CN109994655A - Composite quantum dot, quantum dot solid film and its application - Google Patents
Composite quantum dot, quantum dot solid film and its application Download PDFInfo
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- CN109994655A CN109994655A CN201711482034.9A CN201711482034A CN109994655A CN 109994655 A CN109994655 A CN 109994655A CN 201711482034 A CN201711482034 A CN 201711482034A CN 109994655 A CN109994655 A CN 109994655A
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Abstract
The present invention provides a kind of composite quantum dots, the composite quantum dot is the quantum dot of halide anions dressing agent modification, including quantum dot particle, and it is incorporated in the halide anions dressing agent of the quantum dot particle surface, the halide anions dressing agent is [AMXm+n+1]n‑, wherein M is selected from one of Pb, Cd, Zn, In, Fe, Sb, and X is selected from one of Cl, Br, I, A CH3NH3, m is the valence number of M, and n is the valence mumber of the halide anions dressing agent, and m is 2 or 3, when m is 2, n 1；When m is 3, n is 1 or 2；[the AMXm+n+1]n‑With perovskite structure.The composite quantum dot as characterized above, can be improved the fluorescence intensity of quantum dot, while reduce the transfer of the exciton energy between quantum dot and quantum dot.
Description
Technical field
The invention belongs to field of display technology more particularly to a kind of composite quantum dots, quantum dot solid film and its application.
Background technique
Quantum dot has biggish specific surface area, this also means that the electrical and optical properties of quantum dot by surface electronic
State is dominate, especially the electronic state of band gap, therefore understands that and controlling the electronic state of quantum dot surface and utilizing these electricity
Learning characteristic and making some applications is an important research topic.
The electrical properties of colloidal semiconductor quantum dot are more important.By the ligand molecular on Colloidal Quantum Dots surface, use
The type of ligand contained by the Colloidal Quantum Dots surface of different method preparation synthesis is also different, but these ligands are to Colloidal Quantum Dots
Dispersibility and surface charge passivation it is all more crucial.When preparing photoelectric device using Colloidal Quantum Dots, need colloid amount
Son point is prepared into quantum dot solid film, meanwhile, the insulation long-chain Ligand of quantum dot solid film can also be exchanged according to device requirement
At short chain ligand (electrical conductivity that short chain ligand can significantly improve quantum dot solid film), the biography of Lai Gaishan quantum solid point state film
The property led.The past research of influence of the ligand to quantum dot solid film is concentrated mainly in the chemical property of quantum dot surface ligand
The length of the surface binding characteristic of ligand, ligand molecular (functional group of ligand) usually utilizes short chain in existing technology
Organic ligand (such as thio-alcohol ligand) carries out ligand exchange, however the quantum dot after swapping using such ligand to quantum dot
The defect that usually will cause quantum dot surface increases, and reduces the fluorescence intensity of quantum solid point state film, while can also reduce quantum dot
Stability.Especially Exciton Bohr Radius be greater than particle size a kind of quantum dot, due to quantum dot exciton occur energy
Transfer, when being prepared into quantum dot solid film the fluorescence intensity of corresponding quantum dot solid film quench do not have it is more serious.It is this in order to change
Phenomenon, at present mainly by reducing the energy between quantum dot and quantum dot in quantum dot light emitting layer outgrowth thicker shell
Transfer, but the shell thickeied is unfavorable for the injection of exciton again, it is very big to the influential effect of device.
Summary of the invention
The purpose of the present invention is to provide a kind of composite quantum dots and preparation method thereof, it is intended to solve existing quantum dot table
The short chain organic ligand in face reduces the problem of fluorescence intensity and stability of quantum solid point state film.
Another object of the present invention is to provide a kind of the quantum dot solid film containing above-mentioned composite quantum dot and its preparation
Method.
A further object of the present invention is to provide a kind of luminescent devices containing above-mentioned composite quantum dot.
A kind of composite quantum dot, the composite quantum dot are the quantum dot of halide anions dressing agent modification, including amount
Son point particle, and it is incorporated in the halide anions dressing agent of the quantum dot particle surface, the halide anions are repaired
Decorations agent is [AMXm+n+1]n-, wherein M is selected from one of Pb, Cd, Zn, In, Fe, Sb, and X is selected from one of Cl, Br, I, and A is
CH3NH3, m MXmIn corresponding valence number, n is the valence mumber of the halide anions dressing agent, the and [AMXm+n+1]n-
With perovskite structure.
Correspondingly, a kind of preparation method of composite quantum dot, comprising the following steps:
By halide AMXm+1It is dispersed in polar solvent, obtains halide anions dressing agent, the halide AMXm+1
For the halide with perovskite structure, the halide anions dressing agent is [AMXm+n+1]n-, wherein M be selected from Pb, Cd,
One of Zn, In, Fe, Sb, X are selected from one of Cl, Br, I, A CH3NH3, m is the valence number of M, and n is the halogenation
The valence mumber that anion modified dose of object, and m is 2 or 3, when m is 2, n 1；When m is 3, n is 1 or 2；The polar solvent is
The halide can be made to ionize the organic solvent to form halide anions and halide cation；
The quantum dot that oil-soluble ligand is contained on surface is provided, the quantum dot and the halide anions dressing agent are mixed
Exchange reaction occurs for the ligand of conjunction processing, the halide anions dressing agent and the quantum dot surface, and halogenation is prepared
The quantum dot of anion modified dose of object modification.
And a kind of quantum dot solid film, the quantum dot solid film contain above-mentioned composite quantum dot or the quantum
Point solid film contains the composite quantum dot that the above method prepares.
Correspondingly, a kind of preparation method of quantum dot solid film, comprising the following steps:
The dispersion liquid of composite quantum dot is provided, in the dispersion liquid of the composite quantum dot, composite quantum dot is above-mentioned answers
Close quantum dot；
The dispersion liquid of the composite quantum dot is deposited on substrate, is made annealing treatment, is obtained quantum dot solid film.
And a kind of luminescent device, including anode and cathode, and the amount of setting between the anode and the cathode
Son point luminescent layer, the quantum dot light emitting layer contain composite quantum dot, and the composite quantum dot is halide anions dressing agent
The quantum dot of modification, including quantum dot particle, and it is incorporated in the halide anions dressing agent of the quantum dot particle surface,
The halide anions dressing agent is [AMXm+n+1]n-, wherein M is selected from one of Pb, Cd, Zn, In, Fe, Sb, and X is selected from
One of Cl, Br, I, A CH3NH3, m is the valence number of M, and n is the valence mumber of the halide anions dressing agent, and m is
2 or 3, when m is 2, n 1；When m is 3, n is 1 or 2；[the AMXm+n+1]n-With perovskite structure.
Composite quantum dot provided by the invention, including quantum dot particle, and it is incorporated in the quantum dot particle surface
The halide anions dressing agent of specific structure.The composite quantum dot as characterized above, can be improved the glimmering of quantum dot
Luminous intensity, while reducing the transfer of the exciton energy between quantum dot and quantum dot.
Surface need to only be contained the quantum dot and halogen of oil-soluble ligand by the preparation method of composite quantum dot provided by the invention
Anion modified dose of compound mixing makes halide anions dressing agent and oil-soluble ligand that ligand exchange occur, and then in quantum
Point particle surface combination halide anions dressing agent, obtains making the electronegative composite quantum dot of quantum dot particle.This method letter
It is single, it is easily operated, and repeatability is strong.
Quantum dot solid film provided by the invention, containing above-mentioned composite quantum dot, the composite quantum dot amount of can be improved
The fluorescence intensity of son point, while the transfer of the exciton energy between quantum dot and quantum dot is reduced, and then make the quantum dot solid-state
Film fluorescence intensity with higher and stability.
The preparation method of quantum dot solid film provided by the invention, due to containing above-mentioned composite quantum dot, between quantum dot
Be able to maintain it is good uniformly dispersed, therefore, can will the composite quantum dot dispersion after be deposited directly to substrate surface i.e.
Electro-deposition preparation can be achieved.This method is simple, easily operated, and repeatability is strong.
Luminescent device provided by the invention contains above-mentioned composite quantum dot in the luminescent layer, can effectively improve luminous
The fluorescence intensity and device stability of device, and then improve device efficiency.
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.
The embodiment of the invention provides a kind of composite quantum dot, the composite quantum dot is that halide anions dressing agent is repaired
The quantum dot of decorations, including quantum dot particle, and it is incorporated in the halide anions dressing agent of the quantum dot particle surface, institute
Stating halide anions dressing agent is [AMXm+n+1]n-, wherein M is selected from one of Pb, Cd, Zn, In, Fe, Sb, X be selected from Cl,
One of Br, I, A CH3NH3, m be M valence number, n be the halide anions dressing agent valence mumber, and m be 2 or
3, when m is 2, n 1；When m is 3, n is 1 or 2；[the AMXm+n+1]n-With perovskite structure.Specifically, Pb exists
[AMXm+n+1]n-In with Pb2+Form exist, Cd is in [AMXm+n+1]n-In with Cd2+Form exist, Zn is in [AMXm+n+1]n-In
With Zn2+Form exist, In is in [AMXm+n+1]n-In with In2+Form exist, Fe is in [AMXm+n+1]n-In can be with Fe2+Shape
Formula exists, can also be with Fe3+Form exist；Sb is in [AMXm+n+1]n-In with Sb2+Form exist.
Composite quantum dot provided in an embodiment of the present invention, including quantum dot particle, and it is incorporated in the quantum dot particle
The halide anions dressing agent of the specific structure on surface.The composite quantum dot as characterized above, can be improved quantum
The fluorescence intensity of point, while reducing the transfer of the exciton energy between quantum dot and quantum dot.
Specifically, the selection of the quantum dot particle does not limit strictly in the embodiment of the present invention, can be selected from CdSe,
PbSe、PbS、PbSe/CdSe、PbS/CdS、AgS、HgS、CdTe、CdTe/CdS、CdTe/CdZnS、InP、InP/ZnS、InP/
ZnSeS.The launch wavelength range of above-mentioned quantum dot is in visible region.Further, the size model of the quantum dot particle
Enclose 1~10nm, the Bohr radius of the quantum dot (10~50nm, the value of the Bohr radius of quantum dot specifically correspond to it is above-mentioned not
Congener quantum dot, and discontinuous value) it is greater than the particle size of quantum dot.
The embodiment of the present invention is by making quantum dot in the quantum dot particle surface combination halide anions dressing agent
Grain takes negative electricity, and which can not only guarantee the fluorescence intensity of quantum dot, but also can reduce between quantum dot and quantum dot
Exciton energy transfer.
Specifically, the halide anions dressing agent is [AMXm+n+1]n-, wherein M is selected from Pb, Cd, Zn, In, Fe, Sb
One of, X is selected from one of Cl, Br, I, A CH3NH3, m is halide MX of the M in formationmIn corresponding valence number,
N is the valence mumber of the halide anions dressing agent, the and [AMXm+n+1]n-With perovskite structure.Due to the halide
With perovskite structure, as the band-gap energy that the increase band gap of the number of plies is gradually reduced its corresponding single layer is greater than 1.6eV (transmitted wave
Long 900nm), and the quanta point material that Exciton Bohr Radius is greater than particle size belongs to near-infrared quantum dots material, corresponding band
Gap energy is less than 1.6eV (launch wavelength 900nm).Therefore, the amount of can be improved after changing class quanta point material is modified using halide
The fluorescence intensity of son point simultaneously, and can reduce the transfer of the exciton energy between quantum dot and quantum dot.
Specifically,Wherein, n is preferably 1 or 2.By
This obtained halide anions, can the ligand effectively with the quantum dot swap, and be firmly bonded to quantum dot
Grain surface, keeps quantum dot negatively charged.And the halide anions belong to L-type ligand, only in conjunction with a metallic atom, because
Quantum dot particle quantum dot particle, can be crosslinked by this to avoid dressing agent, lower the reunion between quantum dot.
Composite quantum dot described in the embodiment of the present invention can be prepared by following methods.
Correspondingly, the embodiment of the invention also provides a kind of preparation methods of composite quantum dot, comprising the following steps:
S01. by halide AMXm+1It is dispersed in polar solvent, obtains halide anions dressing agent, the halide
AMXm+1For the halide with perovskite structure, the halide anions dressing agent is [AMXm+n+1]n-, wherein M is selected from
One of Pb, Cd, Zn, In, Fe, Sb, X are selected from one of Cl, Br, I, A CH3NH3, m is the valence number of M, and n is institute
The valence mumber of halide anions dressing agent is stated, and m is 2 or 3, when m is 2, n 1；When m is 3, n is 1 or 2；The polarity
Solvent is that the halide can be made to ionize the organic solvent to form halide anions and halide cation；
S02., the quantum dot for containing oil-soluble ligand in surface is provided, the quantum dot and the halide anions are modified
Exchange reaction occurs for the ligand of agent mixed processing, the halide anions dressing agent and the quantum dot surface, is prepared
The quantum dot of halide anions dressing agent modification.
Surface need to only be contained the quantum of oil-soluble ligand by the preparation method of composite quantum dot provided in an embodiment of the present invention
Point is mixed with halide anions dressing agent, makes halide anions dressing agent and oil-soluble ligand that ligand exchange occur, in turn
In quantum dot particle surface combination halide anions dressing agent, obtain making the electronegative composite quantum dot of quantum dot particle.It should
Method is simple, easily operated, and repeatability is strong.
Specifically, in above-mentioned steps S01, it is described can sufficiently to dissolve for dispersing the polar solvent of the halide
Halide, and the halide is made to ionize the organic solvent to form halide anions and halide cation, that is, have higher
The organic solvent of dielectric constant.Preferably, alms giver's number (DN) of the polar solvent is 10-50, to guarantee filling for halide
Divide ionization.On above-mentioned preferred case basis, boundary's electric constant of the polar solvent increases, and corresponding polarity also will increase,
Electron donation is stronger, therefore can preferably promote the halide to ionize.It is specific preferred, the organic solvent choosing
From at least one in methylformamide, propylene carbonate, dimethylformamide, acetonitrile, dimethyl sulfoxide, methanol, ethyl alcohol, propyl alcohol
Kind, be conducive to the halide and ionization generation halide anions and halide cation occurs.
In above-mentioned steps S02, the quantum dot that oil-soluble ligand is contained on surface is provided, wherein the oil-soluble ligand is selected from
At least one of oleic acid (OA), oleyl amine (OAm) trioctylphosphine phosphorus (TOP), trioctylphosphine oxygen phosphorus (TOPO).Above-mentioned oil-soluble ligand knot
Structure is R1-COOH、R2-NH2、R3-P、R4- P=O, wherein R1、R2、R3、R4For alkyl, with the zwitterion of quantum dot particle
Binding ability is weaker, when standing time is longer in air, is easy to fall off.Therefore, it is necessary to by the quantum of the oil-soluble ligand
The surface ligand of point is replaced.
The preparation method of the quantum dot containing oil-soluble ligand is prepared using conventional oily phase method.Contain by described in
There is the quantum dot of oil-soluble ligand to obtain quantum dot dispersion liquid using organic solvent dispersion.Preferably, it is selected from just with organic solvent
At least one of hexane, chloroform, chlorobenzene, toluene, but not limited to this.Preferred solvent is conducive to the equal of oil-soluble quantum dot
Even dispersion.Preferably, the concentration of the quantum dot dispersion liquid is 10~60mg/ml, and excessive concentration is unfavorable for halide anions
It is modified.
By the quantum dot and the halide anions dressing agent mixed processing, the halide is electric in polar solvent
Halide anions from generation can effectively be exchanged with the surface ligand of quantum dot, so with the metal in quantum dot
Atom combines, and is securely adsorbed on quantum dot surface, keeps the quantum dot surface negatively charged.By the quantum dot and the halogen
In the step of anion modified dose of mixed processing of compound, according to the quality of the quantum dot and the halide anions dressing agent
Molar ratio be 100mg:(0.2~1mmol) ratio mixed processing.The suitable halide anions dressing agent and the amount
The ratio of son point, can make the halide anions dressing agent have suitable distribution density in the quantum dot, favorably
It is sufficiently modified in quantum dot.
The embodiment of the present invention prepares the quantum dot of halide anions dressing agent modification, carries out in an inert atmosphere, reacts
Temperature is 30-60 DEG C, reaction time 1-10h.Further, the quantum dot obtained halide anions dressing agent modified
After being centrifuged by precipitating reagent, it is dried.The quantum dot of obtained halide anions dressing agent modification, preferably divides
Be dispersed in methylformamide, propylene carbonate, dimethylformamide, acetonitrile, dimethyl sulfoxide, methanol, ethyl alcohol, in propyl alcohol at least
In one kind, composite quantum dot solution is formed.
And the embodiment of the invention provides a kind of quantum dot solid film, the quantum dot solid film contains above-mentioned answer
It closes quantum dot or the quantum dot solid film contains the composite quantum dot that the above method prepares.
Quantum dot solid film provided in an embodiment of the present invention, containing above-mentioned composite quantum dot, the composite quantum dot can
The fluorescence intensity of quantum dot is improved, while reducing the transfer of the exciton energy between quantum dot and quantum dot, and then make the quantum
Point solid film fluorescence intensity with higher and stability.
Preferably, the quantum dot solid film with a thickness of 5-60nm.
Correspondingly, the embodiment of the invention also provides a kind of preparation methods of quantum dot solid film, comprising the following steps:
The dispersion liquid of composite quantum dot is provided, in the dispersion liquid of the composite quantum dot, composite quantum dot is above-mentioned answers
Close quantum dot；
The dispersion liquid of the composite quantum dot is deposited on substrate, is made annealing treatment, is obtained quantum dot solid film.
The preparation method of quantum dot solid film provided in an embodiment of the present invention, due to containing above-mentioned composite quantum dot, quantum
Point between be able to maintain it is good uniformly dispersed, therefore, can will the composite quantum dot dispersion after be deposited directly to substrate
Electro-deposition preparation can be realized in surface.This method is simple, easily operated, and repeatability is strong.
Wherein, the composite quantum dot is as described above, and in order to save length, details are not described herein again.The composite quantum
The concentration of the dispersion liquid of point is preferably 5-30mg/ml.
The substrate can be conventional substrate, be also possible to deposit the function substrate of other materials, such as anode grid substrate
Or cathode base.Deposition method of the embodiment of the present invention includes but is not limited to printing, printing, electro-deposition etc..Further, to deposition
The substrate of the dispersion liquid of good composite quantum dot is made annealing treatment, and the temperature of annealing is 60-150 DEG C, time 30-
60min。
And the embodiment of the invention also provides a kind of luminescent devices, including anode and cathode, and are arranged in the sun
Quantum dot light emitting layer between pole and the cathode, the quantum dot light emitting layer contain composite quantum dot, the composite quantum dot
For the quantum dot of halide anions dressing agent modification, including quantum dot particle, and it is incorporated in the quantum dot particle surface
Halide anions dressing agent, the halide anions dressing agent be [AMXm+n+1]n-, wherein M be selected from Pb, Cd, Zn,
One of In, Fe, Sb, X are selected from one of Cl, Br, I, A CH3NH3, m is the valence number of M, and n is the halide yin
The valence mumber of ion modification agent, and m is 2 or 3, when m is 2, n 1；When m is 3, n is 1 or 2；[the AMXm+n+1]n-Have
Perovskite structure.
Luminescent device provided in an embodiment of the present invention contains above-mentioned composite quantum dot in the luminescent layer, can effectively mention
The fluorescence intensity and device stability of high luminescent device, and then improve device efficiency.
Preferably, the luminescent device further includes electronic work ergosphere, at least one layer in the functional layer of hole, the electronic work
Ergosphere is arranged between the cathode and the hair layer, including at least one layer in electron injecting layer and electron transfer layer；It is described
Hole functional layer is arranged between the anode and the luminescent layer, including at least one in hole injection layer and hole transmission layer
Layer.
It is illustrated combined with specific embodiments below.
Embodiment 1
A kind of preparation method of composite quantum dot, comprising the following steps:
Preparing for S1.PbS quantum dot is as follows:
S11. plumbi oleas { Pb (OA)2Precursor preparation: take the lead acetate trihydrate of 0.6mmol, 2ml oleic acid (OA),
10ml 18 dilute (ODE) is added in three-necked flask, and first room temperature is vented 20min, and then temperature is increased to 150 DEG C of stirring 30min
Temperature is reduced to 120 DEG C afterwards.
S12. the preparation of sulphur (S) precursor: claim the S of 4mmol to be added in the trioctylphosphine oxygen phosphorus (TOP) of 6ml, be heated to
170 DEG C of maintenance 30min, then cool to 140 DEG C.
S13. after the mixeding liquid temperature in S11 being increased to 150 DEG C, sulphur (S) precursor of 2ml is taken to be rapidly injected flask
Interior reaction 10min, rapidly take out heating mantle liquid temperature to be mixed is cold go to room temperature after by addition extractant and precipitating reagent carry out
Centrifuge separation cleaning obtains oil-soluble PbS near-infrared quantum dots and is dried, then by dry oil-soluble quantum dot point
It is dispersed in the solution for being prepared into that concentration is 30mg/ml in n-hexane, the ligand on surface is oleic acid (OA).
S2.CH3NH3PbI3Preparing for modification PbS quantum surface is as follows:
S21. the CH of 0.5mmol is taken3NH3PbI3It is dispersed in the methylformamide of 5ml, strong stirring is until CH3NH3PbI3
All dissolution is spare.
S22. the PbS quantum 100mg prepared in S21 is taken to be dispersed in spare in the n-hexane of 3ml.
S23. the solution in S21 and S22 is mixed into stirring 3h strongly under an inert gas.
S24. precipitating reagent is added into S23, and dry be prepared containing CH is centrifuged3NH3PbCl4 -Or
CH3NH3PbCl5 2-The quantum dot of modification.
Embodiment 2
A kind of CH3NH3PbCl4 -Or CH3NH3PbCl5 2The preparation method of the PbS quantum solid film of modification, including following step
It is rapid:
100mg embodiment 1 is taken to prepare containing CH3NH3PbCl4 -Or CH3NH3PbCl5 2The PbS quantum of modification is dispersed in
It is dissolved in the methylformamide of 10ml spare；One layer of quantum dot solid film is prepared by the way of printing；To the quantum prepared
Point solid film uses 80 DEG C of annealing 30min.
Embodiment 3
A kind of preparation method of QLED device, comprising the following steps:
PEDPOT:PSS (AI4083) solution is applied in the way of printing after 0.45 micron of filter is filtered
Then cloth is using 150 DEG C of annealing 15min in the ito glass on piece cleaned up, prepare hole injection layer；Using same side
Formula prints hole transmission layer and electronic barrier layer；
Quantum dot light emitting layer is prepared according to the method for embodiment 2, deposits electron transfer layer by the way of printing coating, most
Afterwards in high vacuum 2x104The aluminium electrode of 150nm thickness is deposited under Pa pressure by way of a mask plate is steamed using heat, preparation
Device area is 4cm2。
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 preparation method of composite quantum dot, which comprises the following steps:
By halide AMXm+1It is dispersed in polar solvent, obtains halide anions dressing agent, the halide AMXm+1For tool
There is the halide of perovskite structure, the halide anions dressing agent is [AMXm+n+1]n-, wherein M be selected from Pb, Cd, Zn,
One of In, Fe, Sb, X are selected from one of Cl, Br, I, A CH3NH3, m is the valence number of M, and n is the halide yin
The valence mumber of ion modification agent, and m is 2 or 3, when m is 2, n 1；When m is 3, n is 1 or 2；The polar solvent is can
The halide is set to ionize the organic solvent to form halide anions and halide cation；
Surface is provided and contains the quantum dot of oil-soluble ligand, by the quantum dot at the halide anions dressing agent mixing
Exchange reaction occurs for the ligand of reason, the halide anions dressing agent and the quantum dot surface, and halide yin is prepared
The quantum dot of ion modification agent modification.
2. the preparation method of composite quantum dot as described in claim 1, which is characterized in that alms giver's number of the polar solvent is
10-50。
3. the preparation method of composite quantum dot as claimed in claim 2, which is characterized in that the organic solvent is selected from methyl first
At least one of amide, propylene carbonate, dimethylformamide, acetonitrile, dimethyl sulfoxide, methanol, ethyl alcohol, propyl alcohol.
4. the preparation method of composite quantum dot as described in any one of claims 1-3, which is characterized in that by the quantum dot with
In the step of halide anions dressing agent mixed processing, according to the quantum dot and the halide anions dressing agent
Quality molar ratio be 100mg:(0.2~1mmol) ratio mixed processing.
5. the preparation method of composite quantum dot as described in any one of claims 1-3, which is characterized in that the oil-soluble ligand
Selected from least one of oleic acid, oleyl amine, trioctylphosphine phosphorus, trioctylphosphine oxygen phosphorus.
6. a kind of composite quantum dot, which is characterized in that the composite quantum dot is the quantum of halide anions dressing agent modification
Point, including quantum dot particle, and it is incorporated in the halide anions dressing agent of the quantum dot particle surface, the halide
Anion modified dose is [AMXm+n+1]n-, wherein M is selected from one of Pb, Cd, Zn, In, Fe, Sb, and X is in Cl, Br, I
One kind, A CH3NH3, m is the valence number of M, and n is the valence mumber of the halide anions dressing agent, and m is 2 or 3, when m is 2
When, n 1；When m is 3, n is 1 or 2, [the AMXm+n+1]n-With perovskite structure.
7. a kind of quantum dot solid film, which is characterized in that the quantum dot solid film contains composite quantum as claimed in claim 6
Point.
8. quantum dot solid film as claimed in claim 7, which is characterized in that the quantum dot solid film with a thickness of 5-
60nm。
9. a kind of preparation method of quantum dot solid film, which comprises the following steps:
The dispersion liquid of composite quantum dot is provided, in the dispersion liquid of the composite quantum dot, composite quantum dot is described in claim 6
Composite quantum dot；
The dispersion liquid of the composite quantum dot is deposited on substrate, is made annealing treatment, is obtained quantum dot solid film.
10. a kind of luminescent device, which is characterized in that including anode and cathode, and setting the anode and the cathode it
Between quantum dot light emitting layer, the quantum dot light emitting layer contains composite quantum dot, and the composite quantum dot is halide anions
The quantum dot of dressing agent modification, including quantum dot particle, and it is incorporated in the halide anions of the quantum dot particle surface
Dressing agent, the halide anions dressing agent are [AMXm+n+1]n-, wherein M in Pb, Cd, Zn, In, Fe, Sb one
Kind, X is selected from one of Cl, Br, I, A CH3NH3, m is the valence number of M, and n is the valence of the halide anions dressing agent
Number, and m is 2 or 3, when m is 2, n 1；When m is 3, n is 1 or 2；[the AMXm+n+1]n-With perovskite structure.
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