CN109585698A - A kind of method that solwution method prepares the low-voltage driving Organic Light Emitting Diode of p-i-n structure - Google Patents
A kind of method that solwution method prepares the low-voltage driving Organic Light Emitting Diode of p-i-n structure Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000000758 substrate Substances 0.000 claims abstract description 53
- 229920001167 Poly(triaryl amine) Polymers 0.000 claims abstract description 46
- 239000002042 Silver nanowire Substances 0.000 claims abstract description 41
- 239000011521 glass Substances 0.000 claims abstract description 30
- 230000005540 biological transmission Effects 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 46
- 229920002873 Polyethylenimine Polymers 0.000 claims description 34
- 238000002360 preparation method Methods 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000004528 spin coating Methods 0.000 claims description 23
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 13
- 238000000137 annealing Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 239000002096 quantum dot Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 230000003760 hair shine Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000007738 vacuum evaporation Methods 0.000 claims description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical class CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 238000002347 injection Methods 0.000 abstract description 9
- 239000007924 injection Substances 0.000 abstract description 9
- 230000004888 barrier function Effects 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 4
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000005360 2-phenylpyridines Chemical class 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
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- 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
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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]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
- H10K50/155—Hole transporting layers comprising dopants
-
- 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]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
- H10K50/165—Electron transporting layers comprising dopants
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
Abstract
A kind of method that solwution method prepares the low-voltage driving Organic Light Emitting Diode (OLED) of p-i-n structure, the OLED device with transparent ito glass substrate, p-type doping transport layer, luminescent layer, n-type doping transport layer, electron buffer layer and metal back electrode superposition by forming.The present invention can effectively improve the transmission performance of hole transmission layer, and reduce hole injection barrier, to reduce the driving voltage of device by the way that composite material PTAA:AgNWs to be introduced into OLED device；PEI:SnS is prepared by solwution method2Electron transfer layer of-the QDs as OLED device further improves the injection and transmittability of electronics in device.Finally while reducing device drive voltage, the luminous efficiency of OLED device is effectively improved.
Description
Technical field
The invention belongs to technical field of organic electroluminescence, in particular to a kind of solwution method prepares the low pressure of p-i-n structure
The method for driving Organic Light Emitting Diode.
Background technique
Organic electroluminescence device (OLED) is with its wide viewing angle, self-luminous, response time are fast, can flexibility the advantages that aobvious
Show and is widely used with lighting area.In the OLED of p-i-n structure, electrons and holes pass through n-type doping and p respectively
The transport layer of type doping can be efficiently transferred in luminescent layer, and the recombination probability of carrier, thus the hair of device greatly improved
Light efficiency is higher.But the OLED of traditional p-i-n structure is all based on the technique of vacuum thermal evaporation to prepare device.However it utilizes true
Empty hot evaporation method is extremely complex come the technique for preparing doping type function film, higher cost, is especially difficult accurately to control low
The doping ratio of concentration Subjective and Objective, to constrain the further development of multilayered structure OLED.
Compared to traditional vacuum hot evaporation process, there is preparation process letter using the OLED that solwution method prepares p-i-n structure
Single, at low cost, many advantages, such as low concentration doping ratio is controllable, if preparing good film-forming property, carrier mobility by solwution method
The high multiplexing of transmission material of rate, and being applied in the OLED of p-i-n structure, will be expected to further increase solwution method and prepares OLED's
Luminescent properties.
Summary of the invention
It is high object of the present invention is to solve carrier mobility in the transport layer of solwution method preparation existing in the prior art,
Film forming is bad to cause device drive voltage higher, the problem of luminescent properties difference, provides a kind of solwution method and prepares p-i-n structure
The method of Organic Light Emitting Diode (OLED) can be effective by the way that composite material PTAA:AgNWs to be introduced into OLED device
The transmission performance of hole transmission layer is improved, and reduces hole injection barrier, to reduce the driving voltage of device；Pass through solution
Method prepares PEI:SnS2Electron transfer layer of-the QDs as OLED device further improves the injection and biography of electronics in device
Movement Capabilities.Finally while reducing device drive voltage, the luminous efficiency of OLED device is effectively improved.
The technical scheme is that
A kind of method that solwution method prepares the low-voltage driving Organic Light Emitting Diode of p-i-n structure, includes the following steps:
(1) the transparent ito glass substrate after surface clean is surface-treated using UV ozone, then by ITO glass
Glass substrate is transferred in the glove box full of argon atmosphere, and using solwution method, successively spin coating preparation p-type is mixed on ito glass substrate
Miscellaneous transport layer, luminescent layer and n-type doping transport layer；
The step of surface clean is carried out before being surface-treated to transparent ito glass substrate is, first by transparent ITO
After glass substrate successively uses ethyl alcohol, acetone, isopropanol ultrasonic cleaning 15min, is rinsed with deionized water, dried at 150 DEG C
30min；
(2) finally using the method preparation electron buffer layer and metal back electrode of vacuum evaporation deposition.
P-type doping transport layer material therefor described in step (1) is poly- [bis- (4- phenyl) (2,4,6- trimethylphenyl)
Amine] doping silver nanowires (PTAA:AgNWs) composite material.P-type doping transport layer preparation step is as follows:
Poly- [bis- (4- phenyl) (2,4,6- trimethylphenyl) amine] (PTAA) powder, which is weighed, with electronic balance is dissolved in toluene
In solution, compound concentration is the PTAA solution of 10mg/ml；Silver nanowires (AgNWs) is dispersed in ethanol solution, and concentration is
10mg/ml；PTAA solution is uniformly mixed with AgNWs solution with volume ratio for 10~30:1, it is molten that PTAA:AgNWs mixing is made
Liquid；Ito glass substrate is placed on sol evenning machine, PTAA:AgNWs mixed solution is taken to be added dropwise on ito glass substrate, with
The revolving speed spin coating 30s of 1500rpm, the substrate for being coated with PTAA:AgNWs film prepared is placed in 100 DEG C of thermal station and is annealed
15min is handled, so that preparing the p-type doping that thicknesses of layers is 60nm on ito glass substrate transmits layer film.
Spin speed in the spin coating process is 1500rpm, spin-coating time 30s.
Luminescent layer material therefor described in step (1) is that polyvinylcarbazole adulterates three (2- phenylpyridines) conjunction iridium and 2- simultaneously
(4 '-xenyl) -5- (4 ' -2-methyl-2-phenylpropane base) -1,3,4- oxadiazoles (PVK:Ir (ppy)3: PBD) composite material.The luminescent layer
Preparation step is as follows: green light phosphor material three (2- phenylpyridine) is closed iridium (Ir (ppy)3) and 2- with electronic transport property
(4 '-xenyl) -5- (4 ' -2-methyl-2-phenylpropane base) -1,3,4- oxadiazoles (PBD) mixes in polymer body polyvinylcarbazole (PVK)
Green light emitting layer is prepared, according to PVK:Ir (ppy)3: the mass ratio of PBD=6:3:2 mixes three kinds of materials and to be dissolved in DMF molten
In liquid, solution stirring and dissolving 2h PVK:Ir produced above (ppy) at normal temperature3: PBD mixed solution, it is spare；P is had by above-mentioned
The substrate of type doping transmission layer film is placed on sol evenning machine, takes PVK:Ir (ppy)3: PBD mixed solution is added dropwise in PTAA:
On AgNWs film, with the revolving speed spin coating 30s of 2000rpm, PVK:Ir (ppy) is coated with by what is prepared3: the substrate of PBD film is set
In making annealing treatment 20min in 100 DEG C of thermal station, to prepare the luminous layer film that thicknesses of layers is 40nm.
Spin speed in the spin coating process is 2000rpm, spin-coating time 30s.
N-type doping transport layer material therefor described in step (1) be polyethyleneimine amino-group doping artificial gold quantum dot (PEI:
SnS2-QDs).The n-type doping transport layer preparation step is as follows: weighing SnS with electronic balance2Powder is dispersed in ethanol solution
In, it is ultrasonically treated the SnS that 1h concentration made above is 10mg/ml2Suspension；By SnS2Suspension is centrifuged 40min with 11000rpm
Afterwards, supernatant is taken to obtain artificial gold quantum dot (SnS2- QDs) solution；The polyethyleneimine (PEI) for being again 1.08g/ml by concentration
Aqueous solution and SnS2- QDs solution is uniformly mixed with the volume ratio of 1:400~600, obtains PEI:SnS2- QDs mixed solution；It will power
Benefit requires the 3 obtained substrates with p-type doping transport layer and luminous layer film to be placed on sol evenning machine, takes PEI:SnS2-QDs
Mixed solution is added dropwise at PVK:Ir (ppy)3: PBD shines on layer film, with the revolving speed spin coating 30s of 3000rpm, by what is prepared
It is coated with PEI:SnS2The substrate of-QDs film is placed in 100 DEG C of thermal station and makes annealing treatment 15min, to prepare thicknesses of layers and be
The n-type doping of 35nm transmits layer film.
Spin speed in the spin coating process is 3000rpm, spin-coating time 30s.
Electron buffer layer described in step (2) is lithium fluoride (LiF), and metal back electrode is aluminium (Al).
The advantages of the present invention:
(1) present invention effectively improves hole transmission layer by the way that composite material PTAA:AgNWs to be introduced into OLED device
Transmission performance, and hole injection barrier is reduced, to reduce the driving voltage of device.
(2) PEI:SnS is prepared by solwution method2Electron transfer layer of-the QDs as OLED device, further improves
The injection and transmittability of electronics, effectively improve the luminous efficiency of OLED device in device.
(3) the low-voltage driving Organic Light Emitting Diode that a kind of solwution method of the present invention prepares p-i-n structure has low
Voltage driving, high brightness, high efficiency, the advantage that stability is good and preparation process is simple.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of organic electroluminescence device.
Fig. 2 is the scanning electron microscope image of AgNWs.
Fig. 3 is the SnS of preparation2The transmission electron microscope image of-QDs.
Fig. 4 is luminescent device pictorial diagram.
Fig. 5 is Current density-voltage-light emission luminance of PTAA and the AgNWs luminescent device of compound preparation in varing proportions
(A, B-1, C-1, D-1 are respectively the luminescent device prepared in embodiment 1, embodiment 2, embodiment 3 and comparative example 1 to curve in figure
Current density-voltage-light emission luminance curve).
Fig. 6 is current efficiency-current density plot of PTAA and the AgNWs luminescent device of compound preparation in varing proportions
(A, B-1, C-1, D-1 are respectively the electricity of the luminescent device prepared in embodiment 1, embodiment 2, embodiment 3 and comparative example 1 in figure
Flow efficiency-current density plot).
Fig. 7 is PEI and SnS2Current density-voltage-luminance of-QDs the luminescent device of compound preparation in varing proportions
Writing music, (A, B-2, C-2, D-2 are respectively the photophore prepared in embodiment 1, embodiment 4, embodiment 5 and comparative example 2 to line in figure
The Current density-voltage of part-light emission luminance curve).
Fig. 8 is PEI and SnS2Current efficiency-current density plot of-QDs the luminescent device of compound preparation in varing proportions
(A, B-2, C-2, D-2 are respectively the electricity of the luminescent device prepared in embodiment 1, embodiment 4, embodiment 5 and comparative example 2 in figure
Flow efficiency-current density plot).
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
The method that solwution method prepares the low-voltage driving Organic Light Emitting Diode of p-i-n structure, specific implementation step are as follows:
The etching of 1.ITO glass substrate: ito glass substrate is formed into strip electrode by chemical attack, by what is etched
After ito glass substrate successively uses ethyl alcohol, acetone, isopropanol ultrasonic cleaning 15min, is rinsed with deionized water, dried at 150 DEG C
30min；
The preparation of 2.p type doping transport layer: it is dissolved in toluene solution, is matched with the PTAA powder that electronic balance weighs 10mg
Concentration processed is the PTAA solution of 10mg/ml.AgNWs is dispersed in ethanol solution, and concentration is 10mg/ml (as shown in Figure 2).It will
PTAA solution is uniformly mixed with AgNWs solution with volume ratio for 20:1, and PTAA:AgNWs mixed solution is made.It will be standby in step 1
Ito glass substrate is placed on sol evenning machine, and suitable PTAA:AgNWs mixed solution is taken to be added dropwise on ito glass substrate,
With the revolving speed spin coating 30s of 1500rpm, the substrate for being coated with PTAA:AgNWs film prepared is placed in 100 DEG C of thermal station and is moved back
Fire processing 15min, so that preparing the p-type doping that thicknesses of layers is 60nm on ito glass substrate transmits layer film.
3. the preparation of luminescent layer: by green light phosphor material Ir (ppy)3Polymerization is mixed with the PBD with electronic transport property
Green light emitting layer is prepared in owner's body PVK, according to PVK:Ir (ppy)3: the mass ratio of PBD=6:3:2 mixes three kinds of materials simultaneously
It is dissolved in DMF solution, solution stirring and dissolving 2h PVK:Ir produced above (ppy) at normal temperature3: PBD mixed solution, it is spare.
The substrate with film that step 2 is obtained is placed on sol evenning machine, takes suitable PVK:Ir (ppy)3: PBD mixed solution drop
It is added on PTAA:AgNWs film, with the revolving speed spin coating 30s of 2000rpm, is coated with PVK:Ir (ppy) for what is prepared3: PBD is thin
The substrate of film is placed in 100 DEG C of thermal station and makes annealing treatment 20min, to prepare the luminous layer film that thicknesses of layers is 40nm.
The preparation of 4.n type doping transport layer: the SnS of 10mg is weighed with electronic balance2Powder is dispersed in ethanol solution, is surpassed
Sonication 1h concentration derived above is the SnS of 10mg/ml2Suspension.By SnS2After suspension is centrifuged 40min with 11000rpm, take
Supernatant obtains SnS2- QDs solution (as shown in Figure 3).The PEI aqueous solution and SnS for being again 1.08g/ml by concentration2- QDs solution
It is uniformly mixed with the volume ratio of 1:500, obtains PEI:SnS2- QDs mixed solution.The substrate with film that step 3 is obtained
It is placed on sol evenning machine, takes suitable PEI:SnS2- QDs mixed solution is added dropwise at PVK:Ir (ppy)3: on PBD film, with
The revolving speed spin coating 30s of 3000rpm, is coated with PEI:SnS for what is prepared2The substrate of-QDs film is placed in 100 DEG C of thermal station and moves back
Fire processing 15min, so that preparing the n-type doping that thicknesses of layers is 35nm transmits layer film.
5. the preparation of electron buffer layer and metal back electrode: the film that step 4 is obtained is placed in vacuum coating equipment, is taken out true
Sky is to 2 × 10-5The metal Al electrode of the electron buffer layer LiF and 120nm of 1nm is deposited in Pa.The effective area of device is ITO sun
The intersection area of pole and metal Al cathode is 3mm × 3mm.
The scanning electron microscope image for testing AgNWs used is shown in Fig. 2, the model of used scanning electron microscope
Hitachi Hitachi SU8010；The SnS of preparation2The transmission electron microscope image of-QDs is shown in that Fig. 3, used transmitted electron are aobvious
The model JEM-2010FEF of micro mirror；The photoelectric properties of the OLED of preparation by the 2400 Current Voltage source U.S. Keithley and
The test of PhotoResearch PR650 spectral scan colorimeter.
Embodiment 2
For specific implementation method in addition to the following conditions are different, other are same as Example 1:
The preparation of p-type doping transport layer: being dissolved in toluene solution with the PTAA powder that electronic balance weighs 10mg, is prepared
Concentration is the PTAA solution of 10mg/ml.It with volume ratio is that 30:1 is mixed by the AgNWs solution that PTAA solution is 10mg/ml with concentration
It closes uniform.Ito glass substrate spare in step 1 is placed on sol evenning machine, suitable PTAA:AgNWs mixed solution is taken to drip
It is added on ito glass substrate, with the revolving speed spin coating 30s of 1500rpm, the substrate for being coated with PTAA:AgNWs film prepared is set
In making annealing treatment 15min in 100 DEG C of thermal station, to prepare the p-type doping that thicknesses of layers is 60nm on ito glass substrate
Transmit layer film.
Embodiment 3
For specific implementation method in addition to the following conditions are different, other are same as Example 1:
The preparation of p-type doping transport layer: being dissolved in toluene solution with the PTAA powder that electronic balance weighs 10mg, is prepared
Concentration is the PTAA solution of 10mg/ml.It with volume ratio is that 10:1 is mixed by the AgNWs solution that PTAA solution is 10mg/ml with concentration
It closes uniform.Ito glass substrate spare in step 1 is placed on sol evenning machine, suitable PTAA:AgNWs mixed solution is taken to drip
It is added on ito glass substrate, with the revolving speed spin coating 30s of 1500rpm, the substrate for being coated with PTAA:AgNWs film prepared is set
In making annealing treatment 15min in 100 DEG C of thermal station, to prepare the p-type doping that thicknesses of layers is 60nm on ito glass substrate
Transmit layer film.
Embodiment 4
For specific implementation method in addition to the following conditions are different, other are same as Example 1:
The preparation of n-type doping transport layer: the SnS of 10mg is weighed with electronic balance2Powder is dispersed in ethanol solution, ultrasound
Handle the SnS that 1h concentration derived above is 10mg/ml2Suspension.By SnS2After suspension is centrifuged 40min with 11000rpm, take
Clear liquid obtains SnS2- QDs solution (as shown in Figure 3).The PEI aqueous solution and SnS for being again 1.08g/ml by concentration2- QDs solution with
The volume ratio of 1:400 is uniformly mixed.The substrate for the film that step 3 obtains is placed on sol evenning machine, suitable PEI:SnS is taken2-
QDs mixed solution is added dropwise at PVK:Ir (ppy)3: on PBD film, with the revolving speed spin coating 30s of 3000rpm, it is coated with what is prepared
PEI:SnS2The substrate of-QDs film is placed in 100 DEG C of thermal station and makes annealing treatment 15min, so that preparing thicknesses of layers is 35nm
N-type doping transmit layer film.
Embodiment 5
For specific implementation method in addition to the following conditions are different, other are same as Example 1:
The preparation of n-type doping transport layer: the SnS of 10mg is weighed with electronic balance2Powder is dispersed in ethanol solution, ultrasound
Handle the SnS that 1h concentration derived above is 10mg/ml2Suspension.By SnS2After suspension is centrifuged 40min with 11000rpm, take
Clear liquid obtains SnS2- QDs solution (as shown in Figure 3).Again by concentration be 1.08g/ml PEI aqueous solution with the volume ratio of 1:600
It is uniformly mixed.The substrate for the film that step 3 obtains is placed on sol evenning machine, suitable PEI:SnS is taken2- QDs mixed solution drop
It is added in PVK:Ir (ppy)3: on PBD film, with the revolving speed spin coating 30s of 3000rpm, PEI:SnS is coated with by what is prepared2- QDs is thin
The substrate of film is placed in 100 DEG C of thermal station and makes annealing treatment 15min, transmits to prepare the n-type doping that thicknesses of layers is 35nm
Layer film.
Comparative example 1
For specific implementation method in addition to the following conditions are different, other are same as Example 1:
The preparation of hole transmission layer: being dissolved in toluene solution with the PTAA powder that electronic balance weighs 10mg, is prepared dense
Degree is the PTAA solution of 10mg/ml.Ito glass substrate spare in step 1 is placed on sol evenning machine, takes suitable PTAA molten
Drop is added on ito glass substrate, and with the revolving speed spin coating 30s of 1500rpm, the substrate for being coated with PTAA film prepared is placed in
15min is made annealing treatment in 100 DEG C of thermal station, to prepare hole transport layer film.
Comparative example 2
For specific implementation method in addition to the following conditions are different, other are same as Example 1:
The preparation of electron transfer layer: the PEI aqueous solution that concentration is 1.08g/ml is mixed with ethyl alcohol with the volume ratio of 1:500
Uniformly.The substrate for the film that step 3 obtains is placed on sol evenning machine, suitable PEI solution is taken to be added dropwise at PVK:Ir (ppy)3:
On PBD film, with the revolving speed spin coating 30s of 3000rpm, the substrate for being coated with PEI film prepared is placed in 100 DEG C of thermal station
15min is made annealing treatment, to prepare electron-transport layer film.
Fig. 5 is Current density-voltage-light emission luminance of PTAA and the AgNWs luminescent device of compound preparation in varing proportions
(A, B-1, C-1, D-1 are respectively the luminescent device prepared in embodiment 1, embodiment 2, embodiment 3 and comparative example 1 to curve in figure
Current density-voltage-light emission luminance curve)；Fig. 6 is PTAA and the AgNWs luminescent device of compound preparation in varing proportions
(A, B-1, C-1, D-1 are respectively embodiment 1, embodiment 2, embodiment 3 and comparative example 1 to current efficiency-current density plot in figure
Current efficiency-current density plot of the luminescent device of middle preparation).Show in figure: with the increase of AgNWs doping concentration, device
The transmission performance of part hole transmission layer is improved, and PTAA:AgNWs relatively reasonable volume ratio is 20:1.As AgNWs is adulterated
Concentration further increases, and device conducts increase, but bad stability.
Fig. 7 is PEI and SnS2Current density-voltage-luminance of-QDs the luminescent device of compound preparation in varing proportions
Writing music, (A, B-2, C-2, D-2 are respectively the photophore prepared in embodiment 1, embodiment 4, embodiment 5 and comparative example 2 to line in figure
The Current density-voltage of part-light emission luminance curve)；Fig. 8 is PEI and SnS2The photophore of-QDs compound preparation in varing proportions
(A, B-2, C-2, D-2 are respectively embodiment 1, embodiment 4, embodiment 5 and right to current efficiency-current density plot of part in figure
Current efficiency-current density plot of the luminescent device prepared in ratio 2).Show in figure: with SnS2- QDs doping concentration
Increase, the injection of electronics and transmission performance are improved in device, PEI:SnS2- QDs relatively reasonable volume ratio is 1:500.
But work as SnS2When-QDs doping concentration further increases, the current density of device is dramatically increased.This is because SnS2- QDs doping is dense
Height is spent, the roughness of film will become larger, this leakage current that will lead to device increases.
SnS in AgNWs doping concentration and n-type doping transport layer in p-type doping transport layer used in device in embodiment 12-
QDs doping concentration is the relatively reasonable doping concentration that experiment obtains.The bright voltage that opens of device is 2.8V in embodiment 1, bright
Degree is 1000cd/m2When voltage be 6.49V, driving voltage be 10V when brightness be about 43000cd/m2, the maximum electricity of device
It flows efficiency and maximum brightness is respectively 15.85cd/A and 43581cd/m2.Compared with the device of comparative example 1 and comparative example 2, implement
The maximum brightness and current efficiency of device are improved significantly in example 1.
The above result shows that: by the way that composite material PTAA:AgNWs to be introduced into OLED device, sky can be effectively improved
The transmission performance of cave transport layer, and hole injection barrier is reduced, to reduce the driving voltage of device；It is prepared by solwution method
PEI:SnS out2Electron transfer layer of-the QDs as OLED device further improves injection and the transmission energy of electronics in device
Power.Finally while reducing device drive voltage, the luminous efficiency of OLED device is effectively improved.
Claims (5)
1. a kind of method that solwution method prepares the low-voltage driving Organic Light Emitting Diode of p-i-n structure, it is characterised in that including such as
Lower step:
(1) the transparent ito glass substrate after surface clean is handled using UV ozone, ito glass substrate is transferred to
In glove box full of argon atmosphere, using solwution method, successively spin coating prepares p-type doping transport layer, hair on ito glass substrate
Photosphere and n-type doping transport layer；Wherein p-type doping transport layer material therefor is PTAA:AgNWs composite material；Used in luminescent layer
Material is PVK:Ir (ppy)3: PBD composite material；N-type doping transport layer material therefor is PEI:SnS2- QDs composite material；
(2) finally using the method preparation electron buffer layer and metal back electrode of vacuum evaporation deposition.
2. the method that solwution method prepares the low-voltage driving Organic Light Emitting Diode of p-i-n structure according to claim 1, special
Sign is that p-type doping transport layer preparation step is as follows: weighing poly- [bis- (4- phenyl) (2,4,6- trimethylbenzenes with electronic balance
Base) amine] (PTAA) powder is dissolved in toluene solution, and compound concentration is the PTAA solution of 10mg/ml；Silver nanowires (AgNWs)
It is dispersed in ethanol solution, concentration 10mg/ml；PTAA solution is mixed with volume ratio for 10~30:1 with AgNWs solution
It is even, PTAA:AgNWs mixed solution is made；Ito glass substrate is placed on sol evenning machine, PTAA:AgNWs mixed solution is taken to drip
It is added on ito glass substrate, with the revolving speed spin coating 30s of 1500rpm, the substrate for being coated with PTAA:AgNWs film prepared is set
In making annealing treatment 15min in 100 DEG C of thermal station, to prepare the p-type doping that thicknesses of layers is 60nm on ito glass substrate
Transmit layer film.
3. the method that solwution method prepares the low-voltage driving Organic Light Emitting Diode of p-i-n structure according to claim 2, special
Sign is that luminescent layer preparation step is as follows: green light phosphor material three (2- phenylpyridine) is closed iridium (Ir (ppy)3) and have electric
2- (4 '-xenyl) -5- (4 ' -2-methyl-2-phenylpropane base) -1,3,4- oxadiazoles (PBD) of sub- transport property mixes the poly- second of polymer body
Green light emitting layer is prepared in alkene carbazole (PVK), according to PVK:Ir (ppy)3: the mass ratio of PBD=6:3:2 mixes three kinds of materials
And it is dissolved in DMF solution, solution stirring and dissolving 2h PVK:Ir produced above (ppy) at normal temperature3: PBD mixed solution, it is standby
With；The substrate with p-type doping transmission layer film that claim 2 is obtained is placed on sol evenning machine, takes PVK:Ir (ppy)3:
PBD mixed solution is added dropwise on PTAA:AgNWs film, with the revolving speed spin coating 30s of 2000rpm, is coated with PVK:Ir for what is prepared
(ppy)3: the substrate of PBD film is placed in 100 DEG C of thermal station and makes annealing treatment 20min, so that preparing thicknesses of layers is 40nm's
Shine layer film.
4. the method that solwution method prepares the low-voltage driving Organic Light Emitting Diode of p-i-n structure according to claim 3, special
Sign is that n-type doping transport layer preparation step is as follows: weighing SnS with electronic balance2Powder is dispersed in ethanol solution, ultrasound
Handle the SnS that 1h concentration made above is 10mg/ml2Suspension；By SnS2After suspension is centrifuged 40min with 11000rpm, take
Clear liquid obtains artificial gold quantum dot (SnS2- QDs) solution；Polyethyleneimine (PEI) aqueous solution for being again 1.08g/ml by concentration
With SnS2- QDs solution is uniformly mixed with the volume ratio of 1:400~600, obtains PEI:SnS2- QDs mixed solution；By claim
The 3 obtained substrates with p-type doping transport layer and luminous layer film are placed on sol evenning machine, take PEI:SnS2- QDs mixing is molten
Drop is added in PVK:Ir (ppy)3: PBD shines on layer film, with the revolving speed spin coating 30s of 3000rpm, is coated with what is prepared
PEI:SnS2The substrate of-QDs film is placed in 100 DEG C of thermal station and makes annealing treatment 15min, so that preparing thicknesses of layers is 35nm
N-type doping transmit layer film.
5. the low-voltage driving Organic Light Emitting Diode of p-i-n structure is prepared to any one of 4 solwution methods according to claim 1
Method, it is characterised in that: electron buffer layer described in step (2) is lithium fluoride (LiF), and metal back electrode is aluminium (Al).
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