CN107452887A - A kind of fluorescent/phosphorescent mixed white light OLED - Google Patents
A kind of fluorescent/phosphorescent mixed white light OLED Download PDFInfo
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- CN107452887A CN107452887A CN201710729799.1A CN201710729799A CN107452887A CN 107452887 A CN107452887 A CN 107452887A CN 201710729799 A CN201710729799 A CN 201710729799A CN 107452887 A CN107452887 A CN 107452887A
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- H—ELECTRICITY
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- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/10—Triplet emission
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- 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
- 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
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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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
- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
- H10K50/13—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit
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Abstract
The invention discloses a kind of fluorescent/phosphorescent mixed white light OLED, by two layers of fluorescent light-emitting layer hybrid illuminating layer is formed with embedded phosphorescence luminescent layer therebetween, it is mingled with the first phosphorescence doping luminescent layer between hole transmission layer, the second phosphorescence doping luminescent layer is mingled between electron transfer layer.It is luminous while OLED of the present invention is by blue fluorescent material and other color phosphor materials complementary with the blue light to realize white light emission, not only device architecture is simple, and high device efficiency can be obtained with 100% internal quantum efficiency on realization theory, reduce device and prepare cost.
Description
Technical field
The invention belongs to organic semiconductor light emitting device technologies field, it is related to a kind of white organic LED, especially
It is a kind of Organic Light Emitting Diode of fluorescent/phosphorescent mixed white light.
Background technology
White organic LED (Organic light-emitting diodes, OLEDs) is used as organic light emission two
One branch of pole pipe, it is a kind of new lighting engineering.Compared with the lighting engineering such as traditional incandescent lamp, fluorescent tube, in vain
Light OLED has the characteristics that high efficiency, energy-conserving and environment-protective, area source, frivolous, flexible, transparent.
As the LED illumination technology got up with newly-developed, white light OLED is also solid-state illumination light source.However, white light
OLED spectrum is adjustable and photochromic softer, white light OLED can be prepared into class sunshine spectrum or without indigo plant evil warm white light
Source, these are all that LED illumination technology is irrealizable.Therefore, white light OLED is a kind of new high efficiency, environmental protection, health photograph
Bright technology, the LED illumination technology with being more suitable for outdoor form complementation, turn into the leading role of room lighting, before having huge application
Scape and the wide market space.
The above-mentioned advantage and huge potential market of white light OLED, make it obtain extensive research in recent years, and
It is constantly ripe.
White light OLED is to use a variety of complementary luminescent materials, by device structure design, makes various luminescent materials simultaneously
It is luminous, form white light emission after the complementary light mixing of different colours.Therefore, white light OLED, high performance complementary luminous material are prepared
Expect most important.
OLED luminescent materials mainly include fluorescent material and phosphor material.Fluorescence luminescent material is due to there was only singlet exciton
It can be used for lighting so that the internal quantum efficiency of the OLED based on fluorescence luminescent material only has 25%, limits high efficiency white light
OLED development.And the singlet and triplet excitons of phosphorescent light-emitting materials may be used to light so that lighted based on phosphorescence
The OLED of material internal quantum efficiency can reach theoretic 100%, be advantageous to prepare high efficiency white light OLED.
But, high-performance, stably immature for preparing the essential blue phosphorescent Development of Photo And Cathodoluminescent Materials of white light OLED
The good blue phosphor materials relative shortage of property, constrains the further industrialized development of full phosphorescence white light OLED.
Relative to blue phosphor materials, stability problem is not present in blue fluorescent material, and alternative high-performance is blue
Color fluorescent material is more.With reference to the high efficiency of the high stability of blue fluorescent material, long-life and long-wave band phosphor material to make
Standby fluorescent/phosphorescent mixed white light OLED, turns into study hotspot new in recent years.Mixed white light OLED can overcome full fluorescence white light
The problem of OLED efficiency is low, and can solve the problems, such as that full phosphorescence white light OLED stability is poor, short life, turn into and develop high property at present
Energy, a kind of feasible program of long-life white light OLED.
In mixed white light OLED, it is important to singlet and triplet excitons caused by electroluminescent in manipulation and management device,
Singlet exciton caused by blue-fluorescence molecule is set to launch blueness by the consumption of blue-fluorescence molecule, and blue-fluorescence molecule produces
Raw triplet excitons then diffuse to the phosphorescent emitter of long-wave band using the life-span of its length, realize the phosphorescent emissions of long-wave band,
So that singlet and triplet excitons all be used to light caused by blue fluorescent material is all.
Therefore, by rational device structure design, mixed white light OLED internal quantum efficiency can also be made to reach full phosphorus
The level of light white light OLED, i.e. 100% internal quantum efficiency in theory.
Reported in document it is a series of by manipulate and manage it is electroluminescent caused by exciton, to obtain high device efficiency and reason
Think the mixed white light OLED structure of white light emission.It is summed up, these devices can be attributed to two kinds of typical structures：It is single
Luminescent layer mixed white light OLED and multi-luminescent layer mixed white light OLED.
Single-shot photosphere mixed white light OLED is led to by blue fluorescent material and with its photochromic complementary long-wave band phosphor material
Cross codoping technology means and be entrained in same material of main part and be prepared；Also have by with the photochromic complementary several long waves of blue light
Section phosphor material is entrained in blue fluorescent material simultaneously, and blue fluorescent material is used as luminescent material and material of main part simultaneously.Liu
Deng (An ideal host-guest system to accomplish high-performance greenish yellow
and hybrid white organic light-emitting diodes[J]. Organic Electronics, 2015,
27:29-34.) by yellow phosphorescence material Ir (dmppy)2And red phosphorescence material Ir (piq) (dpp)3Respectively with 2% and 1% it is low
Doping concentration codope is in blue fluorescent material Bepp2In, realize blue-yellow-red while light to prepare single-shot photosphere white light device
Part.
From preparation technology as can be seen that single-shot photosphere mixed white light OLED has accurate concentration to the luminescent material of codope
Control and ratio arrangement requirement, the energy transmission that the small change of doping concentration can be all had influence between different dopant materials, from
And the glow color of white light OLED is influenceed, not only preparation technology is considerably complicated, and repetitive rate is low, causes this kind of white light OLED
It is higher to prepare cost, is unfavorable for OLED industrialization production.
In multi-luminescent layer mixed white light OLED, particularly with regard to 3 kinds or 4 kinds of luminescent materials it is simultaneously luminous realize compared with
In the device of ideal white light transmitting, extra introducing wall between fluorescent material and phosphor material, and phosphorus are generally required
Luminescent material is typically all in the form of adulterating in introduction means.(the Management of singlet and such as Sun
triplet excitons for efficient white organic light-emitting devices[J].
Nature, 2006, 440:908-912.) luminous layer structure of the mixed white light device of design is：5 wt% BCzVBi:
CBP/ CBP/ 5 wt% Ir(ppy)3: CBP/ 4 wt% PQIr: CBP/ CBP/ 5 wt% BCzVBi: CBP.It can see
Go out, include two blue-fluorescence doped layers and two phosphorescent doped layers in the luminescent layer, and fluorescence coating and phosphorescent layer it
Between also additionally introduced two CBP walls.
Sometimes for more preferably white light emission is obtained, also have and wall is introduced between different phosphorescence luminescent layers to manage
The recombination region and energy transmission of carrier, further balance the emissive porwer of different luminescent layers.
The introducing of additional space layer, the complicated device architectures of multi-luminescent layer mixed white light OLED are caused, further increase
The production cost of device.Meanwhile more Rotating fields have also been introduced more heterojunction boundaries, the stability of device have impact on.
In summary, or the mixed white light OLED device architectures of existing report are complicated, otherwise preparation technology is complicated so that
Mixed white light OLED poor repeatabilities based on these structures, cost are high, limit the high-volume industrialization production of white light OLED.
The content of the invention
It is an object of the invention to provide a kind of fluorescent/phosphorescent mixed white light OLED, to pass through simple device architecture
High device performance is obtained, device is reduced and prepares cost and improve device stability.
Fluorescent/phosphorescent mixed white light OLED of the present invention is as the mixed white light OLED of routine, same bag
The hole transmission layer (HTL) positioned at anode-side is included, positioned at the electron transfer layer (ETL) of cathode side, and positioned at hole transport
Organic luminous layer (EML) between layer (HTL) and electron transfer layer (ETL).
Wherein, described organic luminous layer is by two layers of fluorescent light-emitting layer and the phosphorus being embedded between the fluorescent light-emitting layer
The hybrid illuminating layer that light luminescent layer is formed；Be mingled between the hole transmission layer using hole mobile material as material of main part,
Luminescent layer is adulterated doped with the first phosphorescence of phosphor material, is mingled between the electron transfer layer based on electron transport material
Body material, the second phosphorescence doped with phosphor material adulterate luminescent layer.The fluorescent light-emitting layer uses the indigo plant of high triplet energy level
Color fluorescent material, the phosphorescence material that the phosphorescence luminescent layer, the first phosphorescence doping luminescent layer and the second phosphorescence doping luminescent layer use
Expect identical or different, the blue light of its mixed light and the blue fluorescent material is complementarily shaped to white light.
In fluorescent/phosphorescent mixed white light OLED of the present invention, the phosphorescence luminescent layer has ultra-thin Rotating fields, and it is thick
Degree is not more than 0.1nm.
Further, phosphorescence luminescent layer of the present invention and hole transmission layer/fluorescence radiation bed boundary and electric transmission
The spacing of layer/fluorescence radiation bed boundary is both preferably 3~10nm.
And then, it is preferable that the first phosphorescence doping luminescent layer and the spacing of hole transmission layer/fluorescence radiation bed boundary are
1~3nm, the second phosphorescence doping luminescent layer and the spacing of electron transfer layer/fluorescence radiation bed boundary are 1~3nm.
Further, in fluorescent/phosphorescent mixed white light OLED of the present invention, the triplet state of the blue fluorescent material
Energy level should be more than the triplet of phosphor material used.Complementary green, yellow, feux rouges phosphor material the triplet state energy with blue light
Level is generally no more than 2.4eV, therefore, 2.4eV blue fluorescent material is more than using triplet, can ensure that blueness is glimmering
The triplet excitons of luminescent material are effectively utilized by phosphor material.
Preferably, the present invention is located at 400~480nm blue fluorescent material using emission peak.
The fluorescent/phosphorescent mixed white light OLED of said structure of the present invention, by blue fluorescent material and with it is described
Lighted while other color phosphor materials of blue light complementation, realize white light emission.
Of course, white light OLED device of the present invention also includes the prerequisite ITO of LED device institute
Anode and aluminium negative electrode, hole injection layer (HIL) and/or electron injecting layer (EIL) can also be included.
In the above-mentioned fluorescent/phosphorescent mixed white light OLED of the present invention, by changing different colours phosphor material in device
In doping or insertion order, the white light OLED devices of different EL spectrum can be obtained.Or change different colours phosphorescence material
The doping concentration or phosphorescence light emitting layer thickness of material, the luminescent spectrum of white light OLED can also be easily varied, realized preferably white
Light is launched.
In fluorescent/phosphorescent mixed white light OLED of the present invention, electroluminescent caused singlet in hybrid illuminating layer
Exciton can be realized blue emission, triplet excitons or the sky that 1~3nm is passed through by tunneling effect by blue-fluorescence molecule trapping
Cave/electric transmission wall, the phosphor material being entrained in hole mobile material/electron transport material is transferred energy to, it is real
The phosphorescent emissions of existing long-wave band, or diffuse among hybrid illuminating layer, transfer energy to ultra-thin phosphorescence luminescent layer and realize phosphorus
Light is launched.Based on above-mentioned luminescence mechanism, OLED of the present invention can be with 100% internal quantum efficiency on realization theory, and then obtains
High device efficiency.
The fluorescent/phosphorescent mixed white light OLED of the present invention utilize positioned at phosphorescence doping luminescent layer and fluorescent light-emitting layer it
Between hole transmission layer or electron transfer layer as wall, avoid using extra spacer layer configuration, be effectively simplified device
Part structure and preparation technology.
Meanwhile the present invention has used the ultra-thin phosphorescence luminescent layer for exempting from doping in the devices, is on the one hand advantageous to simplify mixing
The preparation technology of white light OLED, reduce device and prepare cost；On the other hand, with traditional single-shot photosphere and multi-luminescent layer white light OLED
Compare, ultra-thin phosphorescent light-emitting materials (<The phosphorescent light-emitting materials dosage of costliness can 0.1nm) be substantially reduced, largely
Reduce mixed white light OLED cost；3rd, compared with traditional doping techniques, the ultra-thin light-emitting layer for exempting from doping is easier to control
System, mixed white light OLED repeatability can be greatly improved.
Brief description of the drawings
Fig. 1 is the overall structure diagram of fluorescent/phosphorescent mixed white light OLED of the present invention.
Fig. 2 be normalization electroluminescent spectrum and brightness of the corresponding white light parts W1 of embodiment 1 under different voltages, CIE,
CCT and CRI.
Fig. 3 is the corresponding white light parts W1 of embodiment 1 external quantum efficiency-brightness curve.
Fig. 4 be normalization electroluminescent spectrum and brightness of the corresponding white light parts W2 of comparative example 1 under different voltages, CIE,
CCT and CRI.
Fig. 5 is the corresponding white light parts W2 of comparative example 1 external quantum efficiency-brightness curve.
Fig. 6 be normalization electroluminescent spectrum and brightness of the corresponding white light parts W3 of embodiment 2 under different voltages, CIE,
CCT and CRI.Illustration is in kind photos of the device W3 under different voltages.
Fig. 7 is the corresponding white light parts W3 of embodiment 2 external quantum efficiency-brightness curve.
Fig. 8 be normalization electroluminescent spectrum and brightness of the corresponding white light parts W4 of embodiment 3 under different voltages, CIE,
CCT and CRI.
Fig. 9 be normalization electroluminescent spectrum and brightness of the corresponding white light parts W5 of embodiment 4 under different voltages, CIE,
CCT and CRI.
Figure 10 be normalization electroluminescent spectrum and brightness of the corresponding white light parts W6 of embodiment 5 under different voltages,
CIE, CCT and CRI.
Embodiment
The present embodiments relate to all white light OLEDs realized by high vacuum hot evaporation process.All OLED devices
Part is prepared in transparent conductive film substrate, i.e. ITO (indium tin oxide) substrate of glass.Ito glass substrate is purchased from Shenzhen
Magnificent space joint Science and Technology Ltd., 15 Ω of surface resistance/, and ito thin film has patterned.Prepare all organic work(that OLED is used
Energy material and luminescent material and LiF are purchased from Shanghai Han Feng Chemical Industry Science Co., Ltd, and high-purity aluminium wire and tungsten filament are purchased from Beijing
Co., Ltd of Chinese incense cedar woods non-ferrous metal technology development center.
The present embodiments relate to all white light OLED devices preparation method it is as follows.
First, the cleaning of ito glass substrate.
The grease for being adhered to ito glass substrate surface with the cotton balls for being moistened with acetone and dirty wiped clean, then use cleanser
Ito glass substrate is gently wiped, further ito glass is cleaned, it is afterwards that ito glass running water, deionized water is anti-
Rinse well, be sequentially placed into the beaker of the glass cleaning solution for filling dilution, deionized water, acetone again, it is each to be cleaned by ultrasonic
20min。
2nd, the drying of ito glass substrate.
Cleaned ito glass is taken out from acetone soln, dried up with high pure nitrogen, is put into thermostatic drying chamber, 120
DEG C drying process 0.5h.
3rd, the ultraviolet processing of ito glass substrate.
Dried ito glass substrate is taken out from drying box, is put into ultraviolet case, ultra violet lamp processing 20min, with
The organic matter of ito glass substrate adhesion is further removed, improves the work function on ITO surfaces.
4th, ito glass substrate is behave affectedly.
Ito glass substrate is taken out from ultraviolet case, being placed on to load on the pallet of ito glass, and will be loaded with ito glass
Pallet is imported in vacuum cavity.
5th, equipment vacuumizes.
Device power supply (DPS), mechanical pump, molecular pump are opened, vacuum cavity is vacuumized.
6th, prepared by the hot evaporation of OLED.
Treat that vacuum is less than 5 × 10 in vacuum cavity-4During Pa, begin to warm up and organic functional material is housed in cavity and lighted
The thermal evaporation sources of material, the various organic functional materials of heat deposition and luminescent material successively on ito glass substrate.Treat organic functions
After material and luminescent material deposit, the mask plate below ito glass substrate is rotated, makes the mask location pair of deposited aluminium cathode
Quasi- ito glass substrate.Thermal evaporation sources of the heating equipped with high-purity aluminium wire, deposited aluminium cathode, prepare complete OLED.
In the preparation process of device, the evaporation rate and evaporation thicknesses of layers of material are by being connected to outside vacuum cavity
Quartz crystal oscillator frequency meter monitors.Wherein organic material, MoO3, LiF and aluminium evaporation rate be respectively about 1/s, 0.3/s, 0.1
/ s and 3/s.The part overlapping using ito glass and aluminium negative electrode as device effective luminescent layer, efficient lighting area be 3mm ×
3mm。
The detailed process that hot evaporation prepares white light OLED device of the embodiment of the present invention is as follows.
First, high vacuum hot evaporation deposits 1~10nm of a layer thickness MoO in ito glass substrate3Film layer is as hole
Implanted layer (HIL).
Secondly, first in MoO3Continue the first hole transport that high vacuum hot evaporation deposits 20~70nm of a layer thickness in film layer
Layer (HTL)；Then, high vacuum hot evaporation deposits 3~10nm of a layer thickness the first phosphorescence doping hair over the hole-transporting layer
Photosphere, the doping luminescent layer is using hole transport layer material as material of main part, doped with a kind of complementary with blueness in material of main part
Phosphor material；Then, that high vacuum hot evaporation deposits 1~3nm of a layer thickness is continued on the first phosphorescence doping luminescent layer
Two hole transmission layers (HTL).
Again, high vacuum hot evaporation deposition includes being mixed with for fluorescent material and phosphor material on the second hole transmission layer
Machine luminescent layer (EML).The mixing organic luminous layer is specifically that first high vacuum hot evaporation deposits one layer on the second hole transmission layer
3~10nm of thickness the first blue luminescence layer, then high vacuum hot evaporation deposits one layer on the first blue luminescence layer
Ultra-thin, thickness be only 0.01~0.1nm with blue complementary phosphor material as phosphorescence luminescent layer；Then, sent out in phosphorescence
Continue the second blue luminescence layer that hot evaporation deposits 3~10nm of a layer thickness on photosphere.Wherein, the first fluorescent light-emitting layer with
Second fluorescent light-emitting layer uses same blue fluorescent material.
Again, the second electronics that high vacuum hot evaporation deposits 1~3nm of a layer thickness is continued on the second fluorescent light-emitting layer
Transport layer (ETL)；Then, high vacuum hot evaporation deposits 3~10nm of a layer thickness the second phosphorescence and mixed on the electron transfer layer
Miscellaneous luminescent layer, the doping luminescent layer is using electron transport layer materials as material of main part, doped with a kind of and blueness in material of main part
Complementary phosphor material；Then, the second phosphorescence doping luminescent layer on continue high vacuum hot evaporation deposit a layer thickness 20~
70nm the first electron transfer layer (ETL).
Then, the inorganic material LiF of 0.1~3nm of deposition a layer thickness on the first electron transfer layer is continued, as electronics
Implanted layer (EIL).
Finally, the mask plate among rotary-tray, the position of mask plate position alignment electrode evaporation is made, according to the method described above
One layer of aluminum metal film, a certain numerical value of the aluminium film thickness control between 100~500nm, as device are deposited on electron injecting layer
The negative electrode of part.So far prepared by a complete white light OLED device finishes.
The overall structure of the fluorescent/phosphorescent mixed white light OLED of above-mentioned preparation as shown in figure 1, including setting from bottom to top
The transparent glass substrate 1 put, transparent conductive film ito anode 2, hole injection layer 3, hole transmission layer 4, hybrid illuminating layer 5, electricity
Sub- transport layer 6, electron injecting layer 7 and negative electrode 8.Wherein, the first phosphorescence is embedded in the form of doping among hole transmission layer 4 to mix
Miscellaneous luminescent layer 9, phosphorescence luminescent layer 10 is embedded in the form of ultra-thin among the blue fluorescent body of mixing organic luminous layer 5, in electricity
The second phosphorescence doping luminescent layer 11 is embedded among sub- transport layer 6 in the form of doping.
Wherein, hole transmission layer 4 passes using with high triplet energy level, the hole mobile material of high mobility, the hole
Triplet of the triplet of defeated material at least above all luminescent materials；Electron transfer layer 6, which uses, has high three line
The electron transport material of state energy level, high mobility, the triplet of the electron transport material is at least above all luminescent materials
Triplet.Blue fluorescent body is the indigo plant for having carrier transmission characteristics, high triplet energy level, high-fluorescence quantum yield
Color fluorescence luminescent material, the triplet of the blue fluorescent material is at least above all phosphorescent light-emitting materials being complementary to
Triplet.First, second phosphorescence, which adulterates luminescent layer and ultra-thin phosphorescence luminescent layer, can use the luminous material of same phosphorescence
Expect or be entrained in transport layer by different phosphorescent light-emitting materials or formed with ultra-thin luminescent layer, but first, second phosphorus
The mixed light that photodoping luminescent layer and ultra-thin phosphorescence luminescent layer are sent and the light that blue fluorescent body is sent are complementary, are mixed to form white light
Transmitting.
The performance test methods of white light OLED device are as follows in the embodiment of the present invention.
The white light OLED device prepared is taken out from vacuum cavity, utilizes the ST-900M type light of computer integrated control
The parameters such as current density, brightness, current efficiency and the power efficiency of degree meter and the digital sourcemeter measurement devices of Keithley 2400；
Use electroluminescent hair of the Spectra Scan PR655 spectral radiometers test device of computer integrated control under different voltages
Light spectrum, chromaticity coordinates (CIE, Commission Internationale de L'Eclairage), correlated colour temperature (CCT,
Correlated color temperature) and colour rendering index (CRI, Color rendering index) etc..
Current density, brightness and the spectrum number that the external quantum efficiency (EQE) of all devices is obtained by above-mentioned test
According to being calculated.Before all device detections, any encapsulation process is not carried out to device.It is all to test in room temperature, secretly
Completed under room.
To enable the purpose of the present invention, feature and effect more to fully demonstrate and be easier to understand, with reference to specific reality
Example is applied the present invention is further detailed.The embodiment is not used to carry out any restrictions to the present invention.For ability
For field technique personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made appoints
What modification, equivalent substitution, improvement etc., should be included in the scope of the protection.
Embodiment 1.
White light parts W1 is prepared according to above-mentioned embodiment, device architecture is ITO/ MoO3 (3 nm)/ TCTA
(34 nm)/ TCTA: 8 wt% Ir(piq)2(acac) (5 nm)/ TCTA (1 nm)/ Bepp2 (5 nm)/ Ir
(ppy)3 (0.02 nm)/ Bepp2 (5 nm)/ TPBi (1 nm)/ TPBi: 6 wt% Ir(ffpmq)2(acac) (5
nm)/ TPBi (44 nm)/ LiF (1 nm)/ Al (200 nm)。
Blue luminescence layer (Bepps of the device W1 in gross thickness 10nm2Layer) among embedded in a layer thickness and be only
0.02nm ultra-thin Ir (ppy)3Layer is used as green phosphorescent luminescent layer.Meanwhile in the hole transmission layer (TCTA layers) and electricity of device
Among sub- transport layer (TPBi), one layer has been respectively embedded into it and Ir (piq) is adulterated in layer material is transmitted2(acac) red phosphorescence material
With Ir (ffpmq)2(acac) the phosphorescence doping luminescent layer that yellow phosphorescence material is formed.
Fig. 2 gives normalization electroluminescent spectrums of the device W1 under different voltages, and corresponding under different voltages
Brightness, CIE, CCT and CRI.Figure it is seen that device W1 realizes white light emission, and due to ultra-thin Ir thick 0.02nm
(ppy)3Layer is embedded in the thick Bepp of 10nm2In layer, occurs obvious Ir (ppy) in corresponding electroluminescent spectrum3Green glow is sent out
Penetrate peak.Meanwhile device W1 has also shown high spectrum stability, as voltage from 5V increases to 7V, corresponding brightness from
987.1cd/m2Increase to 9268.0cd/m2, but CIE is only changed to (0.405,0.513) from (0.417,0.515), and CRI is maintained
61~64.
Fig. 3 gives device W1 external quantum efficiency-brightness curve, and device W1 other electric parameters are also general
Include in table 1.It is can be seen that by table 1 and Fig. 3 with ultra-thin Ir (ppy) thick 0.02nm3It is embedded in the thick Bepp of 10nm2Layer
In, device W1 realizes higher efficiency, and maximum current efficiency, power efficiency and external quantum efficiency respectively reach 44.69cd/A,
40.20lm/W with 16.83%.High device efficiency is attributed to the thick ultra-thin Ir (ppy) of 0.02nm3Effectively capture and be limited in
Bepp2The exciton of layer so that exciton caused by its is electroluminescent is utilized effectively.
Comparative example 1.
Remove the green phosphorescent luminescent layer Ir (ppy) in the white light parts W1 of embodiment 13, other structures are the same as embodiment 1, system
Standby white light parts W2, device architecture is ITO/ MoO3 (3 nm)/ TCTA (34 nm)/ TCTA: 8 wt% Ir(piq)2
(acac) (5 nm)/ TCTA (1 nm)/ Bepp2 (10 nm)/ TPBi (1 nm)/ TPBi: 6 wt% Ir(ffpmq)2
(acac) (5 nm)/ TPBi (44 nm)/ LiF (1 nm)/ Al (200 nm)。
Fig. 4 gives normalization electroluminescent spectrums of the device W2 under different voltages, and corresponding under different voltages
Brightness, CIE, CCT and CRI.It is corresponding as can be seen that device W2 also achieves white light emission, and as voltage from 5V increases to 7V
In brightness from 842.3cd/m2Increase to 6743.0cd/m2, device W2 shows preferable color stability, CIE only from (0.493,
0.441) change to (0.482,0.421).
Fig. 5 gives device W2 external quantum efficiency-brightness curve, and device W2 other electric parameters are also general
Include in table 1.Maximum current efficiency, power efficiency and the external quantum efficiency of device W2 acquisitions are can be seen that by table 1 and Fig. 5
Respectively 28.57cd/A, 26.77lm/W and 12.11%.Its external quantum efficiency is far below the mixed white light OLED of embodiment 1
W1, this is probably to cause the exciton in luminescent layer can not without embedded ultra-thin phosphorescence luminescent layer in the luminescent layer due to device W2
It is utilized effectively so that device shows low device efficiency.
Embodiment 2.
The device W1 of embodiment 1 efficiency is effectively improved, but colour rendering index is still significantly lower than required by illuminating
Threshold value 80.The present embodiment keeps white light parts W1's to further improve efficiency and improve the colour rendering index of white light parts
It is constant that device architecture and device prepare material, changes the first phosphorescence doping luminescent layer and phosphorescence in ultra-thin phosphorescence luminescent layer and lights material
The order of material, it is prepared for white light parts W3.Device architecture is：ITO/ MoO3 (3 nm)/ TCTA (35 nm)/ TCTA: 6
wt% Ir(ppy)3 (4 nm)/ TCTA (1 nm)/ Bepp2 (5 nm)/ Ir(piq)2(acac) (0.05 nm)/
Bepp2 (5 nm)/ TPBi (1 nm)/ TPBi: 6 wt% Ir(ffpmq)2(acac) (5 nm)/ TPBi (44 nm)/
LiF (1 nm)/ Al (200 nm)。
Fig. 6 gives normalization electroluminescent spectrums of the device W3 under different voltages, and corresponding under different voltages
Brightness, CIE, CCT and CRI, illustration are in kind photos of the device W3 under different voltages.As can be seen that as the first phosphorescence is mixed
After the order of miscellaneous luminescent layer and ultra-thin phosphorescence luminescent layer luminescent material changes, device W3 shows preferable white light emission, electroluminescent
Luminescent spectrum is presented from blue, green, yellow to the red transmitting strengthened successively, realizes class candle light white light emission.Equally, device W3
High spectrum stability is shown, as voltage from 5V increases to 7V, corresponding brightness is from 721.3cd/m2Increase to
7353.0cd/m2, but CIE is only changed to (0.498,0.438) from (0.503,0.448), and CRI is also maintained at 82~89, high
Colour rendering index meets the requirement of white-light illuminating.
Fig. 7 gives device W3 external quantum efficiency-brightness curve, and device W3 other electric parameters are also general
Include in table 1.It can be seen that by table 1 and Fig. 7 and change the first phosphorescence doping luminescent layer and ultra-thin phosphorescence luminescent layer luminescent material
After order, thicker feux rouges Ir (piq)2(acac) ultra-thin light-emitting layer further increases device efficiency, and external quantum efficiency reaches
17.71%, closer to 20% theoretical value.High device performance further demonstrate that device architecture of the present invention can be to the electroluminescent production of device
Raw singlet and triplet excitons implement effective management and use.
Embodiment 3.
Keep the white light parts W1 of embodiment 1 overall structure and material constant, by the thick blue luminescence layers of each 5nm
Bepp2Layer increases to 8nm, and blue luminescence layer gross thickness increases to 16nm, prepare device W4.Device architecture：ITO/ MoO3
(3 nm)/ TCTA (34 nm)/ TCTA: 8 wt% Ir(piq)2(acac) (5 nm)/ TCTA (1 nm)/ Bepp2 (8
nm)/ Ir(ppy)3 (0.02 nm)/ Bepp2 (8 nm)/ TPBi (1 nm)/ TPBi: 6 wt% Ir(ffpmq)2
(acac) (5 nm)/ TPBi (44 nm)/ LiF (1 nm)/ Al (200 nm)。
Fig. 8 gives normalization electroluminescent spectrums of the device W4 under different voltages, and corresponding under different voltages
Brightness, CIE, CCT and CRI.As can be seen that device W4 also achieves white light emission.Compared to device W1, increased Bepp2It is blue
Color fluorescent light-emitting layer thickness causes blue emission of the device at 440nm to have certain enhancing.In addition, device W4 is also shown
High spectrum stability, as voltage from 5V increases to 7V, corresponding brightness is from 950.2cd/m2Increase to 8973.0cd/m2, but
CIE is only changed to (0.391,0.484) from (0.397,0.496), and CRI there has also been certain increase, maintain 70~72.
Embodiment 4.
Keep the white light parts W2 of embodiment 2 overall structure and material constant, by the ultra-thin red phosphorescent luminescent layer of centre
Ir(piq)2(acac) thickness increases to 0.08nm, prepares device W5, device architecture：ITO/ MoO3 (3 nm)/ TCTA
(35 nm)/ TCTA: 6 wt% Ir(ppy)3 (4 nm)/ TCTA (1 nm)/ Bepp2 (5 nm)/ Ir(piq)2
(acac) (0.08 nm)/ Bepp2 (5 nm)/ TPBi (1 nm)/ TPBi: 6 wt% Ir(ffpmq)2(acac) (5
nm)/ TPBi (44 nm)/ LiF (1 nm)/ Al (200 nm)。
Fig. 9 gives normalization electroluminescent spectrums of the device W5 under different voltages, and corresponding under different voltages
Brightness, CIE, CCT and CRI.As can be seen that with ultra-thin red phosphorescent luminescent layer Ir (piq)2(acac) thickness increases to
0.08nm, device W5 red emission significantly increase, along with blue and green light and the decrease of yellow light intensity.As voltage is from 5V
Increase to 7V, corresponding brightness is from 701.2cd/m2Increase to 7160.0cd/m2, device W5 also shows good color stability,
CIE only changes to (0.521,0.424) from (0.531,0.424), and CRI is maintained at 83~85, belongs to comparatively ideal warm white
Transmitting.
Embodiment 5.
White light parts W6 is prepared according to above-mentioned embodiment, device architecture is ITO/ MoO3 (3 nm)/ TCTA
(32 nm)/ TCTA: 6 wt% Ir(ppy)3 (4 nm)/ TCTA (3 nm)/ Bepp2 (5 nm)/ Ir(ffpmq)2
(acac) (0.05 nm)/ Bepp2 (5 nm)/ TPBi (1 nm)/ TPBi: 8 wt% Ir(piq)2(acac) (5
nm)/ TPBi (44 nm)/ LiF (1 nm)/ Al (200 nm)。
The device is structurally characterized in that in Bepp2Ir (ffpmq) among layer after insertion 0.05nm2(acac) yellow phosphorescence
Luminescent layer, hole transmission layer TCTA sides doping Ir (ppy)3Green light emitting layer, electron transfer layer TPBi sides doping Ir (piq)2
(acac) red light luminescent layer.Meanwhile hole transmission layer side 1nm wall is increased to 3nm.
Figure 10 gives normalization electroluminescent spectrums of the device W6 under different voltages, and corresponding under different voltages
Brightness, CIE, CCT and CRI.As can be seen that as TCTA sides space layer increases to 3nm, Bepp2Blue emission show
Write enhancing, while 4nm Ir (ppy)3It is relatively weak for gold-tinted and red emission to adulterate the luminous intensity of luminescent layer,
Part exciton is effectively limited in Bepp by the wall that this explanation increases to 3nm2Blue light-emitting, realize the blue light hair of enhancing
Penetrate, and inhibit Bepp2Diffusion of the triplet excitons to green glow doped layer.As voltage from 5V increases to 7V, corresponding brightness
From 913.2cd/m2Increase to 8960.0cd/m2, device W6 shows preferable color stability, and CIE is only from (0.459,0.437)
(0.435,0.416) is changed to, CRI maintains 68~73.
Particular compound title is as follows corresponding to the abbreviation of involved chemical substance in the present invention.
TCTA：4,4',4''-tris(N-carbazolyl)triphenylamine.
TPBi：1,3,5-tris(phenyl-2-benzimidazolyl)benzene.
Bepp2：bis[2-(2-hydroxyphenyl)-pyridine]ber-yllium.
Ir(ppy)3：tris(2-phenylpyridine)iridium(III).
Ir(ffpmq)2(acac)：phosphor(bis(2-(3-trifluoromethyl-4-fluorophenyl)-4
-methylquinolyl)(acetylacetonate)iridium(III)。
Ir(piq)2(acac)：bis(1-phenylisoquinoline)(acetylacetonate)iridium
(III)。
Claims (9)
1. a kind of fluorescent/phosphorescent mixed white light OLED, including the hole transmission layer positioned at anode-side, positioned at the electricity of cathode side
Sub- transport layer, and the organic luminous layer between hole transmission layer and electron transfer layer, it is characterized in that：
The organic luminous layer is by two layers of fluorescent light-emitting layer and the phosphorescence luminescent layer structure being embedded between the fluorescent light-emitting layer
Into hybrid illuminating layer；
It is mingled between the hole transmission layer using hole mobile material as material of main part, doped with the first phosphorescence of phosphor material
Adulterate luminescent layer；
It is mingled between the electron transfer layer using electron transport material as material of main part, doped with the second phosphorescence of phosphor material
Adulterate luminescent layer；
The fluorescent light-emitting layer uses the blue fluorescent material of high triplet energy level, the phosphorescence luminescent layer, the doping of the first phosphorescence
The phosphor material that luminescent layer and the second phosphorescence doping luminescent layer use is identical or different, its mixed light and the blue fluorescent material
Blue light be complementarily shaped to white light.
2. fluorescent/phosphorescent mixed white light OLED according to claim 1, it is characterized in that the thickness of the phosphorescence luminescent layer
Degree is not more than 0.1nm.
3. fluorescent/phosphorescent mixed white light OLED according to claim 1 or 2, it is characterized in that the phosphorescence luminescent layer
Spacing with hole transmission layer/fluorescence radiation bed boundary is 3~10nm.
4. fluorescent/phosphorescent mixed white light OLED according to claim 1 or 2, it is characterized in that the phosphorescence luminescent layer
Spacing with electron transfer layer/fluorescence radiation bed boundary is 3~10nm.
5. fluorescent/phosphorescent mixed white light OLED according to claim 1, it is characterized in that first phosphorescence doping hair
Photosphere and the spacing of hole transmission layer/fluorescence radiation bed boundary are 1~3nm.
6. fluorescent/phosphorescent mixed white light OLED according to claim 1, it is characterized in that second phosphorescence doping hair
Photosphere and the spacing of electron transfer layer/fluorescence radiation bed boundary are 1~3nm.
7. fluorescent/phosphorescent mixed white light OLED according to claim 1, it is characterized in that the blue fluorescent material
Triplet is more than the triplet of phosphor material used.
8. fluorescent/phosphorescent mixed white light OLED according to claim 7, it is characterized in that the blue fluorescent material
Triplet is more than 2.4eV.
9. fluorescent/phosphorescent mixed white light OLED according to claim 7, it is characterized in that the blue fluorescent material
Emission peak is located at 400~480nm.
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| CN108269937A (en) * | 2017-12-27 | 2018-07-10 | 广东工业大学 | A kind of hydridization white light organic electroluminescent device of efficient high color rendering index (CRI) |
| CN109786570A (en) * | 2018-12-31 | 2019-05-21 | 瑞声科技（南京）有限公司 | A kind of phosphorescent OLED device and its manufacturing method |
| CN110635056A (en) * | 2019-09-25 | 2019-12-31 | 京东方科技集团股份有限公司 | OLED device, display panel, display device and lighting device |
| CN111146258A (en) * | 2019-12-30 | 2020-05-12 | 维沃移动通信有限公司 | Display screen and electronic equipment |
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| CN105206754A (en) * | 2015-09-30 | 2015-12-30 | 云南大学 | Color-temperature-adjustable high-color-rendering-index WOLED device and adjusting principle thereof |
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| US20150287948A1 (en) * | 2014-04-04 | 2015-10-08 | Seiko Epson Corporation | Light-emitting element, light-emitting device, display device, and electronic apparatus |
| CN105206754A (en) * | 2015-09-30 | 2015-12-30 | 云南大学 | Color-temperature-adjustable high-color-rendering-index WOLED device and adjusting principle thereof |
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| CN109786570A (en) * | 2018-12-31 | 2019-05-21 | 瑞声科技（南京）有限公司 | A kind of phosphorescent OLED device and its manufacturing method |
| CN110635056A (en) * | 2019-09-25 | 2019-12-31 | 京东方科技集团股份有限公司 | OLED device, display panel, display device and lighting device |
| CN111146258A (en) * | 2019-12-30 | 2020-05-12 | 维沃移动通信有限公司 | Display screen and electronic equipment |
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