CN103242831B - Preparation method of CuInS2/ZnS core-shell structure quantum dot and CuInS2/CdS/ZnS core-shell structure quantum dot - Google Patents
Preparation method of CuInS2/ZnS core-shell structure quantum dot and CuInS2/CdS/ZnS core-shell structure quantum dot Download PDFInfo
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Abstract
The invention relates to a preparation method of a CuInS2/ZnS core-shell structure quantum dot and a CuInS2/CdS/ZnS core-shell structure quantum dot. The method comprises a preparation method of a CuInS2 multilayer core-shell structure quantum dot by using CuInS2 nano particles as follows: (1) dissolving a copper source and an indium source with a sulphur source to obtain a CuInS2 quantum dot solution; (2) centrifugally purifying the quantum dot solution; dropwise adding zinc and a sulphur precursor liquid to obtain a CuInS2/ZnS core-shell structure quantum dot solution; and (3) dropwise adding the sulphur source and the sulphur precursor liquid into the CuInS2 quantum dot solution, and dropwise adding zinc and sulphur precursor liquid to obtain a CuInS2/CdS/ZnS-type quantum dot. The preparation method is easy to operate, low in requirement on equipment and high in repeatability; and finally, the fluorescence quantum yield of the quantum dot is more than 50 percent, and a fluorescence-emission peak can be regulated in spectral ranges of visible light and infrared rays.
Description
Technical field
The present invention relates to the preparing technical field of semiconductor nano material, be specifically related to CuInS
2the preparation method of/ZnS core-shell structured quantum dot and CuInS
2the preparation method of/CdS/ZnS nuclear shell structure quantum point.
Background technology
Quantum dot is also called semiconductor nano, its practical physical diameter is less than or close to exciton Bohr radius, due to quantum size effect, it is wide that quantum dot has excitation wavelength range, and emission peak is narrow and in Gaussian symmetric, without hangover, the advantage such as Stokes shift is large, photochemical stability is strong.When being subject to the stimulation of light or electricity, quantum dot just can send the light of a wavelength range, and the scope of emmission spectrum and intensity are determined by the modification situation of the composition material of quantum dot, size shape and particle surface.The optical physics of quantum dot uniqueness and spectrochemical property, make it be widely used in biological detection, false proof, LED, the field such as display and photoelectric device as luminescent material.
The CuInS obtained by general technology means at present
2the fluorescence efficiency of quantum dot is general lower, general less than 5%.In order to improve CuInS further
2the fluorescence efficiency of quantum dot, strengthens its photochemical stability, and the technology of current comparative maturity adopts continuous ionic adsorption method at CuInS
2the inorganic shell of quantum dot surface growing ZnS, but adopt the CuInS that existing technique is synthesized
2the fluorescence efficiency of/ZnS quantum dot still cannot more than 50%.And the ZnS adopting this kind of method to obtain wraps up CuInS
2after quantum dot, can cause its fluorescence emission spectrum blue shift, the quantum yield in ruddiness and region of ultra-red is lower, cannot meet CuInS
2quantum dot is in the application of false proof, LED and field of biological detection.
In order to improve CuInS further
2the fluorescence efficiency of/ZnS quantum dot, strengthens its optical stability, just needs at the inorganic shell of the ZnS that the surperficial synthesis ratio of core is more firm.There is gross differences in the reactive behavior that the present invention have studied each ion in reaction system, starts with, improve quantum yield and high stability, for follow-up further bag multi-layer core-shell structure lays the first stone from the existing ZnS nucleation material of improvement.
Summary of the invention
The object of the present invention is to provide a kind of simple to operate, equipment requirements is low, favorable repeatability, fluorescence quantum yield is greater than 50%, and fluorescence emission peak is at visible and that infrared range of spectrum is adjustable CuInS
2the preparation method of/ZnS core-shell structured quantum dot.
Another object of the present invention is, provides a kind of CuInS
2the preparation method of/CdS/ZnS nuclear shell structure quantum point.
The present invention is realized by following technical scheme: a kind of CuInS
2the preparation method of/ZnS core-shell structured quantum dot, comprises the following steps:
(1) copper source and indium source are dissolved in sulphur source, under the protection of nitrogen, are heated to 120 DEG C, insulation also until solid particulate dissolves completely, obtains body fluid before copper indium; Continue to be warming up to 220 DEG C and be incubated 10 ~ 25 minutes, obtaining the CuInS of different-grain diameter and fluorescent characteristic
2quantum dot solution;
(2) by CuInS that step (1) obtains
2cuInS is obtained after quantum dot solution centrifugal purification
2quantum dot, by the CuInS obtained
2quantum dot is distributed to post-heating to 230 DEG C in vaccenic acid, drips body fluid before zinc and sulphur in 20 ~ 30 minutes, then insulation reaction 30 minutes, the CuInS obtained
2/ ZnS core-shell structured quantum dot solution, is cooled to room temperature;
(3) by CuInS that step (2) obtains
2cuInS is obtained after/ZnS core-shell structured quantum dot solution centrifugal purifying
2/ ZnS core-shell structured quantum dot.
Copper source in described step (1) is any one in cuprous iodide, cuprous acetate or neutralized verdigris; Described indium source is indium acetate or stearic acid indium; To be backbone c atoms number be in described sulphur source 12 ~ 18 saturated fatty mercaptan.Backbone c atoms number be 12 ~ 18 saturated fatty mercaptan be not only CuInS
2the reaction of quantum dot provides sulphur source, because it has high boiling characteristic, also as the solvent of reaction.Simultaneously because mercaptan itself and copper and indium ion have good coordination, body fluid before copper indium can also be prepared as the effective part of one, and can effectively prevent quantum dot from reuniting under the high temperature conditions.In this step, need to vacuumize, then react under the protection of nitrogen, with the oxygen in removing system and moisture, avoid copper and indium are at high temperature hydrolyzed and are oxidized.
Before described copper indium, in body fluid, copper source is 2:1 ~ 1:8 with the amount of substance ratio in indium source.
Before described zinc and sulphur, body fluid is than being that the zinc source of 1:1 and sulphur powder are dissolved in tributyl phosphorus solution and are prepared from by amount of substance; Described zinc source is two butyl disulfide amido acid zinc or zinc diethyldithiocarbamate.The amount of tributyl phosphorus is dissolved in sulphur powder and wherein forms homodisperse suspension and be as the criterion, so that follow-up dropwise operation.In addition because tributyl phosphorus price is more expensive, also solving zinc source and sulphur powder can be come, to reduce costs with the mixed solution of vaccenic acid and tributyl phosphorus.Traditional copper indium sulphur quantum dot parcel ZnS using backbone c atoms number be mainly the saturated fatty mercaptan of 12 ~ 18 as the sulphur source of ZnS housing, in involucrum process, blue shift is larger, mainly because of zinc doping at CuInS
2core in, instead of at CuInS
2involucrum passivation is carried out on surface, and easily generates the ZnS particle of single-phase.In the present invention, the zinc source of ZnS housing is provided by two butyl disulfide amido acid zinc or zinc diethyldithiocarbamate, and so between zinc source and sulphur source, speed of reaction is relatively more suitable, can at CuInS
2surface Creation ZnS shell, and ZnS can not be generated by spontaneous nucleation.
A kind of CuInS
2the preparation method of/CdS/ZnS nuclear shell structure quantum point, comprises the following steps:
(1) copper source and indium source are dissolved in sulphur source, under the protection of nitrogen, are heated to 120 DEG C, insulation also until solid particulate dissolves completely, obtains body fluid before copper indium; Continue to be warming up to 220 DEG C and be incubated 10 ~ 25 minutes, obtaining the CuInS of different-grain diameter and fluorescent characteristic
2quantum dot solution;
(2) by CuInS that step (1) obtains
2quantum dot solution is cooled to 210 DEG C, drips body fluid before cadmium and sulphur, obtain CuInS in 20 ~ 30 minutes
2/ CdS quantum dot solution with core-shell structure;
(3) by CuInS that step (2) obtains
2cuInS is obtained after/CdS quantum dot solution with core-shell structure centrifugal purification
2/ CdS nuclear shell structure quantum point, by the CuInS obtained
2/ CdS nuclear shell structure quantum point is distributed to post-heating to 230 DEG C in vaccenic acid, drips body fluid before zinc and sulphur, the CuInS obtained in 20 ~ 30 minutes
2/ CdS/ZnS quantum dot solution with core-shell structure, is cooled to room temperature;
(4) by CuInS that step (3) obtains
2cuInS is obtained after/CdS/ZnS quantum dot solution with core-shell structure centrifugal purification
2/ CdS/ZnS nuclear shell structure quantum point.
At CuInS
2nano grain surface first wraps up one deck CdS layer, and the outermost ZnS layer of regeneration, adopts this structure, can utilize CdS layer as transition layer to reduce CuInS
2and the lattice misfit coefficient between ZnS layer, form better repeatedly shell integument, thus improve quantum dot fluorescent stability and fluorescence quantum efficiency.
Copper source in described step (1) is any one in cuprous iodide, cuprous acetate or neutralized verdigris; Described indium source is indium acetate or stearic acid indium; To be backbone c atoms number be in described sulphur source 12 ~ 18 saturated fatty mercaptan.
Before described copper indium, in body fluid, copper source is 2:1 ~ 1:8 with the amount of substance ratio in indium source.
Before described cadmium and sulphur body fluid by amount of substance than being that the cadmium source of 1:1 and sulphur powder are dissolved in tributyl phosphorus and are prepared from; Described cadmium source is any one in cadmium oleate, cadmium stearate, cadmium acetate or cadmium diethyl dithiocarbamate.The amount of tributyl phosphorus is as the criterion, so that follow-up dropwise operation to make zinc source and sulphur powder be dissolved in wherein formation emulsion.In addition because tributyl phosphorus price is more expensive, also solving zinc source and sulphur powder can be come, to reduce costs with the mixed solution of vaccenic acid and tributyl phosphorus.Traditional copper indium sulphur quantum dot parcel ZnS using backbone c atoms number be mainly the saturated fatty mercaptan of 12 ~ 18 as the sulphur source of ZnS housing, in involucrum process, blue shift is larger, mainly because of zinc doping at CuInS
2core in, instead of at CuInS
2involucrum passivation is carried out on surface, and easily generates the ZnS particle of single-phase.In the present invention, the sulphur source of ZnS housing is provided by the sulphur powder in sulphur precursor, and between zinc source and sulphur source, speed of reaction is relatively more suitable, can at CuInS
2surface Creation ZnS shell, and ZnS can not be generated by spontaneous nucleation.
Before described zinc and sulphur, body fluid is than being that the zinc source of 1:1 and the tributyl phosphorus solution of sulphur powder are prepared from by amount of substance; Described zinc source is any one in two butyl disulfide amido acid zinc, zinc oleate, Zinic stearas, zinc acetate or zinc diethyldithiocarbamate.
Described centrifugal purification in quantum dot solution, adds the dehydrated alcohol and chloroformic solution that volume ratio is 5 ~ 10:1, centrifugation, and removing upper liquid, remaining solid is gained quantum dot.Purification procedures general in triplicate more than, obtain the finished product.
CuInS disclosed by the invention
2the preparation method of core-shell quanta dots is simple to operate, equipment requirements is low, favorable repeatability, fluorescence quantum yield is greater than 50%, adjustable in 570 ~ 670nm spectral range, by carrying out centrifugal purification to quantum dot solution in reaction process, be conducive to improving fluorescence quantum yield; Adopt the CuInS that the method can be synthesized
2/ CdS/ZnS nuclear shell structure quantum point, can be widely used in the fields such as biology, illumination, display.
Quantum dot fluorescence quantum yield is as a most important performance perameter of material, and the size degree of numerical value depends on the state on quantum dot core surface completely.The surface of quantum dot core also exists a large amount of defects and unsaturated link(age), these surface imperfection thus a large amount of radiationless deathnium caused, so fluorescence quantum yield is lower.By the inorganic materials shell in quantum dot core outer cladding last layer broad-band gap, just effectively can reduce surface imperfection, thus improve its fluorescence quantum yield and fluorescent stability.How to form one to match and complete shell with the lattice of core, thus improve CuInS
2the fluorescence quantum yield of type quantum dot is exactly the most important inventive point that this patent is paid close attention to.By a large amount of simultaneous tests, we find at synthesis CuInS
2after core, after will purifying to core solution, then it is coated to carry out ZnS shell, can obtain higher quantum fluorescent yield.By the purification step of midway, CuInS can be rejected
2cu, In ion excessive in the middle of core the first step synthesis step, thus avoid a impact rear step being formed to ZnS layer.If do not carry out above-mentioned purification step, often obtain CuInZnS
3or CuZnS
2deng impurity alloy shell, this shell can not play the effect eliminating core upper surface defect, thus the fluorescence quantum yield causing quantum dot final is not high.This patent, by the nucleocapsid synthesis step adopting improvement and the ZnS layer material matched, makes the fluorescence quantum yield of the finished product all higher, is generally greater than 50%.
The measuring process of fluorescence quantum yield is:
(1) fluorescent substance to be measured and the absorbancy of reference material under certain selected wavelength is measured;
(2) under selected wavelength, with same shooting conditions, the fluorescence emission spectrum of test substance and reference material is recorded respectively;
(3) quantum yield of test substance is calculated by following formula:
Wherein,
with
represent the quantum yield of test substance and reference material respectively, F and F
sthe integral area of the emission spectrum of test substance and reference material respectively, A and A
srepresent test substance and the absorbancy of reference material under corresponding laser respectively, n and n
srepresent the specific refractory power of test substance and reference material solvent for use respectively.The reference material that the present invention adopts is rhodamine 6G (95%), and organic solvent solvent is toluene.The measuring method of fluorescence quantum yield of the present invention is the standard determination method (Analyst.1983,108,1067-1071) adopting Miller group nineteen eighty-three to deliver.
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
Accompanying drawing explanation
Fig. 1 is CuInS of the present invention
2/ ZnS and CuInS
2the process flow sheet of the preparation method of/CdS/ZnS nuclear shell structure quantum point.
Fig. 2 is CuInS of the present invention
2the structural representation of/ZnS core-shell structured quantum dot.
Fig. 3 is CuInS of the present invention
2/
cdS/the structural representation of ZnS core-shell structured quantum dot.
Fig. 4 be different Cu:In amount of substance than time CuInS
2the fluorescence emission spectrum schematic diagram of/ZnS core-shell structured quantum dot.
Fig. 5 is Cu:In amount of substance ratio when being respectively 1:4, CuInS
2fluorescence emission spectrum schematic diagram before and after quantum dot parcel ZnS layer.
Fig. 6 is Cu:In amount of substance ratio when being respectively 1:4, CuInS
2the fluorescent emission of/ZnS core-shell structured quantum dot and absorption spectrum schematic diagram.
Fig. 7 is CuInS
2, CuInS
2/ CdS, CuInS
2the fluorescence emission spectrum schematic diagram of/CdS/ZnS quantum dot
Embodiment
As shown in Figures 1 to 7, CuInS
2the preparation method of/ZnS core-shell structured quantum dot, comprises the following steps:
(1) the copper source of the ratio of the amount of predetermined substance and indium source are dissolved in sulphur source, under the protection of nitrogen, are heated to 120 DEG C, insulation also until solid particulate dissolves completely, obtains body fluid before copper indium; Continue be warming up to 220 ° of C and be incubated 10 ~ 25 minutes, obtain the CuInS of different-grain diameter and fluorescent characteristic
2quantum dot solution;
(2) by CuInS that step (1) obtains
2cuInS is obtained after quantum dot solution centrifugal purification
2quantum dot, by the CuInS obtained
2quantum dot is distributed to post-heating to 230 DEG C in vaccenic acid, drips body fluid before zinc and sulphur in 20 ~ 30 minutes, then insulation reaction 30 minutes, the CuInS obtained
2/ ZnS core-shell structured quantum dot solution, is cooled to room temperature;
(3) by CuInS that step (2) obtains
2cuInS is obtained after/ZnS core-shell structured quantum dot solution centrifugal purifying
2/ ZnS core-shell structured quantum dot, its structure as shown in Figure 2.
CuInS
2the preparation method of/CdS/ZnS nuclear shell structure quantum point, comprises the following steps:
(1) the copper source of the ratio of the amount of predetermined substance and indium source are dissolved in sulphur source, under the protection of nitrogen, are heated to 120 DEG C, insulation also until solid particulate dissolves completely, obtains body fluid before copper indium; Continue be warming up to 220 ° of C and be incubated 10 ~ 25 minutes, obtain the CuInS of different-grain diameter and fluorescent characteristic
2quantum dot solution;
(2) by CuInS that step (1) obtains
2quantum dot solution is cooled to 210 DEG C, drips body fluid before cadmium and sulphur, obtain CuInS in 20 ~ 30 minutes
2/ CdS quantum dot solution with core-shell structure;
(3) by CuInS that step (2) obtains
2cuInS is obtained after/CdS quantum dot solution with core-shell structure centrifugal purification
2/ CdS nuclear shell structure quantum point, by the CuInS obtained
2/ CdS nuclear shell structure quantum point is distributed to post-heating to 230 DEG C in vaccenic acid, drips body fluid before zinc and sulphur, the CuInS obtained in 20 ~ 30 minutes
2/ CdS/ZnS quantum dot solution with core-shell structure, is cooled to room temperature;
(4) by CuInS that step (3) obtains
2cuInS is obtained after/CdS/ZnS quantum dot solution with core-shell structure centrifugal purification
2/ CdS/ZnS core-shell quanta dots.
Embodiment 1:
Adopt Dodecyl Mercaptan as sulphur source and solvent.
The preparation of body fluid before zinc and sulphur: the 10ml vaccenic acid solution of 4.8mmol two butyl disulfide amido acid zinc and 4.8mmol sulphur powder are distributed in 15ml tributyl phosphorus.
The preparation of body fluid before copper indium: by 2.4mmol cuprous iodide, 2.4mmol indium acetate, 30ml Dodecyl Mercaptan is placed in there-necked flask, under the protection of nitrogen, is heated to 120 DEG C, and insulation is until solid particulate dissolves completely.
CuInS
2the preparation of quantum dot: under nitrogen protection, continues to be warming up to 220 DEG C by body fluid before copper indium, reacts 20 minutes, obtained CuInS
2quantum dot solution.
CuInS
2the preparation of/ZnS core-shell structured quantum dot: by CuInS obtained above
2after quantum dot solution centrifugal purification, obtain CuInS
2quantum dot, by the CuInS obtained
2quantum dot is distributed in the vaccenic acid of 30ml, vacuumizes draining and exhaust post-heating to 230 DEG C, drips body fluid before zinc and sulphur, the CuInS obtained in 30 minutes
2/ ZnS core-shell structured quantum dot solution, is cooled to room temperature; By the CuInS obtained
2cuInS is obtained after/ZnS core-shell structured quantum dot solution centrifugal purifying
2/ ZnS core-shell structured quantum dot.
Obtained CuInS
2/ ZnS core-shell structured quantum dot fluorescence quantum efficiency is 55%, and its fluorescence emission wavelengths is 670nm, as shown in Figure 4.
Embodiment 2:
Adopt stearylmercaptan as sulphur source and solvent.
The preparation of body fluid before zinc and sulphur: the 10ml vaccenic acid solution of 4.8mmol zinc diethyldithiocarbamate and 4.8mmol sulphur powder are distributed in 15ml tributyl phosphorus.
The preparation of body fluid before copper indium: by 2.4mmol cuprous iodide, 2.4mmol indium acetate, is dispersed in 30ml stearylmercaptan, is placed in there-necked flask, under the protection of nitrogen, is heated to 120 DEG C, and insulation is until solid particulate dissolves completely.
CuInS
2the preparation of quantum dot: under nitrogen protection, continues to be warming up to 220 DEG C, reacts 25 minutes, obtained CuInS
2quantum dot solution.
CuInS
2the preparation of/ZnS core-shell structured quantum dot: by CuInS obtained above
2after quantum dot solution centrifugal purification, obtain CuInS
2quantum dot, by the CuInS obtained
2quantum dot is distributed in the vaccenic acid of 30ml, vacuumizes post-heating to 230 DEG C, drips body fluid before zinc and sulphur, the CuInS obtained in 30 minutes
2/ ZnS core-shell structured quantum dot solution, is cooled to room temperature; By the CuInS obtained
2cuInS is obtained after/ZnS core-shell structured quantum dot solution centrifugal purifying
2/ ZnS core-shell structured quantum dot.
Adopt different mercaptan also can obtain identical CuInS
2/ ZnS core-shell structured quantum dot, fluorescence quantum efficiency is 55%, and its fluorescence emission wavelengths is 670nm.
Embodiment 3:
Different Cu indium proportioning is adopted to prepare CuInS
2/ ZnS core-shell structured quantum dot.
The preparation of zinc and sulphur precursor: the 10ml vaccenic acid solution of 4.8mmol zinc diethyldithiocarbamate and 4.8mmol sulphur powder are distributed in 15ml tributyl phosphorus.
The preparation of body fluid before copper indium: by 1.2mmol cuprous iodide, 2.4mmol indium acetate, 30ml Dodecyl Mercaptan is placed in there-necked flask, under the protection of nitrogen, is heated to 120 DEG C, and insulation is until solid particulate dissolves completely.
CuInS
2the preparation of quantum dot: under nitrogen protection, continues to be warming up to 220 DEG C, reacts 17 minutes, obtained CuInS
2quantum dot solution.
CuInS
2the preparation of/ZnS core-shell structured quantum dot: by CuInS obtained above
2after quantum dot solution centrifugal purification, obtain CuInS
2quantum dot, by the CuInS obtained
2quantum dot is distributed in the vaccenic acid of 30ml, vacuumizes post-heating to 230 DEG C, drips zinc and sulphur precursor solution is complete, the CuInS obtained in 25 minutes
2/ ZnS core-shell structured quantum dot solution, is cooled to room temperature; By the CuInS obtained
2cuInS is obtained after/ZnS core-shell structured quantum dot solution centrifugal purifying
2/ ZnS core-shell structured quantum dot.
Obtained CuInS
2the fluorescence emission wavelengths of/ZnS core-shell structured quantum dot is 665nm, and fluorescence quantum efficiency is 55%.
Embodiment 4:
Different Cu indium proportioning is adopted to prepare CuInS
2/ ZnS core-shell structured quantum dot.
The preparation of body fluid before zinc and sulphur: the 10ml vaccenic acid solution of 4.8mmol two butyl disulfide amido acid zinc and 4.8mmol sulphur powder are distributed in 15ml tributyl phosphorus.
The preparation of body fluid before copper indium: by 0.6mmol cuprous iodide, 2.4mmol indium acetate, 30ml Dodecyl Mercaptan is placed in there-necked flask, under the protection of nitrogen, is heated to 120 DEG C, and insulation is until solid particulate dissolves completely.
CuInS
2the preparation of quantum dot: under nitrogen protection, continues to be warming up to 220 DEG C, reacts 15 minutes, obtained CuInS
2quantum dot solution.
CuInS
2the preparation of/ZnS core-shell structured quantum dot: by CuInS obtained above
2after quantum dot solution centrifugal purification, obtain CuInS
2quantum dot, by the CuInS obtained
2quantum dot is distributed in the vaccenic acid of 30ml, vacuumizes post-heating to 230 DEG C, and before dripping zinc and sulphur in 23 minutes, body fluid is complete, the CuInS obtained
2/ ZnS core-shell structured quantum dot solution, is cooled to room temperature; By the CuInS obtained
2cuInS is obtained after/ZnS core-shell structured quantum dot solution centrifugal purifying
2/ ZnS core-shell structured quantum dot.
As shown in Figure 4, obtained CuInS
2the fluorescence emission wavelengths of/ZnS core-shell structured quantum dot is 595nm, and fluorescence quantum efficiency is 55%.
Embodiment 5:
Different Cu indium proportioning is adopted to prepare CuInS
2/ ZnS quantum dot.
The preparation of body fluid before zinc and sulphur: the 10ml vaccenic acid solution of 4.8mmol two butyl disulfide amido acid zinc and 4.8mmol sulphur powder are distributed in 15ml tributyl phosphorus.
The preparation of body fluid before copper indium: by 0.3mmol cuprous acetate, 2.4mmol indium acetate, 30ml Dodecyl Mercaptan is placed in there-necked flask, under the protection of nitrogen, is heated to 120 DEG C, and insulation is until solid particulate dissolves completely.
CuInS
2the preparation of quantum dot: under nitrogen protection, continues to be warming up to 220 DEG C, reacts 20 minutes, obtained CuInS
2quantum dot solution.
CuInS
2the preparation of/ZnS core-shell structured quantum dot: by CuInS obtained above
2cuInS is obtained after quantum dot solution separation and purification
2quantum dot, by the CuInS obtained
2quantum dot is distributed in the vaccenic acid of 30ml, vacuumizes post-heating to 230 DEG C, drips zinc and sulphur precursor solution is complete, the CuInS obtained in 27 minutes
2/ ZnS core-shell structured quantum dot solution, is cooled to room temperature; By the CuInS obtained
2cuInS is obtained after/ZnS core-shell structured quantum dot solution centrifugal purifying
2/ ZnS core-shell structured quantum dot.
As shown in Figure 4, obtained CuInS
2the fluorescence emission wavelengths of/ZnS core-shell structured quantum dot is 570nm, and fluorescence quantum efficiency is 53%.
Fig. 5 is CuInS
2fluorescence emission spectrum schematic diagram before and after quantum dot parcel ZnS layer, as can be seen from figure we: compared with before involucrum, the CuInS after bag ZnS
2the fluorescence intensity of/ZnS core-shell structured quantum dot is greatly improved, and proves the success of this involucrum strategy.Blue shift simultaneously after involucrum, lower than 30nm, illustrates that the very most of zinc of this involucrum strategy is involucrum passivation to core, and few part zinc is diffused into the doping of core inside, this enhances the stability of quantum dot.
Fig. 6 is CuInS
2the fluorescent emission of/ZnS core-shell structured quantum dot and absorption spectrum schematic diagram, from figure, we can see CuInS
2the Stoke displacement of/ZnS core-shell structured quantum dot is about 100nm, and self-absorption is smaller, and this just effectively avoids this kind of material in the application of biological detection, living imaging and light emitting diode due to problem that self-absorption causes luminous efficiency to reduce.
Embodiment 6:
The preparation of body fluid before cadmium and sulphur: 4.8mmol cadmium oleate and 4.8mmol sulphur powder are dissolved in 4.8ml tributyl phosphorus.
The preparation of body fluid before zinc and sulphur: 1.2mmol zinc oleate and 1.2mmol sulphur powder are distributed in 15ml tributyl phosphorus.
The tributyl phosphorus added in above-mentioned preparation wherein forms emulsion for optimal way to make front physical efficiency disperse to be dissolved in.
CuInS
2the preparation of quantum dot: add 2.4mmol cuprous iodide, 2.4mmol indium acetate and 30ml Dodecyl Mercaptan in there-necked flask, be heated to 120 DEG C under the protection of nitrogen, insulation is until solid particulate dissolves completely; Then continue to be warming up to 220 DEG C and be incubated 10 minutes, obtaining CuInS
2quantum dot solution.
CuInS
2the preparation of/CdS nuclear shell structure quantum point: the CuInS obtained by above-mentioned reaction
2quantum dot solution is cooled to 210 DEG C, drips body fluid before cadmium and sulphur, be down to room temperature, obtain CuInS in 20 minutes
2/ CdS quantum dot solution with core-shell structure, by CuInS
2cuInS is obtained after/CdS quantum dot solution with core-shell structure centrifugal purification
2/ CdS nuclear shell structure quantum point.
CuInS
2the preparation of/CdS/ZnS nuclear shell structure quantum point: by above-mentioned CuInS
2/ CdS nuclear shell structure quantum point is distributed in 40ml vaccenic acid, is heated to 230 DEG C, drips body fluid before zinc and sulphur, the CuInS obtained in 20 minutes
2/ CdS/ZnS quantum dot solution with core-shell structure, is cooled to room temperature; By the CuInS obtained
2cuInS is obtained after/CdS/ZnS quantum dot solution with core-shell structure centrifugal purification
2/ CdS/ZnS nuclear shell structure quantum point.
As shown in Figure 7, the CuInS of acquisition
2the fluorescence emission wavelengths of/CdS/ZnS nuclear shell structure quantum point is 655nm, and fluorescence quantum efficiency is 72%.
Embodiment 7:
The preparation of body fluid before cadmium and sulphur: with the preparation method of embodiment 6.
The preparation of body fluid before zinc and sulphur: with the preparation method of embodiment 6.
CuInS
2the preparation of quantum dot: add 1.2mmol cuprous iodide, 2.4mmol indium acetate and 30ml Dodecyl Mercaptan in there-necked flask, under the protection of nitrogen, insulation also until solid particulate dissolves completely, then continues be warming up to 225 ° of C and be incubated 10min, obtains CuInS
2quantum dot solution.
CuInS
2the preparation of/CdS nuclear shell structure quantum point: with the preparation method of embodiment 6.
CuInS
2the preparation of/CdS/ZnS nuclear shell structure quantum point: with the preparation method of embodiment 6.
Finally obtained CuInS
2the fluorescence emission wavelengths of/CdS/ZnS nuclear shell structure quantum point is 610nm, and fluorescence quantum efficiency is 70%.
Embodiment 8:
The preparation of body fluid before cadmium and sulphur: with the preparation method of embodiment 6.
The preparation of body fluid before zinc and sulphur: with the preparation method of embodiment 6.
CuInS
2the preparation of quantum dot: add 0.6mmol cuprous iodide, 2.4mmol indium acetate and 30ml Dodecyl Mercaptan in there-necked flask, under the protection of nitrogen, insulation also until solid particulate dissolves completely, then continues be warming up to 225 ° of C and be incubated 10min, obtains CuInS
2quantum dot solution.
CuInS
2the preparation of/CdS nuclear shell structure quantum point: with the preparation method of embodiment 6.
CuInS
2the preparation of/CdS/ZnS nuclear shell structure quantum point: with the preparation method of embodiment 6.
Finally obtained CuInS
2the fluorescence emission wavelengths of/CdS/ZnS nuclear shell structure quantum point is 590nm, and fluorescence quantum efficiency is 65%.
Embodiment 9:
The preparation of body fluid before cadmium and sulphur: with the preparation method of embodiment 6.
The preparation of body fluid before zinc and sulphur: with the preparation method of embodiment 6.
CuInS
2the preparation of quantum dot: add 4.8mmol cuprous iodide, 2.4mmol indium acetate and 30ml Dodecyl Mercaptan in there-necked flask, under the protection of nitrogen, insulation also until solid particulate dissolves completely, then continues be warming up to 225 ° of C and be incubated 10min, obtains CuInS
2quantum dot solution.
CuInS
2the preparation of/CdS nuclear shell structure quantum point: with the preparation method of embodiment 6.
CuInS
2the preparation of/CdS/ZnS nuclear shell structure quantum point: with the preparation method of embodiment 6.
Finally obtained CuInS
2the fluorescence emission wavelengths of/CdS/ZnS nuclear shell structure quantum point is 690nm, and fluorescence quantum efficiency is 75%.
The present invention is not limited to above-mentioned embodiment, if do not depart from the spirit and scope of the present invention to various change of the present invention or distortion, if these are changed and distortion belongs within claim of the present invention and equivalent technologies scope, then the present invention is also intended to comprise these changes and distortion.
Claims (5)
1. a CuInS
2the preparation method of/CdS/ZnS nuclear shell structure quantum point, is characterized in that: comprise the following steps:
(1) copper source and indium source are dissolved in sulphur source, under the protection of nitrogen, are heated to 120 DEG C, insulation also until solid particulate dissolves completely, obtains body fluid before copper indium; Continue to be warming up to 220 DEG C and be incubated 10 ~ 25 minutes, obtaining the CuInS of different-grain diameter and fluorescent characteristic
2quantum dot solution;
(2) by CuInS that step (1) obtains
2quantum dot solution is cooled to 210 DEG C, drips body fluid before cadmium and sulphur, obtain CuInS in 20 ~ 30 minutes
2/ CdS quantum dot solution with core-shell structure;
(3) by CuInS that step (2) obtains
2cuInS is obtained after/CdS quantum dot solution with core-shell structure centrifugal purification
2/ CdS nuclear shell structure quantum point, by the CuInS obtained
2/ CdS nuclear shell structure quantum point is distributed to post-heating to 230 DEG C in vaccenic acid, drips body fluid before zinc and sulphur, the CuInS obtained in 20 ~ 30 minutes
2/ CdS/ZnS quantum dot solution with core-shell structure, is cooled to room temperature;
(4) by CuInS that step (3) obtains
2cuInS is obtained after/CdS/ZnS quantum dot solution with core-shell structure centrifugal purification
2/ CdS/ZnS nuclear shell structure quantum point;
Described centrifugal purification in quantum dot solution, adds the dehydrated alcohol and chloroformic solution that volume ratio is 5 ~ 10:1, centrifugation, and removing upper liquid, remaining solid is gained quantum dot.
2. CuInS according to claim 1
2the preparation method of/CdS/ZnS nuclear shell structure quantum point, is characterized in that: the copper source in described step (1) is any one in cuprous iodide, cuprous acetate or neutralized verdigris; Described indium source is indium acetate or stearic acid indium; To be backbone c atoms number be in described sulphur source 12 ~ 18 saturated fatty mercaptan.
3. CuInS according to claim 1
2the preparation method of/CdS/ZnS nuclear shell structure quantum point, is characterized in that: before described copper indium, in body fluid, copper source is 2:1 ~ 1:8 with the amount of substance ratio in indium source.
4. CuInS according to claim 1
2the preparation method of/CdS/ZnS nuclear shell structure quantum point, is characterized in that: before described cadmium and sulphur body fluid by amount of substance than being that the cadmium source of 1:1 and sulphur powder are dissolved in tributyl phosphorus and are prepared from; Described cadmium source is any one in cadmium oleate, cadmium stearate, cadmium acetate or cadmium diethyl dithiocarbamate.
5. CuInS according to claim 1
2the preparation method of/CdS/ZnS nuclear shell structure quantum point, is characterized in that: before described zinc and sulphur, body fluid is than being that the zinc source of 1:1 and the tributyl phosphorus solution of sulphur powder are prepared from by amount of substance; Described zinc source is any one in two butyl disulfide amido acid zinc, zinc oleate, Zinic stearas, zinc acetate or zinc diethyldithiocarbamate.
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| CN104861964B (en) | 2015-05-14 | 2016-06-29 | 中国科学院广州能源研究所 | A kind of CuInS2/In2S3/ ZnS two-layer core shell structured fluorescence quantum dot and preparation method thereof |
| KR20180027629A (en) * | 2015-07-30 | 2018-03-14 | 퍼시픽 라이트 테크놀로지스 코포레이션 | Nanocrystalline quantum dot heterostructure with low cadmium content |
| CN105219380B (en) * | 2015-10-20 | 2018-01-23 | 广东昭信光电科技有限公司 | A kind of synthetic method of the high quality colloid without cadmium quantum dot |
| CN106634963A (en) * | 2016-12-22 | 2017-05-10 | Tcl集团股份有限公司 | CuInS2/ZnS core-shell quantum dots and preparation method thereof |
| CN109116028A (en) * | 2017-06-26 | 2019-01-01 | 刘宏飞 | A kind of preparation method based on the in-vitro diagnosis test strips that CdSe quantum dot is marker |
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| CN109513450B (en) * | 2018-12-07 | 2021-05-25 | 信阳师范学院 | CdS nanotube and spiral CuInS2Heterostructure composite material and preparation method thereof |
| CN110643348A (en) * | 2019-09-25 | 2020-01-03 | 电子科技大学 | quasi-II type energy band structure quantum dot and preparation method thereof |
| CN110724518B (en) * | 2019-10-21 | 2022-12-20 | 福建医科大学 | Fe applicable to dual-mode imaging system 3 O 4 @CuInS 2 Construction of core-shell structures |
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