CN108249391A - A kind of preparation method of the anisotropic infiltration asymmetrical siloxy nm cylinder array of soda acid response - Google Patents
A kind of preparation method of the anisotropic infiltration asymmetrical siloxy nm cylinder array of soda acid response Download PDFInfo
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- CN108249391A CN108249391A CN201810081118.XA CN201810081118A CN108249391A CN 108249391 A CN108249391 A CN 108249391A CN 201810081118 A CN201810081118 A CN 201810081118A CN 108249391 A CN108249391 A CN 108249391A
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- infiltration
- silicon chip
- silicon
- cylinder array
- soda acid
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- 239000002253 acid Substances 0.000 title claims abstract description 63
- 230000008595 infiltration Effects 0.000 title claims abstract description 55
- 238000001764 infiltration Methods 0.000 title claims abstract description 55
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 230000004044 response Effects 0.000 title claims abstract description 19
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 title claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 110
- 239000010703 silicon Substances 0.000 claims abstract description 110
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 109
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000009825 accumulation Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 58
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 29
- 235000019441 ethanol Nutrition 0.000 claims description 26
- GWOLZNVIRIHJHB-UHFFFAOYSA-N 11-mercaptoundecanoic acid Chemical class OC(=O)CCCCCCCCCCS GWOLZNVIRIHJHB-UHFFFAOYSA-N 0.000 claims description 25
- 238000012986 modification Methods 0.000 claims description 24
- 230000004048 modification Effects 0.000 claims description 24
- 239000004793 Polystyrene Substances 0.000 claims description 23
- 238000005530 etching Methods 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- -1 amido modified silicon Chemical class 0.000 claims description 19
- 229920002223 polystyrene Polymers 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 17
- 239000010931 gold Substances 0.000 claims description 17
- 229910052737 gold Inorganic materials 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 230000008020 evaporation Effects 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 13
- 238000007740 vapor deposition Methods 0.000 claims description 11
- 239000004005 microsphere Substances 0.000 claims description 10
- 238000002604 ultrasonography Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 7
- 229910001882 dioxygen Inorganic materials 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000001020 plasma etching Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 238000003491 array Methods 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- 238000005576 amination reaction Methods 0.000 claims description 2
- 238000004381 surface treatment Methods 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 210000003739 neck Anatomy 0.000 claims 1
- 229920006389 polyphenyl polymer Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 230000006698 induction Effects 0.000 abstract description 3
- 238000001338 self-assembly Methods 0.000 abstract description 3
- 238000000054 nanosphere lithography Methods 0.000 abstract description 2
- 238000005316 response function Methods 0.000 abstract description 2
- 230000004936 stimulating effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- 239000002086 nanomaterial Substances 0.000 description 7
- 230000003068 static effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 230000005595 deprotonation Effects 0.000 description 2
- 238000010537 deprotonation reaction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000001617 migratory effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 101100441413 Caenorhabditis elegans cup-15 gene Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000404144 Pieris melete Species 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000007876 drug discovery Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920002246 poly[2-(dimethylamino)ethyl methacrylate] polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Geometry (AREA)
- Medicinal Preparation (AREA)
Abstract
A kind of preparation method of the anisotropic infiltration asymmetrical siloxy nm cylinder array of soda acid response, belongs to materials science field.Combination interface self assembly of the present invention and the method for nanosphere lithography, the nm cylinder array of the not close accumulation of six sides is prepared in silicon substrate surface, by asymmetrically modifying soda acid response function group in the left and right sides of column array, we realize " Janus " substrate that induction strong acid and strong base is unidirectionally infiltrated along different directions, the substrate can equally induce liquid of the acid-base value between 1 and 13 unidirectionally to infiltrate conversion to anisotropic infiltration, isotropism infiltration, negative direction anisotropic infiltration, negative direction from unidirectional infiltration." Janus " substrate equally illustrates response infiltration behavior after being handled by soda acid, to water, and water can mutually be converted between the unidirectional infiltration of both direction.Step of the present invention is simple, is not related to expensive instrument, and remarkable stimulating responsive can have important application in many fields.
Description
Technical field
The invention belongs to materials science fields, and in particular to a kind of anisotropic infiltration of soda acid response is asymmetric
The preparation method of silicon nm cylinder array.
Background technology
Preparation with stimuli responsive wellability surface has become component part important in materials science field, and
And applied to many research fields, including sensor (J.Chapman, F.Regan, Adv.Eng.Mater. 2012,14,
B175.), medicament slow release (P.Gupta, K.Vermani, S.Garg, Drug Discovery Today 2002,7,569.) with
And micro-fluidic device (K.M.Grant, J.W.Hemmert, H.S.White, J.Am. Chem.Soc.2002,124,462.).Closely
Nian Lai, people develop and have studied the stimulus of many novel types, including temperature, light, counter ion counterionsl gegenions, solvent/solute,
Potential and acid-base property etc..
In current most of researchs, stimuli responsive wellability surface is mainly the shape in isotropism Wettability
State is mutually converted between that is, hydrophilic (super hydrophilic) and hydrophobic (super-hydrophobic).And anisotropic infiltration is since it is in liquid biography
The application prospect of defeated, water-oil separating and microfluidic field receive researchers extensive concern (D.Xia,
L.M.Johnson,G.P.Lopez,Adv.Mater.2012,24,1287.).In view of following application prospect, if will be each
Anisotropy Wettability is introduced into the application range that will increase material in the transfer process on stimuli responsive wellability surface.Compared with
A small number of research reports the mutual conversion between anisotropy and isotropism infiltration of the material surface with stimuli responsive.
However, the unidirectional infiltration mutually conversion of both direction of the material surface under environmental stimuli does not realize that this will be greatly improved also
The application value of material in itself.Therefore, develop that a kind of preparation process is simple, the different directions of intelligent stimuli responsive unidirectionally soak
Lubricant nature surface is significantly.
Invention content
The object of the present invention is to provide a kind of simply a kind of anisotropic infiltration of soda acid response of intelligent, step not
The preparation method of symmetrical silicon nm cylinder array.
It is non-tight to prepare six sides in silicon substrate surface for combination interface self assembly of the present invention and the method for nanosphere lithography
Closely packed nm cylinder array.The anisotropic infiltration table that soda acid responds is prepared by the method for asymmetry modification
Face.Whole process is easy to operate, is not related to the technology of preparing of complex and expensive, and prepared intelligent surface has to be stablized well
Property and invertibity.The material that the unidirectional Wettability of different directions that the soda acid prepared using our method is responded mutually is converted,
All have great importance in scientific research or in practical applications.
A kind of preparation side of the anisotropic infiltration asymmetrical siloxy nm cylinder array of soda acid response of the present invention
Method is as follows：
1) surface treatment of silicon chip：Silicon chip is sequentially placed in acetone, absolute ethyl alcohol and deionized water ultrasonic
Clean 5~15min；Then the silicon chip after ultrasonic cleaning being placed in acidic oxidation treatment fluid, (mass fraction is 30% peroxide
Change the mixed solution of hydrogen and mass fraction for 98% concentrated sulfuric acid, the two volume ratio is 3：7) 30~50min of processing is boiled, most
It is cleaned to no acid solution and remained with deionized water afterwards, is stored in deionized water for use；
2) a diameter of 1~3 μm of surface-hydrophobicized processing polystyrene (PS) microballoon is dispersed in 5~10 mL, volume
Than being 1：1 water is in absolute ethyl alcohol mixed solution, obtaining polystyrene (PS) microballoon dispersion liquid of a concentration of 5~10wt%；
By PS microballoons dispersion liquid under the conditions of 15~25 DEG C, 90~110W of power 60~80min of ultrasound, then with 1~4 μ L min-1Speed
Degree is pushed through with syringe pump in the culture dish equipped with deionized water；100~200 μ L, concentration is added dropwise then along culture dish side wall
For the aqueous surfactant solution (lauryl sodium sulfate) of 2~5wt%, PS microballoons is made closely to be piled into individual layer；By step
1) silicon chip obtained in extend into the water surface hereinafter, slowly vertically lifting upwards below individual layer microballoon, slant setting is in filter paper
It is finished up to moisture evaporation, so as to obtain the closelypacked PS micro-sphere arrays of six side of individual layer on a silicon substrate；
3) by silicon chip oxygen gas plasma obtained in step 2) etch 1~20min (etching air pressure for 5~
20mTorr, 10~20 DEG C of etching temperature etch silicon chip 10~50sccm of gas flow rate, and it is 0~400W that etching power, which is RF,
ICP is 0~400W), PS micro-sphere arrays become the not close accumulation of six sides, i.e. microballoon from six original sides are tightly packed after etching
Diameter reduce, spacing increase；Then using the PS microballoons of the not close accumulation of individual layer as version is covered, SF is used6/CHF3Plasma etching
0.5~10min of silicon chip (etching air pressure be 5~20 mTorr, 10~20 DEG C of etching temperature, SF60~20sccm of gas flow rate,
CHF35~40sccm of gas flow rate, etching power are that RF is 0~400W, and ICP is 0~400W)；Silicon chip after etching is put
1~5min of ultrasound in toluene, nitrogen dries up after ethyl alcohol rinses, and so as to remove the PS microballoons of silicon substrate surface remnants, obtains
Silicon nm cylinder array, obtained 100~900nm of body diameter are highly 50~1000nm；
4) silicon nm cylinder array obtained in step 3) is cleaned into 5~10min with oxygen gas plasma, be then placed in
In drier equipped with small measuring cup, γ-aminopropyl triethoxysilane of 20~30 μ L is added in small measuring cup, it will be dry
Dry device heats the amination modification that 2~4h carries out silicon nm cylinder array at 60~80 DEG C；Amido modified silicon nanometer is justified
Column array is put into another measuring cup, and sequentially adds 5~15mL of dichloromethane, 100~200 μ L of triethylamine, at -4 DEG C
After placing 10~20min, alpha-brominated 50~150 μ L of isopropyl acylbromide are added, after placing 2~5h at -4 DEG C, by measuring cup
15~18h of reaction under room temperature is placed in, is cleaned 2~4 times with dichloromethane and ethyl alcohol after taking out silicon chip, is dried up with nitrogen respectively；
Sequentially added in three-neck flask 2~3mL of water, 2~3mL of methanol, 2~6mL of methacrylic N, N-dimethylamino ethyl ester,
1, Isosorbide-5-Nitrae, 7,10,10- hexamethyl trien, 50~100 μ L, 6~10mg of copper bromide, after ultrasound dissolving in 5~10 minutes
20~60min of logical nitrogen, adds 15~30mg of stannous chloride, is then placed in aforementioned obtained silicon chip in the solution instead
0.5~40min is answered, is cleaned 2~4 times with second alcohol and water respectively after taking-up, nitrogen drying, so as to make silicon nm cylinder array
Surface is by polymethylacrylic acid N, the modification of N- dimethylaminoethyls；
5) silicon chip obtained in step 4) is tilted 30~60 degree to be placed in vapor deposition instrument, in this way in the process of vapor deposition
In, metal can only be vaporized on silicon nm cylinder array towards the side of evaporation source；Vapor deposition last layer thickness is 2~5nm's first
The gold that thickness is 15~30nm is then deposited in chromium again；Prepared silicon chip is placed in containing lauryl mercaptan and 11- sulfydryls
In the ethanol solution of hendecanoic acid after 6~8h, ethyl alcohol rinses, nitrogen drying；Lauryl mercaptan and 11- Mercaptoundecanoic acids it is total
The molar concentration ratio of a concentration of 0.05~0.2mM, lauryl mercaptan and 11- Mercaptoundecanoic acids is 0.25~4：1；By this
After step, lauryl mercaptan and 11- Mercaptoundecanoic acids are modified at golden surface, so as to which " Janus " structure be prepared
Soda acid responds the side modification polymethylacrylic acid of anisotropic infiltration asymmetrical siloxy nm cylinder array, i.e. silicon cylindrical-array
N, N- dimethylaminoethyl, and opposite side modification lauryl mercaptan and 11- Mercaptoundecanoic acids.
In step 4), method that we utilize atom transfer radical polymerization, by the polymethylacrylic acid N containing amino,
N- dimethylaminoethyl molecules connect skill on silicon nm cylinder array；In step 5), we, will using the method for tilting vapor deposition
Gold is deposited on the side of silicon cylindrical-array, then the method by self assembly, lauryl mercaptan and 11- mercaptos in the surface modification of gold
Base hendecanoic acid." Janus " substrate prepared by the present invention is non-same using nano-structure array both sides under soda acid incentive condition
When protonated/deprotonated behavior, so as to fulfill soda acid response anisotropic infiltration row.Realize induction strong acid and strong base
It is unidirectionally infiltrated along different directions, which can equally induce liquid of the acid-base value between 1 and 13 to be infiltrated from unidirectional,
The conversion unidirectionally infiltrated to anisotropic infiltration, isotropism infiltration, negative direction anisotropic infiltration, negative direction.Prepared
" Janus " substrate equally illustrates response infiltration behavior after being handled by soda acid, to water, and water can be in the unidirectional of both direction
It is mutually converted between infiltration.
In order to explain that the soda acid of " Janus " asymmetrical siloxy nm cylinder array responds anisotropic infiltration property, we
Silicon nm cylinder array obtained in step 3) is lain in a horizontal plane in vapor deposition instrument, is deposited in the whole surface of silicon nm cylinder
Metal；The gold that thickness is 15~30nm is then deposited in the chromium that vapor deposition last layer thickness is 2~5nm first again；By prepared by
Silicon chip be placed in the ethanol solution containing lauryl mercaptan and 11- Mercaptoundecanoic acids after 6~8h, ethyl alcohol rinses, and nitrogen blows
It is dry；The total concentration of lauryl mercaptan and 11- Mercaptoundecanoic acids is 0.05~0.2mM, lauryl mercaptan and 11- Mercaptoundecanoic acids
Molar concentration ratio be 0.25~4：1；After this step, lauryl mercaptan and 11- Mercaptoundecanoic acids will be modified entire
The surface of silicon nm cylinder array；Test the solution (pH=1,2,3,4,5,6,7,8,9,10,11,12,13) of different pH values
In foregoing silicon substrate piece, i.e. the whole surface modification lauryl mercaptan of silicon nm cylinder array and 11- Mercaptoundecanoic acids and step 4)
Wellability on surface.
The silicon chip used in step 1) is monocrystalline silicon substrate.
The evaporation rate of crome metal is 0.03~0.08nm min in step 4) and step 6)-1。
The evaporation rate of metallic gold is 0.08~0.13nm min in step 4) and step 6)-1。
Step of the present invention is simple, does not need to expensive instrument and equipment, using nano-structure array it is anisopleual modify
The non-concurrent protonated/deprotonated behavior that soda acid response function group is shown, realize the response of intelligent soda acid it is each to
Different in nature wellability surface.The class of liquids being not only directed on anisotropic infiltration surface has breakthrough (for special nature liquid
Body：Soda acid), the more mutual conversion between the unidirectional infiltration of different directions has full progress.
Description of the drawings
Fig. 1：The scanning electron microscope (SEM) photograph of " Janus " silicon nanostructure array of the embodiment of the present invention 5；
(a) schematic diagram based on prepared " Janus " silicon nm cylinder array of structures, the side modification of cylindrical-array
Polymethylacrylic acid N, N- dimethylaminoethyl, and opposite side modification lauryl mercaptan and 11- Mercaptoundecanoic acids；
(b) " Janus " silicon nanostructure array scanning Electronic Speculum vertical view, arrow represent the direction of gold evaporation, " crescent moon "
The shade of shape demonstrates the asymmetric nature of silicon chip；
(c) " Janus " silicon nm cylinder array of structures scanning electron microscope cross-sectional view.Pass through the section of " Janus " structure
Figure, it may be clearly seen that the asymmetry of nanostructured, the side of column array is covered by gold, and opposite side is without gold.In figure
MUA, DDT and PDMAEMA represent lauryl mercaptan, 11- Mercaptoundecanoic acids and polymethylacrylic acid N, N- dimethylamino respectively
Ethyl ester.
Fig. 2：Test surfaces are to the infiltration behavior figure of different pH values liquid；
Silicon substrate surface prepared in embodiment 5 is injected by concentrated hydrochloric acid and hydrogen-oxygen using the syringe for dripping form instrument
Change the solution (pH=0.98,1.99,3.99,7.04,9.99,12.00,13.05) for the different pH values that sodium is prepared, test table
Solution in the infiltration behavior of different pH values liquid, syringe is discharged with the speed of 1 μ L/s.Arrow is triple line
The infiltration direction of migratory direction, i.e. liquid.Corresponding embodiment 6.-CH3,-COOH and-N (CH3)2Respectively from lauryl mercaptan,
11- Mercaptoundecanoic acids and polymethylacrylic acid N, N- dimethylaminoethyl.
Fig. 3：The static infiltration behavior figure of the solution of different pH values；
(a) 3 μ L different pH values solution (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) in the silicon of whole surface modification polymethylacrylic acid N, N- dimethylaminoethyl 10min
Static infiltration behavior on nm cylinder；Corresponding embodiment 7；
(b) 3 μ L different pH values solution (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) the silicon nm cylinder of lauryl mercaptan and 11- Mercaptoundecanoic acids is modified in whole surface
On static infiltration behavior, the total concentration of lauryl mercaptan and 11- Mercaptoundecanoic acids is 0.1mM, lauryl mercaptan and 11- sulfydryls
The molar concentration ratio of hendecanoic acid is 0.45：0.55；It is corresponding
Embodiment 8；
(c) difference of static contact angle of the solution of different pH values on a) and b), passes through this difference, it is possible to
Experimental phenomena in explanation figure 2 and embodiment 5.Due to the non-concurrent protonated/deprotonated behavior in " Janus " both sides,
The both sides wellability of nanostructured can be made to generate difference.The protonated/deprotonated degree increase of strong acid and strong base, so as to increase
The infiltration sex differernce of both sides, results in and is unidirectionally infiltrated along different directions on " Janus " silicon chip in strong acid and strong base.With
The reduction of acid-base value, infiltration behavior can be converted from unidirectionally infiltrating to anisotropy, eventually become isotropism infiltration.
Fig. 4：Behavior phenogram is infiltrated to the dynamic of prepared sample surfaces deionized water using droplet morphology instrument, water is with 1
The speed discharge of μ L/s.
(a) " Janus " silicon chip prepared in embodiment 5 is immersed in 2s in the hydrochloric acid solution that pH is 0.98, uses second
Alcohol rinses nitrogen drying；
(b) the dynamic infiltration behavior on " Janus " silicon chip that directly test water is prepared in embodiment 5；
(c) " Janus " silicon chip prepared in embodiment 5 is immersed in 2s in the sodium hydroxide solution that pH is 13.05, ethyl alcohol
It rinses, when nitrogen dries up.Infiltration direction of the arrow for the migratory direction, i.e. water of triple line；
(d) the dynamic infiltration behavior of rear water per treatment is tested in continuous soda acid processing." Janus " silicon chip presents non-
Often good reversible transition behavior, i.e., water is along the direction for modifying polymethylacrylic acid N, N- dimethylaminoethyl after acid is handled
Unidirectional to infiltrate, water is unidirectionally infiltrated along the direction of modification lauryl mercaptan and 11- Mercaptoundecanoic acids after alkali process.
Specific embodiment
Embodiment 1：The cleaning of silicon chip and hydrophilicity-imparting treatment
Monocrystalline silicon substrate (100) is cut out with glass cutter to the square that size is length of side 2cm, respectively with acetone, ethyl alcohol with
And after deionized water ultrasound 5min, it is placed in the mixing that mass fraction is 98% concentrated sulfuric acid and mass fraction is 30% hydrogen peroxide
Solution (volume ratio 7:3) processing 40min is boiled in heating in, makes surface hydrophilic；Then mixed solution is poured into waste liquid bottle,
Hydrophilic silicon chip with deionized water is washed 3 times repeatedly, is preserved for use in deionized water.
Embodiment 2：The preparation of hydrophobic PS microballoons
Measure 5mL, concentration 10wt% PS microballoons (1 μm of diameter) alcohol dispersion liquid, be with ethyl alcohol and water volume ratio
1：1 mixed solution carries out 10 eccentric cleanings so as to which the surfactant in stoste be removed, and is finally dispersed in ethyl alcohol and water
Volume ratio is 1：In 1 solution, a concentration of 5wt%.
Embodiment 3：Colloid monolayer microballoon is deposited on silicon chip
By the water of PS microballoons and ethyl alcohol (volume ratio 1 that mass fraction in embodiment 2 is 5%:1) mixed liquor is in 100% work(
Ultrasound 80min (temperature is 20 DEG C) under rate (power 100W), then with syringe pump with 1.6 μ L min-1Speed mixed liquor is injected
Into the culture dish equipped with deionized water, gone by the lauryl sodium sulfate aqueous solution that a concentration of 2 wt% of 150 μ L are added dropwise
Ion water surface obtains the compact arranged PS microballoons of individual layer；Silicon chip in embodiment 1 is extend into the water surface hereinafter, from individual layer
Slowly vertically lift upwards below microballoon, slant setting is finished in filter paper up to moisture evaporation, so as to obtain list on a silicon substrate
The closelypacked PS micro-sphere arrays of layer.
Embodiment 4：The preparation of silicon nm cylinder array
Individual layer PS micro-sphere arrays closelypacked on the silicon chip obtained in embodiment 3 are placed in plasma etching machine
In, with oxygen gas plasma etching 12.5min (etching air pressure be 10mTorr, 10 DEG C, gas flow rate 50sccm of etching temperature,
It is 100W, ICP 0W that etching power, which is RF)；And then it is carved using the PS microballoons of the not close accumulation of individual layer as version, selectivity is covered
Silicon chip is lost, uses SF6/CHF33.5 min of plasma etching (etching air pressure be 5mTorr, 10 DEG C of etching temperature, SF6Gas stream
Fast 4sccm, CHF3Gas flow rate 30sccm, it is 50W, ICP 100W that etching power, which is RF)；Silicon chip after etching is placed in
Ultrasound 2min in toluene, nitrogen dries up after ethyl alcohol rinses, and so as to remove the PS microballoons of surface residual, obtains silicon nm cylinder battle array
Row.Obtained body diameter 700nm is highly 380nm.
Embodiment 5：The preparation of " Janus " silicon nm cylinder array
1) silicon nm cylinder array obtained in embodiment 4 is placed in oxygen gas plasma cleaning machine and cleans 5 min, put
Enter in the drier equipped with small measuring cup, γ-aminopropyl triethoxysilane of 20 μ L is added in measuring cup, by drier
It is put into 60 DEG C of baking ovens and heats 2h.After this step, silicon nm cylinder array is just successfully modified by amino.It will be amido modified
Silicon nm cylinder array be put into another measuring cup, and sequentially add dichloromethane 10mL, 140 μ L of triethylamine, at -4 DEG C
After lower placement 10min, alpha-brominated 100 μ L of isopropyl acylbromide are added in, are placed in silicon chip under room temperature instead after placing 2h at -4 DEG C
It answers 18 hours, is cleaned 3 times with dichloromethane and ethyl alcohol respectively after taking out silicon chip, dried up with nitrogen for use.In three-neck flask
Sequentially add water 2mL, methanol 2mL, methacrylic acid N, N- dimethylaminoethyl 4mL, 1,1,4,7,10,10- hexamethyl three
100 μ L of ethylene tetra, copper bromide 8mg lead to nitrogen 30min after ultrasound dissolving in 5 minutes, add in stannous chloride 25mg, will be aforementioned
10min is reacted respectively in obtained silicon chip merging solution, is cleaned 3 times with second alcohol and water respectively after taking-up, nitrogen drying.Through
After crossing this step, the surface of silicon nm cylinder array is by polymethylacrylic acid N, the modification of N- dimethylaminoethyls.
2) by obtained surface by polymethylacrylic acid N, the silicon chip of N- dimethylaminoethyls modification tilts 45 degree and puts
It puts in instrument is deposited.The chromium for being first 3nm in the side of silicon nm cylinder array vapor deposition last layer thickness, is then deposited again
Thickness is the gold of 20nm；Prepared silicon chip is placed in the ethanol solution containing lauryl mercaptan and 11- Mercaptoundecanoic acids
After 8h, ethyl alcohol rinses, nitrogen drying.The total concentration of lauryl mercaptan and 11- Mercaptoundecanoic acids be 0.1mM, lauryl mercaptan and
The molar concentration ratio of 11- Mercaptoundecanoic acids is 0.45:0.55.
Embodiment 6：A kind of " Janus " silicon chip that soda acid is induced unidirectionally to be infiltrated along different directions
The dynamic infiltration behavior of prepared sample surfaces is characterized using droplet morphology instrument.The note of droplet morphology instrument
The different pH values that emitter is prepared silicon substrate surface injection prepared in embodiment 5 by concentrated hydrochloric acid and sodium hydroxide it is molten
Liquid (pH=0.98,1.99,3.99,7.04,9.99,12.00,13.05), the solution in syringe are arranged with the speed of 1 μ L/s
Go out, strong acid (pH=0.98) can be along the direction of modification polymethylacrylic acid N, N- dimethylaminoethyl after silicon chip is contacted
Unidirectional infiltration；With the increase of pH value of solution, infiltration behavior can from unidirectionally infiltrate become anisotropic infiltration (pH=1.99, along
Modify polymethylacrylic acid N, N- dimethylaminoethyl direction)；With further increasing for pH value of solution, infiltration behavior can be by original
The anisotropic infiltration come is changed into isotropism infiltration (pH=3.99,7.04,9.99)；When the pH value of solution reaches 12,
Silicon chip can induce the liquid to be infiltrated along the direction anisotropic of gold evaporation；And highly basic (pH=13.05) is in contact silicon substrate
It can unidirectionally be infiltrated along the direction of gold evaporation after piece.Due to silicon chip soda acid respond different directions, we term it
" Janus " silicon chip.
Embodiment 7：The preparation of the silicon nanostructure array of polymethylacrylic acid N, N- dimethylaminoethyl modification
In order to explain that the soda acid of " Janus " silicon chip responds anisotropic infiltration property, the step 1) of embodiment 5 is repeated
Part obtains the identical silicon chip in step 1) part with embodiment 5, i.e. polymethylacrylic acid N, N- dimethylamino second
The silicon nanostructure array of ester modification, modification time are 10min.Using droplet morphology instrument to the static state of prepared sample surfaces
Wettability is characterized.Test solution is the solution (pH=of the different pH values by concentrated hydrochloric acid and sodium hydroxide preparation
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), amount of liquid is 3 μ
L.The good pH responses wellability of silicon nanostructure array display of polymethylacrylic acid N, N- dimethylaminoethyl modification
Matter, the silicon chip can realize the mutual conversion of close acid and thin alkali.This is because in acid condition, polymethylacrylic acid N,
N- dimethylaminoethyls protonate, positively charged, become more lyophily, and under alkaline condition, deprotonation occurs, no
Electrification becomes opposite lyophoby.
Embodiment 8：The preparation of lauryl mercaptan and the silicon nm cylinder array of 11- Mercaptoundecanoic acids mixing modification
For the purposes of explaining that the soda acid of " Janus " silicon chip responds anisotropic infiltration property, will be made in embodiment 4
Silicon nm cylinder array lie in a horizontal plane in vapor deposition instrument, the chromium that last layer thickness is 3nm is deposited first, is then deposited again
Thickness is the gold of 20nm；Prepared silicon chip is placed in the ethanol solution containing lauryl mercaptan and 11- Mercaptoundecanoic acids
After 8h, ethyl alcohol rinses, nitrogen drying.The total concentration of lauryl mercaptan and 11- Mercaptoundecanoic acids be 0.1mM, lauryl mercaptan and
The molar concentration rate of 11- Mercaptoundecanoic acids is 0.45：0.55.Repeat the testing procedure of embodiment 7.Lauryl mercaptan and 11- mercaptos
Base hendecanoic acid mixes the good pH responses Wettability of the silicon nm cylinder array display of modification, which can be real
Now with polymethylacrylic acid N, the opposite close alkali of N- dimethylaminoethyls modification silicon chip (embodiment 7) result and the phase for dredging acid
Mutually conversion.This is because under alkaline condition, deprotonation occurs for 11- mercapto-undecanoics acid molecule, negatively charged, becomes more
Lyophily, and in acid condition, it protonates, it is not charged, become opposite lyophoby.
Embodiment 9：A kind of " Janus " silicon chip for changing induction water flowing behavior by acid-base value
The dynamic infiltration behavior of prepared sample surfaces is characterized using droplet morphology instrument.It will be prepared in embodiment 7
Sample be immersed in pH be 0.98 hydrochloric acid solution in 2s, with ethyl alcohol rinse nitrogen dry up.Use the syringe of droplet morphology instrument
To prepared silicon substrate surface injection deionized water, the water in syringe is discharged with the speed of 1 μ L/s, and water is in contact silicon substrate
It can unidirectionally be infiltrated along the direction of modification polymethylacrylic acid N, N- dimethylaminoethyl after piece；It is immersed in when by this silicon chip
2s in the sodium hydroxide solution that pH is 13.05, ethyl alcohol rinse, and when nitrogen dries up, silicon chip at this time can induce water along modification
Polymethylacrylic acid N, N- dimethylaminoethyl opposite direction, i.e., unidirectionally infiltrate along the direction of gold evaporation.This phenomenon is similary
It is attributed to the non-concurrent protonated/deprotonated behavior in " Janus " both sides.
Claims (6)
1. a kind of preparation method of the anisotropic infiltration asymmetrical siloxy nm cylinder array of soda acid response, its step are as follows：
1) surface treatment of silicon chip：Silicon chip is sequentially placed and is cleaned by ultrasonic 5 in acetone, absolute ethyl alcohol and deionized water
~15min；Then the silicon chip after ultrasonic cleaning is placed in acidic oxidation treatment fluid and boils 30~50min of processing, finally spent
Ionized water is cleaned to no acid solution and is remained, and is stored in deionized water for use；
2) a diameter of 1~3 μm of polystyrene microsphere of surface-hydrophobicized processing is dispersed in 5~10mL, volume ratio 1：1
Water is in absolute ethyl alcohol mixed solution, obtaining the polystyrene microsphere dispersion liquid of a concentration of 5~10wt%；By polystyrene microsphere
Dispersion liquid 60~80min of ultrasound under the conditions of 15~25 DEG C, 90~110W of power, then with 1~4 μ L min-1Speed injection
Pump is pushed through in the culture dish equipped with deionized water；Then along culture dish side wall be added dropwise 100~200 μ L, it is a concentration of 2~
The aqueous surfactant solution of 5wt% makes PS microballoons closely be piled into individual layer；The silicon chip obtained in step 1) is extend into
Hereinafter, slowly vertically lifting upwards below individual layer microballoon, slant setting finishes the water surface in filter paper up to moisture evaporation, thus
The closelypacked PS micro-sphere arrays of six side of individual layer are obtained on silicon chip；
3) silicon chip obtained in step 2) oxygen gas plasma is etched into 1~20min, polystyrene microsphere array after etching
Become the not close accumulation of six sides from six original sides are tightly packed, i.e. the diameter of microballoon reduces, spacing increase；Then it is non-with individual layer
Closelypacked polystyrene microsphere uses SF to cover version6/CHF30.5~10min of plasma etching silicon chip；After etching
Silicon chip is placed in 1~5min of ultrasound in toluene, and nitrogen dries up after ethyl alcohol rinses, so as to remove the polyphenyl second of silicon substrate surface remnants
Alkene microballoon, obtains silicon nm cylinder array, and obtained 100~900nm of body diameter is highly 50~1000nm；
4) silicon nm cylinder array obtained in step 3) is cleaned into 5~10min with oxygen gas plasma, be then placed in equipped with small
In the drier of measuring cup, γ-aminopropyl triethoxysilane of 20~30 μ L is added in small measuring cup, drier is existed
The amination modification that 2~4h carries out silicon nm cylinder array is heated at 60~80 DEG C；By amido modified silicon nm cylinder array
It is put into another measuring cup, and sequentially adds 5~15mL of dichloromethane, 100~200 μ L of triethylamine place 10 at -4 DEG C
After~20min, alpha-brominated 50~150 μ L of isopropyl acylbromide are added, after placing 2~5h at -4 DEG C, measuring cup is placed in often
Temperature 15~18h of lower reaction, is cleaned 2~4 times respectively with dichloromethane and ethyl alcohol after taking out silicon chip, is dried up with nitrogen；In three necks
2~3mL of water, 2~3mL of methanol, 2~6mL of methacrylic N, N-dimethylamino ethyl ester, 1,1,4,7 are sequentially added in flask,
10,10- hexamethyl trien, 50~100 μ L, 6~10mg of copper bromide, ultrasound 5~10 minutes dissolving after lead to nitrogen 20~
60min adds 15~30mg of stannous chloride, then by aforementioned obtained silicon chip be placed in the solution reaction 0.5~
40min is cleaned 2~4 times after taking-up with second alcohol and water respectively, nitrogen drying, so as to which the surface for making silicon nm cylinder array is gathered
Methacrylic acid N, N- dimethylaminoethyl are modified；
5) silicon chip obtained in step 4) is tilted 30~60 degree to be placed in vapor deposition instrument, in this way during vapor deposition, gold
Belonging to only can be vaporized on silicon nm cylinder array towards the side of evaporation source；The chromium that vapor deposition last layer thickness is 2~5nm first, with
The gold that thickness is 15~30nm is deposited again afterwards；Prepared silicon chip is placed in containing lauryl mercaptan and 11- mercapto-undecanoics
In the ethanol solution of acid after 6~8h, ethyl alcohol rinses, nitrogen drying；The total concentration of lauryl mercaptan and 11- Mercaptoundecanoic acids is
The molar concentration ratio of 0.05~0.2mM, lauryl mercaptan and 11- Mercaptoundecanoic acids is 0.25~4：1；After this step,
Lauryl mercaptan and 11- Mercaptoundecanoic acids are modified at the surface of gold, so as to which the anisotropic infiltration of soda acid response be prepared
Asymmetrical siloxy nm cylinder array.
2. a kind of preparation side of the anisotropic infiltration asymmetrical siloxy nm cylinder array of soda acid response as described in claim 1
Method, it is characterised in that：The acidic oxidation treatment fluid that step 1) uses is the hydrogen peroxide and mass fraction of mass fraction 30%
The mixed solution of 98% concentrated sulfuric acid, the two volume ratio are 3：7.
3. a kind of preparation side of the anisotropic infiltration asymmetrical siloxy nm cylinder array of soda acid response as described in claim 1
Method, it is characterised in that：The silicon chip used in step 1) is monocrystalline silicon substrate.
4. a kind of preparation side of the anisotropic infiltration asymmetrical siloxy nm cylinder array of soda acid response as described in claim 1
Method, it is characterised in that：The surfactant used in step 2) is lauryl sodium sulfate.
5. a kind of preparation side of the anisotropic infiltration asymmetrical siloxy nm cylinder array of soda acid response as described in claim 1
Method, it is characterised in that：The etching air pressure etched in step 3) with oxygen gas plasma is 5~20mTorr, etching temperature 10~20
DEG C, silicon chip 10~50sccm of gas flow rate is etched, etching power is that RF is 0~400W, and ICP is 0~400W；SF6/CHF3Deng
The etching air pressure of plasma etching be 5~20mTorr, 10~20 DEG C of etching temperature, SF6Gas flow rate 0~20sccm, CHF3Gas
Body 5~40sccm of flow velocity, etching power are that RF is 0~400W, and ICP is 0~400W.
6. a kind of preparation side of the anisotropic infiltration asymmetrical siloxy nm cylinder array of soda acid response as described in claim 1
Method, it is characterised in that：The evaporation rate of crome metal is 0.03~0.08nm min in step 4)-1, the evaporation rate of metallic gold is
0.08~0.13nm min-1。
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