CN106010511A - Method for removing residual cationic precursors from oil-soluble quantum dots - Google Patents
Method for removing residual cationic precursors from oil-soluble quantum dots Download PDFInfo
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- C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
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- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
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Abstract
The invention provides a method for removing residual cationic precursors from oil-soluble quantum dots. The method includes steps: providing oil-soluble quantum dot mixed liquid with the residual cationic precursors; adding organic amine into the oil-soluble quantum dot mixed liquid under an air, inertia or vacuum atmosphere, and performing thermal mixing at a temperature of 80-350 DEG C to obtain first mixed liquid; cooling the first mixed liquid to 30-120 DEG C, and adding a nonpolar organic solvent to perform secondary mixing to obtain second mixed liquid; cooling the second mixed liquid to the room temperature, adding a polar organic solvent to form turbid liquid, and centrifuging the turbid liquid to obtain the oil-soluble quantum dots.
Description
Technical field
The invention belongs to oil-soluble quantum dot purification technique field, particularly relate to a kind of removal oil-soluble quantum dot
The method of middle remaining cation presoma.
Background technology
In recent years, owing to light excitation is high, luminous quantum efficiency is high, glow color is adjustable, service life is long
Etc. advantage, receive extensively using quanta point material as the light emitting diode with quantum dots (QLED) of luminescent layer
Concern, become current New LED research Main way.Along with the development of QLED printing technology,
QLED most possibly becomes the product of following typographical display.For printing preparation QLED device, pure
It is necessary for spending higher RGB quantum dot solution.But, the luminescence of the light emitting diode of blue light quantum point
Efficiency and life-span are far from reaching to show requirement, become the key factor of restriction QLED typographical display.Quantum
Point is as the material of main part of QLED, and its purity is bigger to luminous efficiency and the aging effects of device.
At present, the synthesis of relevant RGB quantum dot be all based on cadmium (Cd), zinc (Zn), selenium (Se),
The alloy system that four kinds of elements of sulfur (S) are formed.A large amount of core-shell quanta dots compound experiments show, are carrying out shell
When zinc sulfide (ZnS) or the growth such as cadmium sulfide (CdS) or zinc selenide (ZnSe), if cation presoma
Higher with the ratio of anion presoma (such as Zn:S, Cd:S, Zn:Se), the most beneficially shell is uniform
Grow and reduce the defect of lattice mismatch, and then improve the quantum yield of quantum dot.But, highly concentrated
The quantum dot mixed liquor obtained under the conditions of the cation precursor synthesis of degree easily remains a large amount of cation forerunners
Body, and some cation presoma such as zinc oleate easily separates out when mixeding liquid temperature is less than a certain temperature,
Cleaning purification to quantum dot brings a lot of trouble.Concrete, under room temperature, these cation presomas not only exist
In the organic solvents such as toluene, normal hexane, chloroform, dissolubility is relatively low, easily separates out, and as well as centrifugal
The process of quantum dot (QD) forms co-precipitation, has a strong impact on the purity of quantum dot solution and then affects QLED
The luminous efficiency of device and life-span.
Summary of the invention
It is an object of the invention to provide a kind of method removing in oil-soluble quantum dot remaining cation presoma,
Aim to solve the problem that in oil-soluble quantum dot, the cation presoma of residual affects the purity of quantum dot solution, Jin Erying
Ring luminous efficiency and the problem in life-span of QLED device.
The present invention is achieved in that a kind of method removing in oil-soluble quantum dot remaining cation presoma,
Comprise the following steps:
The oil-soluble quantum dot mixed liquor of remaining cation presoma is provided；
Described oil-soluble quantum dot mixed liquor is added under air, inert atmosphere or vacuum organic amine enter
Row hot mixing processes, and the temperature that described hot mixing processes is 80-350 DEG C, obtains the first mixed liquor；
Described first mixed liquor is carried out cooling process so that the temperature of described first mixed liquor is down to
30-120 DEG C, add non-polar organic solvent and carry out the second mixed processing, obtain the second mixed liquor；
Add polar organic solvent after described second mixed liquor is cooled to room temperature and form turbid solution, to described muddy
Turbid liquid is centrifuged processing, and obtains oil-soluble quantum dot.
What the present invention provided removes the method for remaining cation presoma in oil-soluble quantum dot, first by described sun
Ion presoma is dissolved in described organic amine and obtains the first mixed liquor, then addition use in described first mixed liquor
Non-polar organic solvent in dispersed oil dissolubility quantum dot forms the second mixed liquor, finally uses polarity organic molten
Described oil-soluble quantum dot is precipitated out by agent, obtains highly purified oil-soluble quantum dot.The method controllability
Get well and be prone to repeat, it is often more important that, the oil-soluble quantum dot obtained by the inventive method can be glimmering
Under the guarantee that light intensity does not weaken, it is thus achieved that higher purity, thus it is prevented effectively from described oil-soluble quantum dot
Described in the luminous efficiency of the excessive residual of the cation presoma QLED device to preparing and life-span
Impact and the impact of other Unpredictabilities.Prepared by the oil-soluble quantum dot using the inventive method to purify
QLED device, can avoid the interference that device performance is brought by described cation presoma, thus improve
The repeatability of QLED device performance.
Accompanying drawing explanation
Fig. 1 is the method for remaining cation presoma in the removal oil-soluble quantum dot that the embodiment of the present invention provides
Flow chart；
Fig. 2 is blue oil dissolubility quantum dot and the warp of the remaining cation presoma that the embodiment of the present invention 1 provides
The fluorescence intensity curves figure of the blue oil dissolubility quantum dot after the process of embodiment of the present invention method.
Detailed description of the invention
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, with
Under in conjunction with the embodiments, the present invention is further elaborated.Should be appreciated that described herein specifically
Embodiment only in order to explain the present invention, is not intended to limit the present invention.
In conjunction with Fig. 1, embodiments provide remaining cation forerunner in a kind of removal oil-soluble quantum dot
The method of body, comprises the following steps:
S01., the oil-soluble quantum dot mixed liquor of remaining cation presoma is provided；
S02. described oil-soluble quantum dot mixed liquor is added organic under air, inert atmosphere or vacuum
Amine carries out hot mixing process, and the temperature that described hot mixing processes is 80-350 DEG C, obtains the first mixed liquor；
S03. described first mixed liquor is carried out cooling process so that the temperature of described first mixed liquor is down to
30-120 DEG C, add non-polar organic solvent and carry out the second mixed processing, obtain the second mixed liquor；
S04. add polar organic solvent after described second mixed liquor is cooled to room temperature and form turbid solution, to institute
State turbid solution to be centrifuged processing, obtain oil-soluble quantum dot.
Concrete, in above-mentioned steps S01, when described cation presoma is for preparing nucleocapsid oil-soluble quantum dot
Common shell source organometallic cation presoma, includes but not limited to zinc oleate
{Zn[CH3(CH2)7CH=CH (CH2)7COO]2, cadmium oleate
{Cd[CH3(CH2)7CH=CH (CH2)7COO]2, plumbi oleas
{Pb[CH3(CH2)7CH=CH (CH2)7COO]2, oleic acid indium { In [CH3(CH2)7CH=CH (CH2)7COO]3}
In at least one.The oil-soluble quantum dot mixed liquor of remaining cation presoma, described oil-soluble amount are provided
The sub acquiring way ordering mixed liquor the most clearly limits, and can use in oil-soluble quantum dot preparation process direct
The oil-soluble quantum dot mixed liquor of the remaining cation presoma obtained；The oil-soluble quantum that can also will obtain
Select the oil-soluble quantum dot mixed liquor of the remaining cation presoma of preparation after material dissolves.Wherein, described
Oil-soluble quantum dot is alloy compositions structure quantum point, nucleocapsid component structure quantum dot or homogeneous components structure amount
Sub-point.Concrete, described oil-soluble quantum dot includes but not limited to CdxZn1-xS/ZnS、
CdxZn1-xSySe1-y/ZnS、CdZnSeS、CdSe/ZnS、InP/ZnS、CuInS/ZnS、ZnS、ZnSe、
ZnTe quantum dot.
As a specific embodiment, the oil-soluble quantum dot mixed liquor of described remaining cation presoma is permissible
Prepared by following method: oil-soluble quantum dot is dissolved and is formed after quantum dot solution, add oleic acid and
Octadecylene, the oil-soluble quantum dot mixed liquor of the remaining cation presoma of preparation.Wherein, described oil soluble is dissolved
The solvent of property quantum dot is preferably low boiling point solvent, such as normal hexane, methanol, toluene, chloroform etc.；Described oil
Acid forms cation presoma with remaining cation；Described octadecylene is used for advantageously promoting described oil-soluble
The dissolving of quantum dot.Mix to obtain the oil-soluble quantum dot of solubility property preferably remaining cation presoma
Closing liquid, as the presently preferred embodiments, the volume ratio of described oleic acid and described octadecylene is (10:1)-(1:10), more excellent
Elect 1:1 as.Herein, it will be appreciated that in the oil-soluble quantum dot mixed liquor of described remaining cation presoma,
Described oil-soluble quantum dot and/or cation presoma are likely not to have and are completely dissolved.
In above-mentioned steps S02, in order to prevent some oil-soluble quantum dot aoxidize (as CdSe, PbS,
PbSe etc., but it is not limited to this), by described oil-soluble quantum dot mixed liquor in air, inert atmosphere or vacuum
Carrying out hot mixing process under atmosphere, wherein, described inert atmosphere includes but not limited to nitrogen atmosphere, argon gas
Atmosphere, helium atmosphere.
Described oil-soluble quantum dot mixed liquor and described organic amine are carried out hot mixing process by the embodiment of the present invention,
And the temperature that described hot mixing processes is 80-350 DEG C, it is ensured that described cation presoma is described organic
Fully dispersed, dissolving in amine.The method that described hot mixing processes can be realized by following method:
Described oil-soluble quantum dot mixed liquor and described organic amine are stirred mixing, are heated to 80-350 DEG C,
And maintain more than 5min, form the first mixed liquor；Or
After described oil-soluble quantum dot mixed liquor agitating heating is warming up to 80-350 DEG C, add described organic amine,
Maintain more than temperature, agitating heating 5min, form the first mixed liquor.
In order to ensure the safety of heating process, advantageously promote the dissolving of described cation presoma simultaneously,
As the presently preferred embodiments, the method that described hot mixing processes is: heated by described oil-soluble quantum dot mixed liquor
It is warming up to 80 DEG C, maintains 10-30min, be warming up to 80 DEG C-350 DEG C the most again, maintain more than 5min.Should
Preferably mode of heating, it is possible, firstly, to remove low boiling present in described quantum dot solution when 80 DEG C molten
Agent, such as normal hexane, ethanol, toluene or chloroform etc., thus when avoiding high-temperature heating, low boiling point solvent violent
The potential safety hazard that boiling brings.Then, it is warming up to the high temperature of 80-350 DEG C, before described cation can be promoted
Drive the abundant dissolving of body, in order to follow-up remove described cation presoma the most fully.During Gai,
After described cation presoma fully dissolves, mixed liquor becomes clear.Finally, suitably temperature is selected
Degree, maintains a period of time so that described cation presoma is more fully dispersed, it is molten to be dissolved in described organic amine
In agent.During Gai, after described cation presoma fully dissolves, the color of described first mixed liquor by
Light brown become transparent dark brown.
The embodiment of the present invention, described organic amine include but be not limited to oleyl amine, ethamine, triethylamine, propylamine,
Tripropyl amine (TPA), butylamine, tri-n-butylamine, amylamine, triamylamine, n-hexylamine, trihexylamine, heptyl amice, octylame, three pungent
Amine, two 1-Aminooctane, decyl amine, lauryl amine, Alamine 304, tetradecy lamine, cetylamine, 18-amine.,
At least one in trioctadecylamine.Described cation presoma is gone by the addition of described organic amine
Except degree or the performance impact of oil-soluble quantum dot that obtains are bigger.Concrete, when described organic amine amount mistake
Time few, it be not enough to dispersion, dissolve all of described cation presoma, it is thus impossible to reach effectively to remove
The purpose of described cation presoma；And when described organic amine amount is too much, described organic amine can be with described
Oil-soluble quantum dot surface group (part) swaps, and forms aggregate, thus affects described oil-soluble
The performance of quantum dot.Accordingly, as preferred embodiment, in described first mixed liquor, described cation forerunner
The mol ratio of body and described organic amine is 1:10-10:1；More preferably 1:2, in order to remove remnants as much as possible
Described cation presoma and do not affect the performance of described oil-soluble quantum dot.
In above-mentioned steps S03, add described non-polar organic solvent at described first mixed liquor, to described the
One mixed liquor is diluted, simultaneously by fully dispersed for described oil-soluble quantum dot.As the presently preferred embodiments, exist
Carry out cooling process before adding described non-polar organic solvent, cool the temperature to 30-120 DEG C, more preferably
100℃.If temperature is too low, the bad dispersibility of the most described oil-soluble quantum dot；If temperature is too high, then add institute
State non-polar organic solvent to be likely to be due to acutely seethe with excitement and bring potential safety hazard.
In order to described oil-soluble quantum dot is completely dispersed, as the presently preferred embodiments, in described second mixed liquor,
The volume ratio of described first mixed liquor and described non-polar organic solvent is 1:5-10:1；More preferably 5:1.
Further, as the presently preferred embodiments, described non-polar organic solvent is that boiling point is less than 80 DEG C nonpolar and has
Machine solvent, is specifically including but not limited at least one in toluene, chloroform, normal hexane, hexamethylene, chlorobenzene.
In above-mentioned steps S04, in order to by described second mixed liquor described oil-soluble quantum dot separate out, from
And realize oil-soluble quantum dot and separate with the cation presoma of dissolved state, by cold for described second mixed liquor
Add polar organic solvent, now, the described oil soluble of the oil phase being dissolved in described non-polar organic solvent the most afterwards
Property quantum dot in described polar organic solvent, form precipitation, and described cation presoma keeps solution state,
Through centrifugation, i.e. can obtain removing the described oil-soluble quantum dot of remaining cation presoma.As excellent
Select embodiment, in order to fully realize the precipitation of described oil-soluble quantum dot, the interpolation of described polar organic solvent
Amount meets: the volume ratio of described oil-soluble quantum dot mixed liquor and described polar organic solvent is 1:10-10:1,
More preferably 1:5.
As another preferred embodiment, described polar organic solvent be in alcohols, ketone or esters at least
A kind of.Further, described polar organic solvent is preferably low polar organic solvent, specifically include but not
It is limited at least one in ethanol, methanol, acetone, ethyl acetate, butanol.
Further, it is also possible to be carried out processing to the described oil-soluble quantum dot obtained after being centrifuged.
What the embodiment of the present invention provided removes the method for remaining cation presoma in oil-soluble quantum dot, first will
Described cation presoma is dissolved in described organic amine and obtains the first mixed liquor, then in described first mixed liquor
Add and form the second mixed liquor for the non-polar organic solvent of dispersed oil dissolubility quantum dot, finally use polarity
Described oil-soluble quantum dot is precipitated out by organic solvent, obtains highly purified oil-soluble quantum dot.The method
Controllability is good and is prone to repeat, it is often more important that, the oil-soluble quantum dot obtained by the inventive method can
With under the guarantee that do not weakens in fluorescence intensity, it is thus achieved that higher purity, thus it is prevented effectively from described oil-soluble
The luminous efficiency of the excessive residual of cation presoma described in the quantum dot QLED device to preparing and
The impact in life-span and the impact of other Unpredictabilities.Use the oil-soluble of embodiment of the present invention Methods For Purification
Quantum dot prepares QLED device, can avoid the interference that device performance is brought by described cation presoma,
Thus improve the repeatability of QLED device performance.
Illustrate below in conjunction with specific embodiment.
Embodiment 1
A kind of Cd removing blue-light-emittingxZn1-xRemaining cation presoma in S/ZnS oil-soluble quantum dot
Method, comprises the following steps:
S11., under Ar gas shielded, the Cd of 20ml is takenxZn1-xS/ZnS quantum dot (0.05mg/ml) normal hexane
In the there-necked flask of the octadecylene (ODE) that solution is injected into the oleic acid (OA) containing 3ml and 3ml,
Obtain the blue oil dissolubility quantum dot mixed liquor of remaining cation presoma；
S12. the blue oil dissolubility quantum dot mixed liquor in there-necked flask is heated to 80 DEG C and maintains 20
Minute, it is warmed up to 180 DEG C the most again and makes blue oil dissolubility quantum dot mixed liquor become the liquid of clear also
Maintain 30 minutes, then add oleyl amine after blue oil dissolubility quantum dot mixeding liquid temperature is dropped to 150 DEG C, obtain
First mixture, wherein, the addition of described oleyl amine meets: described cation presoma and described oleyl amine
Mol ratio is 1:2；
S13. described first mixed liquor is carried out cooling process so that the temperature of described first mixed liquor is down to
100 DEG C, add the normal hexane of 8ml, obtain the second mixed liquor；
S14. described second mixed liquor is cooled to room temperature, adds containing ethyl acetate and the mixed solvent of ethanol,
Precipitate described blue oil dissolubility quantum dot, be centrifuged, cleaning treatment, obtain highly purified blueness
CdxZn1-xS/ZnS oil-soluble quantum dot.
The blue Cd of the embodiment of the present invention 1 preparationxZn1-xS/ZnS oil-soluble quantum dot, its solution formed is clear
Clear transparent, it is practically free of zinc oleate { Zn (OA)2}.The Cd that embodiment 1 step S11 is providedxZn1-xS/ZnS
The Cd that quantum dot and step S14 providexZn1-xS/ZnS quantum dot carries out fluorescence intensity test, and experimental result is such as
Shown in Fig. 2.As seen from the figure, the oil-soluble quantum dot after the embodiment of the present invention 1 processes, its fluorescence is strong
Degree does not change, it is seen then that method described in the embodiment of the present invention can ensure on the premise of fluorescence intensity,
Effectively remove remaining cation presoma.
Embodiment 2
A kind of Cd removing redness or green emitting1-xZnxSe1-ySyIn oil-soluble quantum dot before remaining cation
The method driving body, comprises the following steps:
S21., under Ar gas shielded, the Cd of 20ml is taken1-xZnxSe1-ySyQuantum dot (0.05mg/ml) normal hexane
In the there-necked flask of the octadecylene (ODE) that solution is injected into the oleic acid (OA) containing 3ml and 3ml,
Obtain the blue oil dissolubility quantum dot mixed liquor of remaining cation presoma；
S22. the redness in there-necked flask or green emitting oil-soluble quantum dot mixed liquor are heated to 80 DEG C
And maintain 20 minutes, it is warmed up to 180 DEG C the most again and makes redness or green oil dissolubility quantum dot mixed liquor become clear
Clear bright liquid also maintains 30 minutes, then redness or green oil dissolubility quantum dot mixeding liquid temperature is dropped to
Adding oleyl amine after 150 DEG C, obtain the first mixture, wherein, the addition of described oleyl amine meets: described sun from
The mol ratio of sub-presoma and described oleyl amine is 1:2；
S23. described first mixed liquor is carried out cooling process so that the temperature of described first mixed liquor is down to
100 DEG C, add the normal hexane of 8ml, obtain the second mixed liquor；
S24. described second mixed liquor is cooled to room temperature, adds containing ethyl acetate and the mixed solvent of ethanol,
Precipitate described redness or green oil dissolubility quantum dot, be centrifuged, cleaning treatment, obtain highly purified redness
Or green Cd1-xZnxSe1-ySyOil-soluble quantum dot.
Embodiment 3
A kind of remnants cation presoma of directly removing in reaction system obtains high-purity oil-soluble quantum dot
Method, the present embodiment is suitable for use with oleic acid and the octadecylene system as reaction dissolvent synthesis quantum dot, amount
Son point synthesis is with reference to Chemistry of Materials 2008,20,5307-5313, and its synthesis comprises the following steps:
S311. zinc oleate, the preparation of cadmium oleate mixed liquor: by 9mmol zinc acetate, 1mmol Aska-Rid.,
8mL oleic acid, 15mL octadecylene are placed in the there-necked flask of 50mL.Deaerate under room temperature, and be warming up to
120 DEG C of insulation 20mins, logical argon is also warming up to 120 DEG C of insulation 10mins, is finally heated by mixed liquor
To 250 DEG C until forming clarification, clear solution.
The preparation of S312.S-ODE: the S of 1.8mmol is joined in the octadecylene of 3ml, be heated to 230
DEG C until formed clarification, clear solution, be incubated in 140 DEG C subsequently.
The preparation of S313.S-TOP: the S of 6mmol is joined in the tri octyl phosphine of 3ml, be heated to 170
DEG C until formed clarification, clear solution, be then cooled to room temperature.
S314.CdxZn1-xThe preparation of S/ZnS: at temperature 350 DEG C, by the S-ODE in step 2 once
In zinc oleate that property is rapidly injected to step 1, cadmium oleate mixed liquor mixed liquor, after 10mins, by step
S-TOP in 3 is injected in above-mentioned reactant liquor with the speed of 3mL/h by syringe pump.
Cleaning process comprises the following steps:
S32. add 4.4mmol oleyl amine after above-mentioned mixeding liquid temperature being dropped to 150 DEG C, obtain the first mixture,
Wherein, the addition of described oleyl amine meets: the mol ratio of described cation presoma and described oleyl amine is 1:2；
S32. described first mixed liquor is carried out cooling process so that the temperature of described first mixed liquor is down to
100 DEG C, add the normal hexane of 8ml, obtain the second mixed liquor；
S33. described second mixed liquor is cooled to room temperature, adds containing ethyl acetate and the mixed solvent of ethanol,
Precipitate described redness or green oil dissolubility quantum dot, be centrifuged, cleaning treatment, obtain highly purified blueness
Luminous CdxZn1-xS/ZnS oil-soluble quantum dot.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all at this
Any amendment, equivalent and the improvement etc. made within bright spirit and principle, should be included in the present invention
Protection domain within.
Claims (10)
1. remove a method for remaining cation presoma in oil-soluble quantum dot, comprise the following steps:
The oil-soluble quantum dot mixed liquor of remaining cation presoma is provided；
Described oil-soluble quantum dot mixed liquor is added under air, inert atmosphere or vacuum organic amine enter
Row hot mixing processes, and the temperature that described hot mixing processes is 80-350 DEG C, obtains the first mixed liquor；
Described first mixed liquor is carried out cooling process so that the temperature of described first mixed liquor is down to
30-120 DEG C, add non-polar organic solvent and carry out the second mixed processing, obtain the second mixed liquor；
Add polar organic solvent after described second mixed liquor is cooled to room temperature and form turbid solution, to described muddy
Turbid liquid is centrifuged processing, and obtains oil-soluble quantum dot.
2. the method for remaining cation presoma in removal oil-soluble quantum dot as claimed in claim 1, its
Being characterised by, described organic amine is oleyl amine, ethamine, triethylamine, propylamine, tripropyl amine (TPA), butylamine, three fourths
Amine, amylamine, triamylamine, n-hexylamine, trihexylamine, heptyl amice, octylame, trioctylamine, two 1-Aminooctane, decyl amine,
At least one in lauryl amine, Alamine 304, tetradecy lamine, cetylamine, 18-amine., trioctadecylamine.
3. the method for remaining cation presoma in removal oil-soluble quantum dot as claimed in claim 1, its
Being characterised by, in described first mixed liquor, the mol ratio of described cation presoma and described organic amine is
1:10-10:1。
4. the method for remaining cation presoma in removal oil-soluble quantum dot as claimed in claim 1, its
It is characterised by, in described second mixed liquor, described first mixed liquor and the volume of described non-polar organic solvent
Ratio is 1:5-10:1.
5. the method for remaining cation presoma in removal oil-soluble quantum dot as claimed in claim 1, its
Being characterised by, the addition of described polar organic solvent meets: described oil-soluble quantum dot mixed liquor and described
The volume ratio of polar organic solvent is 1:10-10:1.
6. the side of remaining cation presoma in the removal oil-soluble quantum dot as described in claim 1-5 is arbitrary
Method, it is characterised in that the method that described hot mixing processes is: by described oil-soluble quantum dot mixed liquor and institute
State organic amine stirring mixing, be heated to 80-350 DEG C, and maintain more than 5min, form the first mixing
Liquid；Or
After described oil-soluble quantum dot mixed liquor agitating heating is warming up to 80-350 DEG C, add described organic amine,
Maintain more than temperature, agitating heating 5min, form the first mixed liquor.
7. remaining cation presoma in the removal oil-soluble quantum dot as described in claim 1-5 is arbitrary
Method, it is characterised in that described non-polar organic solvent is the non-polar organic solvent that boiling point is less than 80 DEG C.
8. the method for remaining cation presoma in removal oil-soluble quantum dot as claimed in claim 7, its
Be characterised by, described non-polar organic solvent be in toluene, chloroform, normal hexane, hexamethylene, chlorobenzene extremely
Few one.
9. the side of remaining cation presoma in the removal oil-soluble quantum dot as described in claim 1-5 is arbitrary
Method, it is characterised in that described polar organic solvent is at least one in alcohols, ketone or esters.
10. remaining cation presoma in the removal oil-soluble quantum dot as described in claim 1-5 is arbitrary
Method, it is characterised in that described cation presoma is in zinc oleate, cadmium oleate, plumbi oleas, oleic acid indium
At least one；And/or
Described oil-soluble quantum dot is CdxZn1-xS/ZnS、CdxZn1-xSySe1-y/ZnS、CdZnSeS、
CdSe/ZnS, InP/ZnS, CuInS/ZnS, ZnS, ZnSe, ZnTe quantum dot.
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| CN201610334646.2A CN106010511B (en) | 2016-05-18 | 2016-05-18 | Method for removing residual cation precursor in oil-soluble quantum dots |
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| CN201610334646.2A CN106010511B (en) | 2016-05-18 | 2016-05-18 | Method for removing residual cation precursor in oil-soluble quantum dots |
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| CN106010511B CN106010511B (en) | 2020-01-03 |
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| CN201610334646.2A Active CN106010511B (en) | 2016-05-18 | 2016-05-18 | Method for removing residual cation precursor in oil-soluble quantum dots |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106398686A (en) * | 2016-09-05 | 2017-02-15 | Tcl集团股份有限公司 | Quantum dot and preparation method thereof |
| CN106753343A (en) * | 2016-12-27 | 2017-05-31 | Tcl集团股份有限公司 | The method and quantum dot of remaining cation presoma in a kind of effective removal quantum dot |
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| CN109666478A (en) * | 2017-10-16 | 2019-04-23 | Tcl集团股份有限公司 | A kind of method of purification of oil-soluble quantum dot |
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| CN113046054A (en) * | 2019-12-27 | 2021-06-29 | Tcl集团股份有限公司 | Post-processing method of oil-soluble quantum dots |
| CN114672315A (en) * | 2020-12-25 | 2022-06-28 | Tcl科技集团股份有限公司 | Quantum dot ligand exchange method, preparation method of quantum dot film and QLED device |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936058A (en) * | 2014-05-07 | 2014-07-23 | 吉林大学 | Method for preparing cadmium sulfide quantum dots |
| CN103936056A (en) * | 2014-05-07 | 2014-07-23 | 吉林大学 | Preparation method of cadmium phosphide quantum dots |
| CN103936069A (en) * | 2014-05-07 | 2014-07-23 | 吉林大学 | Preparation method of cadmium arsenide quantum dots |
-
2016
- 2016-05-18 CN CN201610334646.2A patent/CN106010511B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936058A (en) * | 2014-05-07 | 2014-07-23 | 吉林大学 | Method for preparing cadmium sulfide quantum dots |
| CN103936056A (en) * | 2014-05-07 | 2014-07-23 | 吉林大学 | Preparation method of cadmium phosphide quantum dots |
| CN103936069A (en) * | 2014-05-07 | 2014-07-23 | 吉林大学 | Preparation method of cadmium arsenide quantum dots |
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