CN108249391B - Preparation method of acid-base response anisotropic infiltration asymmetric silicon nano cylindrical array - Google Patents
Preparation method of acid-base response anisotropic infiltration asymmetric silicon nano cylindrical array Download PDFInfo
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- CN108249391B CN108249391B CN201810081118.XA CN201810081118A CN108249391B CN 108249391 B CN108249391 B CN 108249391B CN 201810081118 A CN201810081118 A CN 201810081118A CN 108249391 B CN108249391 B CN 108249391B
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 140
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- 239000010703 silicon Substances 0.000 title claims abstract description 140
- 230000008595 infiltration Effects 0.000 title claims abstract description 30
- 238000001764 infiltration Methods 0.000 title claims abstract description 30
- 230000004044 response Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 238000009736 wetting Methods 0.000 claims description 32
- GWOLZNVIRIHJHB-UHFFFAOYSA-N 11-mercaptoundecanoic acid Chemical compound OC(=O)CCCCCCCCCCS GWOLZNVIRIHJHB-UHFFFAOYSA-N 0.000 claims description 31
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
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- 238000007664 blowing Methods 0.000 claims description 3
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- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 3
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims 1
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- 239000002086 nanomaterial Substances 0.000 description 9
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- HMLSBRLVTDLLOI-UHFFFAOYSA-N 1-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)C(C)OC(=O)C(C)=C HMLSBRLVTDLLOI-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 241000416536 Euproctis pseudoconspersa Species 0.000 description 1
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- 239000000084 colloidal system Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00436—Shaping materials, i.e. techniques for structuring the substrate or the layers on the substrate
- B81C1/00444—Surface micromachining, i.e. structuring layers on the substrate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00436—Shaping materials, i.e. techniques for structuring the substrate or the layers on the substrate
- B81C1/00555—Achieving a desired geometry, i.e. controlling etch rates, anisotropy or selectivity
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/225—Oblique incidence of vaporised material on substrate
- C23C14/226—Oblique incidence of vaporised material on substrate in order to form films with columnar structure
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
- H01L21/30608—Anisotropic liquid etching
Abstract
A preparation method of an acid-base response anisotropic infiltration asymmetric silicon nanometer cylindrical array belongs to the technical field of material science. The invention combines the method of interface self-assembly and colloidal crystal etching, a hexagonal non-close packed nano cylindrical array is prepared on the surface of a silicon substrate, acid-base response functional groups are asymmetrically modified on the left side and the right side of the cylindrical array, so that a 'Shuangshen' substrate for inducing the unidirectional infiltration of strong acid and strong base along different directions is realized, and the substrate can also induce the conversion of the unidirectional infiltration of liquid with the pH value between 1 and 13 from anisotropic infiltration, isotropic infiltration, reverse direction anisotropic infiltration and reverse direction unidirectional infiltration. The Shuangmianshen substrate shows a response infiltration behavior to water after being treated by acid and alkali, and the water can be mutually converted between unidirectional infiltration in two directions. The invention has simple steps, does not relate to expensive instruments, and has important application in many fields due to excellent stimulus responsiveness.
Description
Technical Field
The invention belongs to the technical field of material science, and particularly relates to a preparation method of an acid-base response anisotropic infiltration asymmetric silicon nano cylindrical array.
Background
The preparation of wetting surfaces with stimulus response has become an important component in the field of material science and is applied in many research areas, including sensors (j.chapman, f.regan, adv.eng.mater. 2012,14, B175.), Drug release (p.gupta, k.vermani, s.garg, Drug Discovery Today 2002,7,569.) and microfluidic devices (k.m.grant, j.w.hemmert, h.s.white, j.am. chem.soc.2002,124, 462). In recent years, many new classes of stimuli have been developed and studied, including temperature, light, counter ions, solvents/solutes, electrical potentials, and acid-base.
In most of the studies at present, stimulus-responsive wetting surfaces are mainly switched between states of isotropic wetting nature, i.e. hydrophilic (superhydrophilic) and hydrophobic (superhydrophobic). The anisotropic wettability is widely concerned by researchers due to the application prospect in the fields of liquid transmission, oil-water separation and microfluidics (d.xia, l.m.johnson, g.p.lopez, adv.mater.2012,24,1287.). In consideration of future application prospect, the application range of the material is enlarged if anisotropic wetting property is introduced into the conversion process of the stimulus response wetting surface. A few studies report a material surface with a trade-off between anisotropic and isotropic wetting of the stimulus response. However, the mutual conversion of the unidirectional infiltration of the two directions of the material surface under the external stimulation is not realized, which greatly improves the application value of the material. Therefore, it is very significant to develop a one-way wettability surface with simple preparation process and intelligent stimulus response in different directions.
Disclosure of Invention
The invention aims to provide an intelligent and simple-step preparation method of an acid-base response anisotropic infiltration asymmetric silicon nano cylindrical array.
The invention combines the methods of interface self-assembly and colloidal crystal etching to prepare the hexagonal non-close packed nano cylindrical array on the surface of the silicon substrate. And further preparing the acid-base responsive anisotropic wettability surface by an asymmetric modification method. The whole process is simple and convenient to operate, complex and expensive preparation technology is not involved, and the prepared intelligent surface has good stability and reversibility. The material prepared by the method and having the one-way infiltration properties in different directions of acid-base response and capable of being mutually converted has important meanings in scientific research and practical application.
The invention relates to a preparation method of an acid-base responsive anisotropic infiltrated asymmetric silicon nano cylindrical array, which comprises the following specific steps:
1) surface treatment of a silicon substrate: sequentially placing the silicon substrate in acetone, absolute ethyl alcohol and deionized water, and ultrasonically cleaning for 5-15 min; then, placing the silicon substrate subjected to ultrasonic cleaning in an acidic oxidation treatment solution (a mixed solution of 30% by mass of hydrogen peroxide and 98% by mass of concentrated sulfuric acid in a volume ratio of 3: 7) for boiling for 30-50 min, and finally cleaning with deionized water until no acid solution remains and storing in the deionized water for later use;
2) dispersing Polystyrene (PS) microspheres with the surface hydrophobization treatment diameter of 1-3 mu m in 5-10 mL with the volume ratio of 1:1, obtaining Polystyrene (PS) microsphere dispersion liquid with the concentration of 5-10 wt% in a mixed solution of water and absolute ethyl alcohol; carrying out ultrasonic treatment on the PS microsphere dispersion liquid for 60-80 min at the temperature of 15-25 ℃ and the power of 90-110W, and then carrying out ultrasonic treatment for 1-4 mu L min-1Pushing the mixture into a culture dish filled with deionized water by using a syringe pump; then, dripping 100-200 mu L of surfactant aqueous solution (sodium dodecyl sulfate) with the concentration of 2-5 wt% along the side wall of the culture dish to enable the PS microspheres to be tightly stacked into a single layer; stretching the silicon substrate obtained in the step 1) below a water surface, slowly and vertically lifting the silicon substrate from the lower part of the single-layer microsphere, and obliquely placing the silicon substrate on filter paper until the water is volatilized completely, so that a single-layer hexagonal close-packed PS microsphere array is obtained on the silicon substrate;
3) etching the silicon substrate prepared in the step 2) for 1-20 min by using oxygen plasma (the etching pressure is 5-20 mTorr, the etching temperature is 10-20 ℃, the etching gas flow rate of the silicon substrate is 10-50 sccm, the etching power is 0-400W (radio frequency) and 0-400W (inductively coupled plasma), and changing the original hexagonal close packing into hexagonal non-close packing of the PS microsphere array after etching, namely reducing the diameter of the microspheres and increasing the space; then taking a single-layer non-close packed PS microsphere as a mask and using SF6/CHF3Etching the silicon substrate with the plasma for 0.5-10 min (the etching pressure is 5-20 mTorr, the etching temperature is 10-20 ℃, and the temperature is SF6Gas flow rate of 0 to 20sccm, CHF3The gas flow rate is 5-40 sccm, the etching power is RF 0-400W, and ICP 0-400W); placing the etched silicon substrate in toluene for 1-5 min by ultrasonic waves, washing the silicon substrate by ethanol, and drying the silicon substrate by nitrogen, so as to remove residual PS microspheres on the surface of the silicon substrate and obtain a silicon nano cylindrical array, wherein the diameter of the obtained cylinder is 100-900 nm, and the height of the obtained cylinder is 50-1000 nm;
4) cleaning the silicon nano cylindrical array prepared in the step 3) for 5-10 min by using oxygen plasma, then placing the silicon nano cylindrical array into a dryer provided with a small weighing bottle, adding 20-30 mu L of gamma-aminopropyl triethoxy silane into the small weighing bottle, heating the dryer for 2-4 h at the temperature of 60-80 ℃ to carry out amination modification on the silicon nano cylindrical array, placing the amino-modified silicon nano cylindrical array into another weighing bottle, sequentially adding 5-15 mL of dichloromethane and 100-200 mu L of triethylamine, placing the silicon nano cylindrical array at the temperature of-4 ℃ for 10-20 min, then adding 50-150 mu L of α -bromoisopropylacyl bromide, placing the silicon nano cylindrical array at the temperature of-4 ℃ for 2-5 h, placing the weighing bottle at the temperature of-4 ℃ for reaction for 15-18 h, taking out the silicon nano cylindrical array, respectively cleaning 2-4 times by using dichloromethane and ethanol, drying the silicon nano cylindrical array by using nitrogen, sequentially adding 2-3 mL of water, 2-3 mL of methanol, N, 2-6-dimethylaminoethyl methacrylate, 1 min, 1-4 min, cleaning the silicon nano cylindrical array by using 2-4 min, drying the acetone, adding 0-10 mu L of ethyl chloride, drying the cuprous chloride and 10mg of the ammonia, respectively, drying the cuprous chloride in a three-5-3 mL of the silicon nano cylindrical array by using 2-3 min, adding 2-3 mL of ethyl methacrylate, drying the ethyl chloride, and 10min, and the ammonia to obtain cuprous chloride solution, respectively, and drying the cuprous chloride solution by using the cuprous chloride, and the cuprous chloride to obtain a solution of the cuprous chloride solution of the;
5) placing the silicon substrate prepared in the step 4) in an evaporation instrument in a way of inclining 30-60 degrees, so that metal is only evaporated on one side of the silicon nano cylindrical array facing to the evaporation source in the evaporation process; firstly, evaporating a layer of chromium with the thickness of 2-5 nm, and then evaporating gold with the thickness of 15-30 nm; placing the prepared silicon substrate in an ethanol solution containing dodecyl mercaptan and 11-mercapto undecanoic acid for 6-8 h, washing with ethanol, and drying with nitrogen; the total concentration of the dodecyl mercaptan and the 11-mercapto undecanoic acid is 0.05-0.2 mM, and the molar concentration ratio of the dodecyl mercaptan to the 11-mercapto undecanoic acid is 0.25-4: 1; after the step, dodecanethiol and 11-mercaptoundecanoic acid are modified on the surface of gold, so that the acid-base response anisotropic infiltration asymmetric silicon nano cylindrical array with a 'dihedral' structure is prepared, namely, one side of the silicon cylindrical array is modified with poly (N, N-dimethylaminoethyl methacrylate), and the other side is modified with dodecanethiol and 11-mercaptoundecanoic acid.
In the step 4), grafting poly (N, N-dimethylaminoethyl methacrylate) molecules containing amino on a silicon nano cylindrical array by using an atom transfer radical polymerization method; in step 5), gold is deposited on one side of the silicon cylinder array by using an oblique evaporation method, and then dodecanethiol and 11-mercaptoundecanoic acid are modified on the surface of the gold by using a self-assembly method. The Shuangshen substrate prepared by the invention utilizes the non-simultaneous protonation/deprotonation behaviors of the nano-structure array on two sides under the acid-base stimulation condition, thereby realizing the anisotropic infiltration of acid-base response. The substrate can induce the conversion of the liquid with the pH value between 1 and 13 from unidirectional infiltration to anisotropic infiltration, isotropic infiltration, opposite direction anisotropic infiltration and opposite direction unidirectional infiltration. After the prepared Shuangshen substrate is treated by acid and alkali, the prepared Shuangshen substrate also shows a response infiltration behavior to water, and the water can be mutually converted between unidirectional infiltration in two directions.
In order to explain the acid-base response anisotropic infiltration property of the 'Shuangshen' asymmetric silicon nano cylinder array, the silicon nano cylinder array prepared in the step 3) is horizontally placed in an evaporation instrument, and metal is evaporated on the whole surface of the silicon nano cylinder; firstly, evaporating a layer of chromium with the thickness of 2-5 nm, and then evaporating gold with the thickness of 15-30 nm; placing the prepared silicon substrate in an ethanol solution containing dodecyl mercaptan and 11-mercapto undecanoic acid for 6-8 h, washing with ethanol, and drying with nitrogen; the total concentration of the dodecyl mercaptan and the 11-mercapto undecanoic acid is 0.05-0.2 mM, and the molar concentration ratio of the dodecyl mercaptan to the 11-mercapto undecanoic acid is 0.25-4: 1; after the step, dodecyl mercaptan and 11-mercapto undecanoic acid are modified on the surface of the whole silicon nano cylinder array; solutions of different pH values ( pH 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13) were tested for wettability on the surface of the aforementioned silicon substrate, i.e., the entire surface of the silicon nanocylinder array, modified with dodecyl mercaptan and 11-mercaptoundecanoic acid and step 4).
The silicon substrate used in step 1) is a single crystal silicon substrate.
The evaporation speed of the metal chromium in the step 4) and the step 6) is 0.03-0.08 nm min-1。
The evaporation speed of the metal gold in the step 4) and the step 6) is 0.08-0.13 nm min-1。
The method has simple steps, does not need expensive instruments and equipment, and realizes the intelligent acid-base responsive anisotropic wettability surface by utilizing the non-simultaneous protonation/deprotonation behaviors exhibited by the acid-base responsive functional groups asymmetrically modified on two sides of the nano-structure array. Not only has breakthrough on the types of the liquid on the anisotropic wettability surface (specific property liquid: acid and alkali), but also has great progress on the mutual conversion between the unidirectional wettability in different directions.
Drawings
FIG. 1: scanning electron microscopy of the 'bishen' silicon nanostructure array of example 5 of the present invention;
(a) based on the schematic diagram of the prepared Liangshen silicon nano cylindrical structure array, one side of the cylindrical array is modified with poly N, N-dimethylaminoethyl methacrylate, and the other side is modified with dodecyl mercaptan and 11-mercapto-undecylic acid;
(b) the scanning electron microscope top view of the Shuangshen silicon nanostructure array, the arrow represents the direction of gold evaporation plating, and the crescent-shaped shadow proves the asymmetric property of the silicon substrate;
(c) the cross section of the 'Shuangshen' silicon nano cylindrical structure array is shown by a scanning electron microscope. The asymmetry of the nanostructure can be clearly seen by the cross-sectional view of the "dihedral" structure, with one side of the pillar array covered with gold and the other side without gold. MUA, DDT and PDMAEMA in the figure represent dodecyl mercaptan, 11-mercaptoundecanoic acid and poly (N, N-dimethylaminoethyl methacrylate), respectively.
FIG. 2: testing the wetting behavior diagram of the surface to different pH value liquids;
the silicon substrate prepared in example 5 was surface-injected with solutions of different pH values (pH 0.98, 1.99, 3.99, 7.04, 9.99, 12.00, 13.05) prepared from concentrated hydrochloric acid and sodium hydroxide using a syringe of a drop-shape analyzer, and the surface was testedThe solution in the syringe is discharged at a speed of 1 muL/s for the wetting behavior of liquids with different pH values. The arrow indicates the direction of migration of the three-phase line, i.e. the direction of wetting of the liquid. Corresponding to example 6. -CH3-COOH and-N (CH3)2From dodecanethiol, 11-mercaptoundecanoic acid and poly (N, N-dimethylaminoethyl methacrylate), respectively.
FIG. 3: static wetting behavior diagrams of solutions with different pH values;
(a) a static wetting behavior of 3 μ L of solutions of different pH values (pH 0.98, 1.99, 2.99, 3.99, 5.01, 5.99, 7.04, 7.99, 8.93, 9.99, 11, 12.00, 13.05) on a silicon nanocylinder with the entire surface modified with N, N-dimethylaminoethyl methacrylate for 10 min; corresponding to example 7;
(b) mu.L of solutions of different pH values (pH 0.98, 1.99, 2.99, 3.99, 5.01, 5.99, 7.04, 7.99, 8.93, 9.99, 11, 12.00, 13.05) had a static wetting behavior on silicon nanocylinders with the entire surface modified with dodecanethiol and 11-mercaptoundecanoic acid, a total concentration of dodecanethiol and 11-mercaptoundecanoic acid of 0.1mM, a molar concentration ratio of dodecanethiol and 11-mercaptoundecanoic acid of 0.45: 0.55; correspond to
Example 8;
(c) the difference in the static contact angles of the solutions of different pH values in a) and b) can be used to explain the experimental phenomena in FIG. 2 and example 5. Due to the non-simultaneous protonation/deprotonation behavior on both sides of the Shuangshen, the wettability of both sides of the nanostructure is different. The protonation/deprotonation degree of the strong acid and the strong base is increased, so that the wettability difference of two sides is increased, and the strong acid and the strong base are unidirectionally infiltrated on the Shuangshen silicon substrate along different directions. With the reduction of the pH value, the wetting behavior can be changed from unidirectional wetting to anisotropic wetting, and finally to isotropic wetting.
FIG. 4: and (3) a dynamic wetting behavior representation diagram of deionized water on the surface of the prepared sample by using a droplet morphology instrument, wherein the water is discharged at the speed of 1 mu L/s.
(a) Immersing the Shuangmian silicon substrate prepared in the example 5 into a hydrochloric acid solution with the pH value of 0.98 for 2s, flushing with ethanol and drying with nitrogen;
(b) the dynamic wetting behavior of water on the "Shuangshen" silicon substrate prepared in example 5 was tested directly;
(c) the "Janus" silicon substrate prepared in example 5 was immersed in a sodium hydroxide solution at pH 13.05 for 2s, rinsed with ethanol and blown dry with nitrogen. The arrow is the migration direction of the three-phase line, namely the infiltration direction of water;
(d) and (4) continuous acid and alkali treatment, and testing the dynamic infiltration behavior of the water after each treatment. The 'Janus' silicon substrate piece shows very good reversible transformation behavior, namely, after acid treatment, the water is unidirectionally infiltrated along the direction of modifying poly (N, N-dimethylaminoethyl methacrylate), and after alkali treatment, the water is unidirectionally infiltrated along the direction of modifying dodecyl mercaptan and 11-mercapto undecanoic acid.
Detailed Description
Example 1: cleaning and hydrophilizing treatment of silicon substrates
Cutting a monocrystalline silicon substrate (100) into a square with the size of 2cm on side by using a glass cutter, performing ultrasonic treatment for 5min by using acetone, ethanol and deionized water respectively, and then placing the monocrystalline silicon substrate into a mixed solution (volume ratio is 7:3) of concentrated sulfuric acid with the mass fraction of 98% and hydrogen peroxide with the mass fraction of 30% for heating and boiling for 40min to make the surface hydrophilic; then pouring the mixed solution into a waste liquid bottle, repeatedly washing the hydrophilic silicon substrate with deionized water for 3 times, and storing the hydrophilic silicon substrate in deionized water for later use.
Example 2: preparation of hydrophobic PS microspheres
5mL of ethanol dispersion of PS microspheres (diameter 1 μm) with concentration of 10 wt% was measured, and the volume ratio of ethanol to water was 1:1, performing centrifugal cleaning for 10 times to remove the surfactant in the stock solution, and finally dispersing in ethanol and water in a volume ratio of 1:1, at a concentration of 5 wt%.
Example 3: single layer colloid microballoon deposited on silicon substrate
Subjecting the mixture of 5% PS microspheres in example 2 with water and ethanol (volume ratio 1:1) to ultrasonic treatment at 100% power (power 100W) for 80min (temperature 20 deg.C), and injecting with syringe pump for 1.6 μ L min-1Will mixInjecting the solution into a culture dish filled with deionized water, and dripping 150 mu L of 2 wt% sodium dodecyl sulfate aqueous solution on the surface of the deionized water to obtain single-layer PS microspheres which are closely arranged; the silicon substrate in example 1 was extended below the water surface, slowly lifted vertically from below the monolayer of microspheres, and placed on filter paper with an inclination until the water evaporation was completed, thereby obtaining a monolayer of closely packed PS microsphere array on the silicon substrate.
Example 4: preparation of silicon nano-cylinder array
Placing the single-layer PS microsphere array densely packed on the silicon substrate obtained in the embodiment 3 in a plasma etching machine, and etching for 12.5min by using oxygen plasma (the etching pressure is 10mTorr, the etching temperature is 10 ℃, the gas flow rate is 50sccm, the etching power is 100W (RF), and the ICP is 0W); then, selectively etching the silicon substrate by using the single-layer non-close packed PS microspheres as a mask, and using SF6/CHF3Plasma etching for 3.5 min (etching pressure of 5mTorr, etching temperature of 10 deg.C, SF)6Gas flow rate 4sccm, CHF3The gas flow rate is 30sccm, the etching power is RF of 50W, and ICP is 100W); and (3) placing the etched silicon substrate in toluene, performing ultrasonic treatment for 2min, washing with ethanol, and drying with nitrogen, so as to remove the PS microspheres remaining on the surface, thereby obtaining the silicon nano cylindrical array. The resulting cylinder had a diameter of 700nm and a height of 380 nm.
Example 5: preparation of 'Liangmianshen' silicon nano cylinder array
1) Placing the silicon nanocylinder array prepared in example 4 in an oxygen plasma cleaning machine, cleaning for 5min, placing the silicon nanocylinder array in a dryer with a small weighing bottle, adding 20 mul of gamma-aminopropyltriethoxysilane into the weighing bottle, placing the dryer in a 60 ℃ oven, heating for 2h, after the step, successfully modifying the silicon nanocylinder array with amino groups, placing the amino-modified silicon nanocylinder array in another weighing bottle, sequentially adding 10mL of dichloromethane and 140 mul of triethylamine, placing the silicon nanocylinder array at-4 ℃ for 10min, adding α -bromoisopropyl acyl bromide 100 mul, placing the silicon chip at-4 ℃ for 2h, reacting for 18h at normal temperature, taking out the silicon chip, cleaning with dichloromethane and ethanol for 3 times, blowing dry with nitrogen for later use, adding 2mL of water, 2mL of methanol, 2mL of N, 4mL of N-dimethylaminoethyl methacrylate, 1,4,7,10, 10-triethylenetetramine, modifying with copper chloride for 8mg, adding 5min, ultrasonic cleaning the surface of the silicon nanocylinder array, drying with nitrogen to obtain a cuprous chloride solution, drying the silicon nanocylinder by adding ammonia, and drying by ultrasonic treatment.
2) The prepared silicon substrate with the surface modified by the poly N, N-dimethylaminoethyl methacrylate is placed in an evaporation instrument in an inclined way of 45 degrees. Firstly, evaporating a layer of chromium with the thickness of 3nm on one side of a silicon nano cylindrical array, and then evaporating gold with the thickness of 20 nm; and (3) placing the prepared silicon substrate in an ethanol solution containing dodecyl mercaptan and 11-mercaptoundecanoic acid for 8 hours, washing with ethanol, and drying with nitrogen. The total concentration of dodecanethiol and 11-mercaptoundecanoic acid was 0.1mM, and the molar ratio of the concentrations of dodecanethiol and 11-mercaptoundecanoic acid was 0.45: 0.55.
Example 6: 'Shuangshen' silicon substrate for inducing acid-base to unidirectionally infiltrate along different directions
And (3) characterizing the dynamic wetting behavior of the prepared sample surface by using a droplet morphology instrument. A syringe of a droplet morphology instrument injects solutions (with pH 0.98, 1.99, 3.99, 7.04, 9.99, 12.00, 13.05) with different pH values prepared by concentrated hydrochloric acid and sodium hydroxide into the surface of the silicon substrate prepared in example 5, the solution in the syringe is discharged at a speed of 1 μ L/s, and a strong acid (with pH 0.98) is soaked in the silicon substrate in a unidirectional way along the direction of the modified poly (N, N-dimethylaminoethyl methacrylate); as the pH of the solution increases, the wetting behavior changes from unidirectional to anisotropic (pH 1.99, along the direction of the modified N, N-dimethylaminoethyl methacrylate); as the pH of the solution is further increased, the wetting behavior changes from the original anisotropic wetting to an isotropic wetting (pH 3.99, 7.04, 9.99); when the pH value of the solution reaches 12, the silicon substrate can induce the liquid to be soaked in an anisotropic way along the direction of the evaporated gold; and strong alkali (pH 13.05) is soaked in the silicon substrate in a unidirectional way along the direction of the evaporated gold after contacting the silicon substrate. Due to the different directivities of the acid-base response of the silicon substrate, the silicon substrate is called as a 'Shuangshen' silicon substrate.
Example 7: preparation of poly N, N-dimethylamino ethyl methacrylate modified silicon nano structure array
In order to explain the acid-base response anisotropic wetting property of the Liangshen silicon substrate, the step 1) of the example 5 is repeated to obtain the silicon substrate which is completely the same as the step 1) of the example 5, namely the poly N, N-dimethylaminoethyl methacrylate modified silicon nanostructure array, wherein the modification time is 10 min. And (3) using a liquid drop morphology instrument to characterize the static wetting property of the prepared sample surface. The test solutions were solutions of different pH values (pH 0.98, 1.99, 2.99, 3.99, 5.01, 5.99, 7.04, 7.99, 8.93, 9.99, 11, 12.00, 13.05) prepared from concentrated hydrochloric acid and sodium hydroxide in an amount of 3 μ L. The poly N, N-dimethylaminoethyl methacrylate modified silicon nanostructure array shows good pH response infiltration property, and the silicon substrate can realize the interconversion of parent acid and base. This is because poly (N, N-dimethylaminoethyl methacrylate) is protonated, positively charged and becomes more lyophilic under acidic conditions, while deprotonated, uncharged and becomes relatively lyophobic under alkaline conditions.
Example 8: preparation of silicon nano-cylinder array modified by mixing of dodecyl mercaptan and 11-mercaptoundecanoic acid
In order to explain the acid-base response anisotropic wetting property of the Shuangshen silicon substrate, the silicon nano cylindrical array prepared in the example 4 is horizontally placed in an evaporation instrument, chromium with the thickness of 3nm is evaporated firstly, and then gold with the thickness of 20nm is evaporated; and (3) placing the prepared silicon substrate in an ethanol solution containing dodecyl mercaptan and 11-mercaptoundecanoic acid for 8 hours, washing with ethanol, and drying with nitrogen. The total concentration of dodecanethiol and 11-mercaptoundecanoic acid was 0.1mM, and the molar concentration ratio of dodecanethiol to 11-mercaptoundecanoic acid was 0.45: 0.55. the test procedure of example 7 was repeated. The silicon nanocylinder array modified by the mixture of the dodecyl mercaptan and the 11-mercaptoundecanoic acid shows good pH response infiltration property, and the silicon substrate can realize the mutual conversion of alkalophilic and hydrophobic acids which is opposite to the result of the poly (N, N-dimethylaminoethyl methacrylate) modified silicon substrate (example 7). This is due to the fact that under basic conditions, the 11-mercaptoundecanoic acid molecule becomes deprotonated, negatively charged, and becomes more lyophilic, while under acidic conditions, it becomes protonated, uncharged, and becomes relatively lyophobic.
Example 9: 'Shuishen' silicon substrate for changing flow behavior of induced water through pH value
And (3) characterizing the dynamic wetting behavior of the prepared sample surface by using a droplet morphology instrument. The sample prepared in example 7 was immersed in a hydrochloric acid solution having a pH of 0.98 for 2s, and purged with ethanol and nitrogen to dry. Injecting deionized water to the surface of the prepared silicon substrate by using an injector of a drop morphology instrument, discharging water in the injector at the speed of 1 mu L/s, and soaking the water in a single direction along the direction of the modified poly (N, N-dimethylaminoethyl methacrylate) after the water contacts the silicon substrate; when the silicon substrate is immersed in a sodium hydroxide solution with the pH value of 13.05 for 2s, washed by ethanol and dried by nitrogen, the silicon substrate induces water to be infiltrated along the opposite direction of the modified poly (N, N-dimethylaminoethyl methacrylate), namely along the direction of the gold evaporation plating. This phenomenon is also attributed to the non-simultaneous protonation/deprotonation behavior of the two sides of the "dihedral".
Claims (6)
1. A preparation method of an acid-base response anisotropic infiltration asymmetric silicon nanometer cylindrical array comprises the following steps:
1) surface treatment of a silicon substrate: sequentially placing the silicon substrate in acetone, absolute ethyl alcohol and deionized water, and ultrasonically cleaning for 5-15 min; then, placing the silicon substrate subjected to ultrasonic cleaning in an acidic oxidation treatment solution for boiling treatment for 30-50 min, finally cleaning with deionized water until no acid solution remains, and storing in the deionized water for later use;
2) dispersing polystyrene microspheres with the surface hydrophobization treatment diameter of 1-3 mu m in 5-10 mL with the volume ratio of 1:1, obtaining 5-10 wt% polystyrene microsphere dispersion liquid; subjecting the polystyrene microsphere dispersion to ultrasonic treatment at 15-25 ℃ and 90-110W power60-80 min, then 1-4 μ L min-1Pushing the mixture into a culture dish filled with deionized water by using a syringe pump; then, dripping 100-200 mu L of surfactant aqueous solution with the concentration of 2-5 wt% along the side wall of the culture dish to enable the PS microspheres to be tightly stacked into a single layer; stretching the silicon substrate obtained in the step 1) below the water surface, slowly and vertically lifting the silicon substrate from the lower part of the single-layer microsphere, and obliquely placing the silicon substrate on filter paper until the water is volatilized completely, thereby obtaining a single-layer hexagonal close-packed PS microsphere array on the silicon substrate;
3) etching the silicon substrate prepared in the step 2) for 1-20 min by using oxygen plasma, wherein the original hexagonal close packing of the etched polystyrene microsphere array is changed into hexagonal non-close packing, the diameter of the microspheres is reduced, and the space is increased; then taking the single-layer non-close packed polystyrene microsphere as a mask and using SF6/CHF3Etching the silicon substrate by using the plasma for 0.5-10 min; placing the etched silicon substrate in toluene, performing ultrasonic treatment for 1-5 min, washing with ethanol, and drying with nitrogen, so as to remove residual polystyrene microspheres on the surface of the silicon substrate, thereby obtaining a silicon nano cylindrical array, wherein the diameter of the obtained cylinder is 100-900 nm, and the height of the obtained cylinder is 50-1000 nm;
4) cleaning the silicon nano cylindrical array prepared in the step 3) for 5-10 min by using oxygen plasma, then placing the silicon nano cylindrical array into a dryer provided with a small weighing bottle, adding 20-30 mu L of gamma-aminopropyltriethoxysilane into the small weighing bottle, heating the dryer for 2-4 h at 60-80 ℃ for amination modification of the silicon nano cylindrical array, placing the amino-modified silicon nano cylindrical array into another weighing bottle, sequentially adding 5-15 mL of dichloromethane and 100-200 mu L of triethylamine, placing the silicon nano cylindrical array at-4 ℃ for 10-20 min, then adding 50-150 mu L of α -bromoisopropyl acyl bromide, placing the silicon nano cylindrical array at-4 ℃ for 2-5 h, placing the weighing bottle at normal temperature for reaction for 15-18 h, taking out the silicon nano cylindrical array, cleaning 2-4 times by using dichloromethane and ethanol, blowing the silicon nano cylindrical array by using nitrogen, sequentially adding 2-3 mL of water, 2-3 mL of methanol, N, 2-6 mL of methacrylic acid, 2-dimethylaminoethyl methacrylate, 1-4 min, cleaning the silicon nano cylindrical array for 2-4 min, drying the silicon nano cylindrical array by using 10-10 min, drying the silicon nano cylindrical array by using 10-5 min, adding 2-10 mg of ethyl chloride, blowing the cuprous chloride and 10-5 min, drying the cuprous chloride to obtain cuprous chloride, and the cuprous chloride, respectively, and the cuprous chloride, and;
5) placing the silicon substrate prepared in the step 4) in an evaporation instrument in a way of inclining 30-60 degrees, so that metal is only evaporated on one side of the silicon nano cylindrical array facing to the evaporation source in the evaporation process; firstly, evaporating a layer of chromium with the thickness of 2-5 nm, and then evaporating gold with the thickness of 15-30 nm; placing the prepared silicon substrate in an ethanol solution containing dodecyl mercaptan and 11-mercapto undecanoic acid for 6-8 h, washing with ethanol, and drying with nitrogen; the total concentration of the dodecyl mercaptan and the 11-mercapto undecanoic acid is 0.05-0.2 mM, and the molar concentration ratio of the dodecyl mercaptan to the 11-mercapto undecanoic acid is 0.25-4: 1; after the step, dodecyl mercaptan and 11-mercapto undecanoic acid are modified on the surface of gold, so that the acid-base responsive anisotropic wetting asymmetric silicon nano cylindrical array is prepared.
2. The method for preparing the acid-base responsive anisotropic wetting asymmetric silicon nanocylinder array according to claim 1, wherein the method comprises the following steps: the acidic oxidation treatment solution used in the step 1) is a mixed solution of 30% by mass of hydrogen peroxide and 98% by mass of concentrated sulfuric acid, and the volume ratio of the hydrogen peroxide to the concentrated sulfuric acid is 3: 7.
3. the method for preparing the acid-base responsive anisotropic wetting asymmetric silicon nanocylinder array according to claim 1, wherein the method comprises the following steps: the silicon substrate used in step 1) is a single crystal silicon substrate.
4. The method for preparing the acid-base responsive anisotropic wetting asymmetric silicon nanocylinder array according to claim 1, wherein the method comprises the following steps: the surfactant used in step 2) is sodium lauryl sulfate.
5. The acid-base responsive anisotropically-infiltrated asymmetric silicon nanocylinder array of claim 1The preparation method is characterized by comprising the following steps: in the step 3), etching pressure of oxygen plasma etching is 5-20 mTorr, etching temperature is 10-20 ℃, gas flow rate of the silicon substrate etching is 10-50 sccm, etching power RF is 0-400W, and ICP is 0-400W; SF6/CHF3The etching pressure of the plasma etching is 5-20 mTorr, the etching temperature is 10-20 ℃, and SF (sulfur hexafluoride) is6The gas flow rate is 0-20 sccm, CHF3The gas flow rate is 5-40 sccm, the etching power RF is 0-400W, and the ICP is 0-400W.
6. The method for preparing the acid-base responsive anisotropic wetting asymmetric silicon nanocylinder array according to claim 1, wherein the method comprises the following steps: in the step 4), the evaporation speed of the metal chromium is 0.03-0.08 nm/min, and the evaporation speed of the metal gold is 0.08-0.13 nm/min.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102285629A (en) * | 2011-05-05 | 2011-12-21 | 厦门大学 | Preparation method for surface-enhanced Raman spectrum active substrate |
| CN102530846A (en) * | 2012-02-14 | 2012-07-04 | 中国人民解放军国防科学技术大学 | Method for preparing metal nanobelt array with tip |
| CN106570300A (en) * | 2016-11-17 | 2017-04-19 | 中南大学 | Acquiring method for regular second-order structure surface liquid drop contact angle |
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| US20100300562A1 (en) * | 2008-02-21 | 2010-12-02 | Pinkerton Joseph F | Molecular-scale beam pump assemblies and uses thereof |
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| CN102285629A (en) * | 2011-05-05 | 2011-12-21 | 厦门大学 | Preparation method for surface-enhanced Raman spectrum active substrate |
| CN102530846A (en) * | 2012-02-14 | 2012-07-04 | 中国人民解放军国防科学技术大学 | Method for preparing metal nanobelt array with tip |
| CN106570300A (en) * | 2016-11-17 | 2017-04-19 | 中南大学 | Acquiring method for regular second-order structure surface liquid drop contact angle |
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