CN107369774B - A kind of compound multiple quantum wells LED of perovskite and preparation method thereof - Google Patents
A kind of compound multiple quantum wells LED of perovskite and preparation method thereof Download PDFInfo
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- CN107369774B CN107369774B CN201710563461.3A CN201710563461A CN107369774B CN 107369774 B CN107369774 B CN 107369774B CN 201710563461 A CN201710563461 A CN 201710563461A CN 107369774 B CN107369774 B CN 107369774B
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- H10K50/00—Organic light-emitting devices
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Abstract
A kind of compound multiple quantum wells LED of perovskite of present invention offer and preparation method thereof.The compound multiple quantum wells LED of perovskite provided by the invention includes the substrate set gradually, electron injecting layer, luminescent layer, hole injection layer and electrode, and the luminescent layer includes CH3NH3PbBr3Film and it is embedded in the CH3NH3PbBr3CH in film3NH3PbI3Quantum dot.The present invention is by the perovskite continuous phase CH of wider band gap3NH3PbBr3The perovskite quantum dot CH of narrow band gap is inlayed in film3NH3PbI3, due to high electronics, hole mobility and the carrier diffusion length of perovskite, in addition the multiple quantum wells that the quantum effect of quantum dot and the two are formed, carrier are continuously preferentially oriented to the Quantum Well recombination luminescence of low potential barrier；In addition, Lattice Matching is preferable between the perovskite of different component, and it is few compared to other quantum well structure boundary defects, effectively reduce non-radiative recombination center.
Description
Technical field
The present invention relates to electronic component preparing technical field, more particularly to the compound multiple quantum wells LED of a kind of perovskite and its
Preparation method.
Background technology
In recent years, organic inorganic hybridization perovskite (CH3NH3PbX3, X=Cl, I, Br) and material is because of its carrier diffusion distance
Long, directly band system width, absorption line width and bandwidth is sent out from blue light to advantageous characteristics such as near-infrared continuously adjustables in semiconductor
The application of fields of light devices causes the extensive concern of people.Especially its preparation process does not need large-scale vacuum or high temperature is set
It is standby, there is the huge market advantage in terms of reducing cost.
On the basis of perovskite solar cell is studied, the research and development of perovskite LED also enter the new stage.From 2013
It rising, perovskite solar battery technology marches toward Rapid development stage,Seminar is prepared using two step sedimentations for the first time
Perovskite thin film layer, the final photoelectric conversion efficiency for obtaining battery device reach 15%.The preparation of perovskite thin film has certain skill
Art basis, the common CH of conceptual phase3NH3PbBr3Green light LED and CH3NH3PbI3Red-light LED is also prepared out in succession.Close
In improvement in 3 years, for structure by just setting inversion, luminescent layer, to quantum dot, or even adulterates some dielectricity organic matters by film, uses
To improve the coverage rate of luminescent layer, reduction leakage current and non-radiative recombination etc..But the complex centre of carrier radioluminescence also has
Prodigious room for promotion inherently improves the efficiency of luminescent device.
In market-oriented GaN types LED, the application of multi-quantum pit structure allows its efficiency to have qualitative leap.Quantum
Trap refers to electronics by 2 kinds of spaced formation of different semi-conducting materials, with apparent quantum limitation effect or hole
Potential well.Its structure feature is the multilayered structure formed by 2 kinds of different thin layers of semiconductor material alternating growths, forms many separation
Quantum Well, referred to as multiple quantum wells (Multiple Quantum Well, MQW).Existing related perovskite energy band is reconciled or amount
In the report of sub- trap, it is confined to adjust perovskite (CH3NH3PbX3, X=Cl, I, Br) and microscopical compositon reaches band-gap tuning, and it cannot
Realize that the energy band of macrostructure is controllable, and quantum well structure boundary defect is more.
Invention content
The purpose of the present invention is to provide compound multiple quantum wells LED of a kind of perovskite and preparation method thereof.The present invention provides
The compound multiple quantum wells LED boundary defects of perovskite it is few, and energy band is controllable.
The present invention provides a kind of compound multiple quantum wells LED of perovskite, including set gradually substrate, electron injecting layer,
Luminescent layer, hole injection layer and electrode, the luminescent layer include CH3NH3PbBr3Film and it is embedded in the CH3NH3PbBr3It is thin
CH in film3NH3PbI3Quantum dot.
Preferably, the CH3NH3PbBr3The thickness of film is 280~350nm.
Preferably, the CH3NH3PbBr3Film includes along the transversely arranged crystal grain of film surface, the transverse direction of the crystal grain
Size is 300~600nm.
Preferably, the CH3NH3PbI3The grain size of quantum dot is 10~20nm.
Preferably, the CH3NH3PbI3Quantum dot is in CH3NH3PbBr3Volume fraction in film is 2~5%.
Preferably, the thickness of the electron injecting layer is 100~120nm.
Preferably, the electron injecting layer includes anatase TiO2Or β-Ga2O3。
Preferably, the thickness of the hole injection layer is 100~120nm.
Preferably, the hole injection layer includes 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyls) amino] -9,9'-
Two fluorenes of spiral shell.
The present invention provides the preparation methods of the compound multiple quantum wells LED of perovskite described in above-mentioned technical proposal a kind of, including
Following steps：
(1) electron injecting layer is prepared in substrate surface；
(2) with CH3NH3PbI3Quantum dot, PbBr2And CH3NH3Br is raw material, using low temperature solution polycondensation in the step (1)
Obtained electron injection layer surface prepares luminescent layer；
(3) the luminous layer surface for using low temperature solution polycondensation to be obtained in the step (2) prepares hole injection layer；
(4) electrode is prepared on the hole injection layer surface that the step (3) obtains using thermal evaporation, it is multiple obtains perovskite
Close multiple quantum wells LED.
The compound multiple quantum wells LED of perovskite provided by the invention includes the substrate set gradually, electron injecting layer, shines
Layer, hole injection layer and electrode, the luminescent layer include CH3NH3PbBr3Film and it is embedded in the CH3NH3PbBr3In film
CH3NH3PbI3Quantum dot.The compound multiple quantum wells LED of perovskite provided by the invention is by the perovskite continuous phase of wider band gap
CH3NH3PbBr3The perovskite quantum dot CH of narrow band gap is inlayed in film3NH3PbI3, since the high electronics of perovskite, hole are moved
Shifting rate and carrier diffusion length, in addition the multiple quantum wells that the quantum effect of quantum dot and the two are formed, carrier is continually
Ground is preferentially oriented to the Quantum Well recombination luminescence of low potential barrier；In addition, Lattice Matching is preferable between the perovskite of different component, other are compared
Quantum well structure boundary defect is few, effectively reduces non-radiative recombination center.
Description of the drawings
Fig. 1 is anatase TiO in the embodiment of the present invention 12The height map of atomic force microscope (AFM)；
Fig. 2 is anatase TiO in the embodiment of the present invention 12The phasor of atomic force microscope (AFM)；
Fig. 3 is CH in the embodiment of the present invention 13NH3PbBr3Scanning electron microscope (SEM) photo of film；
Fig. 4 is CH in the embodiment of the present invention 13NH3PbBr3The X ray diffracting spectrum (XRD) of film；
Fig. 5 is the structural schematic diagram of the compound multiple quantum wells LED of perovskite in the embodiment of the present invention 1；
Fig. 6 is the compound multi-quantum well luminescence layer energy band diagram of perovskite and Quantum Well schematic diagram in the embodiment of the present invention 1.
Specific implementation mode
The present invention provides a kind of compound multiple quantum wells LED of perovskite, including set gradually substrate, electron injecting layer,
Luminescent layer, hole injection layer and electrode, the luminescent layer include CH3NH3PbBr3Film and it is embedded in the CH3NH3PbBr3It is thin
CH in film3NH3PbI3Quantum dot.
The compound multiple quantum wells LED of perovskite provided by the invention includes substrate.The present invention does not have the type of the substrate
Special restriction, using LED substrates well known to those skilled in the art.In the present invention, the substrate is preferably saturating
Bright conductive substrates, more preferably FTO electro-conductive glass or ITO electro-conductive glass.In the present invention, when the substrate is FTO conduction glass
When glass, the thickness of FTO films is preferably 150~200nm in the substrate, more preferably 160~190nm, most preferably 170~
180nm；The sheet resistance of the FTO films is preferably 7~14 Ω, more preferably 8~12 Ω.In the present invention, in the substrate
FTO films or the cathode that ito thin film is LED.
The compound multiple quantum wells LED of perovskite provided by the invention includes the electron injecting layer being set on the substrate.?
In the present invention, the thickness of the electron injecting layer is preferably 100~120nm, more preferably 105~115nm.In the present invention,
The electron injecting layer preferably includes anatase TiO2Or β-Ga2O3, more preferably anatase TiO2.In the present invention, described sharp
Titanium ore TiO2The length of side be preferably 400~600nm, more preferably 450~550nm.
In the present invention, the anatase TiO2Preferably surface treated anatase TiO2；The surface treatment is preferred
To use ethanolamine treatment.In the present invention, the surface treatment can improve TiO2Energy level, reinforce in LED to hole
Limitation ensures that electron hole pair is compound in luminescent layer.
The compound multiple quantum wells LED of perovskite provided by the invention includes the luminescent layer being set on the electron injecting layer,
The luminescent layer includes CH3NH3PbBr3Film and it is embedded in the CH3NH3PbBr3CH in film3NH3PbI3Quantum dot.?
In the present invention, the CH3NH3PbBr3The thickness of film is preferably 280~350nm, more preferably 200~330nm, most preferably
210~220nm.In the present invention, the CH3NH3PbBr3Film preferably includes single layer crystal grain side by side；The transverse direction of the crystal grain
It is preferably dimensioned to be 300~600nm, more preferably 400~500nm；The longitudinal size of the crystal grain is film thickness.In the present invention
In, the CH3NH3PbI3The grain size of quantum dot is preferably 10~20nm, more preferably 12~18nm, most preferably 14~16nm.
In the present invention, the CH3NH3PbI3Quantum dot is in CH3NH3PbBr3Volume fraction in film is preferably 2~
5%, more preferably 3~4%.In the present invention, the perovskite continuous phase CH of wider band gap3NH3PbBr3It is inlayed in film relatively narrow
The perovskite quantum dot CH of band gap3NH3PbI3, due to high electronics, hole mobility and the carrier diffusion length of perovskite, add
The multiple quantum wells that the quantum effect and the two of upper quantum dot are formed, carrier are continuously preferentially oriented to the Quantum Well of low potential barrier
Recombination luminescence；In addition, Lattice Matching is preferable between the perovskite of different component, and it is few compared to other quantum well structure boundary defects, have
Effect reduces non-radiative recombination center.
The compound multiple quantum wells LED of perovskite provided by the invention includes the hole injection layer being set on the luminescent layer.
In the present invention, the thickness of the hole injection layer is preferably 100~120nm, more preferably 105~115nm.In the present invention
In, the hole injection layer preferably includes 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyls) amino] -9,9'- spiral shells, two fluorenes
(Spiro-OMeTAD)。
The compound multiple quantum wells LED of perovskite provided by the invention includes the electrode being set on the hole injection layer.?
In the present invention, the electrode is preferably silver electrode or silver electrode composite；The silver electrode composite preferably includes to be set in turn in institute
State the MoO on hole injection layer3Layer and silver layer.In the present invention, the thickness of the silver electrode is preferably 80~120nm, more excellent
It is selected as 90~110nm, most preferably 100nm.In the present invention, the MoO3The thickness of layer is preferably 8~12nm, more preferably
9~11nm；The thickness of the silver layer is preferably 80~120nm, more preferably 90~110nm, most preferably 100nm.
The present invention does not have the number of the electrode special restriction, is carried out according to number well known to those skilled in the art
Setting.In an embodiment of the present invention, the electrode is preferably 4~10.
The present invention also provides the preparation methods of the compound multiple quantum wells LED of perovskite described in above-mentioned technical proposal, including with
Lower step：
(1) electron injecting layer is prepared in substrate surface；
(2) with CH3NH3PbI3Quantum dot, PbBr2And CH3NH3Br is raw material, using low temperature solution polycondensation in the step (1)
Obtained electron injection layer surface prepares luminescent layer；
(3) the luminous layer surface for using low temperature solution polycondensation to be obtained in the step (2) prepares hole injection layer；
(4) electrode is prepared on the hole injection layer surface that the step (3) obtains using thermal evaporation, it is multiple obtains perovskite
Close multiple quantum wells LED.
The present invention cleans the substrate preferably before preparing electron injecting layer.In the present invention, the cleaning is excellent
It is selected as being cleaned by ultrasonic；The cleaning preferably includes acetone cleaning, isopropanol cleaning and washing successively.In the present invention, described third
Ketone cleans and the time of isopropanol cleaning is preferably independently 10~15min, more preferably 12~13min；The acetone cleaning
Number with isopropanol cleaning is preferably independently 2~3 times.In the present invention, the time of the washing is preferably 8~12min；
The number of the washing is preferably 1~2 time.
After the completion of cleaning, preferably the substrate after the cleaning is dried by the present invention.Behaviour of the present invention to the drying
Make not special restriction, using the technical solution of drying well known to those skilled in the art.In the present invention, described dry
It is dry preferably to be dried up with high pure nitrogen.
The present invention prepares electron injecting layer in substrate surface.The present invention does not have the source of the substrate special restriction,
Using commercial product well known to those skilled in the art.The present invention is to the operation of the preparation of the electron injecting layer without spy
Different restriction, using the technical solution well known to those skilled in the art for preparing electron injecting layer.
In the present invention, when the electron injecting layer includes anatase TiO2When, present invention preferably employs precursor solutions
Heat treating process prepares electron injecting layer in substrate surface.In the present invention, the precursor solution heat treating process preferably include with
Lower step：TiO is coated in substrate surface2Then precursor solution is calcined, the electron injecting layer of substrate surface is obtained.
In the present invention, the TiO2Presoma is preferably titanium tetraisopropylate；The molar concentration of the titanium tetraisopropylate is excellent
It is selected as 0.2~0.3mol/L.In the present invention, the solvent is preferably isopropanol.In the present invention, the TiO2Presoma is molten
It preferably further include hydrochloric acid solution in liquid；The molar concentration of the hydrochloric acid solution is preferably 1.9~2.1mol/L.In the present invention,
The volume ratio of the hydrochloric acid and titanium tetraisopropylate is preferably 1:9~12.The present invention is to the preparation TiO2Precursor solution
The not special restriction of operation, using the technical solution well known to those skilled in the art for preparing mixed solution.In this hair
In bright, the hydrochloric acid can inhibit the hydrolysis of titanium tetraisopropylate.
The present invention is to the TiO2Precursor solution coating operates not special restriction, using those skilled in the art
The technical solution of well known coating.In the present invention, the TiO2The coating of precursor solution is preferably spin coating；The rotation
The rate of painting is preferably 4000~6000rpm, more preferably 4500~5500rpm.Time and thickness of the present invention to the spin coating
The not special restriction of degree, is adjusted according to the thickness of required electron injecting layer.
The present invention preferably carries out ultraviolet oxygen treatments applied to the substrate before coating.In the present invention, the ultraviolet oxygen
The oxygen flow of processing is preferably 3~4L/min；In the present invention, the time of the ultraviolet oxygen treatments applied be preferably 5~
10min, more preferably 6~8min.In the present invention, the ultraviolet oxygen treatments applied can improve the apparent activation energy of FTO films,
Make TiO2It is easier to form a film when precursor solution coats.
After the completion of coating, the present invention preferably calcines the product after the coating, obtains the electronics note of substrate surface
Enter layer.In the present invention, the temperature of the calcining is preferably 450~500 DEG C, more preferably 480~490 DEG C；The calcining
Time is preferably 30~50min, more preferably 35~45min.In the present invention, the calcining can obtain anatase TiO2。
Obtain anatase TiO2Afterwards, the present invention is preferably to the anatase TiO2It is surface-treated, obtains electron injection
Layer.In the present invention, the surface treatment preferably uses ethanolamine treatment.The present invention does not have the operation of the ethanolamine treatment
There is special restriction, using processing method well known to those skilled in the art.In the present invention, the ethanolamine treatment is excellent
Choosing includes：Ethanolamine solutions are spun on anatase TiO2Then surface is heat-treated.
In the present invention, the mass concentration of the ethanolamine solutions is preferably 0.35~3.35%, and more preferably 1~2%.
In the present invention, the volume ratio of the ethanolamine solutions and titanium tetraisopropylate is preferably 1:9~12.In the present invention, the rotation
The rate of painting is preferably 2000~3000rpm, more preferably 2200~2500rpm.The present invention is preferably after the completion of the spin coating
It is heat-treated again after keeping 30~45s.In the present invention, the temperature of the heat treatment is preferably 120~140 DEG C, more preferably
It is 125~135 DEG C；The time of the heat treatment is preferably 8~10min.In the present invention, the surface treatment can improve TiO2
Energy level, reinforce LED in the limitation to hole, ensure electron hole pair it is compound in luminescent layer.
In the present invention, when the electron injecting layer includes β-Ga2O3When, present invention preferably employs electron beam evaporation or magnetic
Control sputtering method prepares electron injecting layer in substrate surface.The present invention does not have the operation of the electron beam evaporation and magnetron sputtering method
Special restriction prepares β-Ga using electron beam evaporation known to those skilled in the art and magnetron sputtering method2O3Technical solution be
It can.
After obtaining electron injecting layer, the present invention is with CH3NH3PbI3Quantum dot, PbBr2And CH3NH3Br is raw material, and use is low
Warm solwution method prepares luminescent layer in the electron injection layer surface.In the present invention, the preparation of the luminescent layer preferably include with
Lower step：
CH is prepared respectively3NH3PbI3Quantum dot solution, PbBr2Solution and CH3NH3Br solution；
PbBr is coated in electron injection layer surface2The first annealing is carried out after solution, obtains PbBr2Layer；
In the PbBr2Layer surface coats CH3NH3PbI3The second annealing is carried out after quantum dot solution, obtains PbBr2Quantum
Point composite construction；
In the PbBr2Quantum dot composite structure surface coats CH3NH3Third annealing is carried out after Br solution, is shone
Layer.
The present invention preferably prepares CH3NH3PbI3Quantum dot solution.The present invention is to the CH3NH3PbI3The system of quantum dot solution
Standby not special restriction, using the technical solution well known to those skilled in the art for preparing mixed solution.The present invention is excellent
It selects the CH3NH3PbI3Quantum dot is mixed to get CH with solvent3NH3PbI3Quantum dot solution.In the present invention, described
CH3NH3PbI3The solvent of quantum dot solution is preferably n-hexane；The CH3NH3PbI3The molar concentration of quantum dot solution is preferably
0.5~1mol/L, more preferably 0.6~0.8mol/L.
The present invention is to the CH3NH3PbI3The source of quantum dot does not have special restriction, ripe using those skilled in the art
The commercial product known, or prepared according to preparation method well known to those skilled in the art.In the present invention, described
CH3NH3PbI3The preparation of quantum dot is preferably prepared according to emulsion polymerization, referring in particular to Huang H, Zhao F, Liu L,
et al.Emulsion Synthesis of Size-Tunable CH3NH3PbBr3Quantum Dots:An
Alternative Route toward Efficient Light-Emitting Diodes[J].Acs Applied
Materials&Interfaces,2015,7(51):Technical solution disclosed in 28128..
The present invention preferably prepares PbBr2Solution.The present invention is to the PbBr2The technical solution of the preparation of solution is not special
Restriction, using the technical solution well known to those skilled in the art for preparing mixed solution.The present invention is preferably by PbBr2With
Solvent is mixed to get PbBr2Solution.In the present invention, the PbBr2The solvent of solution preferably includes dimethylformamide (DMF)
With dimethyl sulfoxide (DMSO) (DMSO).In the present invention, the PbBr2The amount of substance, the volume of dimethylformamide and dimethyl
The ratio between amount of substance of sulfoxide is preferably 0.8~1.2mol:1L:0.8~1.2mol.
The present invention preferably prepares CH3NH3Br solution.The present invention is to the CH3NH3The technical solution of the preparation of Br solution does not have
There is special restriction, using the technical solution well known to those skilled in the art for preparing mixed solution.The present invention preferably will
CH3NH3Br is mixed to get CH with solvent3NH3Br solution.In the present invention, the CH3NH3The solvent of Br solution is preferably isopropyl
Alcohol；The CH3NH3The concentration of Br solution is preferably 8~10g/L.
Obtain PbBr2After solution, the present invention preferably coats the PbBr in electron injection layer surface2First is carried out after solution
Annealing, obtains PbBr2Layer.In the present invention, the PbBr2The coating of solution is preferably spin coating；The rate of the spin coating is preferably
3500~4500r/min, more preferably 3800~4200r/min；The time of the spin coating is preferably 20~40s, more preferably
25~35s；The spin coating preferably carries out under an inert atmosphere.
In the present invention, the temperature of first annealing is preferably 60~80 DEG C, more preferably 65~75 DEG C；Described first
The time of annealing is preferably 8~12min, more preferably 9~11min.In the present invention, first annealing can remove
PbBr2Solvent in solution obtains loose PbBr2Layer.
Obtain PbBr2After layer, the present invention is preferably in the PbBr2Layer surface coats CH3NH3PbI3It is carried out after quantum dot solution
Second annealing, obtains PbBr2Quantum dot composite construction.In the present invention, the CH3NH3PbI3Quantum dot solution coating is excellent
It is selected as spin coating；The rate of the spin coating is preferably 2500~3500r/min, more preferably 2800~3200r/min；The spin coating
Time be preferably 20~40s, more preferably 25~35s；The spin coating preferably carries out under an inert atmosphere.
In the present invention, the temperature of second annealing is preferably 60~80 DEG C, more preferably 65~75 DEG C；Described and
The time of annealing is preferably 8~12min, more preferably 9~11min.In the present invention, second annealing makes evaporation of the solvent,
Obtain PbBr2Quantum dot composite construction.
Obtain PbBr2After quantum dot composite construction, the present invention is preferably in the PbBr2Quantum dot composite structure surface applies
Cover CH3NH3Third annealing is carried out after Br solution, obtains luminescent layer.In the present invention, the CH3NH3The coating of Br solution is preferred
For spin coating；The rate of the spin coating is preferably 3500~4500r/min, more preferably 3800~4200r/min；The spin coating
Time is preferably 20~40s, more preferably 25~35s；The spin coating preferably carries out under an inert atmosphere.
In the present invention, the temperature of the third annealing is preferably 60~80 DEG C, more preferably 65~75 DEG C；The third
The time of annealing is preferably 25~35min, more preferably 28~32min.In the present invention, in the third annealing process,
CH3NH3Br and PbBr before2It can reaction generation perovskite structure.
After obtaining luminescent layer, the present invention prepares hole injection layer using low temperature solution polycondensation in the luminous layer surface.At this
In invention, the preparation of the hole injection layer preferably includes following steps：By 2,2', [(the 4- methoxybenzenes of N, N- bis- of 7,7'- tetra-
Base) amino] -9,9'- spiral shells, two fluorenes (Spiro-OMeTAD) precursor solution be coated on shine layer surface, obtained after oxidation hole note
Enter layer.
The not special restriction of composition of the present invention to the Spiro-OMeTAD precursor solutions, using art technology
Spiro-OMeTAD precursor solutions known to personnel.In the present invention, the Spiro-OMeTAD precursor solutions are excellent
Choosing includes Spiro-OMeTAD, chlorobenzene, tributyl phosphate (TBP), two (trimethyl fluoride sulfonyl) lithiums (Li-TFSI) and acetonitrile；Institute
The mass volume ratio for stating Spiro-OMeTAD and chlorobenzene is preferably 120~160g/L, more preferably 140~150g/L；Described two
(trimethyl fluoride sulfonyl) lithium (Li-TFSI) and the mass volume ratio of acetonitrile are preferably 500~600g/L, more preferably 520~
550g/L；The chlorobenzene, tributyl phosphate (TBP) and the volume ratio of acetonitrile are preferably 1000:50~60:30~40.The present invention
The restriction not special to the operation of the preparation of the Spiro-OMeTAD precursor solutions, using known to those skilled in the art
The technical solution for preparing mixed solution.
In the present invention, the coating of the Spiro-OMeTAD precursor solutions is preferably spin coating；The rate of the spin coating
Preferably 4000~6000r/min, more preferably 4500~5500r/min；The time of the spin coating is preferably 25~35s.
After the completion of coating, product of the present invention preferably by the coating cures, and then oxidation obtains hole injection layer.
In the present invention, the cured temperature is preferably room temperature；The cured time is preferably 1.8~2.2h.In the present invention,
The solidification preferably carries out in a vacuum or inert atmosphere.In the present invention, the temperature of the oxidation is preferably room temperature；The oxygen
The time of change is preferably 11~13h, more preferably 11.5~12.5h.In the present invention, the oxidation is preferably dried in low humidity
It is carried out in tower；The humidity of the oxidation is preferably 40% hereinafter, more preferably 10~30%.
Preferably after the completion of prepared by the hole injection layer, part electron injecting layer, luminescent layer, hole are injected by the present invention
Layer removal exposes FTO films or ito thin film as cathode.The present invention is to the electron injecting layer, luminescent layer, hole injection layer
Removal size there is no special restriction, be adjusted according to required cathode area.
After obtaining hole injection layer, the present invention prepares electrode using thermal evaporation on the hole injection layer surface, obtains
The compound multiple quantum wells LED of perovskite.In the present invention, the thermal evaporation is preferably vacuum thermal evaporation；The vacuum thermal evaporation
Vacuum degree be preferably (3~4) × 10-4Pa, more preferably (3.4~3.6) × 10-4Pa.In the present invention, when the electrode
For silver electrode when, the present invention preferably the hole injection layer surface be deposited silver；When the electrode is silver electrode composite, this hair
It is bright that MoO is preferably deposited successively on the hole injection layer surface3And silver.Temperature and time of the present invention to the vacuum thermal evaporation
There is no special requirement, is adjusted according to the type of electrode and thickness.
In order to further illustrate the present invention, with reference to embodiment to the compound multiple quantum wells of perovskite provided by the invention
LED and preparation method thereof is described in detail, but cannot they be interpreted as limiting the scope of the present invention.
Embodiment 1:
(1) transparent conductive substrate is cleaned, used substrate is etched FTO glass.
Using the FTO glass of electrically conducting transparent as substrate, chemical cleaning is carried out, cleaning step is：First by substrate
Then respectively it is cleaned by ultrasonic 10min with acetone and aqueous isopropanol successively, recycling is primary；Use deionized water ultrasonic irrigation dry later
Only, spare after finally being dried up with high pure nitrogen.The thickness of FTO films is 150nm.
(2) N-shaped TiO is prepared2Electron injecting layer.
FTO glass after cleaning is put into Plasma, ultraviolet oxygen treatments applied 10min is carried out.Then it is transferred to glove box
(nitrogen atmosphere) is with 5000rpm spin coatings TiO2Precursor solution is taken out glove box and is added with 4505 DEG C in tube furnace at once later
Hot 40min, then when being naturally cooling to 120 DEG C, put back to glove box.(TiO2Precursor solution formula：The titanium tetraisopropylate of 369uL
(TTIP) it is dissolved in the isopropanol of 5mL, then the concentrated hydrochloric acid of the 2mol/L of 35uL is added dropwise.)
Ethanol amine (EA) is dissolved in 2-methyl cellosolve (concentration 0.35%), and 35uL ethanolamine solutions are taken with liquid-transfering gun,
4000rpm is spun on TiO230s is kept on layer, then 130 DEG C of heat treatment 10min make solvent volatilize in thermal station, and obtaining thickness is
The electron injecting layer of 100nm.TiO2The height map and phasor of the atomic force microscope (AFM) of electron injecting layer respectively such as Fig. 1 and
Shown in Fig. 2, it can be seen from the figure that TiO2The length of side of wafer-like triangular in shape, triangle chip is 500nm.
(3) the compound multi-quantum well luminescence layer of perovskite is prepared using two step solwution methods.
CH is prepared first3NH3PbI3Quantum dot：By the CH of 0.16mmol3NH31. the DMF that I is dissolved in 0.3mL forms solution, will
The PbI of 0.2mmol22. the DMF for being dissolved in 0.5mL forms solution, by the hexane of 10mL, the octylame of the oleic acid of 0.5mL and 20uL
Mix resulting mixture 3.；Stirring forms lotion, magnetic agitation reaction solidification 2 hours in 1. and being 2. added dropwise again 3.；Finally
Add 8mL acetone as demulsifier, generate precipitation, 5min, taking precipitate redisperse to nonpolarity are centrifuged using centrifuge 6000rpm
Quantum dispensing liquid solution is formed in solvent hexane.
Two-step method prepares the compound multi-quantum well luminescence layer specific steps of perovskite：First by the PbBr of 1mmol2Powder is dissolved in
In the dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) (DMSO) mixed solution of 1mL, wherein dimethyl sulfoxide (DMSO) and PbBr2Equal objects
The amount of matter；By the CH of 10mg3NH3Br is dissolved in 1mL isopropanols；Secondly it is first revolved with 4000r/min in the glove box of nitrogen atmosphere
Apply 30sPbBr2Solution, 70 DEG C of annealing 10min remove solvent and leave loose PbBr in glove box2Layer；Then quantum is mixed
Point, the quantum dot colloidal solution of drop coating n-hexane, 70 DEG C of annealing 10min after sol evenning machine 3000r/min spin coatings 30s；Last calcium titanium
The growth of mine, drop coating CH3NH34000r/min spin coatings 30s after Br solution, 70 DEG C of annealing 30min, completes the crystallization of perovskite, obtains
To luminescent layer.Fig. 3 is CH in the present embodiment3NH3PbBr3The XRD spectrum of film, it can be seen from the figure that perovskite crystallizes
To single-phase CH3NH3PbBr3.Luminescent layer includes CH3NH3PbBr3Film inlaying CH3NH3PbI3Quantum dot.
Fig. 4 is CH in the present embodiment3NH3PbBr3The scanning electron microscope piece of film, it can be seen from the figure that
CH3NH3PbBr3Film includes along the transversely arranged crystal grain of film surface, and the lateral dimension of crystal grain is 500nm, the longitudinal ruler of crystal grain
Very little (and film thickness) is 300nm.
(4) p-type hole passes the preparation and its oxidation of implanted layer.
Spiro-OMeTAD precursor solutions are prepared first：The Spiro- of 144.6mg will be sequentially added in 1mL chlorobenzenes
The Li-TFSI salting liquids of OMeTAD, the TBP of 57.6 μ L and 35 μ L (520mgLi-TFSI is dissolved in the acetonitrile of 1mL).It has annealed cooling
After slice, thin piece, in the compound multi-quantum well luminescence layer of perovskite with the holes 5000r/min spin coating 30sSpiro-OMeTAD inject
Layer is placed 2 hours or so in glove box and is cured, then takes out glove box later, puts into low humidity drying tower and aoxidizes 12 hours,
Obtain the hole injection layer that thickness is 100nm.
Partial coating is wiped off with tweezers, exposes FTO films as common cathode.
(5) bar shaped combination electrode is prepared on the hole injection layer of p-type using thermal evaporation.
The slice, thin piece aoxidized is put into the copper mold plate for exposing strip electrode, is less than with vacuum degree in multi-source hot evaporation equipment
3.4×10-4The MoO of 10nm is deposited in Pascal successively3Ag with 100nm is as combination electrode.
The compound multiple quantum wells LED structure of perovskite manufactured in the present embodiment is as shown in Figure 5, wherein 1 is substrate, and 2 be electronics
Implanted layer, 3 be luminescent layer, and 4 be hole injection layer, and 5 be electrode.
Fig. 6 is the compound multi-quantum well luminescence layer energy band diagram of perovskite and Quantum Well schematic diagram in the present embodiment, can from figure
To find out, hole and electronics are respectively from cathode and electrode injection, and electronics is filled out toward the low place of energy band, and hole is opposite；Energy band is formed
Potential well, electrons and holes could be easy into but be not easy out, increase the compound of electron hole pair.
Embodiment 2:
This example is with embodiment 1 the difference is that preparing N-shaped TiO2In electron injecting layer：
FTO glass after cleaning is put into Plasma, ultraviolet oxygen treatments applied 10min is carried out.Then it is transferred to glove box
(nitrogen atmosphere) is with 5000rpm spin coatings TiO2Precursor solution is taken out glove box and is heated with 500 DEG C in tube furnace at once later
40min, then when being naturally cooling to 120 DEG C, put back to glove box.
(TiO2Precursor solution formula：The titanium tetraisopropylate (TTIP) of 369uL is dissolved in the isopropanol of 2.5mL in 1 bottle, 2 bottles
The concentrated hydrochloric acid of the 2mol/L of middle 35uL is dissolved in the isopropanol of 2.5mL, then the acid solution in 2 bottles is added dropwise to 1 bottle.)
In this implementation, for TiO2The raising of precursor solution spin coating rotating speed, for TiO2The control of film thickness,
5000rpm film thicknesses are reduced to 80nm.
Embodiment 3:
This example is with embodiment 1 the difference is that preparing the compound multiple quantum well light emitting of perovskite using two step solwution methods
In layer:
CH is prepared first3NH3PbI3Quantum dot：By the CH of 0.16mmol3NH31. the DMF that I is dissolved in 0.3mL forms solution, will
The PbI of 0.2mmol22. the DMF for being dissolved in 0.5mL forms solution, the octylame of the hexane of 10mL, the oleic acid of 1mL and 20uL is mixed
Synthetic mixture is 3.；Stirring forms lotion, magnetic agitation reaction solidification 2 hours in 1. and being 2. added dropwise again 3.；Finally plus
8mL acetone generates precipitation as demulsifier, centrifuges 5min using centrifuge 6000rpm, taking precipitate redisperse is molten to nonpolarity
Quantum dispensing liquid solution is formed in agent n-hexane.
In the present embodiment, the adjustment for emulsion polymerization " grease " ratio improves the ratio of reaction phase, and reative cell becomes larger,
The quantum dot size 20nm of corresponding synthesis.
Embodiment 4：
This example is with embodiment 1 the difference is that two-step method prepares the compound multi-quantum well luminescence layer specific steps of perovskite
In:
First by the PbBr of 1mmol2Powder is dissolved in the dimethylformamide (DMF) of 1mL and dimethyl sulfoxide (DMSO) (DMSO) mixes
It closes in solution, wherein dimethyl sulfoxide (DMSO) and PbBr2The amount of equal substances；By the CH of 15mg3NH3Br is dissolved in 1mL isopropanols.Secondly
First with 4000r/min spin coatings 30sPbBr in the glove box of nitrogen atmosphere2Solution, 70 DEG C of annealing 10min are removed in glove box
Solvent leaves loose PbBr2Layer.Then quantum dot, the quantum dot colloidal solution of drop coating n-hexane, sol evenning machine 3000r/ are mixed
70 DEG C of annealing 10min after min spin coatings 30s.The growth of last perovskite, drop coating CH3NH34000r/min spin coatings 30s after Br solution,
70 DEG C of annealing 30min, preceding 10min dissolve the irregular perovskite recrystallization in surface in DMSO solvent atmospheres, and rear 20min exists
The crystallization of perovskite is completed in nitrogen atmosphere.
In the present embodiment, second step CH is improved3NH3The solution concentration of Br, and annealed using solvent method, make perovskite thin film
It is fine and close smooth.
As can be seen from the above embodiments, the compound multiple quantum wells LED of perovskite provided by the invention is by the calcium of wider band gap
Titanium ore continuous phase CH3NH3PbBr3The perovskite quantum dot CH of narrow band gap is inlayed in film3NH3PbI3, due to the height of perovskite
Electronics, hole mobility and carrier diffusion length, in addition the multiple quantum wells that the quantum effect of quantum dot and the two are formed, current-carrying
Son is continuously preferentially oriented to the Quantum Well recombination luminescence of low potential barrier；In addition, between the perovskite of different component Lattice Matching compared with
It is good, it is few compared to other quantum well structure boundary defects, effectively reduce non-radiative recombination center.
The above is only a preferred embodiment of the present invention, it is not intended to limit the present invention in any form.It should
It points out, for those skilled in the art, without departing from the principle of the present invention, if can also make
Dry improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (9)
1. a kind of compound multiple quantum wells LED of perovskite, including set gradually substrate, electron injecting layer, luminescent layer, hole injection
Layer and electrode, the luminescent layer include perovskite CH3NH3PbBr3Film and it is embedded in the CH3NH3PbBr3Calcium titanium in film
Mine CH3NH3PbI3Quantum dot, the CH3NH3PbBr3Film includes along the transversely arranged crystal grain of film surface, the cross of the crystal grain
It is 300~600nm to size.
2. the compound multiple quantum wells LED of perovskite according to claim 1, which is characterized in that the CH3NH3PbBr3Film
Thickness be 280~350nm.
3. the compound multiple quantum wells LED of perovskite according to claim 1, which is characterized in that the CH3NH3PbI3Quantum dot
Grain size be 10~20nm.
4. the compound multiple quantum wells LED of perovskite according to claims 1 to 3 any one, which is characterized in that described
CH3NH3PbI3Quantum dot is in CH3NH3PbBr3Volume fraction in film is 2~5%.
5. the compound multiple quantum wells LED of perovskite according to claim 1, which is characterized in that the thickness of the electron injecting layer
Degree is 100~120nm.
6. the compound multiple quantum wells LED of perovskite according to claim 1 or 5, which is characterized in that the electron injecting layer packet
Include anatase TiO2Or β-Ga2O3。
7. the compound multiple quantum wells LED of perovskite according to claim 1, which is characterized in that the thickness of the hole injection layer
Degree is 100~120nm.
8. the compound multiple quantum wells LED of perovskite according to claim 1 or claim 7, which is characterized in that the hole injection layer packet
Include 2,2', two fluorenes of 7,7'- tetra- [N, N- bis- (4- methoxyphenyls) amino] -9,9'- spiral shells.
9. the preparation method of the compound multiple quantum wells LED of perovskite described in claim 1~8 any one, includes the following steps：
(1) electron injecting layer is prepared in substrate surface；
(2) with perovskite CH3NH3PbI3Quantum dot, PbBr2And CH3NH3Br is raw material, using low temperature solution polycondensation in the step
(1) the electron injection layer surface obtained prepares luminescent layer；
(3) the luminous layer surface for using low temperature solution polycondensation to be obtained in the step (2) prepares hole injection layer；
(4) electrode is prepared on the hole injection layer surface that the step (3) obtains using thermal evaporation, it is compound more obtains perovskite
Quantum Well LED.
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| CN108682749B (en) * | 2018-06-13 | 2020-08-28 | 西南大学 | Perovskite light emitting diode with multi-quantum well structure and preparation method thereof |
| CN109599497B (en) * | 2018-11-23 | 2020-10-20 | 哈尔滨工业大学（深圳） | Color-adjustable perovskite LED based on micro-nano structure and preparation method thereof |
| CN109638116B (en) * | 2018-11-27 | 2020-12-25 | 华灿光电（浙江）有限公司 | Preparation method of epitaxial wafer of light emitting diode and epitaxial wafer |
| CN109962172B (en) * | 2019-03-20 | 2021-01-08 | 浙江大学 | Photoelectric device and preparation method thereof |
| CN110190198A (en) * | 2019-04-03 | 2019-08-30 | 华中科技大学 | A kind of perovskite Quantum Well electroluminescent device and preparation method thereof |
| CN111584767B (en) * | 2020-05-27 | 2022-12-02 | 合肥福纳科技有限公司 | Quantum dot light-emitting diode and preparation method thereof |
| CN111952475B (en) * | 2020-08-18 | 2024-02-06 | 福州大学 | Preparation method of perovskite light-emitting diode device containing silver nano particles |
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