CN118166332A - A method for manufacturing a large-area atomic-level hierarchical structure mold and device on a free-form surface - Google Patents
A method for manufacturing a large-area atomic-level hierarchical structure mold and device on a free-form surface Download PDFInfo
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- CN118166332A CN118166332A CN202410194444.7A CN202410194444A CN118166332A CN 118166332 A CN118166332 A CN 118166332A CN 202410194444 A CN202410194444 A CN 202410194444A CN 118166332 A CN118166332 A CN 118166332A
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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
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D29/00—Removing castings from moulds, not restricted to casting processes covered by a single main group; Removing cores; Handling ingots
- B22D29/04—Handling or stripping castings or ingots
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0254—Physical treatment to alter the texture of the surface, e.g. scratching or polishing
- C23C16/0263—Irradiation with laser or particle beam
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
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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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
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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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
- G03F7/2059—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a scanning corpuscular radiation beam, e.g. an electron beam
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- Moulds For Moulding Plastics Or The Like (AREA)
Abstract
The invention discloses a large-area atomic level hierarchical structure die on a free curved surface and a manufacturing method of a device. Coating photoresist on the surface of the free-form surface substrate and performing a photoetching step to obtain a patterned concave surface structure; carrying out electroforming replication process steps after coating metallization on the pattern surface, and demolding to obtain a convex metal mold; then carrying out nano-imprinting on the metal sheet by taking the metal mold as a template to realize structure transfer printing; anodic oxidation is carried out on the structured metal sheet to form a hierarchical nano structure, and atomic layer deposition is carried out to bridge the nano structure to the atomic size; finally, polymer pouring technology is carried out by taking an atomic layer metal sheet as a template, and a large-area atomic layer hierarchical structure device on a free curved surface is obtained through demoulding; the invention provides a precise manufacturing method.
Description
Technical Field
The invention belongs to the technical field of micro-nano manufacturing and semiconductor processing, and particularly relates to a large-area atomic level hierarchical structure die on a free curved surface and a manufacturing method of a device.
Background
With the rapid development of micro-nano technology and micro-electromechanical system technology, the application of micro-nano structure in the fields of optoelectronic devices, gene sequencing, optical imaging and the like is becoming more interesting. In particular, many devices or systems require the construction of functional structures on curved or non-planar surfaces, the precision and complexity of which structures need to be precisely controlled on an atomic scale to meet specific functional requirements. Atomic scale fabrication on curved surfaces from optical elements to biomedical sensors can change the optical, electrical, mechanical, etc. properties of the device, creating innovations for multiple fields of optoelectronics, biomedical and mechanical engineering, etc. In addition, curved designs can optimize device performance, such as increasing the transmittance or reflectance of the optical device, and can better utilize limited space, particularly in micro-and nano-devices. Therefore, atomic scale fabrication on curved surfaces is of great importance in today's technological development.
However, machining on free-form surfaces is a challenging task. The shape of the face structure is various and complex, making it extremely difficult to achieve precise control on an atomic scale. At the same time, the local curvature, asperities and three-dimensional morphology of the curved surface increase manufacturing challenges. Because the traditional planar micro-nano processing technology is difficult to be directly suitable for a curved surface structure, and is also difficult to adapt to the atomic scale manufacturing requirement on a curved surface, special technology and technology are required for processing a free curved surface, and particularly, the preparation of a large-area atomic level hierarchical structure die and a device is more complex.
Based on the existing micro-nano manufacturing technology, the processing of the atomic scale structure of the curved surface is basically impossible to achieve by a single process, so that the search for a new manufacturing method is urgent. Anodic oxidation is a processing method for forming a porous nano structure through self-assembly, the shape and the size of the nano structure can be flexibly regulated and controlled according to an anodic oxidation process, and the aperture can be from a few nanometers to a micrometer scale. For atomic scale fabrication methods, common techniques utilize Atomic Layer Deposition (ALD) and Chemical Vapor Deposition (CVD) methods to deposit materials layer by layer with precise control at the molecular level. In addition, as technology advances, photolithography technology continues to evolve, allowing smaller and smaller feature sizes to be achieved. In advanced fabrication processes in recent years, for example using Extreme Ultraviolet (EUV) advanced lithography, fabrication of structure dimensions approaching or even smaller than 3 nm has been enabled. Electroforming techniques have a replication accuracy on the surface atomic scale and can be used to produce metal parts or metal molds having fine structures and high accuracy. By combining these methods of precision micro-nano structure processing, processing of large-area atomic level hierarchical structures on free-form surfaces can be made possible.
Disclosure of Invention
The invention provides a manufacturing method of a large-area atomic level hierarchical structure die and a device on a free curved surface, and aims to break through the current micro-nano manufacturing scale, and provides a micro-nano processing method on the curved surface, wherein the atomic level hierarchical structure die and the device structure are obtained by combining methods such as anodic oxidation.
The invention provides a method for manufacturing a large-area atomic level hierarchical structure die and a device on a free curved surface, which is characterized by sequentially comprising the following steps:
(1) A gluing step;
precisely cutting aluminum by ultra-precise laser cutting processing to obtain a free-form aluminum substrate, and uniformly coating photoresist with a layer thickness of about tens of nanometers on the aluminum substrate;
(2) A photoetching step;
the photoresist is baked and solidified, then ultraviolet/electron beam exposure treatment is utilized to prepare a pattern with nanometer scale, and a photoresist pattern structure with nanometer-sized pits is obtained on an aluminum sheet after post-baking, development and shaping, and the structure size is specifically dependent on the photoetching process capability and is about several nanometers to hundreds of nanometers;
(3) A coating step;
Depositing a metal conductive film with nanometer thickness on the surface of the concave photoresist pattern structure by using a chemical vapor deposition/physical vapor deposition method, wherein the thickness of the nanometer layer is about one micron to several microns depending on the structure size after photoetching;
(4) Electroforming;
Electroforming the pattern structure plated with the conductive film, and accurately copying the photoresist pattern through electrodeposition to obtain a convex metal nickel mold with nano-scale feature size and thickness of hundreds of micrometers;
(5) Demolding a metal mold;
Corroding the combination of the convex metal nickel die and the aluminum substrate by utilizing hydrofluoric acid/sodium hydroxide until the aluminum substrate is completely removed, and reserving the convex metal nickel die with the required nanoscale feature size;
(6) A nano imprinting step;
Carrying out molecular coating treatment on the convex metal nickel die to ensure that the nanoscale characteristic structure keeps a shape in the demolding process, and then transferring a pattern structure on the convex metal nickel die onto an aluminum sheet by taking the convex metal nickel die as a template by utilizing a nanoimprint technology;
(7) Demolding an aluminum sheet;
Cleaning the aluminum sheet obtained by stamping to obtain an aluminum sheet with a concave nano structure;
(8) An anodic oxidation step;
Performing an anodic oxidation process on the aluminum sheet with the concave nano structure to obtain hierarchical nano array structures with different sizes;
(9) An atomic layer deposition step;
Depositing a metal film with controllable monoatomic layer thickness on the surface of the hierarchical nano array structure by utilizing an atomic layer deposition technology, and enabling gaps of the nano array structure to be bridged to atomic and near-atomic dimensions as much as possible to obtain an aluminum-based die with an atomic-level hierarchical structure on a free curved surface;
(10) Pouring;
Casting an aluminum-based mold with an atomic level hierarchical structure by using a polymer, and copying and transferring the atomic level hierarchical structure on the aluminum-based mold to a polymer material;
(11) A polymer film demolding step;
After the polymer is completely solidified, demolding and cleaning the polymer and the aluminum die to obtain the convex polymer film device with the hierarchical structure of atomic and near-atomic dimensions.
A manufacturing method of a large-area atomic-level hierarchical structure mold and a device on a free-form surface is characterized in that the photoresist is required to have high resolution and accurate thickness control capability, and meanwhile, an aluminum substrate is required to be cleaned and treated before gluing so as to ensure stable adhesion of a glue layer.
A method for manufacturing a die with a large-area atomic-level hierarchical structure on a free curved surface and a device are characterized in that the conductive film can be a material with good conductive performance and certain adhesion capability so as to ensure durability and stability, such as copper, chromium, gold and the like.
A method for manufacturing a large-area atomic-level hierarchical structure die and a device on a free curved surface is characterized in that the specific size of a nano structure on a metal convex die is determined by the photoetching technology level.
A method for manufacturing a large-area atomic-level hierarchical structure die and a device on a free curved surface is characterized in that the thickness of a convex nickel die with nanometer size characteristics is precisely controlled by electroforming process conditions.
The method for manufacturing the large-area atomic-level hierarchical structure die and the device on the free curved surface is characterized in that the specific size of the nano-pore is determined by the anodic oxidation process conditions and can be regulated by the conditions of anodic oxidation electrolyte, voltage, temperature and the like.
A method for manufacturing a large-area atomic-level hierarchical structure die and a device on a free curved surface is characterized in that atomic layer deposition is required to be controlled and deposited with the precision of an atomic layer, required film thickness and certain conductivity are provided, and a metal film material can be chromium, copper, platinum and other materials.
A method for manufacturing a large-area atomic-level hierarchical structure die and a device on a free-form surface is characterized in that the polymer is made of a specific polymer material with higher hardness and stability so as to ensure that the polymer is not deformed and damaged in the subsequent imprinting process.
The invention has the remarkable advantages that:
(1) By combining the advanced processing technology and the nano manufacturing process, the complexity of the shape of the curved surface can be overcome, and the accurate control and processing of the free curved surface can be realized. The method can realize fine atomic level processing no matter for curved surfaces with bending and uneven or structures with large curvature change, and expands the application range of atomic level manufacturing.
(2) Breaks through the dimension limit of a single manufacturing method and does not need to use professional atomic manufacturing equipment.
(3) Compared with the traditional manufacturing method, the method combines common technologies such as photoetching, film plating, electroforming, atomic layer deposition, anodic oxidation and the like, and can realize accurate processing of free curved surfaces. Such a process combination means lower manufacturing costs and the resulting atomic-scale structured metal mold and polymer device can be adapted for mass production on a large scale while maintaining high precision and complexity.
Drawings
Fig. 1 is a schematic flow chart of a method for manufacturing a large-area atomic level hierarchical structure mold and a device on a free-form surface.
In the figure: 1, a free-form aluminum substrate; 2, photoresist; 3 concave nanostructured surfaces; 4, a conductive metal film; 5, a convex metal nickel mold; 6, a concave aluminum sheet die; 7, a concave nano-level structure aluminum sheet mold; 8 atomic layer metal film; a 9-convex atomic level polymer thin film device.
Detailed Description
The following describes the specific embodiments of the present invention in detail with reference to the technical scheme and the accompanying drawings.
The invention relates to an atomic-level-layer polymethyl methacrylate mold on a free-form surface and a manufacturing method of a device.
Example 1, the method for manufacturing the same comprises the following sequential steps:
(1) A gluing step;
Firstly, cleaning the aluminum surface by using isopropanol or acetone to ensure that the surface is dust-free and oil-free, and then uniformly coating photoresist on the surface of the aluminum substrate by using a spin coater to obtain the aluminum substrate with the thickness of about tens of nanometers. Then baking the photoresist at a preset temperature to solidify the photoresist;
(2) A photoetching step;
treating the surface of the photoresist by using electron beam exposure, developing and shaping, and cleaning the aluminum sheet to obtain a nano-sized microstructure shown in the figure 1 (b);
(3) A coating step;
The above sample was placed in a vacuum chamber of a PVD (physical vapor deposition) apparatus, and the sample was heated to increase the surface activity. Then sputtering and depositing metal chromium on the surface of the sample in a thermal evaporation or sputtering mode to form a conductive film which is used as an electroformed conductive layer;
(4) Electroforming;
And (3) performing nickel electroforming after the structure subjected to the film plating is subjected to sulfamic acid activation treatment, and adopting pulse current density smaller than 0.01A/dm 2 in the nano structure electrodeposition filling stage so as to accurately copy the photoresist pattern on a nickel mold. Once the nanostructure is filled, converting to a current density of 1A/dm 2, electrodepositing the nickel mold substrate to thicken to a thickness of hundreds of microns;
(5) Demolding a metal mold;
The combination of the aluminum substrate and the nickel mold (fig. 1 (d)) obtained after electroforming was etched using 2% hydrofluoric acid, and the temperature was kept at 30 ℃ to chemically etch the aluminum substrate. After demolding is completed, taking out a sample, and thoroughly cleaning with water or sodium bicarbonate solution to remove residual acidic solution and any other impurities, thereby obtaining a nickel nanostructure mold with a convex structure, as shown in fig. 1 (e);
(6) A nano imprinting step;
In order to prevent deformation distortion of the fine structure in the demolding process, a BGL-GZ-83 molecular film is plated on the surface of a metal nickel concave mold in advance to promote nondestructive demolding of the mold and the polymer. After 8 hours, transferring the pattern structure of the metal nickel convex mold onto an aluminum sheet substrate by using a nano imprinting technology by taking the metal nickel concave mold as a template;
(7) Demolding an aluminum sheet;
demolding and cleaning the aluminum sheet mold with the convex microstructure obtained by nanoimprint (as shown in fig. 1 (g));
(8) An anodic oxidation step;
carrying out anodic oxidation treatment on the obtained aluminum flake die, wherein different anodic oxidation conditions are adopted for different aperture requirements;
Specifically, if a pore size structure of several nanometers to more than ten nanometers is needed, firstly, anodic oxidation is carried out on an aluminum sheet in a solution of 20wt.% H 2SO4 for 10 minutes at the temperature of 1 ℃ by using 25V voltage, then the aluminum sheet is taken out and washed cleanly and then soaked in a mixed solution of 6wt.% H 3PO4 and 1.8wt.% H 2CrO4 at the temperature of 60 ℃ for 15 minutes, and finally the aluminum sheet is anodized in a solution of 20wt.% H 2SO4 for 45-870 minutes after the aluminum sheet is washed cleanly;
Specifically, if a pore size structure of tens to one hundred nanometers is needed, firstly, in a mixed solution of 0.4M H 2CrO4 and 0.6M H 2SO4, an aluminum sheet is anodized for 12 hours at 0 ℃ simultaneously by using 15-55V voltage, then taken out and washed cleanly, soaked in a mixed solution of 6wt.% H 3PO4 and 1.8wt.% H 2CrO4 at 60 ℃ for 90 minutes, and finally anodized in a mixed solution of 0.4M H 2CrO4 and 0.6M H 2SO4 for 12 hours after being washed cleanly;
Specifically, if a pore size structure of hundreds of nanometers is needed, firstly, anodizing an aluminum sheet in 2wt.% H 3PO4 solution for 200 seconds at 10 ℃ by using 40-120V voltage, then taking out and cleaning, soaking in 30 ℃ 5wt.% H 3PO4 solution for 12.5 minutes, and repeating the two steps for 5 times;
(9) An atomic layer deposition step;
Performing atomic layer deposition treatment on the pattern (fig. 1 (h)) with the nano-level structure after anodic oxidation, and isotropically depositing a chromium film with controllable atomic layer thickness layer by layer on the surface, so that the nano-array structure obtained by anodic oxidation is bridged to the atomic scale as much as possible (as shown in fig. 1 (i));
(10) Pouring;
The prepared PMMA (polymethyl methacrylate polymer) solution was poured uniformly into the mold frame to cover the entire atomic level aluminum mold surface to achieve the desired hundred microns thickness. Ensuring that PMMA liquid is uniformly distributed and fills the mold frame, and then exposing to ultraviolet light for curing;
(11) A polymer film demolding step;
and mechanically demolding the PMMA film and the metal aluminum die, and cleaning to obtain the polymer device with the atomic level hierarchical structure.
Although the specific embodiments of the present invention have been described above with reference to the accompanying drawings, the scope of the present invention is not limited thereto, and all equivalent processes using the present invention and the contents of the accompanying drawings, or direct or indirect application to other technical fields, are included in the scope of the present invention.
Claims (8)
1. A manufacturing method of a large-area atomic level hierarchical structure die and a device on a free curved surface is characterized by sequentially comprising the following steps:
(1) A gluing step;
Precisely cutting aluminum by ultra-precise laser cutting processing to obtain a free-form aluminum substrate, and uniformly coating photoresist on the aluminum substrate;
(2) A photoetching step;
Baking and curing the photoresist, preparing a nano-scale pattern by ultraviolet/electron beam exposure treatment, and obtaining a photoresist pattern structure with nano-scale pits on an aluminum sheet after post baking, development and shaping, wherein the structure size is from a few nanometers to hundreds of nanometers;
(3) A coating step;
Depositing a metal conductive film with nanometer thickness on the surface of the concave photoresist pattern structure by using a chemical vapor deposition/physical vapor deposition method, wherein the nanometer thickness is one micron to a plurality of microns;
(4) Electroforming;
Electroforming the pattern structure plated with the conductive film, and accurately copying the photoresist pattern through electrodeposition to obtain a convex metal nickel mold with nano-scale feature size and thickness of hundreds of micrometers;
(5) Demolding a metal mold;
Corroding the combination of the convex metal nickel die and the aluminum substrate by utilizing hydrofluoric acid/sodium hydroxide until the aluminum substrate is completely removed, and reserving the convex metal nickel die with the required nanoscale feature size;
(6) A nano imprinting step;
Carrying out molecular coating treatment on the convex metal nickel die to ensure that the nanoscale characteristic structure keeps a shape in the demolding process, and then transferring a pattern structure on the convex metal nickel die onto an aluminum sheet by taking the convex metal nickel die as a template by utilizing a nanoimprint technology;
(7) Demolding an aluminum sheet;
Cleaning the aluminum sheet obtained by stamping to obtain an aluminum sheet with a concave nano structure;
(8) An anodic oxidation step;
Performing an anodic oxidation process on the aluminum sheet with the concave nano structure to obtain hierarchical nano array structures with different sizes;
(9) An atomic layer deposition step;
depositing a metal film with controllable monoatomic layer thickness on the surface of the hierarchical nano array structure by utilizing an atomic layer deposition technology, and bridging gaps of the nano array structure to atomic and near-atomic dimensions to obtain an atomic-level hierarchical structure aluminum-based mold on a free curved surface;
(10) Pouring;
Casting an aluminum-based mold with an atomic level hierarchical structure by using a polymer, and copying and transferring the atomic level hierarchical structure on the aluminum-based mold to a polymer material;
(11) A polymer film demolding step;
After the polymer is completely solidified, demolding and cleaning the polymer and the aluminum die to obtain the convex polymer film device with the hierarchical structure of atomic and near-atomic dimensions.
2. The method of claim 1, wherein the photoresist in step (1) is required to have high resolution and precise thickness control capability, and the aluminum substrate is required to be cleaned and treated before the photoresist is coated to ensure stable adhesion of the photoresist layer.
3. The method of claim 1, wherein the conductive film in the step (3) is copper, chromium or gold having conductivity and a certain adhesion capability.
4. The method of claim 1, wherein the specific dimensions of the nanostructures on the convex metal mold in step (4) are determined by the level of photolithography.
5. The method of claim 1, wherein the thickness of the convex nickel mold with nano-scale features in step (5) is precisely controlled by electroforming process conditions.
6. The method of fabricating a large area atomic scale hierarchical structure mold and device according to claim 1, wherein the specific size of the nano-pore in step (8) is determined by the anodizing process conditions, and is adjusted by the anodizing electrolyte, voltage level, and temperature conditions.
7. The method of claim 1, wherein the atomic layer deposition in step (9) is controlled with atomic layer accuracy to provide the desired film thickness and conductivity, and the metal film material is chromium, copper, or platinum.
8. The method of fabricating a large area atomic scale hierarchical mold and device according to claim 1, wherein the polymer in step (10) is selected from specific polymer materials with higher hardness and stability to ensure no deformation and damage during subsequent imprinting.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410194444.7A CN118166332B (en) | 2024-02-22 | 2024-02-22 | A method for manufacturing large-area atomic-level hierarchical structure molds and devices on free-form surfaces. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410194444.7A CN118166332B (en) | 2024-02-22 | 2024-02-22 | A method for manufacturing large-area atomic-level hierarchical structure molds and devices on free-form surfaces. |
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| Publication Number | Publication Date |
|---|---|
| CN118166332A true CN118166332A (en) | 2024-06-11 |
| CN118166332B CN118166332B (en) | 2026-01-06 |
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