CN107382744A - A kind of perovskite quantum dot film and preparation method thereof, backlight module and display device - Google Patents
A kind of perovskite quantum dot film and preparation method thereof, backlight module and display device Download PDFInfo
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Abstract
The invention discloses a kind of perovskite quantum dot film and preparation method thereof, backlight module, belongs to LCD backlight module field.The quantum dot film includes：Perovskite quantum dot and dentritic polyamidoamine；In the space that the side base that the perovskite quantum dot is scattered in dentritic polyamidoamine is formed.The preparation method includes：Perovskite quantum dot perovskite quantum dot is added in the solution of dentritic polyamidoamine and obtains mixed solution, mixed solution is applied in substrate and is solidified to obtain cured film, obtains perovskite quantum dot film.The backlight module includes：Perovskite quantum dot film, construction package and backlight and reflector plate.The side base structure that the present invention possesses using dentritic polyamidoamine is disperseed perovskite quantum dot, and the side base of dentritic polyamidoamine plays a part of separating, fixes perovskite quantum dot, reduces the reunion or overlapping between perovskite quantum dot.
Description
Technical field
The present invention relates to LCD backlight module field, more particularly to a kind of perovskite quantum dot film and its preparation side
Method, backlight module and display device.
Background technology
The function of LCD backlight module is in liberal supply brightness and the light source being evenly distributed, and can normally show
Show image, luminescent material (such as fluorescent material) can be added in backlight module as a component in backlight module, pass through the back of the body
During the monochromatic light exposure perovskite quantum dot film of the light source such as light emitting diode in optical mode group, due to luminescence generated by light make it is different
Fluorescent material can send the light of different colours, can form white light after the light mixing of different colours, then by colour transition filter disc optical filtering at
The coloured image obtained after reason develops the color, and can lift the color gamut performance of liquid crystal display, makes color distincter.Perovskite amount
Son point film possesses the performance of luminescence generated by light, possessed applied to the feasibility in backlight module as a kind of advanced luminescent material.
Perovskite quantum dot refers to the perovskite nano material of quasi-zero dimension, it can be understood as the size of three dimensions all exists
Less than 100 nanometers of perovskite, perovskite are that general molecular formula is ABX3A kind of compound general designation, wherein organic and inorganic class
A is usually organic cation (such as CH in perovskite3NH3 +), B is usually divalent metal (such as Pb2+), X is usually
Halide anion (such as Cl-).At present, the preparation method of perovskite quantum dot film is as follows, to prepare CH3NH3PbBr3Quantum dot
Exemplified by, first by the raw material methyl bromide ammonium CH of default mol ratio3NH3Br, lead bromide PbBr2, surface modifier (such as octylame)
It is dissolved in dimethylformamide (DMF), forms precursor liquid, then the precursor liquid of predetermined amount is added dropwise in toluene and stirred,
The solution of acquisition is spin-coated on substrate, CH can be obtained after drying3NH3PbBr3Quantum dot film, by feed change and together
The preparation method of sample can obtain sending after luminescence generated by light the perovskite quantum dot film of different colours.
During the present invention is realized, inventor has found that prior art at least has problems with：
In the above-mentioned method that quantum dot is initially formed to solution and then is coated and dries, when quantum dot content compared with
Gao Shi, these quantum dots are easily reunited in the solution, cause after quantum dot film is shaped to quantum dot in quantum dot film
In exist with aggregating state so that absorption to exciting light forms barrier to quantum dot each other, ultimately result in fluorescent quantum
Efficiency is low.
The content of the invention
In order to solve the problems, such as that prior art is above-mentioned, the embodiments of the invention provide a kind of perovskite quantum dot film, prepare
Method and its application.The technical scheme is as follows：
In a first aspect, the invention provides a kind of perovskite quantum dot film, the quantum dot film includes：Perovskite quantum dot
And dentritic polyamidoamine；
In the space that the side base that the perovskite quantum dot is scattered in the dentritic polyamidoamine is formed.
Preferably, the dentritic polyamidoamine is reacted to obtain by diamines monomer and beta-unsaturated esters.
Preferably, the gap length that the side base of the dentritic polyamidoamine is formed is 2-8nm.
Preferably, the perovskite quantum dot includes green glow perovskite quantum dot, feux rouges perovskite quantum dot, blue light calcium titanium
At least one of ore deposit quantum dot, and the green glow perovskite quantum dot, the feux rouges perovskite quantum dot, the blue light calcium titanium
Ore deposit quantum dot is respectively CH3NH3PbBr3、CH3NH3PbBr1.5I1.5And CH3NH3PbBrCl2。
Second aspect, the invention provides a kind of preparation method of perovskite quantum dot film, methods described includes：
Step 1, addition perovskite quantum dot obtains mixed solution in the solution of dentritic polyamidoamine, wherein in institute
Stating has the space that can accommodate the perovskite quantum dot in dentritic polyamidoamine；
Step 2, the mixed solution is applied on PET substrate solidified
Film, the cured film is removed from PET substrate, obtain perovskite quantum dot film.
Preferably, dentritic polyamidoamine solution is prepared via a method which to obtain described in the step 1：
Beta-unsaturated esters monomer is added in diamines monomer and carries out addition reaction；
Diamines monomer is added in the product of the addition reaction and carries out substitution reaction, it is tree-like to obtain 1 generation daiamid
Molecule；
Repeat to add the beta-unsaturated esters monomer and the diamines monomer N- in the 1 generation dentritic polyamidoamine
1 time, N is obtained for dentritic polyamidoamine, wherein N is the integer more than or equal to 2；
Monoamine terminating reaction is added, obtains dentritic polyamidoamine of the gap length in preset range of side base formation.
Specifically, the diamines monomer includes：Octadecyl diamines, ethylenediamine, butanediamine, p-phenylenediamine and naphthylenediamine
In one kind, the beta-unsaturated esters monomer includes 3- phenylpropen acid butyl esters.
Preferably, the N is 6.
Preferably, the green glow perovskite quantum dot, the feux rouges perovskite quantum dot, the blue light perovskite quantum dot
It is prepared via a method which to obtain respectively：
By organic amine salt and lead bromide mixed dissolution in organic solvent, the solution after dissolving is added to daiamid tree
In shape molecular solution, surface modifier is added, toluene is added, obtains the green glow perovskite quantum dot；
By organic amine salt and lead bromide and lead iodide mixed dissolution in organic solvent, the solution after dissolving is added to poly-
In amide amine dendrimer solution, surface modifier is added, toluene is added, obtains the feux rouges perovskite quantum dot；
By organic amine salt and lead bromide and lead chloride mixed dissolution in organic solvent, the solution after dissolving is added to poly-
In amide amine dendrimer solution, surface modifier is added, toluene is added, obtains the blue light perovskite quantum dot.
Preferably, the organic ammonium salt is methyl bromide amine.
Preferably, the methyl bromide amine is 3 according to mol ratio with the lead bromide:1-2 is mixed, the methyl bromide
It is (2-3) according to mol ratio to change amine with lead bromide and lead iodide:1:1 is mixed, the methyl bromide amine and lead bromide and chlorine
It is (3-4) to change lead according to mol ratio:2:1 is mixed.
Preferably, the organic solvent is dimethyl formamide solution.
Preferably, the volume fraction shared by the dimethyl methyl phthalein amine aqueous solution is 80%.
Preferably, the surface modifier is oleyl amine and octylame.
Preferably, the addition toluene, specially under 70 DEG C of water bath conditions, toluene is added to system ultraviolet light
Exciting light stops when being steady state value.
The third aspect, the invention provides a kind of backlight module, the backlight module includes above-mentioned perovskite quantum dot
Film, construction package and backlight and reflector plate.
Fourth aspect, the invention provides a kind of display device, the display device includes what the above-mentioned third aspect was provided
Backlight module.
The beneficial effect that technical scheme provided in an embodiment of the present invention is brought is：
The side base structure that perovskite quantum dot film provided in an embodiment of the present invention possesses using dentritic polyamidoamine will
Perovskite quantum dot is disperseed, and the side base of dentritic polyamidoamine plays a part of separating, fixes perovskite quantum dot, calcium
In the space that the side base that titanium ore quantum dot is regularly scattered in dentritic polyamidoamine is formed, perovskite quantum dot point is improved
The uniformity and uniformity of cloth, avoid the reunion easily occurred between perovskite quantum dot or overlapping phenomenon.
Brief description of the drawings
Technical scheme in order to illustrate the embodiments of the present invention more clearly, make required in being described below to embodiment
Accompanying drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for
For those of ordinary skill in the art, on the premise of not paying creative work, other can also be obtained according to these accompanying drawings
Accompanying drawing.
Fig. 1 is the back light module unit structure schematic diagram for the addition perovskite quantum dot film that Application Example 2 of the present invention provides；
Fig. 2 is that the present invention characterizes the photoluminescence spectra figure that embodiment 3 provides.
Wherein, illustrate and be：1st, construction package；2nd, perovskite quantum dot film；3rd, backlight and reflector plate.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing to embodiment party of the present invention
Formula is described in further detail.
In a first aspect, the embodiments of the invention provide a kind of perovskite quantum dot film, the quantum dot film includes：Perovskite
Quantum dot and dentritic polyamidoamine；
In the space that the side base that the perovskite quantum dot is scattered in the dentritic polyamidoamine is formed.
The side base structure that perovskite quantum dot film provided in an embodiment of the present invention possesses using dentritic polyamidoamine will
Perovskite quantum dot is disperseed, and the side base of dentritic polyamidoamine plays a part of separating, fixes perovskite quantum dot, calcium
In the space that the side base that titanium ore quantum dot is regularly scattered in dentritic polyamidoamine is formed, perovskite quantum dot point is improved
The uniformity and uniformity of cloth, the reunion easily occurred between perovskite quantum dot or overlapping phenomenon are avoided, also simultaneously
The light absorbing of perovskite quantum dot that different colours can be reduced interacts, and improves the fluorescent quantum effect of perovskite quantum dot film
Rate.
Lighted it should be noted that quantum dot light excites to light for 360 ° of full angle, the light absorbing wavelength of quantum dot
Less than the wavelength that itself lights, so a kind of color quantum dot may absorb the light that the quantum dot of another color is sent, and
Cause loss of the light inside perovskite quantum dot membrane material, fluorescence quantum efficiency is low.And the embodiment of the present invention improves calcium titanium
The uniformity and uniformity of ore deposit quantum dot distribution, when different colours being present in perovskite quantum dot film provided in an embodiment of the present invention
Perovskite quantum dot when, the light absorbing of quantum dot that can reduce different colours interacts, improve perovskite quantum dot
The fluorescence quantum efficiency of film.In addition, perovskite quantum dot film provided in an embodiment of the present invention will using dentritic polyamidoamine
Specific surface area is big, and the perovskite quantum dot being oxidized easily is wrapped up, and avoids perovskite quantum dot and is oxidized.
Further, the dentritic polyamidoamine is reacted to obtain by diamines monomer and beta-unsaturated esters.The polyamides
Amine amine dendrimer possesses the principle of side base structure using diamines monomer as triggering core to set out, and addition occurs with beta-unsaturated esters
Reaction, short chain side base is formed, then chain occurs with diamines monomer again based on the ester functional groups in the short chain side base and increases
Long reaction, the short chain side base is increased, and the dendrimer of daiamid can be obtained after more secondary responses, " tree herein
Shape " refers to the dendritic structure that the side base of daiamid is formed.The diamines monomer include octadecyl diamines, ethylenediamine,
One kind in butanediamine, p-phenylenediamine and naphthylenediamine, the beta-unsaturated esters monomer include 3- phenylpropen acid butyl esters.
The gap length that the side base of the dentritic polyamidoamine is formed is 2-8nm, preferably 4.4nm.Pass through space
The restriction of width ensure that the uniformity and uniformity of perovskite quantum dot distribution.
The perovskite quantum dot includes CH3NH3PbBr3Quantum dot, CH3NH3PbBr1.5I1.5Quantum dot and
CH3NH3PbBrCl2At least one of quantum dot.The general molecular formula of perovskite quantum dot is ABX3, wherein organic and inorganic class calcium
A is usually organic cation (such as CH in titanium ore3NH3 +), B is usually divalent metal (such as Pb2+), X is usually halogen
Plain anion (such as Cl-).Different perovskite quantum dot films is after the irradiation by light emitting diode due to photic hair
Light and the light for sending different colours, its principle are by controlling halogen atom X ratio to control organic and inorganic perovskite-like
The energy gap of quantum dot, so as to regulate and control the emission wavelength of the organic and inorganic perovskite-like quantum dot.With CH3NH3PbBr3Amount
Based on son point, Cl-The increase of component causes organic and inorganic perovskite-like quantum dot energy gap to become big, luminous peak position blue shift；
I-The increase of component can cause organic and inorganic perovskite-like quantum dot energy gap to reduce, luminous peak position red shift.Described above
Perovskite quantum dot CH3NH3PbBr3、CH3NH3PbBr1.5I1.5And CH3NH3PbBrCl2Sent respectively under ultraviolet excitation green
Light, feux rouges and blue light.
Second aspect, the embodiments of the invention provide a kind of preparation method of perovskite quantum dot film, methods described includes：
Step 1, addition perovskite quantum dot obtains mixed solution in the solution of dentritic polyamidoamine, wherein in institute
Stating has the space that can accommodate the perovskite quantum dot in dentritic polyamidoamine；
Step 2, the mixed solution is applied on PET substrate solidified
Film, the cured film is removed from PET substrate, obtain perovskite quantum dot film.
Perovskite quantum dot, perovskite quantum dot are added in dentritic polyamidoamine solution using above-mentioned preparation method
Regularly be scattered in dentritic polyamidoamine side base formed space in, perovskite quantum dot distribution uniformity with it is consistent
Property it is high, avoid the reunion easily occurred between perovskite quantum dot or overlapping phenomenon.
Specifically, when preparing monochromatic perovskite quantum dot film, green glow or feux rouges or blue light perovskite quantum dot are added
Into the solution of dentritic polyamidoamine, it is set regularly to be scattered in the space of the side base of dentritic polyamidoamine formation
In.
When preparing the double-colored perovskite quantum dot film of green glow and feux rouges, respectively in the solution of 2 parts of dentritic polyamidoamines
It is middle addition green glow perovskite quantum dot and feux rouges perovskite quantum dot obtain mixed solution, then will 2 parts of solution mixing and
Obtain mixed solution；And then the light of different colours is sent by luminescence generated by light, and white light is formed after the light mixing of different colours, can
So that the double-colored perovskite quantum dot film of acquisition to be applied in backlight module.
When preparing green glow, feux rouges and the double-colored perovskite quantum dot film of blue light, respectively in 3 parts of dentritic polyamidoamines
Green glow perovskite quantum dot, feux rouges perovskite quantum dot, blue light perovskite quantum dot are added in solution and obtains mixed solution, then
3 parts of solution is obtained by mixing mixed solution；And then the light of different colours is sent by luminescence generated by light, different colours
White light is formed after light mixing, the double-colored perovskite quantum dot film of acquisition can be applied in backlight module.
In preparation method described above, dentritic polyamidoamine solution passes through such as lower section described in the step 1
Method is prepared：
Beta-unsaturated esters monomer is added in diamines monomer and carries out addition reaction；
Diamines monomer is added in the product of the addition reaction and carries out substitution reaction, it is tree-like to obtain 1 generation daiamid
Molecule；
Repeat to add the beta-unsaturated esters monomer and the diamines monomer N- in the 1 generation dentritic polyamidoamine
1 time, N is obtained for dentritic polyamidoamine, wherein N is the integer more than or equal to 2；
Excessive monoamine terminating reaction is added, obtains daiamid tree-like point of the gap length in preset range of side base formation
Son.Wherein, monoamine can be chain alkyl amine, such as the monoamine can be even number for the carbon atom number in six to octadecylamine
Monoamine.
Specifically, added in diamines monomer before the progress addition reaction of beta-unsaturated esters monomer, by the Diamines list
Body is heated, and heating-up temperature is 70-80 DEG C, and the diamines monomer includes：Octadecyl diamines, ethylenediamine, butanediamine are right
One kind in phenylenediamine and naphthylenediamine, the beta-unsaturated esters monomer include 3- phenylpropens acid butyl ester, methyl acrylate.By not
With diamines monomer Micheal addition reactions occur for saturation ester monomer, and diamines monomer herein is preferably alkyldiamine monomer,
, can be as the warp-wise template strand of dentritic polyamidoamine, on the basis of the template strand such as eight to octadecyl diamines
Side base is re-formed, the uniformity and uniformity of the distribution of perovskite quantum dot can be improved.In the product of the addition reaction again
Add excessive diamines monomer progress substitution reaction and obtain alcohol and 1 generation dentritic polyamidoamine, then repeat to add insatiable hunger
N-1 progress substitution reaction of diamines monomer, beta-unsaturated esters herein are added with N-1 progress addition reaction of ester monomer and repetition
The monomer preferably beta-unsaturated esters containing phenyl ring or naphthalene nucleus, such as naphthylenediamine, p-phenylenediamine etc., can be used as daiamid tree
The broadwise template strand of shape molecule, keep the rigidity of structure of dentritic polyamidoamine and macroscopical compactness.As a kind of preferred side
Case, the N are 6, obtain 6 generation dentritic polyamidoamines.
It should be noted that added described in diamines monomer during beta-unsaturated esters monomers carries out addition reaction
A small amount of unsaturated polyester (UP) can be added, amidation process is prevented and generates impurity.Wherein, the unsaturated polyester (UP) can pass through two
First acid and dihydric alcohol condensation obtains, and the binary acid can be phthalic acid, adipic acid.The binary acid when in use, Ke Yiwei
The form of acid anhydrides, such as phthalic anhydride, adipic anhydride.The dihydric alcohol can be propane diols, diglycol.
In preparation method described above, green glow perovskite quantum dot, feux rouges perovskite quantum dot, blue light perovskite amount
Son point is prepared via a method which to obtain respectively：
By organic amine salt and lead bromide mixed dissolution in organic solvent, the solution after dissolving is added to daiamid tree
In shape molecular solution, surface modifier is added, toluene is added, obtains the green glow perovskite quantum dot；
By organic amine salt and lead bromide and lead iodide mixed dissolution in organic solvent, the solution after dissolving is added to poly-
In amide amine dendrimer solution, surface modifier is added, toluene is added, obtains the feux rouges perovskite quantum dot；
By organic amine salt and lead bromide and lead chloride mixed dissolution in organic solvent, the solution after dissolving is added to poly-
In amide amine dendrimer solution, surface modifier is added, toluene is added, obtains the blue light perovskite quantum dot.
Specifically, the organic ammonium salt is methyl bromide amine.The methyl bromide amine is with the lead bromide according to mol ratio
For 3:1-2 is mixed, and the methyl bromide amine is (2-3) according to mol ratio with lead bromide and lead iodide:1:1 is mixed,
The methyl bromide amine is (3-4) according to mol ratio with lead bromide and lead chloride:2:1 is mixed.The organic solvent is two
NMF solution.Volume fraction shared by the dimethyl methyl phthalein amine aqueous solution is 80%.The surface modifier is oleyl amine
And octylame, the mol ratio of the oleyl amine and octylame is 1:(1-4).The addition toluene, specially under 70 DEG C of water bath conditions, adds
Enter toluene and penetrated when exciting light is steady state value with UV Light to system to stop.
In step 2, the described mixed solution is applied on PET substrate is solidified
Obtain cured film, in particular to temperature be 70 DEG C, negative pressure be 0.08Mpa under conditions of, be evaporated the mixed solution
To cured film.
By above-mentioned preparation method, in the gap length that side base is formed in the dentritic polyamidoamine solution of steady state value
Be formed in situ perovskite quantum dot, can obtain particle diameter fix, uniform perovskite quantum dot, i.e. perovskite quantum dot uniformly divides
It is distributed in the space of side base formation of dentritic polyamidoamine.
The third aspect, the embodiments of the invention provide a kind of backlight module, and referring to accompanying drawing 1, the backlight module includes calcium titanium
Ore deposit quantum dot film 2, construction package 1 and backlight and reflector plate 3.
In the both sides covering barrier layer of above-mentioned perovskite quantum dot film, the barrier layer is alumina layer or silica
Perovskite quantum dot film after covering barrier layer, is then added in backlight module by layer.
The excitation of perovskite quantum dot film is high, stability is strong, and due to avoiding between perovskite quantum dot easily
The reunion of appearance or overlapping phenomenon, can avoid different colours perovskite quantum dot absorb light between influence each other,
Loss of the light in material internal is reduced, makes its fluorescence quantum efficiency high.It is adapted to be applied in backlight module.
Fourth aspect, the embodiments of the invention provide a kind of display device, the display device includes above-mentioned third aspect institute
The backlight module of offer.
Illustrate technical scheme below specifically to prepare embodiment, Application Example, characterize embodiment：
In specific examples below, the unreceipted condition person of involved operation, according to normal condition or manufacturer
It is recommended that condition carry out.Raw materials used unreceipted production firm and specification person are can be by the conventional products of acquisition purchased in market.
Prepare embodiment 1
The present embodiment provides a kind of perovskite quantum dot film including the color of red, green, blue three, and the perovskite quantum dot film passes through
Following methods are prepared：
Prepare dentritic polyamidoamine
0.1mol octadecyl diamines is heated to 73 DEG C, then adds 0.095mol 3- phenylpropen acid butyl esters, and
Add a small amount of polypropylene glycol adipate；
0.22mol naphthylenediamine is added, obtains 1 generation dentritic polyamidoamine；
0.1mol 3- phenylpropen acid butyl esters are added in the 1 generation dentritic polyamidoamine；
0.1mol naphthylenediamines are added, obtain 2 generation dentritic polyamidoamines；
Repeat to add 0.1mol 3- phenylpropens acid butyl ester and 0.1mol in the 2 generation dentritic polyamidoamine
Naphthylenediamine 4 times, obtain 6 generation dentritic polyamidoamines；
0.05mol octadecylamine terminating reactions are eventually adding, it is 5 × 10 to obtain concentration-4Mol/L dentritic polyamidoamine
Ethanol solution, and dentritic polyamidoamine side base formed gap length be 4.4nm.
Prepare perovskite quantum dot film
A) it is 3 by mol ratio:It is dissolved in after 2 methyl bromide amine, lead bromide mixing in dimethyl formamide solution, wherein two
Volume fraction shared by NMF solution is 80%, and the solution is added to the dentritic polyamidoamine solution of above-mentioned acquisition
In, add oleyl amine and octylame, the wherein addition total amount of oleyl amine and octylame be 0.02mol, and the mol ratio of oleyl amine and octylame is 1:4,
Toluene is added under 70 DEG C of water bath conditions, green is presented to system color and stops when being steady state value with ultraviolet light exciting light
The toluene is added, the CH that the mass fraction for obtaining being formed in dentritic polyamidoamine solution is 0.85%3NH3PbBr3Amount
Sub- point；This, which is in ultraviolet light exciting light, stops when being steady state value adding toluene, is due to instill the initial stage of toluene, molten
Liquid ultraviolet light exciting light it is possible that multiple luminescence peaks, with reaction carry out peak value can be unified for one it is constant
Peak value, now, quantum dot uniformity are good, and luminescence peak is stable；
B) it is 2 by mol ratio:1:By above-mentioned same process after 1 methyl bromide amine, lead bromide and lead iodide mixing,
Toluene is added under 70 DEG C of water bath conditions, red is presented to system color and stops when being steady state value with ultraviolet light exciting light
The toluene is added, the mass fraction for obtaining being formed in dentritic polyamidoamine solution is 0.45%
CH3NH3PbBr1.5I1.5Quantum dot；
C) it is 3 by mol ratio:2:By above-mentioned same process after 1 methyl bromide amine, lead bromide and lead chloride mixing,
Toluene is added under 70 DEG C of water bath conditions, blueness is presented to system color and stops adding when being steady state value with ultraviolet light exciting light
Enter the toluene, the mass fraction for obtaining being formed in dentritic polyamidoamine solution is 1%CH3NH3PbBrCl2Quantum dot；
D) by the CH being formed in dentritic polyamidoamine solution3NH3PbBr3Quantum dot, CH3NH3PbBr1.5I1.5
Quantum dot and CH3NH3PbBrCl2Quantum dot mixed in equal amounts, obtain the mixed solution of perovskite quantum dot and daiamid；
E) mixed solution is applied on PET substrate, is 70 DEG C in temperature, negative pressure is
The mixed solution is evaporated under conditions of 0.08Mpa, obtains cured film, by the cured film from poly terephthalic acid second two
Removed in alcohol ester substrate, obtain perovskite quantum dot film.
Similar, monochromatic perovskite quantum dot film, the preparation process of double-colored perovskite quantum dot film are similar with said process,
Those skilled in the art may be referred to above-mentioned preparation principle and obtain different types of quantum dot film with method, not do herein
Repeat more.Following preparation embodiment 2-4 is the embodiment for preparing three kinds of monochromatic perovskite quantum dot films.
Prepare embodiment 2
Except not comprising above-mentioned step b), c) and d) in addition to, monochromatic quantum dot is prepared in a manner of similarly to Example 1
Film, i.e. CH3NH3PbBr3Quantum dot film, i.e., green quantum dot film.
Prepare embodiment 3
Except not comprising above-mentioned step a), c) and d) in addition to, monochromatic quantum dot is prepared in a manner of similarly to Example 1
Film, i.e. CH3NH3PbBr1.5I1.5Quantum dot film, i.e. red quantum dot film.
Prepare embodiment 4
Except not comprising above-mentioned step a), b) and d) in addition to, monochromatic quantum dot is prepared in a manner of similarly to Example 1
Film, i.e. CH3NH3PbBrCl2Quantum dot film, i.e., blue quantum dot film.
Application Example 5-8
The present embodiment by by prepare the perovskite quantum dot film 2 prepared by embodiment 1-4 respectively with construction package 1, the back of the body
Light and reflector plate 3 are assembled, with the backlight module applied to liquid crystal display device.Wherein, perovskite quantum dot film is added
Back light module unit structure as shown in Figure 1.
Characterize embodiment 9
Three kinds of quantum dot films that the present embodiment will be obtained by preparing embodiment 2-4, i.e. CH3NH3PbBr3Quantum dot film,
CH3NH3PbBr1.5I1.5Quantum dot film, CH3NH3PbBrCl2Quantum dot film carries out ultraviolet excitation respectively, obtains the light in accompanying drawing 2
Photoluminescence spectrogram.And the fluorescence quantum efficiency of three kinds of quantum dot films is measured respectively, measuring method is the light for using 365nm to be sharp
It is luminous, model FluoroMax-4 XRF (producer HORIBA) is used in model EVERFINE-0.5m product
Its absorption spectrum and exciting light spectrum are tested in bulb separation (distance light), and fluorescence quantum efficiency is obtained by following formula：Fluorescent quantum is imitated
The light quantity subnumber of light quantity subnumber/absorption of rate (η)=transmitting.
By accompanying drawing 2 it can be seen that CH3NH3PbBr3Quantum dot film appearance between 500-600nm, illustrates it in ultraviolet light
Green glow can be sent by exciting, and the fluorescence quantum efficiency for determining its green glow is 40.6%.CH3NH3PbBr1.5I1.5Quantum dot film exists
Appearance between 600-700nm, illustrate that it can send feux rouges in ultraviolet excitation, and the fluorescence quantum efficiency for determining its feux rouges is
65.8%.CH3NH3PbBrCl2Quantum dot film appearance between 400-500nm, illustrate that it can send blue light in ultraviolet excitation,
And the fluorescence quantum efficiency for determining its blue light is 10.1%.It in summary it can be seen, under ultraviolet excitation, for a variety of colors
Quantum dot film fluorescence quantum efficiency it is high.
Prepare comparative example 1
(1) it is 3 by mol ratio:2.5L dimethyl formyls are dissolved in after the common 0.5mol mixing of 2 methyl bromide amine, lead bromide
In amine, add oleyl amine and octylame and form precursor liquid, the wherein addition total amount of oleyl amine and octylame is 0.06mol, oleyl amine and octylame
Mol ratio is 1:4,
Then above-mentioned 0.5mol precursor liquids are added dropwise in 2.5L toluene and stirred, obtain CH3NH3PbBr3Quantum dot concentration
For 0.05mol/L solution,
The solution of the acquisition is spin-coated on PET substrate, can be obtained after drying
CH3NH3PbBr3Quantum dot film.
(2) it is 2 by mol ratio:1:1 methyl bromide amine, lead bromide and the common 0.4mol of lead iodide is dissolved in 2.5L after mixing
In dimethylformamide, add oleyl amine and octylame forms precursor liquid, the wherein addition total amount of oleyl amine and octylame is 0.04mol, oil
The mol ratio of amine and octylame is 1:3
Then above-mentioned 0.4mol precursor liquids are added dropwise in 2.5L toluene and stirred, obtain CH3NH3PbBr1.5I1.5Quantum dot
Concentration is 0.04mol/L solution,
The solution of the acquisition is spin-coated on PET substrate, can be obtained after drying
CH3NH3PbBr1.5I1.5Quantum dot film.
(3) it is 3 by mol ratio:2:2.5L bis- is dissolved in after 1 methyl bromide amine, lead bromide and the common 0.6mol mixing of lead chloride
In NMF, add oleyl amine and octylame and form precursor liquid, the wherein addition total amount of oleyl amine and octylame is 0.05mol, oleyl amine
Mol ratio with octylame is 1:4,
Then above-mentioned 0.6mol precursor liquids are added dropwise in 2.5L toluene and stirred, obtain CH3NH3PbBrCl2Quantum dot is dense
The solution for 0.06mol/L is spent,
The solution of the acquisition is spin-coated on PET substrate, can be obtained after drying
CH3NH3PbBrCl2Quantum dot film.
CH is respectively obtained by above-mentioned preparation process3NH3PbBr3Quantum dot film, CH3NH3PbBr1.5I1.5Quantum dot film and
CH3NH3PbBrCl2Quantum dot film.
Comparison study example 2
The present embodiment by by prepare the perovskite quantum dot film 2 prepared by comparative example 1 respectively with construction package 1, backlight
And reflector plate 3 is assembled, with the backlight module applied to liquid crystal display device.Wherein, perovskite quantum dot film 2 is
CH3NH3PbBr3Quantum dot film, CH3NH3PbBr1.5I1.5Quantum dot film and CH3NH3PbBrCl2This quantum dot film in 3 of quantum dot film
Formed after fitting together such as the overall structure of the perovskite quantum dot film 2 in Fig. 1.
Characterize comparative example 3
The present embodiment is by by preparing the CH obtained in comparative example 13NH3PbBr3Quantum dot film, CH3NH3PbBr1.5I1.5Amount
Son point film and CH3NH3PbBrCl2Quantum dot film measures its fluorescence quantum efficiency respectively, and its measuring method is with characterizing in embodiment 9
It is identical.
CH3NH3PbBr3The fluorescence quantum efficiency of quantum dot film is 30%, CH3NH3PbBr1.5I1.5The fluorescence volume of quantum dot film
Sub- efficiency is 50%, CH3NH3PbBrCl2The fluorescence quantum efficiency of quantum dot film is 8%.
To sum up, the result for characterizing embodiment 9 and sign comparative example 3 is compared as can be seen that being prepared by the present invention
The CH that embodiment 2 obtains3NH3PbBr3The fluorescence quantum efficiency of quantum dot film is higher than the CH in comparative example3NH3PbBr3Quantum dot film
Fluorescence quantum efficiency,
The CH obtained by present invention preparation embodiment 33NH3PbBr1.5I1.5The fluorescence quantum efficiency of quantum dot film higher than pair
CH in ratio3NH3PbBr1.5I1.5The fluorescence quantum efficiency of quantum dot film,
The CH obtained by present invention preparation embodiment 43NH3PbBrCl2The fluorescence quantum efficiency of quantum dot film is higher than contrast
CH in example3NH3PbBrCl2The fluorescence quantum efficiency of quantum dot film.
Above-mentioned all optional technical schemes, any combination can be used to form the alternative embodiment of the disclosure, herein no longer
Repeat one by one.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.
Claims (10)
1. a kind of perovskite quantum dot film, it is characterised in that the quantum dot film includes：Perovskite quantum dot and daiamid tree
Shape molecule；
In the space that the side base that the perovskite quantum dot is scattered in the dentritic polyamidoamine is formed.
2. quantum dot film according to claim 1, it is characterised in that the dentritic polyamidoamine is by diamines monomer
React to obtain with beta-unsaturated esters.
3. quantum dot film according to claim 1, it is characterised in that what the side base of the dentritic polyamidoamine was formed
Gap length is 2-8nm.
4. quantum dot film according to claim 1, it is characterised in that the perovskite quantum dot includes green glow perovskite amount
At least one of sub- point, feux rouges perovskite quantum dot, blue light perovskite quantum dot, and the green glow perovskite quantum dot, institute
State feux rouges perovskite quantum dot, the blue light perovskite quantum dot is respectively CH3NH3PbBr3、CH3NH3PbBr1.5I1.5With
CH3NH3PbBrCl2。
5. a kind of preparation method of perovskite quantum dot film, it is characterised in that methods described includes：
Step 1, addition perovskite quantum dot obtains mixed solution in the solution of dentritic polyamidoamine, wherein described poly-
There is the space that can accommodate the perovskite quantum dot in amide amine dendrimer；
Step 2, the mixed solution be applied on PET substrate solidified to obtain cured film,
The cured film is removed from PET substrate, obtains perovskite quantum dot film.
6. according to the method for claim 5, it is characterised in that dentritic polyamidoamine solution described in the step 1
It is prepared via a method which to obtain：
Beta-unsaturated esters monomer is added in diamines monomer and carries out addition reaction；
Diamines monomer is added in the product of the addition reaction and carries out substitution reaction, obtains 1 generation dentritic polyamidoamine；
Repeat to add the beta-unsaturated esters monomer and diamines monomer N-1 times in the 1 generation dentritic polyamidoamine,
N is obtained for dentritic polyamidoamine, wherein N is the integer more than or equal to 2；
Monoamine terminating reaction is added, obtains dentritic polyamidoamine of the gap length in preset range of side base formation.
7. according to the method for claim 6, it is characterised in that the diamines monomer includes：Octadecyl diamines, second two
One kind in amine, butanediamine, p-phenylenediamine and naphthylenediamine, the beta-unsaturated esters monomer include 3- phenylpropen acid butyl esters.
8. according to the method for claim 6, it is characterised in that the N is 6.
9. a kind of backlight module, it is characterised in that the backlight module includes the perovskite amount described in claim any one of 1-4
Son point film.
10. a kind of display device, it is characterised in that the display device includes the backlight module described in claim 9.
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