CN104357058B - A kind of strong reddish yellow photoemissive polyhedron shape CdSe/ZnSe/ZnS nuclear shell structure quantum point and preparation method thereof - Google Patents
A kind of strong reddish yellow photoemissive polyhedron shape CdSe/ZnSe/ZnS nuclear shell structure quantum point and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to semi-conductor and technical field of nano material, be specifically related to the preparation method of a kind of strong reddish yellow photoemissive polyhedron shape CdSe/ZnSe/ZnS nuclear shell structure quantum point: in cadmium solution, inject TOP-Se solution; Treat that quantum dot grows to desired size, inject ODPA-Zn solution; Reaction solution obtains quantum dot through aftertreatment; The toluene solution of quantum dot is injected in the solution of zinc source; Inject TOP-S solution, insulation, reaction solution, through aftertreatment, to obtain final product.Experimental implementation of the present invention is simple, only needs two steps to synthesize three injections and can obtain the coated CdSe quantum dot of ZnSe/ZnS, and fast, productive rate is high in reaction; By regulate reaction conditions can the CdSe/ZnSe pattern that obtains of conveniently regulating and controlling by uniform-spherical to even rice particle shape, fast, the quantum dot of acquisition has very high luminous intensity in ruddiness-near infrared range to coating reaction.
Description
Technical field
The present invention relates to semi-conductor and technical field of nano material, be specifically related to a kind of strong reddish yellow photoemissive polyhedron shape CdSe/ZnSe/ZnS nuclear shell structure quantum point and preparation method thereof.
Background technology
Quantum dot be a kind of by II-VI race or III-group Ⅴ element form stablize, dispersible in a solvent, the nanocrystal of size between 1 ~ 10nm.Can fluorescence be produced after quantum dot accepts exciting light, compared with traditional organic fluorescent dye, quantum dot have anti-light Bleachability strong, excitation spectrum wide ranges, emmission spectrum narrow range, spatial compatibility are good, fluorescence intensity and the good characteristic such as stability is high.Especially anti-light Bleachability, because traditional organic dye fluorescence intensity under high cell autofluorescence background dies down rapidly, the such as typical organic dye Cy photobleaching cycle is that 35 seconds, FITC are within 5 minutes, long-term tracing observation is made to be difficult to realize, and luminescent quantum dot has the long anti-light bleaching cycle, be generally dozens of minutes, several hours even higher, this just makes long-time continuous imaging tracking vital process become possibility, and the comparative of imaging is fine.So anti-light Bleachability in quantum dot have an enormous advantage.The raising of high-efficiency fluorescence quantum dot brightness also makes the requirement of immunofluorescence to concentration greatly reduce, some reports even overcome the flicker of sample, the luminous energy that single quantum dot is sent is arrived by continuous capturing, each target molecule marks a quantum dot and can mark so in the limiting case, and this just makes high-efficiency fluorescence quantum dot for having extremely low concentrations during biological detection.In white-light illuminating LED field, because quantum dot has higher fluorescence efficiency than conventional fluorescent powder, continuously adjustable emission wavelength and obtaining is studied widely.Wherein nucleocapsid structure luminescent quantum dot is again with the luminescent properties of the stability of its uniqueness and enhancing, has unique advantage in biomarker, luminescent material etc.
But the existence due to heavy metal ion such as inevitable Cd ions in quantum dot makes the biological safety of quantum dot become the bottleneck of its life science application.Therefore need to do passivation layer at the coated nontoxic ZnS of quantum dot surface.In addition, in order to obtain better tissue penetration depths and become image contrast, people are by great effort for the preparation of the quantum dot glowed, and this just requires to prepare the large quantum dot of particle size.The method time and effort consuming of the ZnS coating layer that current preparation is thick or large core quantum dot, simultaneously due to characteristic that crystalline structure is intrinsic quantum dot is grown up after present the trend of oriented growth and to develop into polypody gradually even dendritic by spherical.Polypody or dendritic morphology can increase the specific surface area of quantum dot and reduce the toxicity that coated validity increases quantum dot.Therefore need to improve further current preparation method, while reduction preparation cost improves preparation speed, keep good brightness.
Summary of the invention
Present the trend of oriented growth after growing up for the quantum dot existed in above-mentioned quantum dot preparation process and by the spherical even dendritic problem of polypody that develops into gradually, the invention provides a kind of quantum dot pattern by uniform-spherical to even riziform strong reddish yellow photoemissive polyhedral CdSe/ZnSe/ZnS nuclear shell structure quantum point.
Present invention also offers the preparation method of described strong reddish yellow photoemissive polyhedral CdSe/ZnSe/ZnS nuclear shell structure quantum point.With industrial extractant three octyl tertiary amine (N235) for solvent, effectively reduce preparation cost, reproducible, fast, product is reliable in synthesis.
The present invention is achieved by the following measures:
A preparation method for the polyhedron shape CdSe/ZnSe/ZnS nuclear shell structure quantum point of strong red emission, comprises the following steps:
(1) preparation of solution: under nitrogen atmosphere, selenium powder is dissolved in tri-n-octyl phosphine, is made into TOP-Se solution; Sulphur powder is dissolved in tri-n-octyl phosphine and is made into TOP-S solution; Zinc source is dissolved in octadecylphosphonic acid and three octyl tertiary amines and is made into ODPA-Zn solution;
(2) Cadmium oxide, octadecylphosphonic acid and three octyl tertiary amines are added four-hole bottle, heating for dissolving obtains cadmium solution;
(3) under agitation, in cadmium solution, TOP-Se solution is injected, injection length 0.25-1 minute;
(4) observing response liquid colour-change, treats that quantum dot grows to desired size, injects the ODPA-Zn solution of 70-90 DEG C, injection length 1-2.5 minute;
(5) by after the reaction solution held for some time of step (4), fast cooling is to room temperature;
(6) reaction solution of step (5) obtains quantum dot through aftertreatment, and the quantum dot obtained is dissolved in toluene;
(7) zinc source, oleic acid, three octyl tertiary amines are added four-hole bottle, mixture is heated to 260-310 DEG C of insulation 15 minutes, then temperature is fixed on 230-310 DEG C;
(8) toluene solution of the quantum dot obtained to implantation step (6) in the reaction solution of step (7), continues heating and remains on the selected temperature 0-15 minute of step (7) to make temperature;
(9) slowly inject TOP-S solution in the reaction solution under agitation obtained to step (8), in step (7) selected temperature insulation 10-30 minute, reaction solution, through aftertreatment, to obtain final product.
Described preparation method, the mol ratio injecting Se and cadmium solution Cd in preferred steps (3) is 2-5:1, and preferred molar ratio is 3.3-4.2.
Described preparation method, the mol ratio of the Zn added in preferred steps (4) and the middle cadmium of step (2) is 0.5-2:1, and preferred molar ratio is 0.8-1.2:1.
Described preparation method, in preferred steps (7), the mol ratio of zinc source and the middle cadmium of step (2) is 1:1-3, and preferred molar ratio is 1:1.5-3, and the mol ratio in oleic acid and zinc source is 36-120:1, and preferred molar ratio is 47-84:1.
Described preparation method, in preferred steps (2), the mol ratio of octadecylphosphonic acid and cadmium is
2.1-
2.5:1, preferred molar ratio is the concentration of 2.1-2.25:1, Cd is 0.02-0.03 mole often liter.
Described preparation method, preferred steps (9) inject S mole number be the 1.5-5 in step (7) zinc source doubly, be preferably 1.9-3.8 doubly.
Described preparation method, in preferred steps (1), in TOP-Se solution, selenium powder concentration is 0.25-1 mole often liter; In TOP-S solution, sulphur powder concentration is 0.15-0.75 mole often liter; In ODPA-Zn solution, zinc source concentration is 0.08-0.3 mole often liter, and the mol ratio of described Zn source and octadecylphosphonic acid is 1:2.05-2.5, preferred 1:2.1-2.3.
Described preparation method, preferred zinc source is ZnO, zinc nitrate, zinc sulfate, zinc acetate or zinc acetylacetonate.
Described preparation method, in preferred steps (2), in four-hole bottle, mixture is heated to 270-310 DEG C under nitrogen atmosphere, is incubated 3 minutes and obtains cadmium solution after solution clear, colorless is transparent.
Described preparation method, aftertreatment is add toluene and the mixture of ethanol contend than 1:1 to reaction solution in preferred steps (6), until liquid is muddy, centrifugation, repeats again, centrifugal go out solid be quantum dot; Reaction solution aftertreatment is add toluene and the ethanol contend mixture than 1:1 until muddiness in step (9), and centrifugation, repeats once afterwards throw out to be dissolved in toluene again.
Octadecane base phosphonic acids (ODPA), molecular formula C
18h
37p (O) (OH)
2, CAS accession number 4724-47-4.
Tri-n-octyl phosphine (TOP), molecular formula C
24h
51p, CAS accession number: 4731-53-7.
Three octyl tertiary amines (N235), molecular formula C
24h
51n, CAS accession number 1116-76-3.
Beneficial effect of the present invention:
(1) experimental implementation of the present invention is simple, only needs two steps to synthesize three injections and can obtain the coated CdSe quantum dot of ZnSe/ZnS, and fast, productive rate is high in reaction;
(2) reagent selected in materials synthesis is preserved convenient, can be easy to precise, and experiment difficulty is low.With industrial extractant N235 for solvent can utilize hydrochloric acid soln to extract wherein contained metal ion, economical environment-protective in post synthesis easily.Meanwhile, this compound experiment is insensitive to moisture, without the need to extra vacuum stripping step, effectively shortens experimental period and reduces experimental cost; (3) by regulate reaction conditions can the CdSe/ZnSe pattern that obtains of conveniently regulating and controlling by uniform-spherical to even rice particle shape, fast, the quantum dot of acquisition has very high luminous intensity in ruddiness-near infrared range to coating reaction;
(4) uniform thick ZnS is coated ensure that the permanent stability of quantum dot and low heavy ion separate out concentration, reduces bio-toxicity.
Accompanying drawing explanation
Fig. 1 is the transmitting of CdSe/ZnSe/ZnS quantum dot prepared of embodiment 1 and the temporal evolution of absorption spectrum, the transmitting of what wherein 0min sample was corresponding be coated front CdSe/ZnSe quantum dot and absorption spectrum;
Fig. 2 is CdSe/ZnSe quantum dot (a) of embodiment 1 preparation and the TEM photo of CdSe/ZnSe/ZnS quantum dot (b);
Fig. 3 is the Absorption and emission spectra of (left side) (right side) CdSe/ZnSe quantum dot afterwards before the coated ZnS of embodiment 2;
Fig. 4 is the Absorption and emission spectra of (a) (b) CdSe/ZnSe quantum dot afterwards before the coated ZnS of embodiment 3;
Fig. 5 is that the CdSe/ZnSe quantum dot of comparative example 1 is in the transmitting of coated ZnS process and absorption spectrum evolution in time;
Fig. 6 is transmitting and the absorption spectrum of the CdSe/ZnSe quantum dot of comparative example 2.
Embodiment
Below in conjunction with specific embodiment, technical solution of the present invention is further described.
embodiment 1
(1) stir under nitrogen atmosphere, selenium powder is dissolved in tri-n-octyl phosphine TOP, be made into the TOP-Se solution that concentration is 0.5 mole often liter; Sulphur powder is dissolved in TOP and is made into the TOP-S solution that concentration is 0.375 mole often liter; Octadecylphosphonic acid ODPA and N235 zinc oxide ZnO being dissolved in 2.1 times of mole numbers is made into the ODPA-Zn solution that concentration is 0.23 mole often liter;
(2) by Cadmium oxide CdO0.15mmol, ODPA0.32mmol and N2355mL adds four-hole bottle, is heated to 310 under nitrogen atmosphere
oc, is incubated 3 minutes after solution achromaticity and clarification is transparent;
(3) under fast stirring, inject TOP-Se solution 1mL, wherein Se content is 0.5mmol, injection length 0.25 minute;
After (4) 2 minutes, solution becomes orange, injects 70
othe ODPA-Zn solution 1mL of C, wherein Zn content is 0.23mmol, injection length 1.5 minutes;
(5) after being incubated 2 minutes, solution becomes burgundy, and fast cooling is to room temperature;
(6) add equivalent toluene, ethanol is until liquid is muddy, and centrifugation, is dissolved in 7mL toluene again from effluent, centrifugally stays supernatant liquor, again repeats first time centrifugal step, centrifugal go out solid be again dissolved in toluene 7mL;
(7) by zinc oxide 0.1mmol, oleic acid 4.7mmol, N2355mL adds four-hole bottle; Mixture is heated to 310
oc is incubated 15 minutes; Then temperature is fixed on 310
oc;
(8) inject the toluene solution 2mL of quantum dot, be incubated 5 minutes;
(9) slowly inject TOP-S solution 0.5mL under fast stirring, wherein S content is 0.19mmol, is incubated 15 minutes;
(10) add equivalent toluene, ethanol until muddiness, centrifugation, repeat once afterwards throw out to be dissolved in toluene again.
From Fig. 1 a, quantum dot after ZnSe is coated keeps good luminescent properties, luminescent spectrum is symmetrical, but emission wavelength mainly concentrates on yellow green light wave band, and luminous efficiency is only 27%, but if further coated ZnS, its emission wavelength can rapid red shift to about 660nm, simultaneously luminous efficiency also brings up to 76% rapidly, but along with the growth of coated time, its luminous efficiency can be reduced to 57%.As shown in Figure 2, intermediate steps injects the anisotropic growth that ODPA-Zn can cause quantum dot, obtain the particle of grain of rice shape, but coated ZnS passivation layer can be uniformly distributed at quantum dot surface, grows up to uniform polyhedral.
embodiment 2
(1) stir under nitrogen atmosphere, selenium powder is dissolved in tri-n-octyl phosphine TOP, be made into the TOP-Se solution that concentration is 0.5 mole often liter; Sulphur powder is dissolved in TOP and is made into the TOP-S solution that concentration is 0.375 mole often liter; ODPA and N235 zinc oxide ZnO being dissolved in 2.3 times of mole numbers is made into the ODPA-Zn solution that concentration is 0.1 mole often liter;
(2) by Cadmium oxide CdO0.12mmol, ODPA0.27mmol and N2355mL adds four-hole bottle, is heated to 310 under nitrogen atmosphere
oc, is incubated 3 minutes after solution achromaticity and clarification is transparent;
(3) under fast stirring, inject TOP-Se solution 1mL, wherein Se content is 0.5mmol, injection length 0.25 minute;
After (4) 1.5 minutes, solution becomes red, injects 70
othe ODPA-Zn solution 1mL of C, wherein Zn content is 0.1mmol, injection length 1 minute;
(5) after being incubated 1.5 minutes, solution becomes burgundy, and fast cooling is to room temperature;
(6) add equivalent toluene, methyl alcohol is until liquid is muddy, and centrifugation, is dissolved in 5mL toluene again from effluent, centrifugally stays supernatant liquor, again repeats first time centrifugal step, centrifugal go out solid be again dissolved in toluene 5mL;
(7) by two water zinc acetate 0.075mmol, oleic acid 6.3mmol, N2355mL adds four-hole bottle; Mixture is heated to 310
oc is incubated 15 minutes; Then temperature is fixed on 260
oc;
(8) inject the toluene solution 2mL of quantum dot, be incubated 5 minutes;
(9) slowly inject TOP-S solution 0.5mL under fast stirring, wherein S content is 0.19mmol, is incubated 15 minutes;
(10) add equivalent toluene, ethanol until muddiness, centrifugation, repeat once afterwards throw out to be dissolved in toluene again.
As shown in Figure 3, by coated by quantum dot light emitting peak by green Region red shift to yellow light area, simultaneously quantum dot light emitting efficiency has also brought up to 94% by 27%.
embodiment 3
(1) stir under nitrogen atmosphere, selenium powder is dissolved in tri-n-octyl phosphine TOP, be made into the TOP-Se solution that concentration is 0.5 mole often liter; Sulphur powder is dissolved in TOP and is made into the TOP-S solution that concentration is 0.375 mole often liter; Zinc oxide ZnO is dissolved in ODPA2.1 times of mole number and N235 be made into the ODPA-Zn solution that concentration is 0.1 mole often liter;
(2) by Cadmium oxide CdO0.12mmol, ODPA0.27mmol and N2355mL adds four-hole bottle, is heated to 310 under nitrogen atmosphere
oc, is incubated 3 minutes after solution achromaticity and clarification is transparent;
(3) under fast stirring, inject TOP-Se solution 1mL, wherein Se content is 0.5mmol, injection length 1.5 minutes;
After (4) 2 minutes, solution becomes red, injects 70
othe ODPA-Zn solution 1.5mL of C, wherein Zn content is 0.15mmol, injection length 1.5 minutes;
(5) after being incubated 2 minutes, solution becomes scarlet, and fast cooling is to room temperature;
(6) add equivalent toluene, methyl alcohol is until liquid is muddy, and centrifugation, is dissolved in 5mL toluene again from effluent, centrifugally stays supernatant liquor, again repeats first time centrifugal step, centrifugal go out solid be again dissolved in toluene 5mL;
(7) by two water zinc acetate 0.075mmol, oleic acid 6.3mmol, N2355mL adds four-hole bottle; Mixture is heated to 310
oc is incubated 15 minutes; Then temperature is fixed on 270
oc;
(8) inject the toluene solution 2mL of quantum dot, be incubated 5 minutes;
(9) slowly inject TOP-S solution 0.5mL under fast stirring, wherein S content is 0.19mmol, is incubated 15 minutes;
(10) add equivalent toluene, ethanol until muddiness, centrifugation, repeat once afterwards throw out to be dissolved in toluene again.
As shown in Figure 4, by coated by quantum dot light emitting peak by yellow light area red shift to red light district, simultaneously quantum dot light emitting efficiency has also brought up to 71% by 20%.
embodiment 4
(1) stir under nitrogen atmosphere, selenium powder is dissolved in tri-n-octyl phosphine TOP, be made into the TOP-Se solution that concentration is 0.5 mole often liter; Sulphur powder is dissolved in TOP and is made into the TOP-S solution that concentration is 0.375 mole often liter; Zinc oxide ZnO is dissolved in ODPA2.1 times of mole number and N235 be made into the ODPA-Zn solution that concentration is 0.1 mole often liter;
(2) by Cadmium oxide CdO0.15mmol, ODPA0.32mmol and N2355mL adds four-hole bottle, is heated to 310 under nitrogen atmosphere
oc, is incubated 3 minutes after solution achromaticity and clarification is transparent;
(3) under fast stirring, inject TOP-Se solution 1.2mL, wherein Se content is 0.6mmol, injection length 0.25 minute;
After (4) 2 minutes, solution becomes red, injects 70
othe ODPA-Zn solution 1mL of C, wherein Zn content is 0.15mmol, injection length 1.5 minutes;
(5) after being incubated 2 minutes, solution becomes orange, and fast cooling is to room temperature;
(6) add equivalent toluene, ethanol is until liquid is muddy, and centrifugation, repeats again, centrifugal go out solid be again dissolved in toluene 5mL;
(7) by two water zinc acetate 0.05mmol, oleic acid 3.2mmol, N2355mL adds four-hole bottle; Mixture is heated to 270
oc is incubated 15 minutes; Then temperature is fixed on 270
oc;
(8) inject the toluene solution 2mL of quantum dot, be incubated 5 minutes;
(9) slowly inject TOP-S solution 0.5mL under fast stirring, wherein S content is 0.19mmol, is incubated 15 minutes;
(10) add equivalent toluene, ethanol until muddiness, centrifugation, repeat once afterwards throw out to be dissolved in toluene again, obtain the quantum dot of red emission.
comparative example 1
(1) stir under nitrogen atmosphere, selenium powder is dissolved in tri-n-octyl phosphine TOP, be made into the TOP-Se solution that concentration is 0.5 mole often liter; Sulphur powder is dissolved in TOP and is made into the TOP-S solution that concentration is 0.375 mole often liter; ZnO0.23mmol is dissolved in oleic acid 1.03mmol and N2350.7mL;
(2) by Cadmium oxide CdO0.15mmol, oleic acid 200 μ L(0.63mmol) and N2355mL add four-hole bottle, be heated to 310 under nitrogen atmosphere
oc, is incubated 3 minutes after solution achromaticity and clarification is transparent;
(3) under fast stirring, inject TOP-Se solution 1mL, wherein Se content is 0.5mmol, injection length 0.25 minute;
After (4) 2 minutes, solution becomes burgundy, injects zinc oleate solution, injection length 1.5 minutes;
(5) after being incubated 1min, sampling is also cleaned according to step shown in embodiment 1, and measures transmitting and absorption spectrum;
As shown in Figure 5, when ODPA being changed into oleic acid and making tensio-active agent, quantum dot size presents serious polymolecularity, there is multimodal in luminescence, absorb and also no longer include obvious absorption peak, the fluorescence efficiency of further coated rear quantum dot also only brings up to 4.7% by less than 2%, quantum dot quality degradation to such an extent as to lose utility value, and therefore selecting of ODPA here plays a key effect.Select strong ligand solvent trioctylphosphine (TOPO) that emission peak broadening can be caused according to document (J.AM.CHEM.SOC.2010,132,18206 – 18213, FigureS11), occur multimodal, there is no value coated further equally.
comparative example 2
(1) stir under nitrogen atmosphere, selenium powder is dissolved in tri-n-octyl phosphine TOP, be made into the solution that TOP-Se concentration is 0.5 mole often liter; Sulphur powder is dissolved in TOP and is made into the solution that TOP-S concentration is 0.375 mole often liter; Octadecylphosphonic acid ODPA and ODE zinc oxide ZnO being dissolved in 2.1 times of mole numbers makes the ODPA-Zn solution that concentration is 0.23 mole often liter;
(2) by Cadmium oxide CdO0.15mmol, ODPA0.32mmol and ODE5mL adds four-hole bottle, is heated to 310 under nitrogen atmosphere
oc, is incubated 3 minutes after solution achromaticity and clarification is transparent;
(3) under fast stirring, inject TOP-Se solution 1mL, wherein Se content is 0.5mmol, injection length 0.25 minute;
After (4) 2 minutes, solution becomes burgundy, and inject zinc oleate solution 1mL, wherein Zn content is 0.23mmol injection length 1.5 minutes;
(5) after being incubated 1min, termination reaction is also cleaned according to step shown in embodiment 1, and measures transmitting and absorption spectrum;
(6) coated process is with step shown in embodiment 1 (7)-(10)
As shown in Figure 6, when N-235 being changed into ODE and making solvent, quantum dot size sharply increases, the rapid red shift of glow peak is to red light district and luminous efficiency is reduced to 2%, absorption peak broadening, further coated rear completely unglazed, therefore N235 can not have ODE to replace under this reaction conditions.Equally, according to document (JournalofLuminescence149 (2014) 369 – 373), select non-coordinating solvent octadecylene (ODE) and oleic acid the short-and-medium wavelength zone of the coated process of ZnS can be caused to occur strong glow peak to replace ODPA and N-235, and quantum dot light emitting intensity is low, the further application of restriction nuclear shell structure quantum point.
As can be seen from the result of above embodiment and comparative example, technical scheme of the present invention adopts ODPA and N235 conbined usage, by reasonably limiting the surface tissue optimization that the quantum dot speed of growth and direction realize quantum dot in the process of growth of quantum dot, thus the fluorescence efficiency of raising quantum dot.Simultaneously, inject Zn source introducing CdSe quantum dot growth stoste by once simple, ODPA makes quantum dot can successfully introduce ZnSe transition layer to the rational even summation intensity of quantum dot, and this optimizes the energy band structure of quantum dot further, achieves the luminous efficiency that quantum dot is high.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not by the restriction of embodiment; other is any do not deviate from spirit of the present invention and principle under make change, modification, combination, substitute, simplify and all should be equivalent substitute mode, be included within protection scope of the present invention.
Claims (9)
1. a preparation method for the polyhedron shape CdSe/ZnSe/ZnS nuclear shell structure quantum point of strong red emission, is characterized in that comprising the following steps:
(1) preparation of solution: under nitrogen atmosphere, selenium powder is dissolved in tri-n-octyl phosphine, is made into TOP-Se solution; Sulphur powder is dissolved in tri-n-octyl phosphine and is made into TOP-S solution; Zinc source is dissolved in octadecylphosphonic acid and three octyl tertiary amines and is made into ODPA-Zn solution;
(2) Cadmium oxide, octadecylphosphonic acid and three octyl tertiary amines are added four-hole bottle, heating for dissolving obtains cadmium solution;
(3) under agitation, in cadmium solution, TOP-Se solution is injected, injection length 0.25-1 minute;
(4) observing response liquid colour-change, treats that quantum dot grows to desired size, injects the ODPA-Zn solution of 70-90 DEG C, injection length 1-2.5 minute;
(5) by after the reaction solution held for some time of step (4), fast cooling is to room temperature;
(6) reaction solution of step (5) obtains quantum dot through aftertreatment, and the quantum dot obtained is dissolved in toluene;
(7) zinc source, oleic acid, three octyl tertiary amines are added four-hole bottle, mixture is heated to 260-310 DEG C of insulation 15 minutes, then temperature is fixed on 230-310 DEG C;
(8) toluene solution of the quantum dot obtained to implantation step (6) in the reaction solution of step (7), continues heating and remains on the selected temperature 0-15 minute of step (7) to make temperature;
(9) slowly inject TOP-S solution in the reaction solution under agitation obtained to step (8), in step (7) selected temperature insulation 10-30 minute, reaction solution, through aftertreatment, to obtain final product;
The mol ratio injecting Se and cadmium solution Cd in step (3) is 2-5:1.
2. preparation method according to claim 1, is characterized in that the mol ratio of Zn and the middle cadmium of step (2) added in step (4) is 0.5-2:1.
3. preparation method according to claim 1, it is characterized in that the mol ratio of zinc source and the middle cadmium of step (2) in step (7) is 1:1-3, the mol ratio in oleic acid and zinc source is 36-120:1.
4. preparation method according to claim 1, is characterized in that the mol ratio of octadecylphosphonic acid and cadmium in step (2) be the concentration of 2.1-2.5:1, Cd is 0.02-0.03 mole often liter.
5. preparation method according to claim 1, it is characterized in that step (9) inject S mole number be the 1.5-5 in step (7) zinc source doubly.
6. preparation method according to claim 1, is characterized in that in step (1), in TOP-Se solution, selenium powder concentration is 0.25-1 mole often liter; In TOP-S solution, sulphur powder concentration is 0.15-0.75 mole often liter; In ODPA-Zn solution, zinc source concentration is 0.08-0.3 mole often liter, and the mol ratio of described Zn source and octadecylphosphonic acid is 1:2.05-2.5.
7. preparation method according to claim 1, is characterized in that zinc source is ZnO, zinc nitrate, zinc sulfate, zinc acetate or zinc acetylacetonate.
8. preparation method according to claim 1, is characterized in that in step (2), in four-hole bottle, mixture is heated to 270-310 DEG C under nitrogen atmosphere, is incubated 3 minutes and obtains cadmium solution after solution clear, colorless is transparent.
9. preparation method according to claim 1, it is characterized in that aftertreatment is add toluene and the mixture of ethanol contend than 1:1 to reaction solution in step (6), until liquid is muddy, centrifugation, repeats again, centrifugal go out solid be quantum dot; Reaction solution aftertreatment is add toluene and the ethanol contend mixture than 1:1 until muddiness in step (9), and centrifugation, repeats once afterwards throw out to be dissolved in toluene again.
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| CN103952136B (en) * | 2014-04-29 | 2016-05-11 | 吉林大学 | Cu doping Type-II type nucleocapsid structure white light quanta point material and preparation method |
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