CN104803348A - Method for preparing high depth-width ratio polymer nanorod array by sacrificing template - Google Patents
Method for preparing high depth-width ratio polymer nanorod array by sacrificing template Download PDFInfo
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Abstract
The invention relates to a method for preparing a high depth-width ratio polymer nanorod array by sacrificing a template, and belongs to the field of micro-nano structure processing. The preparation method comprises the following steps: taking a corrodible nanopore array structure as the template; coating a polymer material on the surface of the template by utilizing a coating process, and adjusting the viscosity and Young modulus of the polymer material, wherein not only is the defect that surface tension of nanopores flows into the holes overcome, but also the resolution and the depth-width ratio of nanorods can be effectively improved; placing the template coated with the polymer material under proper environment to be cured and formed; corroding the template by utilizing a corrosive solution so as to leave over the cured polymer material nanorod structure. The size and the depth-width ratio of the nanorods are controlled by the template and the polymer, the nanorods with small size and high depth-width ratio can be prepared, and meanwhile the same template can be prepared into the nanorods with different depths. The operation in the preparation process is simple, the cost is low, the depth-width ratio is controllable, and wide application prospects are realized in the field of biochemical sensing, biochemical analysis and the like.
Description
Technical field
The invention belongs to micro-nano structure processing, be specifically related to a kind of method of sacrificing Template preparation high-aspect-ratio polymer nanocomposite post array.
Background technology
At present, nano column array has extensive use in many fields such as magnetic recording, photoelectric subassembly, sensor, heterogeneous catalysis.Wherein, the nano column array of small size, high-aspect-ratio, because of its special Wuli-Shili-Renli system approach, has huge potentiality, causes the great interest of material supply section scholars in structure nanoelectronic and optics.
Traditional nanostructured preparation mainly contains two kinds of approach, the conventional lithographic techniques that one is is representative with " ultraviolet, deep ultraviolet, extreme ultraviolet, X-ray ", these photoetching techniques mainly realize high-resolution nano-photoetching by constantly shortening exposure wavelength, but the shortening of optical wavelength introduces a series of other problems, not only technically brought great difficulty, R&D costs also will sharply rise violently simultaneously; Another nanostructured processing method is processed by the straight write device such as electron beam and FIB, sweep time is long, working (machining) efficiency is very low, cost intensive, be not easy to carry out related work in common laboratory, therefore, these two kinds of technology are difficult to meet the wilderness demand of research and production to nanostructured.
The simple preparation appearing as nanostructured of nanometer embossing provides a kind of new method, can produce the nano column array of characteristic size 10nm, depth-to-width ratio 3:1.More the structure of high-aspect-ratio is owing to limiting by the demoulding, structural collapse, incompleteness, is difficult to realize.The people such as Craig J.Hawker start with from impression materials, have studied a kind of high Young's modulus polymeric material, have prepared the polymer nanocomposite post array that maximum depth-to-width ratio is 5:1.The people such as Stephen Y Chou utilize nano impression to copy more shallow structure (depth-to-width ratio 1:1) on impression glue, by etching, the structure on impression glue is delivered on base material, by regulating the etching ratio of impression glue and substrate, produce the nano column array that depth-to-width ratio is 50:1.But manufacturing process difficulty improves, cost increases.Therefore, the new method finding simple preparation high-aspect-ratio nano column array is needed.
Based on above current situation, the present invention proposes a kind of method of sacrificing Template preparation high-aspect-ratio polymer nanocomposite post array.The method with nano-pore array structure that is perishable, that make simple, low processing cost for template, pass through duplication process, to sacrifice the mode demoulding of template, achieve the simpler production of small size (10nm), high-aspect-ratio (100:1) polymer nanocomposite post array.
Summary of the invention
The object of this invention is to provide a kind of method of sacrificing Template preparation high-aspect-ratio polymer nanocomposite post array, by processes such as simple material coating, solidification and chemical attacks, realize the preparation of large area polymer nanocomposite post.Compared with existing nanostructured preparation technology, there is the advantages such as resolution ratio is high, depth ratio is controlled, technique is simple, cost is low, prepared by large area.
The technical solution used in the present invention is: a kind of method of sacrificing Template preparation high-aspect-ratio polymer nanocomposite post array, comprises the steps:
Step (1), requirement according to target nano-pillar, select the nano-pore array structure meeting size condition as template;
Step (2), utilize coating processes by the template surface of coating polymeric materials in step (1), make in polymer flow inlet hole;
Step (3), the double-decker in step (2) is placed on suitable environment under be cured shaping;
Step (4), select suitable corrosive solution the nano-pore array structure template in step (1) to be eroded, residual lower part with after ultra-clean water cleaning, acquisition target high-aspect-ratio polymeric material nano column array.
Further, in described step (1) nano-pore array structure possess perishable, make the features such as simple, low processing cost, as metal, metal oxide, alloy nano casement plate and nano-pore silicon template.
Further, the size of nano-pore, shape, arrangement mode and the degree of depth can arbitrarily regulate and control in manufacturing process in described step (1), and diameter is 10 nanometer to 500 nanometers; The degree of depth is 1 micron to 50 microns; Shape has circle, rectangle, triangle, polygon; Arrangement mode has preiodic type, stochastic pattern, part stochastic pattern.
Further, polymeric material performance controllable in described step (2), possesses the feature of low viscosity and high Young's modulus.Low viscosity can overcome the degree in surface tension transition flow of material inlet hole, and high Young's modulus effectively can improve resolution ratio and the depth-to-width ratio of nano-pillar.As ultraviolet light polymerization sulfydryl-alkene material, epoxy resin, acrylate material and heat cure polymethyl methacrylate materials, viscosity is lower than 5 centipoises, and Young's modulus is greater than 5000 MPas.
Further, the degree in the polymer flow inlet hole of described step (2) can control, and same template can prepare the nano-pillar structure of different depth, with template complete complementary or can be less than the template degree of depth.
Further, in described step (3), suitable curing environment is under the environment rocked in the static nothing of uniform temperature, humidity, is cured by UV-irradiation or high-temperature and high-pressure conditions.
Further, corrosive solution in (4) of described step can be strong acid or strong alkali solution, the selection principle of corrosive solution has stronger corrosivity to porous alumina formwork and on polymeric material without impact, as sodium hydroxide solution, potassium hydroxide solution, hydrochloric acid solution, salpeter solution, hydrofluoric acid solution.。
Further, the depth-to-width ratio 10:1 to 100:1 of the polymer nanocomposite post in described step (4), reach as high as 100:1, size, shape are identical with template with arrangement mode, can realize the nano column array of high-resolution, high-aspect-ratio arbitrary shape and arrangement.
The invention has the advantages that:
(1), the present invention passes through viscosity and the Young's modulus of telomerized polymer material, template sacrifice method is utilized to solve a demoulding difficult problem, the preparation of small size and high-aspect-ratio nano column array can be realized, technical process is reproducible, reliability is high, make efficiency is high.
(2), the present invention flows to the degree of nano-pore by controlling material, realizes the nano column array of the same template construct different structure degree of depth, has stronger technological flexibility.
In sum, the invention solves the existing cost preparing polymer nanostructures method high, inefficient problem, achieve high-resolution by adjusting template structure and material performance, high-aspect-ratio nano column array makes.Polymer nanocomposite post array has good biocompatibility, has broad application prospects in the field such as bio-sensing and biochemical analysis.
Accompanying drawing explanation
In order to make the object, technical solutions and advantages of the present invention clearly, below in conjunction with accompanying drawing, the present invention is described in further detail, wherein:
Fig. 1 is the preparation flow figure of the sulfydryl-alkene material nano post based on porous anodic alumina template;
Fig. 2 is the preparation flow block diagram of the sulfydryl-alkene material nano post based on porous anodic alumina template;
Fig. 3 is the electron scanning micrograph of porous anodic alumina template;
Fig. 4 is the electron scanning micrograph of the sulfydryl-alkene material nano rod structure based on porous anodic alumina template;
Fig. 5 is the nano column array schematic diagram of difformity and arrangement mode.
Detailed description of the invention
The present invention is introduced in detail below in conjunction with the drawings and the specific embodiments.Protection scope of the present invention should comprise the full content of claim.By following examples, namely those skilled in the art can realize the full content of the claims in the present invention.
As shown in 1-1 in Figure 1, utilize one piece of bore dia to be 300 nanometers, the porous anodic alumina template 1 that the degree of depth is 30 microns, template area is 3 cm x 3 centimetres, and quality is 2 grams, utilizes alcoholic solution to carry out cleaning to its surface.
As shown in 1-2 in Figure 1, preparation viscosity is 3.5 centipoises, Young's modulus is the liquid sulfydryl-alkene material of 5GPa, dropper is utilized to drip a drop of liquid sulfydryl-alkene material in template 1, tilt shake template 1 gently, form sulfydryl-alkene material layer 2 that the uniform thickness of one deck is 1 millimeter, sulfydryl-alkene material also can overcome in the surface tension run-in-hole of nano-pore simultaneously, and depth of cracking closure is 20 microns.
As shown in 1-3 in Figure 1, be placed on by double-decker on static experimental bench, at ultraviolet light 3 times curing moldings, optical intensity density is 40 milliwatt every cubic centimetre, and hardening time is 1 minute.
As shown in 1-4 in Figure 1, the sulfydryl-alkene material after solidification and template are placed in sodium hydrate aqueous solution 4 and carry out chemical attack, the concentration of sodium hydrate aqueous solution is 10 grams every milliliter.Sodium hydrate aqueous solution can corrosion oxidation aluminum, but the sulfydryl-alkene material after solidification is had no effect, alumina material concentration to be corrosion rate in the sodium hydrate aqueous solution of 10 grams every milliliter be 6 grams per hour, therefore the porous alumina formwork 1 in this experiment erodes needs 20 minutes completely, the sulfydryl-alkene material structure 2 under final residual after solidification.
As shown in 1-5 in Figure 1, take out residual structure, dry up after repeatedly rinsing with ultra-pure water, the sulfydryl-alkene material nano rod structure 5 of acquisition, the diameter of nano-pillar is 300 nanometers, is highly 20 microns, and depth-to-width ratio is 66:1.
The electron scanning micrograph of porous anodic alumina template as shown in Figure 3, as shown in Figure 4 based on the electron scanning micrograph of the sulfydryl-alkene material nano rod structure of porous anodic alumina template, the nano column array schematic diagram of difformity and arrangement mode as shown in Figure 5.
In the present invention, polymeric material can be that ultraviolet photocureable material such as acrylate, epoxy resin, sulfydryl-alkene etc. meet macromolecular material or the thermoset copolymer material of low viscosity and high rigidity condition; The structure of nano-pillar is decided by the structure of template and the performance of polymeric material completely, can the different nanostructured different with distribution of preparation size.
The techniques well known related in the present invention does not elaborate.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. sacrifice a method for Template preparation high-aspect-ratio polymer nanocomposite post array, it is characterized in that comprising the steps:
Step (1), requirement according to target nano-pillar, select the nano-pore array structure meeting size condition as template;
Step (2), utilize coating processes by the template surface of coating polymeric materials in step (1), make in polymer flow inlet hole;
Step (3), the double-decker in step (2) is placed on suitable environment under be cured shaping;
Step (4), select suitable corrosive solution the nano-pore array structure template in step (1) to be eroded, residual lower part with after ultra-clean water cleaning, acquisition target high-aspect-ratio polymeric material nano column array.
2. a kind of method of sacrificing Template preparation high-aspect-ratio polymer nanocomposite post array according to claim 1, is characterized in that: in described step (1), nano-pore array structure is metal, metal oxide, alloy nano casement plate and nano-pore silicon template.
3. a kind of method of sacrificing Template preparation high-aspect-ratio polymer nanocomposite post array according to claim 1, it is characterized in that: the size of nano-pore, shape, arrangement mode and the degree of depth can arbitrarily regulate and control in manufacturing process in described step (1), and diameter is 10 nanometer to 500 nanometers; The degree of depth is 1 micron to 50 microns; Shape has circle, rectangle, triangle, polygon; Arrangement mode has preiodic type, stochastic pattern, part stochastic pattern.
4. a kind of method of sacrificing Template preparation high-aspect-ratio polymer nanocomposite post array according to claim 1, it is characterized in that: polymeric material performance controllable in described step (2), possesses the feature of low viscosity and high Young's modulus, low viscosity can overcome the degree in surface tension transition flow of material inlet hole, high Young's modulus effectively can improve resolution ratio and the depth-to-width ratio of nano-pillar, polymeric material is ultraviolet light polymerization sulfydryl-alkene material, epoxy resin, acrylate material and heat cure polymethyl methacrylate materials, viscosity is lower than 5 centipoises, Young's modulus is greater than 5GPa.
5. a kind of method of sacrificing Template preparation high-aspect-ratio polymer nanocomposite post array according to claim 1, it is characterized in that: the degree in the polymer flow inlet hole of described step (2) can control, same template can prepare the nano-pillar structure of different depth, with template complete complementary or can be less than the template degree of depth.
6. a kind of method of sacrificing Template preparation high-aspect-ratio polymer nanocomposite post array according to claim 1, it is characterized in that: in described step (3), suitable curing environment is under the environment rocked in the static nothing of uniform temperature, humidity, is cured by UV-irradiation or high-temperature and high-pressure conditions.
7. a kind of method of sacrificing Template preparation high-aspect-ratio polymer nanocomposite post array according to claim 1, it is characterized in that: the corrosive solution in (4) of described step can be strong acid or strong alkali solution, the selection principle of corrosive solution has stronger corrosivity to porous alumina formwork and on polymeric material without impact, strong acid or strong alkali solution are sodium hydroxide solution, potassium hydroxide solution, hydrochloric acid solution, salpeter solution, hydrofluoric acid solution.
8. a kind of method of sacrificing Template preparation high-aspect-ratio polymer nanocomposite post array according to claim 1, it is characterized in that: the depth-to-width ratio 10:1 to 100:1 of the polymer nanocomposite post in described step (4), reach as high as 100:1, size, shape are identical with template with arrangement mode, can realize the nano column array of high-resolution, high-aspect-ratio arbitrary shape and arrangement.
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Cited By (6)
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| CN105061798A (en) * | 2015-08-13 | 2015-11-18 | 东莞市泰和塑胶制品有限公司 | Super-hydrophobic LLDPE (linear low density polyethylene) film and preparation method thereof |
| CN105621353B (en) * | 2015-12-31 | 2017-04-05 | 中山大学 | A kind of large-area nano graphic method based on multi-layered anode alumina formwork |
| CN108344725A (en) * | 2018-03-15 | 2018-07-31 | 南通大学 | Top coats the flexible nano column array and its preparation method and application of noble metal |
| CN109594142A (en) * | 2018-11-23 | 2019-04-09 | 深圳大学 | A kind of preparation method of controllable molecularly oriented polymer nano rice noodles |
| CN109745150A (en) * | 2017-11-06 | 2019-05-14 | 中国科学院上海硅酸盐研究所 | A kind of bone implant and its preparation method and application having immunoloregulation function |
| CN114477078A (en) * | 2022-04-08 | 2022-05-13 | 中国科学技术大学 | Processing method and application of integrated cross-scale micro-nano column array |
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| CN105621353B (en) * | 2015-12-31 | 2017-04-05 | 中山大学 | A kind of large-area nano graphic method based on multi-layered anode alumina formwork |
| CN109745150A (en) * | 2017-11-06 | 2019-05-14 | 中国科学院上海硅酸盐研究所 | A kind of bone implant and its preparation method and application having immunoloregulation function |
| CN108344725A (en) * | 2018-03-15 | 2018-07-31 | 南通大学 | Top coats the flexible nano column array and its preparation method and application of noble metal |
| CN109594142A (en) * | 2018-11-23 | 2019-04-09 | 深圳大学 | A kind of preparation method of controllable molecularly oriented polymer nano rice noodles |
| CN109594142B (en) * | 2018-11-23 | 2021-07-30 | 深圳大学 | Preparation method of controllable molecular orientation polymer nanowire |
| CN114477078A (en) * | 2022-04-08 | 2022-05-13 | 中国科学技术大学 | Processing method and application of integrated cross-scale micro-nano column array |
| CN114477078B (en) * | 2022-04-08 | 2022-07-15 | 中国科学技术大学 | Processing method and application of integrated cross-scale micro-nano column array |
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