CN1524783A - Method and apparatus for preparing water-soluble CdTe nanocrystalline - Google Patents
Method and apparatus for preparing water-soluble CdTe nanocrystalline Download PDFInfo
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- CN1524783A CN1524783A CNA031271669A CN03127166A CN1524783A CN 1524783 A CN1524783 A CN 1524783A CN A031271669 A CNA031271669 A CN A031271669A CN 03127166 A CN03127166 A CN 03127166A CN 1524783 A CN1524783 A CN 1524783A
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- necked bottle
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Abstract
The invention relates to a water-soluble CdTe nano-crystalline preparing process and appraratus, wherein the process comprises the steps of, preparing cadmium-sulfhydryl compound, preparing tellurium source, and inverse flow, while the tellurium source preparation comprises deacidizing NaBH4 through reducing agent to obtain NaHTe, vacuum-pumping, adding nitrogen and water, reacting for 10-40 minutes under the condition of 30-80 deg. C. The invention also discloses the apparatus for preparing the nano-crystalline.
Description
Technical field
The invention belongs to a kind of preparation method of semiconductor nano material, particularly the fluorescent emission wavelength covers the CdTe preparation of nano crystal and the preparation facilities of whole visibility region.
Background technology
Cadmium telluride (CdTe) is nanocrystalline to be a kind of semiconductor material of important quantum yield occurred frequently.In recent years, be that stablizer is studied synthetic nanocrystalline beginning of high-quality CdTe of water with sulfhydryl compound, and the CdTe that sulfhydryl compound coats has begun to be employed at aspects such as photodiode, photonics device, laser apparatus and biomarkers.Research recently shows that also CdTe is a kind of extremely promising semiconductor material aspect opto-electronic conversion.
The at present synthetic nanocrystalline main method of CdTe is with sulfuric acid and Al
2Te
3Reaction generates H
2Te is again with H
2Te is passed into nitrogen gas stream in the system that contains cadmium source, sulfhydryl compound, controls size by the difference of return time.Specifically can be referring to J.Phys.Chem.B, 2002,106, the article of 7177-7185 publication, exercise question is " Thiol-capping of CdTe nanocrystals:An alternative to organometallicsynthetic routes ".Reaction unit as shown in Figure 1.This device is divided into two portions---preparation H
2The three-necked bottle 1 of the three-necked bottle 11 of Te, preparation CdTe.Preparation H
222, two side ecks of dress sulfuric acid injection tube are made N respectively on the middle eck of the three-necked bottle 11 of Te
2(nitrogen) inlet 23 and H
2Te, N
2Outlet 24.An eck of the three-necked bottle 1 of preparation CdTe is H
2Te, N
2Inlet 12, it and H
2Te, N
2Outlet 24 is communicated with by connecting leg.Using this device, is with raw material A l
2Te
3Put into preparation H
2In the three-necked bottle 11 of Te, pass through N
223 nitrogen injections that enter the mouth inject sulfuric acid, sulfuric acid and Al by sulfuric acid injection tube 22
2Te
3The H that reaction generates
2Te imports the three-necked bottle 1 of preparation CdTe with nitrogen, and with the three-necked bottle 1 of preparation CdTe in the cadmium source, the solution of sulfhydryl compound of being equipped with react, after that reflux makes CdTe is nanocrystalline.
This method has some tangible limitation, 1) preparation H
2The raw material A l that Te is required
2Te
3Dangerous big, very easily oxidized, and cost an arm and a leg, be difficult on the market buy.2) H
2Te has severe toxicity, requires reaction unit, experiment place that the corresponding protection measure is arranged.3) H
2The difficult control of the formation speed of Te, its chemical process that enters system and the reaction of cadmium source is also wayward, generally needs the time longer.4) this reaction system is difficult to amplify, and difficulty is used for industrial production, is difficult to satisfy requirement of large-scale production.
Summary of the invention
The technical problem to be solved in the present invention is to overcome disadvantages of background technology, improve the preparation method of water-soluble CdTe nano crystal, comprise the treatment process, order of addition(of ingredients) in reaction unit, tellurium source etc., the preparation of realization one kettle way, reaction times is shortened greatly, operate more easyly, avoid because the high toxicity in tellurium source and the very easily detrimentally affect that brings of oxidisability.
A kind of preparation method of water-soluble CdTe nano crystal,---the preparation tellurium source---technological process of backflow that comprises preparation cadmium-sulfydryl mixture, preparation cadmium-sulfydryl mixture is that cadmium salt is water-soluble, adding sulfhydryl compound mixes, it is characterized in that said preparation cadmium-sulfydryl mixture carries out under pH value 6～11 conditions; Said preparation tellurium source is tellurium powder reductive agent NaBH
4Reduction obtains NaHTe, promptly adds tellurium powder and NaBH in container
4, vacuumize logical nitrogen and add water, under 0～80 ℃ of condition, reacted 10～480 minutes; Said backflow is after tellurium source NaHTe generates, and cadmium-sulfydryl mixture is joined in the tellurium source and mixes, and it is to reflux 5～1500 minutes under 90～100 ℃ of conditions that reheat makes system temperature; Raw material cadmium salt, tellurium source, sulfhydryl compound are Cd in molar ratio
2+: The
-: sulfhydryl compound=1: (0.7～0.1): (1.5～5).
In the preparation method of water-soluble CdTe nano crystal, said preparation tellurium source is to react 10～40 minutes under 30～80 ℃ of conditions.This is can promote reaction by heating because generate the reaction of NaHTe, shortens the reaction times greatly.This also is a key character of the present invention.
Said cadmium salt can be cadmium perchlorate, Cadmium chloride fine powder, cadmium nitrate or cadmium acetate or their hydrate, and cadmium salt concentration is 10
-5～10
-2The M scope; Said sulfhydryl compound can be mercaptoethanol, mercaprol, Thiovanic acid, thiohydracrylic acid, mercaptoethylamine sulfydryl propylamine, N, N-dimethyl sulfydryl propylamine, halfcystine, thiophenol, Thiosalicylic acid or mercaptoaniline.
A kind of device that is used for the preparation method of water-soluble CdTe nano crystal, structure comprise three-necked bottle, are installed in the reflux condensing tube on the middle eck of three-necked bottle, the heating unit below three-necked bottle; Airtight constant pressure funnel is installed on a side eck of three-necked bottle, and there is discharge valve the below, and there is communicating pipe the side, the logical constant pressure funnel of communicating pipe one end, and the other end is at the following square tube three-necked bottle of discharge valve; Logical nitrogen pipe is housed on the constant pressure funnel.
In the water-soluble CdTe nano crystal preparation facilities, can on another side eck of three-necked bottle, thermometer be installed, be used for the observing response temperature; Said heating unit can adopt the magnetic agitation well heater.
When using device of the present invention, can easily finish the preparation method of water-soluble CdTe nano crystal of the present invention.Preparation cadmium-sulfydryl mixture is to carry out in constant pressure funnel, preparation tellurium source is to carry out in three-necked bottle, reflux is to open the discharge valve of constant pressure funnel below, directly cadmium-sulfydryl mixture is joined after the tellurium source, use the magnetic agitation heater heats, realize reflux course by the reflux condensing tube on the eck in the middle of the three-necked bottle.
The present invention cheap tellurium powder and NaBH
4Reaction has prepared ionic tellurium source NaHTe, has avoided expensive and very easily oxidized raw material A l
2Te
3, avoided intermediate product H simultaneously
2Insecurity that Te brings and uncertainty.Realize separating of cadmium source and tellurium source with constant pressure funnel, made NaHTe on the thronely to react, saved the transfer process in tellurium source.The reaction conditions for preparing NaHTe is optimised, by heating reaction is accelerated greatly, has shortened the reaction times greatly, and it is complete to make that the reaction that needed 8 hours originally or finish for more time shortens to the dozens of minutes internal reaction.Difference by the reflux time can obtain different-grain diameter, and it is nanocrystalline promptly to launch the different CdTe of peak position.It is nanocrystalline that difference by selected part can obtain the CdTe of different surfaces electric charge and functional group.Use this reaction unit can make reaction system amplify (referring to embodiment 5).
In a word, method and apparatus of the present invention reduces the cost of the nanocrystalline preparation of CdTe, and efficient improves, equipment is simple, easy to operate, not only make more convenient, the safety of breadboard research work, also provide a kind of practicality, reliable method for large-scale industrial production.
Description of drawings
Fig. 1 is the device synoptic diagram of background technology.
Fig. 2 is a water-soluble CdTe nano crystal preparation facilities synoptic diagram of the present invention.
Embodiment
Below in conjunction with specific embodiment the present invention is further set forth, rather than will limit the invention with this.
Embodiment 1: device of the present invention
Specify water-soluble CdTe nano crystal preparation facilities of the present invention with reference to figure 2.
Among Fig. 2,1 is three-necked bottle, and 2 for being installed in the reflux condensing tube on the three-necked bottle 1 middle eck, and 3 is the heating unit below three-necked bottle 1, can be the magnetic agitation well heater.Three-necked bottle 1 is preparation tellurium source---tellurium powder reductive agent NaBH
4The reductive container is again as the container of reflux.
Airtight constant pressure funnel 4 is installed on a side eck of three-necked bottle 1, is used to prepare cadmium-sulfydryl mixture; Logical nitrogen pipe 5 is housed on the constant pressure funnel 4; The structure of constant pressure funnel 4 also comprises following discharge valve 6 and lateral communicating pipe 7, the logical constant pressure funnel 4 of communicating pipe 7 one end, and the other end is at the following square tube three-necked bottle 1 of discharge valve 6.Feed nitrogen by logical nitrogen pipe 5 on airtight constant pressure funnel 4, nitrogen can not only charge into constant pressure funnel 4, can also charge into three-necked bottle 1 by communicating pipe 7, vacuumizes the logical nitrogen in back during for preparation tellurium source and uses.Discharge valve 6 is contained on the leakage neck of constant pressure funnel 4 belows, and is to be contained on communicating pipe 7 times end interfaces.The cadmium that discharge valve 6 prepares when opening-sulfydryl mixture bleed three-necked bottle 1 and the reaction of tellurium source, reflux.
Embodiment 2: the reaction process of ice-water bath
Take by weighing 0.042g Cd (ClO
4)
26H
2O is dissolved in the 50mL high purity water as the cadmium source, adds the 21uL Thiovanic acid, mix, and be 10 with 1M NaOH adjust pH, place constant pressure funnel 4.In three-necked bottle 1, add 6.38mg tellurium powder and make raw material, 5mg NaBH
4Make reductive agent.System vacuumizes, logical nitrogen.Three-necked bottle 1 is placed ice-water bath, and in three-necked bottle 1, add a certain amount of water.Treat that the tellurium powder reacted after 8 hours, open discharge valve 6,, join in the three-necked bottle 1 cadmium in the constant pressure funnel 4-sulfydryl mixture.The system heating also keeps refluxing.
It is nanocrystalline to obtain the electronegative different luminous CdTe with carboxylate radical in surface by the control return time.The general backflow 5 minutes to 2 hours can obtain launching the green emitting of peak position at 520-550nm; Refluxed 3 hours to 8 hours, and can obtain launching peak position Yellow luminous at 555-575nm; Reflux and to obtain launching the orange luminescence of peak position in 9 hours to 14 hours at 580-595nm; Backflow 15-20 hour, it was luminous in the reddish orange of 600-615nm to obtain launching peak position; Can obtain launching the emitting red light of peak position in backflow 21-24 hour at 620-650nm.
Embodiment 3:NaHTe generates under the condition of heating
Use embodiment 1 described reaction unit.
Take by weighing 0.042g Cd (ClO
4)
26H
2O is dissolved in the 50mL high purity water, adds the 21uL Thiovanic acid, mix, and be 10 with 1M NaOH adjust pH, place constant pressure funnel 4.In three-necked bottle 1, add 6.38mg tellurium powder, 5mg NaBH4.System vacuumizes, logical nitrogen.Add a certain amount of water in three-necked bottle 1, the tellurium powder is reacted under 30～80 ℃ condition, it is complete that generation NaHTe is reflected at 10～40 minutes internal reactions.With the cadmium in the constant pressure funnel 4-sulfydryl mixture, join in the three-necked bottle 1.The system heating also keeps refluxing.
It is nanocrystalline that the control return time can obtain the electronegative different luminous CdTe with carboxylate radical in surface.
Embodiment 4: change nanocrystalline surface charge and the functional group of CdTe
Use embodiment 1 described reaction unit.
Take by weighing 0.262g Cd (ClO
4)
26H
2O is dissolved in the 250mL high purity water, adds the 170.4mg mercaptoethylamine, mix, and be 6 with 1M NaOH adjust pH, place constant pressure funnel 4.In three-necked bottle 1, add 31.85mg tellurium powder, 30mg NaBH
4System vacuumizes, logical nitrogen.Add a certain amount of water in three-necked bottle 1, the tellurium powder is reacted under 40～80 ℃ condition, it is complete that generation NaHTe is reflected at 10～40 minutes internal reactions.With the cadmium in the constant pressure funnel 4-sulfydryl mixture, join in the three-necked bottle 1.The system heating also keeps refluxing.
It is positively charged nanocrystalline with amino different luminous CdTe to obtain the surface by the control return time.
It is nanocrystalline that embodiment 4 explanation, the difference by selected part can obtain the CdTe of different surfaces electric charge and functional group.
Embodiment 5: the amplification of system and the change of cadmium salt
As reaction unit as described in the embodiment 1, the volume of three-necked bottle 1 is 5L, and constant pressure funnel 4, reflux condensing tube 2 are done corresponding the amplification.
Get 7.446g CdCl
2XH
2O (32.6mmol) is dissolved in 2000 milliliters of high purity waters, adds the 5.46mL Thiovanic acid, mix, and be 10 with 5M NaOH adjust pH, place big constant pressure funnel 4.In three-necked bottle 1, add 2.1g tellurium powder, 2g NaBH4.System vacuumizes, logical nitrogen.Add a certain amount of water in three-necked bottle 1, the tellurium powder is reacted under 30～80 ℃ condition, it is complete that generation NaHTe is reflected at 10～40 minutes internal reactions.With the cadmium in the constant pressure funnel 4-sulfydryl mixture, join in the three-necked bottle 1.The system heating also keeps refluxing.
It is nanocrystalline to obtain the electronegative different luminous CdTe with carboxylate radical in surface by the control return time.
Claims (5)
1, a kind of preparation method of water-soluble CdTe nano crystal,---the preparation tellurium source---technological process of backflow that comprises preparation cadmium-sulfydryl mixture, preparation cadmium-sulfydryl mixture is that cadmium salt is water-soluble, adding sulfhydryl compound mixes, it is characterized in that said preparation cadmium-sulfydryl mixture carries out under pH value 6～11 conditions; Said preparation tellurium source is tellurium powder reductive agent NaBH
4Reduction obtains NaHTe, promptly adds tellurium powder and NaBH in container
4, vacuumize logical nitrogen and add water, under 0～80 ℃ of condition, reacted 10～480 minutes; Said backflow is after tellurium source NaHTe generates, and cadmium-sulfydryl mixture is joined in the tellurium source and mixes, and it is to reflux 5～1500 minutes under 90～100 ℃ of conditions that reheat makes system temperature; Raw material cadmium salt, tellurium source, sulfhydryl compound are Cd in molar ratio
2+: HTe: sulfhydryl compound=1: (0.7～0.1): (1.5～5).
According to the preparation method of the described water-soluble CdTe nano crystal of claim 1, it is characterized in that 2, said preparation tellurium source is to react 10～40 minutes under 30～80 ℃ of conditions.
According to the preparation method of claim 1 or 2 described water-soluble CdTe nano crystals, it is characterized in that 3, said cadmium salt is cadmium perchlorate or Cadmium chloride fine powder or cadmium nitrate or cadmium acetate or their hydrate, cadmium salt concentration is 10
-5～10
-2The M scope; Said sulfhydryl compound is mercaptoethanol or mercaprol or Thiovanic acid or thiohydracrylic acid or mercaptoethylamine sulfydryl propylamine or N, N-dimethyl sulfydryl propylamine or halfcystine or thiophenol or Thiosalicylic acid or mercaptoaniline.
4, a kind of preparation method's of the water-soluble CdTe nano crystal that is used for claim 1 water-soluble CdTe nano crystal preparation facilities, structure comprise three-necked bottle (1), be installed in the reflux condensing tube (2) on the eck in the middle of the three-necked bottle (1), at the heating unit (3) of three-necked bottle (1) below; It is characterized in that, airtight constant pressure funnel (4) is installed on a side eck of three-necked bottle (1), and there is discharge valve (6) below, and there is communicating pipe (7) side, the logical constant pressure funnel (4) of communicating pipe (7) one end, the other end is at the following square tube three-necked bottle (1) of discharge valve (6); Logical nitrogen pipe (5) is housed on the constant pressure funnel (4).
5, according to the described water-soluble CdTe nano crystal preparation facilities of claim 4, it is characterized in that, on another side eck of three-necked bottle (1), thermometer (8) is installed; Said heating unit (3) is the magnetic agitation well heater.
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| CNA031271669A CN1524783A (en) | 2003-09-18 | 2003-09-18 | Method and apparatus for preparing water-soluble CdTe nanocrystalline |
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|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305998C (en) * | 2005-06-30 | 2007-03-21 | 复旦大学 | Water-soluble CdTe nano crystal polymer sulface modifying method |
| CN100379902C (en) * | 2006-08-16 | 2008-04-09 | 中国科学技术大学 | Low-temperature solvent heat growth method of cadmium telluride single-crystal |
| CN101431148B (en) * | 2008-10-13 | 2010-06-02 | 同济大学 | Method for improving illumination intensity of CdTe nano compound film |
| CN102043006A (en) * | 2010-10-29 | 2011-05-04 | 济南大学 | Method for preparing water-soluble quantum dot carbon paste electrode for detecting trace amino acid in food |
| CN101423760B (en) * | 2007-10-31 | 2011-11-09 | 南京大学 | High fluorescent efficiency cadmium telluride quantum point prepared by cathodic tellurium electric pole |
| CN102925138A (en) * | 2012-11-06 | 2013-02-13 | 大连理工大学 | II-VI long-life quantum dot and preparation method thereof |
| CN103043631A (en) * | 2013-01-16 | 2013-04-17 | 四川大学 | Method for preparing cadmium telluride powder by liquid phase reduction and hydrogen treatment |
-
2003
- 2003-09-18 CN CNA031271669A patent/CN1524783A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305998C (en) * | 2005-06-30 | 2007-03-21 | 复旦大学 | Water-soluble CdTe nano crystal polymer sulface modifying method |
| CN100379902C (en) * | 2006-08-16 | 2008-04-09 | 中国科学技术大学 | Low-temperature solvent heat growth method of cadmium telluride single-crystal |
| CN101423760B (en) * | 2007-10-31 | 2011-11-09 | 南京大学 | High fluorescent efficiency cadmium telluride quantum point prepared by cathodic tellurium electric pole |
| CN101431148B (en) * | 2008-10-13 | 2010-06-02 | 同济大学 | Method for improving illumination intensity of CdTe nano compound film |
| CN102043006A (en) * | 2010-10-29 | 2011-05-04 | 济南大学 | Method for preparing water-soluble quantum dot carbon paste electrode for detecting trace amino acid in food |
| CN102925138A (en) * | 2012-11-06 | 2013-02-13 | 大连理工大学 | II-VI long-life quantum dot and preparation method thereof |
| CN102925138B (en) * | 2012-11-06 | 2015-07-22 | 大连理工大学 | II-VI long-life quantum dot and preparation method thereof |
| CN103043631A (en) * | 2013-01-16 | 2013-04-17 | 四川大学 | Method for preparing cadmium telluride powder by liquid phase reduction and hydrogen treatment |
| CN103043631B (en) * | 2013-01-16 | 2014-12-17 | 四川大学 | Method for preparing cadmium telluride powder by liquid phase reduction and hydrogen treatment |
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