CN102251232A - Method for preparing silver nanowire array in ordered porous alumina template - Google Patents
Method for preparing silver nanowire array in ordered porous alumina template Download PDFInfo
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Abstract
The invention belongs to the field of nano material preparation, and discloses a method for preparing a silver nanowire array in an ordered porous alumina template. The method comprises the following steps: (1) sequentially carrying out annealing and ultrasonic cleaning on a high-purity aluminium sheet, removing a natural oxidation film of the high-purity aluminium sheet, sequentially carrying out electrochemical polishing and two-step anodic oxidation on the high-purity aluminium sheet, and removing an unoxidized aluminum substrate and unoxidized through holes of the high-purity aluminium sheet so as to prepare a two-way ordered porous alumina template; (2) filling silver bromide nanowires into the ordered porous alumina template by using a double-chamber chemical deposition method; and (3) irradiating the ordered porous alumina template filled with the silver bromide nanowires by using an ultraviolet lamp so as to carry out photodecomposition on silver bromides, then forming a silver nanowire array in the ordered porous alumina template. By using the method disclosed by the invention, the process for preparing a silver nanowire array is simplified; the method has low requirements on experimental equipment; and the method is simple in operation, low in cost, and favorable for the low-cost fast filling of a silver nanowire array in an ordered porous alumina template.
Description
Technical field
The invention belongs to field of nano material preparation, be specifically related to a kind of method that in ordered porous alumina template, prepares silver nano line array.
Background technology
Ordered porous alumina is a kind of oxide film with nano ordered pore passage structure that high-purity aluminum foil obtains behind electrochemical anodic oxidation.Nineteen ninety-five, Masuda etc. have delivered the method for utilizing twice anodic oxidation rafifinal and have prepared the porous alumina of high-sequential (Ordered Metal Nanohole Arrays Made by a Two-Step Replication of Honeycomb Structures of Anodic Alumina on the Science magazine, Science), this method becomes the main method of the orderly porous alumina of preparation.The ordered porous alumina of twice anonizing preparation has higher hardness and intensity, good thermostability, chemical stability and optical transparence, arrange in order in its duct, pore size is even, aperture and thickness are adjustable, the preparation method is simple, cost is low, is suitable as very much the mould material of preparation nano wire, nanotube and nano-array material.Considering that ordered porous alumina is transparent in visible-range, is that template is filled nano-array with it, can realize the research to nano-array/porous alumina matrix material optical property.
The one dimension silver nano material is widely studied owing to have very high specific conductivity and very strong photocatalysis performance.Nano silver wire is filled in the template, can be used in preparation metal-dielectric medium photonic crystal and lead.The preparation silver nano line array mainly contains electrochemical deposition method and oxidation reduction process in porous alumina formwork.Utilizations such as Yang Rui are immersed porous alumina formwork in the silver nitrate solution, utilize the principle of Silver Nitrate decomposes then, prepare nano silver wire (utilizing template to prepare the Ag nano wire, the molecular science journal) in alumina formwork.Employing acetaldehyde reduction Silver Nitrates such as Hu have been prepared Ag nano-wire array (Template preparation of high-density in porous alumina formwork, and large-area Ag nanowire array by acetaldehyde reduction, Materials Science and Engineering A).Sun Xiuyu etc. adopt cyclic voltammetry, as electrode, are electrolytic solution with the silver nitrate solution at alumina formwork evaporation silverskin, have prepared Ag nano-wire array (cyclic voltammetry prepares Ag nano-wire array, Chinese Journal of Inorganic Chemistry).Sauer etc. adopt the pulse electrodeposition method, prepare monocrystal silver nano line array (Highly ordered monocrystalline silver nanowire arrays, Journal of Applied Physics) with silver sulfate solution in alumina formwork.Dalchiele etc. are sputter one deck gold film on alumina formwork, with Sulfuric acid disilver salt and potassium thiocyanate mixing solutions is electrolytic solution, adopt the constant voltage method to prepare silver nano line array (Silver nanowires electrodeposited into nanoporous templates:Study of the influence of sizes on crystallinity and structural properties, Physica E).In addition, adopt galvanostatic method, direct current deposition method etc. are prepared silver nano line array in alumina formwork also have report more.
Though electrochemical deposition method is the most popular method of preparation nano silver wire in ordered porous alumina template, also there is certain defective in it.Because the bilateral alumina formwork is non-conductive, thereby before carrying out galvanic deposit, need earlier at alumina formwork one side evaporation conductive metal layer to remove again after the nano silver wire deposition as electrode.Though electro-deposition method can be prepared the silver nano line array of excellent property, but it is high that it requires experimental installation, cost is higher, the process complexity of evaporation and removal metal conducting layer is loaded down with trivial details, experiment condition is difficult to control, and these all are unfavorable for the extensive synthetic and follow-up performance study of matrix material of nano silver wire.Therefore, the preparation technology who seeks a kind of low cost, silver nano line array/porous alumina matrix material simple to operate just seems very necessary.
Summary of the invention
The purpose of this invention is to provide a kind of method that in ordered porous alumina template, prepares silver nano line array, realized that the preparation process with nano silver wire changes into the electroless plating and the photodissociation process of simple Silver monobromide nano wire, avoided electrochemical deposition technique to want earlier in the porous alumina formwork sprayed metal layer as electrode the complex operations process of again conductive layer being removed after the deposition; This method has been simplified the preparation process of silver nano line array, helps silver nano line array low-cost filling fast in ordered porous alumina template.
Technical scheme of the present invention is as follows:
The invention provides a kind of method for preparing silver nano line array in ordered porous alumina template, this method may further comprise the steps:
(1) high-purity aluminium flake is annealed, natural oxide film is removed in ultrasonic cleaning, carries out electrochemical etching, carries out two-step anodization, removes unoxidized aluminium substrate, and through hole is prepared ordered porous alumina (AAO) template of bilateral;
(2) adopt two chambers chemical deposition, in ordered porous alumina template, fill the Silver monobromide nano wire;
(3) with the ordered porous alumina template behind the ultra violet lamp filling Silver monobromide nano wire, Silver monobromide generation photodissociation forms silver nano line array in ordered porous alumina template.
Described high-purity aluminium flake purity 〉=99.99%.
It is that high-purity aluminium flake is incubated 3～8h in 450～550 ℃ of retort furnaces that described high-purity aluminium flake is annealed, and takes out after cooling to room temperature with the furnace; Preferably, high-purity aluminium flake is incubated 5h in 500 ℃ of retort furnaces, takes out after cooling to room temperature with the furnace.
Described ultrasonic cleaning is that the aluminium flake after the annealing is cleaned 3～5min in pure acetone, ethanol, deionized water for ultrasonic successively, removes the spot on aluminium surface.
Described removal natural oxide film is to place 5～10wt% sodium hydroxide solution of 40～70 ℃ to corrode 1～3min the aluminium flake after cleaning, and takes out the back and rinses well with deionized water, removes natural oxide film; Preferably, with the aluminium flake after cleaning immerse massfraction be in 8% the sodium hydroxide solution 60 ℃ soak 2min, take out the back and rinse well with deionized water, remove natural oxide film.
Described electrochemical etching, polishing fluid are 95vol% phosphoric acid+5vol% sulfuric acid+20g/L CrO
3Mixed solution, aluminium flake is loaded onto electrolyzer, anode connects aluminium flake, immerses in the polishing fluid, and adopts whipping device that polishing fluid is stirred, and takes out behind polishing 3～7min and rinses well; The electropolishing parameter is: 70～90 ℃ of constant temperature water baths, and the polishing electric current is at 0.5～0.9A; Preferably, aluminium flake is loaded onto electrolyzer, anode connects aluminium flake, immerses in the polishing fluid, and adopts whipping device that polishing fluid is stirred, and takes out behind the polishing 5min and rinses well, and the electropolishing parameter is: 85 ℃ of constant temperature water baths, polishing electric current 0.8A.
Described two-step anodization comprises anodic oxidation for the first time, removes once oxidation layer and anodic oxidation for the second time, wherein, anodic oxidation for the first time is that the oxalic acid with 0.2～0.4M is electrolytic solution, oxidation voltage is 30～50V, electrolyte temperature is controlled at 0～5 ℃, oxidization time is 4～10h, and the aluminium flake after the oxidation is rinsed well with deionized water; Preferably, concentration of oxalic acid is 0.3M, and oxidation voltage is 40V, and 5 ℃ of electrolyte temperatures, oxidization time are 6h; Removing the once oxidation layer is aluminium flake to be put into the phosphoric acid of 6wt% with the chromic acid mixing acid of 1.8wt% corrodes, and temperature is 40～70 ℃ and soaks 5～10h with the removal oxide film, cleans up with deionized water after finishing; Preferably, aluminium flake is immersed in the chromic acid mixing acid of the phosphoric acid of 6wt% and 1.8wt%, 60 ℃ are soaked 6h, remove oxide film; Anodic oxidation for the second time is that the aluminium flake that will remove behind the once oxidation layer carries out two-step anodization, is electrolytic solution with the oxalic acid of 0.2～0.4M, and oxidation voltage is 30～50V, and electrolyte temperature is controlled at 0～5 ℃, oxidization time 4～10h; Preferably, concentration of oxalic acid is 0.3M, and oxidation voltage is 40V, and 5 ℃ of electrolyte temperatures, oxidization time are 6h.
The unoxidized aluminium substrate of described removal be adopt 15wt% Cupric Chloride Solution with secondary oxidation after unoxidized aluminium substrate remove.
Described through hole operation steps comprises: the alumina formwork that will remove after the aluminium substrate at room temperature carries out through hole with 5wt% phosphoric acid, removes compact aluminum oxide blocking layer, bottom, obtains the porous alumina formwork of bilateral; Further, in order to regulate the aperture of alumina formwork, it is 5wt% phosphoric acid solution reaming 5～40min of 20～40 ℃ that the alumina formwork behind the through hole is put into temperature, prepares the bilateral alumina formwork of different pore sizes.
Described pair of chamber chemical deposition may further comprise the steps: the bilateral porous alumina formwork for preparing is packed in the reactor of two chambers, add equal-volume respectively in both sides, concentration is all Sodium Bromide and the silver nitrate solution of 0.01M mutually, at room temperature place 5～20h, Sodium Bromide and Silver Nitrate react in the duct of alumina formwork and form Silver monobromide, and the reaction rear pattern plate is faint yellow.
Because template adopts the alumina formwork in different apertures to the confinement effect of nanowire growth, can prepare the Silver monobromide nano wire of different diameter in porous alumina formwork.
Further, step (3) may further comprise the steps: the alumina formwork that will fill behind the Silver monobromide nano wire is placed on the ceramic boat support, place 3cm place, high voltage mercury lamp below to carry out UV-irradiation 5～20h, every 1～2h once, guarantee that the complete photodissociation of Silver monobromide nano wire forms nano silver wire therebetween with the sample upset.
The Silver monobromide nano wire is converted into nano silver wire behind the ultraviolet photolysis, and template is black.
The present invention compares with prior art, has following advantage and beneficial effect:
Preparation technology of the present invention compares with existing electrochemical deposition technique, advantage is: the electroless plating and the photodissociation process that the preparation process of nano silver wire are changed into simple Silver monobromide nano wire, avoided electrochemical deposition technique to want earlier in the porous alumina formwork sprayed metal layer as electrode the complex operations process of again conductive layer being removed after the deposition.This work simplification the preparation process of silver nano line array, it requires low, simple to operate to experimental installation, cost is low, helps that silver nano line array is low-cost in ordered porous alumina template fills fast.
Of the present invention pair of chamber deposits the silver nano line array of preparing in conjunction with the ultraviolet photolysis method, is convenient to study the optical property of nano silver wire composite porous aluminium oxide material.In addition, by the control ultraviolet photolysis time, the photodissociation degree of control Silver monobromide nano wire can be prepared silver-Silver monobromide heterojunction nano-wire, and its special light electrical property is explored in porous alumina formwork.
Description of drawings
Fig. 1 is the positive FESEM figure of porous alumina formwork.
Fig. 2 is porous alumina formwork side FESEM figure.
Fig. 3 is that two chambers method deposits Silver monobromide nano wire synoptic diagram in ordered porous alumina template, among the figure: Silver Nitrate 1, Sodium Bromide 2, Silver monobromide 3, alumina formwork 4.
Fig. 4 is the XRD spectrum of two sedimentary Silver monobromide nano wires of chamber method.
Fig. 5 is the low power FESEM figure in Silver monobromide nano wire front.
Fig. 6 is the lateral high power FESEM figure of Silver monobromide nano wire.
Fig. 7 is a Silver monobromide nano wire ultraviolet photolysis synoptic diagram, among the figure: high voltage mercury lamp 5, sample 6, ceramic boat 7.
Fig. 8 is the positive FESEM figure of silver nano line array.
Fig. 9 is the lateral low power FESEM figure of silver nano line array.
Figure 10 is the lateral high power FESEM figure of silver nano line array.
Figure 11 is the EDS spectrum of silver nano line array.
Embodiment
The present invention is further illustrated below in conjunction with the accompanying drawing illustrated embodiment.
The present invention has simplified the technology of preparation silver nano line array in ordered porous alumina template, its preparation process with nano silver wire changes into the electroless plating and the photodissociation process of simple Silver monobromide nano wire, at first adopt two chambers chemical deposition in porous alumina formwork, to prepare the nano-wire array of Silver monobromide, then sedimentary Silver monobromide nano wire is shone under ultraviolet lamp, Silver monobromide generation photodissociation obtains silver-colored nano-wire array in porous alumina formwork.By adopting the different high-purity aluminium flakes of voltage anodic oxidation, can obtain the porous alumina formwork in different apertures, thereby prepare the silver nano line array of different diameter.This technology need not to remove the sprayed metal conductive layer after preparing silver nano line array as electrodip process, is convenient to directly silver nano line array/ordered porous alumina matrix material be carried out performance study.
Embodiment 1
1, annealing: high-purity aluminium flake of purity 〉=99.99% is annealed,, shear the stress that the aluminium flake process is produced, take out after cooling to room temperature with the furnace to eliminate at 500 ℃ of following insulation 5h.
2, ultrasonic cleaning: the aluminium flake after will annealing immerses in pure acetone, ethanol and the deionized water successively, and ultrasonic cleaning 3min removes the spot on aluminium surface respectively.
3, remove natural oxide film: it is that (60 ℃ of constant temperature) soaks 2min in 8% the NaOH solution that the aluminium flake after will cleaning immerses massfraction, takes out with deionized water then and cleans up the removal natural oxide film.
4, electrochemical etching: aluminium flake is loaded onto electrolyzer (anode connects aluminium flake), immerse electropolishing liquid (95vol%H
3PO
4(85%)+5vol%H
2SO
4(97%)+20g/L CrO
3) in, and adopting whipping device that polishing fluid is stirred, polishing 5min takes out, and rinses well with deionized water.The electropolishing parameter is: 85 ℃ of constant temperature water baths; Faradaic current 0.8A.
5, an anodic oxidation: the anodic oxidation device of packing into of the aluminium flake after will polishing, the oxalic acid solution that adds 0.3M stirs with magnetic stirring apparatus as electrolytic solution, and regulating voltage is to 40V, oxidation 6h under 5 ℃ of conditions of constant temperature.Aluminium flake after the oxidation is rinsed well with deionized water.
6, remove the once oxidation layer: the aluminium flake behind the once oxidation is immersed in the mixing acid (6wt% phosphoric acid+1.8wt% chromic acid), put into 60 ℃ of baking oven insulations of constant temperature 6h, rinse well with deionized water after finishing to remove oxide film.
7, two-step anodization: concrete operations are identical with an anodic oxidation, and as electrolytic solution, regulating voltage is to 40V with the oxalic acid solution of 0.3M, oxidation 6h under 5 ℃ of conditions of constant temperature.Aluminium flake after the oxidation is rinsed well with deionized water.
8, remove unoxidized aluminium substrate: with massfraction is the aluminium flake back side after 15% Cupric Chloride Solution is added drop-wise to secondary oxidation, oxidized portion and cupric chloride do not react and molten going to make aluminium flake, aluminium substrate is removed the back fully and is cleaned up with deionized water, obtains transparent alumina formwork.
9, through hole and reaming: under the room temperature condition, at the phosphoric acid liquid of the pellumina back side Dropwise 5 wt% that removes aluminium substrate to remove the compact aluminum oxide blocking layer, when the another side of oxide film have solution by the time show that via process finishes, obtain the porous alumina formwork of bilateral.In order further to adjust the size of pore size of template, template is put into 5wt% phosphoric acid, 30min is handled in 35 ℃ of (heating in water bath) reamings of constant temperature.After reaming was finished, the ordered porous alumina template of bilateral had good light transmission.
10, electroless plating Silver monobromide nano wire: the bilateral porous alumina formwork for preparing is packed in the reactor of two chambers, add equal-volume in both sides respectively, concentration is all Sodium Bromide and the silver nitrate solution of 0.01M mutually.Two chambers reactor is in the dark, room temperature condition places down 20h, Sodium Bromide and Silver Nitrate mutual diffusion mutually in the duct of alumina formwork, and reaction forms Silver monobromide.Reaction finishes the back and takes out template, cleans up with deionized water, and dry rear pattern plate is faint yellow.
11, ultraviolet photolysis prepares nano silver wire: the Silver monobromide nano wire/porous alumina matrix material for preparing is placed on the ceramic boat support, place 3cm place, high voltage mercury lamp below to carry out UV-irradiation 20h then, every 2h once, guarantee that the complete photodissociation of Silver monobromide nano wire forms nano silver wire therebetween with the sample upset.The Silver monobromide nano wire is converted into nano silver wire behind the ultraviolet photolysis, and template becomes black.
By field emission scanning electron microscope (FE-SEM) sample of method preparation of the present invention is analyzed.
Fig. 1 is the positive FESEM figure of porous alumina formwork, and alumina formwork is orderly at very big regional inner height as seen from Figure 1, and hole is rounded, and pore size is even, and surface shape is similar cellular; Fig. 2 is porous alumina formwork side FESEM figure, can observe the height-oriented unanimity in duct, and is parallel to each other and vertical film is surperficial, and the duct is smooth, even aperture distribution.The alumina formwork aperture of reaming is not about 60nm, and the pore size of reaming alumina formwork is relevant with the reaming time.Utilize the ordered porous alumina template of this bilateral can deposit good Silver monobromide nano wire.
Fig. 3 is two chambers method deposition Silver monobromide nano wire synoptic diagram.The bilateral porous alumina formwork 4 for preparing is packed in the reactor of two chambers, add equal-volume respectively in both sides, the Sodium Bromide 2 of concentration identical (0.01M) and Silver Nitrate 1 solution, at room temperature place certain hour (5～20h), Sodium Bromide 2 and Silver Nitrate 1 react in the duct of alumina formwork and form Silver monobromide 3, and the reaction rear pattern plate is faint yellow.Because template adopts the alumina formwork in different apertures to the confinement effect of nanowire growth, can prepare the Silver monobromide nano wire of different diameter in porous alumina formwork.
Fig. 4 composes for the X-ray diffraction (XRD) of the Silver monobromide nano wire that present embodiment is prepared.As we can see from the figure, the diffraction peak of Silver monobromide (200) and (400) crystal face is very strong, proves Silver monobromide nano wire preferential growth in template, and ordered porous alumina template has played good guide effect to the growth of Silver monobromide nano wire.
Fig. 5 is the low power FESEM figure in Silver monobromide nano wire front, and Fig. 6 is the lateral high power FESEM figure of Silver monobromide nano wire.Can be seen that by Fig. 5 the filling ratio of Silver monobromide nano wire in ordered porous alumina template is very high, under current mode of deposition, the Silver monobromide nano wire has grown template surface, and the nano wire that loses the template support because of surface energy reunion has taken place greatly.As seen from Figure 6, the Silver monobromide nano wire of ordered arrangement is smooth mellow and full, straight, is keeping good array structure, and its diameter is about 100nm.The diameter of nano wire is bigger than the aperture of native aluminum oxide template, and this is owing to the corrosive nature of alumina formwork through the reaming of peroxophosphoric acid long period, due to the aperture becomes greatly.
Fig. 7 is a Silver monobromide nano wire ultraviolet photolysis synoptic diagram.The sample 6 (Silver monobromide nano wire/porous alumina matrix material) for preparing is placed on the ceramic boat 7, place 3cm place, high voltage mercury lamp 5 below to carry out UV-irradiation then, at regular intervals once, guarantee that the complete photodissociation of Silver monobromide nano wire forms nano silver wire therebetween with the sample upset.The Silver monobromide nano wire is converted into nano silver wire behind the ultraviolet photolysis, and template is black.
Field emission scanning electron microscope (FE-SEM) figure and energy dispersive spectrum (EDS) figure of the silver nano line array that Fig. 8 to Figure 11 forms after for Silver monobromide ultraviolet photolysis in the present embodiment.Fig. 8 is the positive FESEM figure of silver nano line array, can see that the termination of a lot of nano wires is arranged in parallel, and its filling ratio is near 100%.Fig. 9 is the lateral low power FESEM figure of silver nano line array, and Figure 10 is the lateral high power FESEM figure of silver nano line array.Can see the nano silver wire of a lot of high length-diameter ratios from Fig. 9 and Figure 10, nanowire surface is smooth, mellow and full, diameter is about 100nm, consistent with the diameter of the Silver monobromide nano wire for preparing previously, the shape of nano wire is keeping highly consistent with the template duct, has duplicated the pore passage structure of template and the symmetry of arranging in the hole.Figure 11 is the EDS spectrum of silver nano line array, and the peak value silver-colored as can be known by power spectrum Figure 11 is very high, shows that products therefrom is a nano silver wire, does not find bromo element in the EDS spectrum, shows that this regional Silver monobromide has been decomposed to form nano silver wire fully.Al and O come from alumina formwork, and Au comes from the gold-plated processing of sample surfaces.
1, annealing: high-purity aluminium flake of purity 〉=99.99% is annealed,, shear the stress that the aluminium flake process is produced, take out after cooling to room temperature with the furnace to eliminate at 500 ℃ of following insulation 5h.
2, ultrasonic cleaning: the aluminium flake after will annealing immerses in pure acetone, ethanol and the deionized water successively, and ultrasonic cleaning 3min removes the spot on aluminium surface respectively.
3, remove natural oxide film: it is that (60 ℃ of constant temperature) soaks 2min in 8% the NaOH solution that the aluminium flake after will cleaning immerses massfraction, takes out with deionized water then and cleans up the removal natural oxide film.
4, electrochemical etching: aluminium flake is loaded onto electrolyzer (anode connects aluminium flake), immerse electropolishing liquid (95vol%H
3PO
4(85%)+5vol%H
2SO
4(97%)+20g/L CrO
3) in, and adopting whipping device that polishing fluid is stirred, polishing 5min takes out, and rinses well with deionized water.The electropolishing parameter is: 85 ℃ of constant temperature water baths; Faradaic current 0.8A.
5, an anodic oxidation: the anodic oxidation device of packing into of the aluminium flake after will polishing, add 0, the oxalic acid solution of 3M stirs with magnetic stirring apparatus as electrolytic solution, and regulating voltage is to 40V, oxidation 6h under 5 ℃ of conditions of constant temperature.Aluminium flake after the oxidation is rinsed well with deionized water.
6, remove the once oxidation layer: the aluminium flake behind the once oxidation is immersed in the mixing acid (6wt% phosphoric acid+1.8wt% chromic acid), put into 60 ℃ of baking oven insulations of constant temperature 6h, rinse well with deionized water after finishing to remove oxide film.
7, two-step anodization: concrete operations are identical with an anodic oxidation, and as electrolytic solution, regulating voltage is to 40V with the oxalic acid solution of 0.3M, oxidation 6h under 5 ℃ of conditions of constant temperature.Aluminium flake after the oxidation is rinsed well with deionized water.
8, remove unoxidized aluminium substrate: with massfraction is the aluminium flake back side after 15% Cupric Chloride Solution is added drop-wise to secondary oxidation, oxidized portion and cupric chloride do not react and molten going to make aluminium flake, aluminium substrate is removed the back fully and is cleaned up with deionized water, obtains transparent alumina formwork.
9, through hole and reaming: under the room temperature condition, at the phosphoric acid liquid of the pellumina back side Dropwise 5 wt% that removes aluminium substrate to remove the compact aluminum oxide blocking layer, when the another side of oxide film have solution by the time show that via process finishes, obtain the porous alumina formwork of bilateral.In order further to adjust the size of pore size of template, template is put into 5wt% phosphoric acid, 30min is handled in 35 ℃ of (heating in water bath) reamings of constant temperature.After reaming was finished, the ordered porous alumina template of bilateral had good light transmission.
10, electroless plating Silver monobromide nano wire: the bilateral porous alumina formwork for preparing is packed in the reactor of two chambers, add equal-volume in both sides respectively, concentration is all Sodium Bromide and the silver nitrate solution of 0.01M mutually.Two chambers reactor is in the dark, room temperature condition places down 5h, Sodium Bromide and Silver Nitrate mutual diffusion mutually in the duct of alumina formwork, and reaction forms Silver monobromide.Reaction finishes the back and takes out template, cleans up with deionized water, and dry rear pattern plate is faint yellow.
11, ultraviolet photolysis prepares nano silver wire: the Silver monobromide nano wire/porous alumina matrix material for preparing is placed on the ceramic boat support, place 3cm place, high voltage mercury lamp below to carry out UV-irradiation 5h then, every 1h once, guarantee that the complete photodissociation of Silver monobromide nano wire forms nano silver wire therebetween with the sample upset.The Silver monobromide nano wire is converted into nano silver wire behind the ultraviolet photolysis, and template becomes black.
1, annealing: high-purity aluminium flake of purity 〉=99.99% is annealed,, shear the stress that the aluminium flake process is produced, take out after cooling to room temperature with the furnace to eliminate at 500 ℃ of following insulation 5h.
2, ultrasonic cleaning: the aluminium flake after will annealing immerses in pure acetone, ethanol and the deionized water successively, and ultrasonic cleaning 3min removes the spot on aluminium surface respectively.
3, remove natural oxide film: it is that (60 ℃ of constant temperature) soaks 2min in 8% the NaOH solution that the aluminium flake after will cleaning immerses massfraction, takes out with deionized water then and cleans up the removal natural oxide film.
4, electrochemical etching: aluminium flake is loaded onto electrolyzer (anode connects aluminium flake), immerse electropolishing liquid (95vol%H
3PO
4(85%)+5vol%H
2SO
4(97%)+20g/L CrO
3) in, and adopting whipping device that polishing fluid is stirred, polishing 5min takes out, and rinses well with deionized water.The electropolishing parameter is: 85 ℃ of constant temperature water baths; Faradaic current 0.8A.
5, an anodic oxidation: the anodic oxidation device of packing into of the aluminium flake after will polishing, the oxalic acid solution that adds 0.3M stirs with magnetic stirring apparatus as electrolytic solution, and regulating voltage is to 40V, oxidation 6h under 5 ℃ of conditions of constant temperature.Aluminium flake after the oxidation is rinsed well with deionized water.
6, remove the once oxidation layer: the aluminium flake behind the once oxidation is immersed in the mixing acid (6wt% phosphoric acid+1.8wt% chromic acid), put into 60 ℃ of baking oven insulations of constant temperature 6h, rinse well with deionized water after finishing to remove oxide film.
7, two-step anodization: concrete operations are identical with an anodic oxidation, and as electrolytic solution, regulating voltage is to 40V with the oxalic acid solution of 0.3M, oxidation 6h under 5 ℃ of conditions of constant temperature.Aluminium flake after the oxidation is rinsed well with deionized water.
8, remove unoxidized aluminium substrate: with massfraction is the aluminium flake back side after 15% Cupric Chloride Solution is added drop-wise to secondary oxidation, oxidized portion and cupric chloride do not react and molten going to make aluminium flake, aluminium substrate is removed the back fully and is cleaned up with deionized water, obtains transparent alumina formwork.
9, through hole and reaming: under the room temperature condition, at the phosphoric acid liquid of the pellumina back side Dropwise 5 wt% that removes aluminium substrate to remove the compact aluminum oxide blocking layer, when the another side of oxide film have solution by the time show that via process finishes, obtain the porous alumina formwork of bilateral.In order further to adjust the size of pore size of template, template is put into 5wt% phosphoric acid, 30min is handled in 35 ℃ of (heating in water bath) reamings of constant temperature.After reaming was finished, the ordered porous alumina template of bilateral had good light transmission.
10, electroless plating Silver monobromide nano wire: the bilateral porous alumina formwork for preparing is packed in the reactor of two chambers, add equal-volume in both sides respectively, concentration is all Sodium Bromide and the silver nitrate solution of 0.01M mutually.Two chambers reactor is in the dark, room temperature condition places down 10h, Sodium Bromide and Silver Nitrate mutual diffusion mutually in the duct of alumina formwork, and reaction forms Silver monobromide.Reaction finishes the back and takes out template, cleans up with deionized water, and dry rear pattern plate is faint yellow.
11, ultraviolet photolysis prepares nano silver wire: the Silver monobromide nano wire/porous alumina matrix material for preparing is placed on the ceramic boat support, place 3cm place, high voltage mercury lamp below to carry out UV-irradiation 20h then, every 2h once, guarantee that the complete photodissociation of Silver monobromide nano wire forms nano silver wire therebetween with the sample upset.The Silver monobromide nano wire is converted into nano silver wire behind the ultraviolet photolysis, and template becomes black.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (10)
1. method that in ordered porous alumina template, prepares silver nano line array, it is characterized in that: this method may further comprise the steps:
(1) high-purity aluminium flake is annealed, natural oxide film is removed in ultrasonic cleaning, carries out electrochemical etching, carries out two-step anodization, removes unoxidized aluminium substrate, and through hole is prepared the ordered porous alumina template of bilateral;
(2) adopt two chambers chemical deposition, in ordered porous alumina template, fill the Silver monobromide nano wire;
(3) with the ordered porous alumina template behind the ultra violet lamp filling Silver monobromide nano wire, Silver monobromide generation photodissociation forms silver nano line array in ordered porous alumina template.
2. the root method for preparing silver nano line array in ordered porous alumina template according to claim 1 is characterized in that: described high-purity aluminium flake purity 〉=99.99%; It is that high-purity aluminium flake is incubated 3～8h in 450～550 ℃ of retort furnaces that described high-purity aluminium flake is annealed, and takes out after cooling to room temperature with the furnace; Preferably, high-purity aluminium flake is incubated 5h in 500 ℃ of retort furnaces, takes out after cooling to room temperature with the furnace.
3. the root method for preparing silver nano line array in ordered porous alumina template according to claim 1 is characterized in that: described ultrasonic cleaning is that the aluminium flake after the annealing is cleaned 3～5min in pure acetone, ethanol, deionized water for ultrasonic successively.
4. the root method that in ordered porous alumina template, prepares silver nano line array according to claim 1, it is characterized in that: described removal natural oxide film is to place 5～10wt% sodium hydroxide solution of 40～70 ℃ to corrode 1～3min the aluminium flake after cleaning, take out the back and rinse well, remove natural oxide film with deionized water; Preferably, the aluminium flake after cleaning being immersed massfraction is that 60 ℃ are soaked 2min, take out the back and rinse well with deionized water, remove natural oxide film in 8% the sodium hydroxide solution.
5. the root method for preparing silver nano line array in ordered porous alumina template according to claim 1, it is characterized in that: described electrochemical etching, polishing fluid are 95vol% phosphoric acid+5vol% sulfuric acid+20g/L CrO
3Mixed solution, aluminium flake is loaded onto electrolyzer, anode connects aluminium flake, immerses in the polishing fluid, and adopts whipping device that polishing fluid is stirred, and takes out behind polishing 3～7min and rinses well; The electropolishing parameter is: 70～90 ℃ of constant temperature water baths, and the polishing electric current is at 0.5～0.9A; Preferably, aluminium flake is loaded onto electrolyzer, anode connects aluminium flake, immerses in the polishing fluid, and adopts whipping device that polishing fluid is stirred, and takes out behind the polishing 5min and rinses well, and the electropolishing parameter is: 85 ℃ of constant temperature water baths, polishing electric current 0.8A.
6. the root method that in ordered porous alumina template, prepares silver nano line array according to claim 1, it is characterized in that: described two-step anodization comprises anodic oxidation for the first time, removes once oxidation layer and anodic oxidation for the second time, wherein, anodic oxidation for the first time is that the oxalic acid with 0.2～0.4M is electrolytic solution, oxidation voltage is 30～50V, electrolyte temperature is controlled at 0～5 ℃, and oxidization time is 4～10h, and the aluminium flake after the oxidation is rinsed well with deionized water; Preferably, concentration of oxalic acid is 0.3M, and oxidation voltage is 40V, and 5 ℃ of electrolyte temperatures, oxidization time are 6h; Removing the once oxidation layer is aluminium flake to be put into the phosphoric acid of 6wt% with the chromic acid mixing acid of 1.8wt% corrodes, and temperature is 40～70 ℃ and soaks 5～10h with the removal oxide film, cleans up with deionized water after finishing; Preferably, aluminium flake is immersed in the chromic acid mixing acid of the phosphoric acid of 6wt% and 1.8wt%, 60 ℃ are soaked 6h, remove oxide film; Anodic oxidation for the second time is that the aluminium flake that will remove behind the once oxidation layer carries out two-step anodization, is electrolytic solution with the oxalic acid of 0.2～0.4M, and oxidation voltage is 30～50V, and electrolyte temperature is controlled at 0～5 ℃, oxidization time 4～10h; Preferably, concentration of oxalic acid is 0.3M, and oxidation voltage is 40V, and 5 ℃ of electrolyte temperatures, oxidization time are 6h.
7. the root method for preparing silver nano line array in ordered porous alumina template according to claim 1 is characterized in that: the unoxidized aluminium substrate of described removal be adopt 15wt% Cupric Chloride Solution with secondary oxidation after unoxidized aluminium substrate remove.
8. the root method that in ordered porous alumina template, prepares silver nano line array according to claim 1, it is characterized in that: described through hole operation steps comprises: the alumina formwork that will remove after the aluminium substrate at room temperature carries out through hole with 5wt% phosphoric acid, remove compact aluminum oxide blocking layer, bottom, obtain the porous alumina formwork of bilateral; Further, in order to regulate the aperture of alumina formwork, it is 5wt% phosphoric acid solution reaming 5～40min of 20～40 ℃ that the alumina formwork behind the through hole is put into temperature, prepares the bilateral alumina formwork of different pore sizes.
9. the root method that in ordered porous alumina template, prepares silver nano line array according to claim 1, it is characterized in that: described pair of chamber chemical deposition may further comprise the steps: the bilateral porous alumina formwork for preparing is packed in the reactor of two chambers, add equal-volume respectively in both sides, concentration is all Sodium Bromide and the silver nitrate solution of 0.01M mutually, at room temperature place 5～20h, Sodium Bromide and Silver Nitrate react in the duct of alumina formwork and form Silver monobromide, and the reaction rear pattern plate is faint yellow.
10. the root method that in ordered porous alumina template, prepares silver nano line array according to claim 1, it is characterized in that: described step (3) may further comprise the steps: the alumina formwork that will fill behind the Silver monobromide nano wire is placed on the ceramic boat support, place 3cm place, high voltage mercury lamp below to carry out UV-irradiation 5～20h, every 1～2h once, guarantee that the complete photodissociation of Silver monobromide nano wire forms nano silver wire therebetween with the sample upset.
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