CN114538413A - 一种大面积纳米线阵列膜及其制备方法 - Google Patents
一种大面积纳米线阵列膜及其制备方法 Download PDFInfo
- Publication number
- CN114538413A CN114538413A CN202210187658.2A CN202210187658A CN114538413A CN 114538413 A CN114538413 A CN 114538413A CN 202210187658 A CN202210187658 A CN 202210187658A CN 114538413 A CN114538413 A CN 114538413A
- Authority
- CN
- China
- Prior art keywords
- sheet
- zirconium
- array film
- titanium
- pretreated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002070 nanowire Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 42
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 17
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 16
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 16
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 11
- 239000000956 alloy Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 238000005530 etching Methods 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 239000000945 filler Substances 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 29
- 239000010936 titanium Substances 0.000 claims description 28
- 229910052719 titanium Inorganic materials 0.000 claims description 27
- 239000002071 nanotube Substances 0.000 claims description 26
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 25
- 229910052782 aluminium Inorganic materials 0.000 claims description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- 229910052726 zirconium Inorganic materials 0.000 claims description 23
- 239000003792 electrolyte Substances 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 15
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- 230000004888 barrier function Effects 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910018503 SF6 Inorganic materials 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 238000003754 machining Methods 0.000 claims description 5
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 claims description 5
- 229960000909 sulfur hexafluoride Drugs 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 238000003980 solgel method Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 239000011889 copper foil Substances 0.000 claims description 2
- 238000004070 electrodeposition Methods 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 2
- NJTGANWAUPEOAX-UHFFFAOYSA-N molport-023-220-454 Chemical compound OCC(O)CO.OCC(O)CO NJTGANWAUPEOAX-UHFFFAOYSA-N 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 238000007740 vapor deposition Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 5
- 238000001020 plasma etching Methods 0.000 abstract description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 4
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910010342 TiF4 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910007998 ZrF4 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical group 0.000 description 1
- -1 fluorine ions Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/02—Oxides
- C01G21/08—Lead dioxide [PbO2]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/42—Preparation of aluminium oxide or hydroxide from metallic aluminium, e.g. by oxidation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- 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
- C23C14/0005—Separation of the coating from the substrate
-
- 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
- C23C14/0605—Carbon
-
- 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
- C23C14/08—Oxides
-
- 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
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
-
- 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
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/01—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes on temporary substrates, e.g. substrates subsequently removed by etching
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- Thermal Sciences (AREA)
- Geology (AREA)
- Electrochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Ceramic Engineering (AREA)
- Composite Materials (AREA)
- Dispersion Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
本发明属于纳米线技术领域，具体涉及一种大面积纳米线阵列膜及其制备方法。本发明在模板法的基础上，通过氟化物等离子体刻蚀三氧化二铝、二氧化钛或二氧化锆等氧化物管膜，裸露出其中的沉积碳、金属、合金、氧化物等填充物，从而得到大面积纳米线阵列膜，而刻蚀三氧化二铝、二氧化钛或二氧化锆等氧化物管膜的副产物氟化物则升华脱离体系。该方法易于控制等离子体刻蚀的进程，副产物易分离，降低了制备难度。
Description
技术领域
本发明属于纳米线技术领域，具体涉及一种大面积纳米线阵列膜及其制备方法。
背景技术
纳米线阵列是由大量相互独立并垂直于基层的纳米线组成的有序整体，其中不仅保留了单根纳米线结构及功能，而且还具有大规模协同效应。纳米线阵列由于具有大比表面积，晶体取向稳定的特点而表现出极高的表面活性，提高了活性材料的利用率。此外，纳米线阵列结构还可以减轻电化学过程中体积变化引起的应力，因此在物理和化学领域有广阔的应用前景。
在众多制备纳米线阵列的方法中，模板法具有可控性高、制备过程简便、可大规模生产的优点而具有广阔的应用前景。然而，由于模板法制备的模板通常为氧化物膜，为获得纳米线阵列必须溶掉其氧化物膜，通常选择磷酸、氢氧化钠等溶液。但是溶解模板的过程是不稳定的，比如无法确定有效的溶解温度和溶解时间、无法完全去除模板、溶解得到的纳米线无法保持阵列结构等等。
目前，模板法制备的纳米线阵列过程如下。首先制备出纳米管阵列膜，再将含有基底的纳米管阵列膜放入溶液中，用水热法、溶胶-凝胶法填充金属、合金、氧化物等，然后在膜一侧沉积一层支撑物，最后用磷酸、氢氧化钠等溶液溶解模板得到纳米线阵列。但是，该方法存在诸多问题，如支撑物无法支撑纳米线得到阵列、模板的溶解难以掌控和操作不够安全等。
近年来，等离子清洗技术逐渐成熟，等离子体和固体、液体或气体一样，是物质的一种状态，也叫做物质的第四态。等离子清洗技术常用气氛有四氟化碳、三氟化氮、六氟化硫等氟化物气体。氟化物气体在真空腔体里，通过射频电源在一定的电压情况下起辉产生高能量的无序的等离子体，可通过等离子体轰击三氧化二铝、二氧化钛等氧化物膜，产生三氟化铝、四氟化钛等，其中三氟化铝遇强热易升华、四氟化钛本身具有284℃的低沸点，高能环境中两者易升华，从而达到去除氧化物膜的要求。
发明内容
为解决现有技术的不足，本发明提供了一种大面积纳米线阵列膜及其制备方法。本发明在模板法的基础上，通过氟化物等离子体刻蚀三氧化二铝、二氧化钛或二氧化锆等氧化物纳米管膜，裸露出其中的沉积碳、金属、合金、氧化物等填充物，从而得到大面积纳米线阵列膜，而刻蚀副产物氟化物则升华脱离体系。该方法易于控制等离子体刻的进程，副产物易分离，降低了制备难度。
本发明所提供的技术方案如下：
一种大面积纳米线阵列膜的制备方法，该方法包括以下步骤：
步骤一、对经预处理的纯铝片、钛片或锆片进行阳极氧化，其包括以下步骤：
1)预处理纯铝片、钛片或锆片：
采用机械加工方式去除待处理纯钛片表面的氧化层，所述纯铝片、钛片或锆片为一平整且厚度为0.1～1mm的片材；
2)配制电解液：
分别配置0.2-0.5M草酸水溶液、0.25-1wt.％的NH4F的乙二醇溶液和0.5-2wt.％的NH4F甘油-丙三醇溶液，分别用于纯铝片、钛片或锆片的阳极氧化的电解液；
3)将经预处理的纯铝片、钛片、锆片置于所述电解液中进行阳极氧化反应后，制得三氧化二铝、二氧化钛或二氧化锆纳米管阵列膜的一级初步产品：
以经预处理的纯铝片、钛片或锆片作为阳极，不锈钢箔电极或铜箔或钛箔或铂箔或石墨电极作为阴极，且分别利用电压为10-50V、20-110V、20-80V的直流电源对预处理的纯铝片、钛片、锆片进行阳极氧化，氧化温度为0～30℃，氧化时间为1～168h；
步骤二、将所述一级初步产品从所述电解液中立即取出且用去离子水清洗后，放入液溴的甲醇溶液中，液溴与甲醇的体积比为1:1-1:9，常温下反应12-96h，溶解去除铝、钛、锆金属基体，获得三氧化二铝、二氧化钛或二氧化锆纳米管阵列膜；
步骤三、将得到的二级初步产品用无水乙醇清洗干净后，放入临界CO2气氛干燥箱中进行干燥，获得底部带有阻挡层的三级初步产品；
步骤四、采用物理或化学方法向三氧化二铝、二氧化钛或二氧化锆纳米管阵列膜中沉积碳、金属、合金或氧化物填充物，获得管中有沉积填充物的纳米管阵列膜四级初步产品；
步骤五、将所述四级初步产品底部一面朝上放入含有氟化物气体的等离子体清洗仪中进行模板的刻蚀，功率1-50kW，放置时间为2h-24h，反应后既得所述大面积纳米线阵列膜。
上述技术方案在对三氧化二铝、二氧化钛或二氧化锆纳米管阵列膜进行沉积碳、金属、合金、氧化物等填充物后，采用氟化物气体进行等离子体刻蚀模板，该刻蚀方法进程易于控制，副产物易分离，降低了制备难度。
具体的，纯铝片、钛片或锆片的纯度大于99.9％，形状为长方形或圆形。
具体的，碳、金属、合金、氧化物中金属元素为镁、铟、锡、铅、砷、锑或铋中的一种或几种。
具体的，步骤4)中所述的用物理或化学方法为原子层气相沉积法、磁控溅射法、溶胶凝胶法、电沉积法、物理液压法中的一种。沉积后可以采用物理方法清除多余的沉积物，例如物理剥离、超声清洗、胶粘去除等方式或各方式的组合。
具体的，步骤4)中所述的氟化物气体为四氟化碳、三氟化氮、六氟化硫中的任一种或多种混合而成的混合气体。
具体的，步骤5)中所述的成品的面积为1-100cm2。
本发明还提供了上述制备方法制备得到的大面积纳米线阵列膜。
制得的成品可作为传感、光电转换或传导材料。
本发明通过氟化物气体的等离子体清洗的简单方法实现了对三氧化二铝、二氧化钛或二氧化锆模板的刻蚀。在氟化物气体的等离子体刻蚀中，因为氟离子的存在，氟离子会和Al3+、Ti4+、Zr4+生成易于气化的AlF3、TiF4、ZrF4等物质，进而三氧化二铝、二氧化钛或二氧化锆阵列膜底部的阻挡层被去除，形成纳米线阵列膜结构。该方法制备过程简单，制备参数容易控制，对模板的刻蚀效果好，从而降低了获得大面积纳米线阵列膜的制备难度。
附图说明
图1是本发明实施例1所得到的In0.9Sn0.1纳米线阵列膜的扫描电镜图。
图2是本发明实施例2所得到的C纳米线阵列膜的扫描电镜图。
图3是本发明实施例3所得到的PbO2纳米线阵列膜的扫描电镜图。
具体实施方式
以下对本发明的原理和特征进行描述，所举实施例只用于解释本发明，并非用于限定本发明的范围。
实施例1
将长为5cm的正方形铝片(纯度大于等于99.9％，厚度为0.2mm)采用常规机械加工方式去除表面的氧化层。电解液由草酸、水配制而成，草酸的含量为0.3M。将处理好的铝片放入反应装置，暴露在电解液中的铝片直径为4cm。使用冰箱将电解液温度固定在5℃，使用铂箔作为阴极，在阳极电压为40V条件下阳极氧化2小时，得到平均孔径60nm的纳米管阵列膜。反应结束从电解液中立即取出样品且用去离子水清洗后，放入液溴的甲醇溶液中，液溴与甲醇的体积比为1:5，常温下反应12h，去除铝基底。从液溴的甲醇溶液中取出样品后，用无水乙醇清洗干净，放入临界CO2气氛干燥箱中进行干燥，获得底部带有阻挡层的三氧化二铝纳米管阵列膜。
采用物理液压法制备的In0.9Sn0.1纳米线阵列，具体步骤为：将先前制备的三氧化二铝纳米管阵列膜正面朝上放在真空液压装置中，再将熔炼好的In0.9Sn0.1压成片状放置在阵列膜上方。打开真空泵，将装置温度升至170℃，略高于合金熔点，保持10分钟，合金熔化并散布在阵列膜表面，然后施加一个液压力，将合金注入纳米管阵列膜中。将至室温后剥离剩余的In0.9Sn0.1片,再超声清洗16h。
将膜的底部朝上放入含有六氟化硫等离子体清洗仪中进行模板的刻蚀，功率40kW，放置时间为24h，反应后既得In0.9Sn0.1纳米线阵列膜，结构如图1所示。
实施例2
将直径为2cm的圆形钛片(纯度大于等于99.9％，厚度为0.2mm)采用常规机械加工方式去除表面的氧化层。电解液由NH4F、乙二醇配制而成，NH4F的含量为0.5wt.％。将处理好的钛片放入反应装置，暴露在电解液中的钛片直径为1cm。使用冰箱将电解液温度固定在5℃，使用石墨电极作为阴极，在阳极电压为60V条件下阳极氧化12小时，得到平均孔径为80nm的纳米管阵列膜。反应结束从电解液中立即取出样品且用去离子水清洗后，放入液溴的甲醇溶液中，液溴与甲醇的体积比为1:5，常温下反应24h，去除钛基底。从液溴的甲醇溶液中取出样品后，用无水乙醇清洗干净，放入临界CO2气氛干燥箱中进行干燥，获得底部带有阻挡层的二氧化钛纳米管阵列膜。
采用化学气相沉积法制备的C纳米线，具体步骤为：将二氧化钛纳米管阵列膜置于管式炉中，空气条件下，从室温以2℃/min升至设定温度450℃，然后保温3h，再以2℃/min降至室温。将晶化的二氧化钛纳米管样品和一定含量的尿素和聚乙烯醇放入石墨槽中，抽真空，在氮气的氛围中，从室温以1℃/min升至设定温度600℃，然后保温3h，再以1℃/min降至室温，得到填充碳纳米线的二氧化钛纳米管阵列膜。然后超声清洗24h。
将膜的底部朝上放入含有六氟化硫等离子体清洗仪中进行模板的刻蚀，功率50kW，放置时间为16h，反应后既得C纳米线阵列膜，结构如图2所示。
实施例3
将长为4cm的正方形锆片(纯度大于等于99.9％，厚度为0.3mm)采用常规机械加工方式去除表面的氧化层。电解液由NH4F、甘油、丙三醇配制而成，甘油和丙三醇1：1混合，NH4F的含量为1wt.％。将处理好的锆片放入反应装置，暴露在电解液中的钛片直径为3cm。室温下，使用石墨电极作为阴极，在阳极电压为50V条件下阳极氧化3小时，得到平均孔径为100nm的纳米管阵列膜。反应结束从电解液中立即取出样品且用去离子水清洗后，放入液溴的甲醇溶液中，液溴与甲醇的体积比为1:6，常温下反应36h，去除锆基底。从液溴的甲醇溶液中取出样品后，用无水乙醇清洗干净，放入临界CO2气氛干燥箱中进行干燥，获得底部带有阻挡层的二氧化锆纳米管阵列膜。
采用溶胶凝胶法沉积PbO2纳米线，具体步骤为：取0.005mol硝酸铅,经磁力搅拌将其溶于10ml去离子水中,形成溶液A；称取0.005mol柠檬酸,经磁力搅拌将其溶于10ml的去离子水中，形成溶液B；将溶液B缓慢滴加到溶液A中,形成混合溶液。该溶液在60℃条件下磁力搅拌1h，用氨水调节pH至5～6之间；继续加热蒸发溶液中的水分,待溶液变成水溶胶时,将清洗和干燥过的二氧化锆纳米管阵列膜浸入其中,并在60℃水浴条件下保温2h。取出二氧化锆纳米管阵列膜,擦去表面的溶胶,在80℃下干燥1h后,放入马弗炉中升温到800℃退火2h。得到PbO2纳米线沉积的二氧化锆纳米管阵列膜。然后超声清洗24h。
将膜的底部朝上放入含有四氟化碳等离子体清洗仪中进行模板的刻蚀，功率45kW，放置时间为18h，反应后既得PbO2纳米线阵列膜，结构如图3所示。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (7)
1.一种大面积纳米线阵列膜的制备方法，其特征在于，该方法包括以下步骤：
步骤一、对经预处理的纯铝片、钛片或锆片进行阳极氧化，其包括以下步骤：
1)预处理纯铝片、钛片或锆片：
采用机械加工方式去除待处理纯钛片表面的氧化层，所述纯铝片、钛片或锆片为一平整且厚度为0.1～1mm的片材；
2)配制电解液：
分别配置0.2-0.5M草酸水溶液、0.25-1wt.％的NH4F的乙二醇溶液和0.5-2wt.％的NH4F甘油-丙三醇溶液，分别用于纯铝片、钛片或锆片的阳极氧化的电解液；
3)将经预处理的纯铝片、钛片或锆片置于所述电解液中进行阳极氧化反应后，制得三氧化二铝、二氧化钛或二氧化锆纳米管阵列膜的一级初步产品：
以经预处理的纯铝片、钛片或锆片作为阳极，不锈钢箔电极或铜箔或钛箔或铂箔或石墨电极作为阴极，且分别利用电压为10-50V、20-110V、20-80V的直流电源对预处理的纯铝片、钛片或锆片进行阳极氧化，氧化温度为0～30℃，氧化时间为1～168h；
步骤二、将所述一级初步产品从所述电解液中立即取出且用去离子水清洗后，放入液溴的甲醇溶液中，液溴与甲醇的体积比为1:1-1:9，常温下反应12-96h，溶解去除铝、钛、锆金属基体，获得三氧化二铝、二氧化钛或二氧化锆纳米管阵列膜；
步骤三、将得到的二级初步产品用无水乙醇清洗干净后，放入临界CO2气氛干燥箱中进行干燥，获得底部带有阻挡层的三级初步产品；
步骤四、采用物理或化学方法向三氧化二铝、二氧化钛或二氧化锆纳米管阵列膜中沉积碳、金属、合金或氧化物填充物，获得管中有沉积填充物的纳米管阵列膜四级初步产品；
步骤五、将所述四级初步产品底部一面朝上放入含有氟化物气体的等离子体清洗仪中进行模板的刻蚀，功率1-50kW，放置时间为2h-24h，反应后既得所述的大面积纳米线阵列膜。
2.按照权利要求1所述的一种大面积纳米线阵列膜的制备方法，其特征在于：纯铝片、钛片或锆片的纯度大于99.9％，形状为长方形或圆形。
3.按照权利要求1所述的一种大面积纳米线阵列膜的制备方法，其特征在于：碳、金属、合金或氧化物中金属元素为镁、铟、锡、铅、砷、锑或铋中的一种或几种。
4.按照权利要求1所述的一种大面积纳米线阵列膜的制备方法，其特征在于：步骤4)中所述的用物理或化学方法为原子层气相沉积法、磁控溅射法、溶胶凝胶法、电沉积法、物理液压法中的一种。
5.按照权利要求1所述的一种大面积纳米线阵列膜的制备方法，其特征在于：步骤4)中所述的氟化物气体为四氟化碳、三氟化氮或六氟化硫中的任一种或多种混合而成的混合气体。
6.按照权利要求1所述的一种大面积纳米线阵列膜的制备方法，其特征在于：步骤5)中所述的成品的面积为1-100cm2。
7.一种按照权利要求1至6任一所述的制备方法制备得到的大面积纳米线阵列膜。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2021113762395 | 2021-11-19 | ||
| CN202111376239 | 2021-11-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114538413A true CN114538413A (zh) | 2022-05-27 |
Family
ID=81678877
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210187658.2A Pending CN114538413A (zh) | 2021-11-19 | 2022-02-28 | 一种大面积纳米线阵列膜及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114538413A (zh) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050224360A1 (en) * | 2004-04-02 | 2005-10-13 | The Penn Research Foundation | Titania nanotube arrays for use as sensors and method of producing |
| CN101550581A (zh) * | 2009-04-03 | 2009-10-07 | 西北有色金属研究院 | 一种双通大面积TiO2纳米管阵列膜的制备方法 |
| CN101591001A (zh) * | 2009-06-29 | 2009-12-02 | 西北有色金属研究院 | 一种Pd掺杂TiO2纳米管阵列复合材料的制备方法 |
| CN101768771A (zh) * | 2008-12-31 | 2010-07-07 | 北京大学 | 圆柱形和圆筒形二氧化钛纳米管阵列及其制备方法与应用 |
| CN105668540A (zh) * | 2014-11-19 | 2016-06-15 | 清华大学 | 一种纳米线阵列的制备方法 |
| CN112331845A (zh) * | 2020-09-21 | 2021-02-05 | 昆明理工大学 | 一种四氧化三钴纳米线阵列负极材料的制备方法 |
-
2022
- 2022-02-28 CN CN202210187658.2A patent/CN114538413A/zh active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050224360A1 (en) * | 2004-04-02 | 2005-10-13 | The Penn Research Foundation | Titania nanotube arrays for use as sensors and method of producing |
| CN101768771A (zh) * | 2008-12-31 | 2010-07-07 | 北京大学 | 圆柱形和圆筒形二氧化钛纳米管阵列及其制备方法与应用 |
| CN101550581A (zh) * | 2009-04-03 | 2009-10-07 | 西北有色金属研究院 | 一种双通大面积TiO2纳米管阵列膜的制备方法 |
| CN101591001A (zh) * | 2009-06-29 | 2009-12-02 | 西北有色金属研究院 | 一种Pd掺杂TiO2纳米管阵列复合材料的制备方法 |
| CN105668540A (zh) * | 2014-11-19 | 2016-06-15 | 清华大学 | 一种纳米线阵列的制备方法 |
| CN112331845A (zh) * | 2020-09-21 | 2021-02-05 | 昆明理工大学 | 一种四氧化三钴纳米线阵列负极材料的制备方法 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8808523B2 (en) | Method for forming ZrO2 film by plasma electrolytic oxidation | |
| CN101651046B (zh) | 一种Al2O3/TiO2复合介质膜铝电极箔的制备方法 | |
| CN105845918B (zh) | 一种高容量的多孔硅材料及其制备方法和应用 | |
| CN101775586A (zh) | 在非铝基底上电化学定向生长多孔Al2O3膜的制备方法 | |
| CN109537021B (zh) | 一种用于钠离子电池负极的氧化钛/氧化锡复合膜的制备方法 | |
| CN108172402A (zh) | 铝电解电容器用高压阳极氧化膜的制备方法 | |
| Djenizian et al. | Electrochemical fabrication of Sn nanowires on titania nanotube guide layers | |
| JP2011190466A (ja) | アルミニウム合金基板および太陽電池用基板 | |
| CN114538413A (zh) | 一种大面积纳米线阵列膜及其制备方法 | |
| CN116288636B (zh) | 一种耐高压有序多孔钽箔及其制备方法与应用 | |
| US11358124B2 (en) | Preparation method of a nanometer metal oxide supported carrier based on anodic oxidation | |
| CN102995097A (zh) | 镁合金表面蚀刻电解质溶液及其蚀刻方法 | |
| CN102888642A (zh) | 大面积高度有序多孔阳极氧化铝膜的制备方法 | |
| KR100379999B1 (ko) | 전극, 이차 전지 및 그 제조 방법 | |
| CN114229964B (zh) | 一种以Ti4O7为基底的表面刻蚀和氟化的阳极制备方法及应用 | |
| CN1988101A (zh) | 一种场发射阴极的制备方法 | |
| JP2007095772A (ja) | 電気二重層キャパシタ | |
| JP2012084460A (ja) | プロトン伝導体薄膜の作製方法 | |
| JP2000150005A (ja) | 色素増感型太陽電池の製造方法 | |
| CN111276672B (zh) | 含锡阵列结构的电极的制备及应用 | |
| CN109811313B (zh) | 一种高电阻率基底上多孔氧化铝模板的制备方法 | |
| CN111554872A (zh) | 一种锂离子电池自支撑硒化锑负极及其制备方法 | |
| CN109817891B (zh) | 一种钛材料表面原位制备纳米结构的方法 | |
| KR102582119B1 (ko) | 실리콘 나노선을 구비한 이차전지용 음극 활물질 및 그 제조 방법 | |
| CN108417411B (zh) | 一种超级电容器及其制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |