CN102925138A - II-VI long-life quantum dot and preparation method thereof - Google Patents
II-VI long-life quantum dot and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a II-VI long-life quantum dot and a preparation method thereof, in particular to a II-VI long-life quantum dot material prepared by a conjugated structure ligand and belongs to the field of material preparation. The II-VI long-life quantum dot is formed by combining an organic ligand L and a metal ion of a II-VI l inorganic semiconductor quantum dot through a coordinate chemical bond and has a following structure: MX:L, wherein the M=Cd2+ or Zn2+; and the X=S2+, Te2- or Se2-. The organic ligand L comprises at least one conjugate ligand L1, wherein the conjugate ligand L1 is an organic ligand substituted by at least on sulfydryl or selenyl and containing 1-6 aromatic rings, and the sulfydryl or the selenyl are substituted by the aromatic rings. A luminescent material prepared by the II-VI long-life quantum dot can be widely applied to photoelectric devices and electronic devices including single electron transistors, light emitting diodes, lasers, sensors, infrared detectors and the like.
Description
Technical field
The present invention relates to a kind of II-VI type long lifetime quantum dot and preparation method thereof, be specifically related to the long lifetime semiconductor-quantum-point material of a kind of II by the preparation of conjugated structure part-VI type, belong to field of material preparation.
Background technology
Semiconductor-quantum-point has caused common concern and the broad research of every field researcher owing to having the unique optical properties of Size dependence and potential using value.Compare with traditional organic dye molecule, semiconductor-quantum-point presents the absorb light spectrum width and continuous, and the emmission spectrum shape is narrow and symmetrical, and emission wavelength is adjustable with quantum spot size size, a series of characteristics such as photochemical stability height.The synthetic method of quantum dot is mainly synthetic in the organic solvent and the synthetic two kinds of methods of aqueous phase.The semiconductor-quantum-point that synthesizes in the organic solvent, its preparation condition are relatively harsher, and cost is higher, give and produce in batches and apply and brought certain difficulty; Although water phase synthesis method has simply, the economic dispatch advantage.No matter be that the synthetic semiconductor-quantum-point of which kind of means all exists the short problem of fluorescence lifetime, usually only has 10 ~ 30ns, and synthetic quantum dot generally can only dissolve in water or oil phase, can not be both water-soluble, oily molten again, these problems are all given semiconductor material aspect photovoltaic applications and the biologic applications aspect has caused the difficulty that is difficult to overcome.Have no report for prolonging semiconductor-quantum-point fluorescence lifetime and preparing the research that has water-soluble and oil-soluble quantum dot concurrently at present.
Summary of the invention
The objective of the invention is for the short problem of the fluorescence lifetime that solves quantum dot, it is good that research has prepared a kind of luminescent properties, has concurrently water-soluble and oil soluble, the semiconductor-quantum-point material of the II of long fluorescence lifetime-VI type.
Technical scheme of the present invention is to consist of a kind of long fluorescence lifetime luminescent material with closing by the coordination chemistry bond between the metal ion on the organic ligand of conjugated structure and semiconductor-quantum-point surface.
To be organic ligand L be combined the quantum dot of formation by the coordination chemistry key with the metal ion of II-VI type inorganic semiconductor quantum dot for a kind of II-VI type long lifetime quantum dot, described quantum dot, has following structure:
MX：L
Wherein, M=Cd
2+Or Zn
2+X=S
2-, Te
2-Or Se
2-
Described organic ligand L comprises at least a conjugated ligand L
1, described conjugated ligand L
1Be the organic ligand that contains 1 ~ 6 aromatic ring that at least one sulfydryl or selenium hydrogen base replace, described sulfydryl or selenium hydrogen base are that aromatic ring replaces.
The organic ligand L of quantum dot of the present invention comprises at least a conjugated ligand L
1This conjugated ligand L
1On have at least one sulfydryl or selenium hydrogen base substituting group, contain simultaneously 1 ~ 6 aromatic ring, aromatic ring of the present invention is the structure aromatic ring with 2n+2 electronics with conjugated structure, comprises six-ring, hexa-member heterocycle, five-membered ring etc.This part has bi-functional, the one, the sulfydryl on it or selenium hydrogen base functional group can with the coordination of quantum dot surface metal ion; The 2nd, this part is conjugated structure, this conjugated structure provides the possibility of resonance for the electronics of quantum dot conduction band, metal ion and part link by the chemical bond complexing, so that the fragrant delocalization system of electron deficiency can interact in the nanocrystalline middle conduction band of II-VI N-type semiconductorN and the part, promote the electronics in the conduction band to enter fragrant delocalization system, so that the electronics after exciting falls time lengthening after rise, thereby increase quantum dot fluorescence lifetime.
The preferred described organic ligand L of quantum dot of the present invention is by at least a conjugated ligand L
1With at least a non-conjugated ligand L
2Form conjugated ligand L
1With non-conjugated ligand L
2Ratio be 5:0 ~ 1:5, wherein, described non-conjugated ligand L
2Be Thiovanic acid, thiohydracrylic acid or Cys.
Of the present invention have conjugated ligand L simultaneously
1With non-conjugated ligand L
2Quantum dot have high quantum yield and long fluorescence lifetime, have simultaneously excellent stability.
The preferred described organic ligand L of quantum dot of the present invention is by a kind of conjugated ligand L
1With a kind of non-conjugated ligand L
2Form.
Conjugated ligand L among the preferred described organic ligand L of quantum dot of the present invention
1With non-conjugated ligand L
2Ratio be 5:0 ~ 1:5, further be preferably 5:1 ~ 1:5, most preferably be 1:2～3:1.
The preferred described conjugated ligand L of quantum dot of the present invention
1In aromatic ring be hexa-atomic phenyl ring, comprise and contain substituting group and do not contain substituent hexa-atomic phenyl ring.
The preferred described conjugated ligand L of quantum dot of the present invention
1At least one aromatic ring on contain heteroatoms, described heteroatoms is selected from least a among N, O, S, the Se, the heteroatoms number is less than 5.
The preferred described conjugated ligand L of quantum dot of the present invention
1Aromatic ring on have at least one substituting group, described substituting group independently is selected from carbonyl, carboxyl, amino, hydroxyl, ester group, alkylsulfonyl, nitro, methoxyl group, oxyethyl group, methylol, hydroxyethyl, kharophen, sulfonic group, methyl, ethyl, cyano group and trifluoromethyl separately.
The preferred described conjugated ligand L of quantum dot of the present invention
1Be sulfydryl or selenium hydrogen base substituted benzene ring, comprise and contain and do not contain other substituent sulfydryl substituted benzene rings.
Further preferred described conjugated ligand L
1For having the organic ligand of structure I:
Wherein, R
1, R
2Be selected from independently of one another hydrogen, methylol, hydroxyl, carboxyl, sulfonic group, boronate, ester group, amino and formyl radical.
Preferred described conjugated ligand L further
1A kind of in amino-3 Thiosalicylic acids of selected from mercapto benzene, 4-Thiosalicylic acid, 4-, mercaptoaniline, mercapto-phenol and the sulfydryl Phenylsulfonic acid.
Amino-3 Thiosalicylic acids of sulfydryl benzene 4-Thiosalicylic acid 4-
Mercaptoaniline mercapto-phenol sulfydryl Phenylsulfonic acid
The preferred described conjugated ligand L of quantum dot of the present invention
1Benzothiazole, benzoglyoxaline, benzothiazole, benzo selenazoles, benzoxazole for sulfydryl or the replacement of selenium hydrogen base comprise and contain and do not contain other substituent benzothiazoles, benzoglyoxaline, benzothiazole, benzo selenazoles, benzoxazole.
Further preferred described conjugated ligand L
1The organic ligand that replaces for the sulfydryl with structure I I:
Wherein, A is selected from a kind of among N, O, S and the Se; R
3Be selected from a kind of in amino, difluoro-methoxy, methyl, halogen, methoxyl group, hydrogen and the nitro.
Preferred described conjugated ligand L further
1A kind of in selected from mercapto benzothiazole, mercaptobenzoxazole, 2-sulfydryl-5-nitrobenzimidazole, 2-sulfydryl-6-methoxybenzothiazole, 6-chloro-2-mercaptobenzoxazole and the 2-sulfydryl benzo selenazoles.
Mercaptobenzothiazole mercaptobenzoxazole 2-sulfydryl-5-nitrobenzimidazole
2-sulfydryl-6-methoxybenzothiazole 6-chloro-2-mercaptobenzoxazole 2-sulfydryl benzo selenazoles
The preferred described conjugated ligand L of quantum dot of the present invention
1The hexa-member heterocycle organic ligand that contains 1,2 or 3 N for sulfydryl or the replacement of selenium hydrogen base comprises and contains and do not contain other substituent hexa-member heterocycle organic ligands that contains 1,2 or 3 N.
Further preferred described conjugated ligand L1 is the organic ligand with structure III:
Wherein: R
4, R
5Be selected from independently of one another hydrogen, methylol, hydroxyl, carboxyl, halogen, ester group, amino, formyl radical, methyl, sulfonamido, trifluoromethyl, cyano group and sulfydryl; Described B, C and D are selected from hydrogen and nitrogen independently of one another.
Preferred described conjugated ligand L further
1For:
Wherein: R
4, R
5Be selected from independently of one another hydrogen, methylol, hydroxyl, carboxyl, halogen, ester group, amino, formyl radical, methyl, sulfonamido, trifluoromethyl, cyano group and sulfydryl.
Most preferably be: 2-mercaptopyrimidine, 2-sulfydryl-6 picoline, 2-sulfydryl pyrazine, tri-thiol s-triazine, 3-sulfydryl-6-methyl pyridazine.
The preferred described conjugated ligand L of quantum dot of the present invention
1The five-membered ring organic ligand that contains 1,2,3 or 4 N for sulfydryl or the replacement of selenium hydrogen base comprises and contains and do not contain other substituent five-membered ring organic ligands that contains 1,2,3 or 4 N.
Further preferred described conjugated ligand L
1For having the organic ligand of structure I V:
Wherein, R
6Be hydrogen, methyl, R
7Be hydrogen, amino, itrile group, R
8Be hydrogen, sulfydryl, methyl or kharophen; Described E, F and G are selected from hydrogen, nitrogen and sulphur independently of one another.
Preferred described conjugated ligand L further
1For:
Wherein, R
6Be methyl, R
7Be hydrogen, amino, itrile group, R
8Be hydrogen, sulfydryl, methyl or kharophen.
Most preferably be: 2-thyroidan, 2,5-dimercaptothiodiazole, 3-amino-5-sulfydryl-1,2,4-triazole or 1-methyl-5-sulfydryl-1H-tetrazole.
2-thyroidan 2,5-dimercaptothiodiazole 3-amino-5-sulfydryl-1,2,4-triazole 1-methyl-5-sulfydryl-1H-tetrazole
The preferred described conjugated ligand L of quantum dot of the present invention
1Metal-salt, drone salt, inner salt or oxide compound for organic ligand with structure I ~ IV.
More preferably:
2-mercaptobenzothiazole zinc salt pyrithione mantoquita
5-sulfydryl-1-sulfonic acid methyl tetrazolium double sodium salt (S)-alpha-carboxy-N, N, N-trimethylammonium-2-sulfydryl-1H-imidazoles-4-second ammonium
Pyrithione
The preferred described conjugated ligand L of quantum dot of the present invention
1Be selected from 4,4-dimercapto diphenyl sulfide, 4,4-dimercapto phenyl ether, 2-sulfydryl-4-phenyl thiazole and 2-sulfydryl-4-(4-pyridyl) thiazole, 8-purinethol, 2-hydrophobic-5-methoxy-diazole (4,5-b) pyridine and 2-sulfydryl-4-amino-7H-pyrroles (2,3-d) a kind of in the pyrimidine.
Another object of the present invention provides the preparation method of above-mentioned II-VI type long lifetime quantum dot.
The preparation method of a kind of II-VI type long lifetime quantum dot comprises following processing step:
Normal temperature and pressure, stirring lower is to press conjugated ligand L in the metal salt solution of 0.2 ~ 2mmol/L to concentration
1With non-conjugated ligand L
2Mol ratio be that 5:0 ~ 1:5 adds ligand compound, metal-salt and ligand compound mol ratio are 1:0.3 ~ 1:2, add ligand compound after, the pH value accent 7 ~ 13 with solution gets precursor solution; In precursor solution, add inorganic salt solution, stir; Then add reductive agent in mentioned solution, the mol ratio of reductive agent and inorganic salt is 50:1～3:1, is back to 1 ~ 13 hour 50 ~ 220 ℃ of thermostatically heating, obtains the long lifetime quantum dot solution;
Wherein, described metal-salt is cadmium salt or zinc salt; Described inorganic salt are Cadmium Sulfide, cadmium acetate, zinc acetate, zinc nitrate, cadmium nitrate, potassium tellurite or potassium selenite; The solvent of described metal salt solution is selected from a kind of in deionized water, ethanol and water mixed solvent, DMF, dimethyl sulfoxide (DMSO), the oleic acid; Described reductive agent is selected from one or more in sodium borohydride, hydrazine hydrate and the glucose.
Used ligand compound is organic ligand L of the present invention among the above-mentioned preparation method, and described organic ligand L comprises at least a conjugated ligand L
1, described conjugated ligand L
1Be the organic ligand that contains 1 ~ 6 aromatic ring that at least one sulfydryl or selenium hydrogen base replace, described sulfydryl or selenium hydrogen base are that aromatic ring replaces.
Described cadmium salt or zinc salt are preferably nitrate or acetate.
The concentration of the preferred inorganic salt solution of preparation method of the present invention is 1mmol/L.
The preparation method of II of the present invention-VI type long lifetime quantum dot, preferably undertaken by following processing condition:
Normal temperature and pressure, stirring lower is to press conjugated ligand L in the metal salt solution of 0.2 ~ 2mmol/L to concentration
1With non-conjugated ligand L
2Mol ratio be that 5:0 ~ 1:5 adds ligand compound, metal-salt and ligand compound mole are 1:0.3 ~ 1:2, add ligand compound L after, with the pH value accent 7 ~ 13 of sodium hydroxide solution with solution, get precursor solution; Add inorganic salt solution in precursor solution, the concentration of inorganic salt solution is 1mmol/L, stirs 10 ~ 50 minutes; Then add reductive agent in mentioned solution, the mol ratio of reductive agent and inorganic salt is 50:1～3:1, is back to 1 ~ 13 hour 50 ~ 220 ℃ of thermostatically heating, obtains the long lifetime quantum dot solution, and wherein, described metal-salt is cadmium salt or zinc salt; Described inorganic salt are Cadmium Sulfide, cadmium acetate, zinc acetate, zinc nitrate, cadmium nitrate, potassium tellurite or potassium selenite; The solvent of described metal salt solution is selected from deionized water, ethanol and water mixed solvent, N, a kind of in N-METHYLFORMAMIDE, dimethyl sulfoxide (DMSO), the oleic acid; Described reductive agent is selected from one or more in sodium borohydride, hydrazine hydrate and the glucose.
The invention has the beneficial effects as follows: by the modification of conjugated structure organic ligand, obtained the quantum dot of high quantum production rate, high fluorescent, and prolonged the fluorescence lifetime of quantum dot, it is innovation and significant that aromatic conjugated structure is incorporated in the quantum dot light emitting material by coordination, and then the application of widening luminescent material.In addition, some specific part so that quanta point material can be simultaneously water-soluble and oily molten, can be widened its range of application such as the coordination of 2-mercaptobenzothiazole.Luminescent material of the present invention can be widely used in quantum dot some application in photoelectric device and electron device, comprises single-electronic transistor, light emitting diode, laser apparatus, sensor and infrared eye etc.
Description of drawings
Fig. 1 is Cd among the embodiment 1
2+: the MBA:TGA ratio is respectively 5:3:3, and pH is 10,100 ℃, during reaction 2h, 405nm excites, and the lower fluorescence lifetime that obtains of 550nm emission is the time resolved fluorescence spectrogram of the CdTe quantum dot of 80ns, and Fig. 1 shows that 4-MBA-TGA-CdTe can reach 80ns in reaction after two hours;
Fig. 2 is dissolved in the solid red solid quantum dot 2-MBTH-TGA-CdTe of 625nm among the DMF among the embodiment 2 again, excites down the fluorogram that obtains, Fig. 2 to show that it except can be water-soluble, also has certain solvability in DMF in 365nm;
Fig. 3 is the quantum yield spectrogram of different return time CdTe quantum dots among the embodiment 3, and Fig. 3 shows that the quantum yield of CdTe quantum dot is the trend that rises first and reduce afterwards along with return time;
Fig. 4 is the XRD spectra of embodiment 1 solid 4-MBA-TGA-CdTe quantum dot powder, Fig. 4 shows and standard spectrogram JCPDS 15-0770 contrasts discovery, the crystalline structure of product belongs to zink sulphide cube crystalline phase, and the position of emission peak is between CdTe and the CdS, and the main body composition is CdTe.
Embodiment
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
Embodiment 1
At first 0.0199 gram (0.075 mmole) two water cadmium acetates are dissolved in the deionized water, be mixed with 50 milliliters of cadmium acetate solution, add 0.007 gram 4-Thiosalicylic acid (4-MBA), then drip 4.5 microlitres (0.045 mmole) Thiovanic acids (TGA), solution is creamy white, the pH of the sodium hydroxide solution regulator solution by 1M is 10, stirs and makes cadmium source solution in 5 minutes; 0.0039 gram (0.015 mmole) potassium tellurite is dissolved in the ionized water, is mixed with 50 milliliters of potassium tellurite solution, join in the solution of cadmium source, stirred 5 minutes; Then, in mentioned solution, add 0.04 gram sodium borohydride, stirred 15 minutes; Be warming up at last 100 degrees centigrade, refluxed 4 hours.In reaction soln, add isopyknic acetone, centrifugal with 5000 rev/mins rotating speed, clean 3 times with acetone, obtain pure solid quantum dot 4-MBA-TGA-CdTe, react the quantum yield 81% of solution after 2 hours, fluorescence lifetime can reach 80ns.
At first 0.0199 gram (0.075 mmole) cadmium acetate is dissolved in the deionized water, be mixed with 50 milliliters of cadmium acetate solution, add 0.005 gram 2-mercaptobenzothiazole (2-MBTH), the pH of the sodium hydroxide solution regulator solution by 1M is 10, stirs and makes cadmium source solution in 5 minutes; 0.0039 gram (0.015 mmole) potassium tellurite is dissolved in the ionized water, is mixed with 50 milliliters of potassium tellurite solution, join in the solution of cadmium source, stirred 5 minutes; Then, in mentioned solution, add 0.04 gram sodium borohydride, stirred 15 minutes; Be warming up at last 100 degrees centigrade, refluxed 2 hours.In reaction soln, add isopyknic acetone, centrifugal with 5000 rev/mins rotating speed, clean 3 times with acetone, obtain pure solid quantum dot 2-MBTH-TGA-CdTe, react the quantum yield 73% of solution after 2 hours, fluorescence lifetime can reach 55ns.
Embodiment 3
At first 0.0222 gram (0.075 mmole) cadmium nitrate is dissolved in the deionized water, be mixed with 50 milliliters of cadmium acetate solution, add 0.007 gram 4-Thiosalicylic acid, then drip 4.5 microlitres (0.045 mmole) Thiovanic acid, solution is creamy white, the pH of the sodium hydroxide solution regulator solution by 1M is 12, stirs and makes cadmium source solution in 5 minutes; 0.0039 gram (0.015 mmole) potassium tellurite is dissolved in the ionized water, is mixed with 50 milliliters of potassium tellurite solution, join in the solution of cadmium source, stirred 5 minutes; Then, in mentioned solution, add 0.04 gram sodium borohydride, stirred 15 minutes; Be warming up at last 100 degrees centigrade, refluxed 20 hours.In reaction soln, add isopyknic acetone, centrifugal with 5000 rev/mins rotating speed, clean 3 times with acetone, obtain pure solid quantum dot 4-MBA-TGA-CdTe, react the quantum yield 75% of solution after 20 hours, fluorescence lifetime can reach 80ns.
At first 0.0222 gram (0.075 mmole) cadmium nitrate is dissolved in the deionized water, be mixed with 50 milliliters of cadmium acetate solution, add 0.007 gram 3-Thiosalicylic acid (3-MBA), the pH of the sodium hydroxide solution regulator solution by 1M is 9, stirs and makes cadmium source solution in 5 minutes; 0.0039 gram (0.015 mmole) potassium tellurite is dissolved in the ionized water, is mixed with 50 milliliters of potassium tellurite solution, join in the solution of cadmium source, stirred 5 minutes; Then, in mentioned solution, add 0.04 gram sodium borohydride, stirred 15 minutes; Be warming up at last 100 degrees centigrade, refluxed 7 hours.In reaction soln, add isopyknic acetone, centrifugal with 5000 rev/mins rotating speed, clean 3 times with acetone, obtain pure solid quantum dot 3-MBA-TGA-CdTe, react the quantum yield 70% of solution after 7 hours, fluorescence lifetime can reach 60ns.
Embodiment 5
At first that 0.04 gram (0.15 mmole) two water cadmium acetates are soluble in water, be mixed with 50 milliliters of cadmium acetate solution, add 0.014 gram 4-Thiosalicylic acid, the pH of the sodium hydroxide solution regulator solution by 1M is 10, stirs and makes cadmium source solution in 5 minutes; 0.0078 gram (0.03 mmole) potassium tellurite is soluble in water, be mixed with 50 milliliters of potassium tellurite solution, join in the solution of cadmium source, stirred 5 minutes; Then, in mentioned solution, add 0.08 gram sodium borohydride, stirred 15 minutes; Be warming up at last 100 degrees centigrade, refluxed 2 hours.In reaction soln, add isopyknic acetone, centrifugal with 5000 rev/mins rotating speed, clean 3 times with acetone, obtain pure solid quantum dot 4-MBA-CdTe, react the quantum yield 65% of solution after 2 hours, fluorescence lifetime can reach 58ns.
At first 0.0199 gram (0.075 mmole) cadmium nitrate is dissolved in the ethylene glycol, is mixed with 50 milliliters of cadmium acetate solution, add 0.005 gram 4-Thiosalicylic acid, the pH of the sodium hydroxide solution regulator solution by 1M is 10.5, stirs and makes cadmium source solution in 5 minutes; 0.0039 gram (0.015 mmole) potassium tellurite is dissolved in the ethylene glycol, is mixed with 50 milliliters of potassium tellurite solution, join in the solution of cadmium source, stirred 5 minutes; Then, in mentioned solution, add 0.04 gram sodium borohydride, stirred 15 minutes; Be warming up at last 100 degrees centigrade, refluxed 6 hours.In reaction soln, add isopyknic acetone, centrifugal with 5000 rev/mins rotating speed, clean 3 times with acetone, obtain pure solid quantum dot 4-MBA-CdTe.React the quantum yield 67% of solution after 6 hours, fluorescence lifetime can reach 56ns.
Embodiment 7
At first 0.0199 gram (0.075 mmole) two water cadmium acetates are dissolved in the deionized water, be mixed with 50 milliliters of cadmium acetate solution, add 0.005 gram 4-Thiosalicylic acid, the pH of the sodium hydroxide solution regulator solution by 1M is 12.5, stirs and makes cadmium source solution in 5 minutes; 0.0039 gram (0.015 mmole) potassium tellurite is dissolved in the ionized water, is mixed with 50 milliliters of potassium tellurite solution, join in the solution of cadmium source, stirred 5 minutes; Then, in mentioned solution, add 0.04 gram sodium borohydride, stirred 15 minutes; Be warming up at last 120 degrees centigrade, refluxed 8 hours.In reaction soln, add isopyknic acetone, centrifugal with 5000 rev/mins rotating speed, clean 3 times with acetone, obtain pure solid quantum dot 4-MBA-CdTe.React the quantum yield 65% of solution after 8 hours, fluorescence lifetime can reach 57ns.
At first 0.0199 gram (0.075 mmole) two water cadmium acetates are dissolved in the deionized water, be mixed with 50 milliliters of cadmium acetate solution, add 0.0075 gram, 4,4-dimercapto diphenyl sulfide, the pH of the sodium hydroxide solution regulator solution by 1M is 10, stirs and makes cadmium source solution in 5 minutes; 0.0039 gram (0.015 mmole) sodium tellurite is dissolved in the ionized water, is mixed with 50 milliliters of potassium tellurite solution, join in the solution of cadmium source, stirred 5 minutes; Then, in mentioned solution, add 0.105 gram sodium borohydride, stirred 15 minutes; Be warming up at last 100 degrees centigrade, refluxed 9 hours.In reaction soln, add isopyknic acetone, centrifugal with 5000 rev/mins rotating speed, clean 3 times with acetone, obtain pure solid quantum dot 4,4-dimercapto diphenyl sulfide-CdTe.React the quantum yield 63% of solution after 9 hours, fluorescence lifetime can reach 55ns.
Embodiment 9
At first 0.0199 gram (0.075 mmole) two water cadmium acetates are dissolved in the ethanol, be mixed with 50 milliliters of cadmium acetate solution, add 0.005 gram 5-sulfydryl-1-sulfonic acid methyl tetrazolium double sodium salt, the pH of the sodium hydroxide solution regulator solution by 1M is 10, stirs and makes cadmium source solution in 5 minutes; 0.0039 gram (0.015 mmole) potassium tellurite is dissolved in the ionized water, is mixed with 50 milliliters of potassium tellurite solution, join in the solution of cadmium source, stirred 5 minutes; Then, in mentioned solution, add 0.105 gram sodium borohydride, stirred 15 minutes; Be warming up at last 100 degrees centigrade, refluxed 11 hours.In reaction soln, add isopyknic acetone, centrifugal with 5000 rev/mins rotating speed, clean 3 times with acetone, obtain pure solid quantum dot 5-sulfydryl-1-sulfonic acid methyl tetrazolium double sodium salt-CdTe.React the quantum yield 61% of solution after 11 hours, fluorescence lifetime can reach 58ns.
At first 0.0199 gram (0.075 mmole) two water cadmium acetates are dissolved in the deionized water, be mixed with 50 milliliters of cadmium acetate solution, add 0.005 gram 4-Thiosalicylic acid, then drip 4.5 microlitres (0.045 mmole) Thiovanic acid, solution is creamy white, the pH of the sodium hydroxide solution regulator solution by 1M is 12, stirs and makes cadmium source solution in 5 minutes; 0.0039 gram (0.015 mmole) potassium tellurite is dissolved in the ionized water, is mixed with 50 milliliters of potassium tellurite solution, join in the solution of cadmium source, stirred 5 minutes; Then, in mentioned solution, add 0.04 gram sodium borohydride, stirred 15 minutes; Be warming up at last 100 degrees centigrade, refluxed 2 hours.In reaction soln, add isopyknic acetone, centrifugal with 5000 rev/mins rotating speed, clean 3 times with acetone, obtain pure solid quantum dot 4-MBA-TGA, react the quantum yield 40% of solution after 2 hours, fluorescence lifetime can reach 54ns.
Embodiment 11
At first 0.0199 gram (0.075 mmole) two water cadmium acetates are dissolved in the deionized water, be mixed with 50 milliliters of cadmium acetate solution, add 0.005 gram 4-Thiosalicylic acid, then drip 4.5 microlitres (0.045 mmole) Thiovanic acid, solution is creamy white, the pH of the sodium hydroxide solution regulator solution by 1M is 9, stirs and makes cadmium source solution in 5 minutes; 0.0039 gram (0.015 mmole) potassium tellurite is dissolved in the ionized water, is mixed with 50 milliliters of potassium tellurite solution, join in the solution of cadmium source, stirred 5 minutes; Then, in mentioned solution, add 0.04 gram sodium borohydride, stirred 15 minutes; Be warming up at last 100 degrees centigrade, 1 hours refluxes.In reaction soln, add isopyknic acetone, centrifugal with 5000 rev/mins rotating speed, clean 3 times with acetone, obtain pure solid quantum dot 4-MBA-TGA-CdTe, react the quantum yield 63% of solution after 1 hour, fluorescence lifetime can reach 55ns.
At first 0.0199 gram (0.075 mmole) two water cadmium acetates are dissolved in the deionized water, be mixed with 50 milliliters of cadmium acetate solution, add 0.005 gram 4-Thiosalicylic acid, then drip 4.5 microlitres (0.045 mmole) Thiovanic acid, solution is creamy white, the pH of the sodium hydroxide solution regulator solution by 1M is 13, stirs and makes cadmium source solution in 5 minutes; 0.0039 gram (0.015 mmole) potassium tellurite is dissolved in the ionized water, is mixed with 50 milliliters of potassium tellurite solution, join in the solution of cadmium source, stirred 5 minutes; Then, in mentioned solution, add 0.04 gram sodium borohydride, stirred 15 minutes; Be warming up at last 140 degrees centigrade, refluxed 3 hours.In reaction soln, add isopyknic acetone, centrifugal with 5000 rev/mins rotating speed, clean 3 times with acetone, obtain pure solid quantum dot 4-MBA-TGA-CdTe, react the quantum yield 72% of solution after 3 hours, fluorescence lifetime can reach 59ns.
Claims (13)
1. II-VI type long lifetime quantum dot is characterized in that: to be organic ligand L be combined the quantum dot of formation by the coordination chemistry key to described quantum dot with the metal ion of II-VI type inorganic semiconductor quantum dot, has following structure:
MX：L
Wherein, M=Cd
2+Or Zn
2+X=S
2-, Te
2-Or Se
2-
Described organic ligand L comprises at least a conjugated ligand L
1, described conjugated ligand L
1Be the organic ligand that contains 1 ~ 6 aromatic ring that at least one sulfydryl or selenium hydrogen base replace, described sulfydryl or selenium hydrogen base are that aromatic ring replaces.
2. quantum dot according to claim 1, it is characterized in that: described ligand L is by at least a conjugated ligand L
1With at least a non-conjugated ligand L
2Form conjugated ligand L
1With non-conjugated ligand L
2Mol ratio be 5:0 ~ 1:5.
Wherein, described non-conjugated ligand L 2 is Thiovanic acid, thiohydracrylic acid or Cys.
3. quantum dot according to claim 1 is characterized in that: described conjugated ligand L
1At least one aromatic ring on contain heteroatoms, described heteroatoms is selected from least a among N, O, S, the Se, the heteroatoms number is less than 5.
4. quantum dot according to claim 1 is characterized in that: described conjugated ligand L
1Aromatic ring on have at least one substituting group, described substituting group independently is selected from carbonyl, carboxyl, amino, hydroxyl, ester group, alkylsulfonyl, nitro, methoxyl group, oxyethyl group, methylol, hydroxyethyl, kharophen, sulfonic group, methyl, ethyl, cyano group and trifluoromethyl separately.
5. quantum dot according to claim 1 is characterized in that: described conjugated ligand L
1For having the organic ligand of structure I:
Wherein, R
1, R
2Be selected from independently of one another hydrogen, methylol, hydroxyl, carboxyl, sulfonic group, boronate, ester group, amino and formyl radical.
6. quantum dot according to claim 5 is characterized in that: described conjugated ligand L
1A kind of in amino-3 Thiosalicylic acids of selected from mercapto benzene, 4-Thiosalicylic acid, 4-, mercaptoaniline, mercapto-phenol and the sulfydryl Phenylsulfonic acid.
7. quantum dot according to claim 1 is characterized in that: described conjugated ligand L
1The organic ligand that replaces for the sulfydryl with structure I I:
Wherein, A is selected from a kind of among N, O, S and the Se; R
3Be selected from a kind of in amino, difluoro-methoxy, methyl, halogen, methoxyl group, hydrogen and the nitro.
8. quantum dot according to claim 7 is characterized in that: described conjugated ligand L
1A kind of in selected from mercapto benzothiazole, mercaptobenzoxazole, 2-sulfydryl-5-nitrobenzimidazole, 2-sulfydryl-6-methoxybenzothiazole, 6-chloro-2-mercaptobenzoxazole and the 2-sulfydryl benzo selenazoles.
9. quantum dot according to claim 1 is characterized in that: described conjugated ligand L
1For having the organic ligand of structure III:
Wherein: R
4, R
5Be selected from independently of one another hydrogen, methylol, hydroxyl, carboxyl, halogen, ester group, amino, formyl radical, methyl, sulfonamido, trifluoromethyl, cyano group and sulfydryl;
Described B, C and D are selected from hydrogen and nitrogen independently of one another.
10. quantum dot according to claim 1 is characterized in that: described conjugated ligand L
1For having the organic ligand of structure I V:
Wherein, R
6Be hydrogen, methyl, R
7Be hydrogen, amino, itrile group, R
8Be hydrogen, sulfydryl, methyl or kharophen; Described E, F and G are selected from hydrogen, nitrogen and sulphur independently of one another.
11. the described quantum dot of arbitrary claim is characterized in that: described conjugated ligand L according to claim 5 ~ 10
1Metal-salt, drone salt, inner salt or oxide compound for organic ligand with structure I ~ IV.
12. quantum dot according to claim 1 is characterized in that: described conjugated ligand L
1Be selected from 4,4-dimercapto diphenyl sulfide, 4,4-dimercapto phenyl ether, 2-sulfydryl-4-phenyl thiazole and 2-sulfydryl-4-(4-pyridyl) thiazole, 8-purinethol, 2-hydrophobic-5-methoxy-diazole (4,5-b) pyridine and 2-sulfydryl-4-amino-7H-pyrroles (2,3-d) a kind of in the pyrimidine.
13. the preparation method of II-VI type long lifetime quantum dot is characterized in that: normal temperature and pressure, stirring lower is to press conjugated ligand L in the metal salt solution of 0.2 ~ 2mmol/L to concentration
1With non-conjugated ligand L
2Mol ratio be that 5:0 ~ 1:5 adds ligand compound, metal-salt and ligand compound mol ratio are 1:0.3 ~ 1:2, add ligand compound after, the pH value accent 7 ~ 13 with solution gets precursor solution; In precursor solution, add inorganic salt solution, stir; Then add reductive agent in mentioned solution, the mol ratio of reductive agent and inorganic salt is 50:1～3:1, is back to 1 ~ 13 hour 50 ~ 220 ℃ of thermostatically heating, obtains the long lifetime quantum dot solution;
Wherein, described metal-salt is cadmium salt or zinc salt; Described inorganic salt are Cadmium Sulfide, cadmium acetate, zinc acetate, zinc nitrate, cadmium nitrate, potassium tellurite or potassium selenite; The solvent of described metal salt solution is selected from a kind of in deionized water, ethanol and water mixed solvent, DMF, dimethyl sulfoxide (DMSO), the oleic acid; Described reductive agent is selected from one or more in sodium borohydride, hydrazine hydrate and the glucose.
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