CN103397326B - The preparation method of nano ordered Zinc oxide film material - Google Patents
The preparation method of nano ordered Zinc oxide film material Download PDFInfo
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- CN103397326B CN103397326B CN201310329070.7A CN201310329070A CN103397326B CN 103397326 B CN103397326 B CN 103397326B CN 201310329070 A CN201310329070 A CN 201310329070A CN 103397326 B CN103397326 B CN 103397326B
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Abstract
The present invention relates to field of inorganic material preparing technology, be specially a kind of preparation method of nano ordered Zinc oxide film material.Solve current nano ordered Zinc oxide film material preparation process complexity and the uppity technical problem of reaction process.A preparation method for nano ordered Zinc oxide film material, comprises following step: (a) configures alkaline solution, and adds tensio-active agent and additive in alkaline solution; (b) activated zinc matrix; Zinc Matrix after polishing is put into ethanol ultrasonic washing, steeps in acetone afterwards; C () is immersed in the Zinc Matrix activated in alkaline solution; D Zinc Matrix takes out and puts into temperature control device by (); E () takes out Zinc Matrix, washing and drying, and obtaining take zinc as the nano ordered Zinc oxide film material of matrix.The present invention adopts Zinc Matrix to immerse the mode of solution, prepares nano ordered Zinc oxide film material, and preparation method is unique, and easy and simple to handle, cost is low, is easy to carry out large-scale production.
Description
Technical field
The present invention relates to field of inorganic material preparing technology, be applied to photovoltaic cell field, be specially a kind of preparation method of nano ordered Zinc oxide film material.
Background technology
ZnO is a kind of wide direct band gap (3.37eV), greatly exciton bind energy (60meV) and has piezoelectric property
nn-type semiconductorN.Its dye sensitization solar battery (JPhysChemB,
2006, 110:2087-2092), photochemical catalysis, electrocatalysis (Electroanalysis
2007, 19:1008-1014), sensing (Nanotechnology,
2006, 17:2266-2270), Flied emission (AdvMater,
2007, 19:1627-1631), anisotropic magnetic (NatureMater,
2004, 3:533-538), thermoelectric effect (Nature,
2008, 451:163-167) and waveguide (AdvMater,
2008, 20:4455-4459) etc. aspect there is application, show powerful function.
Nano ordered zinc oxide has lower electronics induced defects and good electromechanical coupling performance, in substrate, the nano structure of zinc oxide film of high-sequential growth can make electrode of solar battery, it is conducive to electric transmission, reduces the compound at electronics and interface, improves battery efficiency.The photic ultraviolet lasing phenomenon of particularly at room temperature regular zinc oxide nano array, has greatly promoted the research of the zinc oxide nano array preparing high-sequential in solid substrate.In addition, micro-nanometer ordered structure zinc oxide has the order of the distribution of orientations being similar to optical crystal, and this characteristic can reduce scattering of light, thus can obtain stronger photoabsorption and the photoelectric current of Geng Gao.In dimensional attributes, compared with two peacekeeping zero dimensional nanometer materials, monodimension nanometer material (single crystal structure) has more excellent performance in dye sensitization solar battery, electronic conductivity, sensing, field emmision material, anisotropic magnetic, thermoelectric effect and waveguide etc., and its major cause is the anisotropy of the structure of one dimension, large specific surface area and portraitlandscape.（Science,
2001,292:1897-1899;AdvMater,
2007,19:749-753;Science,
2001,291:1947-1949;Science,
2005,309:1700-1704;NanoLett,
2003,3:1625-1631;Science,
2004,303:1348-1351;JAmChemSoc,
2004,126:6703-6709;JPhysChemB,
2005,109:11209-11214;JPhysChemC,
2007,111:6678-6683;JAmChemSoc,
2003,125:4728-4729;AdvFunctMater,
2007,17:1303-1310;NanoLett,
2002,2:1287-1291）
At present, report that many methods prepare nano zinc oxide material, comprised chemical Vapor deposition process, Metalorganic Chemical Vapor Deposition, physical vaporous deposition, solid-gas process, electron beam lithography, scan-probe lithography, nano-form method, phase shift replica technology, ultrasonic method, Biomimetic synthesis method, solvent-thermal method, molten salt method for synthesizing, electrochemical method and sol-gel process.The each tool relative merits of various method.Such as, the sample purity that gas phase process is generally prepared is high, but needs high temperature and high end instrument.The condition that liquid phase method is adjustable is many, but brings the complicacy of control simultaneously.For template, some Template preparation itself is more difficult, as biological template or micella class template.When needs removing template, may impact the pattern of sample and structure.Hydro-thermal rule is more restive reaction process.In addition, being in the hydrothermal reactor under hot environment, there is potentially dangerous in itself.Therefore a kind of preparation method of lower-cost orderly nano zinc oxide material simple to operate is needed.
Summary of the invention
The present invention be solve the complicated and cost of current nano zinc oxide material preparation process higher technical problem, a kind of preparation method of nano ordered Zinc oxide film material is provided.
The present invention realizes by the following technical solutions: a kind of preparation method of nano ordered Zinc oxide film material, comprises following step: (a) configures alkaline solution, and in alkaline solution, adds tensio-active agent and ammoniacal liquor makes caustic corrosion solution; (b) activated zinc matrix; Zinc Matrix after polishing is put into ethanol ultrasonic washing 1 ~ 10 minute, steeps 1 ~ 10 minute in acetone afterwards, take out dry; C () is immersed in the Zinc Matrix activated in caustic corrosion solution, soak time is 10 ~ 60 seconds; D Zinc Matrix takes out and puts into temperature control device by (), temperature remains in 10 ~ 80oC, places 0.5 ~ 5 hour; E () takes out Zinc Matrix, through washing with after drying, obtaining take zinc as the nano ordered Zinc oxide film material of matrix; Described alkaline solution is the NaOH of concentration between 1.8 ~ 2mol/L or KOH solution; Described tensio-active agent adopts wherein a kind of in sodium laurylsulfonate, sodium lauryl sulphate, tween or with two or three of arbitrary proportion mixing, the add-on of tensio-active agent is add 0.01 ~ 2g in every 1L alkaline solution; Ammoniacal liquor add-on is that every 1L alkaline solution adds 0.01 ~ 0.2L.
Add tensio-active agent and ammoniacal liquor in alkaline solution after, make caustic corrosion solution, to the surface of Zinc Matrix, there is corrosive nature, can react with Zinc Matrix surface.Described Zinc Matrix adopts laminar metallic zinc.Zinc Matrix is immersed in caustic corrosion solution, and caustic corrosion solution can immerse the surface of Zinc Matrix.Put into the equipment of temperature-controllable after being taken out by Zinc Matrix, carry out heating or lowering the temperature; The equipment of temperature-controllable selects refrigeration equipment or baking oven as required; The surface attachment of the Zinc Matrix taken out from caustic corrosion solution has the liquid film of one deck caustic corrosion solution, liquid film to start to react with Zinc Matrix and drying gradually in the reaction.Zinc and NaOH or KOH solution are reacted and are generated meta-sodium zincate or potassium zincate partially under normal circumstances, the present invention is by preventing the generation of meta-sodium zincate or potassium zincate partially after adding tensio-active agent and ammoniacal liquor, and control zinc and alkaline solution and react and generate zinc oxide, it is nano level orderly crystal grain that the zinc oxide of generation grows into yardstick gradually.Tensio-active agent and ammoniacal liquor have the effect reducing zinc oxide surface tension force, promote the zinc reaction on Zinc Matrix surface; The content of the concentration of alkaline solution, tensio-active agent, ammoniacal liquor and the temperature and time be placed in temperature control device ensure that the generation of nano ordered Zinc oxide film material.Sodium laurylsulfonate is a kind of anion surfactant, has excellent infiltration, washing, wetting, decontamination and emulsifying effect; Sodium lauryl sulphate is a kind of nontoxic anion surfactant; Tween is polysorbate, and Chang Zuowei tensio-active agent uses.
Adopt the ordered nano film material that method of the present invention is produced, its photoelectric response characteristic is very excellent, the photoelectric response testing method of employing standard is tested, when illumination, the electric current of the ordered nano film material that the present invention prepares rises fast, peak current has met or exceeded the requirement of relevant criterion completely, proves that the nano material adopting the method for the invention to prepare is orderly nano film material.
Innovative point of the present invention is, adopts mode Zinc Matrix being immersed solution first, certainly sacrifices reaction by Zinc Matrix, prepares nano ordered Zinc oxide film material.This method have simple, consume amount of solution considerably less, environmental friendliness, output are high, cost is low, are easy to the advantage of carrying out large-scale production.
Accompanying drawing explanation
Fig. 1 adopts length-to-diameter ratio that described in embodiment 1, method is produced to be about the ZnO nano-rod array pattern of 10.
The hexagonal columnar appearance of ZnO that Fig. 2 adopts method described in embodiment 2 to produce.
What Fig. 3 adopted method described in embodiment 14 to produce has the loose ZnO nanorod pattern of distribution.
The hyperstructure ZnO nanorod that Fig. 4 adopts method described in embodiment 15 to produce.
The photocurrent response curve of the hyperstructure ZnO nanorod that Fig. 5 adopts method described in embodiment 15 to produce.
Fig. 6 adopts the photocurrent response curve of the ZnO nano-rod array that described in embodiment 1, method is produced.
Fig. 7 adopts the photocurrent response curve of the zinc oxide nano rod that described in embodiment 14, method is produced.
Embodiment
A preparation method for nano ordered Zinc oxide film material, comprises following step: (a) configures alkaline solution, and in alkaline solution, adds tensio-active agent and additive makes caustic corrosion solution; (b) activated zinc matrix; Zinc Matrix after polishing is put into ethanol ultrasonic washing 1 ~ 10 minute, steeps 1 ~ 10 minute in acetone afterwards; C () is immersed in the Zinc Matrix activated in caustic corrosion solution, soak time is 10 ~ 60 seconds; D Zinc Matrix takes out and puts into temperature control device by (), temperature remains in 10 ~ 80oC, places 0.5 ~ 5 hour; E () takes out Zinc Matrix, through washing with after drying, obtaining take zinc as the nano ordered Zinc oxide film material of matrix; Described alkaline solution is the NaOH of concentration between 2mol/L or KOH solution; Described tensio-active agent adopts wherein a kind of in sodium laurylsulfonate, sodium lauryl sulphate, tween or with two or three of arbitrary proportion mixing, the add-on of tensio-active agent is add 0.01 ~ 2g in every 1L alkaline solution; Additive is ammoniacal liquor, and add-on is that every 1L alkaline solution adds 0.01 ~ 0.2L.
Deionized water is adopted to carry out during washing.
Quartzy sand papering Zinc Matrix is adopted during activated zinc matrix.
Below enumerate some specific embodiments, described embodiment is some concrete data of Stochastic choice testing under reaction conditions of the present invention all, all obtain the Nano zinc oxide film material of ordered arrangement.
Embodiment 1
Prepare the KOH solution of 10 milliliters of 2mol/L with deionized water, add the sodium laurylsulfonate of 0.02g, then add 2 milliliters of ammoniacal liquor, join to obtain corrosion zinc matrix alkali lye.Cut out one and be about the zinc metal sheet of 2 centimetres, wide about 1 centimetre as Zinc Matrix, with sand papering light, then ethanolic soln ultrasonic cleaning 1 minute, then in acetone, soak about 1 minute.The Zinc Matrix of activation dipping by lye is soaked for 10 seconds, takes out with tweezers, Zinc Matrix surface self-assembling formation one deck liquid film.Carefully wetting Zinc Matrix is put in Glass tubing, clogs the mouth of pipe of Glass tubing with stopper gently, but blow-by.React after 5 hours under 10oC, take out sample, spend Ion Cleaning, then use ethanol rinse, post-drying, obtain nano zinc oxide material.Its pattern is shown in Fig. 1, and product is the nanometer stick array of high-sequential, diameter about 30 nanometer, and length about 300 nanometer, length-to-diameter ratio can reach 10.
Embodiment 2
Except adding the sodium laurylsulfonate of 0.0001g, join to obtain corrosion zinc matrix alkali lye, other step is identical with embodiment 1.Products obtained therefrom pattern is as Fig. 2, and product is larger-size hexagonal columnar (bar-shaped) array.
Embodiment 3
Except preparing the KOH solution of 10 milliliters of 1.8mol/L with deionized water, add the sodium laurylsulfonate of 0.01g, join to obtain corrosion zinc matrix alkali lye, other step is identical with embodiment 1.Obtain the nanometic zinc oxide rod array similar to embodiment 1.
Embodiment 4
Except adding the sodium lauryl sulphate of 2g/L, join to obtain corrosion zinc matrix alkali lye, other step is identical with embodiment 1.Obtain the nanometic zinc oxide rod array similar to embodiment 1.
Embodiment 5
Except adding the tween of 0.02g, join to obtain corrosion zinc matrix alkali lye, other step is identical with embodiment 1.Obtain the nanometic zinc oxide rod array similar to embodiment 1.
Embodiment 6
Except preparing 10 milliliters with deionized water, the KOH solution of 1.9mol/L, add the sodium laurylsulfonate of 0.01g, the sodium lauryl sulphate of 0.005g and the tween of 0.005g, join to obtain corrosion zinc matrix alkali lye, other step is identical with embodiment 1.Obtain the nanometic zinc oxide rod array similar to embodiment 1.
Embodiment 7
Except adding the sodium laurylsulfonate of 0.01g and the tween of 0.005g, join to obtain corrosion zinc matrix alkali lye, other step is identical with embodiment 1.Obtain the nanometic zinc oxide rod array similar to embodiment 1.
Embodiment 8
Except adding the ammoniacal liquor of 0.1 milliliter, join to obtain corrosion zinc matrix alkali lye, other step is identical with embodiment 1.Obtain hexagonal columnar (bar-shaped) array similar to embodiment 2.
Embodiment 9
Except adding the ammoniacal liquor of 0.5 milliliter, join to obtain corrosion zinc matrix alkali lye, other step is identical with embodiment 1.Obtain hexagonal columnar (bar-shaped) array similar to embodiment 2.
Embodiment 10
Except the tween of the ammoniacal liquor and 0.01g that add 0.5 milliliter, join to obtain corrosion zinc matrix alkali lye, other step is identical with embodiment 1.Obtain hexagonal columnar (bar-shaped) array similar to embodiment 2.
Embodiment 11
By Zinc Matrix ethanolic soln ultrasonic cleaning 10 minutes, then in acetone, soak about 10 minutes, the Zinc Matrix dipping by lye 60s of activation, other steps are identical with example 1.Obtain the nanometic zinc oxide rod array similar to embodiment 1.
Embodiment 12
By Zinc Matrix ethanolic soln ultrasonic cleaning 5 minutes, then in acetone, soak about 5 minutes, the Zinc Matrix of activation dipping by lye 30 seconds, other steps are identical with example 1.Obtain the nanometic zinc oxide rod array similar to embodiment 1.
Embodiment 13
Except preparing the NaOH solution of 10 milliliters of 2mol/L with deionized water, all the other steps are identical with embodiment 1.Obtain the nanometic zinc oxide rod array similar to embodiment 1.
Embodiment 14
Be except 2 hours except temperature of reaction is 60oC and reaction times, other step is identical with embodiment 1, and products obtained therefrom pattern is shown in Fig. 3, and product pattern is uniform club shaped structure, and distribution is evenly loose, and diameter about 200 nanometer, length is between 2 ~ 3 microns.
Embodiment 15
Adopt the alkali lye identical with embodiment 1, but raise temperature of reaction to 80oC.At the temperature that this is higher, the speed of liquid film evaporation is accelerated, and sample can not all grow under liquid film state.Fig. 4 is the scanning electron microscope (SEM) photograph growing 30 minutes gained samples in this case.Club shaped structure also can grow, but the surface of club shaped structure, particularly top, have a lot of strip structure, small pieces become vertical relation with nanorod surfaces.A kind of structure like this belongs to multilayered structure, or is called hyperstructure, is similar to dendrimer.These hyperstructure diameters comparatively thick (between 200 ~ 300 nanometers), length shorter (less than 1 micron), the pellet diameter on rod at 25 ran, the small pieces at top weave in (becoming the angled relationships of 60o or 120o between each small pieces) in an orderly manner mutually.
Embodiment 16
Except preparing NaOH solution and the 0.0001g sodium lauryl sulphate of 10 milliliters of 1.8mol/L with deionized water, all the other steps are identical with embodiment 1.Obtain the nanometic zinc oxide rod array similar to embodiment 1.
Embodiment 17
Except preparing the NaOH solution of 10 milliliters of 1.9mol/L with deionized water, all the other steps are identical with embodiment 1.Obtain the nanometic zinc oxide rod array similar to embodiment 1.
Embodiment 18
Except adding the tween of 0.0001g, join to obtain corrosion zinc matrix alkali lye, other step is identical with embodiment 1.Obtain the nanometic zinc oxide rod array similar to embodiment 1.
Embodiment 19
Except adding the sodium lauryl sulphate of 0.01g and the tween of 0.005g, join to obtain corrosion zinc matrix alkali lye, other step is identical with embodiment 1.Obtain the nanometic zinc oxide rod array similar to embodiment 1.
Embodiment 20
Except adding the sodium lauryl sulphate of 0.01g and the sodium laurylsulfonate of 0.003g, join to obtain corrosion zinc matrix alkali lye, other step is identical with embodiment 1.Obtain the nanometic zinc oxide rod array similar to embodiment 1.
Below the application of nano ordered Zinc oxide film material in photovoltaic response of different-shape is illustrated.
The solution adopted is the S-WAT of 0.1mol/L and the hypo solution of 0.15mol/L.The battery system of photovoltaic test is three-electrode system: working electrode is the Zinc Matrix electrode having nano zinc oxide material, and supporting electrode is platinum plate electrode, and reference electrode is saturated earthenware mercury electrode.The light source adopted is the xenon lamp of 500 watts.Photovoltaic test is carried out on electrochemical workstation (model C HI660D).Do photovoltaic response test time, equal biasing 0.5V, illumination be 30 seconds without light application time.
Working electrode is adopted to the hyperstructure nano zinc oxide material of embodiment 15, its photovoltaic response curve is shown in Fig. 5, visible, and during illumination, electric current rises fast, and peak current is about 0.04mA/cm
2.
Working electrode is adopted to the ZnO nano-rod array of embodiment 1, its photovoltaic response curve is shown in Fig. 6, visible, and during illumination, electric current rises very fast, and peak current is about 0.002mA/cm
2.
For the zinc oxide nano rod that working electrode adopts the distribution of embodiment 14 loose, its photovoltaic response curve is shown in Fig. 7, visible, and during illumination, electric current rises very fast, and peak current is about 0.003mA/cm
2.
Claims (3)
1. a preparation method for nano ordered Zinc oxide film material, is characterized in that, comprises following step: (a) configures alkaline solution, and in alkaline solution, adds tensio-active agent and ammoniacal liquor makes caustic corrosion solution; (b) activated zinc matrix; Zinc Matrix after polishing is put into ethanol ultrasonic washing 1 ~ 10 minute, steeps 1 ~ 10 minute in acetone afterwards; C () is immersed in the Zinc Matrix activated in caustic corrosion solution, soak time is 10 ~ 60 seconds; D Zinc Matrix takes out and puts into temperature control device by (), temperature remains in 10 ~ 80oC, places 0.5 ~ 5 hour; E () takes out Zinc Matrix, through washing with after drying, obtaining take zinc as the nano ordered Zinc oxide film material of matrix; Described alkaline solution is the NaOH of concentration between 1.8 ~ 2mol/L or KOH solution; Described tensio-active agent adopts wherein a kind of in sodium laurylsulfonate, sodium lauryl sulphate, tween or with two or three of arbitrary proportion mixing, the add-on of tensio-active agent is add 0.01 ~ 2g in every 1L alkaline solution; Ammoniacal liquor add-on is that every 1L alkaline solution adds 0.01 ~ 0.2L.
2. the preparation method of nano ordered Zinc oxide film material as claimed in claim 1, is characterized in that, adopts deionized water to carry out during washing.
3. the preparation method of nano ordered Zinc oxide film material as claimed in claim 1 or 2, is characterized in that, activated zinc matrix adopts quartzy sand papering Zinc Matrix.
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