CN101845651B - Preparation method of cadmium oxide micro-nanometer ordered structural material - Google Patents
Preparation method of cadmium oxide micro-nanometer ordered structural material Download PDFInfo
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- CN101845651B CN101845651B CN2009102181250A CN200910218125A CN101845651B CN 101845651 B CN101845651 B CN 101845651B CN 2009102181250 A CN2009102181250 A CN 2009102181250A CN 200910218125 A CN200910218125 A CN 200910218125A CN 101845651 B CN101845651 B CN 101845651B
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Abstract
The invention discloses a preparation method of cadmium oxide micro-nanometer ordered structural material, belonging to the technical field of preparing nanometer structural material according to electrochemical deposition method. The method comprises the specific preparation steps: using deionized water and cadmium nitrate to prepare electrolyte; putting two cadmium foil electrodes in parallel on a silicon chip substrate which is arranged horizontally, pouring the electrolyte between the two electrodes, covering a cover glass over the electrodes and putting the electrodes in a temperature control system; refrigerating electrolyte until icing is achieved; applying -1.5 to -0.4V of stable voltage after standing still for about 1 hour; observing the generation of a nano array on the substrate in real time; and finally using the deionzied water to clean the substrate to result in cadmium oxide nanometer structural material. The preparation method is simple in synthesis and free from addition of any additive in the process of preparation; the preparation cost is low and templates are not required; the preparation process is easy and fast, samples do not need to be heated and oxidized; the controllability of the preparation process is high, and the growth speed of the samples can be controlled by controlling growth voltage.
Description
Technical field
The invention belongs to the technical field for preparing the cadmium oxide micro-nanometer structured material with the method for electrochemical deposition.Through making up ultra-thin liquid layer, additive-free, need not heated oxide and the direct method that on two dimensional surface, prepares large-area ordered micro-nanometer structural material.
Background technology
Nano structural material has unique optics, electrology characteristic.In many nano structural material preparing methods; Galvanic deposit is as effective synthetic technology of nano structural material; Because of its effective control to institute's synthetic materials pattern, and the low requirement of experiment condition and the feasibility of large-scale production, and become a kind of very promising technique means.Mostly present electro-deposition method is porous aluminium sheet method; It is put into alumina formwork in the solution earlier; Through controlling different sedimentation potentials, make ion in the hole of aluminum oxide masterplate, carry out galvanic deposit, through chemical treatment alumina formwork is removed then; Obtain corresponding nano material, the place one's entire reliance upon pattern of template of the pattern of product.In this preparation process, because technology is comparatively complicated, the cost of manufacture of template is higher, and transmission has very big influence to ionic in the aluminium sheet aperture, has influenced the formation of deposition material.These all become the unfavorable factor in its preparation process.And accurate two-dimentional electro-deposition method can be on the two dimensional surface, under the condition of no template, prepare nano structural material, and this is the preparation of micro-nanometer ordered structural, and a kind of effective means is provided.
Cadmium oxide is a kind of n N-type semiconductorN, and direct band gap is 2.5eV, because of its in the special property aspect optics and the electricity, and at the high transmission rate of solar spectrum visible region, it has good application prospects at aspects such as sun power, phototransistor, catalyzer.And because of its susceptibility unique to gases such as liquefied gas, it also has very big application potential aspect gas sensor.Relevant survey article is seen: (1) Pan, Z.W.; Dai, Z.R.; Wang, Z.L.Science 2001,291, and 1947; (2) Liu, X.; Li, C.; Han, S.; Han, J.; Zhou, C.Appl.Phys.Lett.2003,82,1950; (3) Tz-Jun Kuo and Michael H.Huang.J.Phys.Chem.B 2006,110,13717-13721; (4) R.R.Salunkhe, D.S.Dhawale, D.P.Dubal, C.D.Lokhande.Sensors and Actuators B 140 (2009) 86-91.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method of new cadmium oxide micro-nanometer ordered structural material, additive-free on two dimensional surface, without extra oxide treatment, directly obtain the cadmium oxide micro-nanometer material.And the cadmium oxide micro-nanometer material that generates is made up of by a graded the flaky crystalline grain of many nanometer scale.This structure has greatly improved its specific surface area, makes it that very big application potential arranged aspect gas sensor.
This preparation method comprises the steps:
(1) configuration electrolytic solution.
(2) according to the material that will prepare, prepare needed electrode.Thickness of electrode will approach, and thickness is even.
(3) the parallel silicon chip surface of step (2) being made that is placed on surface oxidation treatment of two electrodes; At a distance of certain distance; The electrolytic solution that then step (1) is configured is got a little and is placed in the middle of the prepared electrode, the last deckglass that a slice approaches on the electrode upper cover.
(4) electrolyzer that step (3) is obtained places water-bath accurately to lower the temperature in the cold cycle chamber of control, freezes.
(5) make it the electrodeposition temperature that reaches suitable through the temperature of regulating water-bath, make that the solution between the glass and silicon chip freezes in the electrolyzer.
(6) place certain hour,, separate out solute between ice and the silicon chip and form ultra-thin liquid layer according to the principle of solute segregation.Two electrodes in the electrolyzer are received on the waveform generator respectively as negative electrode and anode.According to the nano structural material that will prepare, editor's required voltage deposits.
(7) after galvanic deposit finishes, take off deckglass, behind ice-out, on silicon chip, obtain large-area Cadmium oxide semiconductor nano oldered array.
The concrete technical scheme of the present invention is:
1. adopt deionized water, cadmium nitrate configuration electrolytic solution, make Cd
2+Concentration is regulated pH value to 1.0～3.0 of electrolytic solution with nitric acid between 0.002～0.100mol/L;
2. the silicon chip that adopts surface oxidation treatment is as substrate, in the substrate that is placed on horizontal positioned that two cadmium foil electrodes is parallel, between two electrodes, pours electrolytic solution into, covering deckglass on the electrode, forms semi-enclosed electrolyzer, puts into temperature controlling system;
3. temperature is controlled at-2.0～-7.0 ℃, it is icing that electrolytic solution is freezed; Placed 40～100 minutes, and on electrode, applied stable voltage, current potential-1.5～-0.4V; With the nano-array that generates in the substrate of opticmicroscope Real Time Observation; Use the washed with de-ionized water substrate at last, obtain the Cadmium oxide nano structural material.
Proper electrode height is 20～200um; Two proper interelectrode distances are 5～15mm.
The ESEM picture of cadmium oxide micro-nanometer material of the present invention shows that the diameter of material is at 200～700nm.And its high power ESEM picture shows that this nano wire is to have the flaky crystalline grain of many nanometer scale to rearrange by a graded.
In the preparation process of material, deposition voltage is low more, and the speed of growth is fast more, and deposition voltage is high more, and the speed of growth is slow more.When the pH value increases, there is little metal to generate.The concentration of cadmium ion mainly influences the thickness of gained nano wire, and when concentration of cadmium ions was high, the gained nano wire was thicker, and when concentration was low, the gained nano wire was thinner.Utilize electrolyzer that temperature is controlled, can regulate electrolyte layer thickness, when temperature was high more, ice sheet was thin more, and liquid layer is thick more, and corresponding Cadmium oxide nano material is also thick more, and temperature is when low, and layers of ice is thicker, and liquid layer is thin more, and the Cadmium oxide nano material is thin more.
Compare with the method for existing preparation Cadmium oxide semiconductor nano material, advantage of the present invention is: compound method is simple, in the preparation process, does not add any additives; Preparation cost is low, on two dimensional surface, need not template; The preparation process is succinct, and sample need not pass through heated oxide and handle; Preparation controllable process property is high, can pass through control growing voltage control sample grown speed.
Description of drawings
Fig. 1 is the x-ray diffraction pattern of the prepared CdO nano material product of the embodiment of the invention 1.
Fig. 2 is the low power stereoscan photograph of the prepared CdO nano material product of the embodiment of the invention 1.
Fig. 3 is the high power stereoscan photograph of the prepared CdO nano material product of the embodiment of the invention 1.
Fig. 4 is the transmission electron microscope photo of the prepared CdO nano material product of the embodiment of the invention 1.
Fig. 5 is the electron diffraction photo of the prepared CdO nano material product of the embodiment of the invention 1.
Embodiment
The preparation method of embodiment 1CdO nano structural material
With deionized water and cadmium nitrate configuration solution, Cd
2+Concentration is 0.05M/L, utilizes the pH value to 2.0 of nitric acid regulator solution then.Use length to be 2cm, thickness is that 40 μ m cadmium metal paper tinsels are done electrode.The silicon chip of process oxide treatment is as the two-dimensional growth substrate, and silicon chip, reaction soln, deckglass and electrode constitute electrolyzer, and electrolyzer is put into temperature controlling system; Temperature is controlled at-4.75 ℃ through water-bath; It is icing that electrolytic solution in the electrolyzer is freezed, and after ice sheet left standstill through 40～100 minutes, the voltage of the waveform generator that edits is applied on the electrode; Institute's voltage that applies is-0.7V can observe its upgrowth situation through opticmicroscope.Preparation is used the washed with de-ionized water substrate after finishing, and obtains the CdO nano structural material.Fig. 2, Fig. 3 have showed the ESEM picture of the CdO semiconductor nano material for preparing, and Fig. 1, Fig. 4, Fig. 5 are for to characterize its structure with XRD and transmission electron microscope.
The enforcement explanation of 2 pairs of electrolytic solution conditions of embodiment
In the scope of electrolytic solution condition of the present invention, all can prepare the CdO nano structural material.
When preparation CdO nano structural material, Cd
2+Concentration between 0.002～0.100mol/L, adopt Cd
2+Concentration is that the electrolytic solution of 0.05mol/L is thicker than the sample that the electrolytic solution of 0.01mol/L prepares.The pH value along with the pH value increases, has little metal to generate in 1.0～3.0 scope.
Thickness of electrode (electrode height when promptly forming semi-enclosed electrolyzer) mainly influences ice layer thickness, and is little to growth process affects.Two distance between electrodes depend primarily on the size of prepared sample.
The enforcement explanation of embodiment 3 pairs of growths voltage and temperature
In the preparation process, the growth current potential-1.5～-scope of 0.4V in, all can prepare the CdO nano structural material.
The growth voltage that applies will be lower than the ionic equilibrium electrode potential, and along with the reduction of growth voltage, the transmission speed of electronics increases, and the speed of growth increases.Growth voltage be-speed of growth quickening during obviously than-0.5V during 1V, and the diameter of gained nano structural material reduces.But when the growth brownout, ion can not get replenishing effectively, and prepared nano structural material forms branch easily.
The size of temperature depends primarily on the icing situation of electrolytic solution.In-2.0～-7.0 ℃ scope,, will in substrate, obtain the Cadmium oxide nano material as long as cadmium ion is separated out.
Claims (2)
1. the preparation method of a cadmium oxide micro-nanometer ordered structural material,
Adopt deionized water, cadmium nitrate configuration electrolytic solution, make Cd
2+Concentration is regulated pH value to 1.0～3.0 of electrolytic solution with nitric acid between 0.002～0.100mol/L;
The silicon chip that adopts surface oxidation treatment is as substrate, in the substrate that is placed on horizontal positioned that two cadmium foil electrodes is parallel, between two electrodes, pours electrolytic solution into, covering deckglass on the electrode, forms semi-enclosed electrolyzer, puts into temperature controlling system;
Temperature is controlled at-2.0～-7.0 ℃, it is icing that electrolytic solution is freezed; Placed 40～100 minutes, and on electrode, applied stable voltage, current potential-1.5～-0.4V; With the nano-array that generates in the substrate of opticmicroscope Real Time Observation; Use the washed with de-ionized water substrate at last, obtain the Cadmium oxide nano structural material.
2. according to the preparation method of the described cadmium oxide micro-nanometer ordered structural material of claim 1, it is characterized in that the spacing of two electrodes is 5～15mm.
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| CN105714351B (en) * | 2016-05-09 | 2018-04-20 | 吉林大学 | A kind of method that electro-deposition in flexible plastic substrate prepares ZnO nano piece film |
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Non-Patent Citations (2)
| Title |
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| 张兰月等.阳极氧化铝(AAO)模板法制备Cd(OH)2和CdO纳米棒.《无机化学学报》.2008,第24卷(第11期),1919-1922. * |
| 杨阳等.硅基多孔氧化铝模板非水电沉积CdS纳米线的研究.《无机化学学报》.2004,(第1期),65-68. * |
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