CN1986726A - Preparing process of CdS semiconduct quantum dot - Google Patents
Preparing process of CdS semiconduct quantum dot Download PDFInfo
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- CN1986726A CN1986726A CN 200510133953 CN200510133953A CN1986726A CN 1986726 A CN1986726 A CN 1986726A CN 200510133953 CN200510133953 CN 200510133953 CN 200510133953 A CN200510133953 A CN 200510133953A CN 1986726 A CN1986726 A CN 1986726A
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Abstract
The present invention discloses precursor pyrolyzing process for preparing high dispersive liposoluble CdS semiconductor quantum dot. Precursor is first formed with long carbon chain containing dialkyl thiophosphinic acid as the ligand of metal Cd ion and then pyrolyzed in a simple pyrolysis process, and through further precipitating, filtering, drying, etc, nanometer CdS semiconductor powder is prepared. The produced nanometer CdS semiconductor powder has homogeneous particle size of about 5 nm and excellent optical property, and may be dissolved in benzene, toluene, petroleum ether and other nonpolar and weak polar solvent to form transparent nanometer disperse system.
Description
Technical field
The present invention relates to a kind of preparation method who obtains highly monodispersed oil soluble CdS semiconduct quantum dot by unit molecule presoma pyrolysis method.
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.CdS is the more material of studying in the II-VI family semiconductor compound, is a kind of direct band-gap semicondictor material, and the performance of photoelectricity is than more excellent.The reunion tendency of its nano particle is general relatively more serious.
The synthetic method of semiconductor nanoparticle is divided into vapor growth method and wet-chemical reaction method two big classes.With regard to the vapor phase growth technology, majority is that deposition generates quantum dot on solid substrate, and the another kind of semi-conductor of substrate multidigit.Completely different with it, utilize the wet-chemical reaction method to prepare when nanocrystalline, normally its reaction product is dispersed in certain medium, this medium can be liquid, glass or plastics, the quantum dot system that obtains so relatively is suitable for optical application.Generally speaking, the cost of wet-chemical reaction method is well below vapor growth method, so development in recent years is very fast.The wet-chemical reaction method mainly comprises sol method, sol-gel method, microemulsion method, hydrothermal synthesis method with forerunner's body heat solution or the like, and is wherein noticeable with forerunner's body heat solution.The presoma pyrolysis method mainly is divided into organometallic precursor method and unit molecule precursor process, because a kind of method in back has not only been inherited the former advantage, gained quantum dot good dispersity, size are even, and greatly reduce the toxicity of reaction, by numerous investigators are accepted.But the main drawback that exists is that the introducing in sulphur source and the modifier of participating in reaction mainly concentrate on TOPO (trialkyl oxygen is seen)/TOP expensive reagent such as (trialkyl are seen) at present, and application prospect is subjected to the restriction of certain degree ground.
Summary of the invention
The purpose of this invention is to provide a kind of synthetic oil soluble that has, single scattered, the simple preparation method of the uniform CdS semiconduct quantum dot high yield of particle diameter.
We adopt cheap two alkylthio phosphoric acid to synthesize a kind of body molecule that drives as raw material: two alkylthio cadmium phosphates, and prepared CdS semiconduct quantum dot by normal pressure pyrolysis method high productivity.This method also has the characteristics of in-situ modification except the above-mentioned advantage with presoma pyrolysis method, promptly do not need to add modifier especially again, thereby simplified process of the test greatly, improved the particulate quality; And the thermostability of presoma is relatively poor, has also reduced the requirement to reaction solvent; Add that cheap raw material has reduced cost, therefore improved output again greatly.
The present invention realizes by following measure:
A kind of preparation method of CdS semiconduct quantum dot is characterized in that this method may further comprise the steps:
The preparation of a, presoma: (O, O ')-two-positive alkyl dithiophosphates is dissolved in the ethanol, and after-filtration stirs; In filtrate, add cadmium salt soln, continue to stir, react down until there being the ivory buff precipitation to occur, it is leached drying at 140～250 ℃;
B, the ivory buff powder is dispersed in the low polar organic solvent then, under the nitrogen protection, is heated to 140～200 ℃ of reactions 4～6 hours;
After c, reaction finished, cooling also added precipitation agent in reaction solution, have a large amount of yellow mercury oxides to separate out, and ageing is filtered, washing, and the gained yellow powder is the powder sample of monodispersed oil soluble CdS semiconduct quantum dot.
Cadmium salt of the present invention is 1: 1～1: 2 with the mass ratio of (O, O ')-two-positive alkyl dithiophosphates.
The said low polar solvent of the present invention mainly refers to some organic amines and amide solvent, is cetylamine or oleyl amine.
The said precipitation agent of the present invention refers to and reacts the intensive polar solvent that is with an organic solvent dissolved each other mutually, a kind of in acetone, methyl alcohol, the second eyeball.
The substituting group carbon chain lengths of the present invention (O, O ')-two-positive alkyl dithiophosphates is 8～18.
This preparation method has that raw material is cheap and easy to get, cost is low, and characteristics such as synthesis technique is easy, productive rate height are fit to large-scale production.The particle diameter of the quantum dot of preparing with this law is very even, does not have agglomeration basically, and optical phenomena is very remarkable; The another one outstanding feature is its organic phase capacitive, promptly is scattered in the dissolved form to form transparent nanometer disperse system in the nonpolar or weak polar solvent such as benzene, toluene, sherwood oil, chloroform.This characteristic provides good basis for the research and the assembling of the nanometer system structure of carrying out each side later on.
The present invention adopts the novel two alkyl sulfide phosphonic acids of long carbochain that contain to form presoma as cadmium metal ionic part, through simple pyrolytic reaction process and precipitation, filters, and back process such as drying is handled and can be obtained the CdS semiconduct nano powder.The product particle diameter is even, about about 5nm, can the dissolved form be scattered in the nonpolar or weak polar solvent such as benzene, toluene, sherwood oil, chloroform and forms transparent nanometer disperse system; The optical property of the prepared cadmium sulfide nano granular powder of this method is very excellent.
Description of drawings
Fig. 1 is the transmission electron micrograph of cadmiumsulfide quantum dot: a is the pattern photo under the quantum dot low power; B is the lattice image under the high-amplification-factor of quantum dot; C is the selected area electron diffraction figure of quantum dot; It is very even to observe the semiconductor-quantum-point dispersion from photo, the situation of not reuniting basically, and particle diameter is greatly about about 5nm.
Fig. 2 be cadmiumsulfide quantum dot normal hexane dispersion liquid optical photograph with and under ultra violet lamp the optical photograph of fluorescence picture; Under ultra violet lamp, the solution of cadmiumsulfide quantum dot sends tangible red fluorescence.
Fig. 3 is the uv-visible absorption spectra and the fluorescence emission spectrum of cadmiumsulfide quantum dot normal hexane dispersion liquid; Approximately near 437nm, obvious blue shift phenomenon appears to the absorption peak position of quantum dot in the block materials of Cadmium Sulfide relatively, and absorption peak is comparatively sharp-pointed, and the narrow diameter distribution of gained quantum dot can be described; The peak width at half height of emission spectrum is also narrow, approximately has only about 15nm, illustrates that emission light monochromaticity is fine.
Fig. 4 is the X-ray powder diffraction collection of illustrative plates of cadmiumsulfide quantum dot, and products therefrom is a hexagonal system.
Embodiment
In order to understand the present invention better, describe by example.
Embodiment 1:
The 100g lauryl alcohol is dissolved in 250mL toluene, under agitation adds 30g powdered thiophosphoric anhydride, heating refluxed 4 hours in nitrogen gas stream, and tail gas absorbs with strong caustic.Reaction finishes after-filtration, and cooling adds the Cadmium chloride fine powder aqueous solution of 50mL 500g/L in the filtrate, stirs, and the generation of ivory buff precipitation is arranged.Leach precipitation, use alcohol flushing, after the vacuum-drying it is dissolved in N, in the dinethylformamide, be heated to 160 ℃ of reactions 4 hours.Reaction adds 100mL acetone after finishing, and stirs after-filtration, and the gained yellow powder is product.
Claims (5)
1, a kind of preparation method of CdS semiconduct quantum dot is characterized in that this method may further comprise the steps:
The preparation of a, presoma: (O, O ')-two-positive alkyl dithiophosphates is dissolved in the ethanol, and after-filtration stirs; In filtrate, add cadmium salt soln, continue to stir, react down until there being the ivory buff precipitation to occur, it is leached drying at 140～250 ℃;
B, the ivory buff powder is dispersed in the low polar organic solvent then, under the nitrogen protection, is heated to 140～200 ℃ of reactions 4～6 hours;
After c, reaction finished, cooling also added precipitation agent in reaction solution, have a large amount of yellow mercury oxides to separate out, and ageing is filtered, washing, and the gained yellow powder is the powder sample of monodispersed oil soluble CdS semiconduct quantum dot.
2, the method for claim 1 is characterized in that the cadmium salt and the mass ratio of (O, O ')-two-positive alkyl dithiophosphates are 1: 1～1: 2.
3, the method for claim 1 is characterized in that low polar solvent is cetylamine or oleyl amine.
4, the method for claim 1 is characterized in that precipitation agent is selected from a kind of in acetone, methyl alcohol, the second eyeball.
5, the method for claim 1, it is characterized in that (O, O ')-two-just the substituting group carbon chain lengths of alkyl dithiophosphates is 8～18.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200510133953 CN1986726A (en) | 2005-12-20 | 2005-12-20 | Preparing process of CdS semiconduct quantum dot |
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| CN 200510133953 CN1986726A (en) | 2005-12-20 | 2005-12-20 | Preparing process of CdS semiconduct quantum dot |
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| CN1986726A true CN1986726A (en) | 2007-06-27 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559918B (en) * | 2009-04-30 | 2012-01-18 | 上海大学 | Preparation method of graphene/cadmium sulfide quantum dot composite material applied to photoelectric conversion |
| CN103936058A (en) * | 2014-05-07 | 2014-07-23 | 吉林大学 | Method for preparing cadmium sulfide quantum dots |
| CN106398686A (en) * | 2016-09-05 | 2017-02-15 | Tcl集团股份有限公司 | Quantum dot and preparation method thereof |
| CN106698500A (en) * | 2015-11-16 | 2017-05-24 | 天津大学 | Cadmium sulfide ultrathin nanometer flaky material preparation method and application thereof |
| CN110776917A (en) * | 2019-11-19 | 2020-02-11 | 宁波纳鼎新材料科技有限公司 | Quantum dot and synthetic method thereof |
-
2005
- 2005-12-20 CN CN 200510133953 patent/CN1986726A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559918B (en) * | 2009-04-30 | 2012-01-18 | 上海大学 | Preparation method of graphene/cadmium sulfide quantum dot composite material applied to photoelectric conversion |
| CN103936058A (en) * | 2014-05-07 | 2014-07-23 | 吉林大学 | Method for preparing cadmium sulfide quantum dots |
| CN103936058B (en) * | 2014-05-07 | 2016-02-17 | 吉林大学 | A kind of preparation method of cadmiumsulfide quantum dot |
| CN106698500A (en) * | 2015-11-16 | 2017-05-24 | 天津大学 | Cadmium sulfide ultrathin nanometer flaky material preparation method and application thereof |
| CN106398686A (en) * | 2016-09-05 | 2017-02-15 | Tcl集团股份有限公司 | Quantum dot and preparation method thereof |
| CN106398686B (en) * | 2016-09-05 | 2020-05-22 | Tcl科技集团股份有限公司 | Quantum dot and preparation method thereof |
| CN110776917A (en) * | 2019-11-19 | 2020-02-11 | 宁波纳鼎新材料科技有限公司 | Quantum dot and synthetic method thereof |
| CN110776917B (en) * | 2019-11-19 | 2023-07-21 | 南通惟怡新材料科技有限公司 | Quantum dot and synthesis method thereof |
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