CN102344811A - Method for preparing ternary alloy quantum dots in ole-morpholine solvent - Google Patents
Method for preparing ternary alloy quantum dots in ole-morpholine solvent Download PDFInfo
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- CN102344811A CN102344811A CN2011102109043A CN201110210904A CN102344811A CN 102344811 A CN102344811 A CN 102344811A CN 2011102109043 A CN2011102109043 A CN 2011102109043A CN 201110210904 A CN201110210904 A CN 201110210904A CN 102344811 A CN102344811 A CN 102344811A
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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 36
- 239000002904 solvent Substances 0.000 title claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 37
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- 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
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- 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 25
- 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
- 238000002360 preparation method Methods 0.000 claims description 12
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 9
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- 238000009987 spinning Methods 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
- MDSVGJAUFNXYRR-TUNPWDSISA-N (2s)-n-[(4-aminocyclohexyl)methyl]-1-[(2r)-2-(methylamino)-3-phenylpropanoyl]pyrrolidine-2-carboxamide Chemical compound C([C@@H](NC)C(=O)N1[C@@H](CCC1)C(=O)NCC1CCC(N)CC1)C1=CC=CC=C1 MDSVGJAUFNXYRR-TUNPWDSISA-N 0.000 claims description 2
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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 the ternary semiconductor technical field of nano material, be specifically related in the oleoyl morpholine solvent, prepare CdSe
xS
1-xThe method of (0＜x＜1) ternary alloy quantum dot.
Background technology
" semiconductor nano quantum dot " (Semiconductor Nanocrystal Quantum Dots according to Springer press (Springer-Verlag/Wien) publication in 2008; By Andrey L.Rogach; 1～72 page) the middle introduction; Size is commonly referred to quantum dot less than the semiconductor nanocrystal of the exciton Bohr radius of respective material; The photoelectric characteristic that quantum dot is relevant with size and pattern because of quantum confined effect has can be applicable to fields such as biological stain label, photorectifier, single electron laser apparatus and quantum dot solar cell.At present, studying maximum is II-VI family binary quantum dot, like CdSe, CdS quantum dot, mainly through changing the quantum dot that synthesis technique makes the different size size, thereby obtains the quantum dot light emitting spectrum of ultraviolet near infrared range.But only the quantum dot for preparing different glow colors of the adjusting through size has limitation in practical application.In the bio-imaging technology, not only require quantum dot that wide emmission spectrum is arranged, and require the size of quantum dot to remain on a little size range, this moment, the binary quantum dot was difficult to satisfy simultaneously two such requirements.Address the above problem, can adopt the ternary alloy quantum dot.The ternary alloy quantum dot can be launched the fluorescence of different wave length through regulation and control chemical element component relative proportion under the situation that keeps size constancy.
Existing about in the ternary alloy quantum dot synthetic report, 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 with hot injection (hot-injection) preparation CdSeS ternary quantum dots: earlier Cadmium oxide (CdO), trioctylphosphine amine (TOA) and oleic acid (OA) are heated to 300 ℃ up to the clarifying cadmium precursor liquid A of formation under nitrogen protection; Descend and accompany by magnetic agitation consumingly at 300 ℃; Tri octyl phosphine (TOP) the mixing solutions B of the Se for preparing in advance, S is injected solution A fast, react stop after 10 seconds to 4 minutes the heating, promptly obtain the CdSeS quantum dot through aftertreatment.The TOP that use costs an arm and a leg in this technology, toxicity is big, inflammable and explosive is as solvent; In use operational condition is required very harsh; And synthesis temperature higher (300 ℃), building-up process need be carried out under nitrogen protection, has therefore limited scale preparation CdSeS quantum dot." American Chemical Society's meeting will " (J.Am.Chem.Soc.2004; The 126th volume; The 14336th page) point out that the key that hot injection prepares the quantum point operation is in a kind of hot soln, to inject the injection speed of another solution, stirring mixed solution in the time of injection consumingly also is prerequisite.Under a higher temperature, let two kinds of instantaneous thorough mixing that reach of precursor solution that contain different ions, could make forming core and growth process that quantum dot nano is brilliant that of short duration separating takes place, 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 prepares quantum dot except that the defective of the employing poor stability of the above, poisonous phosphine thing, operate wayward, deficiencies such as reproducibility is unstable, difficult realization production in enormous quantities in addition.
The technology of preparing that proposes among one Chinese patent application publication number CN 101191052A, CN 101328407A and the CN 101319139A all belongs to the synthesis technique of hot injection method; And used phosphine thing TOP in preceding two technology, be difficult for realizing batch preparations ternary alloy quantum.
In a word, existing ternary alloy quantum dot synthetic technology exists deficiency to be: 1. with the phosphine thing be the synthesis technique cost of solvent and part high, have an environmental pollution property, simultaneously to the requirement height of preparation condition; Wayward when 2. existing hot injection is operated, repeatable unstable, be unfavorable for batch preparations.
Summary of the invention
The purpose of this invention is to provide and a kind ofly in the oleoyl morpholine solvent, prepare CdSe
xS
1-xThe method of (0＜x＜1) ternary alloy quantum dot is to reach synthetic target easy and simple to handle, good reproducibility.
The present invention prepares CdSe in the oleoyl morpholine solvent
xS
1-xThe method of (0＜x＜1) ternary alloy quantum dot is characterized in that may further comprise the steps:
(1) according to the Cadmium oxide of every 1mmol or the inorganic salt of cadmium, mix with lipid acid and the 5～10mL oleoyl morpholine of 3～15mmol, heating makes its dissolving, after forming clear soln, stops heating, and is cooled to room temperature, obtains containing the precursor liquid of Cd;
(2) molar weight according to cadmium in the inorganic salt of the integral molar quantity of Se and S and above-mentioned Cadmium oxide or cadmium equates, according to setting CdSe
xS
1-xThe molar ratio of required Se/S in the ternary alloy quantum dot takes by weighing the Se powder and the S powder of respective quality, adds in the oleoyl morpholine of 3～5mL, is heated to dissolving fully, is cooled to room temperature then, obtains containing the precursor liquid of Se and S;
(3) precursor liquid that contains Cd with above-mentioned preparation mixes with the precursor liquid that contains Se and S, is warming up to 110～130 ℃ earlier, and the speed with 10～15 ℃/min is warming up to 220～250 ℃ of growth temperatures again, reacts 1～3 hour, obtains containing CdSe
xS
1-xThe reaction solution of ternary alloy quantum dot;
(4) with the above-mentioned CdSe that contains
xS
1-xThe reaction solution of ternary alloy quantum dot shifts out the methyl alcohol, ethanol or the propyl alcohol that inject under the normal temperature back reduces temperature of reaction; Be settled out the quantum dot crude product; And with methyl alcohol, ethanol or propyl alcohol to this crude product wash, spinning, with non-polar organic solvent dissolving, promptly obtain CdSe again
xS
1-x, 0＜x＜1, ternary alloy quantum dot solution.
The inorganic salt of said cadmium can be selected cadmium acetate or cadmium stearate for use;
Said lipid acid can be selected LAURIC ACID 99 MIN or tetradecanoic acid or palmitinic acid or oleic acid for use;
Said non-polar organic solvent can be selected normal hexane or toluene for use.
Adopt the inventive method to prepare CdSe
xS
1-x(0＜x＜1) ternary alloy quantum dot; Wherein the key during two kinds of precursor liquids of Hybrid Heating is a temperature controlling; Need to make earlier that under 110～130 ℃ solution reaches thorough 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 that obtains is of poor quality, phenomenons such as distribution of sizes is wide, the ultraviolet-visible optical absorption peak is not obvious, fluorescent emission intensity is weak can occur; Also should not be higher than 15 ℃/min, otherwise the quantum dot crystallinity that makes is bad, influences luminescent properties.
Employing the inventive method can be through changing the CdSe that different Se/S feed moles recently obtains different components
xS
1-xThe ternary alloy quantum dot, its component can be regulated between 0＜x＜1, can make the CdSe for preparing
xS
1-xThe 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 compound method, the effect of the inventive method marked improvement is embodied in:
Because employed oleoyl morpholine solvent has good dissolving power to the Se powder in the inventive method, the high poison of therefore using in the alternative existing compound method, expensive phosphine thing (like TOP) thus realize green non-poisonous chemosynthesis;
Because the oleoyl morpholine is except that having good dissolution characteristics; The chemical property that also has 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 the handled easily process.
Of the present invention other one big remarkable advantage is: owing to adopt the compound method of solution heating; Promptly make earlier precursor liquid that contains Cd and the precursor liquid that contains Se and S respectively; Then two kinds of precursor liquids are mixed; Be heated to the Quantum Dots Growth temperature from room temperature,, needn't take such complicated quick implantation step in the existing hot injection method in the actual fabrication process so only need reasonable controlled temperature speed and reaction times can obtain the CdSeS quantum dot; So adopt the inventive method synthesis condition gentle, easy and simple to handle, be easy to control, good reproducibility, help batch process.
The inventive method is a kind of environmental friendliness, economic and practical ternary alloy quantum dot compound method owing to do not use phosphine thing and other that environment is had contaminative and expensive solvent or tensio-active agent fully.
Description of drawings
Fig. 1 is CdSe
0.05S
0.95The absorption of ternary alloy quantum dot and fluorescence emission spectrogram;
Fig. 2 is CdSe
0.3S
0.7The absorption of ternary alloy quantum dot and fluorescence emission spectrogram;
Fig. 3 is CdSe
0.5S
0.5The absorption of ternary alloy quantum dot and fluorescence emission spectrogram;
Fig. 4 is CdSe
0.7S
0.3The absorption of ternary alloy quantum dot and fluorescence emission spectrogram;
Fig. 5 is CdSe
0.9S
0.1The absorption of ternary alloy quantum dot and fluorescence emission spectrogram.
Embodiment
Embodiment 1: preparation CdSe
0.05S
0.95The ternary alloy quantum dot
(1) 0.130g (1mmol) Cadmium oxide, 5mL (15mmol) oleic acid and 9mL oleoyl morpholine are heated to dissolving, are cooled to room temperature then, promptly obtain containing the precursor liquid of cadmium;
(2) 0.004g (0.05mmol) Se powder, 0.030g (0.95mmol) S powder and 3mL oleoyl morpholine are heated to dissolving, are cooled to room temperature, obtain containing the precursor liquid of Se and S;
(3) above-mentioned two kinds of precursor liquids are added in the three-necked bottle of 50mL, under agitation are heated to 110 ℃ earlier, be incubated 1 hour and make two kinds of precursor liquid thorough mixing, the temperature rise rate with 15 ℃/min is heated to 210 ℃ then, reacts to stop heating after 1 hour;
(4) reaction solution taken out add in the methyl alcohol normal temperature under, be settled out the quantum dot crude product, crude product is carried out spinning, washing after, dissolve with toluene again, promptly obtain containing CdSe
0.05S
0.95The toluene solution of ternary alloy quantum dot.
Fig. 1 has provided CdSe
0.05S
0.95The absorption of ternary alloy quantum dot and fluorescence emission spectrogram.
As shown in fig. 1, the prepared CdSe that obtains 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
0.7The ternary alloy quantum dot
(1) 0.266g (1mmol) cadmium acetate, 1.024g (4mmol) palmitinic acid and 10mL oleoyl morpholine are heated to dissolving, are cooled to room temperature then, promptly obtain containing the precursor liquid of cadmium;
(2) 0.024g (0.3mmol) Se powder, 0.022g (0.7mmol) S powder and 4mL oleoyl morpholine are heated to dissolving, are cooled to room temperature, obtain containing the precursor liquid of Se and S;
(3) above-mentioned two kinds of precursor liquids are added in the three-necked bottle of 50mL, under agitation are heated to 120 ℃ earlier, insulation 50min makes two kinds of precursor liquid thorough mixing, and the temperature rise rate with 12 ℃/min is heated to 220 ℃ then, react to stop after 2 hours heating;
(4) the reaction solution taking-up is added in the methyl alcohol under the normal temperature, be settled out the quantum dot crude product, after spinning, washing, with the toluene dissolving, can obtain containing CdSe again
0.3S
0.7The toluene solution of ternary alloy quantum dot.
Fig. 2 has provided CdSe
0.3S
0.7The absorption of ternary alloy quantum dot and fluorescence emission spectrogram.
As shown in Figure 2, the prepared CdSe that obtains 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
0.5The ternary alloy quantum dot
(1) 0.678g (1mmol) cadmium stearate, 0.684g (3mmol) tetradecanoic acid and 10mL oleoyl morpholine are heated to dissolving, are cooled to room temperature then, promptly obtain containing the precursor liquid of cadmium;
(2) 0.039g (0.5mmol) Se powder, 0.016g (0.5mmol) S powder and 5mL oleoyl morpholine are heated to dissolving, are cooled to room temperature, obtain containing the precursor liquid of 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 heated to 130 ℃ earlier, insulation is also stirred 40min and is made two kinds of precursor liquid thorough mixing; Temperature rise rate with 10 ℃/min is heated to 230 ℃ then, stops heating after 3 hours;
(4) the reaction solution taking-up is added in the propyl alcohol under the normal temperature, be settled out the quantum dot crude product, after spinning, washing, use n-hexane dissolution again, 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 of ternary alloy quantum dot and fluorescence emission spectrogram.
As shown in Figure 3, the prepared CdSe that obtains 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
0.3The ternary alloy quantum dot
(1) 0.130g (1mmol) Cadmium oxide, 1.200g (6mmol) LAURIC ACID 99 MIN and 8mL oleoyl morpholine are heated to dissolving, are cooled to room temperature then, promptly obtain containing the precursor liquid of cadmium;
(2) 0.055g (0.7mmol) Se powder, 0.010g (0.3mmol) S powder and 5mL oleoyl morpholine are heated to dissolving, are cooled to room temperature, obtain containing the precursor liquid of Se and S;
(3) above-mentioned two kinds of precursor liquids are added in the three-necked bottle of 50mL, under agitation are heated to 120 ℃ earlier, insulation 30min makes two kinds of precursor liquid thorough mixing, and the temperature rise rate with 13 ℃/min is heated to 240 ℃ then, stops heating after 2 hours;
(4) the reaction solution taking-up is added in the ethanol under the normal temperature, be settled out the quantum dot crude product, after spinning, washing, with the toluene dissolving, promptly obtain containing CdSe again
0.7S
0.3The toluene solution of ternary alloy quantum dot.
Fig. 4 has provided CdSe
0.7S
0.3The absorption of ternary alloy quantum dot and fluorescence emission spectrogram.
As shown in Figure 4, the prepared CdSe that obtains 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
0.1The ternary alloy quantum dot
(1) 0.130g (1mmol) Cadmium oxide, 3mL (10mmol) oleic acid and 5mL oleoyl morpholine are heated to dissolving, are cooled to room temperature then, promptly obtain containing the precursor liquid of cadmium;
(2) 0.071g (0.9mmol) Se powder, 0.003g (0.1mmol) S powder and 5mL oleoyl morpholine are heated to dissolving, are cooled to room temperature, obtain containing the precursor liquid of Se and S;
(3) above-mentioned two kinds of precursor liquids are added in the three-necked bottle of 50mL, under agitation are heated to 130 ℃ earlier, be incubated 1 hour and make two kinds of precursor liquid thorough mixing, the temperature rise rate with 15 ℃/min is heated to 250 ℃ then, stops heating after 2 hours;
(4) the reaction solution taking-up is added in the methyl alcohol under the normal temperature, be settled out the quantum dot crude product, after spinning, washing, with the toluene dissolving, can obtain containing CdSe again
0.9S
0.1The toluene solution of ternary alloy quantum dot.
Fig. 5 is CdSe
0.9S
0.1The absorption of ternary alloy quantum dot and fluorescence emission spectrogram.
As shown in Figure 5, the prepared CdSe that obtains 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. one kind prepares CdSe in the oleoyl morpholine solvent
xS
1-xThe method of ternary alloy quantum dot is characterized in that may further comprise the steps:
(1) according to the Cadmium oxide of every 1mmol or the inorganic salt of cadmium, mix with lipid acid and the 5～10mL oleoyl morpholine of 3～15mmol, heating is cooled to room temperature after making and forming settled solution, obtains containing the precursor liquid of Cd;
(2) molar weight according to cadmium in the inorganic salt of the integral molar quantity of Se and S and above-mentioned Cadmium oxide or cadmium equates, according to setting CdSe
xS
1-xThe ternary alloy quantum dot, 0＜x＜1, in the molar ratio of required Se/S, take by weighing the Se powder and the S powder of respective quality, add in the oleoyl morpholine of 3～5mL, be heated to dissolving fully, be cooled to room temperature then, obtain containing the precursor liquid of Se and S;
(3) precursor liquid that contains Cd with above-mentioned preparation mixes with the precursor liquid that contains Se and S, is warming up to 110～130 ℃ earlier, and the speed with 10～15 ℃/min is warming up to 220～250 ℃ again, reacts 1～3 hour, obtains containing CdSe
xS
1-xThe reaction solution of ternary alloy quantum dot;
(4) with the above-mentioned CdSe that contains
xS
1-xThe reaction solution of ternary alloy quantum dot injects methyl alcohol, ethanol or propyl alcohol and is settled out the quantum dot crude product, and with methyl alcohol, ethanol or propyl alcohol to this crude product wash, spinning, dissolve with non-polar organic solvent again, promptly obtain CdSe
xS
1-x, 0＜x＜1, ternary alloy quantum dot solution.
2. in the oleoyl morpholine solvent, prepare CdSe according to claim 1
xS
1-xThe method of ternary alloy quantum dot is characterised in that the inorganic salt of said cadmium are selected from cadmium acetate or cadmium stearate;
3. in the oleoyl morpholine solvent, prepare CdSe according to claim 1
xS
1-xThe method of ternary alloy quantum dot is characterised in that said lipid acid is selected from LAURIC ACID 99 MIN, tetradecanoic acid, palmitinic acid or oleic acid;
4. in the oleoyl morpholine solvent, prepare CdSe according to claim 1
xS
1-xThe method of ternary alloy quantum dot is characterised in that said non-polar organic solvent is selected from normal hexane or toluene.
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