CN106010511B - Method for removing residual cation precursor in oil-soluble quantum dots - Google Patents
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Abstract
The invention provides a method for removing residual cation precursors in oil-soluble quantum dots, which comprises the following steps: providing oil-soluble quantum dot mixed liquid of residual cation precursors; adding organic amine into the oil-soluble quantum dot mixed solution in air, inert atmosphere or vacuum atmosphere to carry out thermal mixing treatment, wherein the temperature of the thermal mixing treatment is 80-350 ℃, so as to obtain a first mixed solution; cooling the first mixed solution to reduce the temperature of the first mixed solution to 30-120 ℃, and adding a non-polar organic solvent for second mixing treatment to obtain a second mixed solution; and cooling the second mixed solution to room temperature, adding a polar organic solvent to form a turbid solution, and performing centrifugal treatment on the turbid solution to obtain the oil-soluble quantum dots.
Description
Technical Field
The invention belongs to the technical field of oil-soluble quantum dot purification, and particularly relates to a method for removing residual cation precursors in oil-soluble quantum dots.
Background
In recent years, quantum dot light emitting diodes (QLEDs) using quantum dot materials as light emitting layers have attracted much attention due to advantages such as high light color purity, high light emission quantum efficiency, adjustable light emission color, and long service life, and are the main direction of research on new LEDs. With the development of QLED printing technology, QLEDs are most likely to become products of future printed displays. The red, green and blue quantum dot solution with higher purity is necessary for preparing the QLED device by printing. However, the luminous efficiency and the service life of the light emitting diode with the blue light quantum dots far do not meet the display requirements, and the luminous efficiency and the service life of the light emitting diode with the blue light quantum dots become key factors for restricting the QLED printing display. The quantum dots are used as the main material of the QLED, and the purity of the quantum dots has great influence on the luminous efficiency and the service life of the device.
At present, the synthesis of related red, green and blue quantum dots is an alloy system formed on the basis of four elements, namely cadmium (Cd), zinc (Zn), selenium (Se) and sulfur (S). A large number of core-shell quantum dot synthesis experiments show that when shell zinc sulfide (ZnS) or cadmium sulfide (CdS) or zinc selenide (ZnSe) or the like grows, if the ratio of a cation precursor to an anion precursor (such as Zn: S, Cd: S, Zn: Se) is high, uniform growth of the shell is facilitated, the defect of lattice mismatch is reduced, and the quantum yield of the quantum dots is improved. However, a large amount of cation precursors are easily left in the quantum dot mixed liquid obtained under the condition of synthesizing the high-concentration cation precursors, and some cation precursors such as zinc oleate are easily separated out when the temperature of the mixed liquid is lower than a certain temperature, which brings many troubles for cleaning and purifying the quantum dots. Specifically, at room temperature, the cationic precursors not only have low solubility in organic solvents such as toluene, n-hexane and chloroform, and are easy to precipitate, but also form coprecipitation along with the treatment of the centrifugal Quantum Dots (QDs), and the purity of the quantum dot solution is seriously influenced, so that the luminous efficiency and the service life of the QLED device are influenced.
Disclosure of Invention
The invention aims to provide a method for removing residual cation precursors in oil-soluble quantum dots, and aims to solve the problem that the residual cation precursors in the oil-soluble quantum dots influence the purity of a quantum dot solution and further influence the luminous efficiency and the service life of a QLED device.
The invention is realized in such a way that a method for removing residual cation precursors in oil-soluble quantum dots comprises the following steps:
providing oil-soluble quantum dot mixed liquid of residual cation precursors;
adding organic amine into the oil-soluble quantum dot mixed solution in air, inert atmosphere or vacuum atmosphere to carry out thermal mixing treatment, wherein the temperature of the thermal mixing treatment is 80-350 ℃, so as to obtain a first mixed solution;
cooling the first mixed solution to reduce the temperature of the first mixed solution to 30-120 ℃, and adding a non-polar organic solvent for second mixing treatment to obtain a second mixed solution;
and cooling the second mixed solution to room temperature, adding a polar organic solvent to form a turbid solution, and performing centrifugal treatment on the turbid solution to obtain the oil-soluble quantum dots.
The method for removing the residual cation precursor in the oil-soluble quantum dots comprises the steps of dissolving the cation precursor in the organic amine to obtain a first mixed solution, adding a nonpolar organic solvent for dispersing the oil-soluble quantum dots into the first mixed solution to form a second mixed solution, and finally precipitating the oil-soluble quantum dots by using a polar organic solvent to obtain the high-purity oil-soluble quantum dots. The method has good controllability and is easy to repeat, and more importantly, the oil-soluble quantum dots obtained by the method can obtain higher purity without the guarantee of weakening the fluorescence intensity, so that the influence of the excessive residue of the cation precursor in the oil-soluble quantum dots on the luminous efficiency and the service life of the prepared QLED device and other unpredictable influences are effectively avoided. The QLED device prepared by the oil-soluble quantum dots purified by the method can avoid the interference of the cation precursor to the device performance, thereby improving the reproducibility of the QLED device performance.
Drawings
FIG. 1 is a flow chart of a method for removing residual cation precursors in oil-soluble quantum dots according to an embodiment of the present invention;
FIG. 2 is a graph of fluorescence intensity of blue oil-soluble quantum dots of residual cation precursors provided in example 1 of the present invention and blue oil-soluble quantum dots treated by the method of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
With reference to fig. 1, an embodiment of the present invention provides a method for removing residual cation precursors in oil-soluble quantum dots, including the following steps:
s01, providing an oil-soluble quantum dot mixed solution of a residual cation precursor;
s02, adding organic amine into the oil-soluble quantum dot mixed solution in air, inert atmosphere or vacuum atmosphere to carry out hot mixing treatment, wherein the temperature of the hot mixing treatment is 80-350 ℃, so as to obtain a first mixed solution;
s03, cooling the first mixed solution to reduce the temperature of the first mixed solution to 30-120 ℃, and adding a non-polar organic solvent to perform second mixing treatment to obtain a second mixed solution;
and S04, cooling the second mixed solution to room temperature, adding a polar organic solvent to form a turbid solution, and performing centrifugal treatment on the turbid solution to obtain the oil-soluble quantum dots.
Specifically, in step S01, the cation precursor is a shell-source organometallic cation precursor commonly used in the preparation of core-shell oil-soluble quantum dots, including but not limited to zinc oleate
{Zn[CH3(CH2)7CH＝CH(CH2)7COO]2Cadmium oleate
{Cd[CH3(CH2)7CH＝CH(CH2)7COO]2}, lead oleate
{Pb[CH3(CH2)7CH＝CH(CH2)7COO]2}, indium oleate { In [ CH3(CH2)7CH＝CH(CH2)7COO]3At least one of them. Providing oil-soluble quantum dot mixed liquor of the residual cation precursor, wherein the obtaining way of the oil-soluble quantum dot mixed liquor is not definitely limited, and the oil-soluble quantum dot mixed liquor of the residual cation precursor directly obtained in the preparation process of the oil-soluble quantum dot can be adopted; or the obtained oil-soluble quantum dot material can be prepared after being dissolvedAnd (3) oil-soluble quantum dot mixed liquid of residual cation precursors. The oil-soluble quantum dots are alloy component structure quantum dots, core-shell component structure quantum dots or homogeneous component structure quantum dots. Specifically, the oil-soluble quantum dots include, but are not limited to CdxZn1-xS/ZnS、CdxZn1-xSySe1-yThe quantum dots comprise/ZnS, CdZnSeS, CdSe/ZnS, InP/ZnS, CuInS/ZnS, ZnSe and ZnTe.
As a specific example, the oil-soluble quantum dot mixed solution of the residual cation precursor can be prepared by the following method: and dissolving the oil-soluble quantum dots to form a quantum dot solution, and adding oleic acid and octadecene to prepare the oil-soluble quantum dot mixed solution of the residual cation precursor. Wherein, the solvent for dissolving the oil-soluble quantum dots is preferably a low boiling point solvent, such as n-hexane, methanol, toluene, chloroform and the like; the oleic acid forms a cationic precursor with residual cations; the octadecene serves to better facilitate dissolution of the oil-soluble quantum dots. In order to obtain the oil-soluble quantum dot mixed solution of the residual cation precursor with better solubility, as a preferred embodiment, the volume ratio of the oleic acid to the octadecene is (10:1) - (1:10), and more preferably 1: 1. here, it should be understood that the oil-soluble quantum dots and/or the cation precursor may not be completely dissolved in the oil-soluble quantum dot mixed solution of the residual cation precursor.
In step S02, in order to prevent some oil-soluble quantum dots from being oxidized (such as, but not limited to, CdSe, PbS, PbSe, etc.), the oil-soluble quantum dot mixture is subjected to a thermal mixing process in air, an inert atmosphere or a vacuum atmosphere, wherein the inert atmosphere includes, but is not limited to, a nitrogen atmosphere, an argon atmosphere, and a helium atmosphere.
According to the embodiment of the invention, the oil-soluble quantum dot mixed liquid and the organic amine are subjected to thermal mixing treatment, the temperature of the thermal mixing treatment is 80-350 ℃, and the cation precursor can be ensured to be fully dispersed and dissolved in the organic amine. The method of the thermal mixing treatment can be realized by the following methods:
stirring and mixing the oil-soluble quantum dot mixed solution and the organic amine, heating to 80-350 ℃, and maintaining for more than 5min to form a first mixed solution; or
Stirring and heating the oil-soluble quantum dot mixed solution to 80-350 ℃, adding the organic amine, maintaining the temperature, stirring and heating for more than 5min, and forming a first mixed solution.
In order to ensure the safety of the heating process and better promote the dissolution of the cation precursor, as a preferred embodiment, the method of the thermal mixing process is as follows: heating the oil-soluble quantum dot mixed solution to 80 ℃, maintaining for 10-30min, then heating to 80-350 ℃, and maintaining for more than 5 min. In the preferred heating mode, firstly, the low-boiling point solvent such as n-hexane, ethanol, toluene or chloroform existing in the quantum dot solution can be removed at 80 ℃, so that the potential safety hazard caused by the violent boiling of the low-boiling point solvent during high-temperature heating is avoided. Then, the temperature is raised to a high temperature of 80-350 ℃, so that the cation precursor can be promoted to be fully dissolved, and the cation precursor can be fully removed in the following process. In the process, when the cation precursor is fully dissolved, the mixed solution becomes clear and transparent. And finally, selecting a proper temperature and maintaining for a period of time to ensure that the cation precursor is more fully dispersed and dissolved in the organic amine solvent. In this process, when the cation precursor is sufficiently dissolved, the color of the first mixed solution changes from light brown to transparent dark brown.
In the embodiment of the present invention, the organic amine includes, but is not limited to, at least one of oleylamine, ethylamine, triethylamine, propylamine, tripropylamine, butylamine, tributylamine, pentylamine, tripentylamine, hexylamine, trihexylamine, heptylamine, octylamine, trioctylamine, di-n-octylamine, decylamine, dodecylamine, trilaurylamine, tetradecylamine, hexadecylamine, octadecylamine, and tricaprylene. The addition amount of the organic amine has a large influence on the removal degree of the cation precursor or the performance of the obtained oil-soluble quantum dot. Specifically, when the amount of the organic amine is too small, the organic amine is not enough to disperse and dissolve all the cation precursors, and therefore, the purpose of effectively removing the cation precursors cannot be achieved; when the dosage of the organic amine is excessive, the organic amine can exchange with the surface group (ligand) of the oil-soluble quantum dot to form an agglomerate, so that the performance of the oil-soluble quantum dot is influenced. Therefore, as a preferred embodiment, in the first mixed solution, the molar ratio of the cation precursor to the organic amine is 1:10 to 10: 1; more preferably 1: 2, so as to remove residual cationic precursor as much as possible without affecting the performance of the oil-soluble quantum dots.
In step S03, the nonpolar organic solvent is added to the first mixed solution to dilute the first mixed solution, and the oil-soluble quantum dots are sufficiently dispersed. As a preferred embodiment, the temperature is reduced to 30-120 ℃ and more preferably to 100 ℃ before the addition of the non-polar organic solvent. If the temperature is too low, the dispersibility of the oil-soluble quantum dots is poor; if the temperature is too high, the addition of the non-polar organic solvent may pose a safety hazard due to vigorous boiling.
In order to completely disperse the oil-soluble quantum dots, in the second mixed solution, the volume ratio of the first mixed solution to the nonpolar organic solvent is 1:5-10:1 as a preferable embodiment; more preferably 5: 1. further, as a preferred embodiment, the non-polar organic solvent is a non-polar organic solvent with a boiling point lower than 80 ℃, and specifically includes but is not limited to at least one of toluene, chloroform, n-hexane, cyclohexane and chlorobenzene.
In step S04, in order to separate the oil-soluble quantum dots in the second mixed solution and separate the oil-soluble quantum dots from the dissolved cation precursor, the second mixed solution is cooled and then a polar organic solvent is added, at this time, the oil-soluble quantum dots dissolved in the oil phase of the nonpolar organic solvent form a precipitate in the polar organic solvent, and the cation precursor is kept in a solution state and centrifuged to obtain the oil-soluble quantum dots from which the residual cation precursor is removed. As a preferred embodiment, in order to sufficiently realize the precipitation of the oil-soluble quantum dots, the addition amount of the polar organic solvent satisfies: the volume ratio of the oil-soluble quantum dot mixed solution to the polar organic solvent is 1:10-10:1, and more preferably 1: 5.
as another preferred embodiment, the polar organic solvent is at least one of alcohols, ketones, or esters. Further, the polar organic solvent is preferably a low-polar organic solvent, and specifically includes, but is not limited to, at least one of ethanol, methanol, acetone, ethyl acetate, and butanol.
Furthermore, the oil-soluble quantum dots obtained after centrifugation can be cleaned.
According to the method for removing the residual cation precursor in the oil-soluble quantum dot, provided by the embodiment of the invention, the cation precursor is dissolved in the organic amine to obtain a first mixed solution, then a nonpolar organic solvent for dispersing the oil-soluble quantum dot is added into the first mixed solution to form a second mixed solution, and finally the oil-soluble quantum dot is precipitated by adopting a polar organic solvent, so that the high-purity oil-soluble quantum dot is obtained. The method has good controllability and is easy to repeat, and more importantly, the oil-soluble quantum dots obtained by the method can obtain higher purity without the guarantee of weakening the fluorescence intensity, so that the influence of the excessive residue of the cation precursor in the oil-soluble quantum dots on the luminous efficiency and the service life of the prepared QLED device and other unpredictable influences are effectively avoided. The QLED device prepared by adopting the oil-soluble quantum dots purified by the method provided by the embodiment of the invention can avoid the interference of the cation precursor on the device performance, thereby improving the reproducibility of the QLED device performance.
The following description will be given with reference to specific examples.
Example 1
Blue-light-emitting-removed CdxZn1-xThe method for preparing the residual cation precursor in the S/ZnS oil-soluble quantum dot comprises the following steps:
s11, under the protection of Ar gas, taking 20ml of CdxZn1-xAn N-hexane solution of S/ZnS quantum dots (0.05mg/ml) was poured into a three-necked flask containing 3ml of Oleic Acid (OA) and 3ml of Octadecene (ODE) to obtain a residueBlue oil soluble quantum dot mixed liquid of cation precursor;
s12, heating the blue oil soluble quantum dot mixed solution in the three-neck flask to 80 ℃ and maintaining the temperature for 20 minutes, then heating to 180 ℃ to change the blue oil soluble quantum dot mixed solution into a clear and transparent liquid and maintaining the liquid for 30 minutes, then cooling the blue oil soluble quantum dot mixed solution to 150 ℃, and then adding oleylamine to obtain a first mixture, wherein the addition amount of the oleylamine meets the following requirements: the molar ratio of the cation precursor to the oleylamine is 1: 2;
s13, cooling the first mixed solution to reduce the temperature of the first mixed solution to 100 ℃, and adding 8ml of normal hexane to obtain a second mixed solution;
s14, cooling the second mixed solution to room temperature, adding a mixed solvent containing ethyl acetate and ethanol, precipitating the blue oil soluble quantum dots, and performing centrifugation and cleaning treatment to obtain high-purity blue CdxZn1-xAnd the S/ZnS oil-soluble quantum dots.
Blue Cd prepared in embodiment 1 of the inventionxZn1-xS/ZnS oil-soluble quantum dot, the solution formed by the quantum dot is clear and transparent, and the quantum dot contains almost no zinc oleate { Zn (OA)2}. Cd obtained in step S11 of example 1xZn1-xS/ZnS quantum dot and Cd provided in step S14xZn1-xFluorescence intensity test is carried out on the S/ZnS quantum dots, and the experimental result is shown in FIG. 2. As can be seen from the figure, the fluorescence intensity of the oil-soluble quantum dot treated in the embodiment 1 of the present invention is not changed, and thus, the method according to the embodiment of the present invention can effectively remove the residual cationic precursor while ensuring the fluorescence intensity.
Example 2
Red or green luminous Cd removal1-xZnxSe1-ySyA method for preparing residual cation precursors in oil-soluble quantum dots comprises the following steps:
s21, under the protection of Ar gas, taking 20ml of Cd1-xZnxSe1-ySyQuantum dot (0.05mg/ml) n-hexane solution was injected into a solution containing 3ml of Oleic Acid (OA) and 3ml ofIn a three-neck flask containing ml Octadecene (ODE), obtaining blue oil soluble quantum dot mixed liquor of residual cation precursors;
s22, heating the red or green luminous oil-soluble quantum dot mixed liquor in the three-neck flask to 80 ℃ and maintaining the temperature for 20 minutes, then heating to 180 ℃ to enable the red or green oil-soluble quantum dot mixed liquor to become clear and transparent liquid and maintaining the liquid for 30 minutes, then cooling the red or green oil-soluble quantum dot mixed liquor to 150 ℃, and adding oleylamine to obtain a first mixture, wherein the addition amount of the oleylamine meets the following requirements: the molar ratio of the cation precursor to the oleylamine is 1: 2;
s23, cooling the first mixed solution to reduce the temperature of the first mixed solution to 100 ℃, and adding 8ml of normal hexane to obtain a second mixed solution;
s24, cooling the second mixed solution to room temperature, adding a mixed solvent containing ethyl acetate and ethanol, precipitating the red or green oil-soluble quantum dots, and performing centrifugation and cleaning treatment to obtain high-purity red or green Cd1-xZnxSe1-ySyOil-soluble quantum dots.
Example 3
The embodiment is suitable for a system for synthesizing quantum dots by using oleic acid and octadecene as reaction solvents, and the quantum dot synthesis is referred to Chemistry of Materials 2008,20,5307-5313, and the synthesis comprises the following steps:
s311, preparing a mixed solution of zinc oleate and cadmium oleate: 9mmol of zinc acetate, 1mmol of cadmium oxide, 8mL of oleic acid and 15mL of octadecene were placed in a 50mL three-necked flask. Degassing at room temperature, heating to 120 deg.C, keeping the temperature for 20mins, introducing argon, heating to 120 deg.C, keeping the temperature for 10mins, and heating the mixture to 250 deg.C to obtain a clear and transparent solution.
S312. preparation of S-ODE: 1.8mmol of S was added to 3ml of octadecene, heated to 230 ℃ until a clear, transparent solution formed, and then incubated at 140 ℃.
S313. preparation of S-TOP: 6mmol of S was added to 3ml of trioctylphosphine, heated to 170 ℃ until a clear, transparent solution formed, and subsequently cooled to room temperature.
S314.CdxZn1-xPreparation of S/ZnS: and (2) rapidly injecting the S-ODE in the step (2) into the mixed liquid of the zinc oleate and the cadmium oleate in the step (1) at one time at the temperature of 350 ℃, and injecting the S-TOP in the step (3) into the reaction liquid at the speed of 3mL/h through an injection pump after 10 mins.
The cleaning process comprises the following steps:
s32, cooling the temperature of the mixed solution to 150 ℃, and adding 4.4mmol of oleylamine to obtain a first mixture, wherein the addition amount of the oleylamine meets the following requirements: the molar ratio of the cation precursor to the oleylamine is 1: 2;
s32, cooling the first mixed solution to reduce the temperature of the first mixed solution to 100 ℃, and adding 8ml of normal hexane to obtain a second mixed solution;
s33, cooling the second mixed solution to room temperature, adding a mixed solvent containing ethyl acetate and ethanol, precipitating the red or green oil-soluble quantum dots, and performing centrifugation and cleaning treatment to obtain high-purity blue luminescent CdxZn1-xAnd the S/ZnS oil-soluble quantum dots.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. A method for removing residual cation precursors in oil-soluble quantum dots comprises the following steps:
providing oil-soluble quantum dot mixed liquid of residual cation precursors;
adding organic amine into the oil-soluble quantum dot mixed solution in air, inert atmosphere or vacuum atmosphere to carry out thermal mixing treatment, dissolving the cation precursor, wherein the temperature of the thermal mixing treatment is 80-350 ℃, and obtaining a first mixed solution;
cooling the first mixed solution to reduce the temperature of the first mixed solution to 30-120 ℃, and adding a non-polar organic solvent for second mixing treatment to obtain a second mixed solution;
and cooling the second mixed solution to room temperature, adding a polar organic solvent to form a turbid solution, and performing centrifugal treatment on the turbid solution to obtain the oil-soluble quantum dots.
2. The method for removing the residual cationic precursor from the oil-soluble quantum dots according to claim 1, wherein the organic amine is at least one of oleylamine, ethylamine, triethylamine, propylamine, tripropylamine, butylamine, tributylamine, pentylamine, tripentylamine, n-hexylamine, trihexylamine, heptylamine, octylamine, trioctylamine, di-n-octylamine, decylamine, dodecylamine, trilaurylamine, tetradecylamine, hexadecylamine, and octadecylamine.
3. The method for removing the residual cation precursor in the oil-soluble quantum dot according to claim 1, wherein the molar ratio of the cation precursor to the organic amine in the first mixed solution is 1:10-10: 1.
4. The method for removing the residual cation precursor from the oil-soluble quantum dots according to claim 1, wherein the volume ratio of the first mixed solution to the nonpolar organic solvent in the second mixed solution is 1:5 to 10: 1.
5. The method for removing residual cationic precursor from oil-soluble quantum dots according to claim 1, wherein the polar organic solvent is added in an amount satisfying: the volume ratio of the oil-soluble quantum dot mixed liquid to the polar organic solvent is 1:10-10: 1.
6. The method for removing the residual cation precursor in the oil-soluble quantum dot according to any one of claims 1 to 5, wherein the thermal mixing treatment method comprises: stirring and mixing the oil-soluble quantum dot mixed solution and the organic amine, heating to 80-350 ℃, and maintaining for more than 5min to form a first mixed solution; or
Stirring and heating the oil-soluble quantum dot mixed solution to 80-350 ℃, adding the organic amine, maintaining the temperature, stirring and heating for more than 5min, and forming a first mixed solution.
7. The method for removing residual cationic precursors from oil-soluble quantum dots according to any of claims 1 to 5, wherein the non-polar organic solvent is a non-polar organic solvent with a boiling point below 80 ℃.
8. The method for removing the residual cation precursor from the oil-soluble quantum dot according to claim 7, wherein the non-polar organic solvent is at least one of toluene, chloroform, n-hexane, cyclohexane, and chlorobenzene.
9. The method for removing the residual cation precursor in the oil-soluble quantum dot according to any one of claims 1 to 5, wherein the polar organic solvent is at least one of alcohols, ketones or esters.
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| CN111378450A (en) * | 2018-12-29 | 2020-07-07 | Tcl集团股份有限公司 | Quantum dot purification method |
| CN112760091B (en) * | 2019-11-01 | 2022-10-11 | Tcl科技集团股份有限公司 | Purification method of quantum dots |
| CN113046054B (en) * | 2019-12-27 | 2023-06-27 | Tcl科技集团股份有限公司 | Post-treatment method of oil-soluble quantum dots |
| CN114672315B (en) * | 2020-12-25 | 2024-10-18 | Tcl科技集团股份有限公司 | Quantum dot ligand exchange method, quantum dot film preparation method and QLED device |
| CN116162459B (en) * | 2023-04-21 | 2023-07-25 | 广东聚华新型显示研究院 | Quantum dot purification method, quantum dot, light-emitting device and electronic equipment |
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