the nano structure is improved. And (3) repeating the related operations from (1) to (5), thereby realizing the controllable preparation of the heterogeneous protein nano cantilever.
(6) The deformation of the gene recombination spider silk protein nano cantilever beam sensitive to the electron irradiation can restore the operation:
the low-energy electron irradiation accelerating voltage is 0.1-3kV, the dose is 100-2Irradiating the free end of the gene recombinant spider silk protein nano cantilever beam to realize upward bending of the nano cantilever beam by 0-60 degrees; the high-energy electron irradiation accelerating voltage is 2-30kV, the dosage is 500-100000 mu c/cm2And continuously irradiating the free end of the gene recombinant spider silk protein nano cantilever beam to realize that the nano cantilever beam is restored to the initial state from the upward bending state to the downward bending state.
Fig. 6 is a schematic diagram of the deformation recovery of a nano-cantilever beam provided in this embodiment, and fig. 7 is a schematic diagram of the deformation recovery of another nano-cantilever beam provided in this embodiment, as shown in fig. 6 to 7, the deformation recovery process of a gene recombinant spider silk protein nano-cantilever beam is as follows: the gene recombination spider silk protein nanometer cantilever beam obtained by the electron beam direct writing is wholly in a crystalline state; (1) when the free end of the gene recombinant spider silk protein nano cantilever is irradiated by low-energy electron irradiation, electrons can only penetrate into a part of the cantilever beam body, so that the crystalline state of the region is converted into an amorphous state, and the rest regions are still in the crystalline state; (2) when the free end of the nano cantilever beam which is bent upwards is irradiated by high-energy electron irradiation, the electron can completely enter the whole beam body, so that the beam body is changed into a uniform crystalline state from a partial amorphous state and a partial crystalline state, a new mechanical balance is formed, and the nano cantilever beam is restored to the initial state again.
It should be noted that the constituent amino acid sequences of the proteins can be precisely edited at the molecular level, the proportion of amino acids responsible for mechanical strength or etching resistance and the like can be actively regulated and controlled according to the actual application requirements, the length of the protein molecular chain can be flexibly customized, the molecular structure of the finally expressed and prepared protein is highly controllable, and the molecular weight of the gene recombinant spider silk protein is uniformly distributed and presents a single band through the analysis of gel electrophoresis (SDS-PAGE). In general, the properties of a photoresist are closely related to its molecular structure. The narrower the molecular weight distribution and the more uniform the molecular structure, the higher the accuracy of the formed photoetching pattern; the smaller the molecular weight is, the easier the high-resolution nano pattern can be prepared, but the mechanical property of the fibroin is weaker, and the fibroin is not beneficial to preparing the pattern with large depth-width ratio. When the gene recombinant spider silk protein and the fibroin are used for photoetching, the relationship between the molecular structure characteristics and the photoetching performance is shown in FIG. 3.
The foregoing description has disclosed fully preferred embodiments of the present invention. It should be noted that those skilled in the art can make modifications to the embodiments of the present invention without departing from the scope of the appended claims. Accordingly, the scope of the appended claims is not to be limited to the specific embodiments described above.

Claims (10)

1. A method for manufacturing a deformation recoverable nano cantilever beam is characterized by comprising the following steps:
providing a substrate;
arranging a photoetching material on the substrate to form a film corresponding to the size of a cantilever beam, wherein the cantilever beam comprises a cantilever beam body and a support upright post which are connected with each other;
sequentially carrying out electron beam three-dimensional direct writing exposure on a cantilever body area and a support column area set in the film by using an electron beam based on a cantilever structure diagram input in advance to obtain a cantilever structure to be developed;
and developing and fixing the cantilever beam structure to be developed to obtain a cantilever beam structure corresponding to the cantilever beam structure diagram, wherein the cantilever beam body in the cantilever beam structure can be restored by deformation under the action of electronic irradiation.
2. The method for manufacturing a deformation recoverable nano cantilever according to claim 1, wherein the step of sequentially performing electron beam three-dimensional direct writing exposure on the cantilever body region and the support pillar region set in the thin film by using an electron beam based on a pre-input cantilever structure diagram to obtain the cantilever structure to be developed comprises:
setting exposure doses of different exposure layers according to the requirements of the processing line width, the structural mechanical property and the structural height of the cantilever beam structure diagram;
and dynamically adjusting the exposure focus of the electron beam by controlling the acceleration voltage and combining with the working distance to realize the three-dimensional direct writing exposure of the electron beam in the film to obtain the cantilever beam structure to be developed.
3. The method of claim 1, wherein disposing a photolithographic material on the substrate to form a thin film corresponding to the dimensions of the cantilever comprises:
arranging a photoetching material on the substrate, and baking to form a single-layer film;
repeatedly executing: and arranging a photoetching material on the single-layer film, and baking until the film corresponding to the size of the cantilever beam is formed.
4. The method of claim 3, wherein the thickness of each single layer of the film is 0.1nm-1000 μm.
5. The method for manufacturing a deformation recoverable nano-cantilever according to claim 1, wherein the method comprises sequentially performing electron beam three-dimensional direct writing exposure on a cantilever body region and a support column region set in the thin film by using an electron beam based on a pre-input cantilever structure diagram to obtain a cantilever structure to be developed, and then:
baking the cantilever beam structure to be developed to obtain a baked three-dimensional nanostructure to be developed;
the cantilever beam structure corresponding to the cantilever beam structure diagram is obtained by developing and fixing the cantilever beam structure to be developed, and the method comprises the following steps:
and developing and fixing the baked to-be-developed three-dimensional nanostructure to obtain a cantilever beam structure corresponding to the cantilever beam structure chart.
6. The method for manufacturing a deformation recoverable nano cantilever according to claim 5, wherein the developing and fixing the baked three-dimensional nano structure to be developed to obtain a cantilever structure corresponding to the cantilever structure diagram comprises:
and (3) placing the substrate comprising the three-dimensional nanostructure to be developed after baking in a developing solution, keeping the temperature for 1s-1000h at-100 to 300 ℃, taking out the substrate, and keeping the temperature for 1s-1000h at-100 to 300 ℃ to obtain the cantilever beam structure corresponding to the cantilever beam structure diagram.
7. A method for fabricating a deformation recoverable nano-cantilever according to any one of claims 1 to 6, wherein the photolithographic material comprises: the method comprises the following steps of preparing an existing polymer photoetching material, a novel protein biological photoetching material and a composite functional photoetching material loaded with one or more of gold nanoparticles, graphene, carbon nanotubes, quantum dots, drug molecules, fluorescent molecules, dye molecules, biological enzymes, blood and DNA, wherein the concentration of the photoetching material is as follows: 0.001-100 g/ml.
8. A method of fabricating a deformation recoverable nanocantilever according to any of claims 1 to 6, wherein the substrate comprises: silicon base, metal, ceramic, oxide semiconductor, conductive glass, conductive polymer and plastic.
9. The method for fabricating a deformation recoverable nano-cantilever according to any one of claims 1 to 4, wherein disposing a photo-etching material on the substrate to form a multi-layer film comprises:
the multilayer film is formed by disposing a photolithographic material on the substrate using one or more of a drop coating method, a spin coating method, a draw-film forming method, a blade coating method, a spray coating method, a slit die coating method.
10. A method of fabricating a deformation recoverable nanocantilever according to claim 9, wherein the membrane is formed from at least one of the photolithographic materials.
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