CN107452886A - A kind of laminated film and Organic Light Emitting Diode and preparation method thereof - Google Patents

A kind of laminated film and Organic Light Emitting Diode and preparation method thereof Download PDF

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CN107452886A
CN107452886A CN201710688589.2A CN201710688589A CN107452886A CN 107452886 A CN107452886 A CN 107452886A CN 201710688589 A CN201710688589 A CN 201710688589A CN 107452886 A CN107452886 A CN 107452886A
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layer
organic
light emitting
emitting diode
laminated film
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高春红
张月
马兴娟
玉福星
熊自阳
贾亚兰
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Southwest University
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Southwest University
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18—Carrier blocking layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass

Abstract

The invention provides a kind of laminated film and the Organic Light Emitting Diode based on the laminated film, the laminated film has biexction blocking capability, it is made up of full-inorganic perovskite and the organic carrier transport small molecule material with high exciton energy, wherein the perovskite thin film of full-inorganic and organic small molecule material can be prepared by the methods of spin-coating method, vapour deposition method, ink-jet printing process, knife coating, chemical vapour deposition technique.The laminated film has good singlet exciton and triplet excitons blocking capability.The laminated film is used as hole transmission layer in Organic Light Emitting Diode, has good photoelectric properties, is significantly improved than electroluminescent efficiency of traditional organic molecule as the device of hole transmission layer.

Description

A kind of laminated film and Organic Light Emitting Diode and preparation method thereof
Technical field
The present invention relates to technical field of film preparation, and in particular to a kind of full-inorganic perovskite-organic molecule THIN COMPOSITE The preparation method of film, and it is related to a kind of Organic Light Emitting Diode with the laminated film and preparation method thereof.
Background technology
Due to its unique photoelectric characteristic, inexpensive and solution-processible halide perovskite has been widely used in luminous The luminescent layer of diode (LEDs), the light absorbing layer and the gain media of detector and laser of solar cell (SC).Halogen Compound perovskite has typical chemical formula ABX3, wherein A, B and X section can substitute (A=CH by various elements3NH3 +、 NH2CHNH2 +、Cs+、Li+、Na+、K+、Rb+B=Pb2+,Zn2+、Ge2+、Sn2+X=F-、Cl-、Br-、 I-), it shows the insensitive high colour purity of the color tunable in whole visible-range, the size to particle Spend (halfwidthNm), (scope is 10 to 1000cm to high charge carrier mobility2V-1s-1), big diffusion length (very To more than 1 μm) and low trap density (1016cm-3) and amplification spontaneous emission.The researchers such as Y.Tian are in highly effective green light Using hybrid inorganic-organic halide Ca-Ti ore type CH in phosphorescence Organic Light Emitting Diode (PhOLED)3NH3PbCl3 (MAPbCl3) hole transmission layer (HTL) is used as, it is 29.2cd/A to obtain maximum current efficiency.Afterwards, J.Wang et al. make use of Another hybrid inorganic-organic halide perovskite NH2CHNH2PbCl3(FAPbCl3) showed as HTL in polymer SCs Go out high efficiency and good stability.Although these devices have a good performance, hybrid inorganic-organic perovskite it is steady Qualitative difference.
Nowadays, mainly there is three kinds of solution processing HTLs method in OLED：Solution-processed polymer, organic molecule material Material and transition metal oxide.Due to its good electric conductivity, the high grade of transparency and suitable work function, poly- (3,4- ethylenes Oxygen thiophene)：Poly- (p styrene sulfonic acid salt) (PEDOT：PSS it is) one of most widely used polymer, but it is limited to it The limitation of low lowest unoccupied molecular orbital (LUMO) energy level, causes weak electronic blocking, and narrow band gap causes and serious swashed Son is quenched.Solution processing conjugated polymer is also widely used as HTL, but is more difficult to synthesize and purifies than small molecule material.This Outside, the order of conjugated molecule is difficult to control by spin-coating method, causes the generation of a large amount of crystal boundaries and defect.Although have fraction has Machine small molecule material is solution-processible, but the quality of spin-coating film is not fine, and particularly those have slight dissolving The organic molecule hole mobile material of degree.Transition metal oxide can turn into as solvable due to their low HOMO energy levels The HTL of liquid processing selection.However, it is necessary to the building-up process of high annealing temperature, so may be in transition metal oxide film It is middle to produce the defects of a large amount of, and obstacle is formed to its large-scale production process.A kind of suitable material is found as effective HTL be very urgent.
In OLEDs luminescence process, compound by carrier can produce two kinds of excitons：Singlet exciton and triplet state Exciton.Triplet excitons have longer diffusion length, if in its main body of the triplet excitons energy ratio of luminescent layer adjacent layer Triplet excitons energy it is small, the triplet excitons in main body are readily diffused into adjacent layer, therefore, for efficient The exciton diffusion limited for OLEDs in luminescent layer is very important.The method of generally use be carrier blocking layers with Organic molecule/organic molecule biexction the barrier layer being made up of full stress-strain small molecule is introduced between luminescent layer.It is but organic The carrier mobility of small molecule material is smaller, ordinarily be about 1 the percent or smaller of inorganic material carrier mobility, this The transmission for resulting in carrier in device is extremely limited.
The content of the invention
The present invention provides a kind of laminated film, and it can use spin-coating method, vapour deposition method, ink-jet printing process, knife coating, chemical gas The method for manufacturing thin film such as phase sedimentation prepare, preparation method is simple, easily operated, the laminated film can effectively stop carrier, The diffusion of singlet exciton and triplet excitons.
The laminated film includes：Basic unit；Form the full-inorganic calcium titanium ore bed in basic unit；And formed in full-inorganic calcium Organic small molecule material layer on titanium ore layer.
The full-inorganic calcium titanium ore bed is ABX3, wherein A is Li+、Na+、K+、Rb+Or Cs+, B Zn2+、Ge2+、Sn2+Or Pb2+, X F-、Br-、Cl-Or I-In one kind, the organic small molecule material layer material includes hole mobile material TAPC, CBP, TCTA or mCP.
By introducing the full-inorganic perovskite with appropriate valence-band edge and conduction band side, broad-band gap, high mobility, (mobility surpasses Cross 1000cm2V-1s-1) with high singlet and triplet excitons energy, organic small point of appropriate HOMO and lumo energy Inorganic/organic hybrid biexction barrier layer prepared by sub- carrier transmission material, can further improve stop carrier, Singlet exciton and the ability of triplet excitons diffusion, so as to which exciton preferably is limited in into luminescent layer, improve the electroluminescent of device Luminous efficiency.
The present invention also provides a kind of Organic Light Emitting Diode based on above-mentioned laminated film, and its electroluminescent properties is more excellent It is different.
Described Organic Light Emitting Diode, including：ITO substrates and the hole injection layer being arranged on ITO substrates, described Full-inorganic calcium titanium ore bed is set on hole injection layer, and organic small-molecule material layer is set on full-inorganic calcium titanium ore bed, it is described Full-inorganic calcium titanium ore bed and organic small molecule material layer form laminated film, as hole transmission layer；In the hole transmission layer On set gradually luminescent layer, electron transfer layer and negative electrode.
Wherein, hole injection layer material can be PEDOT:PSS、MoO3、V2O5、GeO2、NiOxDeng electron transport layer materials bag TPBi, Bphen, BCP, TmPyPB etc. are included, electron injection material can be LiF, Liq, CsF, Cs2CO3, ZnO etc..
In addition, the present invention also provides a kind of preparation method for above-mentioned Organic Light Emitting Diode, it comprises the following steps
1) ITO substrates are pre-processed；
2) hole injection layer is formed on ITO substrates；
3) compound hole transmission layer is formed on hole injection layer, wherein, the full-inorganic calcium titanium ore bed and organic small Molecular material layer can pass through any one side in spin-coating method, vapour deposition method, ink-jet printing process, knife coating, chemical vapour deposition technique Method is molded, or using any two kinds different method elder generation aftershapings in the above method；
4) luminescent layer, electron transfer layer and negative electrode are formed on hole transmission layer.
Brief description of the drawings
, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical scheme of the prior art The required accompanying drawing used is briefly described in embodiment or description of the prior art.
Fig. 1 is the chemical constitution schematic diagram of organic material；
Fig. 2 is four feux rouges PhOLEDs in group I：Device IA, IB, IC and ID (a) device architecture schematic diagram, (b) energy level Figure；
Fig. 3 is the EL performances with different HTL devices IA, IB, IC and ID：(a) Current density-voltage (J-V)；(b) it is bright Degree-voltage (L-V)；(c) Current efficiency-voltage (CE-V)；(d) normalized EL intensity-wavelength curve of four devices (7.5V)；
Fig. 4 is in CsPbBr3In/mCP composite beds with different-thickness mCP feux rouges PhOLEDsIIA, IIB, IIC and IID EL performances：(a) Current density-voltage (J-V)；(b) luminance-voltage (L-V)；(c) Current efficiency-voltage (CE-V)； (d) normalized EL intensity-wavelength curve (7.5V) of four devices.
Embodiment
The embodiment of technical solution of the present invention is described in detail below in conjunction with accompanying drawing.Following examples are only used for Clearly illustrate technical scheme, therefore be only used as example, and the protection model of the present invention can not be limited with this Enclose.
In OLED, a preferable hole transmission layer should possess suitable HOMO and lumo energy, big band gap, and three Line state energy and high hole mobility.Due to full-inorganic perovskite CsPbBr3Hole transport mobility be more than 1000cm2V-1s-1, and HOMO energy levels are not very low (5.85eV), can be used as a kind of good hole mobile material, CsPbBr3Band gap width (Eg) be estimated as 2.38eV, than blue light () and green glow () phosphorescence doping three Line state energy is low, but CsPbBr3EgMuch larger than feux rouges phosphorescence doping triplet energy state ().Therefore, in feux rouges In PhOLEDs, CsPbBr3A potential excellent HTL can be turned into and as to Ir (piq)3Triplet excitons it is effective Exciton barrier-layer.These indicate the hole injection layer (PEDOT in feux rouges PhOLEDs:PSS) interleave with luminescent layer (EML) Enter a CsPbBr3Film can improve EL performance.In order to further improve the performance of device, by with high lumo energy (- 2.4eV), wide energy is with band gap (3.5eV) and big triplet energy state (ET=2.90eV) organic small molecule material use Make electronics exciton barrier-layer.
The present embodiment utilizes full-inorganic perovskite material CsPbBr3CsPbBr is made with the advantages of organic molecule mCP3/ The compound HTL of mCP.It is visible by experimental data, show best electricity using the compound HTL, obtained optimal feux rouges PhOLED Stream efficiency is 10.64cd/A, has small machine molecular hole transport material NPB high by 87% than traditional, is to be based on PEDOT:PSS sky Four times of hole transport materials.
The material used in the present embodiment is as follows：
PEDOT:PSS (Heraeus, Clevios AI 4083), PbBr2(Xi'an Polymer Light Technology Co., Ltd., Purity>99.99%), CsBr (Xi'an Polymer Light Technology Co., Ltd., purity>99.99%), 1,3-bis (9- carbazyls) Benzene (mCP, purity>99%), (N, N'-bis (naphthalene -1- bases)-N, N'-bis (phenyl)-benzi (NPB, purity ﹥ 99%), bis (2- methyl -8-hydroxyquinoline) (4- phenylphenols) aluminium (BAlq, purity>99%) three (1- phenyl-isoquinolin) iridium, are mixed (III)(Ir(piq)3, purity>99%), 1,3,5- tri- (3- pyridin-3-yls-phenyl) benzene (TmPyPB, purity>99%), 8- hydroxyls Base quinoline-lithium (Liq, purity>99%), aluminium (Al, purity>99%).All of above material is purchased by market, PEDOT:PSS As hole injection layer, CsPbBr3Film is used as htl layer, and mCP is used as electronics and exciton barrier-layer (EBL).BAlq and Ir (piq)3It is used separately as EML main body and phosphorescent dopants.Ir(piq)3Doping concentration be 3wt%.TmPyPB passes as electronics Defeated layer (ETL)；Liq and Al deposits as two-layer cathode.The molecular machinery of related organic material is as shown in Figure 1.
The preparation method of Organic Light Emitting Diode is as follows：
By device manufacture on the transparent conducting glass substrate of indium tin oxide (ITO, thickness are about 120nm) is coated with. Before thin film deposition, it is cleaned by ultrasonic the ITO bases of etching successively with deionized water, ethanol, acetone, ethanol, acetone (every time 15 minutes) Piece, dried in drying baker (120 DEG C, 15 minutes), finally handle 5 minutes with UV ozone to improve the surface work of ito anode Function, its work function is set to bring up to 5.1eV from 4.7eV.
Hereafter, with sol evenning machine spin coating PEDOT:PSS (4500rpm, 40s), warm table (IKA C- are then used in an atmosphere MAG HS7) annealed 20 minutes with 120 DEG C.Next, substrate is placed into the small transitional storehouse for being connected to glove box, and- Cooled down 30 minutes under conditions of 1.0bar.
Then, with sol evenning machine (4000rpm, 60s) to perovskite CsPbBr3Precursor solution carries out spin coating, and spin coating is completed All substrates are placed in the transitional storehouse of glove box afterwards and handle 20 minutes (- 1.0bar condition) with suction method.Wherein, calcium titanium The preparation of ore deposit precursor solution, it is by PbBr2Powder with CsBr is with 1:1 mol ratio is dissolved in DMSO, and in glove box In continuously stir 12 hours, finally give concentration be 10% perovskite precursor solution.
Finally, substrate is transferred in vacuum deposition system.Functional layer mCP, BAlq, Ir (piq)3, TmPyPB, Liq, Al Sedimentation rate be respectivelyWherein, the luminescent layer of doping It is by from two single sources while evaporating dopant Ir (piq)3Prepared with material of main part BAlq.After the completion of deposition, All devices are transferred in glove box, simply encapsulated.
In order to study the electroluminescent properties of different hole transmission layers (HTL), as shown in Fig. 2 illustrating 4 groups (respectively IA, IB, IC, ID) different structure PhOLEDs.Referring to I is organized in table 1, device architecture is：ITO/Y/BAlq:Ir(piq)33wt% (10nm)/TmPyPB (60nm)/Liq (2.5nm)/Al (120nm), " Y " here correspond respectively to device IA： PEDOT:PSS (30nm), IB：PEDOT:PSS(30nm)/CsPbBr3(30nm), IC：PEDOT:PSS(30nm)/CsPbBr3 (30nm)/mCP (10nm) and ID：PEDOT:PSS(30nm)/NPB(40nm).In device IA, PEDOT:PSS notes as hole Enter layer (HIL) and HTL.But in device IB, IC and ID, PEDOT:PSS is used as HIL, full-inorganic perovskite CsPbBr3It is thin Film, CsPbBr3/ mCP composite membranes, and traditional organic molecule hole mobile material NPB are used as this three groups of devices respectively HTL.Wherein, the device IC is i.e. based on prepared by above-mentioned preparation method.
The PhOLEDs of table 1 structure
Thickness and related evaporation rate with quartz crystal monitor monitoring vacuum deposited layer.By with calibration silicon photoelectricity Programmable source measuring unit (Keithley 2400) measurement of detector (photoelectric instrument factory of Beijing Normal University, ST-86LA) is red Light PhOLEDs Current density-voltage-brightness (J-V-L) characteristic.EL spectrum and CIE chromaticity coordinates are obtained from PR670.PhOLED Light-emitting area be 2 × 3mm2。
Fig. 3 shows the EL performances of PhOLEDs in group I, and correlation properties are listed in table 2., can be with by J-V-L characteristic curves It was found that under the voltage of each application, device IB (PEDOT:PSS makees HIL, CsPbBr3Make HTL) in current density all compare device Part IA (only uses PEDOT:PSS is as HIL and HTL) greatly, and in device IB open bright voltage 3.8V (brightness is equal to 1cd/m2's Relevant voltage value) far below device IA open bright voltage 4.6V, this demonstrate insert CsPbBr in HIL and EML3Film conduct Hole injection and transmittability can be significantly increased in HTL.In addition, L-V curves (Fig. 3 b) and Current efficiency-voltage (CE-V) Curve (Fig. 3 c) shows, device IB (high-high brightness 5234cd/m2, maximum current efficiency is 2.61cd/A) brightness and electric current Efficiency increases, respectively than device IA (high-high brightness 2940cd/m2, maximum current efficiency is 1.61cd/A) and it is high by 78% With 62%.In order to further improve EL performances and prevent Exciton quenching, the CsPbBr in device IC3Inserted between EML 10nm mCP, to limit the electronics and exciton in EML.It should be noted that there is compound htl layer CsPbBr3/ mCP device IC Current density it is each application voltage on be far longer than CsPbBr only3Current density as HTL device IB, it was demonstrated that Because mCP lumo energy (- 2.4eV) is significantly larger than CsPbBr3Lumo energy (- 3.35eV), mCP layers can effective ground resistance Electronics and exciton are kept off, compared with device IB (3.8V), the bright voltage that opens in device IC (3.1V) further reduces, and indicates hole The raising of injection is due to stepped HOMO energy levels.Based on CsPbBr3/ mCP mixed film is as the red of hole transmission layer Light PhOLEDs illustrates optimal electroluminescent properties, and wherein high-high brightness is 20,750cd/m2And maximum current efficiency For 10.64cd/A, than based on CsPbBr3PhOLED difference as hole transmission layer is big 2.96 and 3.07 times, and device IC is most Big external quantum efficiency (EQE) is 2.75%.The raising of device performance is because the mCP layers in laminated film can fill CsPbBr3The hole of film, make laminated film as there is good interracial contact between hole transmission layer and luminescent layer.Finally, By the use of traditional organic molecule hole mobile material NPB as the device ID of hole transmission layer, and with mixed film CsPbBr3/ mCP device IC is compared, and electroluminescent properties are poor, high-high brightness 16,971cd/m2It is with maximum current efficiency 5.67cd/A.Fig. 3 d are the normalization electroluminescent spectrums of four devices.Above all of device shows similar electroluminescent Luminescent spectrum shape, all have from red phosphorescent dopant Ir (piq)3The glow peak at 618nm of transmitting.From inserting for Fig. 3 The amplifier section of spectrum shown in figure, it can be seen that the transmitting of blue light and green glow.In device IA, peak wavelength is in 487nm The blue emission at place should be attributed to BAlq.When being related to device IB, BAlq blue emission greatly reduces, and in 521nm The green emission peak value at place should be attributed to from BAlq to CsPbBr3Singlet energy transfer cause CsPbBr3It is luminous.And For device IC, it is found that compared to device IB, have the more blue emission from BAlq and less come from CsPbBr3's Green emission, because foring more excitons in EML, and mCP film layers are used as electronic blocking and exciton resistance Barrier, so as to form less exciton leakage in EML.Device ID with traditional HTL NPB is four PhOLED devices Middle blue emission ratio maximum.Blue emission may be from BAlq and NPB, although NPB lumo energy is high (- 2.4eV), It is and mCP (Eg=3.5eV) compare, NPB has smaller Eg(3.0eV), this can cause more exciton diffusions to NPB.These As a result show, in these four feux rouges PhOLEDs, from mixed film CsPbBr3The device ICs of/mCP as hole transmission layer Effectively exciton can be limited in EML, and then improve the performance of device.
In order to further verify mCP layers to electronics and the relation of exciton blocking behavior and thickness, manufactured in group II with Lower four kinds of different structures：ITO/PEOOT:PSS(30nm)/CsPbBr3(30nm)/mCP(Z nm)/BAlq:Ir(piq)3 3wt% (10nm)/TmPyPB (60nm)/Liq (2.5nm)/Al (120nm), " Z " therein correspond to device IIA, IIB, IIC With the thickness of mCP layers in IID, respectively 0,5,10 and 20nm.
By using full-inorganic perovskite/organic small molecule material (CsPbBr3/ mCP) feux rouges PhOLED as HTL On the basis of showing optimal electroluminescent properties, by vacuum evaporation 0,5nm, 10nm and 20nm mCP stop to optimize The thickness of layer.In device IIA, IIB, IIC and IID that II is organized in table 1, mCP films are used as electronics and exciton barrier-layer.Institute In some feux rouges PhOLEDs, and only by CsPbBr3Device IIA as HTL is compared, by CsPbBr3Devices of/the mCP as HTL IIB, IIC and IID there is reduced current density and more preferable EL performances.In IIC devices, there is 10nm mCP feux rouges PhOLED has best EL performances, and its high-high brightness is 20,750cd/m2, maximum current efficiency be 10.64cd/A.With The growth of mCP thickness, current density reduce, this demonstrate when mCP layers it is thicker, stop that the ability of electronics is bigger.Because have more Electronics be blocked in mCP/EML interface, and hence in so that electronics, which runs into hole, forms exciton (electron-hole pair) Possibility increase.However, when mCP thickness increases to 20nm from 0, luminosity and current efficiency show different trend. First, when mCP thickness increases to 10nm from 0, brightness and current efficiency reach maximum 20,750cd/m2And 10.64cd/ A, 20nm is changed to from 10nm then as mCP thickness, brightness and current efficiency decline.When mCP thickness increases to from 0 10nm, it is possible to achieve higher EL performances, because due to E big mCPgAnd ET, exciton formed more can be limited in EML In layer.However, with the increase of exciton density, non-radiative recombination plays a leading role in electroluminescent.Therefore, when mCP thickness Degree from 10nm change to 20nm when, due to too many exciton is formed and blocked in EML, EL performances subtract with exciton annihilation It is small.Therefore, under optimal thickness (10nm), PhOLED shows optimal EL performances.Normalizing of four devices under 7.5V Change electroluminescent spectrum as shown in figure 4d.Except Ir (piq)3Characteristic emission outside, it can also be observed that respectively from BAlq and CsPbBr3Weak blue light (peak value about 480nm) and green emission (peak value about 528nm).Can from Fig. 4 d enlarged drawing Go out, with the increase of mCP thickness, the ratio of blueness and green emitted is all being gradually reduced, and this shows with the increasing of mCP thickness Add, exciton more effectively can be limited in EML, have more preferable exciton limitation capability so as to again demonstrate mCP.Institute in experiment Some feux rouges PhOLEDs electroluminescence characters are counted in table 2.Device IIC with mCP (10nm) shows optimal EL Can, its high-high brightness and EL efficiency are up to 20,750cd/m respectively2And 10.64cd/A, the EL performances of the device are institutes in experiment Have and be based on Ir (piq)3Optimum efficiency as the feux rouges PhOLEDs of illuminator.
The PhOLEDs of table 2 EL performances
Summary, in the above-described embodiments, by composite hole transporting layer CsPbBr3/ mCP introduces red phosphorescent organic light emission two In pole pipe, wherein forming full-inorganic caesium lead halide perovskite CsPbBr by spin-coating method3Film, and deposited by vacuum vapour deposition MCP films.Based on compound hole transmission layer (CsPbBr3/ mCP) PhOLED electroluminescent properties be significantly improved, its Under the driving for showing 7.5V voltages, chromaticity coordinates CIE (0.65,0.33), high-high brightness 20,750cd/m2Imitated with maximum current Rate 10.64cd/A, maximum current efficiency is than parametric device from traditional organic molecule NPB as hole transmission layer PhOLED improves 87%.Laminated film (CsPbBr is based in order to study3/ mCP) PhOLEDs electroluminescent properties enhancing Mechanism, the PhOLEDs with different HTL is made, has been found due to stepped HOMO energy level alignments and compound hole transport There is more preferable interracial contact between layer and luminescent layer, promote the injection in hole；Due to CsPbBr3High hole mobility (1000cm2V-1s-1), improve hole transport performance, mCP high lumo energy (- 2.4eV) and big Eg(3.5eV), Neng Gougeng Exciton is limited in luminescent layer well.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although The present invention is described in detail with reference to the foregoing embodiments, it will be understood by those within the art that：It still may be used To be modified to the technical scheme described in previous embodiment, either which part or all technical characteristic are equal Replace；And these modifications or replacement, the essence of appropriate technical solution is departed from the model of technical scheme of the embodiment of the present invention Enclose, it all should cover among the claim of the present invention and the scope of specification.

Claims (10)

  1. A kind of 1. laminated film, it is characterised in that including：
    Basic unit；
    Form the full-inorganic calcium titanium ore bed in basic unit；
    And form the organic small molecule material layer on full-inorganic calcium titanium ore bed.
  2. 2. laminated film according to claim 1, it is characterised in that：The full-inorganic calcium titanium ore bed is ABX3, wherein A is Li+、Na+、K+、Rb+Or Cs+, B Zn2+、Ge2+、Sn2+Or Pb2+, X F-、Br-、Cl-Or I-In one kind, described organic small point The material of sub- material layer includes hole mobile material TAPC, CBP, TCTA or mCP.
  3. A kind of 3. Organic Light Emitting Diode based on laminated film, it is characterised in that including：
    ITO substrates and the hole injection layer being arranged on ITO substrates,
    Full-inorganic calcium titanium ore bed is set on the hole injection layer, and organic molecule material is set on full-inorganic calcium titanium ore bed The bed of material, the full-inorganic calcium titanium ore bed and organic small molecule material layer form laminated film, as hole transmission layer；
    Luminescent layer, electron transfer layer and negative electrode are set gradually on the hole transport layer.
  4. 4. Organic Light Emitting Diode according to claim 3, it is characterised in that：The organic small molecule material thickness degree is 0-20nm。
  5. 5. a kind of preparation method of Organic Light Emitting Diode as claimed in claim 3, it is characterised in that comprise the following steps：
    1) ITO substrates are pre-processed；
    2) hole injection layer is formed on ITO substrates；
    3) compound hole transmission layer is formed on hole injection layer, wherein, the full-inorganic calcium titanium ore bed and organic molecule Material layer can by any one method in spin-coating method, vapour deposition method, ink-jet printing process, knife coating, chemical vapour deposition technique into Type, or using any two kinds different method elder generation aftershapings in the above method；
    4) luminescent layer, electron transfer layer and negative electrode are formed on hole transmission layer.
  6. 6. the preparation method of Organic Light Emitting Diode according to claim 5, it is characterised in that：Using spin-coating method to calcium titanium Ore deposit precursor solution carries out spin coating, and the suction process under subnormal ambient immediately, transfers it in vacuum deposition system, Deposition forms organic small-molecule material layer, ultimately forms composite hole transporting layer.
  7. 7. the preparation method of Organic Light Emitting Diode according to claim 5, it is characterised in that：By PbX2It is molten with CsX powder Solution obtains the perovskite precursor solution into organic solution, and X is F wherein in formula-、Cl-、Br-、I-Middle one kind.
  8. 8. the preparation method of Organic Light Emitting Diode according to claim 7, it is characterised in that：The PbX2With rubbing for CsX You are than being 1:0.25~4.
  9. 9. the preparation method of Organic Light Emitting Diode according to claim 7, it is characterised in that：The organic solvent is two One kind in methyl sulfoxide, N,N-dimethylformamide, chloroform, chlorobenzene, toluene.
  10. 10. the preparation method of Organic Light Emitting Diode according to claim 6, it is characterised in that：Perovskite presoma is molten The spin coating rotating speed of liquid is 2000rpm~6000rpm, and spin-coating time is 5s~200s.
CN201710688589.2A 2017-08-12 2017-08-12 A kind of laminated film and Organic Light Emitting Diode and preparation method thereof Pending CN107452886A (en)

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Cited By (7)

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CN108807704A (en) * 2018-05-02 2018-11-13 西南大学 A kind of perovskite laminated film and light emitting diode and preparation method thereof
CN108682749A (en) * 2018-06-13 2018-10-19 西南大学 Perovskite light emitting diode of multi-quantum pit structure and preparation method thereof
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
CN109300805A (en) * 2018-08-31 2019-02-01 华南师范大学 Vacuum control CsPbIxBr3-xThe method and photovoltaic device of perovskite growth
CN109545991A (en) * 2018-10-24 2019-03-29 东北石油大学 Application of the gold nano bipyramid in OLED device
CN109273612A (en) * 2018-11-10 2019-01-25 济南大学 CsPbBr3The continuous gas-phase deposition process for preparing of perovskite battery
CN110112305A (en) * 2019-05-24 2019-08-09 京东方科技集团股份有限公司 QLED device and preparation method thereof, display panel and display device
CN110112305B (en) * 2019-05-24 2023-04-07 京东方科技集团股份有限公司 QLED device, manufacturing method thereof, display panel and display device
CN110600617A (en) * 2019-09-19 2019-12-20 重庆大学 Inorganic perovskite solar cell with ammonium chloride modified zinc oxide as electron transport material and preparation method thereof
CN110600617B (en) * 2019-09-19 2021-03-16 重庆大学 Inorganic perovskite solar cell with ammonium chloride modified zinc oxide as electron transport material and preparation method thereof

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