CN102162176A - Micro-nano corrugated structure and preparation method thereof, and device and application of preparation method - Google Patents
Micro-nano corrugated structure and preparation method thereof, and device and application of preparation method Download PDFInfo
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- CN102162176A CN102162176A CN 201110063326 CN201110063326A CN102162176A CN 102162176 A CN102162176 A CN 102162176A CN 201110063326 CN201110063326 CN 201110063326 CN 201110063326 A CN201110063326 A CN 201110063326A CN 102162176 A CN102162176 A CN 102162176A
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Abstract
The invention discloses a preparation method of a micro-nano corrugated structure. The preparation method comprises the following steps of: (1) adding electrostatic spinning macromolecular solution into a syringe of a syringe pump, and fully filling the solution into a metal nozzle connected with the anode of a high pressure generator; (2) placing a metal cathode collecting plate connected with the ground electrode of the high pressure generator below the metal nozzle of the syringe, placing a flexible base material on the collecting plate, controlling the macromolecular solution to flow out at certain velocity, and electrifying the macromolecular solution to form jet flow; and (3) moving the metal collecting plate so that the jet flow falls on the flexible base material, namely the corrugated structure is formed on the whole base material. The invention also discloses the micro-nano corrugated structure prepared by using the method, a device for implementing the method and application of the method. When the elastic rubber base material stretches, the formed nano fiber graph can produce great deformation together with the elastic rubber base material and does not break, so that effective interconnection and stretching of flexible electrons are realized, and the invention has broad application prospect on the aspects of electronic skin, artificial muscles, bioelectronics and the like.
Description
Technical field
The present invention relates to a kind of ripple struction that utilizes the electrostatic spinning process preparation and preparation method thereof, device and application, belong to micro-nano ripple struction technical field.
Background technology
Electrostatic spinning can be produced the fiber of nanoscale as a kind of simple nanofiber production technology.Because single fiber is difficult to collect, and is widely used in the production of nonwoven fabric at present, can't make various figures by weaving manner, limited the application in weaving and its field of nanofiber.In recent years, people more and more pay close attention to make has big elastic deformability or can be by the various complex-curved device that the organically blends (list of references: By Dae-Hyeong Kim et al of Bionic Design and human body or other biology, Advanced Materiels.2010,22,2108), in order to improve the possibility of making this device, propositions such as Huang are a kind of to generate the method for controlled flexing structure (being ripple struction) as the interconnection layer of rigidity components and parts with nanometer band and elastic base plate, since then, ripple struction rises rapidly becomes a focus of research.This method principle is simple, flexible design, and controllability is strong, and material parameter that can be by adjusting the nanometer band, cross section, size etc. realize in the plane or out-of-plane various flexing.Make the product of making in this way have definite bellows-shaped and size, can spread over heart, finger etc. various complex-curved on, and have high stretching, bending property, in a lot of fields good application is arranged all, as (lists of references: Hanqing Jiang et al such as MEMS, thin film metrology, biology and optical devices, PNAS.2007,104,15607; Dahl-Young Khang, Hanqingjiang, Young Huang, John A.Rogers, 2006, A Stretchable Form of Single-Crystal Silicon for High-Performance Electronics on Rubber Substrates, Science, in 311 and Hanqing j iang, Dahl-Young Khang, Jizhou Song, Yugang Sun Younggang Huang, John A.Rogers, 2007, Finite Deformation Mechanics in Buckled Thin Films on Compliant Supports, Appliced Physical Sciences, 104,40).
Adopt the conventional lithography means in the above-mentioned document on silicon substrate, at first generate very thin monocrystalline silicon zone (thickness arrives the sub-micron rank in nanometer) by traditional photoetching method, afterwards monocrystalline silicon zone is transferred on the elastic caoutchouc base material of certain stretching prestrain, remove the prestrain of elastic caoutchouc base material at last, make it return to nature, then be squeezed can be perpendicular to base material direction generation bending deformation for silicon ribbon, generation rule, periodic, stretchable ripple struction.Its deficiency is as follows: (1) efficient is low.Complex technical process, length consuming time can't once be finished the ripple struction preparation on the elastic base plate; (2) cost height.Need expensive device such as litho machine, can't the large tracts of land manufacturing; When (3) making, need shift, the residual stress height can't effectively discharge; (4) to the environment harshness.Need particular surroundings such as vacuum, temperature control is strict, can't prepare under normal condition.
Summary of the invention
One of purpose of the present invention is, proposes a kind of method that adopts electrostatic spinning to prepare ripple struction, can realize low-cost reliable manufacturing of large tracts of land ripple struction on substrate under normal condition.
As follows for realizing the technical scheme that this goal of the invention adopts:
The preparation principle of ripple struction and method, step is as follows:
(1) solution is prepared.The electrostatic spinning Polymer Solution adds in the syringe of syringe pump, is full of the anodal metal needle that links to each other of high pressure generator.
(2) electrostatic spinning.The metallic cathode collecting board that links to each other with the high pressure generator region is placed in 1～5cm position below the syringe metal needle, places the elastic caoutchouc base material on the collecting board; Syringe pump is carried out precision control, make Polymer Solution flow out with certain speed, high pressure generator applies 5～15KV voltage between syringe needle and collecting board simultaneously, when Polymer Solution polarization back produces electrostatic force, when electrostatic force during greater than the drip gauge surface tension, the formation taylor cone, and there is jet to eject from boring point, in the motion of electric field high speed, the electrostatic spinning Polymer Solution is constantly stretched forms the fiber of nanometer grade diameter, and spirality " whip is moving " behavior occurs.
(3) ripple struction deposition.The elastic caoutchouc substrate is fixed on the metal collecting board, is driven by the XY mobile platform, moves along a direction, forms ripple structions such as " telephone wire " or sine wave on whole base material.
Described macromolecule spinning solution, the suitable solution of configuration weight percent concentration uses magnetic stirrer at a certain temperature, and static some hrs, be used for spinning, macromolecular material in this solution, comprise polyethylene glycol oxide, insulation that PEDOT:PSS etc. are water-soluble and conductive material;
Its invention mechanism is: the Polymer Solution after the polarization forms jet under electric field action, the jet surface charging, because like charges is mutually exclusive, jet forms " whip is moving ", base material is flown in acceleration, forms helical form in the space, according to effluxvelocity, select the motion platform appropriate speed, on base material, obtain the ripple struction of different spacing.
Two of purpose of the present invention is, a kind of device of implementing said method is provided, and its concrete technical scheme is:
This device comprises syringe pump, the syringe that is connected with syringe pump, this syringe front end is equipped with and the anodal metallic nozzle that links to each other of high pressure generator, high pressure generator, be positioned at the metal collecting board of the ground connection of locating below the metallic nozzle of syringe,, place flexible parent metal on the described metal collecting board with the motion platform that the metal collecting board is connected, flexible parent metal is to have elasticity, the nonmetallic materials of high-k at least.
The output voltage of described high pressure generator is 5～15KV.
Described metal collecting board is for being the gold thin film of substrate with the silicon chip.
Described metal collecting board is suitable distance apart from the metallic nozzle of syringe, is generally 3～10cm.
The metallic nozzle of described syringe is chosen suitable internal diameter, and general internal diameter is 0.3～0.8mm.
Three of purpose of the present invention is, a kind of micro-nano ripple struction of using above-mentioned preparation method's preparation is provided.
Four of purpose of the present invention is, the application of a kind of above-mentioned micro-nano ripple struction in flexible electronic device is provided.The conducting function ripple struction that adopts the method to prepare in bent device is realized the interconnected of circuit, still keeps UNICOM under the bending situation.Adopt the electronic device optionally-stretchable of the method preparation, as electronic biosensor, solar cell etc.
The present invention adopts " whip the is moving " behavior in a kind of electrostatic spinning, the routing motion platform is directly realized the ripple struction manufacturing on the flexible resilient base material, can make high polymer nanometer fiber under the stretching situation of base material, obtain wave structure, it is simple to have preparation technology, figure is accurate, characteristics such as high duplication and high controllability.This method has following advantage with respect to traditional fabrication ripple struction method: (1) high efficiency: this method can realize the quick preparation of ripple struction by the method for array; (2) low cost: this method directly prepares ripple struction in conventional environment, technologies such as needing no vacuum deposition, photoetching, design transfer, and can combine with the reel-to-reel manufacturing technique; (3) high reliability: conventional method is that ripple struction is transferred on the elastic caoutchouc substrate of prestrain, and release substrate forms the flexing structure then, inevitably introduces residual stress, and this method can effectively be avoided residual stress; (4) low temperature process: this method can directly prepare ripple struction under room temperature environment, with the elastic caoutchouc compatibility.
The advantage that the present invention is used for the flexible electronic manufacturing is: but in the flexible electronic manufacture process on the application of scale and the flexible resilient base material, finish the collection of ripple struction after, it is crooked that flexible parent metal can stretch arbitrarily, ripple struction can be stretched gradually.
Description of drawings
Fig. 1 is the electrostatic spinning schematic diagram;
Wherein 1 is a syringe pump, and 2 is syringe, and 3 is that metallic nozzle 3,4 is a high pressure generator, and 5 is flexible parent metal, and 6 is the metal collecting board, and 7 is motion platform;
The spatial movement schematic diagram of nanofiber when Fig. 2 is spinning;
Fig. 3 when being collecting board with gold-plated silicon chip when adopting example 1, selects polyethylene glycol oxide (PEO) to be prepared resulting optical microscopic image for electrospinning silk macromolecular material;
Fig. 4 is that selecting PEDOT:PSS is that electrospinning silk macromolecular material is prepared resulting optical microscopic image when being collecting board with gold-plated silicon chip when adopting example 3;
Fig. 5 is that PEDOT:PSS is an electrospinning silk macromolecule after stretching on the flexible base, board, resulting optical microscopic image
The specific embodiment
Below in conjunction with concrete preparation method, the present invention is specifically described by example:
Embodiment 1:
A: the configuration weight percent concentration is 6% polyethylene oxide solutions, uses magnetic stirrer 20 hours, static 2 hours down at 30 ℃;
B: above-mentioned solution is injected syringe 3, and the metal shower nozzle internal diameter of syringe is 0.8mm, and the metal shower nozzle links to each other with the positive pole of high pressure generator; As metal collecting board 5, metal collecting board 5 is 5cm apart from the distance of metallic nozzle 4 with gold-plated silicon chip; Metal collecting board 5 is fixed that on motion platform X, moves along a direction with the speed of 5mm/s, applies voltage 7KV and carries out the electrospinning silk.
Embodiment 2:
A: the configuration weight percent concentration is 6% polyethylene oxide solutions, uses magnetic stirrer 20 hours, static 2 hours down at 30 ℃;
B: above-mentioned solution is injected syringe 3, and the metal shower nozzle internal diameter of syringe is 0.8mm, and the metal shower nozzle links to each other with the positive pole of high pressure generator; As metal collecting board 5, metal collecting board 5 is 5cm apart from the distance of metallic nozzle 4 with gold-plated silicon chip; Metal collecting board 5 is fixed that on motion platform X, and PDMS rubber substrate 6 is placed on the metal collecting board 5, moves along a direction with the speed of 5mm/s, applies voltage 8KV and carries out the electrospinning silk.
Embodiment 3:
A: the configuration weight percent concentration is 6% PEDOT:PSS conducting solution, uses magnetic stirrer 10 hours, static 2 hours down at 25 ℃;
B: above-mentioned solution is injected syringe 3, and the metal shower nozzle internal diameter of syringe is 0.6mm, and the metal shower nozzle links to each other with the positive pole of high pressure generator; As metal collecting board 5, metal collecting board 5 is 3cm apart from the distance of metallic nozzle 4 with gold-plated silicon chip; Metal collecting board 5 is fixed that on motion platform X, and PDMS rubber substrate 6 is placed on the metal collecting board 5, moves along a direction with the speed of 7mm/s, applies voltage 10KV and carries out the electrospinning silk.
The above embodiment step that only furnishes an explanation, wherein concentration, voltage, nozzle inside diameter, motion platform speed can be selected suitable numerical value according to the experiment situation.
Claims (8)
1. one kind prepares the method for ripple struction by electrostatic spinning, comprises the steps:
(1) the electrostatic spinning Polymer Solution is added in the syringe of syringe pump, and be full of and the anodal syringe metal shower nozzle that links to each other of high pressure generator;
(2) electrostatic spinning
Below the syringe metallic nozzle, place the metallic cathode collecting board that links to each other with the high pressure generator region, on described collecting board, place flexible parent metal, controlling described Polymer Solution flows out with certain speed, described high pressure generator applies certain voltage between described metal shower nozzle and described collecting board simultaneously, makes the charged and formation jet of Polymer Solution;
(3) ripple struction deposition
Move described metal collecting board, jet is evenly dropped on the flexible parent metal, can on whole base material, form ripple struction.
2. method according to claim 1 is characterized in that, described Polymer Solution is polyethylene oxide solutions or PEDOT:PSS solution.
3. method according to claim 1 and 2 is characterized in that, described flexible parent metal is the elastic caoutchouc base material.
4. according to the described method of one of claim 1-3, it is characterized in that described metallic cathode collecting board is to be the gold thin film of substrate with the silicon chip.
5. according to the described method of one of claim 1-4, it is characterized in that the voltage that applies on the described high pressure generator (4) is 5～15KV.
6. realize the device of one of claim 1-5 described method, comprising:
Syringe pump (1);
The syringe that is connected with syringe pump (2), this syringe (2) front end is equipped with metallic nozzle (3);
High pressure generator (4), this high pressure generator (4) is anodal to link to each other with described metallic nozzle (3); With
Metal collecting board (6), it is positioned at metallic nozzle (3) below of described syringe (2), be placed with flexible parent metal (5) on this metal collecting board (6), this metal collecting board (6) moves by a motion platform (7) that is connected with this metal collecting board (6).
7. the ripple struction of the described method of one of claim 1-4 preparation.
8. the application of the described ripple struction of claim 6 in flexible electronic device.
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| CN102367593A (en) * | 2011-11-30 | 2012-03-07 | 福建农林大学 | Drawing and inserting type collector of nano fiber electrostatic spinning flat plate |
| CN102409462A (en) * | 2011-08-31 | 2012-04-11 | 青岛大学 | Method for printing disordered micro nanofibers into ordered fiber array |
| CN103219280A (en) * | 2013-03-20 | 2013-07-24 | 华中科技大学 | Method for manufacturing ductile circuit interconnection structure by utilization of electrostatic spinning technique and product thereof |
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| CN104358029A (en) * | 2014-10-17 | 2015-02-18 | 华中科技大学 | Method and device for preparing micro-nano corrugated structure by electrostatic spinning |
| CN104909333A (en) * | 2015-04-17 | 2015-09-16 | 广东工业大学 | Micro-nano ripple structure making apparatus and method thereof |
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