CN100417755C - Process of preparing nano sulfide semiconductor line - Google Patents
Process of preparing nano sulfide semiconductor line Download PDFInfo
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- CN100417755C CN100417755C CNB2005101339521A CN200510133952A CN100417755C CN 100417755 C CN100417755 C CN 100417755C CN B2005101339521 A CNB2005101339521 A CN B2005101339521A CN 200510133952 A CN200510133952 A CN 200510133952A CN 100417755 C CN100417755 C CN 100417755C
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Abstract
The present invention is precursor thermally decomposing process for synthesizing nanometer II-VI sulfide semiconductor line in anode alumina template. The preparation process adopts short carbon chain double alkyl group sulfur phosphorus compound coordinated stable organic metal complex as precursor to prepare nanometer II-VI sulfide semiconductor line array and nanometer line through simple soaking and subsequent high temperature treatment. The obtained nanometer line has identical length/diameter ratio, diameter capable of being regulated through the pore size of the template and about 10 micron length. The preparation process of the present invention has the features of cheap facile material, simple synthesis process, low cost, wide application range, etc.
Description
Technical field
The present invention relates to a kind of preparation method based on presoma pyrolysis method synthetic II-VI family sulfide semiconductor nano wire in anodised aluminium (PAA) template.
Background technology
II-VI family semiconductor compound because of it has excellent physical characteristics, is widely used in luminous and display unit, laser and fields such as infrared acquisition, photosensor and photochemical catalysis, is subjected to material scholar's common concern.Along with the development of modern microelectronics, the microminiaturization of various opto-electronic devices is had higher requirement to Materials science, particularly studies low-dimensional materials.Monodimension nanometer material (line, rod, band and pipe) has special structure and anisotropic physical and chemical performance, they promise to be micro connector or functional element, are playing a significant role aspect electronics, photoelectricity, electrochemistry and the electro-mechanical devices of preparation nanoscale.Therefore, materials processing being shaped to one dimension Nano structure is the problem that always is subjected to extensive concern.
Compare with film with nanoparticle, the preparation of one-dimensional nano structure material is more outstanding in the difficulty that technical elements shows.Under normal condition, when molecule and atom are formed solid form by gas phase or solution phase, the tendency of automatic generation particle and film is arranged, and the comparatively difficulty of directly only on the one dimension direction, growing.At present, the confinement growth is the effective way that nanostructure is controlled, and the direct mode of confinement growth is a template.Template is counted as a kind of framework of cast moulding, material can be in template inner or on every side original position produce, and be shaped to and shape of template complementary nanostructure pattern.The comparatively successful template that exists has at present: the step edges on the solid surface, the duct of porous material, organic surface active agent or segmented copolymer are through meso-hole structure, the biomacromolecule (as DNA chain or rhabdovirus) of self-assembly formation and the nanostructure that had existed already.Compare with other templates, the advantage of anodic oxidation aluminium formwork is quite tangible: the first can be by obtaining very high hole density, and become six square arrays to arrange in several microns category; Its two be the duct evenly and parallel each other, and the degree of depth in pitch of holes, bore dia and duct all can be controlled by appropriate parameters; Moreover anodised aluminium self has high chemistry and thermostability, can be in very large scope endoadaptation guest materials and subsequent disposal condition.
Utilize anodic oxidation aluminium formwork to prepare the existing a spot of report of semiconductor nanowires.The method that adopts mainly is and the electro-deposition method coupling carry out electrochemical reaction in (100-160 ℃), the organic system with the acquisition nano-wire array under higher temperature, but this method gained nano wire defective to be more.In addition, also have and adopt and the sol-gel process coupling, though this method has many advantages aspect the preparation nanoparticle, but when preparing nano wire by template, then can run into the difficulty that some are difficult to overcome, for example high viscosity colloidal sol is difficult for being filled to the nano pore of template, causes the nano wire aspect ratio of gained less.In view of the foregoing; we combine the presoma pyrolysis preparation method of semiconductor nanoparticle, have both made full use of the advantage of anodic oxidation aluminium formwork, enrich the growth method of nano wire; further improved nano wire mass-producing synthetic possibility again, had important practical significance.
Summary of the invention
The purpose of this invention is to provide and a kind ofly can in template, synthesize a series of sizes are even, length-to-diameter ratio the is consistent II-VI family sulfide semiconductor nano-wire array and the preparation method of nano wire based on the presoma pyrolysis method.
The present invention realizes by following measure:
The preparation method of II-VI family sulfide semiconductor nano-wire array and nano wire, this method is that the anodic oxidation aluminium formwork with through hole is immersed in the unit molecule precursor solution, through drying at room temperature, can obtain II-VI family sulfide semiconductor nano-wire array and nano wire after the sintering processes.
A kind of preparation method of nano sulfide semiconductor line is characterized in that this method specifically may further comprise the steps:
A, be raw material with soluble metal cadmium or plumbous salt, low-carbon alcohol and thiophosphoric anhydride, low-carbon alcohol and thiophosphoric anhydride are reacted in reflux in toluene, gains at room temperature react with metal salt solution again, the gained solid after filtration, washing, dry after redispersion in polar organic solvent, can obtain transparent precursor solution;
B, under vacuum state, anodic oxidation aluminium formwork was immersed in the precursor solution 15～30 minutes;
C, taking-up template, at room temperature dry 3 hours; Then under the nitrogen protection, 100 ℃ of insulations 0.5～1 hour, 250～700 ℃ of insulation reaction 2～4 hours, gained is a sulfide semiconductor nm-line array.
Anodic oxidation aluminium formwork of the present invention is to prepare by the following method in the laboratory:
Purity is 99.999% rafifinal, after degreasing and removing the zone of oxidation process, adopts two-step anodization technology to carry out anodic oxidation.With the aluminium flake after the oxidation with after the secondary deionized water flushing, with CuCl
2Solution (100ml water+100ml HCl (38%)+3.4g CuCl
2H
2O) remove aluminium substrate in the immersion of aluminium substrate one side, then remove the blocking layer to soak under 5% the phosphoric acid solution room temperature, secondary deionized water is rinsed the anodic alumina films that can obtain through hole well.
The carbon chain lengths of low-carbon alcohol used in the present invention is 2～8.
The effect of polar solvent used in the present invention is to disperse, and preferentially is selected from N, dinethylformamide or organic amine.
The concentration of precursor solution used in the present invention is 0.01～0.05mol/L.
This preparation method has characteristics such as raw material is cheap and easy to get, synthesis technique is easy, cost is low, applied widely, is expected to accomplish scale production.Basic identical with II-VI family sulfide semiconductor nano-wire array and nano wire length-to-diameter ratio that this law is prepared, size is very even, the diameter of nano wire is about 80 nanometers (diameter of nano wire can along with the size adjustment of pore size of template), and line length can reach 10 microns.
Description of drawings
Fig. 1 is the molten SEM photo that goes the cadmium sulfide nano linear array behind the partial oxidation aluminum alloy pattern plate; As can be seen from Figure, the Cadmium oxide nano-wire array is made up of the nano wire of big or small homogeneous, the about 80nm of diameter, and nano wire is evenly and successive conforms to the template diameter, and the cadmium sulfide nano linear array is still keeping the height-oriented property of alumina formwork.
Fig. 2 is the molten SEM photo that removes the lead sulfide nano-wire array behind the partial oxidation aluminum alloy pattern plate.
Embodiment
In order to understand the present invention better, describe by example.
Embodiment 1:
The 50g butanols is dissolved in 500mL toluene, under agitation adds 50g powdered thiophosphoric anhydride, heating refluxed 4 hours in nitrogen gas stream, and tail gas absorbs with dense sodium hydroxide solution.Reaction finishes after-filtration, and cooling adds the Cadmium chloride fine powder aqueous solution of 75mL 500g/L in the filtrate, stirs, and the generation of ivory buff solid is arranged.Leach the ivory buff solid, wash, take by weighing powder 0.3053g (0.001mol) after the drying and it is scattered in 100mL N, in the dinethylformamide with ethanol.To prepare the about 15min of anodic oxidation aluminium formwork decompression vacuum pumping, be immersed in 15min in the precursor solution that configures then, take out, with cotton ball soaked in alcohol wiping template surface for several times, place dry 2h under the room temperature.Under nitrogen protection, template is heated to 100 ℃ of insulation 0.5h, continue to be warming up to 300 reaction 2h, can get the CdS semiconduct nano-wire array.
Embodiment 2:
The 50g butanols is dissolved in 500mL toluene, under agitation adds 50g powdered thiophosphoric anhydride, heating refluxed 4 hours in nitrogen gas stream, and tail gas absorbs with dense sodium hydroxide solution.Reaction finishes after-filtration, and cooling adds the lead nitrate aqueous solution of 130mL 500g/L in the filtrate, stirs the generation of adularescent solid.Leach white solid, wash, take by weighing powder 0.6900g (0.001mol) after the drying and it is scattered in 100mL N, in the dinethylformamide with ethanol.To prepare the about 15min of anodic oxidation aluminium formwork decompression vacuum pumping, be immersed in 15min in the precursor solution that configures then, take out, with cotton ball soaked in alcohol wiping template surface for several times, place dry 2h under the room temperature.Under nitrogen protection, template is heated to 100 ℃ of insulation 0.5h, continue to be warming up to 300 reaction 2h, can get the lead sulfide semiconductor nano-wire array.
Claims (4)
1. the preparation method of a nano sulfide semiconductor line is characterized in that this method specifically may further comprise the steps:
A, be that 2～8 low-carbon alcohol and thiophosphoric anhydride are raw material with soluble metal cadmium or plumbous salt, carbon chain lengths, low-carbon alcohol and thiophosphoric anhydride are reacted in reflux in toluene, gains at room temperature react with soluble metal cadmium or plumbous salt again, the gained solid after filtration, washing, dry after redispersion in polar organic solvent, can obtain transparent precursor solution;
B, under vacuum state, anodic oxidation aluminium formwork was immersed in the precursor solution 15～30 minutes;
C, taking-up template, at room temperature dry 3 hours; Then under the nitrogen protection, 100 ℃ of insulations 0.5～1 hour, 250～700 ℃ of insulation reaction 2～4 hours, gained is a sulfide semiconductor nm-line array.
2. the method for claim 1, the carbon chain lengths that it is characterized in that low-carbon alcohol is 2～8.
3. the method for claim 1 is characterized in that polar solvent is selected from N, dinethylformamide or organic amine.
4. the method for claim 1, the concentration that it is characterized in that precursor solution is 0.01～0.05mol/L.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005101339521A CN100417755C (en) | 2005-12-20 | 2005-12-20 | Process of preparing nano sulfide semiconductor line |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005101339521A CN100417755C (en) | 2005-12-20 | 2005-12-20 | Process of preparing nano sulfide semiconductor line |
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| CN1986911A CN1986911A (en) | 2007-06-27 |
| CN100417755C true CN100417755C (en) | 2008-09-10 |
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| CN103603004A (en) * | 2013-11-27 | 2014-02-26 | 天津大学 | Method for preparing CdS nanowires by using two-step anodized aluminum template |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1522953A (en) * | 2003-09-05 | 2004-08-25 | 同济大学 | Preparation method of metal sulfide semiconductor nanocrystalline |
| CN1608998A (en) * | 2004-09-16 | 2005-04-27 | 复旦大学 | Prepn process of metal oxide and sulfide nanometer linear array |
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2005
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1522953A (en) * | 2003-09-05 | 2004-08-25 | 同济大学 | Preparation method of metal sulfide semiconductor nanocrystalline |
| CN1608998A (en) * | 2004-09-16 | 2005-04-27 | 复旦大学 | Prepn process of metal oxide and sulfide nanometer linear array |
Non-Patent Citations (5)
| Title |
|---|
| Controlled synthesis of semiconductor PbS nanocrystals andnanowires inside mesoporous silica SBA-15 phase. Gao F，Lu Q等.Nano Letters,Vol.1 No.12. 2001 * |
| Studies on the growth and characterization of CdS andnanopartickes using suger-ester nonionic water-in-oilmicroemulion. P S Khiew等.Journal of Crystal Growth,Vol.254 . 2003 * |
| 低温固相法制备CdS纳米线. 许小青等.云南大学学报，第27卷第3A期. 2005 * |
| 溶胶模板法合成CdS纳米棒. 赵启涛等.无机材料学报，第19卷第3期. 2004 * |
| 硫化铅纳米材料合成的新方法. 李文戈等.化学研究，第12卷第04期. 2001 * |
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