CN107452884B - Phosphorescent molecules sensitization multilayered structure light emitting diode with quantum dots of whole soln processing and preparation method thereof - Google Patents
Phosphorescent molecules sensitization multilayered structure light emitting diode with quantum dots of whole soln processing and preparation method thereof Download PDFInfo
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- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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Abstract
The invention discloses phosphorescent molecules sensitization multilayered structure light emitting diode with quantum dots of whole soln processing and preparation method thereof.It successively includes transparent substrates, transparent conductive film anode, hole injection and anode modification layer, phosphorescent molecules doping hole transmission layer, quantum dot active layer, electron transfer layer and metallic cathode that the phosphorescent molecules are sensitized multilayered structure light emitting diode with quantum dots from the bottom to top.The present invention uses orthogonal solvents method, PVK is adulterated as hole transport and phosphorescent molecules sensitizing layer by injecting one layer of phosphorescent molecules of spin coating between anode modification layer and quantum dot active layer in hole, realize that effective interfacial energy shifts between hole transport and phosphorescent molecules sensitizing layer and quantum dot active layer, improve hole injection, improves the efficiency of light emitting diode with quantum dots.Preparation method of the present invention is conducive to the preparation of the light emitting diode with quantum dots of large area, compared with hot evaporation mode, has and prepares advantage simple, at low cost.
Description
Technical field
The present invention relates to light emitting diode with quantum dots technical fields, and in particular to a kind of phosphorescent molecules of whole soln processing are quick
Change multilayered structure light emitting diode with quantum dots and preparation method thereof.
Background technique
Light emitting diode with quantum dots (abbreviation QD-LEDs) is with CdSe/ZnS, CuInS2II-VI race such as/ZnS or III-
Light emitting semiconductor device based on V race's semiconductor.Because it is adjustable with own dimensions with luminescent color, luminous efficiency is high, preparation
The features such as simple, has potential application in fields such as display, illuminations.With development in recent years, quotient is being done step-by-step
Industry.
But in current light emitting diode with quantum dots technology, polyvinyl carbazole (PVK), poly- [bis- (4- are mainly used
Phenyl) (4- butyl phenyl) amine] polymer materials and three (4- carbazole -9- base phenyl) amine (TCTA), 4 such as (Poly-TPD),
4'- it is bis- (NCarbazole) small molecule materials such as -1,1'- biphenyl (CBP) are as hole transmission layer, ZnO, TiO2Equal oxides conduct
Electron transfer layer.It, can be because of excessively high (1 eV ~ 2 of its hole injection barrier if the device architecture being directly injected into using hole and electronics
EV), the problems such as hole and electron transport material mobility mismatch causes its hole and electron injection uneven, to influence
The luminous efficiency of light emitting diode with quantum dots.
In general, Phosphorescent molecule has longer exciton lifetime, it is very suitable to do the donor material in energy transfer process
Material collects triplet excitons, is then transferred to receptor by F rster energy transfer mode, has length using Phosphorescent molecule
The triplet excitons in service life are to enhance the electroluminescent of quantum dot, i.e. phosphorescence sensitization (Nature, 403,750 (2000)).For
Phosphorescent molecules are doped to hole injection layer and form triplet state and swashed by the hole injection for improving light emitting diode with quantum dots device
Son using triplet excitons there is long exciton lifetime to be able to achieve the exciton energies of phosphorescent molecules in hole transmission layer to quantum dot
Between interfacial energy transfer occurs, to improve the efficiency of light emitting diode with quantum dots, i.e. photoactivated two pole of quantum dot light emitting of phosphorus
It manages (Appl. Phys. Lett., 97,253115 (2010)).
In order to realize the light emitting diode with quantum dots of phosphorescent molecules sensitization, it is usually to adopt that phosphorescent molecules, which adulterate hole transmission layer,
(ACS Appl. Mater. Interfaces, 7,25828 (2015)) are prepared with evaporation coating method, seldom report uses whole soln
Processing method prepares the light emitting diode with quantum dots of phosphorescent molecules sensitization multilayered structure.
Summary of the invention
It is an object of the invention to for the sensitization multilayered structure light emitting diode with quantum dots of phosphorescent molecules in the prior art
Preparation process complexity and deficiency at high cost provide a kind of phosphorescent molecules sensitization multilayered structure quantum dot hair of whole soln processing
Optical diode and preparation method thereof.
The present invention use orthogonal solvents method, reduce solution process in bottom functional layer corrosion, be sequentially prepared including
PEDOT:PSS layers, the functional layer of quantum dot active layer and electron transfer layer, and by the poly- enedioxy thiophene of PEDOT:PSS(
Pheno: poly- (styrene sulfonate)) between layer and quantum dot active layer one layer of phosphorescent molecules of spin coating doping PVK as hole transport and
Phosphorescent molecules sensitizing layer using phosphorescent molecules there is long exciton lifetime to realize hole transport and phosphorescent molecules sensitizing layer and quantum
Effective interfacial energy transfer, improves hole injection, improves the efficiency of light emitting diode with quantum dots, reusable heat between point luminescent layer
Evaporation coating method prepares Al metallic cathode, obtains phosphorescent molecules sensitization multilayered structure light emitting diode with quantum dots.
In whole soln method process, the advantage for having preparation simple, at low cost can reduce the cost of manufacture of device, lead to
The concentration of each functional layer solution in process is overregulated to change its thickness, and is changed phosphorescent molecules and adulterated hole transmission layer
The modes such as the proportion adjustment interfacial energy transfer of material optimize the performance of light emitting diode with quantum dots.
The purpose of the present invention is achieved through the following technical solutions.
A kind of phosphorescent molecules of whole soln processing are sensitized multilayered structure light emitting diode with quantum dots, successively include from the bottom to top
Transparent substrates, transparent conductive film anode, hole injection and anode modification layer, phosphorescent molecules adulterate hole transmission layer, quantum dot
Active layer, electron transfer layer and metallic cathode.
Further, the transparent substrates be include glass substrate, polyethylene terephthalate's substrate, polyimides
Substrate, dimethyl silicone polymer substrate, polymethyl methacrylate substrate or polycarbonate substrate.
Further, the transparent conductive film anode be include that ito thin film, metal nanowire thin-films or graphene are thin
Film.
Further, the hole injection and anode modification layer are PEDOT:PSS layers, with a thickness of 30 ~ 50 nm, wherein
The mass ratio of PEDOT:PSS is 1:6 ~ 1:20.
Further, the phosphorescent molecules doping hole transmission layer is the hole transport and phosphorescence that phosphorescent molecules adulterate PVK
Sensitizing layer, the doping of phosphorescent molecules are 5 ~ 20wt%.
Further, the phosphorescent molecules include blue emitting phosphor molecule or green light phosphorescent molecules.
It is further preferred that the blue emitting phosphor molecule is to include bis- (4,6- difluorophenyl pyridinato-N, C2) pyridinecarboxylics
Close iridium (FIrPic), two [2- (4,6- difluorophenyl) -4- (2,4,6- trimethylphenyl) pyridine-C2, N] pyridinecarboxylics
(PhFIrPic) or two [2- (5- cyano -4,6- difluorophenyl) pyridine-C2, N)] pyridinecarboxylics close the blue light of iridium (FCNIrPic)
Ir complex.
It is further preferred that the green light phosphorescent molecules are to include that three (2- phenylpyridines) close iridium (III) (Ir (ppy)3),
Three [2- (p-methylphenyl) pyridines] close iridium (III) (Ir (mppy)3) or acetopyruvic acid two (2- phenylpyridine-C2, N) conjunction iridium
(III) (Ir (ppy)2(acac)) green light Ir complex.
Further, phosphorescent molecules doping hole transmission layer with a thickness of 10 ~ 30nm.
Further, the quantum dot of the quantum dot active layer includes green light quantum point or red light quantum point, the feux rouges
Quantum dot includes CdSe/CdS/ZnS red light quantum point, and the green light quantum point includes CdSe/CdS/ZnS green light quantum point.
It is further preferred that the hole that the phosphorescent molecules doping hole transmission layer is blue emitting phosphor molecular dopant PVK passes
When defeated and phosphorescence sensitizing layer, the quantum dot of corresponding quantum dot active layer is green light quantum point or red light quantum point.
It is further preferred that the phosphorescent molecules doping hole transmission layer is the hole biography that green light phosphorescent molecules adulterate PVK
When defeated and phosphorescence sensitizing layer, the quantum dot of corresponding quantum dot active layer is red light quantum point.
Further, the quantum dot light emitting layer with a thickness of 15 ~ 30 nm.
Further, the electron transfer layer is ZnO nanoparticle electron transfer layer, with a thickness of 30 ~ 50 nm.
Further, the metallic cathode is Al metal electrode.
A kind of method of the phosphorescent molecules sensitization multilayered structure light emitting diode with quantum dots of preparation whole soln processing,
Include the following steps:
(1) after preparing transparent conductive film anode on a transparent substrate, the solution of spin coating PEDOT:PSS, heating is evaporated residual
Remaining solvent obtains the hole injection and anode modification layer；
(2) in the solution of hole injection and spin coating phosphorescent molecules doping PVK in anode modification layer, heating is evaporated remaining molten
Agent obtains the phosphorescent molecules doping hole transmission layer；
(3) the alkane solvents solution of spin coating quantum dot on hole transmission layer is adulterated in phosphorescent molecules, heating is evaporated remnants
Solvent obtains the quantum dot active layer；
(4) on quantum dot active layer spin coating ZnO nanoparticle alcohols solvent solution, heating be evaporated residual solvent, obtain
To the electron transfer layer；
(5) it moves into coating machine, hot evaporation Al obtains the phosphorescent molecules sensitization multilayer of the whole soln processing as cathode
Structure quantum point light emitting diode.
Further, the solvent of the solution of the PEDOT:PSS be include water or chlorobenzene.
Further, it includes chlorobenzene that the phosphorescent molecules, which adulterate the solvent of the solution of PVK to be,.
Further, the alkane solvents be spin coating process in will not corrosion phosphorescent molecules adulterate hole transmission layer it is non-
Polarity alkane solvents, including hexane, octane or certain herbaceous plants with big flowers alkane.
Further, the alcohols solvent be in spin coating process will not corrosion quantum dot light emitting layer and phosphorescent molecules doping it is empty
The low boiling point alcohols solvent of cave transport layer, including methanol, ethyl alcohol or butanol.
Compared with prior art, the invention has the advantages that and the utility model has the advantages that
(1) use the non-polar alkane solvents including hexane, octane or certain herbaceous plants with big flowers alkane as quantum dot in preparation method of the present invention
Dispersing agent, in spin coating process will not corrosion phosphorescent molecules adulterate hole transmission layer, ensure that phosphorescent molecules doping PVK and amount
The generation of interfacial energy transfer between son point, enhances the luminous efficiency and device stability of light emitting diode with quantum dots, to mention
The efficiency of high light emitting diode；
(2) dispersed in preparation method of the present invention by the low boiling point alcohols solvent that spin coating includes methanol, ethyl alcohol or butanol
ZnO nanoparticle forms electron injecting layer, solves solvent corrosion quantum dot light emitting layer and hole transmission layer in spin coating process
Problem；
(3) present invention prepares the light emitting diode with quantum dots of phosphorescent molecules sensitization by whole soln method processing, is conducive to big
The preparation of the light emitting diode with quantum dots of area has compared with hot evaporation mode and prepares advantage simple, at low cost.
Detailed description of the invention
Fig. 1 is that the phosphorescent molecules of whole soln of the present invention processing are sensitized the structural representation of multilayered structure light emitting diode with quantum dots
Figure；
Fig. 2 is that the phosphorescent molecules of whole soln processing in the specific embodiment of the invention are sensitized two pole of multilayered structure quantum dot light emitting
The preparation process flow schematic diagram of pipe；
Fig. 3 is to utilize Ir (ppy) in embodiment 13PVK layers of doping as hole transport and phosphorescent molecules sensitization multilayered structure
Red quantum point luminescent diode device architecture schematic diagram；
Fig. 4 a is to utilize Ir (ppy) in embodiment 13Doping ratio is 10%, different-thickness Ir (ppy)3PVK is adulterated as empty
The brightness of the red light quantum point LED device of cave transport layer-light-emitting efficiency characteristics curve graph；
Fig. 4 b is to utilize Ir (ppy) in embodiment 13Doping ratio is 10%, different-thickness Ir (ppy)3Adulterate PVK conduct
The electroluminescent light spectrogram of the red light quantum point LED device of hole transmission layer；
Fig. 4 c is to utilize Ir (ppy) in embodiment 13Doping PVK layer with a thickness of 20 nm, difference doping ratio Ir
(ppy)3Adulterate red light quantum point LED device of the PVK as hole transmission layer and PVK directly as hole transmission layer
Brightness-light-emitting efficiency characteristics curve graph；
Fig. 4 d is to utilize Ir (ppy) in embodiment 13PVK layer of doping with a thickness of 20 nm, difference doping ratio Ir
(ppy)3Adulterate red light quantum point LED device of the PVK as hole transmission layer and PVK directly as hole transmission layer
Electroluminescent light spectrogram；
Fig. 5 adulterates PVK layers using FIrpic for embodiment 2 and is sensitized the red of multilayered structure as hole transport and phosphorescent molecules
The device architecture schematic diagram of light quanta point light emitting diode；
Fig. 6 a is to adulterate the PVK layers of FIrpic with a thickness of 20nm, different doping ratios using FIrpic in embodiment 2 to adulterate
PVK shines as hole transmission layer and PVK directly as the brightness-of the red light quantum point LED device of hole transmission layer
Efficiency characteristic figure；
Fig. 6 b is to be mixed in embodiment 2 using the FIrpic with a thickness of 20nm, different doping ratios that FIrpic adulterates PVK layers
Miscellaneous PVK is as hole transmission layer and PVK directly as the electroluminescent hair of the red light quantum point LED device of hole transmission layer
Light spectrogram；
Fig. 7 adulterates PVK layers using FIrpic for embodiment 3 and is sensitized the green of multilayered structure as hole transport and phosphorescent molecules
The device architecture schematic diagram of light quanta point light emitting diode；
Fig. 8 a is to be mixed in embodiment 3 using the FIrpic with a thickness of 20nm, different doping ratios that FIrpic adulterates PVK layers
Miscellaneous PVK is as hole transmission layer and PVK directly as brightness-hair of the green light quantum point LED device of hole transmission layer
Light efficiency performance diagram；
Fig. 8 b is to be mixed in embodiment 3 using the FIrpic with a thickness of 20nm, different doping ratios that FIrpic adulterates PVK layers
Miscellaneous PVK is as hole transmission layer and PVK directly as the electroluminescent hair of the green light quantum point LED device of hole transmission layer
Light spectrogram.
Specific embodiment
Technical solution of the present invention is described in further detail below in conjunction with specific embodiments and the drawings, but institute of the present invention
It is required that protection scope be not limited to range involved in embodiment.
Fig. 1 is that the phosphorescent molecules of whole soln of the present invention processing are sensitized the structural representation of multilayered structure light emitting diode with quantum dots
Figure successively includes that transparent substrates, transparent conductive film anode, hole injection and anode modification layer, phosphorescent molecules are mixed from the bottom to top
Miscellaneous hole transmission layer, quantum dot active layer, electron transfer layer and metallic cathode.
Fig. 2 is that the phosphorescent molecules of whole soln processing in the specific embodiment of the invention are sensitized two pole of multilayered structure quantum dot light emitting
The preparation process flow schematic diagram of pipe utilizes rotation using the dispersing agent of suitably each functional layer material of orthogonal solvents method choice
Painting mode is sequentially prepared hole injection and anode modification layer, phosphorescent molecules doping hole transmission layer, quantum dot active layer and electronics
Transport layer, reusable heat evaporation coating method prepare Al metallic cathode, specifically successively comprising steps of
(1) after preparing transparent conductive film anode on a transparent substrate, the solution of spin coating PEDOT:PSS, heating is evaporated residual
Remaining solvent, obtain hole injection and anode modification layer, i.e. PEDOT:PSS layers；
(2) on PEDOT:PSS layer spin coating phosphorescent molecules doping PVK solution, heating be evaporated residual solvent, obtain phosphorescence
Molecular dopant hole transmission layer, i.e. phosphorescent molecules adulterate PVK layers；
(3) the alkane solvents solution of spin coating quantum dot on PVK layer is adulterated in phosphorescent molecules, heating is evaporated residual solvent,
Obtain quantum dot active layer；
(4) on quantum dot active layer spin coating ZnO nanoparticle alcohols solvent solution, heating be evaporated residual solvent, obtain
To electron transfer layer, i.e. ZnO layer；
(5) it moves into coating machine, hot evaporation Al obtains the phosphorescent molecules sensitization multilayered structure of whole soln processing as cathode
Light emitting diode with quantum dots.
Embodiment 1
A kind of red quantum point luminescent diode of the phosphorescent molecules sensitization multilayered structure of whole soln processing, device architecture show
It is intended to as shown in figure 3, being respectively successively from the bottom to top: ito glass substrate, PEDOT:PSS layers, Ir (ppy)3PVK layers of doping,
Red light quantum point active layer, ZnO layer and Al metal electrode.
The preparation step of the red quantum point luminescent diode of the phosphorescent molecules sensitization multilayered structure of the whole soln processing,
It is specific as follows:
(1) preparation hole injection and anode modification layer: on ito glass substrate spin coating PEDOT:PSS solution (PEDOT:
PSS mass ratio is 1:6), corresponding spin coating revolving speed 2000rpm, 1 minute, then, 120 DEG C of heating removal in 30 minutes was residual in thermal station
Remaining solvent obtains the PEDOT:PSS layer with a thickness of 40 nm；
(2) hole transport and phosphorescence sensitizing layer are prepared: by 0.4mg Ir (ppy)3With 3.6mg PVK, 0.8mg Ir (ppy)3
With 7.2mg PVK, 1.6mg Ir (ppy)3It is dissolved in respectively with 14.4mg PVK in the chlorobenzene of 2ml, simultaneously magnetic force stirs for 50 DEG C of heating
Promotion dissolution is mixed, and filters out insoluble part in the filter of 0.22 μ l, then by Ir (ppy)3It is spin-coated on the chlorobenzene solution of PVK
On PEDOT:PSS layer, corresponding spin coating revolving speed 2000rpm, 1 minute, and 150 DEG C of heating removal in 30 minutes is remaining molten in thermal station
Agent obtains Ir (ppy)3Doping ratio is 10% and with a thickness of the Ir of 10nm, 20nm and 40nm (ppy)3PVK layers of doping；
By 0.4mg Ir (ppy)3With 7.6mg PVK, by 0.8mg Ir (ppy)3With 7.2mg PVK and 1.6mg Ir
(ppy)3It is dissolved in respectively with 6.4mg PVK in the chlorobenzene of 2ml, 50 DEG C of heating and magnetic agitation promotion dissolution, and in 0.22 μ l
Filter filter out insoluble part, then by Ir (ppy)3It is spin-coated on PEDOT:PSS layer with the chlorobenzene solution of PVK, it is corresponding to revolve
Revolving speed 2000rpm is applied, 1 minute, and 150 DEG C of heating, 30 minutes removal residual solvents in thermal station, is obtained with a thickness of 20nm and Ir
(ppy)3The Ir (ppy) that doping ratio is 5%, 10% and 20%3PVK layers of doping；
(3) prepare quantum dot active layer: by the CdSe/CdS/ZnS red light quantum point of 10mg (emission peak is 610 ~
It 630nm) is dissolved in 1ml octane solvent, insoluble part is filtered out with the filter of 0.22 μ l, by CdSe/CdS/ZnS red quantum
The octane solution of point is spin-coated on Ir (ppy)3It adulterates on PVK layer, corresponding spin coating revolving speed 2000rpm, 1 minute, and 100 in thermal station
DEG C heating 30 minutes removal residual solvents, obtain the CdSe/CdS/ZnS red light quantum point active layer with a thickness of 20 nm；
(4) electron injection and transport layer are prepared: 30mg ZnO nanoparticle being dispersed in 1ml butanol solvent, with 0.22 μ
The filter of l filters out insoluble part, and it is living that the butanol dispersion liquid of ZnO nanoparticle is spin-coated on CdSe/CdS/ZnS red light quantum point
On property layer, corresponding spin coating revolving speed 2000rpm, 1 minute, and 100 DEG C of heating, 30 minutes removal residual solvents in thermal station, it obtains
With a thickness of the ZnO nanoparticle electron transfer layer of 50 nm；
(5) evaporation metal electrode: moving into hot evaporation Al in evaporator for sample and do cathode, obtains the whole soln processing
It utilizes Ir (ppy)3Adulterate red quantum point luminescent diode of the PVK as hole transmission layer.
It utilizes Ir (ppy)3Adulterate red light quantum point of the PVK as hole transmission layer and PVK directly as hole transmission layer
Respectively as shown in Fig. 4 a and Fig. 4 c, electroluminescent light spectrogram divides the brightness of LED device-light-emitting efficiency characteristics curve graph
Not as shown in Fig. 4 b and Fig. 4 d；By Fig. 4 a it is found that in the case where being mutually all 10% doping ratio, when using 10nm, 20nm and 40nm
Ir(ppy)3When the PVK of doping adulterates hole transmission layer as phosphorescent molecules, the maximum of red quantum point luminescent diode shines
Efficiency promotes the 18.9cd/A to 20nm from the 10.3cd/A of 10nm, then drops to the 6.7cd/A of 40nm；By Fig. 4 c it is found that
In the case where being mutually all the thickness of 20nm, the maximum luminous efficiency of red quantum point luminescent diode is promoted from the 6.88cd/A to undope
To 5% Ir (ppy)3The 11.5cd/A of doping, 10% Ir (ppy)3The 18.9cd/A of doping finally drops to 20% Ir again
(ppy)3The 13.1cd/A of doping；As shown in Fig. 4 b and Fig. 4 d, with thickness and Ir (ppy)3The variation of doping ratio, feux rouges
The glow peak of light emitting diode with quantum dots is 627nm, and halfwidth (FWHM) is 40nm.
Embodiment 2
A kind of red quantum point luminescent diode of the phosphorescent molecules sensitization multilayered structure of whole soln processing, device architecture show
Be intended to as shown in figure 5, being respectively successively from the bottom to top: ito glass substrate, PEDOT:PSS layer, FIrpic doping PVK layers, it is red
Light quanta point active layer, ZnO layer and Al metal electrode.
The preparation step of the red quantum point luminescent diode of the phosphorescent molecules sensitization multilayered structure of the whole soln processing,
It is specific as follows:
(1) preparation hole injection and anode modification layer: on ito glass substrate spin coating PEDOT:PSS solution (PEDOT:
PSS mass ratio is 1:12), corresponding spin coating revolving speed 2000rpm, 1 minute, then, 120 DEG C of heating removal in 30 minutes was residual in thermal station
Remaining solvent obtains the PEDOT:PSS layer with a thickness of 40 nm；
(2) by 0.4mg FIrpic and 7.6mg PVK, 0.8mg FIrpic and 7.2mg PVK and 1.6mg FIrpic and
6.4mg PVK is dissolved in respectively in the chlorobenzene of 2ml, 50 DEG C of heating and magnetic agitation promotion dissolution, and is filtered in the filter of 0.22 μ l
Except insoluble part, then the chlorobenzene solution of FIrpic and PVK is spin-coated on PEDOT:PSS layer, corresponding spin coating revolving speed
2000rpm, 1 minute, and 150 DEG C of heating, 30 minutes removal residual solvents in thermal station, it obtains with a thickness of 20nm and FIrpic mixes
The FIrpic that miscellaneous ratio is 5%, 10% and 20% adulterates PVK layers；
(3) prepare quantum dot active layer: by the CdSe/CdS/ZnS red light quantum point of 10mg (emission peak is 610 ~
It 630nm) is dissolved in 1ml octane solvent, insoluble part is filtered out with the filter of 0.22 μ l, by CdSe/CdS/ZnS red quantum
The octane solution of point is spin-coated on the PVK layer of FIrpic doping, corresponding spin coating revolving speed 2000rpm, and 1 minute, and 100 in thermal station
DEG C heating 30 minutes removal residual solvents, obtain the CdSe/CdS/ZnS red light quantum point active layer with a thickness of 20 nm；
(4) electron injection and transport layer are prepared: 30mg ZnO nanoparticle being dispersed in 1ml butanol solvent, with 0.22 μ
The filter of l filters out insoluble part, and it is living that the butanol dispersion liquid of ZnO nanoparticle is spin-coated on CdSe/CdS/ZnS red light quantum point
On property layer, corresponding spin coating revolving speed 2000rpm, 1 minute, and 100 DEG C of heating, 30 minutes removal residual solvents in thermal station, it obtains
With a thickness of the ZnO nanoparticle electron transfer layer of 50 nm；
(5) evaporation metal electrode: moving into hot evaporation Al in evaporator for sample and do cathode, obtains the whole soln processing
Using FIrpic doping PVK as the red quantum point luminescent diode of hole transmission layer.
It is sent out using FIrpic doping PVK as hole transmission layer and PVK directly as the red light quantum point of hole transmission layer
The brightness of optical diode device-light-emitting efficiency characteristics curve graph and electroluminescent light spectrogram respectively as shown in figures 6 a and 6b, by
Fig. 6 a and Fig. 6 b it is found that when the PVK for using the FIrpic of 20nm thickness to adulterate as phosphorescent molecules adulterate hole transmission layer when, feux rouges
The maximum luminous efficiency of light emitting diode with quantum dots is adulterated from the 11.6cd/A promotion to undope to 5% FIrpic
The 13.7cd/A of 20.4cd/A, 20% the FIrpic doping of 17.2cd/A, 10% FIrpic doping, and different doping FIrpic mix
The glow peak of miscellaneous device is 627nm, FWHM 40nm.
Embodiment 3
A kind of green quantum point luminescent diode of the phosphorescent molecules sensitization multilayered structure of whole soln processing, device architecture show
Be intended to as shown in fig. 7, being respectively successively from the bottom to top: ito glass substrate, PEDOT:PSS layer, FIrpic doping PVK layers, it is green
Light quanta point active layer, ZnO layer and Al metal electrode.
The preparation step of the red quantum point luminescent diode of the phosphorescent molecules sensitization multilayered structure of the whole soln processing,
It is specific as follows:
(1) preparation hole injection and anode modification layer: on ito glass substrate spin coating PEDOT:PSS solution (PEDOT:
PSS mass ratio is 1:20), corresponding spin coating revolving speed 2000rpm, 1 minute, then, 120 DEG C of heating removal in 30 minutes was residual in thermal station
Remaining solvent obtains the PEDOT:PSS layer with a thickness of 40 nm；
(2) 0.4mg FIrpic and 7.6mg PVK and 0.8mg FIrpic and 7.2mg PVK are dissolved in 2ml's respectively
In chlorobenzene, 50 DEG C of heating and magnetic agitation promotion dissolution, and insoluble part is filtered out in the filter of 0.22 μ l, then by FIrpic
It is spin-coated on PEDOT:PSS layer with the chlorobenzene solution of PVK, corresponding spin coating revolving speed 2000rpm, 1 minute, and 150 DEG C in thermal station
30 minutes removal residual solvents are heated, obtain adulterating PVK with a thickness of the FIrpic that 20nm and FIrpic doping ratio is 5% and 10%
Layer；
(3) prepare quantum dot active layer: by the CdSe/CdS/ZnS green light quantum point of 10mg (emission peak is 520 ~
It 550nm) is dissolved in 1ml octane solvent, insoluble part is filtered out with the filter of 0.22 μ l, by CdSe/CdS/ZnS green quantum
The octane solution of point is spin-coated on FIrpic doping PVK layer, corresponding spin coating revolving speed 2000rpm, and 1 minute, and 100 in thermal station
DEG C heating 30 minutes removal residual solvents, obtain the CdSe/CdS/ZnS green light quantum point active layer with a thickness of 20 nm；
(4) electron injection and transport layer are prepared: 30mg ZnO nanoparticle being dispersed in 1ml butanol solvent, with 0.22 μ
The filter of l filters out insoluble part, and it is living that the butanol dispersion liquid of ZnO nanoparticle is spin-coated on CdSe/CdS/ZnS green light quantum point
On property layer, corresponding spin coating revolving speed 2000rpm, 1 minute, and 100 DEG C of heating, 30 minutes removal residual solvents in thermal station, it obtains
With a thickness of the ZnO nanoparticle electron transfer layer of 50 nm；
(5) evaporation metal electrode: moving into hot evaporation Al in evaporator for sample and do cathode, obtains the whole soln processing
Using FIrpic doping PVK as the green quantum point luminescent diode of hole transmission layer.
It is sent out using FIrpic doping PVK as hole transmission layer and PVK directly as the green light quantum point of hole transmission layer
The brightness of optical diode device-light-emitting efficiency characteristics curve graph and electroluminescent light spectrogram respectively as figures 8 a and 8 b show, by
Fig. 8 a and Fig. 8 b it is found that when the PVK for using the FIrpic of 20nm thickness to adulterate as phosphorescent molecules adulterate hole transmission layer when, green light
The maximum luminous efficiency of light emitting diode with quantum dots is adulterated from the 22.4cd/A promotion to undope to 5% FIrpic
The 36.9cd/A of 37.2cd/A and 10%FIrpic doping, and the glow peak of quantum dot device is 527nm, FWHM 30nm.
It can be seen that the multilayered structure light emitting diode with quantum dots result that phosphorescent molecules are sensitized from the result of embodiment 1 ~ 3
With preferable luminous efficiency, meanwhile, there is no shining for functional layer in electroluminescent spectrum, the especially transmitting of phosphorescent molecules is said
Bright phosphorescent molecules sensitizing layer is very complete to the energy transfer between quantum dot.
Claims (9)
1. a kind of phosphorescent molecules of whole soln processing are sensitized multilayered structure light emitting diode with quantum dots, which is characterized in that by down toward
On successively include transparent substrates, transparent conductive film anode, hole injection and anode modification layer, phosphorescent molecules adulterate hole transport
Layer, quantum dot active layer, electron transfer layer and metallic cathode；The phosphorescent molecules doping hole transmission layer is phosphorescent molecules doping
The hole transport and phosphorescence sensitizing layer of PVK, the doping of phosphorescent molecules are 5 ~ 20wt%；The phosphorescent molecules include blue emitting phosphor
Molecule or green light phosphorescent molecules.
2. a kind of phosphorescent molecules of whole soln processing according to claim 1 are sensitized two pole of multilayered structure quantum dot light emitting
Pipe, which is characterized in that the transparent substrates be include glass substrate, polyethylene terephthalate's substrate, polyimides lining
Bottom, dimethyl silicone polymer substrate, polymethyl methacrylate substrate or polycarbonate substrate；The transparent conductive film anode
Being includes ito thin film, metal nanowire thin-films or graphene film.
3. a kind of phosphorescent molecules of whole soln processing according to claim 1 are sensitized two pole of multilayered structure quantum dot light emitting
Pipe, which is characterized in that the hole injection and anode modification layer are PEDOT:PSS layers, with a thickness of 30 ~ 50 nm, wherein
The mass ratio of PEDOT:PSS is 1:6 ~ 1:20.
4. a kind of phosphorescent molecules of whole soln processing according to claim 3 are sensitized two pole of multilayered structure quantum dot light emitting
Pipe, which is characterized in that the blue emitting phosphor molecule is the blue light Ir complex for including FIrPic, PhFIrPic or FCNIrPic；
The green light phosphorescent molecules be include Ir (ppy)3、Ir(mppy)3Or Ir (ppy)2(acac) green light Ir complex.
5. a kind of phosphorescent molecules of whole soln processing according to claim 3 are sensitized two pole of multilayered structure quantum dot light emitting
Pipe, which is characterized in that the hole transport and phosphorescence that the phosphorescent molecules doping hole transmission layer is blue emitting phosphor molecular dopant PVK
When sensitizing layer, the quantum dot of corresponding quantum dot active layer is green light quantum point or red light quantum point；The phosphorescent molecules doping
When hole transmission layer is the hole transport and phosphorescence sensitizing layer that green light phosphorescent molecules adulterate PVK, corresponding quantum dot active layer
Quantum dot is red light quantum point.
6. a kind of phosphorescent molecules of whole soln processing according to claim 1 are sensitized two pole of multilayered structure quantum dot light emitting
Pipe, which is characterized in that phosphorescent molecules doping hole transmission layer with a thickness of 10 ~ 30nm.
7. a kind of phosphorescent molecules of whole soln processing according to claim 1 are sensitized two pole of multilayered structure quantum dot light emitting
Pipe, which is characterized in that the quantum dot active layer with a thickness of 15 ~ 30 nm；The electron transfer layer is ZnO nanoparticle electricity
Sub- transport layer, with a thickness of 30 ~ 50 nm；The metallic cathode is Al metal electrode.
8. preparing a kind of described in any item phosphorescent molecules sensitization multilayered structure quantum dot hairs of whole soln processing of claim 1 ~ 7
The method of optical diode, which comprises the steps of:
(1) after preparing transparent conductive film anode on a transparent substrate, the solution of spin coating PEDOT:PSS, heating is evaporated remaining molten
Agent obtains the hole injection and anode modification layer；
(2) in the solution of hole injection and spin coating phosphorescent molecules doping PVK in anode modification layer, heating is evaporated residual solvent, obtains
Hole transmission layer is adulterated to the phosphorescent molecules；
(3) the alkane solvents solution of spin coating quantum dot on hole transmission layer is adulterated in phosphorescent molecules, heating is evaporated residual solvent,
Obtain the quantum dot light emitting layer；
(4) on quantum dot light emitting layer spin coating ZnO nanoparticle alcohols solvent solution, heating be evaporated residual solvent, obtain institute
State electron transfer layer；
(5) it moves into coating machine, hot evaporation Al obtains the phosphorescent molecules sensitization multilayered structure of the whole soln processing as cathode
Light emitting diode with quantum dots.
9. a kind of phosphorescent molecules of whole soln processing according to claim 8 are sensitized multilayered structure light emitting diode with quantum dots
Preparation method, which is characterized in that the solvent of the solution of the PEDOT:PSS be include water or chlorobenzene；The phosphorescent molecules are mixed
The solvent of the solution of miscellaneous PVK be include chlorobenzene；The alkane solvents are will not corrosion phosphorescent molecules doping sky in spin coating process
The non-polar alkane class solvent of cave transport layer, including hexane, octane or certain herbaceous plants with big flowers alkane；The alcohols solvent is will not be molten in spin coating process
Lose the low boiling point alcohols solvent of quantum dot light emitting layer and phosphorescent molecules doping hole transmission layer, including methanol, ethyl alcohol or butanol.
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