CN104327856A - Method for preparing high-quantum-yield narrow-half-peak-width nuclear-shell quantum dot through TOP-assisted SILAR technology - Google Patents
Method for preparing high-quantum-yield narrow-half-peak-width nuclear-shell quantum dot through TOP-assisted SILAR technology Download PDFInfo
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Abstract
The invention discloses a method for preparing a high-quantum-yield narrow-half-peak-width nuclear-shell quantum dot through a TOP-assisted SILAR technology. The method includes following steps: (1) preparing a Se-TOP stock solution, a Zn stock solution and an S stock solution; (2) carrying out a reaction between CdO and stearic acid to prepare cadmium stearate, cooling the cadmium stearate, adding octadecylamine and octadecene, increasing the temperature, adding the Se-TOP stock solution, performing a growth process, performing an extractive purification process to finally enable the cadmium stearate to be dissolved in normal hexane; and (3) adding the octadecylamine and the octadecene in the normal hexane stock solution containing CdSe quantum dot nuclear for removing the normal hexane, water and oxygen, adding tri-n-octylphosphine, performing a heating process, adding dropwisely the Zn stock solution with full reaction for in-situ growth to form a buffer layer, decreasing the temperature, adding dropwisely the S stock solution with heating for full reaction to in-situ grow a first-layer ZnS shell layer; performing extractive purification for a plurality times and to finally enable the ZnS to be dissolved in normal hexane to obtain the normal hexane solution containing CdSe/ZnS nuclear-shell quantum dot. The CdSe/ZnS nuclear-shell quantum dot is high in quantum yield, is narrow in a half peak width and is accurately adjustable in emitting wavelength.
Description
Technical field
The present invention relates to the method that SILAR technology that a kind of TOP of utilization assists prepares high quantum production rate, narrow peak width at half height core-shell quanta dots.
Background technology
The chemical stability of the optical characteristics that semiconductor-quantum-point is correlated with due to its size and excellence and being widely used.But independent quantum dot core, less stable and have certain bio-toxicity, limits it and applies further.Effectively can prevent the leakage of heavy metal ion at the thick shell of quantum dot core surface parcel, improve the stability of quantum dot simultaneously.But along with the formation of quantum dot shell, its quantum yield (QY), peak width at half height (FWHM) are far undesirable.
Continuous ionic layer absorption reaction (SILAR) method is the most widely used method preparing core-shell quanta dots, effectively can control pattern and the distribution of sizes of gained core-shell quanta dots.But it cannot prevent the dislocation that causes due to lattice mismatch in shell process of growth and defect, and finally cause along with shell increases, quantum yield sharply reduces; Its peak width at half height also cannot be controlled effectively simultaneously.The quantum yield (QY) of general core-shell quanta dots only has 10%-40%; Even if quantum yield (QY) can reach 50-80%, along with the increase (more than 1.5 layers) of shell thickness, its quantum yield also sharply reduces.Even if the peak width at half height (FWHM) of gained CdSe quantum dot core can reach 23nm, the peak width at half height (FWHM) of commercial core-shell quanta dots is general all more than 35nm.
Although core-shell quanta dots is widely used in LED, laser, fluorescent bio-probes etc., prepares high quantum production rate (QY), the core-shell quanta dots of narrow peak width at half height (FWHM) has and still have very large challenge.Thick shell is very important for the stability of semiconductor-quantum-point, particularly the application of biology and LEDs aspect.But along with the increase of shell, the quantum yield (QY) of core-shell quanta dots sharply reduces, emission peak peak width at half height (FWHM) increases greatly simultaneously, seriously constrain the application of core-shell quanta dots, particularly FRET (fluorescence resonance energy transfer) (FRET) and the display of QD-LEDs backlight.
So far, existing some work prepares the thick shell core-shell quantum dot of high quantum production rate (QY), as the people such as Samsung sophisticated technology institute Eunjoo Jang report the CdSe//ZnS/CdSZnS alloy nucleocapsid quantum of green emitting on Angewandte Chemie magazine, quantum yield 100%, and with silicone resin compound after still can retain 71% initial luminescence; Zhejiang University Peng Xiaogang professor research group reports the CdSe/CdS core-shell quanta dots by epitaxy 1-6 layer CdS on JACS magazine, and the sub-productive rate of its maximum amount is more than 90%.But the peak width at half height (FWHM) of the best core-shell quanta dots of its gained reaches 35nm, its emission wavelength is difficult to fine adjustment simultaneously, there is larger fluctuation range (± 10nm).And final for QD-LEDs, particularly for high-quality LEDs as: QD-LEDs backlight shows, and high saturation, narrow emission peak, emission wavelength is adjustable and high circulation ratio is necessary.Therefore, prepare high quantum production rate, narrow peak width at half height, core-shell quanta dots that emission wavelength is accurately adjustable, still have very large challenge.
Still there is many deficiencies in existing core-shell quanta dots preparation method, as the increase (more than 1.5 layers) quantum yield (QY) along with shell sharply reduces, emission peak peak width at half height (FWHM) very large (>=35nm), cannot accurately control and reappear the wavelength of gained core-shell quanta dots emission peak, these shortcomings deposit the widespread use that greatly limit core-shell quanta dots.
Summary of the invention
The SILAR technology that the object of the present invention is to provide a kind of TOP of utilization to assist prepares the method for high quantum production rate, narrow peak width at half height core-shell quanta dots.
The technical solution used in the present invention is:
The SILAR technology utilizing TOP to assist prepares a method for high quantum production rate, narrow peak width at half height core-shell quanta dots, comprises the following steps:
1) preparation of core-shell quanta dots mother solution: Se powder is dissolved in tri-n-octyl phosphine, the Se-TOP storing solution of preparation 1-2mol/L; Under ZnO, oleic acid, octadecylene three are placed in protective atmosphere, 285-295 DEG C of reaction, the Zn storing solution of preparation 0.05-0.2mol/L; Under S powder, octadecylene are placed in protective atmosphere, the S storing solution of reaction preparation 0.05-0.2mol/L at 125-135 DEG C;
2) at the preparation of CdSe core: 215-225 DEG C, CdO, stearic acid are reacted fully under protective atmosphere, prepare cadmium stearate, be cooled to room temperature, add stearylamine, octadecylene, 265-275 DEG C is warming up under protective atmosphere, inject Se-TOP storing solution at this temperature, enough time is grown at 245-255 DEG C, recycling normal hexane/methanol system abstraction purification for several times, CdSe quantum dot core after abstraction purification, is finally dissolved in normal hexane, obtains the normal hexane storing solution of CdSe quantum dot core;
3) preparation of CdSe/ZnS core-shell quanta dots: the normal hexane storing solution getting CdSe quantum dot core, adds stearylamine, octadecylene wherein, removed in vacuo normal hexane, water, oxygen;
Under protective atmosphere, activator tri-n-octyl phosphine is added at 135-145 DEG C, fully activate at this mixed system is heated to 195-205 DEG C, instill Zn storing solution again, fully act on, growth in situ forms buffer layer, be cooled to 175-185 DEG C again, instillation S storing solution, fully acts at being heated to 215-225 DEG C, growth in situ the first layer ZnS shell; Recycling normal hexane/methanol system abstraction purification several, the CdSe/ZnS quantum dot after abstraction purification, then be dissolved in normal hexane, obtain the hexane solution of CdSe/ZnS core-shell quanta dots.
The SILAR technology utilizing TOP to assist prepares a method for high quantum production rate, narrow peak width at half height core-shell quanta dots, comprises the following steps:
1) preparation of core-shell quanta dots mother solution: Se powder is dissolved in tri-n-octyl phosphine, the Se-TOP storing solution of preparation 1-2mol/L; Under ZnO, oleic acid, octadecylene three are placed in protective atmosphere, 285-295 DEG C of reaction, the Zn storing solution of preparation 0.05-0.2mol/L; Under S powder, octadecylene are placed in protective atmosphere, the S storing solution of reaction preparation 0.05-0.2mol/L at 125-135 DEG C;
2) at the preparation of CdSe core: 215-225 DEG C, CdO, stearic acid are reacted fully under protective atmosphere, prepare cadmium stearate, be cooled to room temperature, add stearylamine, octadecylene, 265-275 DEG C is warming up under protective atmosphere, inject Se-TOP storing solution at this temperature, enough time is grown at 245-255 DEG C, recycling normal hexane/methanol system abstraction purification for several times, CdSe quantum dot core after abstraction purification, is finally dissolved in normal hexane, obtains the normal hexane storing solution of CdSe quantum dot core;
3) preparation of CdSe/ZnS core-shell quanta dots: the normal hexane storing solution getting CdSe quantum dot core, adds stearylamine, octadecylene wherein, removed in vacuo normal hexane, water, oxygen;
Under protective atmosphere, activator tri-n-octyl phosphine is added at 135-145 DEG C, fully activate at this mixed system is heated to 195-205 DEG C, instill Zn storing solution again, fully act on, growth in situ forms buffer layer, be cooled to 175-185 DEG C again, instillation S storing solution, fully acts at being heated to 215-225 DEG C, growth in situ the first layer ZnS shell;
4) then cool to 135-145 DEG C, instillation tri-n-octyl phosphine, is warming up to 175-185 DEG C, instill Zn storing solution, S storing solution respectively, fully do in order to shells grow layer at being warming up to 215-225 DEG C, this step that circulates 1-8 time, obtains the core-shell quanta dots with 2-9 layer shell respectively; Recycling normal hexane/methanol system abstraction purification several, the CdSe/ZnS quantum dot after abstraction purification, then be dissolved in normal hexane, obtain the hexane solution of CdSe/ZnS core-shell quanta dots.
Step 2) in, the amount ratio of CdO, stearic acid, stearylamine, octadecylene, Se-TOP is: 0.2mmol:0.8mmol:6mmol:4-10ml:2ml; Step 3) in, the amount ratio of CdSe quantum dot core, normal hexane, stearylamine, octadecylene, tri-n-octyl phosphine, Zn storing solution, S storing solution is 7.7 × 10-5mmol:1.2ml:0.8-1.6g:4-8ml:0.3-0.6ml:0.35ml:0.35ml;
Or, step 2) in, the amount ratio of CdO, stearic acid, stearylamine, octadecylene, Se-TOP is: 0.2mmol:0.8mmol:2.4mmol:4-10ml:2ml; Step 3) in, the amount ratio of CdSe quantum dot core, normal hexane, stearylamine, octadecylene, tri-n-octyl phosphine, Zn storing solution, S storing solution is 7.7 × 10-5mmol:0.8ml:0.8-1.6g:4-8ml:0.3-0.6ml:0.28ml:0.28ml;
Or, step 2) in, the amount ratio of CdO, stearic acid, stearylamine, octadecylene, Se-TOP is: 0.2mmol:0.8mmol:18mmol:4-10ml:2ml; Step 3) in, the amount ratio of CdSe quantum dot core, normal hexane, stearylamine, octadecylene, tri-n-octyl phosphine, Zn storing solution, S storing solution is 7.7 × 10-5mmol:4.8ml:0.8-1.6g:4-8ml:0.3-0.6ml:0.57ml:0.57ml.
Step 2) and 3) in, in normal hexane/methanol system, the volume ratio of normal hexane, methyl alcohol is 15:20, and the number of times of normal hexane/methanol system abstraction purification is 3-5 time.
Step 2) in, at 245-255 DEG C, grow 5-10min.
Step 3) in, the time of fully activation is 20-40min.
Step 3) in, after instillation Zn storing solution, the time of fully effect is 20-30min; After instillation S storing solution, the time of fully effect is 60-70min.
Step 4) in, the timed interval of instillation Zn storing solution, S storing solution is 10-15min; The time being warming up to fully effect at 215-225 DEG C is 60-70min.
The invention has the beneficial effects as follows: thick shell CdSe/ZnS core-shell quanta dots prepared by the present invention, there is high quantum yield (QY), narrow peak width at half height (FWHM), and gained quantum dot emission wavelengths is accurately adjustable.
Furtherly:
The present invention is directed to the some shortcomings that existing core-shell quanta dots preparation method exists, provide a kind of method of easy economy, continuous ionic layer absorption reaction (SILAR) method that the method utilizes tri-n-octyl phosphine (TOP) auxiliary, by simple original position shell growth, prepare thick shell CdSe/ZnS core-shell quanta dots, there is high quantum yield (QY), narrow peak width at half height (FWHM), and gained quantum dot emission wavelengths is accurately adjustable.Prepare thick shell CdSe/ZnS core-shell quanta dots, there is high quantum yield (QY), narrow peak width at half height (FWHM), and gained quantum dot emission wavelengths is accurately adjustable.
Accompanying drawing explanation
The SILAR method that Fig. 1 .TOP assists prepares preparation method's principle simplified schematic diagram of efficient core-shell quanta dots;
The condition optimizing of Fig. 2 .TOP consumption.When the left side one width figure is TOP excessive (square), TOP appropriate (circle) and TOP deficiency (triangle), along with shell grows core-shell quanta dots quantum yield (QY) changing trend diagram obtained; When the right one width figure is TOP excessive (square), TOP appropriate (circle) and TOP deficiency (triangle), along with shell grows core-shell quanta dots emission peak peak width at half height (FWHM) changing trend diagram obtained.
Fig. 3. core-shell quanta dots diameter characterization.A width figure is transmission electron microscope (TEM) figure of CdSe core, and illustration is high-resolution-ration transmission electric-lens (HRTEM) figure of CdSe; B width figure is after parcel three layers of shell, the TEM of CdSe/ZnS core-shell quanta dots figure, and illustration is schemed for its HRTEM; C width figure is dynamic light scattering (DLS) distribution plan of CdSe core; D width figure is after parcel three layers of shell, the DLS figure of CdSe/ZnS core-shell quanta dots.
X-ray powder diffraction (XRD) spectrogram (rolling off the production line) of Fig. 4 .CdSe core, wraps up the XRD spectra (reaching the standard grade) of CdSe/ZnS core-shell quanta dots after three layers of shell.
Fig. 5. along with shell grows the core-shell quanta dots change of size trend map obtained.
Fig. 6. along with shell grows the changing trend diagram of the core-shell quanta dots quantum yield (QY) obtained.
The SILAR method that Fig. 7 .TOP assists prepares core-shell quanta dots, along with shell increases fluorescence emission spectrum figure change.From left to right, corresponding peak width at half height is respectively: core, 23nm; One deck, 24.5nm; Three layers, 25nm; Six layers, 26.5; Nine layers, 28nm.
The SILAR method that Fig. 8 .TOP assists prepares fluorescence (solid line), the contrast of ultraviolet (dotted line) spectrogram of different luminous core-shell quanta dots.A width figure is green (570nm); B width figure is orange (590nm); C width figure is red (615nm).The peak width at half height (FWHM) that core-shell quanta dots is corresponding is respectively: 28nm, 25nm, 27nm; The quantum yield (QY) that core-shell quanta dots is corresponding is respectively: 98%, 95%, 69%.
The SILAR method that Fig. 9 .TOP assists prepares the photo under different luminous core-shell quanta dots daylight and ultraviolet lamp.A width figure is the photo of toluene solution under daylight and ultraviolet lamp of green, orange, red three look quantum dots; B width figure is the photo of orange quantum dot pressed powder under daylight and ultraviolet lamp.
Embodiment
The SILAR technology utilizing TOP to assist prepares a method for high quantum production rate, narrow peak width at half height core-shell quanta dots, and step is as follows:
1) preparation of core-shell quanta dots mother solution: Se powder is dissolved in tri-n-octyl phosphine, the Se-TOP storing solution of preparation 1-2mol/L; Under ZnO, oleic acid, octadecylene three are placed in protective atmosphere, 285-295 DEG C of reaction, the Zn storing solution of preparation 0.05-0.2mol/L; Under S powder, octadecylene are placed in protective atmosphere, the S storing solution of reaction preparation 0.05-0.2mol/L at 125-135 DEG C;
2) at the preparation of CdSe core: 215-225 DEG C, CdO, stearic acid are reacted fully under protective atmosphere, prepare cadmium stearate, be cooled to room temperature, add stearylamine, octadecylene, 265-275 DEG C is warming up under protective atmosphere, inject Se-TOP storing solution at this temperature, enough time is grown at 245-255 DEG C, recycling normal hexane/methanol system abstraction purification for several times, CdSe quantum dot core after abstraction purification, is finally dissolved in normal hexane, obtains the normal hexane storing solution of CdSe quantum dot core;
3) preparation of CdSe/ZnS core-shell quanta dots: the normal hexane storing solution getting CdSe quantum dot core, adds stearylamine, octadecylene wherein, removed in vacuo normal hexane, water, oxygen;
Under protective atmosphere, activator tri-n-octyl phosphine is added at 135-145 DEG C, fully activate at this mixed system is heated to 195-205 DEG C, instill Zn storing solution again, fully act on, growth in situ forms buffer layer, be cooled to 175-185 DEG C again, instillation S storing solution, fully acts at being heated to 215-225 DEG C, growth in situ the first layer ZnS shell; Recycling normal hexane/methanol system abstraction purification several, the CdSe/ZnS quantum dot after abstraction purification, then be dissolved in normal hexane, obtain the hexane solution of CdSe/ZnS core-shell quanta dots.
Above method is the method for the quantum dot of preparation containing one deck ZnS shell.
The SILAR technology utilizing TOP to assist prepares a method for high quantum production rate, narrow peak width at half height core-shell quanta dots, and step is as follows:
1) preparation of core-shell quanta dots mother solution: Se powder is dissolved in tri-n-octyl phosphine, the Se-TOP storing solution of preparation 1-2mol/L; Under ZnO, oleic acid, octadecylene three are placed in protective atmosphere, 285-295 DEG C of reaction, the Zn storing solution of preparation 0.05-0.2mol/L; Under S powder, octadecylene are placed in protective atmosphere, the S storing solution of reaction preparation 0.05-0.2mol/L at 125-135 DEG C;
2) at the preparation of CdSe core: 215-225 DEG C, CdO, stearic acid are reacted fully under protective atmosphere, prepare cadmium stearate, be cooled to room temperature, add stearylamine, octadecylene, 265-275 DEG C is warming up under protective atmosphere, inject Se-TOP storing solution at this temperature, enough time is grown at 245-255 DEG C, recycling normal hexane/methanol system abstraction purification for several times, CdSe quantum dot core after abstraction purification, is finally dissolved in normal hexane, obtains the normal hexane storing solution of CdSe quantum dot core;
3) preparation of CdSe/ZnS core-shell quanta dots: the normal hexane storing solution getting CdSe quantum dot core, adds stearylamine, octadecylene wherein, removed in vacuo normal hexane, water, oxygen;
Under protective atmosphere, activator tri-n-octyl phosphine is added at 135-145 DEG C, fully activate at this mixed system is heated to 195-205 DEG C, instill Zn storing solution again, fully act on, growth in situ forms buffer layer, be cooled to 175-185 DEG C again, instillation S storing solution, fully acts at being heated to 215-225 DEG C, growth in situ the first layer ZnS shell;
4) then cool to 135-145 DEG C, instillation tri-n-octyl phosphine, is warming up to 175-185 DEG C, instill Zn storing solution, S storing solution respectively, fully do in order to shells grow layer at being warming up to 215-225 DEG C, this step that circulates 1-8 time, obtains the core-shell quanta dots with 2-9 layer shell respectively; Recycling normal hexane/methanol system abstraction purification several, the CdSe/ZnS quantum dot after abstraction purification, then be dissolved in normal hexane, obtain the hexane solution of CdSe/ZnS core-shell quanta dots.
Step 2) in, the amount ratio of CdO, stearic acid, stearylamine, octadecylene, Se-TOP is: 0.2mmol:0.8mmol:6mmol:4-10ml:2ml; Step 3) in, the amount ratio of CdSe quantum dot core, normal hexane, stearylamine, octadecylene, tri-n-octyl phosphine, Zn storing solution, S storing solution is 7.7 × 10
-5mmol:1.2ml:0.8-1.6g:4-8ml:0.3-0.6ml:0.35ml:0.35ml;
Or, step 2) in, the amount ratio of CdO, stearic acid, stearylamine, octadecylene, Se-TOP is: 0.2mmol:0.8mmol:2.4mmol:4-10ml:2ml; Step 3) in, the amount ratio of CdSe quantum dot core, normal hexane, stearylamine, octadecylene, tri-n-octyl phosphine, Zn storing solution, S storing solution is 7.7 × 10-5mmol:0.8ml:0.8-1.6g:4-8ml:0.3-0.6ml:0.28ml:0.28ml;
Or, step 2) in, the amount ratio of CdO, stearic acid, stearylamine, octadecylene, Se-TOP is: 0.2mmol:0.8mmol:18mmol:4-10ml:2ml; Step 3) in, the amount ratio of CdSe quantum dot core, normal hexane, stearylamine, octadecylene, tri-n-octyl phosphine, Zn storing solution, S storing solution is 7.7 × 10-5mmol:4.8ml:0.8-1.6g:4-8ml:0.3-0.6ml:0.57ml:0.57ml.
Step 2) and 3) in, in normal hexane/methanol system, the volume ratio of normal hexane, methyl alcohol is 15:20, and the number of times of normal hexane/methanol system abstraction purification is 3-5 time.
Step 2) in, at 245-255 DEG C, grow 5-10min.
Step 3) in, the time of fully activation is 20-40min.
Step 3) in, after instillation Zn storing solution, the time of fully effect is 20-30min; After instillation S storing solution, the time of fully effect is 60-70min.
Step 4) in, the timed interval of instillation Zn storing solution, S storing solution is 10-15min; The time being warming up to fully effect at 215-225 DEG C is 60-70min.
Below in conjunction with specific embodiment, the present invention is described further:
Embodiment 1:
The SILAR technology utilizing TOP to assist prepares a method for high quantum production rate, narrow peak width at half height core-shell quanta dots, comprises the following steps:
1) preparation of core-shell quanta dots mother solution:
In glove box, 20mmol selenium powder (Se) is dissolved in 20mlTOP (tri-n-octyl phosphine), prepares the Se-TOP storing solution of 1mol/L;
Under inert atmosphere, 2mmol zinc oxide (ZnO), 16mmol oleic acid (OA), 20ml octadecylene (ODE) are obtained by reacting transparent settled solution in 290 DEG C, prepare the Zn storing solution of 0.1mol/L;
Under 2mmol sulphur powder (S), 20ml octadecylene (ODE) inert atmosphere, 130 DEG C are obtained by reacting transparent settled solution, prepare the S storing solution of 0.1mol/L;
2) preparation of CdSe core:
In 25ml there-necked flask under an inert atmosphere, 220 DEG C of reactions prepare water white cadmium stearate (Cd (SA) for 0.2mmol Cadmium oxide (CdO), 0.8mmol stearic acid (SA)
2); Be cooled to room temperature, add 6mmol stearylamine (ODA), 4-10ml octadecylene (ODE), under inert atmosphere, be again warming up to 270 DEG C, at this temperature, inject 2mlSe-TOP storing solution, in 250 DEG C of growths 5 minutes, utilize 15ml normal hexane/20ml methanol system abstraction purification three times, the CdSe quantum dot after abstraction purification, finally be dissolved in 20ml normal hexane, obtain the normal hexane storing solution of the orange CdSe quantum dot core that 590nm launches;
3) preparation of CdSe/ZnS core-shell quanta dots:
The normal hexane storing solution of the orange CdSe quantum dot core that the 590nm getting 1.2ml launches is (containing orange CdSe quantum dot core 7.7 × 10
-5mmol), add in 25ml there-necked flask, then add 0.8g stearylamine, 4ml octadecylene successively, vacuum is except normal hexane, water, oxygen;
Under inert atmosphere, add activator tri-n-octyl phosphine (TOP) 0.4ml in 140 DEG C, reaction mixture is heated to 200 DEG C of activation 30 minutes.After activation terminates, instillation 0.1mol/L Zn storing solution 0.35ml, in 200 DEG C of effects 20 minutes, growth in situ formed buffer layer.Then be cooled to 180 DEG C, instillation 0.35ml S storing solution, is heated to 220 DEG C of effects 60 minutes, growth in situ the first layer ZnS shell.
Then be cooled to 140 DEG C, instillation 0.4ml TOP, rapid temperature increases to 180 DEG C, instills 0.49ml Zn, 0.49ml S storing solution, 10 minutes, the two interval respectively.Be warming up to 220 DEG C of effects 60 minutes, growth second layer shell.This process that circulates (consumption of material can change), obtains the core-shell quanta dots of more shells;
After prepared by the core-shell quanta dots with 1-9 layer shell, finally use 15ml normal hexane/20ml methyl alcohol, extracted three times; CdSe/ZnS core-shell quanta dots after abstraction purification, is finally dissolved in 20ml hexane solution.
Below preparation when there is the core-shell quanta dots of 1-9 layer shell, step 3) in, the consumption form (relative to above embodiment, some data dot values can be adjusted to value range) of each material:
Table 1:
Embodiment 2:
The SILAR technology utilizing TOP to assist prepares a method for high quantum production rate, narrow peak width at half height core-shell quanta dots, comprises the following steps:
1) preparation of core-shell quanta dots mother solution:
In glove box, 20mmol selenium powder (Se) is dissolved in 20ml TOP (tri-n-octyl phosphine), prepares the Se-TOP storing solution of 1mol/L;
Under inert atmosphere, 2mmol zinc oxide (ZnO), 16mmol oleic acid (OA), 20ml octadecylene (ODE) are obtained by reacting transparent settled solution in 290 DEG C, prepare the Zn storing solution of 0.1mol/L;
Under 2mmol sulphur powder (S), 20ml octadecylene (ODE) inert atmosphere, 130 DEG C are obtained by reacting transparent settled solution, prepare the S storing solution of 0.1mol/L;
2) preparation of CdSe core:
In 25ml there-necked flask under an inert atmosphere, 220 DEG C of reactions prepare water white cadmium stearate (Cd (SA) for 0.2mmol Cadmium oxide (CdO), 0.8mmol stearic acid (SA)
2); Be cooled to room temperature, add 2.4mmol stearylamine (ODA), 4-10ml octadecylene (ODE), under inert atmosphere, be again warming up to 270 DEG C, at this temperature, inject 2mlSe-TOP storing solution, in 250 DEG C of growths 5 minutes, utilize 15ml normal hexane/20ml methanol system abstraction purification three times, the CdSe quantum dot after abstraction purification, finally be dissolved in 20ml normal hexane, obtain the normal hexane storing solution of the green CdSe quantum dot core that 570nm launches;
3) preparation of CdSe/ZnS core-shell quanta dots:
The normal hexane storing solution of the green CdSe quantum dot core that the 570nm getting 0.8ml launches is (containing green CdSe quantum dot core 7.7 × 10
-5mmol), add in 25ml there-necked flask, then add 0.8g stearylamine (ODA), 4ml octadecylene (ODE) successively, vacuum is except normal hexane, water, oxygen;
Under inert atmosphere, add activator tri-n-octyl phosphine (TOP) 0.4ml in 140 DEG C, reaction mixture is heated to 200 DEG C of activation 30 minutes.After activation terminates, instillation 0.1mol/L Zn storing solution 0.28ml, in 200 DEG C of effects 20 minutes, growth in situ formed buffer layer.Then be cooled to 180 DEG C, instillation 0.28ml S storing solution, is heated to 220 DEG C of effects 60 minutes, growth in situ the first layer ZnS shell.
Then be cooled to 140 DEG C, instillation 0.4ml TOP, is warming up to 180 DEG C, instills 0.40ml Zn, 0.40ml S storing solution respectively, 10 minutes, the two interval.Be warming up to 220 DEG C of effects 60 minutes, growth second layer shell.This process that circulates (consumption of material can change), obtains the core-shell quanta dots of more shells;
After prepared by the core-shell quanta dots with 1-9 layer shell, finally use 15ml normal hexane/20ml methyl alcohol, extracted three times; CdSe/ZnS core-shell quanta dots after abstraction purification, is finally dissolved in 20ml hexane solution.
Below preparation when there is the core-shell quanta dots of 1-9 layer shell, step 3) in, the consumption form (relative to above embodiment, some data dot values can be adjusted to value range) of each material:
Table 2:
Embodiment 3:
The SILAR technology utilizing TOP to assist prepares a method for high quantum production rate, narrow peak width at half height core-shell quanta dots, comprises the following steps:
1) preparation of core-shell quanta dots mother solution:
In glove box, 20mmol selenium powder (Se) is dissolved in 20ml TOP (tri-n-octyl phosphine), prepares the Se-TOP storing solution of 1mol/L;
Under inert atmosphere, 2mmol zinc oxide (ZnO), 16mmol oleic acid (OA), 20ml octadecylene (ODE) are obtained by reacting transparent settled solution in 290 DEG C, prepare the Zn storing solution of 0.1mol/L;
Under 2mmol sulphur powder (S), 20ml octadecylene (ODE) inert atmosphere, 130 DEG C are obtained by reacting transparent settled solution, prepare the S storing solution of 0.1mol/L;
2) preparation of CdSe core:
In 25ml there-necked flask under an inert atmosphere, 220 DEG C of reactions prepare water white cadmium stearate (Cd (SA) for 0.2mmol Cadmium oxide (CdO), 0.8mmol stearic acid (SA)
2); Be cooled to room temperature, add 18mmol stearylamine (ODA), 4-10ml octadecylene (ODE), under inert atmosphere, be again warming up to 270 DEG C, at this temperature, inject 2ml Se-TOP storing solution, in 250 DEG C of growths 5 minutes, utilize 15ml normal hexane/20ml methanol system abstraction purification three times, the CdSe quantum dot after abstraction purification, finally be dissolved in 20ml normal hexane, obtain the normal hexane storing solution of the red CdSe quantum dots core that 615nm launches;
3) preparation of CdSe/ZnS core-shell quanta dots:
The normal hexane storing solution of the red CdSe quantum dots core that the 615nm getting 4.8ml launches is (containing red CdSe quantum dots core 7.7 × 10
-5mmol), add in 25ml there-necked flask, then add 0.8g stearylamine (ODA), 4ml octadecylene (ODE) successively, vacuum is except normal hexane, water, oxygen;
Under inert atmosphere, add activator tri-n-octyl phosphine (TOP) 0.4ml in 140 DEG C, reaction mixture is heated to 200 DEG C of activation 30 minutes.After activation terminates, instillation 0.1mol/LZn storing solution 0.57ml, in 200 DEG C of effects 20 minutes, growth in situ formed buffer layer.Then be cooled to 180 DEG C, instillation 0.57mlS storing solution, is heated to 220 DEG C of effects 60 minutes, growth in situ the first layer ZnS shell.
Then be cooled to 140 DEG C, instillation 0.4ml TOP, is warming up to 180 DEG C, instills 0.73ml Zn, 0.73ml S storing solution respectively, 10 minutes, the two interval.Be warming up to 220 DEG C of effects 60 minutes, growth second layer shell.This process that circulates (consumption of material can change), obtains the core-shell quanta dots of more shells;
After prepared by the core-shell quanta dots with 1-9 layer shell, finally use 15ml normal hexane/20ml methyl alcohol, extracted three times; CdSe/ZnS core-shell quanta dots after abstraction purification, is finally dissolved in 20ml hexane solution.
Below preparation when there is the core-shell quanta dots of 1-9 layer shell, the consumption form of each material:
Table 3:
Mechanism figure of the present invention, as Fig. 1, introduces the activation preparation process of core-shell quanta dots in detail.Due to the solvency action of TOP, the excessive Se in CdSe surface is dissolved in system, causes the surface imperfection of quantum dot core to reactivate; Along with adding of Zn parent, buffer layer gradually original position is formed, and has then repaired most of defect on quantum dot core surface.Along with adding of S parent, further original position forms ZnS shell.
It is pointed out that TOP is in preparation process, play vital effect as part and solvent, not only dissolve and activate shell parent, controlling the size of nano particle, pattern and stability simultaneously.TOP is present in whole one-tenth shell process, by a series of growth dissolution process again, effective control ZnS spontaneous nucleation, removes the surface imperfection that in shell process of growth, core-shell quanta dots is formed simultaneously, thus can obtain the three primary colors quantum dot of high quantum production rate, narrow peak width at half height.TOP reactivation process, significantly improves quantum yield; And TOP is present in whole one-tenth shell process, then effectively can control peak width at half height.
In order to obtain the core-shell quanta dots of optimum luminescent properties, we are optimized the experiment condition of the SILAR method that TOP assists.Due to TOP vital role in the method, we are studied the impact of the consumption of TOP on final product character.(the square line when TOP is excessive; With the method steps identical with the embodiment of the present invention, just the consumption of TOP is 1.2ml)), when its quantum yield variation tendency (the left side one width figure in Fig. 2) is moderate to TOP consumption, (method of the embodiment of the present invention) is similar, quantum yield result is better, but as can be seen from its peak width at half height changing trend diagram (the right one width figure in Fig. 2), along with the increase of shell, its peak width at half height sharply increases; And (triangle line during TOP deficiency, with the method steps identical with the embodiment of the present invention, just the consumption of TOP is 0.1ml), along with its quantum yield of increase of shell is without obvious improvement, and as can be seen from its peak width at half height changing trend diagram, along with shell increases, its peak width at half height is also much larger than the moderate sample of TOP consumption.From Fig. 2, we can draw, when TOP is excessive, although quantum yield result is better, due to the overetch to quantum dot core, peak width at half height are increased greatly; And during TOP deficiency, quantum dot core is well activated, and makes quantum yield without obvious improvement, simultaneously not enough to the reparation of the independent nucleation of ZnS and surface imperfection in shell process of growth, the result of narrow peak width at half height cannot be obtained.
We the core-shell quanta dots of gained have been carried out transmission electron microscope (TEM) and dynamic light scattering (DLS) characterizes, as Fig. 3.From on TEM (the A width figure Fig. 3 and B width figure) and DLS (the C width figure in Fig. 3 and D width figure) data, the formation found out along with shell that can be clear and definite, the particle diameter of core-shell quanta dots increases.Illustrate that we have successfully superscribed shell.Can show that our gained core-shell quanta dots crystal formation is fine from high-resolution-ration transmission electric-lens (HRTEM) (illustration in the upper right corner of the A width figure Fig. 3 and B width figure) simultaneously.Can find out that gained core-shell quanta dots has good crystal formation equally from XRD spectra (Fig. 4).
The particle diameter of quantum dot is along with shell growth change (Fig. 5), and can find out the reactivation process due to TOP, CdSe core has certain reduction, and the Se that namely activation of TOP makes quantum dot surface excessive dissolves; Along with the particle diameter that adds of Zn parent increases, namely define buffer layer.Subsequently along with shell increases, particle diameter increases gradually.
Along with the growth of shell, the variation tendency (Fig. 6) of quantum yield, after can finding out TOP activation, the quantum yield of CdSe quantum dot core has part to reduce, may be because TOP is to the activation on quantum dot core surface, the Se dissolving that quantum dot surface is excessive, makes defect reactivate; And adding Zn parent formation buffer layer, quantum yield sharply increases, and namely the quantum dot core surface imperfection after activation is repaired by buffer layer.Even if wrap up 6 layers of shell, the quantum yield of core-shell quanta dots is still more than 95%, and with existing work shell more than 1.5 layers, namely quantum yield sharply reduces obviously different.Namely our work successfully breaches the low bottleneck of the quantum yield of thick shell core-shell quantum.
We are studied (Fig. 7) along with shell growth emission peak changes for core-shell quanta dots simultaneously, can find out that quantum dot emission peak only has very little red shift, and peak width at half height still keeps very narrow, even if parcel 9 layers of shell, its peak width at half height of orange core-shell quanta dots is still less than 28nm.
Gained three look core-shell quanta dots, analyzes (Fig. 8) its fluorescent ultraviolet spectrogram, and can find out and independent nuclear phase ratio, after wrapping up three layers of shell, quantum yield increases greatly.Emission peak displacement is very little simultaneously, and namely exciton is revealed seldom, can effectively control to obtain the controlled core-shell quanta dots of wavelength.Three look quantum dot quantum yields are respectively: green (98%), orange (95%), red (69%); Its peak width at half height is respectively 28nm, 25nm, 27nm, obtains the core-shell quanta dots of narrow peak width at half height, thus may obtain the QD-LEDs backlight of high color saturation.To the contrast photo (Fig. 9) of core-shell quanta dots under daylight and ultraviolet lamp, we can find out that the core-shell quanta dots prepared all has very strong fluorescent emission at solution and solid state equally.
Claims (8)
1. the SILAR technology utilizing TOP to assist prepares a method for high quantum production rate, narrow peak width at half height core-shell quanta dots, it is characterized in that: comprise the following steps:
1) preparation of core-shell quanta dots mother solution: Se powder is dissolved in tri-n-octyl phosphine, the Se-TOP storing solution of preparation 1-2mol/L; Under ZnO, oleic acid, octadecylene three are placed in protective atmosphere, 285-295 DEG C of reaction, the Zn storing solution of preparation 0.05-0.2mol/L; Under S powder, octadecylene are placed in protective atmosphere, the S storing solution of reaction preparation 0.05-0.2mol/L at 125-135 DEG C;
2) at the preparation of CdSe core: 215-225 DEG C, CdO, stearic acid are reacted fully under protective atmosphere, prepares cadmium stearate, be cooled to room temperature, add stearylamine, octadecylene, be warming up to 265-275 DEG C under protective atmosphere, inject Se-TOP storing solution at this temperature, at 245-255 DEG C, grow enough time, recycling normal hexane/methanol system abstraction purification for several times, CdSe quantum dot core after abstraction purification, is finally dissolved in normal hexane, obtains the normal hexane storing solution of CdSe quantum dot core;
3) preparation of CdSe/ZnS core-shell quanta dots: the normal hexane storing solution getting CdSe quantum dot core, adds stearylamine, octadecylene wherein, removed in vacuo normal hexane, water, oxygen;
Under protective atmosphere, activator tri-n-octyl phosphine is added at 135-145 DEG C, fully activate at this mixed system is heated to 195-205 DEG C, instill Zn storing solution again, fully act on, growth in situ forms buffer layer, be cooled to 175-185 DEG C again, instillation S storing solution, fully acts at being heated to 215-225 DEG C, growth in situ the first layer ZnS shell; Recycling normal hexane/methanol system abstraction purification several, the CdSe/ZnS quantum dot after abstraction purification, then be dissolved in normal hexane, obtain the hexane solution of CdSe/ZnS core-shell quanta dots.
2. the SILAR technology that a kind of TOP of utilization according to claim 1 assists prepares the method for high quantum production rate, narrow peak width at half height core-shell quanta dots, it is characterized in that: comprise the following steps:
1) preparation of core-shell quanta dots mother solution: Se powder is dissolved in tri-n-octyl phosphine, the Se-TOP storing solution of preparation 1-2mol/L; Under ZnO, oleic acid, octadecylene three are placed in protective atmosphere, 285-295 DEG C of reaction, the Zn storing solution of preparation 0.05-0.2mol/L; S powder is dissolved in octadecylene, the S storing solution of reaction preparation 0.05-0.2mol/L at 125-135 DEG C;
2) at the preparation of CdSe core: 215-225 DEG C, CdO, stearic acid are reacted fully under protective atmosphere, prepares cadmium stearate, be cooled to room temperature, add stearylamine, octadecylene, be warming up to 265-275 DEG C under protective atmosphere, inject Se-TOP storing solution at this temperature, at 245-255 DEG C, grow enough time, recycling normal hexane/methanol system abstraction purification for several times, CdSe quantum dot core after abstraction purification, is finally dissolved in normal hexane, obtains the normal hexane storing solution of CdSe quantum dot core;
3) preparation of CdSe/ZnS core-shell quanta dots: the normal hexane storing solution getting CdSe quantum dot core, adds stearylamine, octadecylene wherein, removed in vacuo normal hexane, water, oxygen;
Under protective atmosphere, activator tri-n-octyl phosphine is added at 135-145 DEG C, fully activate at this mixed system is heated to 195-205 DEG C, instill Zn storing solution again, fully act on, growth in situ forms buffer layer, be cooled to 175-185 DEG C again, instillation S storing solution, fully acts at being heated to 215-225 DEG C, growth in situ the first layer ZnS shell;
4) then cool to 135-145 DEG C, instillation tri-n-octyl phosphine, is warming up to 175-185 DEG C, instill Zn storing solution, S storing solution respectively, fully do in order to shells grow layer at being warming up to 215-225 DEG C, this step that circulates 1-8 time, obtains the core-shell quanta dots with 2-9 layer shell respectively; Recycling normal hexane/methanol system abstraction purification several, the CdSe/ZnS quantum dot after abstraction purification, then be dissolved in normal hexane, obtain the hexane solution of CdSe/ZnS core-shell quanta dots.
3. the SILAR technology of assisting according to a kind of TOP of utilization described in claim 1 or 2 prepares the method for high quantum production rate, narrow peak width at half height core-shell quanta dots, it is characterized in that: step 2) in, the amount ratio of CdO, stearic acid, stearylamine, octadecylene, Se-TOP is: 0.2mmol:0.8mmol:6mmol:4-10ml:2ml; In step 3), the amount ratio of CdSe quantum dot core, normal hexane, stearylamine, octadecylene, tri-n-octyl phosphine, Zn storing solution, S storing solution is 7.7 × 10
-5mmol:1.2ml:0.8-1.6g:4-8ml:0.3-0.6ml:0.35ml:0.35ml;
Or, step 2) in, the amount ratio of CdO, stearic acid, stearylamine, octadecylene, Se-TOP is: 0.2mmol:0.8mmol:2.4mmol:4-10ml:2ml; In step 3), the amount ratio of CdSe quantum dot core, normal hexane, stearylamine, octadecylene, tri-n-octyl phosphine, Zn storing solution, S storing solution is 7.7 × 10
-5mmol:0.8ml:0.8-1.6g:4-8ml:0.3-0.6ml:0.28ml:0.28ml;
Or, step 2) in, the amount ratio of CdO, stearic acid, stearylamine, octadecylene, Se-TOP is: 0.2mmol:0.8mmol:18mmol:4-10ml:2ml; In step 3), the amount ratio of CdSe quantum dot core, normal hexane, stearylamine, octadecylene, tri-n-octyl phosphine, Zn storing solution, S storing solution is 7.7 × 10
-5mmol:4.8ml:0.8-1.6g:4-8ml:0.3-0.6ml:0.57ml:0.57ml.
4. the SILAR technology of assisting according to a kind of TOP of utilization described in claim 1 or 2 prepares the method for high quantum production rate, narrow peak width at half height core-shell quanta dots, it is characterized in that: step 2) and 3) in, in normal hexane/methanol system, the volume ratio of normal hexane, methyl alcohol is 15:20, and the number of times of normal hexane/methanol system abstraction purification is 3-5 time.
5. the SILAR technology of assisting according to a kind of TOP of utilization described in claim 1 or 2 prepares the method for high quantum production rate, narrow peak width at half height core-shell quanta dots, it is characterized in that: step 2) in, at 245-255 DEG C, grow 5-10min.
6. the SILAR technology of assisting according to a kind of TOP of utilization described in claim 1 or 2 prepares the method for high quantum production rate, narrow peak width at half height core-shell quanta dots, it is characterized in that: in step 3), and the time of fully activation is 20-40min.
7. the SILAR technology of assisting according to a kind of TOP of utilization described in claim 1 or 2 prepares the method for high quantum production rate, narrow peak width at half height core-shell quanta dots, it is characterized in that: in step 3), and after instillation Zn storing solution, the time of fully effect is 20-30min; After instillation S storing solution, the time of fully effect is 60-70min.
8. the SILAR technology that a kind of TOP of utilization according to any one of claim 2 assists prepares the method for high quantum production rate, narrow peak width at half height core-shell quanta dots, it is characterized in that: in step 4), the timed interval of instillation Zn storing solution, S storing solution is 10-15min; The time being warming up to fully effect at 215-225 DEG C is 60-70min.
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