CN102925138B - 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-life quantum dot and preparation method thereof, be specifically related to a kind of long lifetime semiconductor-quantum-point material of II-VI type prepared by conjugated structure part, belong to field of material preparation.
Background technology
Semiconductor-quantum-point, owing to having the unique optical properties of Size dependence and potential using value, causes common concern and the extensively research of every field researcher.A series of features such as compared with traditional organic dye molecule, semiconductor-quantum-point presents absorb light spectrum width and continuously, emmission spectrum shape is narrow and symmetrical, and emission wavelength is adjustable with quantum dot size size, and photochemical stability is high.The synthetic method of quantum dot is mainly in organic solvent synthesizes two kinds of methods in synthesis and aqueous phase.The semiconductor-quantum-point synthesized in organic solvent, its preparation condition is harsher, and cost is higher, gives batch production and apply to bring certain difficulty; Although water phase synthesis method has simply, economic dispatch advantage.No matter be that the semiconductor-quantum-point which kind of means is synthesized all exists the short problem of fluorescence lifetime, usually 10 ~ 30ns is only had, and the quantum dot of synthesis generally can only dissolve in aqueous phase or oil phase, can not be both water-soluble, oily molten again, these problems cause the difficulty being difficult to overcome all to semiconductor material in photovoltaic applications and in biologic applications.Report is had no with the research preparing both water-soluble and oil-soluble quantum dot at present for extending semiconductor-quantum-point fluorescence lifetime.
Summary of the invention
The object of the invention is the problem that fluorescence lifetime in order to solve quantum dot is short, research has prepared a kind of good luminescence property, both water-soluble and oil soluble, the semiconductor-quantum-point material of II-VI type of long fluorescence lifetime.
Technical scheme of the present invention is bonded a kind of long fluorescence lifetime luminescent material by with between the organic ligand of conjugated structure and the metal ion on semiconductor-quantum-point surface by coordination chemistry key.
A kind of II-VI type long-life quantum dot, described quantum dot is that organic ligand L is combined with the metal ion of II-VI type inorganic semiconductor quantum dot the quantum dot formed by coordination chemistry key, 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 one conjugated ligand L
1, described conjugated ligand L
1be the organic ligand containing 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 one conjugated ligand L
1.This conjugated ligand L
1on there is at least one sulfydryl or selenium hydrogen base substituting group, simultaneously containing 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, one be sulfydryl on it or Xi Qing base functional group can with quantum dot surface metallic ion coordination; Two are these parts is conjugated structure, the electronics that this conjugated structure is quantum dot conduction band provides the possibility of resonance, metal ion and part are linked by chemical bond complexing, the fragrant delocalization system of electron deficiency in the nanocrystalline middle conduction band of II-VI N-type semiconductorN and part can be interacted, promote that the electronics in conduction band enters fragrant extended system, make the electronics after exciting fall time lengthening after rise, thus increase quantum dot fluorescence lifetime.
The preferred described organic ligand L of quantum dot of the present invention is by least one conjugated ligand L
1ligand L non-conjugated with at least one
2composition, conjugated ligand L
1with non-conjugated ligand L
2ratio be 5:0 ~ 1:5, wherein, described non-conjugated ligand L
2for Thiovanic acid, thiohydracrylic acid or Cys.
Of the present invention have conjugated ligand L simultaneously
1with non-conjugated ligand L
2quantum dot there is high quantum yield and long fluorescence lifetime, there is excellent stability simultaneously.
The preferred described organic ligand L of quantum dot of the present invention is by a kind of conjugated ligand L
1ligand L non-conjugated with one
2composition.
Conjugated ligand L in the preferred described organic ligand L of quantum dot of the present invention
1with non-conjugated ligand L
2ratio be 5:0 ~ 1:5, be further 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 containing substituting group with not containing substituent hexa-atomic phenyl ring.
The preferred described conjugated ligand L of quantum dot of the present invention
1at least one aromatic ring on containing heteroatoms, described heteroatoms is selected from least one in N, O, S, Se, and heteroatoms number is less than 5.
The preferred described conjugated ligand L of quantum dot of the present invention
1aromatic ring on there is at least one substituting group, described substituting group is independently 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
1for sulfydryl or selenium hydrogen base substituted benzene ring, comprise containing 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 hydrogen, methylol, hydroxyl, carboxyl, sulfonic group, boronate, ester group, amino and formyl radical independently of one another.
Further preferred described conjugated ligand L
1one in selected from mercapto benzene, 4-Thiosalicylic acid, 4-amino-3 Thiosalicylic acids, mercaptoaniline, mercapto-phenol and 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
1for benzothiazole, benzoglyoxaline, benzothiazole, benzo selenazoles, benzoxazole that sulfydryl or selenium hydrogen base replace, comprise containing and do not contain other substituent benzothiazoles, benzoglyoxaline, benzothiazole, benzo selenazoles, benzoxazole.
Further preferred described conjugated ligand L
1organic ligand for the sulfydryl with structure I I replaces:
Wherein, A is selected from the one in N, O, S and Se; R
3be selected from the one in amino, difluoro-methoxy, methyl, halogen, methoxyl group, hydrogen and nitro.
Further preferred described conjugated ligand L
1one in selected from mercapto benzothiazole, mercaptobenzoxazole, 2-sulfydryl-5-nitrobenzimidazole, 2-sulfydryl-6-methoxybenzothiazole, the chloro-2-mercaptobenzoxazole of 6-and 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
1for the hexa-member heterocycle organic ligand containing 1,2 or 3 N that sulfydryl or selenium hydrogen base replace, comprise containing and do not contain other substituent hexa-member heterocycle organic ligands containing 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 hydrogen, methylol, hydroxyl, carboxyl, halogen, ester group, amino, formyl radical, methyl, sulfonamido, trifluoromethyl, cyano group and sulfydryl independently of one another; Described B, C and D are selected from hydrogen and nitrogen independently of one another.
Further preferred described conjugated ligand L
1for:
Wherein: R
4, R
5be selected from hydrogen, methylol, hydroxyl, carboxyl, halogen, ester group, amino, formyl radical, methyl, sulfonamido, trifluoromethyl, cyano group and sulfydryl independently of one another.
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
1for the five-membered ring organic ligand containing 1,2,3 or 4 N that sulfydryl or selenium hydrogen base replace, comprise containing and do not contain other substituent five-membered ring organic ligands containing 1,2,3 or 4 N.
Further preferred described conjugated ligand L
1for having the organic ligand of structure I V:
Wherein, R
6for hydrogen, methyl, R
7for hydrogen, amino, itrile group, R
8for hydrogen, sulfydryl, methyl or kharophen; Described E, F and G are selected from hydrogen, nitrogen and sulphur independently of one another.
Further preferred described conjugated ligand L
1for:
Wherein, R
6for methyl, R
7for hydrogen, amino, itrile group, R
8for hydrogen, sulfydryl, methyl or kharophen.
Most preferably be: 2-thyroidan, 2,5-dimercaptothiodiazoles, 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
1for having the metal-salt of the organic ligand of structure I ~ IV, drone salt, inner salt or oxide compound.
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) one in thiazole, 8-purinethol, 2-hydrophobic-5-methoxy-diazole (4,5-b) pyridine and 2-sulfydryl-4-amino-7H-pyrroles (2,3-d) pyrimidine.
Another object of the present invention is to provide the preparation method of above-mentioned II-VI type long-life quantum dot.
A preparation method for II-VI type long-life quantum dot, comprises following processing step:
Normal temperature and pressure is by conjugated ligand L to concentration under stirring in the metal salt solution of 0.2 ~ 2mmol/L
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, after adding ligand compound, by the pH value of solution adjust 7 ~ 13, obtain precursor solution; In precursor solution, add inorganic salt solution, stir; Then in above-mentioned solution, add reductive agent, the mol ratio of reductive agent and inorganic salt is 50:1 ~ 3:1, is back to 1 ~ 13 hour, obtains long-life quantum dot solution 50 ~ 220 DEG C of thermostatically heating;
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 the one in deionized water, ethanol and water mixed solvent, DMF, dimethyl sulfoxide (DMSO), oleic acid; Described reductive agent be selected from sodium borohydride, hydrazine hydrate and glucose one or more.
In above-mentioned preparation method, ligand compound used is organic ligand L of the present invention, and described organic ligand L comprises at least one conjugated ligand L
1, described conjugated ligand L
1be the organic ligand containing 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, be 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-VI type long-life quantum dot of the present invention, is preferably undertaken by following processing condition:
Normal temperature and pressure is by conjugated ligand L to concentration under stirring in the metal salt solution of 0.2 ~ 2mmol/L
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, after adding ligand compound L, with sodium hydroxide solution by the pH value of solution adjust 7 ~ 13, obtain precursor solution; In precursor solution, add inorganic salt solution, the concentration of inorganic salt solution is 1mmol/L, stirs 10 ~ 50 minutes; Then in above-mentioned solution, add reductive agent, the mol ratio of reductive agent and inorganic salt is 50:1 ~ 3:1, is back to 1 ~ 13 hour, obtains long-life quantum dot solution 50 ~ 220 DEG C of thermostatically heating, 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, the one in N-METHYLFORMAMIDE, dimethyl sulfoxide (DMSO), oleic acid; Described reductive agent be selected from sodium borohydride, hydrazine hydrate and glucose one or more.
The invention has the beneficial effects as follows: by the modification of conjugated structure organic ligand, obtain the quantum dot of high quantum production rate, high fluorescent, and extend the fluorescence lifetime of quantum dot, aromatic conjugated structure is incorporated in quantum dot light emitting material by coordination and is innovation and significant, and then widen the application of luminescent material.In addition, some specific part, the coordination as 2-mercaptobenzothiazole makes quanta point material can be simultaneously water-soluble and oil is molten, can widen its range of application.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.
Accompanying drawing explanation
Fig. 1 is Cd in embodiment 1
2+: MBA:TGA ratio is respectively 5:3:3, and pH is 10,100 DEG C, during reaction 2h, 405nm excites, and the fluorescence lifetime that 550nm obtains under launching is the time resolved fluorescence spectrogram of the CdTe quantum of 80ns, and Fig. 1 shows 4-MBA-TGA-CdTe can reach 80ns in reaction after two hours;
The solid red solid quantum dot 2-MBTH-TGA-CdTe of 625nm is dissolved in DMF in embodiment 2 by Fig. 2 again, excites down the fluorogram obtained in 365nm, and Fig. 2 shows it except energy is water-soluble, also in DMF, has certain solvability;
Fig. 3 is the quantum yield spectrogram of different return time CdTe quantum in embodiment 3, and Fig. 3 shows the quantum yield of CdTe quantum along with return time is in the trend reduced afterwards that first rises;
Fig. 4 is the XRD spectra of embodiment 1 solid 4-MBA-TGA-CdTe quantum dot powder, Fig. 4 display is carried out contrasting with standard spectrogram JCPDS 15-0770 and is found, the crystalline structure of product belongs to zink sulphide cube crystalline phase, and the position of emission peak is between CdTe and CdS, and bulk 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
First by 0.0199 gram (0.075 mmole) two water cadmium acetate be dissolved in deionized water, be mixed with 50 milliliters of cadmium acetate solution, add 0.007 gram of 4-Thiosalicylic acid (4-MBA), then 4.5 microlitres (0.045 mmole) Thiovanic acid (TGA) is dripped, solution is creamy white, be 10 by the pH of the sodium hydroxide solution regulator solution of 1M, stir 5 points of obtained cadmium source solution; 0.0039 gram of (0.015 mmole) potassium tellurite is dissolved in ionized water, is mixed with 50 milliliters of potassium tellurite solution, join in the solution of cadmium source, stir 5 minutes; Then, in above-mentioned solution, add 0.04 gram of sodium borohydride, stir 15 minutes; Finally be warming up to 100 degrees Celsius, reflux 4 hours.In reaction soln, add isopyknic acetone, centrifugal with the rotating speed of 5000 revs/min, 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.
Embodiment 2
First 0.0199 gram of (0.075 mmole) cadmium acetate is dissolved in deionized water, be mixed with 50 milliliters of cadmium acetate solution, adding 0.005 gram of 2-mercaptobenzothiazole (2-MBTH), is 10 by the pH of the sodium hydroxide solution regulator solution of 1M, stirs 5 points of obtained cadmium source solution; 0.0039 gram of (0.015 mmole) potassium tellurite is dissolved in ionized water, is mixed with 50 milliliters of potassium tellurite solution, join in the solution of cadmium source, stir 5 minutes; Then, in above-mentioned solution, add 0.04 gram of sodium borohydride, stir 15 minutes; Finally be warming up to 100 degrees Celsius, reflux 2 hours.In reaction soln, add isopyknic acetone, centrifugal with the rotating speed of 5000 revs/min, 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
First 0.0222 gram of (0.075 mmole) cadmium nitrate is dissolved in deionized water, be mixed with 50 milliliters of cadmium acetate solution, add 0.007 gram of 4-Thiosalicylic acid, then 4.5 microlitres (0.045 mmole) Thiovanic acid is dripped, solution is creamy white, be 12 by the pH of the sodium hydroxide solution regulator solution of 1M, stir 5 points of obtained cadmium source solution; 0.0039 gram of (0.015 mmole) potassium tellurite is dissolved in ionized water, is mixed with 50 milliliters of potassium tellurite solution, join in the solution of cadmium source, stir 5 minutes; Then, in above-mentioned solution, add 0.04 gram of sodium borohydride, stir 15 minutes; Finally be warming up to 100 degrees Celsius, reflux 20 hours.In reaction soln, add isopyknic acetone, centrifugal with the rotating speed of 5000 revs/min, 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.
Embodiment 4
First 0.0222 gram of (0.075 mmole) cadmium nitrate is dissolved in deionized water, be mixed with 50 milliliters of cadmium acetate solution, adding 0.007 gram of 3-Thiosalicylic acid (3-MBA), is 9 by the pH of the sodium hydroxide solution regulator solution of 1M, stirs 5 points of obtained cadmium source solution; 0.0039 gram of (0.015 mmole) potassium tellurite is dissolved in ionized water, is mixed with 50 milliliters of potassium tellurite solution, join in the solution of cadmium source, stir 5 minutes; Then, in above-mentioned solution, add 0.04 gram of sodium borohydride, stir 15 minutes; Finally be warming up to 100 degrees Celsius, reflux 7 hours.In reaction soln, add isopyknic acetone, centrifugal with the rotating speed of 5000 revs/min, 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
First by soluble in water for 0.04 gram of (0.15 mmole) two water cadmium acetate, being mixed with 50 milliliters of cadmium acetate solution, adding 0.014 gram of 4-Thiosalicylic acid, is 10 by the pH of the sodium hydroxide solution regulator solution of 1M, stirs 5 points of obtained cadmium source solution; By soluble in water for 0.0078 gram of (0.03 mmole) potassium tellurite, be mixed with 50 milliliters of potassium tellurite solution, join in the solution of cadmium source, stir 5 minutes; Then, in above-mentioned solution, add 0.08 gram of sodium borohydride, stir 15 minutes; Finally be warming up to 100 degrees Celsius, reflux 2 hours.In reaction soln, add isopyknic acetone, centrifugal with the rotating speed of 5000 revs/min, 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.
Embodiment 6
First be dissolved in ethylene glycol by 0.0199 gram of (0.075 mmole) cadmium nitrate, being mixed with 50 milliliters of cadmium acetate solution, adding 0.005 gram of 4-Thiosalicylic acid, is 10.5 by the pH of the sodium hydroxide solution regulator solution of 1M, stirs 5 points of obtained cadmium source solution; 0.0039 gram of (0.015 mmole) potassium tellurite is dissolved in ethylene glycol, is mixed with 50 milliliters of potassium tellurite solution, join in the solution of cadmium source, stir 5 minutes; Then, in above-mentioned solution, add 0.04 gram of sodium borohydride, stir 15 minutes; Finally be warming up to 100 degrees Celsius, reflux 6 hours.Isopyknic acetone is added in reaction soln, centrifugal with the rotating speed of 5000 revs/min, 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
First by 0.0199 gram (0.075 mmole) two water cadmium acetate be dissolved in deionized water, be mixed with 50 milliliters of cadmium acetate solution, adding 0.005 gram of 4-Thiosalicylic acid, is 12.5 by the pH of the sodium hydroxide solution regulator solution of 1M, stirs 5 points of obtained cadmium source solution; 0.0039 gram of (0.015 mmole) potassium tellurite is dissolved in ionized water, is mixed with 50 milliliters of potassium tellurite solution, join in the solution of cadmium source, stir 5 minutes; Then, in above-mentioned solution, add 0.04 gram of sodium borohydride, stir 15 minutes; Finally be warming up to 120 degrees Celsius, reflux 8 hours.Isopyknic acetone is added in reaction soln, centrifugal with the rotating speed of 5000 revs/min, 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.
Embodiment 8
First by 0.0199 gram (0.075 mmole) two water cadmium acetate be dissolved in deionized water, be mixed with 50 milliliters of cadmium acetate solution, add 0.0075 gram of 4,4-dimercapto diphenyl sulfide, be 10 by the pH of the sodium hydroxide solution regulator solution of 1M, stir 5 points of obtained cadmium source solution; 0.0039 gram of (0.015 mmole) sodium tellurite is dissolved in ionized water, is mixed with 50 milliliters of potassium tellurite solution, join in the solution of cadmium source, stir 5 minutes; Then, in above-mentioned solution, add 0.105 gram of sodium borohydride, stir 15 minutes; Finally be warming up to 100 degrees Celsius, reflux 9 hours.Isopyknic acetone is added in reaction soln, centrifugal with the rotating speed of 5000 revs/min, 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
First by 0.0199 gram (0.075 mmole) two water cadmium acetate be dissolved in ethanol, be mixed with 50 milliliters of cadmium acetate solution, add 0.005 gram of 5-sulfydryl-1-sulfonic acid methyl tetrazolium double sodium salt, be 10 by the pH of the sodium hydroxide solution regulator solution of 1M, stir 5 points of obtained cadmium source solution; 0.0039 gram of (0.015 mmole) potassium tellurite is dissolved in ionized water, is mixed with 50 milliliters of potassium tellurite solution, join in the solution of cadmium source, stir 5 minutes; Then, in above-mentioned solution, add 0.105 gram of sodium borohydride, stir 15 minutes; Finally be warming up to 100 degrees Celsius, reflux 11 hours.Isopyknic acetone is added in reaction soln, centrifugal with the rotating speed of 5000 revs/min, 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.
Embodiment 10
First by 0.0199 gram (0.075 mmole) two water cadmium acetate be dissolved in deionized water, be mixed with 50 milliliters of cadmium acetate solution, add 0.005 gram of 4-Thiosalicylic acid, then 4.5 microlitres (0.045 mmole) Thiovanic acid is dripped, solution is creamy white, be 12 by the pH of the sodium hydroxide solution regulator solution of 1M, stir 5 points of obtained cadmium source solution; 0.0039 gram of (0.015 mmole) potassium tellurite is dissolved in ionized water, is mixed with 50 milliliters of potassium tellurite solution, join in the solution of cadmium source, stir 5 minutes; Then, in above-mentioned solution, add 0.04 gram of sodium borohydride, stir 15 minutes; Finally be warming up to 100 degrees Celsius, reflux 2 hours.In reaction soln, add isopyknic acetone, centrifugal with the rotating speed of 5000 revs/min, 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
First by 0.0199 gram (0.075 mmole) two water cadmium acetate be dissolved in deionized water, be mixed with 50 milliliters of cadmium acetate solution, add 0.005 gram of 4-Thiosalicylic acid, then 4.5 microlitres (0.045 mmole) Thiovanic acid is dripped, solution is creamy white, be 9 by the pH of the sodium hydroxide solution regulator solution of 1M, stir 5 points of obtained cadmium source solution; 0.0039 gram of (0.015 mmole) potassium tellurite is dissolved in ionized water, is mixed with 50 milliliters of potassium tellurite solution, join in the solution of cadmium source, stir 5 minutes; Then, in above-mentioned solution, add 0.04 gram of sodium borohydride, stir 15 minutes; Finally be warming up to 100 degrees Celsius, reflux 1 hours.In reaction soln, add isopyknic acetone, centrifugal with the rotating speed of 5000 revs/min, 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.
Embodiment 12
First by 0.0199 gram (0.075 mmole) two water cadmium acetate be dissolved in deionized water, be mixed with 50 milliliters of cadmium acetate solution, add 0.005 gram of 4-Thiosalicylic acid, then 4.5 microlitres (0.045 mmole) Thiovanic acid is dripped, solution is creamy white, be 13 by the pH of the sodium hydroxide solution regulator solution of 1M, stir 5 points of obtained cadmium source solution; 0.0039 gram of (0.015 mmole) potassium tellurite is dissolved in ionized water, is mixed with 50 milliliters of potassium tellurite solution, join in the solution of cadmium source, stir 5 minutes; Then, in above-mentioned solution, add 0.04 gram of sodium borohydride, stir 15 minutes; Finally be warming up to 140 degrees Celsius, reflux 3 hours.In reaction soln, add isopyknic acetone, centrifugal with the rotating speed of 5000 revs/min, 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 (11)
1. II-VI type long-life quantum dot, is characterized in that: described quantum dot is that organic ligand L is combined with the metal ion of II-VI type inorganic semiconductor quantum dot the quantum dot formed by coordination chemistry key, has following structure:
MX：L
Wherein, M=Cd
2+or Zn
2+; X=S
2-, Te
2-or Se
2-;
Described ligand L is by least one conjugated ligand L
1ligand L non-conjugated with at least one
2composition, conjugated ligand L
1with non-conjugated ligand L
2mol ratio be 5:0 ~ 1:5,
Wherein, described conjugated ligand L
1be the organic ligand containing 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 non-conjugated ligand L
2for Thiovanic acid, thiohydracrylic acid or Cys.
2. quantum dot according to claim 1, is characterized in that: described conjugated ligand L
1at least one aromatic ring on containing heteroatoms, described heteroatoms is selected from least one in N, O, S, Se, and heteroatoms number is less than 5.
3. quantum dot according to claim 1, is characterized in that: described conjugated ligand L
1aromatic ring on there is at least one substituting group, described substituting group is independently selected from carboxyl, amino, hydroxyl, ester group, alkylsulfonyl, nitro, methoxyl group, oxyethyl group, methylol, hydroxyethyl, kharophen, sulfonic group, methyl, ethyl, cyano group and trifluoromethyl separately.
4. 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 hydrogen, methylol, hydroxyl, carboxyl, sulfonic group, boronate, ester group, amino and formyl radical independently of one another.
5. quantum dot according to claim 4, is characterized in that: described conjugated ligand L
1one in selected from mercapto benzene, 4-Thiosalicylic acid, 4-amino-3-Thiosalicylic acid, mercaptoaniline, mercapto-phenol and sulfydryl Phenylsulfonic acid.
6. quantum dot according to claim 1, is characterized in that: described conjugated ligand L
1one in selected from mercapto benzothiazole, mercaptobenzoxazole, 2-sulfydryl-5-nitrobenzimidazole, 2-sulfydryl-6-methoxybenzothiazole, the chloro-2-mercaptobenzoxazole of 6-and 2-sulfydryl benzo selenazoles.
7. quantum dot according to claim 1, is characterized in that: described conjugated ligand L
1for having the organic ligand of structure III (a) or III (b):
Wherein: R
4, R
5be selected from hydrogen, methylol, hydroxyl, carboxyl, halogen, ester group, amino, formyl radical, methyl, sulfonamido, trifluoromethyl, cyano group and sulfydryl independently of one another.
8. quantum dot according to claim 1, is characterized in that: described conjugated ligand L
1for having the organic ligand of structure I V (a), IV (b) or IV (c):
Wherein, R
6for methyl, R
7for hydrogen, amino, itrile group, R
8for hydrogen, sulfydryl, methyl or kharophen.
9. the quantum dot according to the arbitrary claim of claim 4,7 or 8, is characterized in that: described conjugated ligand L
1for having metal-salt or the inner salt of the organic ligand of structure I, III (a), III (b), IV (a), IV (b) or IV (c).
10. 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 also [4,5-b] one in pyridine and 2-sulfydryl-4-amino-7H-pyrroles [2,3-d] pyrimidine.
The preparation method of 11. a kind of II-VI type long-life quantum dot, is characterized in that: normal temperature and pressure, is by conjugated ligand L under stirring to concentration in the metal salt solution of 0.2 ~ 2mmol/L
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, after adding ligand compound, by the pH value of solution adjust 7 ~ 13, obtain precursor solution; In precursor solution, add inorganic salt solution, stir; Then in above-mentioned solution, add reductive agent, the mol ratio of reductive agent and inorganic salt is 50:1 ~ 3:1, is back to 1 ~ 13 hour, obtains long-life quantum dot solution 50 ~ 220 DEG C of thermostatically heating;
Wherein, described metal-salt is cadmium salt or zinc salt; Described inorganic salt are Cadmium Sulfide, potassium tellurite or potassium selenite; The solvent of described metal salt solution is selected from the one in deionized water, ethanol and water mixed solvent, DMF, dimethyl sulfoxide (DMSO), oleic acid; Described reductive agent be selected from sodium borohydride, hydrazine hydrate and glucose one or more; Described conjugated ligand L
1be the organic ligand containing 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 non-conjugated ligand L
2for Thiovanic acid, thiohydracrylic acid or Cys.
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| JP7468525B2 (en) * | 2019-06-13 | 2024-04-16 | 昭栄化学工業株式会社 | SEMICONDUCTOR NANOPARTICLE COMPLEX, SEMICONDUCTOR NANOPARTICLE COMPLEX DISPERSION, SEMICONDUCTOR NANOPARTICLE COMPLEX COMPOSITION, AND SEMICONDUCTOR NANOPARTICLE COMPLEX CURED FILM |
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