CN106957650A - A kind of preparation method for modifying quantum dot and modification quantum dot film - Google Patents
A kind of preparation method for modifying quantum dot and modification quantum dot film Download PDFInfo
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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Abstract
The present invention provides a kind of preparation method for modifying quantum dot and modification quantum dot film, the modification quantum dot film includes film layer and the multiple modification quantum dots being attached on the film surface, the multiple modification quantum dot is spaced by the effect of transparent substance to be combined as a whole, wherein, each modification quantum dot includes quantum dot and bonding with reference to the aggregation-induced emission molecule in the quantum dot surface.Occur the method for aggregation inducing fluorescent quenching in solid luminescent instant invention overcomes quantum dot, luminous efficiency of the quantum dot in the solid state applications such as optical thin film, device can be effectively improved, can effectively extend the life-span of quantum dot optical thin film and device.
Description
【Technical field】
The present invention relates to field of liquid crystal display, more particularly to a kind of preparation method for modifying quantum dot and modification quantum dot are thin
Film.
【Background technology】
The emission mechanism of fluorescence is that each fluorescent monomer has a series of strict discrete energy levels, at room temperature fluorescence list
Body is mostly in ground state, after these materials absorb luminous energy under the irradiation of light, into excitation state；Monomer in excitation state
It is unstable, ground state can be returned to by launching fluorescent photon from excitation state transition.But because π-π pile up after fluorescent monomer aggregation
Effect, can consume its excited energy and return to ground state, simultaneously because π-π sintering actions, can change orbital energy, it is received light
Fluorescence can not launched after aggregation with fluorescence mode emitted energy, i.e. fluorescent monomer according to after, effect is quenched for aggregation inducing in this
Answer (ACQ).ACQ effects seriously reduce luminous efficiency of the fluorescent material in solid-state, limit fluorescent material display lead
The application in domain.
Quantum dot (quantum dots, QDs) is the former molecular quasi-zero dimension nanometer crystalline particle by finite number, its
Fluorescence can be launched when being excited by short-wavelength light, and it is wide with colour gamut, and color saturation is high, and Stokes shift is big, resists
The advantages of photobleaching ability is strong, and can be realized by controlling the modes such as particle diameter, component and structure from blue light near red
The whole visible light covering of outer light, therefore obtained greatly in terms of light-sensitive cell, liquid crystal display and imaging of medical
Using.It is to launch stronger fluorescence that quanta point material dissolves in weak solution, but in high concentration or is made into solid-state
When, its luminescent properties is often because quantum limitation effect decrease occurs for the formation of state of aggregation and fluorescence intensity occurs and declines even
The phenomenon being wholly absent.It is that QDs is converted into reality by material that quantum dot, which is fixed or is dispersed on nano thin-film in some way,
One of limited means with device.Quantum dot how to be realized in the application of display field and is improved display efficiency and life-span, one
Straight is all the heat subject of scientific research.
【The content of the invention】
It is existing to solve it is an object of the invention to provide a kind of preparation method for modifying quantum dot and modification quantum dot film
Have in technology, quanta point material is in high concentration or when being made into solid-state, and its luminescent properties is often due to the shape of state of aggregation
Weaken into occurring quantum limitation effect, and then fluorescence intensity occur and decline the problem of even disappearing completely.
Technical scheme is as follows：
One kind modification quantum dot film, it includes film layer and the multiple modification quantum dots being attached on the film surface,
The multiple modification quantum dot is spaced by the effect of transparent substance to be combined as a whole；
Wherein, each modification quantum dot includes quantum dot and bonding with reference to the aggregation inducing in the quantum dot surface
Light emitting molecule.
Preferably, the aggregation-induced emission molecule is 4- benzyl-mercapto phenyl -1- talan.
Preferably, multiple modification quantum dots are spaced by the effect of high-molecular compound each other is combined into
One.
A kind of preparation method of modification quantum dot as described above, including：
1) 4- benzyl bromophenyl -1- talan is prepared；
2) 4- benzyl-mercapto phenyl -1- talan solids are prepared using the 4- benzyls bromophenyl -1- talan；
3) bonding is reacted with quantum dot using the 4- benzyl-mercaptos phenyl -1- talan solid, is prepared into the modification
Quantum dot.
Preferably, 4- benzyl bromophenyl -1- talan is prepared, is specifically included：
1) prepare 4- aminomethyl phenyl -1- diphenylethylenes, to bromo biphenyl class, triphen amine, diphenyl dibenzofulvene class,
The one of which intermediate product of Silole class, 9,10- styrene anthracene classes and nitrile substituted diphenylamine vinyl；
2) intermediate product prepared using previous step prepares the 4- benzyls bromophenyl -1- talan.
Preferably, 4- benzyl bromophenyl -1- talan is prepared, is specifically included：
1) benzophenone and 4- methyl benzophenones are dissolved in tetrahydrofuran solution, add zinc powder and be stirred and obtain anti-
Solution is answered, and anaerobic processing is carried out to the reaction solution, untill it reaches anaerobic；
2) in preset temperature range and under agitation, titanium tetrachloride is added dropwise to above-mentioned reaction solution, then slowly
Rise again to room temperature, backflow after design temperature is warming up to after stirring and is stayed overnight；
3) reaction solution after above-mentioned backflow is stayed overnight carries out that reaction is quenched, and is extracted for several times with organic extractant
Take, merge organic layer, and dehydration and filtering purification are dried to the organic layer, obtain 4- aminomethyl phenyl -1- talan and consolidate
Body；
4) the 4- aminomethyl phenyls -1- talan solids are dissolved in azodiisobutyronitrile and carbon tetrachloride, and it is entered
Row stirring obtains reaction solution, then adds the N-bromosuccinimide newly recrystallized to the reaction solution in batches, heats up back
Room temperature is cooled to after stream, the reaction solution is then filtered and removes precipitation and collect filtrate, passes through vacuum revolving and removes solvent, obtain institute
State 4- benzyl bromophenyl -1- talan.
Preferably, 4- benzyl-mercapto phenyl -1- talan solids are prepared using the 4- benzyls bromophenyl -1- talan,
Specifically include：
1) 4- benzyl bromophenyl -1- talan is dissolved in tetrahydrofuran, adds potassium carbonate and be passed through nitrogen, protected
Hold and it is stirred under inert atmosphere；
2) add in watery hydrochloric acid and solution, and removed solvent by rotating, remaining solute solids are dissolved in three chloromethanes
In alkane；
3) rinsed and extracted with pure water, retained chloroform soln and dried with anhydrous magnesium sulfate, pass through revolving after filtering
Remove solvent and obtain the 4- benzyl-mercaptos phenyl -1- talan solids.
Preferably, bonding is reacted using the 4- benzyl-mercaptos phenyl -1- talan solid and quantum dot, be prepared into described
Quantum dot is modified, is specifically included：
Under inert gas shielding, the 4- benzyl-mercaptos are slowly added dropwise into the oil-soluble quantum dot solution for being dissolved in chloroform
Phenyl -1- talan solids, stir under design temperature scope when being added dropwise, its reaction time length is reached preset time
Length；
The 4- benzyl-mercaptos phenyl -1- talan solid solutions after stirring reaction are centrifuged, and by after centrifugation
Obtained solid dissolving obtains the modification quantum dot in chloroform.
Preferably, the quantum dot is structure quantum point, and is CdSe/ZnS, CdTd/CdSe and CdSe/CdS/ZnS
One of which.
Preferably, the design temperature scope is 45 DEG C~55 DEG C, and the predetermined time period is 2h.
Beneficial effects of the present invention：
The invention provides a kind of preparation method for modifying quantum dot and modification quantum dot film, pass through the table in quantum dot
Face bonding combination aggregation-induced emission molecule, overcomes the side that aggregation inducing fluorescent quenching occurs in solid luminescent for quantum dot
Method, can effectively improve luminous efficiency of the quantum dot in the solid state applications such as optical thin film, device, and this method has versatility, fit
Solid-state mode luminous efficiency for all organic and inorganic luminescent materials improves, and improves the luminous efficiency of film, device,
Under comparable optical demand, required energy consumption also can be reduced accordingly, have certain contribution to energy-conserving and environment-protective, by organic compound-
Being combined for inorganic nano-particle, can effectively extend the life-span of optical thin film, device.
【Brief description of the drawings】
Fig. 1 is a kind of overall structure diagram of modification quantum dot film of the embodiment of the present invention one；
Fig. 2 is a kind of overall structure diagram of unmodified quantum dot film of prior art；
Fig. 3 is the synthetic route chart of the modification quantum dot of the embodiment of the present invention two；
Fig. 4 is the synthetic route chart of the 4- benzyl-mercapto phenyl -1- talan of the embodiment of the present invention two；
Fig. 5 is the synthetic route chart of the 4- benzyl bromophenyl -1- talan of the embodiment of the present invention two；
Fig. 6 is the structural representation of the modification quantum dot of the embodiment of the present invention two；
Fig. 7 is the quantum-dot structure schematic diagram of prior art.
【Embodiment】
The explanation of following embodiment is the particular implementation implemented to illustrate the present invention can be used to reference to additional schema
Example.The direction term that the present invention is previously mentioned, such as " on ", " under ", "front", "rear", "left", "right", " interior ", " outer ", " side "
Deng being only the direction with reference to annexed drawings.Therefore, the direction term used is to illustrate and understand the present invention, and is not used to
The limitation present invention.In figure, the similar unit of structure is represented with identical label.
Embodiment one
Fig. 1 is refer to, Fig. 1 is a kind of overall structure diagram of modification quantum dot film of the present embodiment.Can be with from Fig. 1
See：
A kind of modification quantum dot film of the present invention, it includes film layer 10 and is attached to multiple on the surface of film layer 10
Quantum dot 20 is modified, the multiple modification quantum dot 20 is spaced by the effect of transparent substance to be combined as a whole.
In the present embodiment, preferably multiple modification quantum dots 20 each other by the effect of high-molecular compound that
This interval is combined as a whole.
Wherein, each modification quantum dot 20 includes quantum dot and bonding is lured with reference to the aggregation in the quantum dot surface
Lead light emitting molecule.
In the present embodiment, preferably described aggregation-induced emission molecule is 4- benzyl-mercapto phenyl -1- talan.
The principle that the present invention improves quantum dot aggregation inducing quenching effect problem is as follows：
Aggregation-induced emission (AIE, Aggregation-induced emission) phenomenon refers to not light in solution,
And the phenomenon of the very strong characteristics of luminescence is presented in solid-state.Aggregation-induced emission phenomenon (AIE) is and conventional fluorescent chromophore
Cause fluorescent quenching opposite after aggregation, the less fluorescence under unimolecule state or dissolved state, and in solid crystals assemble shape
The phenomenon that fluorescence is significantly increased under state.Compound with AIE effects energy during excitation state electronics rebound ground state in free state
The rotation for phenyl ring is measured, rather than is gone out with fluorescent emission, but it is made with fluorescence side due to singly-bound blocked rotation after aggregation
Formula emitted energy.
When in dissolved state, AIE molecules are received energy by light irradiation and activated, and aromatic substituents pass through singly-bound
Rotate freely and discharge the energy of absorption in the form of kinetic energy, forming a non-radiative decay channel makes AIE molecular-excited states
Energy is reduced, and is caused fluorescent weakening or is quenched.And when it is in coherent condition, the intermolecular spacing of AIE reduces, space is limited
System, generation molecule is overlapping, and intramolecular aromatic substituents can not be rotated freely, and non-radiative decay channel is suppressed, by illumination
The AIE molecules of activation can not be discharged the energy of absorption by way of singly-bound is rotated freely in the form of kinetic energy, can only be passed through
The mode that radiative decay launches photon returns to ground state from excitation state, namely launches fluorescence.Photoelectric functional molecule is generally with thin
The form of film and aggregation realizes display function, and aggregation-induced emission (AIE) molecular system is with very high solid luminescent efficiency
To realize high-performance OLED (i.e. Organic Light Emitting Diode, Organic Light-Emitting Diode)/QLED (i.e. quantum dots
Light emitting diode, Quantum Dot LED) (high efficiency, long-life) provide new approach.The present invention is by quantum dot
Surface bonding combination aggregation-induced emission molecule, solves the problem of aggregation inducing fluorescent quenching (ACQ) under solid-state.
Fig. 2 is refer to, Fig. 2 is a kind of overall structure diagram of unmodified quantum dot film of prior art, should
Film includes film layer 30 and is attached to the quantum dot 40 on the surface of film layer 30.Because these quantum dots 40 are unmodified, its surface does not have
Have with reference to aggregation-induced emission molecule, therefore when these quantum dots 40 flock together, will occur aggregation inducing glimmering
The phenomenon of optical quenching.
Quantum dot film is modified the invention provides one kind, passes through the surface bonding combination aggregation-induced emission in quantum dot
Molecule, overcomes the method that aggregation inducing fluorescent quenching occurs in solid luminescent for quantum dot, can effectively improve quantum dot in light
The luminous efficiency in the solid state applications such as film, device is learned, this method has versatility, it is adaptable to all organic and inorganic luminous materials
The solid-state mode luminous efficiency of material improves, and improves the luminous efficiency of film, device, under comparable optical demand, required energy consumption
Also it can accordingly reduce, there is certain contribution to energy-conserving and environment-protective, by the compound of organic compound-inorganic nano-particle, can have
Effect extension optical thin film, the life-span of device.
Embodiment two
Fig. 3 to Fig. 7 is refer to, Fig. 3 is the synthetic route chart of the modification quantum dot 20 of the present embodiment, and Fig. 4 is the present embodiment
4- benzyl-mercapto phenyl -1- talan synthetic route chart, Fig. 5 for the present embodiment 4- benzyl bromophenyl -1- talan
Synthetic route chart, Fig. 6 is the structural representation of the modification quantum dot 20 of the present embodiment two, and Fig. 7 is the quantum dot knot of prior art
Structure schematic diagram.
It can see from Fig. 3, Fig. 4 and Fig. 5, a kind of individual preparation method for modifying quantum dot 20 of the invention, including it is following
Step：
Step one：Prepare 4- benzyl bromophenyl -1- talan；
Step 2：4- benzyl-mercapto phenyl -1- talan solids are prepared using the 4- benzyls bromophenyl -1- talan；
Step 3：Bonding is reacted using the 4- benzyl-mercaptos phenyl -1- talan solid and quantum dot, is prepared into described
Modify quantum dot 20.
In the present embodiment, 4- benzyl bromophenyl -1- talan is prepared, is specifically included：
First, prepare 4- aminomethyl phenyl -1- diphenylethylenes, to bromo biphenyl class, triphen amine, diphenyl dibenzofulvene
Class, Silole class, the one of which intermediate product of 9,10- styrene anthracene classes and nitrile substituted diphenylamine vinyl.
The preferred 4- aminomethyl phenyls -1- diphenylethylenes of the present embodiment are used as intermediate product.
Second, the intermediate product prepared using previous step prepares the 4- benzyls bromophenyl -1- talan.
The specific implementation step of the present embodiment, as described below：
The first step, benzophenone and 4- methyl benzophenones are placed in condenser pipe and the good twoport round bottom of sealing
In flask, add tetrahydrofuran solution and dissolved, zinc powder is added afterwards, and carry out strong magnetic power stirring, a bite of round-bottomed flask
With rubber stopper seal, another mouthful of connection vavuum pump is vacuumized to round-bottomed flask, and then inflated with nitrogen, is repeated several times, Zhi Daoyuan
In the flask of bottom untill anaerobic.Reaction unit is put in ice salt bath, is kept for -5 DEG C, it is slow with syringe then under strong stirring
Slow titanium tetrachloride is added dropwise into round-bottomed flask.After dripping, kept for -5 DEG C reach and ice salt bath is withdrawn after 30min, slowly risen again
70 DEG C of backflows are warming up to room temperature, after stirring 10min to stay overnight.Add 10% wet chemical afterwards to carry out that reaction is quenched, so
Extracted three times with dichloromethane afterwards, collect organic phase, with saturated salt washing once, anhydrous sulphur is added into the organic phase after separation
Sour magnesium is dried, rotary evaporation in vacuo part organic solvent, and post purification is crossed with chromatographic silica gel post, obtains white as eluant, eluent with petroleum ether
Color 4- aminomethyl phenyl -1- talan solids (TPE-C).
Second step, weighs TPE-C solids and is placed in round-bottomed flask, adds the even chlorine bis-isobutyronitrile (AIBN) and four of catalytic amount
Chlorination carbon (CCl4) dissolves, and carries out magnetic agitation, the N-bromosuccinimide (NBS) newly recrystallized is added in batches, heats up
Flowed back 10 hours to 80 DEG C, be cooled to room temperature, filtering reacting liquid removes precipitation, collect filtrate, vacuum revolving removes solvent, obtained
Reaction intermediate 4- benzyls bromophenyl -1- talan (TPE-Br) solid.
3rd step, synthesis 4- benzyl-mercapto phenyl -1- talan (TPE-SH)：Weigh 5mmoLTPE-Br solid dissolvings in
It is placed in after in 15mL tetrahydrofurans (THF) in twoport flask, adds 12mmoL potassium carbonate (K2CO3) and be passed through N2 gas holding inertia
After atmosphere stirring 10min, the mercaptoacetic acid solution that the concentration that dropwise addition 15mL is dissolved in methanol is 7mmoL is stirred after 40min,
Add in 1.5mL watery hydrochloric acid and solution, revolving removes solvent, remaining solid is dissolved in 20mL chloroforms, pure water is used
Extraction is rinsed, retains chloroform soln and is dried with anhydrous magnesium sulfate, revolving removes solvent and obtains TPE-SH solids after filtering.
4th step, carries out quantum dot ligand exchange：Under inert gas shielding, to the oil-soluble quantum dot for being dissolved in chloroform
The obtained TPE-SH solids are slowly added dropwise in solution, are stirred when being added dropwise at 50 DEG C, and after reaction 2 hours,
Solution is poured into super filter tube and centrifuged, the solid in collected after centrifugation super filter tube, and be dissolved in chloroform, obtain
To TPE-QDs solution, this is the quantum dot solution with aggregation-induced emission effect, is modification quantum dot 20 after drying.
Wherein, the quantum dot is one kind in CdSe/ZnS, CdTd/CdSe and CdSe/CdS/ZnS.
The present invention improves the principle of quantum dot aggregation inducing quenching effect problem, as described in embodiment one, no longer enters herein
Row is described in detail.
The invention provides a kind of preparation method for modifying quantum dot 20, assembled by being combined in the surface bonding of quantum dot
Induced luminescence molecule, overcomes the method that aggregation inducing fluorescent quenching occurs in solid luminescent for quantum dot, can the amount of effectively improving
Luminous efficiency of the son point in the solid state applications such as optical thin film, device, this method has versatility, it is adaptable to all organic, nothings
The solid-state mode luminous efficiency of machine luminescent material improves, and improves the luminous efficiency of film, device, under comparable optical demand,
Required energy consumption also can be reduced accordingly, have certain contribution to energy-conserving and environment-protective, pass through answering for organic compound-inorganic nano-particle
Close, can effectively extend the life-span of optical thin film, device.
In summary, although the present invention it is disclosed above with preferred embodiment, but above preferred embodiment and be not used to limit
The system present invention, one of ordinary skill in the art without departing from the spirit and scope of the present invention, can make various changes and profit
Adorn, therefore protection scope of the present invention is defined by the scope that claim is defined.
Claims (10)
1. one kind modification quantum dot film, it is characterised in that it includes film layer and multiple repairing of being attached on the film surface
Quantum dot is adornd, the multiple modification quantum dot is spaced by the effect of transparent substance to be combined as a whole；
Wherein, each modification quantum dot includes quantum dot and bonding with reference to the aggregation-induced emission in the quantum dot surface
Molecule.
2. modification quantum dot film according to claim 1, it is characterised in that the aggregation-induced emission molecule is 4- benzyls
Mercaptophenyl -1- talan.
3. modification quantum dot film according to claim 1, it is characterised in that multiple modification quantum dots are each other
It is spaced and is combined as a whole by the effect of high-molecular compound.
4. a kind of preparation method of modification quantum dot as described in claims 1 to 3, it is characterised in that including：
1) 4- benzyl bromophenyl -1- talan is prepared；
2) 4- benzyl-mercapto phenyl -1- talan solids are prepared using the 4- benzyls bromophenyl -1- talan；
3) bonding is reacted with quantum dot using the 4- benzyl-mercaptos phenyl -1- talan solid, is prepared into the modification quantum
Point.
5. preparation method according to claim 4, it is characterised in that prepare 4- benzyl bromophenyl -1- talan, specific bag
Include：
1) 4- aminomethyl phenyl -1- diphenylethylenes are prepared, to bromo biphenyl class, triphen amine, diphenyl dibenzofulvene class, sila
The one of which intermediate product of cyclopentadiene, 9,10- styrene anthracene classes and nitrile substituted diphenylamine vinyl；
2) intermediate product prepared using previous step prepares the 4- benzyls bromophenyl -1- talan.
6. preparation method according to claim 5, it is characterised in that prepare 4- benzyl bromophenyl -1- talan, specific bag
Include：
1) benzophenone and 4- methyl benzophenones are dissolved in tetrahydrofuran solution, add zinc powder be stirred obtain reaction it is molten
Liquid, and anaerobic processing is carried out to the reaction solution, untill it reaches anaerobic；
2) in preset temperature range and under agitation, titanium tetrachloride is added dropwise to above-mentioned reaction solution, then slowly rises again
To room temperature, backflow after design temperature is warming up to after stirring and is stayed overnight；
3) reaction solution after above-mentioned backflow is stayed overnight carries out that reaction is quenched, and is extracted for several times with organic extractant,
Merge organic layer, and dehydration and filtering purification are dried to the organic layer, obtain 4- aminomethyl phenyl -1- talan solids；
4) the 4- aminomethyl phenyls -1- talan solids are dissolved in azodiisobutyronitrile and carbon tetrachloride, and it is stirred
Mix and obtain reaction solution, then add the N-bromosuccinimide newly recrystallized to the reaction solution in batches, carry out after temperature rising reflux
Room temperature is cooled to, the reaction solution is then filtered and removes precipitation and collect filtrate, passes through vacuum revolving and removes solvent, obtain the 4-
Benzyl bromophenyl -1- talan.
7. preparation method according to claim 4, it is characterised in that use the 4- benzyls bromophenyl -1- talan systems
Standby 4- benzyl-mercapto phenyl -1- talan solids, are specifically included：
1) 4- benzyl bromophenyl -1- talan is dissolved in tetrahydrofuran, adds potassium carbonate and be passed through nitrogen, keeping lazy
It is stirred under property atmosphere；
2) add in watery hydrochloric acid and solution, and removed solvent by rotating, remaining solute solids are dissolved in chloroform；
3) rinsed and extracted with pure water, retained chloroform soln and dried with anhydrous magnesium sulfate, removed after filtering by rotating
Solvent obtains the 4- benzyl-mercaptos phenyl -1- talan solids.
8. preparation method according to claim 4, it is characterised in that use the 4- benzyl-mercaptos phenyl -1- talan
Solid reacts bonding with quantum dot, is prepared into the modification quantum dot, specifically includes：
Under inert gas shielding, the 4- benzyl-mercaptos benzene is slowly added dropwise into the oil-soluble quantum dot solution for being dissolved in chloroform
Base -1- talan solids, stir under design temperature scope when being added dropwise, its reaction time length is reached that preset time is long
Degree；
The 4- benzyl-mercaptos phenyl -1- talan solid solutions after stirring reaction are centrifuged, and will be obtained after centrifugation
Solid dissolving in chloroform, obtain the modification quantum dot.
9. preparation method according to claim 4, it is characterised in that the quantum dot is structure quantum point, and be CdSe/
ZnS, CdTd/CdSe and CdSe/CdS/ZnS one of which.
10. preparation method according to claim 8, it is characterised in that the design temperature scope is 45 DEG C~55 DEG C, institute
Predetermined time period is stated for 2h.
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