CN108649130A - A kind of lamination blue light organic electroluminescence device and its manufacturing process - Google Patents
A kind of lamination blue light organic electroluminescence device and its manufacturing process Download PDFInfo
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- CN108649130A CN108649130A CN201810442690.4A CN201810442690A CN108649130A CN 108649130 A CN108649130 A CN 108649130A CN 201810442690 A CN201810442690 A CN 201810442690A CN 108649130 A CN108649130 A CN 108649130A
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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
- H10K50/131—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 with spacer layers between the electroluminescent 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
Abstract
A kind of lamination blue light organic electroluminescence device and its manufacturing process is claimed in the present invention; including substrate; stack anode, other functional layers, dual light unit, single charge generation layer and the cathode of setting; the dual light unit is separated by charge generation layer; dual light unit is blue-light-emitting unit; the blue light-emitting layer includes material of main part, guest materials, and object is entrained in 10wt% in material of main part.Hole barrier restrained effectively the hole of blue-light-emitting unit and be diffused into electron transport material and form exciton radiation and send out green light in device architecture, form green acromion.Technical scheme of the present invention not only increases the luminous efficiency of device, also so that device blue emission is purer.
Description
Technical field
The invention belongs to organic electroluminescence device technical field, especially a kind of lamination that there is green acromion to inhibit is blue
Color organic electroluminescence device.
Background technology
Laminated organic electroluminescent device structure includes at least two luminescence units, and middle charge generation layer with this configuration
Luminescence unit is connected.This kind of structure is proved that device performance can be significantly improved, effectively reduces due to being quenched caused by electric current
The generation of effect, and then improve the service life of device.Kido et al. is the study found that theoretically contain the Organic Electricity of N number of luminescence unit
The operating brightness of electroluminescence device can reach N times of single luminescence unit device, therefore laminated organic electroluminescent device is big
Big working efficiency and the service life for improving organic electroluminescence device.
As it can be seen that laminated organic electroluminescent device, the performance of charge generation layer directly affects the overall performance of device, if
Count excellent charge generation layer has important directive significance to obtaining efficient device architecture.Currently, numerous and electroluminescent hair
The relevant researcher of light is all actively seeking good charge generation layer.For different laminated construction, charge generates
Layer also needs to do corresponding improvement.This allows for, to a kind of specific laminated device, designing matched charge generation layer
There is certain difficulty.Meanwhile lamination blue light organic electroluminescence device generally uses fluorescent material to form luminescence unit or incite somebody to action
Phosphor material, which is doped into material of main part, forms luminescence unit, and luminescence unit generally uses single luminous layer structure.Have numerous
Literature research shows Alq3It is both good green fluorescent material or outstanding electron transport material.But it is most of organic
Material hole mobility is more than electron mobility, is the transmission of equilbrium carrier, inhibits carrier unfetteredly at other
Non-luminous region carries out recombination luminescence and obtains non-targeted photochromic phenomenon, it is necessary to the position of limiting carrier, control exciton production
Raw region, adjusts light-emitting mode.Therefore, it also needs to search out corresponding limiting carrier position and control exciton production for device
The material in raw region.
The present invention devises the charge generation layer with superperformance corresponding with a kind of basic blue luminescent device, realizes
Lamination blue light organic electroluminescence device based on charge generation layer design obtains optimum performance.Meanwhile it is selected with economical excellent
The material BCP of gesture and good hole-blocking characteristics is inserted between blue-light-emitting unit and electron transport layer materials, limits current-carrying
Sub- position and control exciton generating region, weaken because of Alq3Influence of the green fluorescence characteristics of luminescence of itself to device,
And then realize purer and efficient lamination blue phosphorescent device.
Invention content
Present invention seek to address that the above problem of the prior art.A kind of raising device is proposed to shine pure degree, another party
Face improves the lamination blue light organic electroluminescence device and its manufacturing process of the luminous efficiency of device.Technical scheme of the present invention
It is as follows：
A kind of lamination blue light organic electroluminescence device comprising：
Substrate is provided with ito anode layer on the substrate, hole transmission layer, the hole is provided on the anode layer
It is provided with blue-light-emitting unit in transport layer, hole blocking layer, the hole blocking layer are provided on the blue-light-emitting unit
On be provided with electron transfer layer, charge generation layer is additionally provided on the electron transfer layer, is set successively on the charge generation layer
It is equipped with hole transmission layer, blue-light-emitting unit, hole blocking layer, electron transfer layer, electron injecting layer and Al cathodes, (repetition is set
It is to be injected into formation exciton inside second luminescence unit using charge generation layer to generate charge to set, this is a kind of novel knot
Structure, therewith the first two luminescence unit directly be located next to difference) wherein ito anode layer be used for be used as device anode, injection hole, sky
Cave transport layer be used for transmission hole reach quickly blue-light-emitting unit, blue-light-emitting unit be used for be used as device core component,
Performance and charge generation layer performance be closely related, hole blocking layer is for stopping hole so that more multi-hole is shining with electronics
It is empty for can both be used as quickening electron-transport to be also used as blocking that exciton recombination luminescence, electron transfer layer are formed in unit
Cave, charge generation layer generate pump for charge between two luminescence units, and side generates electronics, side generates hole, with electrode
The similar injection carrier of effect to each side adjacent to luminescence unit, electron injecting layer for transmit quickly electronics to luminescence unit with
And blocking hole, Al cathodes are used for device cathodes, inject electronics.
Further, the blue-light-emitting unit (3) is two, is separated by charge generation layer (6), the blue-light-emitting list
First (3) include material of main part, guest materials, and guest materials is entrained in 10wt% (mass fraction) in material of main part.
Further, the blue phosphor materials of the blue-light-emitting unit are Firpic.
Further, the material of the hole blocking layer is the functional layer material for having hole-blocking characteristics.
Further, the material of the hole blocking layer uses BCP bromocresol purples.
Further, the material of the electron transfer layer is Alq3(three (8-hydroxyquinoline) aluminium) green fluorescent material.
Further, the material that charge generation layer uses is (Pentacene (pentacene) generates material, C as hole60
(football alkene) generates material, Al (aluminium)/Cs as electronics2CO3(cesium carbonate) improves electricity collectively as charge generation layer decorative material
The charge of lotus generating layer generates ability, and the material that the electron injecting layer uses is Cs2CO3(cesium carbonate), hole transmission layer use
Material be NBP (N, N'- diphenyl-N, N'- (1- naphthalenes) -1,1'- biphenyl -4,4'- diamines).
A kind of technique of the aforementioned lamination blue light organic electroluminescence device of manufacture comprising following steps：
Carry out the cleaning operation of conventional removal its surface and oil contaminant and dust to substrate, including using acetone, absolute ethyl alcohol,
Deionized water is cleaned by ultrasonic；In order to obtain higher surface cleanliness and ITO work functions, early period is cleaned using oxygen plasma
Substrate afterwards is handled, and O is kept in processing procedure2Flow 800ml/min, processing equipment power 80-100W, processing time be
8mins；It is put into immediately after in the vacuum cavity of evaporation coating instrument；Using vacuum thermal evaporation method, make in high vacuum conditions
Standby device, wherein when plating first layer NPB materials, evaporation rate is controlled in 0.1nm/s, duration 400s, blue-light-emitting list
TPBi and Firpic is deposited simultaneously in member forms luminescence unit, TPBi (1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl)
Benzene) in 0.1nm/s, the plated film rate of Firpic is needed to tune up the Tooling factor of film thickness detector, is maintained at rate control
BCP and Alq is deposited in 0.1nm/s, duration 100s3When, rate control is in 0.1nm/s, and Al is as charge generation layer
A part when control in 0.2nm/s, the time continues 200s, when as cathode evaporation rate control in 0.3nm/s, duration
About 333s, Cs2CO3Evaporation rate is controlled in 0.02nm/s, duration 50s, C60Rate is controlled when being deposited with Pentacene
System is in 0.1nm/s.All of above evaporation rate is simultaneously non-fully accurate, rate within the scope of compared with minor swing (about 10%) to device shadow
It rings little.But should be more accurate for the preparation rate control of charge generation layer and luminescence unit, performance directly affects device
Maximum luminous efficiency.
It advantages of the present invention and has the beneficial effect that：
The present invention devises the charge generation layer with superperformance corresponding with a kind of basic blue luminescent device, with biography
The doping type charge generation layer of system is compared, the charge generation layer using undoped method prepare, preparation method is simple, avoid because
To adulterate the influence of lax pair charge generation layer device efficiency.And it studies and finds the charge generation layer to basic in the present invention
There is good charge injection efficiency for blue-light-emitting cellular construction, it is blue to realize the lamination designed based on the charge generation layer
Light organic electroluminescence device obtains optimum performance.Meanwhile the selected material BCP with economic advantages and good hole-blocking characteristics is inserted
Enter between blue-light-emitting unit and electron transport layer materials, limiting carrier position and control exciton generating region weaken
Carrier diffusion is to Alq3Formation exciton compound the phenomenon that sending out green light, reduce green light to blue luminescent device color in region
The influence of purity.Moreover, since more carriers are limited in luminescence unit, hole with to electronically form exciton compound
The probability for sending out blue light increases, and then realizes purer and efficient lamination blue phosphorescent device.The device and no electricity
The double emitting layers device of lotus generating layer is compared, and charge generation layer is functionally similar to cathode and the back-to-back structure of anode so that
Carrier is supplemented, and the carrier concentration in luminescence unit is higher, is a kind of novel organic electroluminescence device structure.
Description of the drawings
Fig. 1 is the structure chart that the present invention provides preferred embodiment device；
Fig. 2 is device and the normalization electroluminescence spectrum of comparative device.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, detailed
Carefully describe.Described embodiment is only a part of the embodiment of the present invention.
The present invention solve above-mentioned technical problem technical solution be：
As shown in Figure 1, its device layers is entitled：1-ITO anodes, 2- hole transmission layers, 3- blue-light-emittings unit, 4-
Hole blocking layer, 5- electron transfer layers, 6- charge generation layers, 7- electron injecting layers, 8-Al cathodes.In blue-light-emitting unit and electricity
Hole barrier layer material is added between sub- transmission material so that hole is effectively limited in blue-light-emitting layer region and electricity
Son forms exciton radioluminescence, can not move to electron transfer layer Alq3It is middle to form non-purpose green light.On the one hand device hair is improved
The pure degree of light, on the other hand improves the luminous efficiency of device.
Its specific preparation method is as follows：Greasy dirt and dust to remove its surface before experiment carry out the clear of routine to substrate
Operation is washed, acetone, absolute ethyl alcohol, deionized water are cleaned by ultrasonic.In order to obtain higher surface cleanliness and ITO work functions, adopt
Substrate after being cleaned to early period with oxygen plasma is handled.O is kept in processing procedure2Flow 800ml/min, processing equipment
Power 80-100W, processing time 8mins.It is put into immediately after in the vacuum cavity of evaporation coating instrument.Using vacuum thermal evaporation
Method, in high vacuum conditions (~10-5Pa device) is prepared.Wherein, when plating first layer NPB materials, evaporation rate control exists
0.1nm/s, duration 400s.TPBi and Firpic is deposited simultaneously in blue-light-emitting unit forms luminescence unit, TPBi (1,
3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene) in 0.1nm/s, the plated film rate needs of Firpic tune up rate control
The Tooling factor of film thickness detector is maintained at 0.1nm/s, duration 100s.BCP and Alq is deposited3When, rate control
System is in 0.1nm/s.The preparation of entire charge generation layer needs great care.Control exists when a parts of the Al as charge generation layer
0.2nm/s, time continue 200s, and evaporation rate control is in 0.3nm/s, duration about 333s when as cathode.Cs2CO3It steams
Rate control is plated in 0.02nm/s, duration 50s.C60Rate is controlled in 0.1nm/s when being deposited with Pentacene.More than
All rates are simultaneously non-fully accurate, and rate (about 10%) within the scope of compared with minor swing is little to component influences.But charge is produced
Generating layer and the preparation rate control of luminescence unit should be more accurate, and performance directly affects the maximum luminous efficiency of device.
Comparative example
The structure of comparative device is：
ITO (200nm)/NPB (40nm)/blue-light-emitting unit/Alq3(60nm)/charge generation layer/NPB (40nm)/indigo plant
Color luminescence unit/Alq3(60nm)/Cs2CO3(1nm)/Al(100nm)
Device is provided with 10nm's compared with the structure of comparative device between electron transfer layer and blue-light-emitting unit
BCP is as hole blocking layer.Due to no hole blocking layer, comparative device electron transfer layer Alq3Thickness be 60nm, remaining
Structure is completely the same.The luminous efficiency of device and comparative device comparison such as table 1, luminous spectrum such as Fig. 2.
By data it can be found that by the example method realize device maximal efficiency and chromaticity coordinates obtained compared with
The earth is promoted, and green acromion has obtained preferably inhibiting.
Used organic matter title and molecular structure are as follows in this invention：
The above embodiment is interpreted as being merely to illustrate the present invention rather than limit the scope of the invention.
After the content for having read the record of the present invention, technical staff can make various changes or modifications the present invention, these equivalent changes
Change and modification equally falls into the scope of the claims in the present invention.
Claims (8)
1. a kind of lamination blue light organic electroluminescence device, which is characterized in that including：Substrate is provided with ITO sun on the substrate
Pole layer (1) is provided with hole transmission layer (2) on the anode layer (1), blue-light-emitting is provided on the hole transmission layer (2)
Unit (3) is provided with hole blocking layer (4) on the blue-light-emitting unit (3), electricity is provided on the hole blocking layer (4)
Sub- transport layer (5), is additionally provided with charge generation layer (6) on the electron transfer layer (5), on the charge generation layer (6) successively
It is provided with hole transmission layer (2), blue-light-emitting unit (3), hole blocking layer (4), electron transfer layer (5), electron injecting layer (7)
And Al cathodes (8), wherein ito anode layer (1) are used to be used as device anode, inject hole, hole transmission layer (2) is used for transmission sky
Cave reaches blue-light-emitting unit (3) quickly, and blue-light-emitting unit (3) is used to be used as device core component, performance to be produced with charge
Generating layer performance is closely related, and hole blocking layer (4) is for stopping hole so that more multi-hole is formed with electronics in luminescence unit
Exciton recombination luminescence, electron transfer layer (5) is for can both be used as quickening electron-transport to be also used as blocking hole, charge production
Generating layer (6) generates pump for charge between two luminescence units, and side generates electronics, side generates hole, and class is acted on electrode
Like injection carrier to each side adjacent to luminescence unit, electron injecting layer (7) for transmit quickly electronics to luminescence unit and
Stop that hole, Al cathodes (8) are used for device cathodes, injects electronics.
2. lamination blue light organic electroluminescence device according to claim 1, which is characterized in that the blue-light-emitting unit
(3) it is two, is separated by charge generation layer (6), the blue-light-emitting unit (3) includes material of main part, guest materials, object material
Material is entrained in 10wt% (mass fraction) in material of main part.
3. lamination blue light organic electroluminescence device according to claim 2, which is characterized in that the blue-light-emitting unit
(3) blue phosphor materials are Firpic (bis- (4,6- difluorophenyl pyridinatos-N, C2) pyridinecarboxylics close iridium).
4. the lamination blue light organic electroluminescence device according to one of claim 1-3, which is characterized in that the hole resistance
The material of barrier (4) is the functional layer material for having hole-blocking characteristics.
5. green light acromion according to claim 4 inhibits lamination blue light organic electroluminescence device, which is characterized in that described
The material of hole blocking layer (4) uses BCP bromocresol purples.
6. the green light acromion according to one of claim 1-3 inhibits lamination blue light organic electroluminescence device, feature to exist
In the material of the electron transfer layer (5) is Alq3Three (8-hydroxyquinoline) aluminium green fluorescent materials.
7. the green light acromion according to one of claim 1-3 inhibits lamination blue light organic electroluminescence device, feature to exist
In the material that the charge generation layer (6) uses is (Pentacene (pentacene) generates material, C as hole60Football alkene is made
Material, Al (aluminium)/Cs are generated for electronics2CO3Cesium carbonate improves the electricity of charge generation layer collectively as charge generation layer decorative material
Lotus generates ability, and the material that the electron injecting layer (7) uses is Cs2CO3Cesium carbonate, the material that hole transmission layer (2) uses for
NBP (N, N'- diphenyl-N, N'- (1- naphthalenes) -1,1'- biphenyl -4,4'- diamines).
8. a kind of technique of one of manufacture preceding claims 1-7 lamination blue light organic electroluminescence devices, which is characterized in that packet
Include following steps：
Carry out the cleaning operation of conventional removal its surface and oil contaminant and dust to substrate, including using acetone, absolute ethyl alcohol, go from
Sub- water is cleaned by ultrasonic；In order to obtain higher surface cleanliness and ITO work functions, after being cleaned to early period using oxygen plasma
Substrate is handled, and O is kept in processing procedure2Flow 800ml/min, processing equipment power 80-100W, processing time be
8mins；It is put into immediately after in the vacuum cavity of evaporation coating instrument；Using vacuum thermal evaporation method, make in high vacuum conditions
Standby device, wherein when plating first layer NPB materials, evaporation rate is controlled in 0.1nm/s, duration 400s, blue-light-emitting list
TPBi and Firpic is deposited simultaneously in member forms luminescence unit, TPBi (1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl)
Benzene) in 0.1nm/s, the plated film rate of Firpic is needed to tune up the Tooling factor of film thickness detector, is maintained at rate control
BCP and Alq is deposited in 0.1nm/s, duration 100s3When, rate control is in 0.1nm/s, and Al is as charge generation layer
A part when control in 0.2nm/s, the time continues 200s, when as cathode evaporation rate control in 0.3nm/s, duration
About 333s, Cs2CO3Evaporation rate is controlled in 0.02nm/s, duration 50s, C60Rate is controlled when being deposited with Pentacene
System is in 0.1nm/s.
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| CN111697156A (en) * | 2019-03-12 | 2020-09-22 | 环球展览公司 | Organic light emitting device |
| CN113178526A (en) * | 2021-04-26 | 2021-07-27 | 京东方科技集团股份有限公司 | Electroluminescent device and display device |
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Application publication date: 20181012 |