CN108893104A - Composite perofskite quantum dot and preparation method thereof based on allyl based quaternary ammonium salt ligand - Google Patents
Composite perofskite quantum dot and preparation method thereof based on allyl based quaternary ammonium salt ligand Download PDFInfo
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Abstract
The present invention provides a kind of composite perofskite quantum dots, including perovskite quantum dot and the allyl based quaternary ammonium salt ligand for being coated on the perovskite quantum dot surface, the molecular structure of the allyl based quaternary ammonium salt ligand as shown in following formula 1,In the formula 1, R is the alkyl or alkenyl that amount of carbon atom is 8-18, X‑For halide anion.
Description
Technical field
The invention belongs to semiconductive luminescent materials technical field more particularly to a kind of answering based on allyl based quaternary ammonium salt ligand
Close perovskite quantum dot and preparation method thereof.
Background technique
Perovskite quantum dot is a kind of new and effective luminescent material, has very high quantum efficiency, and emission wavelength is adjustable,
Luminous mass is high, is a kind of very potential advanced luminescent material, is widely used in the devices such as LED, solar battery, optical detector
The manufacture of part.
In the preparation process of perovskite quantum dot, generally using oleic acid, oleyl amine as ligand, to constrain Quantum Dots Growth
Process, and quantum dot is made to suspend in a solvent, the dispersion liquid of perovskite quantum dot is formed, to facilitate spin coating proceeding to prepare photophore
Part.But since oleic acid and oleyl amine ligand in the absorption of quantum dot surface are a dynamic processes, lead to perovskite quantum dot
Surface defect increases, and reduces fluorescence quantum efficiency；Simultaneously as perovskite quantum dot belongs to ionic crystal, in air
Water, O2It is chemically reacted by ion of the sovent diffusion into quantum dot surface, with quantum dot, destroys the crystal knot of quantum dot
Structure causes the reduction of quantum dot light emitting efficiency.The stability of perovskite quantum dot is the serious hindrance on its practical road, because
This, developing a kind of ligand that can be improved perovskite quantum dot stability has important practical significance.
Summary of the invention
Surface, acquisition high stability are coated on by the ligand polymer containing allyl the purpose of the present invention is to provide a kind of
The composite perofskite quantum dot and preparation method thereof based on allyl based quaternary ammonium salt ligand, it is intended to solve existing perovskite quantum
Point surface defect is more, and water, O2The readily permeable crystal structure for destroying quantum dot, causes perovskite quantum dot stability poor, drops
The problem of low luminescent properties.
For achieving the above object, the technical solution adopted by the present invention is as follows：
One aspect of the present invention provides a kind of composite perofskite quantum dot, including perovskite quantum dot and is coated on the calcium titanium
The allyl based quaternary ammonium salt ligand of mine quantum dot surface, the molecular structure of the allyl based quaternary ammonium salt ligand as shown in following formula 1,
In the formula 1, R is the alkyl or alkenyl that amount of carbon atom is 8-18, X-For halide anion.
Preferably, the X-Selected from Cl-、Br-、I-One of.
Preferably, the allyl based quaternary ammonium salt ligand is cross-linked to form network polymers by double-bond polymerization, is coated on described
Perovskite quantum dot surface.
One aspect of the present invention provides a kind of preparation method of allyl based quaternary ammonium salt ligand, includes the following steps：
Dimethyl long-chain alkanamine, propylene halide and reaction dissolvent are provided, by the dimethyl long-chain alkanamine and described halogenated
Propylene is dissolved in respectively in the reaction dissolvent, and configuration obtains dimethyl long-chain alkanamine solution and propylene halide solution, wherein described
The amount of carbon atom of long alkane in dimethyl long-chain alkanamine is 8-18；
Under conditions of the dimethyl long-chain alkanamine solution heating stirring, the propylene halide solution, reaction system is added
It is standby to obtain allyl based quaternary ammonium salt ligand.
Preferably, in the step of configuring the dimethyl long-chain alkanamine solution, by the dimethyl long-chain alkanamine with it is described
The volume ratio of reaction dissolvent is 1:5~1:50 configurations.
Preferably, in the step of configuring the propylene halide solution, by the body of the propylene halide and the reaction dissolvent
Product is than being 1:5~1:50 configurations.
Preferably, in the step of preparing the allyl based quaternary ammonium salt ligand, the dripping quantity of the propylene halide solution meets：
The volume ratio of the dimethyl long-chain alkanamine and the propylene halide is 1:1~1.5.
Preferably, in the step of preparing the allyl based quaternary ammonium salt ligand, heating stirring makes the temperature of reaction system to be
30-80 DEG C, after dripping the propylene halide solution, keep constant temperature ± 2 DEG C the reaction was continued 0.5-4h.
Further aspect of the present invention provides a kind of preparation method of composite perofskite quantum dot, includes the following steps：
The anion presoma, cationic presoma and allyl based quaternary ammonium salt ligand of perovskite quantum dot are provided, it is described
The molecular structure of allyl based quaternary ammonium salt ligand as shown in following formula 1,
It is molten that the anion presoma, the cationic presoma and the allyl based quaternary ammonium salt ligand are dissolved in first
Precursor solution is prepared in agent；The precursor solution is distributed in the second solvent, the perovskite quantum containing precipitating is obtained
Point suspension；Third solvent is added into the perovskite quantum dot suspension, mixed processing promotes the heavy of perovskite quantum dot
It forms sediment, centrifugal treating under conditions of revolving speed >=8000rpm collects precipitating；Second solvent is dispersed by the precipitating being collected into
In, after mixing under conditions of 3000rpm≤revolving speed≤6000rpm, centrifugal treating removal precipitating collects perovskite quantum
The supernatant selected；
The polymerization reaction for causing perovskite quantum dot surface ligand in the supernatant, prepares composite perofskite quantum dot.
Preferably, first solvent is polar organic solvent, is selected from dimethylformamide, dimethyl sulfoxide, acetonitrile, first
At least one of alcohol, ethyl acetate.
Preferably, second solvent is non-polar organic solvent, in toluene, n-hexane, chloroform, tetrahydrofuran
It is at least one.
Preferably, the third solvent is selected from least one of acetone, acetonitrile, isopropanol, n-butanol, ether.
Preferably, in the step of precursor solution being distributed to the second solvent, the amount of second solvent meets：Institute
State volume ratio≤1 of the first solvent in precursor solution and second solvent of addition：5.
Preferably, in the step of third solvent is added into the perovskite quantum dot suspension, the third solvent
Amount meets：Volume ratio≤1 of the third solvent of the second solvent and addition in the perovskite quantum dot suspension：1.
Preferably, cause the method for the polymerization reaction of perovskite quantum dot surface ligand in the supernatant as heating polymerization
Or photopolymerization.
Composite perofskite quantum dot provided by the invention, using the allyl based quaternary ammonium salt with long-chain and C=C as perovskite amount
The ligand of son point.On the one hand, allyl based quaternary ammonium salt ligand be ionic compound, for perovskite quantum dot provide halogen yin from
Son can be used as ligand and be passivated to quantum dot surface simultaneously because quaternary ammonium ion is positively charged.On the other hand, allyl season
C=C aggregates into long-chain under the action of initiator in ammonium salt ligand, forms network cross linked polymers and is coated on quantum dot surface,
H can not only be prevented2O、O2, organic solvent and perovskite quantum dot surface contact, protect perovskite quantum dot crystal structure not
By H2O、O2, organic solvent destruction, to improve its optical stability；Moreover, allyl based quaternary ammonium salt ligand is fixed on calcium titanium
Mine quantum dot surface can eliminate ligand in the absorption-desorption process of quantum dot surface, to eliminate thus absorption-desorption mistake
Journey bring surface defect improves the optical property and its stability of quantum dot.In addition, in allyl based quaternary ammonium salt ligand structure
Long-chain is conducive to dispersion of the perovskite quantum dot in non-polar organic solvent (polar solvent can destroy perovskite quantum dot).It is comprehensive
On, composite perofskite quantum dot provided by the invention, few surface defects have very high stability.
The preparation method of allyl based quaternary ammonium salt ligand provided by the invention is adding dimethyl long-chain alkanamine, propylene halide
Reaction can be prepared in thermal agitation, and method is simple and easy to control.
The preparation method of composite perofskite quantum dot provided by the invention, using three kinds of different organic solvents, regulation is simultaneously
The composite material that surface is coated with allyl based quaternary ammonium salt ligand is prepared in purifying, and composite calcium titanium is prepared by cross-linking reaction
Mine quantum dot, method are simple and easy to control, it is often more important that, the composite perofskite quantum dot being prepared, few surface defects, and can
Prevent H2O、O2, organic solvent and perovskite quantum dot surface contact, have very high stability.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indication or suggestion relative importance or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more of the features.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
On the one hand the embodiment of the present invention provides a kind of composite perofskite quantum dot, including perovskite quantum dot and be coated on institute
State the allyl based quaternary ammonium salt ligand of perovskite quantum dot surface, the molecular structure of the allyl based quaternary ammonium salt ligand such as 1 institute of following formula
Show,
In the formula 1, R is the alkyl or alkenyl that amount of carbon atom is 8-18, X-For halide anion.Further, institute
State X-Selected from Cl-、Br-、I-One of.It is furthermore preferred that it is straight chained alkyl or alkenyl that the R, which is selected from, to avoid straight chained alkyl sky
Between steric hindrance it is excessive, the polymerization reaction being unfavorable between ligand.Specific preferred, the R is octadecyl, cetyl, pentadecane
Base, myristyl, dodecyl.
In the embodiment of the present invention, the allyl based quaternary ammonium salt ligand is cross-linked to form network polymers by double-bond polymerization, i.e.,
The ligand forms network structure by double-bond polymerization, is coated on the perovskite quantum dot surface.
Composite perofskite quantum dot provided in an embodiment of the present invention, using the allyl based quaternary ammonium salt with long-chain and C=C as calcium
The ligand of titanium ore quantum dot.On the one hand, allyl based quaternary ammonium salt ligand is ionic compound, provides halogen for perovskite quantum dot
Anion can be used as ligand and be passivated to quantum dot surface simultaneously because quaternary ammonium ion is positively charged.On the other hand, allyl
C=C aggregates into long-chain under the action of initiator in based quaternary ammonium salt ligand, forms network cross linked polymers and is coated on quantum dot table
Face can not only prevent H2O、O2, organic solvent and perovskite quantum dot surface contact, protect perovskite quantum dot crystal knot
Structure is not by H2O、O2, organic solvent destruction, to improve its optical stability；Moreover, allyl based quaternary ammonium salt ligand is fixed on
Perovskite quantum dot surface can eliminate ligand in the absorption-desorption process of quantum dot surface, to eliminate thus absorption-solution
It is drawn through journey bring surface defect, improves the optical property and its stability of quantum dot.In addition, allyl based quaternary ammonium salt ligand structure
In long-chain be conducive to dispersion of the perovskite quantum dot in non-polar organic solvent (polar solvent can destroy perovskite quantum
Point).To sum up, composite perofskite quantum dot provided by the invention, few surface defects have very high stability.
On the other hand the embodiment of the present invention provides a kind of preparation method of allyl based quaternary ammonium salt ligand, include the following steps：
E01. dimethyl long-chain alkanamine, propylene halide and reaction dissolvent are provided, by the dimethyl long-chain alkanamine and described
Propylene halide is dissolved in respectively in the reaction dissolvent, and configuration obtains dimethyl long-chain alkanamine solution and propylene halide solution, wherein
The amount of carbon atom of long alkane in the dimethyl long-chain alkanamine is 8-18；
E02. under conditions of the dimethyl long-chain alkanamine solution heating stirring, the propylene halide solution is added, instead
Allyl based quaternary ammonium salt ligand should be prepared.
The preparation method of allyl based quaternary ammonium salt ligand provided in an embodiment of the present invention, by dimethyl long-chain alkanamine, halogenated third
Alkene reacts in heating stirring to be prepared, and method is simple and easy to control.
Specifically, the long alkane in the dimethyl long-chain alkanamine corresponds to allyl based quaternary ammonium salt ligand in above-mentioned steps E01
R in structure, amount of carbon atom 8-18.Halogen atom in the propylene halide is selected from one of Cl, Br, I.The reaction
On the one hand solvent is used to disperse dimethyl long-chain alkanamine, propylene halide, be on the other hand used as reaction medium and product allyl
The precipitation medium of quaternary ammonium salt ligand, for collecting allyl based quaternary ammonium salt ligand.Preferably, reaction dissolvent be acetone or ether, but
It is without being limited thereto.
Preferably, in the step of configuring the dimethyl long-chain alkanamine solution, by the dimethyl long-chain alkanamine with it is described
The volume ratio of reaction dissolvent is 1:5~1:50 configurations are conducive to react uniform generation, prepare high-purity ligand.If the diformazan
The content of reaction dissolvent described in base long-chain alkanamine solution is too low, and ligand, ligand and the reaction raw materials generated in reaction process are poly-
Collection is agglomerated into paste, it is difficult to which heat release is serious among the dough for stirring, and being formed, and causes to react uneven or even aggregate
Miscellaneous side reaction occurs under the conditions of high fever for intermediate material, influences the preparation of ligand.If institute in the dimethyl long-chain alkanamine solution
The too high levels of reaction dissolvent are stated, then are unfavorable for the allyl based quaternary ammonium salt ligand being prepared precipitating, and then be difficult to collect allyl
Based quaternary ammonium salt ligand.It is further preferred that the mass concentration of dimethyl long-chain alkanamine is in the dimethyl long-chain alkanamine solution
0.1~1.5g/ml to be conducive to react uniform progress, while being conducive to product precipitating, collecting.
Preferably, in the step of configuring the propylene halide solution, by the body of the propylene halide and the reaction dissolvent
Product is than being 1:5~1:50 configurations.If the content of reaction dissolvent described in the propylene halide solution is too low, the matter of propylene halide
It is high to measure concentration, is added drop-wise to and is easy to reunite when reacting in the dimethyl long-chain alkanamine solution, and heat release is serious among aggregate, leads
It causes reaction uneven or even miscellaneous side reaction occurs under the conditions of high fever for the intermediate material of aggregate, influence the preparation of ligand.If institute
The too high levels for stating reaction dissolvent described in propylene halide solution, the allyl based quaternary ammonium salt ligand precipitating being equally unfavorable for,
And then it is difficult to collect allyl based quaternary ammonium salt ligand.
In above-mentioned steps E02, in the embodiment of the present invention, by the way that propylene halide system is added dropwise into dimethyl long-chain alkanamine solution
Standby allyl based quaternary ammonium salt ligand.Reaction needs to carry out under condition of heating and stirring, and propylene halide solution low speed addition such as dropwise addition,
Ligand, ligand and the reaction raw materials aggregation for preventing the dimethyl long-chain alkanamine solution from generating are agglomerated into paste, occur reacting not
The problem of miscellaneous side reaction influences product purity uniformly or even among dough occurs.Preferably, the allyl based quaternary ammonium salt is prepared
In the step of ligand, heating stirring makes the temperature of reaction system be 30-80 DEG C, after dripping the propylene halide solution, protects
Hold ± 2 DEG C of steady temperature (identical as temperature when heating stirring) the reaction was continued 0.5-4h.
Preferably, in the step of preparing the allyl based quaternary ammonium salt ligand, the dripping quantity of the propylene halide solution meets：
The volume ratio of the dimethyl long-chain alkanamine and the propylene halide is 1:1~1.5, be conducive to react the direction towards ligand is generated
It carries out.
It further, after the completion of reaction, further include purification processes.Specifically, the mixture after reaction is filtered, obtain
White powder is washed-is filtered 3 times with reaction dissolvent, and vacuum drying for 24 hours, obtains white powder, as described in the embodiment of the present invention
Allyl based quaternary ammonium salt ligand.
Another further aspect of the embodiment of the present invention provides a kind of preparation method of composite perofskite quantum dot, includes the following steps：
S01., the anion presoma, cationic presoma and allyl based quaternary ammonium salt ligand of perovskite quantum dot are provided,
The molecular structure of the allyl based quaternary ammonium salt ligand as shown in following formula 1,
S02. the anion presoma, the cationic presoma and the allyl based quaternary ammonium salt ligand are dissolved in the
Precursor solution is prepared in one solvent；The precursor solution is distributed in the second solvent, the perovskite containing precipitating is obtained
Quantum dot suspension；Third solvent is added into the perovskite quantum dot suspension, mixed processing promotes perovskite quantum dot
Precipitating, centrifugal treating under conditions of revolving speed >=8000rpm, collect precipitating；Described second is dispersed by the precipitating being collected into
In solvent, after mixing under conditions of 3000rpm≤revolving speed≤6000rpm, centrifugal treating removal precipitating collects perovskite
The supernatant of quantum dot；
S03. the polymerization reaction for causing perovskite quantum dot surface ligand in the supernatant, prepares composite perofskite quantum
Point.
The preparation method of composite perofskite quantum dot provided in an embodiment of the present invention, using three kinds of different organic solvents,
Regulate and control and purify and the composite material that surface is coated with allyl based quaternary ammonium salt ligand is prepared, is prepared by cross-linking reaction multiple
Perovskite quantum dot is closed, method is simple and easy to control, it is often more important that, the composite perofskite quantum dot being prepared, few surface defects,
And H can be prevented2O、O2, organic solvent and perovskite quantum dot surface contact, have very high stability.
Specifically, in above-mentioned steps S01, the raw material of the perovskite quantum dot (including before anion presoma, cation
Drive body) it is CsX, PbX2.The allyl based quaternary ammonium salt ligand and its preferred situation are as mentioned before.
In above-mentioned steps S02, using three kinds of different organic solvents, regulate and control and purify to prepare perovskite quantum dot, specifically
, include the following steps：
S021. the anion presoma, the cationic presoma and the allyl based quaternary ammonium salt ligand are dissolved in
Precursor solution is prepared in first solvent.
In the step, by the anion presoma, the cationic presoma and the allyl based quaternary ammonium salt ligand
It is dissolved in the first solvent and prepares precursor solution, due to the anion presoma, the cationic presoma and the alkene
Quaternary ammonium salts ligand is organic matter or crystal structure, therefore, before dissolving the anion presoma, the cation
First solvent for driving body and the allyl based quaternary ammonium salt ligand is organic solvent, preferably dimethylformamide, diformazan
At least one of sulfoxide, acetonitrile, methanol, ethyl acetate, but not limited to this.
Further, when the precursor solution of formation, CsX, PbX2, the allyl based quaternary ammonium salt ligand molar ratio (add
Dosage) it is 1:(0.2~0.9):(0.2~1).In the molar ratio, there are excessive allyl based quaternary ammonium salt ligands.Excessive alkene
Quaternary ammonium salts ligand can be in CsX, PbX2During reaction prepares perovskite quantum dot, quantum dot grain size is controlled,
Quantum dot particle overgrowth is prevented, becomes bulky grain precipitating and loses quantum dot function.
S022. the precursor solution is distributed in the second solvent, obtains the perovskite quantum dot containing precipitating and is suspended
Liquid.
In the step, the precursor solution is distributed to the second solvent, CsX, PbX2Reaction prepares perovskite quantum dot,
Excessive allyl based quaternary ammonium salt ligand can prevent perovskite quantum point grain diameter excessive, but inevitably, part quantum dot is still
Right further growth is precipitated at bulky grain, while also inevitably generating portion particle of impurity.The embodiment of the present invention is counted
Second solvent is nonpolar solvent, preferably at least one of toluene, n-hexane, chloroform, tetrahydrofuran.Described second is molten
Agent precipitates bulky grain, the solubility of particle of impurity is small, by its crystalline deposit.
It is further preferred that in the step of precursor solution is distributed to the second solvent, the amount of second solvent
Meet：Volume ratio≤1 of second solvent of the first solvent and addition in the precursor solution：5.Thus what is provided is molten
Agent system has suitable nonpolar environment, is more advantageous to bulky grain precipitating, the precipitating of particle of impurity.
S023. third solvent is added into the perovskite quantum dot suspension, mixed processing promotes perovskite quantum dot
Precipitating, centrifugal treating under conditions of revolving speed >=8000rpm, collect precipitating.
In the step, third solvent is added in the perovskite quantum dot suspension, the third solvent will be more in system
Remaining ligand elutes, and avoids extra ligand that absorption-desorption process occurs in perovskite quantum dot surface, to form table
Planar defect influences the optical property and its stability of quantum dot.Meanwhile after excess ligand is fallen, perovskite quantum dot is molten at this
It precipitates in agent system.Preferably, the third solvent in acetone, acetonitrile, isopropanol, n-butanol, ether at least
It is a kind of.
Preferably, in the step of third solvent is added into the perovskite quantum dot suspension, the third solvent
Amount meets：Volume ratio≤1 of the third solvent of the second solvent and addition in the perovskite quantum dot suspension：1.By
This dicyandiamide solution provided has suitable polar environment, excessive ligand is sufficiently eluted, while making perovskite quantum dot
Sedimentation completely.
Further, perovskite quantum dot, bulky grain are precipitated, are miscellaneous by centrifugal treating under conditions of revolving speed >=8000rpm
Matter phase particle sufficiently settles, and collects precipitating.
S024. disperse the precipitating being collected into second solvent, after mixing 3000rpm≤revolving speed≤
Under conditions of 6000rpm, centrifugal treating removal precipitating, centrifugation time >=3min collects the supernatant of perovskite quantum dot.
In the step, second solvent is dispersed by the precipitating being collected into, second solvent can effective dissolving calcium
Titanium ore quantum dot, but it is poor to bulky grain precipitating, particle of impurity dissolubility, therefore, it can be realized by second solvent
The purifying of perovskite quantum dot.Specifically, under conditions of 3000rpm≤revolving speed≤6000rpm, centrifugal treating removal precipitating,
Collect the supernatant of perovskite quantum dot, centrifugation time >=3min.Revolving speed is excessively high to be easy to go the sedimentation of part perovskite quantum dot
It removes.
In above-mentioned steps S02, by the multiple regulation of three kinds of solvents, it is molten that the first solvent dissolves (precursor species)-the second
Agent precipitates the sedimentation of (impurity)-third solvent (sedimentation perovskite quantum dot, while removing excess ligand) the-the second solvent dispersion (calcium
Titanium ore quantum dot), high-purity is prepared, and ligand content properly (inhale in perovskite quantum dot surface by extra ligand
Attached-desorption process influences the optical property and its stability of quantum dot to form surface defect) composite material.
In above-mentioned steps S03, it is preferred that cause the polymerization reaction of perovskite quantum dot surface ligand in the supernatant
Method is heating polymerization or photopolymerization.
As a particular preferred embodiment, perovskite quantum dot surface ligand is polymerize using the method for heating.Specifically,
Initiator and crosslinking agent are added into the supernatant, is warming up to 60~90 DEG C, ligand is prepared in 0.5~50h of heating time
It polymerize the perovskite quantum dot of cladding.
Wherein, the initiator is described including but not limited to azodiisobutyronitrile (AIBN), benzoyl peroxide (BPO)
The quality of initiator is the 0.5~10% of the supernatant quality, thus under the premise of guaranteeing higher rate of polymerization, not because
Amount for initiator is excessive and influences the cross-linked polymeric of ligand and the optical property of quantum dot.
Preferably, the crosslinking agent is including but not limited to divinylbenzene, ethylene glycol diacrylate, diacrylate Isosorbide-5-Nitrae-
Butanediol ester etc., the quality of the crosslinking agent are the 0.5~10% of the supernatant quality, thus guaranteeing higher polymerization speed
Under the premise of rate, the cross-linked polymeric of ligand and the optical property of quantum dot are not influenced because the amount of crosslinking agent is excessive.
As another particular preferred embodiment, perovskite quantum dot surface ligand is polymerize using the method for photopolymerization.Tool
Body, after photoinitiator and crosslinking agent is added into the supernatant, puts and irradiate under ultraviolet light, 0.5~50h of irradiation time,
The perovskite quantum dot of ligand polymer cladding is prepared.
Preferably, the photoinitiator is including but not limited to 1- hydroxyl cyclohexyl benzophenone, 2,2- dimethoxy -2- phenyl benzene second
Ketone (BDK), the quality of the photoinitiator are the 0.5~10% of the supernatant quality, thus guaranteeing higher polymerization speed
Under the premise of rate, the cross-linked polymeric of ligand and the optical property of quantum dot are not influenced because the amount of initiator is excessive.
Preferably, the crosslinking agent is including but not limited to divinylbenzene, ethylene glycol diacrylate, diacrylate Isosorbide-5-Nitrae-
Butanediol ester etc., the quality of the crosslinking agent are the 0.5~10% of the supernatant quality, thus guaranteeing higher polymerization speed
Under the premise of rate, the cross-linked polymeric of ligand and the optical property of quantum dot are not influenced because the amount of crosslinking agent is excessive.
Composite perofskite quantum dot provided in an embodiment of the present invention, can be prepared by the above method.
It is illustrated combined with specific embodiments below.
Embodiment 1
A kind of composite perofskite quantum dot, including perovskite quantum dot and the alkene for being coated on the perovskite quantum dot surface
Quaternary ammonium salts ligand, the molecular structure of the allyl based quaternary ammonium salt ligand as shown in following formula 1,
In the formula 1, R is octadecyl, X-For Br-。
The preparation method of the composite perofskite quantum dot is：
The dimethyl octadecylamine of 0.05mol is dissolved in 30ml acetone, 0.05mol bromopropene is dissolved in 20ml acetone, and 40
It DEG C is vigorously stirred down in the acetone soln for being slowly dropped to dimethyl octadecylamine, the reaction was continued after being added dropwise 30min is obtained
Product is white precipitate, is used after suction filtration acetone washing-suction filtration 3 times, and 25 DEG C are dried in vacuo the white powder obtained for 24 hours, as may be used
The allyl based quaternary ammonium salt ligand of polymerization.
By 0.07mmolCsBr, 0.1mmolPbBr2, 0,03mmol ligand be dissolved in 1ml dimethyl sulfoxide, instill 20ml dropwise
In the toluene being vigorously stirred, yellow-green precipitate being generated, 1ml acetonitrile is added, 10min is centrifuged under 10000rpm, supernatant abandons,
Precipitating is scattered in 1ml toluene, and 4400rpm is centrifuged 10min, takes supernatant.
10mg AIBN, 20mg DVB, 90 DEG C of heating 30min are added in supernatant, is cooled to room temperature organic to get arriving
It polymerize the perovskite quantum dot dispersion liquid of the green light of cladding.
Embodiment 2
A kind of composite perofskite quantum dot, including perovskite quantum dot and the alkene for being coated on the perovskite quantum dot surface
Quaternary ammonium salts ligand, the molecular structure of the allyl based quaternary ammonium salt ligand as shown in following formula 1,
In the formula 1, R is octadecyl, X-For Cl-。
The preparation method of the composite perofskite quantum dot is：
The dimethyl octadecylamine of 0.05mol is dissolved in 30ml ether, 0.05mol bromopropene is dissolved in 20ml ether, and 40
It DEG C is vigorously stirred down in the diethyl ether solution for being slowly dropped to dimethyl octadecylamine, the reaction was continued after being added dropwise 30min is obtained
Product is white precipitate, is washed-is filtered 3 times with ether after suction filtration, 25 DEG C are dried in vacuo the white powder obtained for 24 hours, as may be used
The allyl based quaternary ammonium salt ligand of polymerization.
By 0.07mmolCsCl, 0.1mmolPbCl2, 0,03mmol ligand be dissolved in 1ml dimethylformamide, instill dropwise
In the toluene that 20ml is vigorously stirred, blue-green precipitating is generated, 1ml isopropanol is added, 10min, supernatant is centrifuged under 10000rpm
Liquid abandons, and precipitating is scattered in 1ml toluene, and 4400rpm is centrifuged 10min, takes supernatant.
10mg BPO, 20mg 1,4-butanediol diacrylate are added in supernatant, 90 DEG C of heating 30min are cooled to
Room temperature is to get the perovskite quantum dot dispersion liquid for arriving the blue light-emitting that organic polymer coats.
Embodiment 3
A kind of composite perofskite quantum dot, including perovskite quantum dot and the alkene for being coated on the perovskite quantum dot surface
Quaternary ammonium salts ligand, the molecular structure of the allyl based quaternary ammonium salt ligand as shown in following formula 1,
In the formula 1, R is octadecyl, X-For I-。
The preparation method of the composite perofskite quantum dot is：
The dimethyl octadecylamine of 0.05mol is dissolved in 30ml acetone, 0.05mol bromopropene is dissolved in 20ml acetone, and 40
It DEG C is vigorously stirred down in the acetone soln for being slowly dropped to dimethyl octadecylamine, the reaction was continued after being added dropwise 30min is obtained
Product is white precipitate, is used after suction filtration acetone washing-suction filtration 3 times, and 25 DEG C are dried in vacuo the white powder obtained for 24 hours, as may be used
The allyl based quaternary ammonium salt ligand of polymerization.
By 0.07mmolCsI, 0.1mmolPbI2, 0,03mmol ligand be dissolved in 1ml acetonitrile, dropwise instill 20ml acutely stir
In the tetrahydrofuran mixed, red-brown precipitation is generated, 1ml acetonitrile is added, 10min is centrifuged under 10000rpm, supernatant abandons, and sinks
Shallow lake is scattered in 1ml tetrahydrofuran, and 4400rpm is centrifuged 10min, takes supernatant.
It is added 10mg 1- hydroxyl cyclohexyl benzophenone in supernatant, 20mg DVB, irradiation 30min is to get to having under ultraviolet lamp
The perovskite quantum dot dispersion liquid of the green light of machine polymerization cladding.
Embodiment 4
A kind of composite perofskite quantum dot, including perovskite quantum dot and the alkene for being coated on the perovskite quantum dot surface
Quaternary ammonium salts ligand, the molecular structure of the allyl based quaternary ammonium salt ligand as shown in following formula 1,
In the formula 1, R is octadecyl, X-For Cl-。
The preparation method of the composite perofskite quantum dot is：
The dimethyl octadecylamine of 0.05mol is dissolved in 30ml acetone, 0.05mol chloropropene is dissolved in 20ml acetone, and 40
It DEG C is vigorously stirred down in the acetone soln for being slowly dropped to dimethyl octadecylamine, the reaction was continued after being added dropwise 30min is obtained
Product is white precipitate, is used after suction filtration acetone washing-suction filtration 3 times, and 25 DEG C are dried in vacuo the white powder obtained for 24 hours, as may be used
The allyl based quaternary ammonium salt ligand of polymerization.
By 0.07mmolCsBr, 0.1mmolPbCl2, 0,03mmol ligand be dissolved in 1ml dimethylformamide, instill dropwise
In the toluene that 20ml is vigorously stirred, yellow-green precipitate is generated, 1ml acetone is added, 10min, supernatant is centrifuged under 10000rpm
It abandons, precipitating is scattered in 1ml tetrahydrofuran, and 4400rpm is centrifuged 10min, takes supernatant.
10mg AIBN, 20mg DVB, 90 DEG C of heating 30min are added in supernatant, is cooled to room temperature organic to get arriving
It polymerize the perovskite quantum dot dispersion liquid of the blue light-emitting of cladding.
Embodiment 5
A kind of composite perofskite quantum dot, including perovskite quantum dot and the alkene for being coated on the perovskite quantum dot surface
Quaternary ammonium salts ligand, the molecular structure of the allyl based quaternary ammonium salt ligand as shown in following formula 1,
In the formula 1, R is octadecyl, X-For I-。
The preparation method of the composite perofskite quantum dot is：
The dimethyl octadecylamine of 0.05mol is dissolved in 30ml acetone, 0.05mol bromopropene is dissolved in 20ml acetone, and 40
It DEG C is vigorously stirred down in the acetone soln for being slowly dropped to dimethyl octadecylamine, the reaction was continued after being added dropwise 30min is obtained
Product is white precipitate, is used after suction filtration acetone washing-suction filtration 3 times, and 25 DEG C are dried in vacuo the white powder obtained for 24 hours, as may be used
The allyl based quaternary ammonium salt ligand of polymerization.
By 0.07mmolCsBr, 0.1mmolPbI2, 0,03mmol ligand be dissolved in 1ml acetonitrile, dropwise instill 20ml acutely stir
In the toluene mixed, red-brown precipitation is generated, 1ml isopropanol is added, 10min is centrifuged under 10000rpm, supernatant abandons, precipitating
It is scattered in 1ml tetrahydrofuran, 4400rpm is centrifuged 10min, takes supernatant.
10mg BDK is added in supernatant, 20mg ethylene glycol diacrylate heats 30min at 90 DEG C to get arriving
The perovskite quantum dot dispersion liquid of organic polymer cladding to glow.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of composite perofskite quantum dot, which is characterized in that including perovskite quantum dot and be coated on the perovskite quantum
Point surface allyl based quaternary ammonium salt ligand, the molecular structure of the allyl based quaternary ammonium salt ligand as shown in following formula 1,
In the formula 1, R is the alkyl or alkenyl that amount of carbon atom is 8-18, X-For halide anion.
2. composite perofskite quantum dot as described in claim 1, which is characterized in that the X-Selected from Cl-、Br-、I-In one
Kind.
3. composite perofskite quantum dot as claimed in claim 1 or 2, which is characterized in that the allyl based quaternary ammonium salt ligand is logical
It crosses double-bond polymerization and is cross-linked to form network polymers, be coated on the perovskite quantum dot surface.
4. a kind of preparation method of allyl based quaternary ammonium salt ligand, which is characterized in that include the following steps：
Dimethyl long-chain alkanamine, propylene halide and reaction dissolvent are provided, by the dimethyl long-chain alkanamine and the propylene halide
It is dissolved in the reaction dissolvent respectively, configuration obtains dimethyl long-chain alkanamine solution and propylene halide solution, wherein the diformazan
The amount of carbon atom of long alkane in base long-chain alkanamine is 8-18；
Under conditions of the dimethyl long-chain alkanamine solution heating stirring, the propylene halide solution is added, reaction is prepared into
To allyl based quaternary ammonium salt ligand.
5. the preparation method of allyl based quaternary ammonium salt ligand as claimed in claim 4, which is characterized in that it is long to configure the dimethyl
It is 1 by the volume ratio of the dimethyl long-chain alkanamine and the reaction dissolvent in the step of alkane amine aqueous solution:5~1:50 configurations；
And/or
It is 1 by the volume ratio of the propylene halide and the reaction dissolvent in the step of configuring the propylene halide solution:5~
1:50 configurations.
6. the preparation method of allyl based quaternary ammonium salt ligand as claimed in claim 4, which is characterized in that prepare the allyl season
In the step of ammonium salt ligand, the dripping quantity of the propylene halide solution meets：
The volume ratio of the dimethyl long-chain alkanamine and the propylene halide is 1:1~1.5；And/or
In the step of preparing the allyl based quaternary ammonium salt ligand, heating stirring makes the temperature of reaction system be 30-80 DEG C, is added dropwise
After the complete propylene halide solution, temperature ± 2 DEG C are kept constant the reaction was continued 0.5-4h.
7. a kind of preparation method of composite perofskite quantum dot, which is characterized in that include the following steps：
The anion presoma, cationic presoma and allyl based quaternary ammonium salt ligand of perovskite quantum dot, the allyl are provided
The molecular structure of based quaternary ammonium salt ligand as shown in following formula 1,
The anion presoma, the cationic presoma and the allyl based quaternary ammonium salt ligand are dissolved in the first solvent
Prepare precursor solution；The precursor solution is distributed in the second solvent, it is mixed to obtain the perovskite quantum dot containing precipitating
Suspension；Third solvent is added into the perovskite quantum dot suspension, mixed processing promotes the precipitating of perovskite quantum dot,
Centrifugal treating under conditions of revolving speed >=8000rpm collects precipitating；It disperses the precipitating being collected into second solvent, mixes
After closing uniformly under conditions of 3000rpm≤revolving speed≤6000rpm, centrifugal treating removal precipitating collects perovskite quantum dot
Supernatant；
The polymerization reaction for causing perovskite quantum dot surface ligand in the supernatant, prepares composite perofskite quantum dot.
8. the preparation method of composite perofskite quantum dot as claimed in claim 7, which is characterized in that first solvent is pole
Property organic solvent, be selected from least one of dimethylformamide, dimethyl sulfoxide, acetonitrile, methanol, ethyl acetate；
Second solvent is non-polar organic solvent, is selected from least one of toluene, n-hexane, chloroform, tetrahydrofuran；
The third solvent is selected from least one of acetone, acetonitrile, isopropanol, n-butanol, ether.
9. the preparation method of composite perofskite quantum dot as claimed in claim 7, which is characterized in that by the precursor solution
In the step of being distributed to the second solvent, the amount of second solvent meets：The first solvent and addition in the precursor solution
Second solvent volume ratio≤1：5；
In the step of third solvent is added into the perovskite quantum dot suspension, the amount of the third solvent meets：It is described
Volume ratio≤1 of the third solvent of the second solvent and addition in perovskite quantum dot suspension：1.
10. such as the preparation method of the described in any item composite perofskite quantum dots of claim 7-9, which is characterized in that cause institute
The method of the polymerization reaction of perovskite quantum dot surface ligand in supernatant is stated as heating polymerization or photopolymerization.
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| CN110846028A (en) * | 2019-10-24 | 2020-02-28 | 兰州大学 | Polymer-coated perovskite quantum dot, preparation method thereof and semiconductor luminescent material comprising same |
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| CN110129026A (en) * | 2019-05-30 | 2019-08-16 | 苏州星烁纳米科技有限公司 | Perovskite quantum dot dispersion |
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| CN110846028A (en) * | 2019-10-24 | 2020-02-28 | 兰州大学 | Polymer-coated perovskite quantum dot, preparation method thereof and semiconductor luminescent material comprising same |
| CN113025309A (en) * | 2019-12-25 | 2021-06-25 | Tcl集团股份有限公司 | Quantum dot, surface modification method thereof and quantum dot light-emitting diode |
| 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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