CN102344811B - Method for preparing ternary alloy quantum dots in ole-morpholine solvent - Google Patents
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 86
- 229910002058 ternary alloy Inorganic materials 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000002904 solvent Substances 0.000 title claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- 239000012043 crude product Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
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- 239000003495 polar organic solvent Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 3
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 44
- 239000007788 liquid Substances 0.000 claims description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- -1 oleoyl morpholine Chemical compound 0.000 claims description 30
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Natural products C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 15
- 229910052793 cadmium Inorganic materials 0.000 claims description 14
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 14
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 11
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000005642 Oleic acid Substances 0.000 claims description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 6
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 6
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 150000002632 lipids Chemical class 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 239000005639 Lauric acid Substances 0.000 claims description 3
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 3
- GWOWVOYJLHSRJJ-UHFFFAOYSA-L cadmium stearate Chemical compound [Cd+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O GWOWVOYJLHSRJJ-UHFFFAOYSA-L 0.000 claims description 3
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 3
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- 238000013019 agitation Methods 0.000 description 6
- 238000006862 quantum yield reaction Methods 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for preparing CdSexS1-x ternary alloy quantum dots in ole-morpholine. The method is characterized in that: a precursor solution containing Cd and a precursor solution containing Se and S are respectively prepared with ole-morpholine as solvents; the two precursor solutions are mixed under a temperature of 110-130 DEG C; the mixture is heated to 220-250 DEG C with a heating speed of 10-15 DEG C/min, and is subject to a reaction for 1-3 hours; an obtained reaction liquid is injected into methanol, ethanol or propanol, such that a crude product is precipitated; the crude product is washed, processed through centrifugal separation, and is dissolved by using a non-polar organic solvent, such that CdSexS1-x is obtained, wherein 0<x<1. Therefore, a ternary alloy quantum dot solution is obtained. When the adopted molar ratio of Se/S is changed, quantum dots with different stoichiometric ratios can be prepared, wherein an emission spectrum is 450-646nm, and a half emission peak width is 32-48nm. The ternary alloy quantum dot synthesizing method provided by the invention is advantaged in simple operation and good repeatability. Also, the method is environment friendly, economic, and applicable.
Description
Technical field
The invention belongs to ternary semiconductor technical field of nano material, be specifically related to prepare CdSe in oleoyl morpholine solvent<sub TranNum="74">x</sub>s<sub TranNum="75">1-x</sub>the method of (0<x<1) ternary alloy quantum dot.
Background technology
" semiconductor nano quantum dot " (the Semiconductor Nanocrystal Quantum Dots publishing for 2008 according to Springer press (Springer-Verlag/Wien), by Andrey L.Rogach, 1～72 page) middle introduction, the semiconductor nanocrystal that size is less than the exciton Bohr radius of respective material is commonly referred to quantum dot, the photoelectric characteristic that quantum dot is relevant to size and pattern because quantum confined effect has, can be applicable to the fields such as biological stain label, photorectifier, single electron laser apparatus and quantum dot solar cell.At present, most study be II-VI family binary quantum dot, as CdSe, CdS quantum dot, mainly by changing synthesis technique, make the quantum dot of different size size, thereby obtain ultraviolet to the quantum dot light emitting spectrum of near infrared range.But the quantum dot of only preparing different glow colors by the adjusting of size has limitation in actual applications.In bio-imaging technology, not only require quantum dot to have wide emmission spectrum, and require the size of quantum dot to remain on a little size range, now binary quantum dot is difficult to meet two such requirements simultaneously.Address the above problem, can adopt ternary alloy quantum dot.Ternary alloy quantum dot can, in the situation that keeping size constancy, be launched the fluorescence of different wave length by regulation and control chemical element component relative proportion.
Existing about in the synthetic report of ternary alloy quantum dot, mostly adopt the hot injecting method of chemical liquid phase in synthetic.For example, Britain's " chemical communication " (Chem.Commun.2003, the 3rd volume, the 24th phase, the 2964th page) reported first by hot injection (hot-injection), prepare CdSeS ternary quantum dots: first by Cadmium oxide (CdO), trioctylphosphine amine (TOA) and oleic acid (OA) are heated to 300 ℃ until form the cadmium precursor liquid A of clarification under nitrogen protection, at 300 ℃ and accompany by magnetic agitation consumingly, by the Se preparing in advance, the tri octyl phosphine of S (TOP) mixing solutions B injects solution A fast, react after 10 seconds to 4 minutes and stop heating, through aftertreatment, obtain CdSeS quantum dot.In this technique, use the TOP expensive, toxicity is large, inflammable and explosive as solvent; in use operational condition is required very harsh; and synthesis temperature higher (300 ℃), building-up process need to be carried out under nitrogen protection, and therefore having limited mass-producing prepares CdSeS quantum dot." American Chemical Society's meeting will " (J.Am.Chem.Soc.2004, the 126th volume, the 14336th page) to point out, the key that hot injection is prepared quantum point operation is in a kind of hot solution, to inject the injection speed of another solution, in the time of injection, stirring consumingly mixed solution is also prerequisite.At a higher temperature, allow two kinds of precursor solutions that contain different ions are instantaneous reaches abundant mixing, the forming core that just can make quantum dot nano crystalline substance and growth process occur of short duration separated, thereby obtain the high-quality quantum dot that monodispersity is good, luminous intensity is high.And quick injection and violent stirring are difficult in actual fabrication process, so hot injection method is prepared quantum dot except the defect of above-described employing poor stability, poisonous phosphine compound, operate in addition wayward, reproducibility is unstable, be difficult for to realize the deficiencies such as production in enormous quantities.
The technology of preparing proposing in Chinese patent application publication number CN101191052A, CN101328407A and CN101319139A all belongs to the synthesis technique of hot injection method, and in the first two technology, has used phosphine compound TOP, is difficult for realizing preparing in batches ternary alloy quantum.
In a word, existing ternary alloy quantum dot synthetic technology Shortcomings is: synthesis technique cost that the phosphine compound of 1. take is solvent and part is high, have environmental pollution, simultaneously to preparation condition require high; Wayward when 2. existing hot injection operates, repeatable unstable, be unfavorable for preparation in batches.
Summary of the invention
The object of this invention is to provide and a kind ofly in oleoyl morpholine solvent, prepare CdSe<sub TranNum="83">x</sub>s<sub TranNum="84">1-x</sub>the method of (0<x<1) ternary alloy quantum dot, to reach easy and simple to handle, reproducible synthetic target.
The present invention prepares CdSe in oleoyl morpholine solvent<sub TranNum="86">x</sub>s<sub TranNum="87">1-x</sub>the method of (0<x<1) ternary alloy quantum dot, is characterized in that comprising the following steps:
(1) according to the inorganic salt of the Cadmium oxide of every 1mmol or cadmium, mix with lipid acid and the 5～10mL oleoyl morpholine of 3～15mmol, heating is dissolved it, stops heating, and be cooled to room temperature after forming clear soln, obtains the precursor liquid containing Cd;
(2) according to the molar weight of cadmium in the inorganic salt of the integral molar quantity of Se and S and above-mentioned Cadmium oxide or cadmium, equate, according to setting CdSe
xs
1-xthe molar ratio of required Se/S in ternary alloy quantum dot, takes Se powder and the S powder of respective quality, adds in the oleoyl morpholine of 3～5mL, is heated to dissolve completely, is then cooled to room temperature, obtains the precursor liquid containing Se and S;
(3) precursor liquid containing Cd of above-mentioned preparation is mixed with the precursor liquid containing Se and S, be first warming up to 110～130 ℃, then be warming up to 220～250 ℃ of growth temperatures with the speed of 10～15 ℃/min, react 1～3 hour, obtain containing CdSe
xs
1-xthe reaction solution of ternary alloy quantum dot;
(4) by the above-mentioned CdSe that contains<sub TranNum="96">x</sub>s<sub TranNum="97">1-x</sub>methyl alcohol, ethanol or propyl alcohol that the reaction solution of ternary alloy quantum dot shifts out under rear injection normal temperature reduce temperature of reaction, be settled out quantum dot crude product, and with methyl alcohol, ethanol or propyl alcohol to this crude product wash, centrifugation, then dissolve with non-polar organic solvent, obtain CdSe<sub TranNum="98">x</sub>s<sub TranNum="99">1-x</sub>, 0<x<1, ternary alloy quantum dot solution.
The inorganic salt of described Cadmium oxide or cadmium are replaceable is cadmium acetate or cadmium stearate;
Described lipid acid can be selected lauric acid or tetradecanoic acid or palmitinic acid or oleic acid;
Described non-polar organic solvent can be selected normal hexane or toluene.
Adopt the inventive method to prepare CdSe<sub TranNum="104">x</sub>s<sub TranNum="105">1-x</sub>(0<x<1) ternary alloy quantum dot, wherein key during two kinds of precursor liquids of Hybrid Heating is the control of temperature, need at 110～130 ℃, first make solution reach abundant mixing, in being heated to the growth temperature process of CdSeS alloy quantum dot, temperature rise rate should not be lower than 10 ℃/min, otherwise the ternary quantum dots obtaining is of poor quality, there will be the phenomenons such as distribution of sizes is wide, ultraviolet-visible optical absorption peak is not obvious, fluorescent emission intensity is weak; Also should not be higher than 15 ℃/min, otherwise the quantum dot crystallinity making is bad, affects luminescent properties.
Adopt the inventive method can recently obtain by changing different Se/S feed mole the CdSe of different components<sub TranNum="107">x</sub>s<sub TranNum="108">1-x</sub>ternary alloy quantum dot, its component can regulate between 0<x<1, can make the CdSe preparing<sub TranNum="109">x</sub>s<sub TranNum="110">1-x</sub>the emmission spectrum of ternary alloy quantum dot is adjustable continuously in the scope of 450-646nm, and fluorescence intensity is high, and fluorescence quantum yield can reach 70%.
Compare with existing synthetic method, the effect of the inventive method marked improvement is embodied in:
Because the oleoyl morpholine solvent of using in the inventive method has good dissolving power to Se powder, the height poison of therefore using in alternative existing synthetic method, expensive phosphine compound (as TOP) thus realize green non-poisonous chemosynthesis;
Because oleoyl morpholine is except having good dissolution characteristics; the chemical property also with anti-oxidant, high temperature resistant (boiling point is 305 ℃); thereby can remove the anti-oxidation measure of inert atmosphere protection from, can in the system of opening wide, synthesize quantum dot, simplify and handled easily process.
Of the present invention other one large remarkable advantage is: owing to adopting the synthetic method of solution heating, first make respectively precursor liquid and the precursor liquid that contains Se and S containing Cd, then two kinds of precursor liquids are mixed, from room temperature, be heated to Quantum Dots Growth temperature, therefore only need rationally to control temperature speed and reaction times, can obtain CdSeS quantum dot, in actual fabrication process, needn't take quick implantation step complicated like that in existing hot injection method, so adopt the inventive method synthesis condition gentle, easy and simple to handle, be easy to control, reproducible, be conducive to produce in batches.
The inventive method is not owing to being used phosphine compound and other to have contaminative and expensive solvent or tensio-active agent to environment completely, is a kind of environmental friendliness, economic and practical ternary alloy quantum dot synthetic method.
Accompanying drawing explanation
Fig. 1 is CdSe
0.05s
0.95the Absorption and fluorescence utilizing emitted light spectrogram of ternary alloy quantum dot;
Fig. 2 is CdSe
0.3s
0.7the Absorption and fluorescence utilizing emitted light spectrogram of ternary alloy quantum dot;
Fig. 3 is CdSe
0.5s
0.5the Absorption and fluorescence utilizing emitted light spectrogram of ternary alloy quantum dot;
Fig. 4 is CdSe
0.7s
0.3the Absorption and fluorescence utilizing emitted light spectrogram of ternary alloy quantum dot;
Fig. 5 is CdSe
0.9s
0.1the Absorption and fluorescence utilizing emitted light spectrogram of ternary alloy quantum dot.
Embodiment
Embodiment 1: preparation CdSe
0.05s
0.95ternary alloy quantum dot
(1) by 0.130g(1mmol) Cadmium oxide, 5mL(15mmol) oleic acid and 9mL oleoyl morpholine be heated to dissolve, and is then cooled to room temperature, obtains the precursor liquid containing cadmium;
(2) by 0.004g(0.05mmol) Se powder, 0.030g(0.95mmol) S powder and 3mL oleoyl morpholine be heated to dissolve, and is cooled to room temperature, obtains the precursor liquid containing Se and S;
(3) above-mentioned two kinds of precursor liquids are added in the three-necked bottle of 50mL, are under agitation first heated to 110 ℃, be incubated 1 hour two kinds of precursor liquids are fully mixed, then the temperature rise rate with 15 ℃/min is heated to 210 ℃, reacts after 1 hour and stops heating;
(4) reaction solution is taken out and added in the methyl alcohol under normal temperature, be settled out quantum dot crude product, crude product is carried out after centrifugation, washing, then dissolve with toluene, obtain containing CdSe
0.05s
0.95the toluene solution of ternary alloy quantum dot.
Fig. 1 has provided CdSe
0.05s
0.95the Absorption and fluorescence utilizing emitted light spectrogram of ternary alloy quantum dot.
As shown in fig. 1, preparation-obtained CdSe in the present embodiment
0.05s
0.95the absorption peak of ternary alloy quantum dot is 402nm, and the fluorescent emission wavelength under the exciting light of 350nm is 450nm, and the halfwidth of fluorescence emission peak is 32nm, and fluorescence quantum yield is 65%.
Embodiment 2: preparation CdSe
0.3s
0.7ternary alloy quantum dot
(1) by 0.266g(1mmol) cadmium acetate, 1.024g(4mmol) palmitinic acid and 10mL oleoyl morpholine be heated to dissolve, and is then cooled to room temperature, obtains the precursor liquid containing cadmium;
(2) by 0.024g(0.3mmol) Se powder, 0.022g(0.7mmol) S powder and 4mL oleoyl morpholine be heated to dissolve, and is cooled to room temperature, obtains the precursor liquid containing Se and S;
(3) above-mentioned two kinds of precursor liquids are added in the three-necked bottle of 50mL, are under agitation first heated to 120 ℃, insulation 50min fully mixes two kinds of precursor liquids, and then the temperature rise rate with 12 ℃/min is heated to 220 ℃, reacts after 2 hours and stops heating;
(4) reaction solution is taken out and added in the methyl alcohol under normal temperature, be settled out quantum dot crude product, after centrifugation, washing, then dissolve with toluene, can obtain containing CdSe
0.3s
0.7the toluene solution of ternary alloy quantum dot.
Fig. 2 has provided CdSe
0.3s
0.7the Absorption and fluorescence utilizing emitted light spectrogram of ternary alloy quantum dot.
As shown in Figure 2, preparation-obtained CdSe in the present embodiment
0.3s
0.7the absorption peak of ternary alloy quantum dot is 469nm, and the fluorescent emission wavelength under the exciting light of 350nm is 491nm, and the halfwidth of fluorescence emission peak is 39nm, and fluorescence quantum yield is 63%.
Embodiment 3: preparation CdSe
0.5s
0.5ternary alloy quantum dot
(1) by 0.678g(1mmol) cadmium stearate, 0.684g(3mmol) tetradecanoic acid and 10mL oleoyl morpholine be heated to dissolve, and is then cooled to room temperature, obtains the precursor liquid containing cadmium;
(2) by 0.039g(0.5mmol) Se powder, 0.016g(0.5mmol) S powder and 5mL oleoyl morpholine be heated to dissolve, and is cooled to room temperature, obtains the precursor liquid containing Se and S;
(3) above-mentioned two kinds of precursor liquids are added in the three-necked bottle of 50mL, under the effect of magnetic agitation heating jacket, be first heated to 130 ℃, be incubated and stir 40min two kinds of precursor liquids are fully mixed, then the temperature rise rate with 10 ℃/min is heated to 230 ℃, stops heating after 3 hours;
(4) reaction solution is taken out and added in the propyl alcohol under normal temperature, be settled out quantum dot crude product, after centrifugation, washing, then use n-hexane dissolution, can obtain containing CdSe
0.5s
0.5the hexane solution of ternary alloy quantum dot.
Fig. 3 has provided CdSe
0.5s
0.5the Absorption and fluorescence utilizing emitted light spectrogram of ternary alloy quantum dot.
As shown in Figure 3, preparation-obtained CdSe in the present embodiment
0.5s
0.5the absorption peak of ternary alloy quantum dot is 487nm, and the fluorescent emission wavelength under the exciting light of 350nm is 523nm, and the halfwidth of fluorescence emission peak is 43nm, and fluorescence quantum yield is 58%.
Embodiment 4: preparation CdSe
0.7s
0.3ternary alloy quantum dot
(1) by 0.130g(1mmol) Cadmium oxide, 1.200g(6mmol) lauric acid and 8mL oleoyl morpholine be heated to dissolve, and is then cooled to room temperature, obtains the precursor liquid containing cadmium;
(2) by 0.055g(0.7mmol) Se powder, 0.010g(0.3mmol) S powder and 5mL oleoyl morpholine be heated to dissolve, and is cooled to room temperature, obtains the precursor liquid containing Se and S;
(3) above-mentioned two kinds of precursor liquids are added in the three-necked bottle of 50mL, are under agitation first heated to 120 ℃, insulation 30min fully mixes two kinds of precursor liquids, and then the temperature rise rate with 13 ℃/min is heated to 240 ℃, stops heating after 2 hours;
(4) reaction solution is taken out and added in the ethanol under normal temperature, be settled out quantum dot crude product, after centrifugation, washing, then dissolve with toluene, obtain containing CdSe
0.7s
0.3the toluene solution of ternary alloy quantum dot.
Fig. 4 has provided CdSe
0.7s
0.3the Absorption and fluorescence utilizing emitted light spectrogram of ternary alloy quantum dot.
As shown in Figure 4, preparation-obtained CdSe in the present embodiment
0.7s
0.3the absorption peak of ternary alloy quantum dot is 536nm, and the fluorescent emission wavelength under the exciting light of 350nm is 572nm, and the halfwidth of fluorescence emission peak is 48nm, and fluorescence quantum yield is 70%.
Embodiment 5: preparation CdSe
0.9s
0.1ternary alloy quantum dot
(1) by 0.130g(1mmol) Cadmium oxide, 3mL(10mmol) oleic acid and 5mL oleoyl morpholine be heated to dissolve, and is then cooled to room temperature, obtains the precursor liquid containing cadmium;
(2) by 0.071g(0.9mmol) Se powder, 0.003g(0.1mmol) S powder and 5mL oleoyl morpholine be heated to dissolve, and is cooled to room temperature, obtains the precursor liquid containing Se and S;
(3) above-mentioned two kinds of precursor liquids are added in the three-necked bottle of 50mL, are under agitation first heated to 130 ℃, be incubated 1 hour two kinds of precursor liquids are fully mixed, then the temperature rise rate with 15 ℃/min is heated to 250 ℃, stops heating after 2 hours;
(4) reaction solution is taken out and added in the methyl alcohol under normal temperature, be settled out quantum dot crude product, after centrifugation, washing, then dissolve with toluene, can obtain containing CdSe
0.9s
0.1the toluene solution of ternary alloy quantum dot.
Fig. 5 is CdSe
0.9s
0.1the Absorption and fluorescence utilizing emitted light spectrogram of ternary alloy quantum dot.
As shown in Figure 5, preparation-obtained CdSe in the present embodiment
0.9s
0.1the absorption peak of ternary alloy quantum dot is 598nm, and the fluorescent emission wavelength under the exciting light of 350nm is 646nm, and the halfwidth of fluorescence emission peak is 43nm, and fluorescence quantum yield is 58%.
Claims (4)
1. in oleoyl morpholine solvent, prepare CdSe for one kind
xs
1-xthe method of ternary alloy quantum dot, is characterized in that comprising the following steps:
(1) according to the inorganic salt of the Cadmium oxide of every 1mmol or cadmium, mix with lipid acid and the 5～10mL oleoyl morpholine of 3～15mmol, heating makes to form after settled solution, is cooled to room temperature, obtains the precursor liquid containing Cd;
(2) according to the molar weight of cadmium in the inorganic salt of the integral molar quantity of Se and S and above-mentioned Cadmium oxide or cadmium, equate, according to setting CdSe<sub TranNum="215">x</sub>s<sub TranNum="216">1-x</sub>ternary alloy quantum dot, 0<x<1, in the molar ratio of required Se/S, take Se powder and the S powder of respective quality, add in the oleoyl morpholine of 3～5mL, be heated to dissolve completely, be then cooled to room temperature, obtain the precursor liquid containing Se and S;
(3) precursor liquid containing Cd of above-mentioned preparation is mixed with the precursor liquid containing Se and S, be first warming up to 110～130 ℃, then be warming up to 220～250 ℃ with the speed of 10～15 ℃/min, react 1～3 hour, obtain containing CdSe
xs
1-xthe reaction solution of ternary alloy quantum dot;
(4) by the above-mentioned CdSe that contains<sub TranNum="221">x</sub>s<sub TranNum="222">1-x</sub>the reaction solution of ternary alloy quantum dot injects methyl alcohol, ethanol or propyl alcohol and is settled out quantum dot crude product, and with methyl alcohol, ethanol or propyl alcohol to this crude product wash, centrifugation, then with non-polar organic solvent dissolving, obtain CdSe<sub TranNum="223">x</sub>s<sub TranNum="224">1-x</sub>, 0<x<1, ternary alloy quantum dot solution.
2. in oleoyl morpholine solvent, prepare CdSe as claimed in claim 1
xs
1-xthe method of ternary alloy quantum dot, is characterised in that the inorganic salt of described Cadmium oxide or cadmium replace with cadmium acetate or cadmium stearate.
3. in oleoyl morpholine solvent, prepare CdSe as claimed in claim 1
xs
1-xthe method of ternary alloy quantum dot, is characterised in that described lipid acid is selected from lauric acid, tetradecanoic acid, palmitinic acid or oleic acid.
4. in oleoyl morpholine solvent, prepare CdSe as claimed in claim 1
xs
1-xthe method of ternary alloy quantum dot, is characterised in that described non-polar organic solvent is selected from normal hexane or toluene.
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