CN1710018A - Method for preparing CdTe nano fluorescent material using ultrasonic-microwave technique - Google Patents
Method for preparing CdTe nano fluorescent material using ultrasonic-microwave technique Download PDFInfo
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- CN1710018A CN1710018A CN 200510016861 CN200510016861A CN1710018A CN 1710018 A CN1710018 A CN 1710018A CN 200510016861 CN200510016861 CN 200510016861 CN 200510016861 A CN200510016861 A CN 200510016861A CN 1710018 A CN1710018 A CN 1710018A
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Abstract
The method of the invention using ultrasonic wave - microwave technology to produce CdTe nano fluorescence material belongs to the producing method field of crystal material. The specific steps are divided into following processes: prepare chromium metal complex solution, prepare tellurium source, ultrasonic wave prepare CdTe nano crystal core solution, microwave prepare CdTe nano fluorescence material. Dissolve cadmium salt and dispersing agent in water and adjust to strong alkalescence to form chromium metal complex solution. Tellurium hydride sodium is tellurium source. In ultrasonic condition, drop to add chromium metal complex solution into tellurium source, to get CdTe nano crystal core watery solution. Pour CdTe nanometer crystal core watery solution into quartz microwave reaction tube at 70 - 100 Deg. C. to get CdTe nano crystal solution of different fluorescence wavelength. The solution is pellucid and transparent, the covering bound of controllable fluorescence emission spectrum is wide, and its quantum efficiency is high.
Description
Technical field
The invention belongs to the preparation method field of crystalline material, particularly a kind of method of utilizing ultrasonic-microwave technique to prepare the CdTe nano-luminescent material.
Background technology
The semiconductor CdTe nanocrystal is because its special photoelectric property is widely used in fields such as bio-imaging, immunology, laser apparatus, solar cell.By conditioned reaction condition changing crystalline size, thereby change the peak position of nanocrystalline fluorescence emission, make it present distinct colors, and crystalline structure and chemical constitution do not change, this typical spectrum characteristic is fit to the compound token of organism very much.
It all is the nanocrystal of organic synthesis that present compound token uses, though the nanocrystal quantum yield that synthesizes under this system is higher, but must carry out aftertreatment to its surperficial hydrophobic grouping, can be applied to organism, influence biological friendly and technology more complicated to a certain extent, be difficult in enormous quantities synthesizing.The synthetic CdTe nanocrystal technology of water method is fairly simple, directly just can be applicable to biomarker, and toxicity is little, can realize production in enormous quantities.Traditional method is exactly reflux (J.Phys.Chem.B under the system of opening wide, 2003,107,8～13), but the shortcoming of this method just is that synthesis cycle is long, generally all needs about tens hours, and the CdTe nanocrystal quantum yield that synthesizes is lower, mainly be because synthesis cycle is long, cause the crystalline surface imperfection more serious, directly influence the quality and the fluorescent characteristic of nanocrystal.
The prior art close with the present invention is that a name is called the patent of invention of " preparation method of water-soluble CdTe nano crystal and preparation facilities thereof ", publication number CN1524783A.The technological process of backflow that the preparation method of disclosed a kind of water-soluble CdTe nano crystal comprises preparation cadmium-sulfydryl mixture---preparation tellurium source---.Preparation cadmium-sulfydryl mixture is that cadmium salt is water-soluble, adds sulfhydryl compound and mixes, and 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,
Summary of the invention
The technical problem to be solved in the present invention is to disclose a kind of method of utilizing ultrasonic-microwave technique to prepare the CdTe nano-luminescent material, at first utilize ultrasonic one-tenth nuclear technique to prepare the CdTe nanocrystal aqueous solution, under the microwave heating system, finish crystalline growth then, reach that crystalline growth velocity is fast, the measured purpose of matter.
The method of utilizing ultrasonic-microwave technique to prepare the CdTe nano-luminescent material of the present invention, concrete steps can be divided into the process of preparation cadmium metal complex solution, preparation tellurium source, ultrasonic preparation CdTe nanocrystal solution, the nanocrystalline fluorescent material of microwave preparation CdTe:
Preparing cadmium metal complex solution process is, cadmium salt is cadmium nitrate or Cadmium chloride fine powder or cadmium acetate or cadmium perchlorate, and dispersion agent is Thiovanic acid, thiohydracrylic acid, halfcystine.Cadmium salt and dispersion agent mol ratio 1: 2.0～3.0; Dissolving cadmium salt and dispersion agent in water, and transfer to strong basicity, pH value 11.2～13 forms the cadmium metal complex solution, contains Cd in the solution
2+Amount 1.2～29mmol/l.
Preparation tellurium source procedure is, with NaBH
4Reacted 60～90 minutes down in argon gas atmosphere and 15～25 ℃ (room temperature) with the tellurium powder, solution becomes the incarnadine transparent liquid, NaHTe content 0.3～7.1mmol/l in the solution, NaBH
4With tellurium powder mol ratio 2～10: 1.
Said ultrasonic preparation CdTe nanocrystal solution is, under ultrasound condition, steady temperature drips the cadmium metal complex solution at 25～30 ℃ in the transparent liquid of tellurium source, and dripping quantity is Cd in molar ratio
2+: NaHTe=2～5: 1, dropwise the back and continued ultrasonic 0.5 hour, obtain the CdTe nanocrystal aqueous solution.
The process of the nanocrystalline fluorescent material of said microwave preparation CdTe is, the CdTe nanocrystal aqueous solution is poured in the quartzy microwave reaction pipe, and with the speed temperature programming of 2～10 ℃/min, steady temperature is 1～60 minute after 70～100 ℃.Can obtain the fluorescent emission wavelength in different time ranges is the CdTe nanocrystal solution of 500nm～680nm.Reaction finished when the solution in the final reaction pipe precipitation occurred or do not have fluorescence
Experiment shows that generally speaking, temperature is short more high more reaction time, and the scope that emission light covers is wide more, and CdTe nanocrystal solution fluorescent emission optical wavelength is subjected to microwave heating time and Temperature Influence to see Table 1.
Table 1 fluorescent emission optical wavelength (color) and microwave steady temperature and steady temperature time relation
Preparation tellurium source procedure is to make NaBH
4At room temperature react with the tellurium powder, can avoid reaction violent, reaction pressure is excessive, helps the control to reaction.
Under ultrasonic environment, prepare the CdTe nanocrystal aqueous solution, mainly utilize the High Temperature High Pressure of moment in collapse moment bubble, help the characteristic of crystal nucleation, can prepare high-quality CdTe nucleus solution.Can use the ultra-sonic generator of power 100～200W, the temperature that keeps reaction system is in 15～25 ℃ of scopes.
Under microwave heating, finish the growth of nanocrystal, after having utilized the polar molecule in the aqueous solution to accept microwave radiation energy, produce internal heat effect by the molecular dipole high speed rotating and provide enough energy for crystal growth, can finish crystal growth within a short period of time, improve CdTe nanocrystal quality.
The CdTe aqueous nanocrystals solution that the ultrasonic-microwave method obtains at room temperature can be stablized about 1 year of preservation, and stability is fine.In order to obtain the CdTe nanocrystal of solid phase, can adopt high speed centrifugation or add acetone or the ultracentrifugal again method of methyl alcohol.To do corresponding different processing according to its different stabilizing power.
Just can obtain the CdTe solid for the bigger CdTe aqueous nanocrystals solution of particle diameter as long as improve centrifugation rate.The CdTe aqueous nanocrystals solution less for particle diameter need add acetone or methyl alcohol, could the centrifugal CdTe solid that obtains.Centrifugal rotational speed is 10000～24000rad/min, and the time is 10～30min.Centrifugal rotational speed can be lower when adding acetone or methyl alcohol, and centrifugal rotational speed can be not higher when not adding acetone or methyl alcohol.The volume ratio of acetone or methyl alcohol and CdTe aqueous nanocrystals solution is 0.25～0: 1.After the CdTe solid dries naturally, be Powdered, excite down at ultraviolet light (excitation wavelength is 365nm) still to have very strong fluorescence, preservation can not change in 1 year under the room temperature.
The technological process of preparation cadmium metal complex solution, preparation tellurium source, ultrasonic preparation CdTe nanocrystal solution can be carried out in there-necked flask in the method for the present invention, and ultrasonic generator is placed in the there-necked flask below.Wherein, adorn constant pressure funnel on the eck in the middle of the there-necked flask, be used to prepare the cadmium metal complex solution.Feed argon gas from the lateral eck of of there-necked flask, the air in can the whole system of emptying is at first finished the preparation in tellurium source in there-necked flask.Under action of ultrasonic waves, slowly drip in the tellurium source solution of cadmium metal complex solution in the there-necked flask in the constant pressure funnel, finish the preparation of the CdTe nanocrystal aqueous solution.
Characteristics according to CdTe nanocrystal growth different steps, the method that adopts ultrasonic-microwave to combine prepares CdTe nanocrystal fluorescent material, be very easy to the control reaction process, shortened the crystal growth time greatly, fundamentally overcome the serious problem of plane of crystal defective, and microwave is different from the traditional heating principle, but after utilizing polar molecule in the aqueous solution to accept microwave radiation energy, the molecular dipole high speed rotating has produced special internal heat effect, and this is a kind of very novel preparation method.The clarification of the CdTe nanocrystal solution that synthesizes, transparent, controllable fluorescent emission spectrum coverage is wide, the quantum yield height, and without any need for aftertreatment just can be used for biomarker; The pressed powder of CdTe nanocrystal still has very strong fluorescence, easily preserves, and be the good nano-luminescent material of a kind of performance.
Embodiment
The present invention is further elaborated below in conjunction with specific embodiment, rather than will be with this limitation of the present invention.
Embodiment 1:
1, the preparation CdTe nanocrystal aqueous solution under ultrasonic environment.
Dissolving 29mg CdCl in 10ml water
22.5H
2O and 25 μ l Thiovanic acids transfer to 12.5 with the NaOH adjust pH, place the constant pressure funnel on the middle eck of there-necked flask.Get 90ml water and put into there-necked flask, add 2.4mgNaBH
4With 4mg tellurium powder, feed argon gas by the lateral eck of there-necked flask, the air in the emptying system, NaBH under the room temperature
4Reacted about 65 minutes with the tellurium powder.Open the ultrasonic generator that places the there-necked flask below, steady temperature slowly drips the cadmium metal complex solution at 25 ℃, dropwises the back and continues ultrasonic half an hour, obtains the CdTe nanocrystal aqueous solution.
2, under microwave heating, finish the growth of nanocrystal.
The 100ml CdTe nanocrystal aqueous solution is poured in the quartzy microwave reaction pipe into temperature programming to 80 ℃.Different time is got 4ml solution at interval at every turn, is cooled to room temperature.The sample time of sample, fluorescent emission optical wavelength, relative light intensity and quantum yield see Table 2.
The relation of table 2 sample time and fluorescent characteristic
| Sample time | Wavelength of transmitted light | Emission peak intensity | Quantum yield (%) |
| ??5min ??10min ??15min ??25min ??40min ??60min | ??501nm ??532nm ??563nm ??601nm ??639nm ??674nm | ??176.2 ??198.3 ??305.4 ??387.6 ??393.8 ??285.1 | ??17 ??30 ??43 ??35 ??21 ??12 |
3, high speed centrifugation obtains the CdTe nanocrystal.
Get 5ml emission light in the CdTe of 500nm～560nm aqueous nanocrystals solution, add methyl alcohol or acetone about 1ml, behind the mixing, put into whizzer, the setting rotating speed is 10000rad/min, and the time is 25min.Abandoning supernatant obtains the solid of nanocrystal, after drying naturally, just can obtain pulverous nanocrystal, and the fluorescent characteristic of this powder is constant.
Embodiment 2:
1, the preparation CdTe nanocrystal aqueous solution under ultrasonic environment.
Dissolving 644mg CdCl in 10ml water
22.5H
2O and 5.5ml Thiovanic acid transfer to 12.5 with the NaOH adjust pH, place constant pressure funnel.Get 90ml water and put into there-necked flask, add 240mg NaBH
4With 90mg tellurium powder, feed argon gas by the lateral eck of there-necked flask, the air in the emptying system, NaBH under the room temperature
4Reacted about 85 minutes with the tellurium powder.Open the ultrasonic generator that places there-necked flask below, temperature 25 ℃ constant, slowly drip the cadmium metal complex solution, dropwise the back and continue ultrasonic half an hour, obtain the CdTe nanocrystal aqueous solution.
2, the method for finishing nanocrystal growth is as described in the embodiment 1.
The sample time of sample, fluorescent emission optical wavelength, relative light intensity and quantum yield see Table 3.
The relation of table 3 sample time and fluorescent characteristic
| Sample time | Wavelength of transmitted light | Emission light relative intensity | Quantum yield (%) |
| ??5min ??10min ??15min ??25min ??35min ??45min | ??532nm ??541nm ??550nm ??573nm ??604nm ??625nm | ??203.05 ??268.99 ??296.28 ??321.16 ??302.67 ??293.46 | ??24 ??29 ??38 ??33 ??19 ??17 |
Embodiment 3:
1, the preparation CdTe nanocrystal aqueous solution under ultrasonic environment.
Dissolving 29mg CdCl in 10ml water
2H
2O and 25 μ l Thiovanic acids transfer to 12.5 with the NaOH adjust pH, place constant pressure funnel.Get 90ml water and put into there-necked flask, add 80mg NaBH
4With 4mg tellurium powder, feed the air in the argon gas emptying system, NaBH under the room temperature
4Reacted about 70 minutes with the tellurium powder.Open ultrasonic generator, slowly drip the cadmium metal complex solution, dropwise the back and continued ultrasonic 0.5 hour, obtain the CdTe nanocrystal aqueous solution, at this moment the temperature of solution rises to 70 ℃.
2, the method for finishing nanocrystal growth is as described in the embodiment 1.
The sample time of sample, fluorescent emission optical wavelength, relative light intensity and quantum yield see Table 4.
The relation of table 4 sample time and fluorescent characteristic
| Sample time | Wavelength of transmitted light | Emission light relative intensity | Quantum yield (%) |
| ??5min ??10min ??15min ??25min ??40min ??60min | ??503nm ??528nm ??557nm ??606nm ??627nm ??669nm | ??154.3 ??172.1 ??298.4 ??352.2 ??370.0 ??251.8 | ??10 ??15 ??28 ??24 ??11 ??7 |
3, it is described that the method that obtains CdTe nanocrystal powder is gone into embodiment 1.
Embodiment 4:
1, the ultrasonic environment method for preparing down the CdTe nanocrystal aqueous solution is as described in the embodiment 1.
2, under microwave heating, finish the growth of nanocrystal.
The 100ml CdTe nanocrystal aqueous solution is poured in the quartzy microwave reaction pipe into temperature programming to 100 ℃.Different time is got 4ml solution at interval at every turn, is cooled to room temperature.The sample time of sample, fluorescent emission optical wavelength, relative light intensity and quantum yield see Table 5.
The relation of table 5 sample time and fluorescent characteristic
| Sample time | Wavelength of transmitted light | Emission light relative intensity | Quantum yield (%) |
| ??2min ??4min ??9min ??15min ??20min ??25min | ??511nm ??527nm ??578nm ??613nm ??645nm ??670nm | ??115.7 ??341.6 ??758.3 ??920.9 ??812.4 ??840.5 | ??32 ??39 ??51 ??36 ??23 ??21 |
3, it is described that the method that obtains CdTe nanocrystal powder is gone into embodiment 1.
Embodiment 5:
1, the method for preparing the CdTe nanocrystal aqueous solution under the ultrasound environments is as described in the embodiment 1.
2, the method for finishing nanocrystal growth is as described in the embodiment 1.
3, high speed centrifugation obtains the CdTe nanocrystal.
Get 5ml emission light in the CdTe of 630nm～680nm aqueous nanocrystals solution, put into whizzer.The setting rotating speed is 24000rad/min, and the time is 10min.Abandoning supernatant obtains the solid of nanocrystal, after drying naturally, just can obtain pulverous nanocrystal, and the fluorescent characteristic of this powder is constant.
Embodiment 6:
In preparation cadmium metal complex solution process, the dispersion agent Thiovanic acid among the embodiment 1～5 is replaced with thiohydracrylic acid or halfcystine, all the other conditions are constant, can form the cadmium metal complex compound equally.
Cadmium salt Cadmium chloride fine powder among the embodiment 1～5 is replaced with cadmium nitrate or cadmium acetate or cadmium perchlorate, and all the other conditions are constant, also can form the cadmium metal complex compound.
Claims (2)
1, a kind of method of utilizing ultrasonic-microwave technique to prepare the CdTe nano-luminescent material, step is divided into the process in preparation cadmium metal complex solution, preparation tellurium source, said preparation cadmium metal complex solution process is, dissolving cadmium salt and dispersion agent in water, transfer to strong basicity, form the cadmium metal complex solution, contain Cd amount 1.2～29mmol/l in the solution; Said preparation tellurium source procedure is, with NaBH
4Under argon gas atmosphere, react NaBH with the tellurium powder
4With tellurium powder mol ratio 2～10: 1; It is characterized in that after the process in preparation tellurium source, also having the process of ultrasonic preparation CdTe nanocrystal solution and the nanocrystalline fluorescent material of microwave preparation CdTe;
In preparation cadmium metal complex solution process, the said strong basicity that transfers to is to make the pH value 11.2～13;
Said preparation tellurium source procedure is 60～90 minutes reaction times, NaHTe content 0.3～7.1mmol/l in the solution;
Said ultrasonic preparation CdTe nanocrystal solution is, under ultrasound condition, steady temperature drips the cadmium metal complex solution at 25～30 ℃ in the transparent liquid of tellurium source, and dripping quantity is Cd in molar ratio
2+: NaHTe=2～5: 1, dropwise the back and continued ultrasonic 0.5 hour, obtain the CdTe nanocrystal aqueous solution;
The process of the nanocrystalline fluorescent material of said microwave preparation CdTe is, the CdTe nanocrystal aqueous solution is poured in the quartzy microwave reaction pipe, speed temperature programming with 2～10 ℃/min, steady temperature is 1～60 minute after 70～100 ℃, and obtaining the fluorescent emission wavelength is the CdTe nanocrystal solution of 500nm～680nm.
2, according to the described method of utilizing ultrasonic-microwave technique to prepare the CdTe nano-luminescent material of claim 1, it is characterized in that, adopt high speed centrifugation or adding acetone or the ultracentrifugal again method of methyl alcohol to obtain the CdTe solid CdTe aqueous nanocrystals solution; Centrifugal rotational speed is 10000～24000rad/min, and the time is 10～30min; The volume ratio of acetone or methyl alcohol and CdTe aqueous nanocrystals solution is 0.25～0: 1
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| CN105372221A (en) * | 2015-12-09 | 2016-03-02 | 吉林化工学院 | Method used for detecting content of ponceau 4R in beverage via fluorescence quenching |
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| CN105372221A (en) * | 2015-12-09 | 2016-03-02 | 吉林化工学院 | Method used for detecting content of ponceau 4R in beverage via fluorescence quenching |
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