CN104726927A - Bionic micro-nano structure super hydrophobic porous silicon surface preparation method - Google Patents

Bionic micro-nano structure super hydrophobic porous silicon surface preparation method Download PDF

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Publication number
CN104726927A
CN104726927A CN201310708141.4A CN201310708141A CN104726927A CN 104726927 A CN104726927 A CN 104726927A CN 201310708141 A CN201310708141 A CN 201310708141A CN 104726927 A CN104726927 A CN 104726927A
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nano
porous silicon
bionic micro
silicon
super hydrophobic
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王富国
张俊彦
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Lanzhou Institute of Chemical Physics LICP of CAS
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Lanzhou Institute of Chemical Physics LICP of CAS
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Abstract

The invention discloses a bionic micro-nano structure super hydrophilic porous silicon surface preparation method, first, a porous silicon bionic micro-nano structure surface is prepared on monocrystalline silicon surface by the electrochemical etching method, and then a bionic micro-nano structure super hydrophilic porous silicon surface can be obtained by organic molecule modification. The bionic micro-nano structure super hydrophilic porous silicon surface has the advantages of low cost, simple process and short preparation time, and the silicon based bionic micro-nano structure surface has the application prospect in the aspects of bio chip and microfluidic devices and the like.

Description

A kind of preparation method of bionic micro-nano structure porous silicon super hydrophobic surface
Technical field
The present invention relates to a kind of preparation method of bionic micro-nano structure porous silicon super hydrophobic surface, particularly a kind of method being prepared bionic micro-nano structure super-hydrophobic silicon surface by electrochemical etching and organic molecule modification.
Background technology
Super hydrophobic surface refers to water contact angle θ>=150 osurface, it is the bionic functional surface that one comes from " lotus leaf effect ".As a kind of automatically cleaning, protection against corrosion, anti-oxidant etc. in there is the function surface of great potential, application technical research and the exploitation nature of super hydrophobic surface receive much concern.And semiconductor silicon is widely used in microelectromechanical systems, microfluidic device, biosensor, biochip and scientific research, if can by the unreactiveness of silicon and surface super hydrophobic very important in conjunction with this development for association area.Such as, in biochip, the application of super hydrophobic surface is advantageously in realizing the accurate control to liquid droplet, reduces crossed contamination.
The preparation method of silica-based super hydrophobic surface is normally combined with the modification of low-surface energy substance by the structure of bionic micro-nano structure and realizes, and wherein the structure of bionic micro-nano structure mainly contains two kinds of approach: the preparation method of nano material and photoetching technique.Owing to there is nanostructure in the prototype lotus leaf of super hydrophobic surface, and correlative study proves that the binary synergistic effect of micro-nano structure is that it has the crucial factor of ultra-hydrophobicity, therefore preparation method of nano material becomes a kind of approach prepared by super hydrophobic surface, such as chemical Vapor deposition process, template, sol-gel method, hydrothermal method etc.Photoetching technique widespread use in semiconductor silicon based microelectromechanical systems preparation, micron, the nanostructure of many complexity can be realized by this technology.But these two kinds of methods have a common shortcoming: micron, nanometer two kinds of structures can not be prepared in a procedure, and there is the feature that cost is high, efficiency is low, process is complicated simultaneously.Modification as low-surface energy substance is mainly realized by self assembly of organic molecules, and this is a kind of surface modification means of comparative maturity.Therefore find a kind of simple, step to realize method prepared by bionic micro-nano structure, and can combine with organic molecule finishing and realize super hydrophobic surface and prepare, the application for super hydrophobic functional surface is very important, very urgent.
Present stage, the application for a patent for invention of silica-based bionic micro-nano structure super hydrophobic surface is less, and what cut-off 2012.12 was found only has following five sections: 1. CN 102167280A; 2. CN 101249963A; 3. CN 101249964A; 4. CN 101407648A; 5. CN 101817980A.In these five patents, patent 1 is the patent of invention prepared about silica-based bionic micro-nano structure super hydrophobic surface, closely related with this patent; Patent 2-5 is the patent of invention about SiO 2 powder or colloid based superhydrophobic thin films, greatly differs from each other with the preparation of super hydrophobic surface silica-based described in this patent, and obtain surface and only have a kind of nanostructure.Patent 1 comprises two steps: photoetching technique prepares micron columnar structure, and nano thread structure is prepared in metal catalytic corrosion; Photoetching technique cost used is higher, complicated, time-consuming, and the super hydrophobic surface simultaneously obtained is not through finishing, and easily natural oxidation becomes water-wetted surface in atmosphere.And the method that this patent is mentioned prepares bionic micro-nano structure by simple electrochemical etching one step, then modify in conjunction with follow-up organic molecule and obtain bionic micro-nano structure super-hydrophobic silicon surface, and obtain super hydrophobic surface by this method and can stablize use in corrosive medium (medium such as biological fluid, cell culture fluid).
Summary of the invention
The present invention seeks to the preparation method being to provide a kind of bionic micro-nano structure porous silicon super hydrophobic surface.
First the present invention adopts electrochemical etching method to prepare porous silicon bionic micro-nano structure surface at monocrystalline silicon surface, is then modified by organic molecule and obtains the super hydrophobic porous silicon face of bionic micro-nano structure.
A preparation method for bionic micro-nano structure porous silicon super hydrophobic surface, is characterized in that the method step is:
1) by the ultrasonic cleaning in acetone of N-type (100) silicon single crystal, then be fixed in the lateral aperture of a square polytetrafluoroethylene (PTFE) electrolyzer, adding hydrofluoric acid (HF) ethanolic soln, take silicon chip as anode graphite is negative electrode, under UV-light backlight illumination condition, carry out electrochemical etching;
2) porous silicon film obtained obtains porous silicon bionic micro-nano structure surface after ethanol purge, nitrogen dry up;
3) before organic molecule is modified, obtained porous silicon bionic micro-nano structure surface is carried out pre-treatment by the following two kinds method: surface hydroxylation, Si-OH, in the vitriol oil and hydrogen peroxide mixed solution, add heat soaking; Hydrogenation, Si-H, 5%HF soak;
4) obtained hydroxylation or hydrogenation porous silicon bionic micro-nano structure surface are put into corresponding organic molecule solution system and carry out finishing, obtain bionic micro-nano structure porous silicon super hydrophobic surface;
The finishing of hydroxylated surface:
A. directly modify: silane R-SiX 3(R=C nh 2n+1, n=8,9,10 ... 20, X=Cl, OCH 3, OC 2h 5) toluene (X=Cl) or ethanol (X=OCH 3, OC 2h 5) solution;
B. Dopamine HCL grafting: prepare Dopamine HCL tack coat in Dopamine HCL three (methylol) aminomethane-hydrochloric acid soln, then carry out silane R-SiX 3(R=C nh 2n+1, n=8,9,10 ... 20, X=Cl, OCH 3, OC 2h 5), mercaptan R-SH(R=C nh 2n+1, n=8,9,10 ... 20) and primary amine R-NH 3(R=C nh 2n+1, n=8,9,10 ... 20) graft reaction.
The finishing of hydrogenated surface:
Alkene R-CH=CH 2(R=C nh 2n+1, n=6,7,8 ... 18) toluene solution.
The present invention contrasts prior art and has the following advantages:
1, electrochemical etching is used and non-lithographic technique prepares bionic micro-nano structure.
2, obtain surface for porous silicon bionic micro-nano structure surface, it is by nanoporous and micron pyramidal projections Structure composing.
3, according to actual conditions, finishing can pass through Si-H addition reaction, also can select Si-OH dehydration condensation.
4, relative complex, the photoetching technique that consuming time, cost is higher, electrochemical method is simple, efficient, cost is lower.
5, obtain in super hydrophobic surface, the super hydrophobic surface that Dopamine HCL is modified is corrosion-resistant in the medium such as biological fluid or cell culture fluid, stable.
Accompanying drawing explanation
The electron scanning micrograph of the silicon face bionic micro-nano structure prepared by Fig. 1 the present invention.
Water contact angle (CA) picture on the bionic micro-nano structure super-hydrophobic silicon surface prepared by Fig. 2 the present invention.
Embodiment
For a better understanding of the present invention, be described by following examples.
Embodiment 1:
By the ultrasonic cleaning in acetone of N-type (100) monocrystalline silicon piece, be then fixed to the side (porose on groove, one side etches) of a square bodily form PTFE etching groove, positive pole connects silicon chip, and negative pole connects graphite flake.In HF ethanolic soln, under ultraviolet lamp backlight illumination condition, carry out electrochemical etching, under certain etching current density, etch more than 60min.Taken off from PTFE etching groove by silicon chip after electrochemical etching, cleaning, nitrogen dry up in ethanol.Acquisition bionic micro-nano structure porous silicon surface is put into the vitriol oil and hydrogen peroxide mixed solution heat treated 1h, then puts into 1mM CH 3(CH 2) 17siCl 318h in toluene solution, can obtain hydride modified bionic micro-nano structure super-hydrophobic silicon surface.
Embodiment 2:
By the ultrasonic cleaning in acetone of N-type (100) monocrystalline silicon piece, be then fixed to the side (porose on groove, one side etches) of a square bodily form PTFE etching groove, positive pole connects silicon chip, and negative pole connects graphite flake.In HF ethanolic soln, under ultraviolet lamp backlight illumination condition, carry out electrochemical etching, under certain etching current density, etch more than 60min.Taken off from PTFE etching groove by silicon chip after electrochemical etching, cleaning, nitrogen dry up in ethanol.Acquisition bionic micro-nano structure porous silicon surface is put into the vitriol oil and hydrogen peroxide mixed solution heat treated 1h, then puts into 2mg/ml bar amine three (methylol) aminomethane-hydrochloric acid soln and react 4h, finally put into 1mM CH 3(CH 2) 17siCl 3react 18h in toluene solution, the bionic micro-nano structure super-hydrophobic silicon surface of Dopamine HCL tack coat can be obtained.
Embodiment 3:
By the ultrasonic cleaning in acetone of N-type (100) monocrystalline silicon piece, be then fixed to the side (porose on groove, one side etches) of a square bodily form PTFE etching groove, positive pole connects silicon chip, and negative pole connects graphite flake.In HF ethanolic soln, under ultraviolet lamp backlight illumination condition, carry out electrochemical etching, under certain etching current density, etch more than 60min.Taken off from PTFE etching groove by silicon chip after electrochemical etching, cleaning, nitrogen dry up in ethanol.Acquisition bionic micro-nano structure porous silicon surface is put into 5%HF solution 1min, then puts into 1mM CH 3(CH 2) 15cH=CH 2180 DEG C of reaction 18h in toluene solution, can obtain the bionic micro-nano structure super-hydrophobic silicon surface that alkene is modified.
The result of scanning electron microscope shown in Fig. 1 shows, in silica-based micro-nano structure surface, micrometer structure is evenly distributed, in order, size is between 15-30 μm.
Result display shown in Fig. 2, the water contact angle CA=156.1 on bionic micro-nano structure super-hydrophobic silicon surface o.

Claims (1)

1. a preparation method for bionic micro-nano structure porous silicon super hydrophobic surface, is characterized in that the method step is:
1) by the ultrasonic cleaning in acetone of N-type 100 silicon single crystal, then be fixed in the lateral aperture of a square tetrafluoroethylene electrolyzer, adding hydrofluoric acid ethanolic soln, take silicon chip as anode graphite is negative electrode, under UV-light backlight illumination condition, carry out electrochemical etching;
2) porous silicon film obtained obtains porous silicon bionic micro-nano structure surface after ethanol purge, nitrogen dry up;
3) before organic molecule is modified, obtained porous silicon bionic micro-nano structure surface is carried out pre-treatment by the following two kinds method: surface hydroxylation, Si-OH, in the vitriol oil and hydrogen peroxide mixed solution, add heat soaking; Hydrogenation, Si-H, 5%HF soak;
4) obtained hydroxylation or hydrogenation porous silicon bionic micro-nano structure surface are put into corresponding organic molecule solution system and carry out finishing, obtain bionic micro-nano structure porous silicon super hydrophobic surface;
The finishing of hydroxylated surface:
A. directly modify: silane R-SiX 3, R=C nh 2n+1, n=8,9,10 ... 20, X=Cl, OCH 3, OC 2h 5, toluene (X=Cl) or ethanol (X=OCH 3, OC 2h 5) solution;
B. Dopamine HCL grafting: prepare Dopamine HCL tack coat in Dopamine HCL three (methylol) aminomethane-hydrochloric acid soln, then carry out silane R-SiX 3, R=C nh 2n+1, n=8,9,10 ... 20, X=Cl, OCH 3, OC 2h 5, mercaptan R-SH, R=C nh 2n+1, n=8,9,10 ... 20, and primary amine R-NH 3, R=C nh 2n+1, n=8,9,10 ... 20, graft reaction; The finishing of hydrogenated surface: alkene R-CH=CH 2, R=C nh 2n+1, n=6,7,8 ... 18, toluene solution.
CN201310708141.4A 2013-12-20 2013-12-20 Bionic micro-nano structure super hydrophobic porous silicon surface preparation method Pending CN104726927A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104532337A (en) * 2015-01-09 2015-04-22 中国矿业大学 Electro erosion method for rapidly preparing iron base super-hydrophobic surface in large area
CN105200528A (en) * 2015-10-12 2015-12-30 南京理工大学 Method for corrosively preparing silicon-base super-hydrophobic surface by utilizing pine structural porous silver as catalyst
CN105463420A (en) * 2015-11-27 2016-04-06 北京工商大学 Manufacturing method of copper substrate super-hydrophobic surface
CN108314993A (en) * 2017-12-28 2018-07-24 肇庆市华师大光电产业研究院 A kind of preparation method of large area flexible hydrophobic porous silicon fiml
CN110054794A (en) * 2018-01-17 2019-07-26 香港大学 The method of raising polymeric film surface roughness and film prepared therefrom
CN110711686A (en) * 2019-10-18 2020-01-21 大连海事大学 High-adhesion super-hydrophobic surface of bionic locust leaf apple and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FUGUO WANG ET AL.,: ""Conciliating surface superhydrophobicities and mechanical strength of porous silicon films"", 《APPLIED SURFACE SCIENCE》 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104532337A (en) * 2015-01-09 2015-04-22 中国矿业大学 Electro erosion method for rapidly preparing iron base super-hydrophobic surface in large area
CN105200528A (en) * 2015-10-12 2015-12-30 南京理工大学 Method for corrosively preparing silicon-base super-hydrophobic surface by utilizing pine structural porous silver as catalyst
CN105200528B (en) * 2015-10-12 2017-08-04 南京理工大学 Make the method that catalytic erosion prepares silicon substrate super hydrophobic surface using pine structural porous silver
CN105463420A (en) * 2015-11-27 2016-04-06 北京工商大学 Manufacturing method of copper substrate super-hydrophobic surface
CN105463420B (en) * 2015-11-27 2018-04-24 北京工商大学 A kind of preparation method of copper-based baselap hydrophobic surface
CN108314993A (en) * 2017-12-28 2018-07-24 肇庆市华师大光电产业研究院 A kind of preparation method of large area flexible hydrophobic porous silicon fiml
CN108314993B (en) * 2017-12-28 2020-10-02 肇庆市华师大光电产业研究院 Preparation method of large-area flexible hydrophobic porous silicon film
CN110054794A (en) * 2018-01-17 2019-07-26 香港大学 The method of raising polymeric film surface roughness and film prepared therefrom
CN110711686A (en) * 2019-10-18 2020-01-21 大连海事大学 High-adhesion super-hydrophobic surface of bionic locust leaf apple and preparation method thereof

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Application publication date: 20150624