CN105810839A - Monolayer blue light exciplex organic light-emitting device and manufacturing method thereof - Google Patents
Monolayer blue light exciplex organic light-emitting device and manufacturing method thereof Download PDFInfo
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- CN105810839A CN105810839A CN201610137553.0A CN201610137553A CN105810839A CN 105810839 A CN105810839 A CN 105810839A CN 201610137553 A CN201610137553 A CN 201610137553A CN 105810839 A CN105810839 A CN 105810839A
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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
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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]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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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
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
- H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition
Abstract
The invention relates to a monolayer blue light exciplex organic light-emitting device and a manufacturing method thereof, the device is designed based on common OLED hole-transport materials and electron transport materials, and a blue monolayer exciplex layer is generated as a light-emitting layer; PL life test is performed on the monolayer exciplex layer formed by the hole-transport materials m-MTDATA and the electron transport materials TmPyPb, and the layer which has TADF effect is proved; mass mixing ratio of the hole-transport materials m-MTDATA and the electron transport materials TmPyPb is further designed to 60-80%, so that the spectrum peak of the designed organic light-emitting device is less than 465 nm; the invention also relates to a manufacturing method of the monolayer blue light exciplex organic light-emitting device, and the manufacturing efficiency of the designed organic light-emitting device can be effectively improved.
Description
Technical field
The present invention relates to organic electroluminescence device of a kind of single-layer blue light exciplex and preparation method thereof, belong to organic electronic technical field.
Background technology
Organic electroluminescence device (organic light emitting diode, OLED) has huge potentiality in the application of smart mobile phone screen, flat faced display and solid state lighting.From 1987 so far, OLED is the most flourish nearly 30 years.In recent years, high exciton utilization rate material is increasingly becoming the focus of OLED material research, and the exciplex wherein with TADF effect is currently widely studied by everybody.
It is known that exciplex (exciplex) is one is formed at the aggregation between electron donor (D) and electron acceptor (A), when excited state, two molecular actions are relatively strong, produce new energy level (swashing ground state).Finding that the pyrene molecule of excited state and the dimethyl benzene amine molecule of ground state can interact since formation exciplex from Leonhardt and Weller in 1963, importance that Exciplex emission exists because of it and popularity cause the extensive concern of people.Exciplex emission spectral width and have bigger red shift relative to the luminescent spectrum of electron donor (D) and electron acceptor (A), in OLED luminescence, Exciplex emission is widely used in OLED white light parts and spectrum regulates.But initially everybody the Exciplex emission efficiency of research is the most on the weak side, and this most seriously governs its development in efficient OLED luminescence.
2012, Chihaya Adachi seminar had strong intermolecular charge transfer (charge-transfer by selection；CT) exciplex of system, utilizes intermolecular CT state to further singletstate (T1) and singletstate (S1) energy gap, reduce Δ EST, effectively achieve the triplet state reverse intersystem crossing (the reverse intersystem crossing to singletstate；RISC), thus taking full advantage of the sharp ground state triplet excitons of 75% in luminescence, exciton utilization rate is obviously improved (> 86.5%), maximum external quantum efficiency reaches 5.4%.The most a series of high efficiency electroluminous devices based on the exciplex with TADF effect have obtained studying widely, the highest external quantum efficiency reaches 15.4%, and such high efficiency makes this Exciplex emission device not being expected before making again obtain the concern of people.
Summary of the invention
The technical problem to be solved is to provide a kind of based on common commercialization OLED hole mobile material and electron transport material, has the organic electroluminescence device of the single-layer blue light exciplex of TADF effect.
The present invention is to solve above-mentioned technical problem by the following technical solutions: the present invention devises the organic electroluminescence device of a kind of single-layer blue light exciplex, including the indium oxide tin glass substrate set gradually from the bottom to top, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and opaque metal electrode；It is characterized in that: described luminescent layer is to be mixed, by hole mobile material m-MTDATA and electron transport material TmPyPb, the monolayer exciplex layer constituted.
As a preferred technical solution of the present invention: in described exciplex layer, the mass mixing ratio of described hole mobile material m-MTDATA and described electron transport material TmPyPb is 60-80%.
The organic electroluminescence device of a kind of single-layer blue light exciplex of the present invention uses above technical scheme compared with prior art, have following technical effect that the organic electroluminescence device of single-layer blue light exciplex designed by the present invention, it is designed based on common commercialization OLED hole mobile material and electron transport material, produce blue monolayer exciplex layer, as luminescent layer, utilize industrialization；And mix, for used hole mobile material m-MTDATA and electron transport material TmPyPb, the monolayer exciplex layer constituted and carry out PL life test, it was demonstrated that it has hot activation delayed fluorescence effect (TADF effect)；Moreover, for the mass mixing ratio of described hole mobile material m-MTDATA Yu described electron transport material TmPyPb, it is further designed to 60-80% so that the spectrum peak being designed with organic electroluminescence devices can be less than 465nm.
Corresponding to this, the technical problem to be solved is to provide a kind of brand-new design framework, it is possible to the making of organic electroluminescence device for designed single-layer blue light exciplex provides the manufacture method of efficient operation efficiency.
The present invention is to solve above-mentioned technical problem by the following technical solutions: the present invention devises the manufacture method of the organic electroluminescence device of a kind of single-layer blue light exciplex, comprises the steps:
Step 001. is carried out pretreatment operation, subsequently into step 002 for described indium oxide tin glass substrate；
Step 002. uses vacuum deposition method, is attached to by described hole transmission layer in described indium oxide tin glass substrate, subsequently into step 003；
Step 003., for hole mobile material m-MTDATA and electron transport material TmPyPb, is mixed by preset quality mixed proportion, constitutes monolayer exciplex layer, as luminescent layer, subsequently into step 004；
Step 004. uses vacuum deposition method, is adhered on the hole transport layer by described luminescent layer, subsequently into step 005；
Step 005. uses vacuum deposition method, is adhered on the light-emitting layer by described electron transfer layer, subsequently into step 006；
Step 006. uses vacuum deposition method, is adhered on the electron transport layer by described electron injecting layer, subsequently into step 007；
Step 007. uses vacuum deposition method, is attached on described electron injecting layer by described opaque metal electrode, thus constitutes organic electroluminescence device.
As a preferred technical solution of the present invention: described step 001 specifically includes following steps:
Step 00101. uses ionized water to clean 10 minutes for described indium oxide tin glass substrate, subsequently into step 00102；
Step 00102. uses acetone to clean further 15 minutes for described indium oxide tin glass substrate, subsequently into step 00103；
Step 00103. uses ethanol to clean further 15 minutes for described indium oxide tin glass substrate, subsequently into step 00104；
Step 00104. is in the environment of 120 DEG C, for described indium oxide tin glass substrate drying 30 minutes, subsequently into step 00105；
Step 00105. carries out ultraviolet treatment with irradiation for described indium oxide tin glass substrate, completes to be carried out pretreatment operation for described indium oxide tin glass substrate.
As a preferred technical solution of the present invention: in described step 003, for hole mobile material m-MTDATA and electron transport material TmPyPb, mix in the mass mixing ratio of 60-80%, constitute monolayer exciplex layer, as luminescent layer.
As a preferred technical solution of the present invention: in described step 002 to step 007, the vacuum environment in described vacuum deposition method is less than or equal to 5 × 10-4Pa vacuum environment.
The manufacture method of the organic electroluminescence device of a kind of single-layer blue light exciplex of the present invention uses above technical scheme compared with prior art, have following technical effect that the manufacture method of the organic electroluminescence device of single-layer blue light exciplex designed by the present invention, use brand-new design framework, it is effectively increased the making work efficiency of designed organic electroluminescence device, and it is designed with organic electroluminescence devices to be designed based on common commercialization OLED hole mobile material and electron transport material, produce blue monolayer exciplex layer, as luminescent layer, utilize industrialization；And mix, for used hole mobile material m-MTDATA and electron transport material TmPyPb, the monolayer exciplex layer constituted and carry out PL life test, it was demonstrated that it has hot activation delayed fluorescence effect (TADF effect)；Moreover, for the mass mixing ratio of described hole mobile material m-MTDATA Yu described electron transport material TmPyPb, it is further designed to 60-80% so that the spectrum peak being designed with organic electroluminescence devices can be less than 465nm.
Accompanying drawing explanation
Fig. 1 is m-MTDATA；TmPyPb；The PL spectrum schematic diagram of m-MTDATA:TmPyPb thin film；
Fig. 2 is the luminescence generated by light life-span schematic diagram of m-MTDATA:TmPyPb exciplex system, and exciting light is 360nm；
Fig. 3 is device a in embodiment1、a2、a3Electroluminescent spectrum schematic diagram under 7V respectively；
Fig. 4 a is device a in embodiment3Current density-voltage-brightness schematic diagram；
Fig. 4 b is device a in embodiment3Luminance-current-power efficiency relation curve schematic diagram；
Fig. 4 c is device a in embodiment3Electroluminescent spectrum schematic diagram from 3.5V to 10V voltage.
Detailed description of the invention
Below in conjunction with Figure of description, the detailed description of the invention of the present invention is described in further detail.
As depicted in figs. 1 and 2, high vacuum vapor deposition equipment is used to prepare based on the m-MTDATA:TmPyPb mixed monolayer thin film that piezoid is substrate, show that m-MTDATA:TmPyPb system is a kind of blue light exciplex system with TADF effect according to PL life-span and spectrum, comprise the following steps that, wherein, hole mobile material m-MTDATA is 4,4'; 4 "-Tris (N-3-methylphenyl-N-phenylamino) triphenylamine, i.e. C57H48N4；Electron transport material TmPyPb is 1,3,5-tri (m-pyrid-3-yl-phenyl) benzene, i.e. C39H27N3。
(1) quartz plate substrate is cleaned with deionized water, acetone, ethanol equal solvent；
(2) using high vacuum vapor deposition equipment evaporation m-MTDATA:TmPyPb mixed monolayer thin film in quartz plate substrate, thickness is 100nm
(3) test PL life-span and spectrum, obtaining the life-span is 7 μ s, it was demonstrated that it has TADF effect；
Organic electroluminescence device of a kind of single-layer blue light exciplex designed by the present invention and preparation method thereof, in the middle of actual application, specifically includes following steps:
Step 001. is carried out pretreatment operation, subsequently into step 002 for described indium oxide tin glass substrate (ITO substrate).
Wherein, described step 001 specifically includes following steps:
Step 00101. uses ionized water to clean 10 minutes, subsequently into step 00102 for described indium oxide tin glass substrate (ITO substrate).
Step 00102. uses acetone to clean 15 minutes further for described indium oxide tin glass substrate (ITO substrate), subsequently into step 00103.
Step 00103. uses ethanol to clean 15 minutes further for described indium oxide tin glass substrate (ITO substrate), subsequently into step 00104.
Step 00104., in the environment of 120 DEG C, is dried 30 minutes for described indium oxide tin glass substrate (ITO substrate), subsequently into step 00105.
Step 00105. carries out ultraviolet treatment with irradiation for described indium oxide tin glass substrate (ITO substrate), completes to be carried out pretreatment operation for described indium oxide tin glass substrate.
Step 002. is less than or equal to 5 × 10-4Under the vacuum environment of Pa, use vacuum deposition method, described hole transmission layer is attached on described indium oxide tin glass substrate (ITO substrate), subsequently into step 003.
Step 003., for hole mobile material m-MTDATA and electron transport material TmPyPb, is mixed in the mass mixing ratio of 60-80%, constitutes monolayer exciplex layer, as luminescent layer, subsequently into step 004.
Step 004. is less than or equal to 5 × 10-4Under the vacuum environment of Pa, use vacuum deposition method, described luminescent layer is adhered on the hole transport layer, subsequently into step 005.
Step 005. is less than or equal to 5 × 10-4Under the vacuum environment of Pa, use vacuum deposition method, described electron transfer layer is adhered on the light-emitting layer, subsequently into step 006.
Step 006. is less than or equal to 5 × 10-4Under the vacuum environment of Pa, use vacuum deposition method, described electron injecting layer is adhered on the electron transport layer, subsequently into step 007.
Step 007. is less than or equal to 5 × 10-4Under the vacuum environment of Pa, use vacuum deposition method, described opaque metal electrode is attached on described electron injecting layer, thus constitutes organic electroluminescence device.
Thus, the organic electroluminescence of design single-layer blue light exciplex, the indium oxide tin glass substrate set gradually from the bottom to top, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and opaque metal electrode；Wherein, described luminescent layer is to be mixed, by hole mobile material m-MTDATA and electron transport material TmPyPb, the monolayer exciplex layer constituted, and the mass mixing ratio of hole mobile material m-MTDATA and described electron transport material TmPyPb is 60-80%, the manufactured organic electroluminescence obtaining single-layer blue light exciplex, the spectrum peak of organic electroluminescence device can be less than 465nm.
In the middle of actual application, separately design a based on technique scheme1、a2、a3Three kinds of devices, a1、a2、a3Three kinds of devices are respectively as follows: ITO/m-MTDATA (20nm)/Xwt%m-MTDATA:TmPyPb (30nm)/TmPyPb (20nm)/LiF (1nm)/Al (100nm)；Wherein ITO refers to the anode of device, i.e. tin indium oxide；It is m-MTDATA that m-MTDATA (20nm) refers to the hole transmission layer of device, and thickness is 20nm；The luminescent layer of the device that Xwt%m-MTDATA:TmPyPb (30nm) refers to device is m-MTDATA:TmPyPb system, and thickness is 30nm；The quality doping ratio that wt refers to, a1The X=30 of device；a2The X=50 of device；a3The X=70 of device, refers to device a respectively1、a2、a3M-MTDATA quality doping ratio 30% in m-MTDATA:TmPyPb system, 50%, 70%；It is m-MTDATA that TmPyPb (20nm) refers to the electron transfer layer of device, and thickness is 20nm；It is LiF that LiF (1nm) refers to the electron injecting layer of device, and thickness is 1nm；Al (100nm) refers to the negative electrode of device, and thickness is 100nm.
As shown in Fig. 3, Fig. 4 a, Fig. 4 b and Fig. 4 c, it is shown that device a1、a2、a3Actual light Detection results, wherein, as it is shown on figure 3, device a1、a2、a3Electroluminescent spectrum in the case of external voltage is 7V, wherein device a3Spectrum be dark blue transmitting；Fig. 4 a is device a in embodiment3Current density-voltage-brightness schematic diagram；Fig. 4 b is device a in embodiment3Luminance-current-power efficiency relation curve schematic diagram；Fig. 4 c is device a in embodiment3Electroluminescent spectrum schematic diagram from 3.5V to 10V voltage.
Above in conjunction with accompanying drawing, embodiments of the present invention are explained in detail, but the present invention is not limited to above-mentioned embodiment, in the ken that those of ordinary skill in the art are possessed, it is also possible to make a variety of changes on the premise of without departing from present inventive concept.
Claims (6)
1. an organic electroluminescence device for single-layer blue light exciplex, including the tin indium oxide glass set gradually from the bottom to top
Glass substrate, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and opaque metal electrode；It is characterized in that:
Described luminescent layer is to be mixed, by hole mobile material m-MTDATA and electron transport material TmPyPb, the monolayer constituted to swash base
Composite layer.
A kind of organic electroluminescence device of single-layer blue light exciplex, it is characterised in that: institute
State in exciplex layer, the quality of described hole mobile material m-MTDATA and described electron transport material TmPyPb
Mixed proportion is 60-80%.
3. one kind based on the organic electroluminescence device of single-layer blue light exciplex described in any one in claim 1 to 2
Manufacture method, it is characterised in that comprise the steps:
Step 001. is carried out pretreatment operation, subsequently into step 002 for described indium oxide tin glass substrate；
Step 002. uses vacuum deposition method, is attached to by described hole transmission layer in described indium oxide tin glass substrate, then
Enter step 003；
Step 003. is for hole mobile material m-MTDATA and electron transport material TmPyPb, by preset quality mixing ratio
Example mixes, and constitutes monolayer exciplex layer, as luminescent layer, subsequently into step 004；
Step 004. uses vacuum deposition method, is adhered on the hole transport layer by described luminescent layer, subsequently into step
005；
Step 005. uses vacuum deposition method, is adhered on the light-emitting layer by described electron transfer layer, subsequently into step
006；
Step 006. uses vacuum deposition method, is adhered on the electron transport layer by described electron injecting layer, subsequently into step
Rapid 007；
Step 007. uses vacuum deposition method, is attached on described electron injecting layer by described opaque metal electrode, thus structure
Become organic electroluminescence device.
The manufacture method of the organic electroluminescence device of a kind of single-layer blue light exciplex, it is special
Levy and be: described step 001 specifically includes following steps:
Step 00101. uses ionized water to clean 10 minutes for described indium oxide tin glass substrate, subsequently into step 00102；
Step 00102. uses acetone to clean further 15 minutes for described indium oxide tin glass substrate, subsequently into step
00103；
Step 00103. uses ethanol to clean further 15 minutes for described indium oxide tin glass substrate, subsequently into step
00104；
Step 00104. is in the environment of 120 DEG C, for described indium oxide tin glass substrate drying 30 minutes, subsequently into step
00105；
Step 00105. carries out ultraviolet treatment with irradiation for described indium oxide tin glass substrate, completes for described tin indium oxide glass
Glass substrate is carried out pretreatment operation.
The manufacture method of the organic electroluminescence device of a kind of single-layer blue light exciplex, it is special
Levy and be: in described step 003, for hole mobile material m-MTDATA and electron transport material TmPyPb, press
The mass mixing ratio of 60-80% mixes, and constitutes monolayer exciplex layer, as luminescent layer.
6. according to the organic electroluminescence device of single-layer blue light exciplex a kind of described in any one in claim 3 to 5
Manufacture method, it is characterised in that: in described step 002 to step 007, the vacuum environment in described vacuum deposition method is
Less than or equal to 5 × 10-4Pa vacuum environment.
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Application publication date: 20160727 |