CN1522953A - Preparation method of metal sulfide semiconductor nanocrystalline - Google Patents
Preparation method of metal sulfide semiconductor nanocrystalline Download PDFInfo
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- CN1522953A CN1522953A CNA03150857XA CN03150857A CN1522953A CN 1522953 A CN1522953 A CN 1522953A CN A03150857X A CNA03150857X A CN A03150857XA CN 03150857 A CN03150857 A CN 03150857A CN 1522953 A CN1522953 A CN 1522953A
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Abstract
The method for preparing metal sulfide semiconductor nano crystal by using template includes the following steps: firstly, using collodion cotton liquor and making it into the semi-transparent film which has uniform thickness and can meet designed thickness, size and form as artificial active film template, then using metal ion solution of zinc, cadmium copper, mercury, silver, lead, iron, cobalt and nickel whose concentration is 0.05-0.20 mol/L and ionic mole number ratio is correspondent to product chemical formula and providing the solution of sodium sulfide, ammonium sulfide, potassium sulfide and hydrogen sulfide of sulfur ion, respectively placing them at two sides of artificial active film, reacting for 24-48 hr, under the condition of room temp. and stirring, then centrifugal separating reaction solution, removing clear liquor, successively using acetone and deionized water to wash remained product, naturally-drying so as to obtain the metal sulfide semiconductor nano crystal whose grain size (or diameter) is 20-200 nm.
Description
Technical field
The present invention relates to a kind of technology of preparing of metal sulfide semiconductor nanometer crystalline substance.Belong to the method for producing the metal sulfide semiconductor nanometer crystalline substance with template.
Background technology
The metal sulfide semiconductor nanometer crystalline substance is a kind of semi-conductor sulfuration thing (standard) nanoparticle, (standard) nanometer rod with nanometer (1/1000000000th meter) yardstick structural system with characteristic of semiconductor.This semi-conductor sulfuration thing nano material has quantum size effect and surface effects etc., has aspect performances such as excellent light, electricity, magnetic, catalysis, has broad application prospects in industries such as electronics, biology, coating, pharmacy.Therefore, scale production metal sulfide semiconductor nanometer crystalline substance is significant to the development of above-mentioned industry.
At present, in numerous preparation methods of metal sulfide semiconductor nanometer crystalline substance, ultrasonic synthesis method, hydro-thermal-solvent thermal synthesis method are occupied than consequence.Ultrasonic synthesis method needs Vltrasonic device.And hydro-thermal-solvent thermal synthesis method demonstrates its unique glamour owing to stablizing particulate and control size of particles from microcosmic.But hydro-thermal-solvent thermal synthesis method must could obtain under the high-temperature control in airtight high pressure vessel.In recent years, the template synthesis method of nano material to product characteristics such as control action kou and preparation technology be simple preferably, is widely used in the preparation of nano material with it.But, up to the present, do not see the favourable report for preparing the metal sulfide semiconductor nanometer material with artificial active membrane as template as yet.
Summary of the invention
The objective of the invention is to disclose a kind of brand-new artificial active membrane that utilizes and prepare the technology of metal sulfide semiconductor nanometer crystalline substance as template.
In order to achieve the above object, the present invention is performed such.Through studying discovery for a long period of time,, can control the size of product size again as the medium of control mass transfer with having the artificial active membrane that the active collodion of complexing is made.Because the main component of artificial active membrane is that (molecular formula is C to the trinitro-cellulose ester
6H
7O
2(ONO
2)
3).The trinitro-cellulose ester is a macromolecular substance, has very big surface tension.Preparation feedback at the beginning, the nitro (NO on the artificial active membrane
2) just with reactant solution in the rapid complexing of metal ion, and reach capacity.Reacted by the metal ion of complexing and the sulfonium ion that enters the artificial active membrane duct on the artificial active membrane then, generate the metallic sulfide nucleus, also make the concentration of metal ions in the reactant solution " platform " in for some time, occur simultaneously.Nucleus is grown under the effect of artificial active membrane template, forms nanocrystallinely at last, and constantly splits away off from the duct, and new metal ion and the nitro (NO on the artificial active membrane are arranged again
2) complexing, continue said process again, make reaction continue to go on, finish up to reaction.The nucleus that reaction generates is attached to the surface of artificial active membrane, because face trinitro-cellulose ester high molecular form surface tension and face group make the product size reach (standard) nanometer scale to the acting in conjunction of crystal face growth control.
Concrete technology is as follows:
The first step is that the slick sheet glass of surfacing is immersed in the commercially available collodion, repeats to lift twice, and seasoning is peeled off, and gets the artificial active membrane that thin and thick is even, gauge control is determined by design requirements at 0.1mm～0.5mm, size and dimension.
Second step was that to get concentration be 0.05～0.20mol/L, the corresponding sulfocompound solution that the compound solution of metallic cation is provided and sulfonium ion is provided of the ratio of ion mole number and product chemical formula, 24～48h is reacted in the be placed in both sides of artificial active membrane under room temperature and agitation condition.Wherein: what metal ion was provided can be metal ion compounds such as zinc, cadmium, mercury, copper, silver, lead, iron, cobalt, nickel, and what sulfonium ion was provided can be sulfocompounds such as sodium sulphite, ammonium sulfide, potassium sulphide, hydrogen sulfide.
The 3rd step was with above-mentioned reaction soln (dispersion systems of artificial active membrane both sides) centrifugation, discarded clear liquor, and the product that stays is used chemical pure acetone, deionized water wash successively; Take off artificial active membrane, with the product that adheres under the deionized water rinsing, also use acetone, deionized water wash successively, all products that will obtain at last merge, and the light of subsphaeroidal (or bar-shaped), the metal sulfide semiconductor nanometer crystalline substance of superior electrical property are promptly successfully prepared in seasoning.
The present invention has following advantage:
1. because the present invention utilizes a kind of raw material sources wide, in liberal supply, low-cost collodion makes, and to have indexs such as complexing activity and size, shape, thickness artificial adjustable, and semipermeability artificial active membrane that can recycle is as template, therefore make the present invention a step synthesize the metal sulfide semiconductor nanometer crystalline substance efficiently, and whole process of preparation become easily simple more.
2. because the active group that contains on the artificial active mould among the present invention has the good control effect to product: can on template, react the generation metallic sulfide, can make full use of the trend that metal ion and sulfur-containing anion on its both sides move to an other side that splits again, provide power for nanoparticle breaks away from artificial active membrane.Compare with other template, efficient can improve more than 10～100 times.And the product that makes is subsphaeroidal (or bar-shaped) polycrystalline structure, have better degree of crystallinity and good dispersiveness, and purity is higher.
3. technology of the present invention is simple, and whole preparation system makes up easily, and easy and simple to handle, condition is easily controlled, and is with low cost, operation at room temperature, and particle diameter is easily controlled, and is suitable for large-scale commercial production.Whole process of production does not have any pollution simultaneously, meets the Sustainable development requirement.
4. the product prepared of the present invention has performances such as good light, electricity.
Embodiment
Embodiment 1:
The first step is immersed in (C.R. level, Shanghai Stamping Foil Factory) in the commercially available collodion with the slick sheet glass of surfacing, repeat to lift twice, seasoning gets thickness and is about 0.2mm on sheet glass, thickness evenly, size can be by the artificial active membrane of reactor shape and size making.
Second goes on foot, and gets the Hg (NO of 0.1mol/L
3)
2The Na of solution 20mL and 0.1mol/L
2S solution 20mL, the both sides of the artificial active membrane that is placed in, 6511 electric blender of using the accurate mould factory of seamark stir, and behind the reaction 48h, take out the reaction soln of artificial active membrane both sides under the room temperature, carry out conventional centrifugation, discard clear liquor, stay product.Subsequently use commercially available chemical pure acetone, deionized water wash successively.Take off artificial active membrane, attached to the product on the artificial active membrane, also use acetone, deionized water wash successively with deionized water rinsing.All products that will obtain at last merge, and it is nanocrystalline that seasoning promptly obtains metal zunsober HgS.The nanocrystalline transmission electron microscope (TEM) of using of this HgS is observed, and it is shaped as the class spheroidal particle, edge clear, and median size is 33nm.As can be known, this HgS is nanocrystalline good degree of crystallinity from X-ray powder diffraction figure, does not have assorted peak in the collection of illustrative plates and occurs, and its purity height is described.The ultraviolet-visible spectrum analytical results shows that the maximum absorption band of product is compared with conventional zunsober material, in a big way " blue shift " occur, shows tangible quantum size effect.Fluorescent spectroscopy is the result show, product has photoluminescence performance.
Embodiment 2:
CdCl with 0.10mol/L
2Solution 20mL replaces the Hg (NO of 0.10mol/L
3)
2Solution, other conditions and step and embodiment 1 are identical, and the product that obtains is that globular Cadmium Sulfide standard is nanocrystalline, and the product median size is 170nm.Performance is basic nanocrystalline identical with HgS.
Embodiment 3:
The first step is except artificial active membrane thickness is 0.4mm, and all the other are identical with embodiment 1.Second step was got 0.15mol/L AgNO
3Solution 40ml and 0.15mol/L Na
2S solution 20ml, the both sides of the artificial active membrane that is placed in, whole system places place backlight, behind the reaction 24h, the reaction soln of getting the artificial active membrane both sides respectively carries out centrifugation, discards clear liquor under the room temperature, products therefrom and artificial active membrane with merging behind acetone, the deionized water wash, promptly get Ag successively
2S is nanocrystalline, and after tested, optical property is with preceding identical, and the product median size is 28nm.
Embodiment 4
With 40ml 0.10mol/L AgNO
3Solution changes 20ml 0.10mol/L CuSO into
4Outside the solution, other is identical with embodiment 3, obtains the copper sulphide nano crystalline substance.Optical property is good after tested, and the product median size is 20nm.
Embodiment 5
Pb (NO with 0.10mol/L
3)
2Solution 20mL replaces the Hg (NO of 0.10mol/L
3)
2Solution, other conditions and embodiment 1 are identical, and the product that obtains is a sulfide nanocrystalline, and the product median size is 25nm.
Embodiment 6
ZnSO with 0.10mol/L
4Solution 20mL (wherein adding the 0.3mL anhydrous ethylenediamine) replaces the Hg (NO of 0.10mol/L
3)
2Solution, other conditions and embodiment 1 are identical, and the product that obtains is that bar-shaped zinc sulphide standard is nanocrystalline, the about 200nm of product mean diameter, the about 12 μ m of mean length.Through embodiment 1 with the quadrat method test shows, the product purity height, degree of crystallinity and optical property are good.
Claims (2)
1. the preparation method of a metal sulfide semiconductor nanometer crystalline substance, it is characterized in that: be to make as one step of template with artificial active membrane, concrete steps are as follows: the first step is that the slick sheet glass of surfacing is immersed in the commercially available collodion, repeat to lift twice, seasoning, peel off, thickness is even, and the artificial active membrane that adheres to specification at 0.1mm～0.5mm, size and dimension of gauge control; Second step was that to get concentration be 0.05～0.20mol/L, the corresponding compound solution that the compound solution of metal ion is provided and sulfonium ion is provided of the ratio of ion mole number and product chemical formula, 24～48h is reacted in the be placed in both sides of artificial active membrane under room temperature and agitation condition; The 3rd step was with the reacted solution centrifugation, discarded clear liquor, and the product that stays is used chemical pure acetone, deionized water wash successively; Take off artificial active membrane, with the product that adheres under the deionized water rinsing, also use acetone, deionized water wash successively, all products that will obtain at last merge, and it is the light of 20～200nm, subsphaeroidal (or bar-shaped), the metal sulfide semiconductor nanometer crystalline substance of superior electrical property that median size (or diameter) is promptly successfully prepared in seasoning.
2. the preparation method of a kind of metal sulfide semiconductor nanometer crystalline substance according to claim 1 is characterized in that: the metal ion compound solution that metal ion is provided of the both sides of the artificial active membrane that is placed in is the solution of zinc, cadmium, mercury, copper, silver, lead, iron, cobalt, nickel compound; The compound solution that the metal sulfonium ion is provided is sodium sulphite, ammonium sulfide, potassium sulphide, hydrogen sulfide solution.
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| CN 03150857 CN1522953B (en) | 2003-09-05 | 2003-09-05 | Preparation method of metal sulfide semiconductor nanocrystalline |
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| CN 03150857 CN1522953B (en) | 2003-09-05 | 2003-09-05 | Preparation method of metal sulfide semiconductor nanocrystalline |
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| CN1522953B CN1522953B (en) | 2010-05-12 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100417755C (en) * | 2005-12-20 | 2008-09-10 | 中国科学院兰州化学物理研究所 | Process of preparing nano sulfide semiconductor line |
| CN100487856C (en) * | 2005-04-29 | 2009-05-13 | 同济大学 | Method for preparing IIB group semiconductor sulfide nano-material |
| CN100491978C (en) * | 2007-02-13 | 2009-05-27 | 中国科学院上海光学精密机械研究所 | Method for accurately measuring fluorescence parameters of rare earth doped laser glass |
| CN100575261C (en) * | 2005-07-18 | 2009-12-30 | 同济大学 | The method of structure with same quality and different profile with double formworks synchronously barium salt nano-superstructure material |
| US8420186B2 (en) | 2006-12-22 | 2013-04-16 | Industrial Technology Research Institute | Method and apparatus of growing a thin film |
| CN106861599A (en) * | 2015-12-10 | 2017-06-20 | 上海交通大学 | ZnFe2S4Nanocrystalline adsorbent and preparation method thereof and the application in electroplating wastewater processing |
| CN111733194A (en) * | 2020-07-10 | 2020-10-02 | 中山大学 | Method for biologically synthesizing nano metal sulfide |
| CN113621367A (en) * | 2021-06-15 | 2021-11-09 | 哈尔滨理工大学 | Preparation method of rice-grain-shaped lead sulfide quantum dots |
-
2003
- 2003-09-05 CN CN 03150857 patent/CN1522953B/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100487856C (en) * | 2005-04-29 | 2009-05-13 | 同济大学 | Method for preparing IIB group semiconductor sulfide nano-material |
| CN100575261C (en) * | 2005-07-18 | 2009-12-30 | 同济大学 | The method of structure with same quality and different profile with double formworks synchronously barium salt nano-superstructure material |
| CN100417755C (en) * | 2005-12-20 | 2008-09-10 | 中国科学院兰州化学物理研究所 | Process of preparing nano sulfide semiconductor line |
| US8420186B2 (en) | 2006-12-22 | 2013-04-16 | Industrial Technology Research Institute | Method and apparatus of growing a thin film |
| US9221071B2 (en) | 2006-12-22 | 2015-12-29 | Industrial Technology Research Institute | Method and apparatus of growing a thin film |
| CN100491978C (en) * | 2007-02-13 | 2009-05-27 | 中国科学院上海光学精密机械研究所 | Method for accurately measuring fluorescence parameters of rare earth doped laser glass |
| CN106861599A (en) * | 2015-12-10 | 2017-06-20 | 上海交通大学 | ZnFe2S4Nanocrystalline adsorbent and preparation method thereof and the application in electroplating wastewater processing |
| CN106861599B (en) * | 2015-12-10 | 2020-06-19 | 上海交通大学 | ZnFe2S4Nanocrystalline adsorbent, preparation method thereof and application thereof in electroplating wastewater treatment |
| CN111733194A (en) * | 2020-07-10 | 2020-10-02 | 中山大学 | Method for biologically synthesizing nano metal sulfide |
| CN111733194B (en) * | 2020-07-10 | 2021-09-28 | 中山大学 | Method for biologically synthesizing nano metal sulfide |
| CN113621367A (en) * | 2021-06-15 | 2021-11-09 | 哈尔滨理工大学 | Preparation method of rice-grain-shaped lead sulfide quantum dots |
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| Publication number | Publication date |
|---|---|
| CN1522953B (en) | 2010-05-12 |
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