CN110176547A - A kind of modified lamination red OLED and its preparation process based on photovoltaic type CGU - Google Patents
A kind of modified lamination red OLED and its preparation process based on photovoltaic type CGU Download PDFInfo
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Abstract
A kind of modified lamination red OLED and its preparation process based on photovoltaic type CGU is claimed in the present invention; substrate including visible light transmittance between 80%-96%; stack anode, hole transmission layer, red dual light unit, electron transfer layer, CGU and the cathode of setting; the dual light unit is separated by CGU; the luminescent layer includes material of main part, guest materials; object is entrained in material of main part with 10wt%, and the CGU is interior with photovoltaic property with enclosing in 400-780nm.CGU makes lamination red device current efficiency increase above 3 times of corresponding single layer device using its photovoltaic property in laminated device, and driving voltage is lower than twice of single layer device, and device power efficiency is obviously improved more than 70%.It is more than 3 times or more of corresponding single layer device that technical solution of the present invention, which improves the performance parameters such as laminated device current efficiency and brightness, simultaneously device power efficiency is significantly improved more than 70%, solves the problems, such as that laminated device efficiency is difficult to be promoted.
Description
Technical field
The invention belongs to organic electroluminescence device technical fields, and in particular to a kind of high efficiency charge with photovoltaic property
Generating layer structure and entire device preparation technology.
Background technique
Laminated organic light-emitting diode (Tandem Organic Light-emitting Diodes, TOLEDs) because its
There are the advantageous points such as high brightness, high efficiency and long-life under low current density and be widely studied.TOLEDs is external at one
Under power supply, by two or more independent OLEDs units by charge generate unit (Charge Generation Unit,
CGU) series connection is formed.This kind of structure is proved can to significantly improve device performance, reduces device operation current, be effectively reduced due to
The generation of quenching effect caused by electric current, and then improve device performance and service life.Kido et al. is the study found that theoretically contain N
The operating brightness of the organic electroluminescence device of a luminescence unit can achieve N times of single luminescence unit device.Therefore, lamination
Organic electroluminescence device substantially increases working efficiency and the service life of organic electroluminescence device.
In recent years, there are many researchs to be dedicated to being promoted the performance of photovoltaic type CGU to obtain efficient laminated device, and wide
It is general to have used typical p-n junction concept.Wherein, p-type material mainly has metal oxide such as V2O5、WO3And MoO3, p-type doping has
Machine layer such as NPB:FeCl3、ruberne:MoO3And TAPC:MoO3And p-type organic material such as TAPC, m-MTDATA and
Pentacene etc..N-type material removes n-type doping organic layer such as Bphen:Li, Al:Mg and Bphen:Cs2CO3Outside, there are also N-shapeds
Organic semiconducting materials such as HAT-CN, C60And C70Deng.However, with usual Red Organic Electroluminescence Devices (Organic
Light-emitting Diode) field OLED it is common CGU preparation laminated device remain due to its driving voltage
Be multiplied and power efficiency do not obtain improve the problems such as, greatly hinder the development and application of TOLEDs.Thus may be used
Knowing, CGU not only plays a part of each independent OLEDs unit of connection, but also it is required to generate ability with efficient charge, and
Quickly the charge of generation can be injected into successive functional layers.Therefore, the material selection and structure design of CGU is also to influence
The key factor of TOLEDs performance.
The present invention devises a kind of CGU with photovoltaic property, which can form " electricity+light " inside laminated device
Operating mode generates ability to promote its charge, and the separation of charge ability of CGU is promoted by the way that electric charge injection layer is added, and helps
The charge that CGU is generated is efficiently separated and is injected into real time in the luminescence unit at both ends, to realize laminated device efficiency and bright
The performances such as degree are obviously improved, and reduce device drive voltage, obtain a kind of efficient lamination red electroluminescent device.
The lamination organic luminescent device reported at present due to the increase with independent luminescence unit, the driving voltage of device at
Increase again, even if current efficiency increases by 2 times, but the power efficiency of laminated device cannot be promoted effectively, and this seriously inhibits folded
The development and application of layer device.The core of laminated device is that the charge of CGU is generated and separated, first is that CGU wants effectively to generate
Charge；Second is that CGU wants the separation of charge that can be generated in time and injects adjacent luminescence unit, Neither of the two can be dispensed.This
The CGU with photovoltaic property is selected in invention, generates mode using the charge of " electricity+light ", the charge for effectively promoting CGU generates energy
Power, meanwhile, CGU selects Al/LiF and MoO in two sides respectively3Modification, reduces the injection energy barrier of electrons and holes, significantly improves CGU
Separation of charge ability, this is most important for the efficiency for improving entire device.
Summary of the invention
Present invention seek to address that the following problems of the prior art.The lamination organic luminescent device reported at present is due to only
The increase of vertical luminescence unit, the driving voltage of device are multiplied, even if current efficiency increases by 2 times, but the power of laminated device
Efficiency cannot be promoted effectively, and this seriously inhibits the development of laminated device and applications.The core of laminated device is the electricity of CGU
Lotus generates and separation, first is that CGU wants effectively generate charge；Second is that CGU wants the separation of charge that can be generated in time and note
Enter adjacent luminescence unit, Neither of the two can be dispensed.The present invention selects the CGU with photovoltaic property, is produced using the charge of " electricity+light "
Raw mode, the charge for effectively promoting CGU generate ability, meanwhile, CGU selects Al/LiF and MoO in two sides respectively3Modification reduces electricity
The injection energy barrier of son and hole, significantly improves the separation of charge ability of CGU, this is for improving the efficiency of entire device to Guan Chong
It wants.Technical scheme is as follows:
A kind of modified lamination red OLED based on photovoltaic type CGU, including the glass substrate to play a supportive role, the lining
It is provided with the ito anode layer (1) for injecting hole on bottom, the sky for injecting hole is provided on the ito anode layer (1)
Cave implanted layer (2) is provided with the hole transmission layer (3) for being used for transmission hole, the hole transport on the hole injection layer (2)
It is provided with the exciton barrier-layer (4) for being limited in exciton in luminescent layer on layer (3), is arranged on the exciton barrier-layer (4)
Have and be used for electroluminescent emitting red light unit (5), the electronics for electron-transport is provided on the emitting red light unit (5)
Transport layer (6) is provided with for generating electrons and holes on the electron transfer layer (6), and is injected separately into the neighbouring hair on both sides
The CGU (7) of light unit, be also repeated on the CGU (7) be provided with hole transmission layer (3), exciton barrier-layer (4), shine it is single
The electronics note of helpful electron injection luminescence unit (5) is arranged on the electron transfer layer (6) for first (5), electron transfer layer (6)
Enter layer (8), the Al cathode (9) for electron injection is provided on the electron injecting layer (8), Al cathode (9) is opaque, has
The effect of reflected light.
Further, the charge generates unit CGU (7) and uses N-shaped organic semiconducting materials C60(fullerene) is as electricity
Sub- acceptor material, p-type organic semiconductor material ZnPc (Phthalocyanine Zinc) are used as donor material, double-layer structure LiF (lithium fluoride)/Al
(aluminium) is in C60Side is as electron injecting layer and electron extraction layer；MoO3(molybdenum trioxide) is in the side ZnPc as hole injection layer
With hole extract layer；Double-layer structure LiF/Al and single layer MoO3The charge that unit is generated for improving charge generates and separation energy
Power.
Further, the luminescence unit (5) is two, and two luminescence units (5) are separated by charge generation layer (7), institute
Stating luminescence unit (5) includes material of main part, guest materials, and guest materials is entrained in material of main part with 10wt% (mass fraction)
In, 30 nanometers of entire luminescence unit thickness.
Further, the material of main part of the luminescence unit (5) is phosphor material TCTA (4,4', 4 "-three -9- carbazyls
Triphenylamine), guest materials is respectively red phosphorescence material Ir (piq)2Acac (three [1- phenyl isoquinolin quinoline-C2, N] iridium (III)).
Further, the CGU (7) has photovoltaic property, C in visible light wave range60It is combined with both ZnPc, it can not only be
Separation of charge is realized in induction under extraneous bias, while charge can be generated by illumination, realizes that the charge of " electricity+light " generates mould
Formula, so that the charge for improving CGU (7) generates ability.
A kind of preparation process of the modified lamination red OLED based on photovoltaic type CGU comprising following technique:
The processing of step 1, ito glass substrate: toluene, acetone, dehydrated alcohol, deionization are successively pressed to ito glass substrate
The sequence of water (3 times) is cleaned by ultrasonic, every time cleaning 12 minutes；By cleaned glass substrate with being dried with nitrogen, it is placed in 120
Baking 20 minutes in DEG C baking box, the glass substrate of drying is carried out oxygen plasma treatment 20 minutes；
The preparation of step 2, hole injection layer: after the completion of ito glass substrate processing, ITO substrate is put into vacuum evaporation chamber
The interior preparation for carrying out each functional layer, the control of NPB evaporation rate is per second at 1 angstrom, and the duration is about 400 seconds；
The preparation of step 3, hole transmission layer and exciton barrier-layer: being heated to evaporating temperature for hole-injecting material NPB,
Evaporation rate control is per second at 1 angstrom, and evaporation time is about 400 seconds；The control of exciton-blocking material TCTA evaporation rate is every at 0.2 angstrom
Second, the duration is about 250 seconds；
The preparation of step 4, luminescence unit: material of main part and guest materials, main body material need to be opened simultaneously when vapor deposition luminescent layer
Expect that TCTA evaporation rate controls, guest materials Ir (piq) per second at 1.8 angstroms2The evaporation rate control of acac is per second at 0.2 angstrom,
Duration is about 150 seconds；
The preparation of step 5, electron transfer layer: electron transport material TPBi evaporation rate is controlled in 1 angstrom of per second, evaporation time
About 400 seconds；
The preparation of step 6, CGU: CGU is mainly C60The interface /ZnPc generates charge, LiF/Al and MoO3Positioned at C60/ZnPc
Two sides, it is therefore an objective to which the charge generated is respectively detached effectively in real time and injected in corresponding luminescent layer；
The preparation of step 7, LiF/Al: the evaporation rate control of electron injecting layer LiF is per second at 0.1 angstrom, and evaporation time is about
It is 50 seconds；The evaporation rate of Al cathode is about 3 angstroms per second, and the duration is about 400 seconds.
Further, it after the ito glass Substrate treatment is complete, is immediately placed in vacuum evaporation cavity；It is steamed using Vacuum Heat
Electroplating method, in high vacuum conditions (~3.2 × 10-5Pa device) is prepared, wherein vapor deposition MoO3(2) when, evaporation rate control
It is per second at 0.2 angstrom；TCTA and Ir (piq) in luminescence unit2Acac is deposited forms luminescence unit simultaneously, and TCTA rate control exists
1.8 angstroms per second.
Further, in the preparation process of step 6 CGU, LiF/Al/C60/ZnPc/MoO3Evaporation rate respectively
It controls per second at 0.2 angstrom.
It advantages of the present invention and has the beneficial effect that:
The present invention devise with a kind of emitting red light device based on photovoltaic type CGU, with traditional doping type CGU structure phase
Than the present invention is prepared using undoped method, and preparation method is simple, is avoided because doping lax pair CGU efficiency influences；Together
When, traditional CGU is the structure of simply p-n junction form, and CGU of the present invention has photovoltaic property compared with traditional devices, can
Realize that the charge of " electricity+light " generates mode；Meanwhile C60The LiF/Al and MoO at the both ends /ZnPc3Energy barrier can not only be reduced, is helped
The transmission of carrier, and can also effectively in real time detach the CGU charge generated in time, avoid electron-hole due to energy barrier
Excessive can not separate in time and it is compound herein.CGU of the invention can be realized under lesser driving voltage device current efficiency,
The increase of brightness characteristics is greater than 3 times of single layer device or more, while promoting the power efficiency 70% of device, and it is folded that this is effectively improved tradition
Layer device power efficiency promotes difficult problem.
Detailed description of the invention
Fig. 1 is the device junction composition of embodiment 1 (present invention).
Fig. 2 is in device of the present invention, and the spectrum of absorption characteristic and luminescence unit of the CGU in visible-range compares.
Fig. 3 is Current density-voltage-brightness curve of 1 device of embodiment.
Fig. 4 is current density-power efficiency curve of 1 device of embodiment.
Fig. 5 is Current density-voltage-brightness curve of 2 device of embodiment.
Fig. 6 is current density-power efficiency curve of 2 device of embodiment.
Fig. 7 is Current density-voltage-brightness curve of 3 device of embodiment.
Fig. 8 is current density-power efficiency curve of 3 device of embodiment.
Specific embodiment
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 embodiments of the present invention.
The technical solution that the present invention solves above-mentioned technical problem is:
Embodiment 1:
A kind of modified lamination Red Organic Electroluminescence Devices and its preparation process based on photovoltaic type CGU are as follows:
(1) processing of ito glass substrate
Ito glass substrate square resistance is about 7 Ω/, and size is about 17 × 17mm.First is successively pressed to ito glass substrate
Benzene, acetone, dehydrated alcohol, deionized water (3 times) sequence be cleaned by ultrasonic, every time cleaning 12 minutes；By cleaned glass
Glass substrate is placed in baking 20 minutes in 120 DEG C of baking boxes with being dried with nitrogen, and the glass substrate of drying is carried out oxygen plasma treatment
20 minutes (O2Flow is 900 milliliters per minute), it is therefore an objective to improve interfacial contact angle, improves its work function.
(2) preparation of hole injection layer
After the completion of ito glass substrate processing, ITO substrate is put into the intracavitary preparation for carrying out each functional layer of vacuum evaporation.NPB
Evaporation rate control is per second at 1 angstrom, and the duration is about 400 seconds.
(3) preparation of hole transmission layer and exciton barrier-layer
Hole-injecting material NPB is heated to evaporating temperature, evaporation rate control is per second at 1 angstrom, and evaporation time is about
400 seconds；The control of exciton-blocking material TCTA evaporation rate is per second at 0.2 angstrom, and the duration is about 250 seconds.
(4) preparation of luminescence unit
Material of main part and guest materials need to be opened simultaneously when luminescent layer is deposited, the control of material of main part TCTA evaporation rate exists
1.8 angstroms per second, guest materials Ir (piq)2The evaporation rate control of acac is per second at 0.2 angstrom, and the duration is about 150 seconds.
(5) preparation of electron transfer layer
The control of electron transport material TPBi evaporation rate is per second at 1 angstrom, and evaporation time is about 400 seconds.
(6) preparation of CGU
CGU is mainly C60The interface /ZnPc generates charge, LiF/Al and MoO3Positioned at C60The two sides /ZnPc, it is therefore an objective to be produced
Raw charge is respectively detached effectively in real time and is injected in corresponding luminescent layer, LiF/Al/C60/ZnPc/MoO3Evaporation rate
Respectively control is per second at 0.2 angstrom.
(7) preparation of LiF/Al
The evaporation rate control of electron injecting layer LiF is per second at 0.1 angstrom, and evaporation time is about 50 seconds；The vapor deposition of Al cathode
Rate is about 3 angstroms per second, and the duration is about 400 seconds.
Fig. 3 and Fig. 4 is respectively the Current density-voltage-brightness curve and current density-power effect of the OLED device prepared
Rate curve.In 20mA/cm it can be seen from Fig. 2 and Fig. 32When, the brightness of laminated device compares single layer device and improves about 3.27
Times；In 1000cd/m2When, the driving voltage of laminated device is lower than twice of single layer device, and current efficiency compares single layer device
3.35 times are improved, while its power efficiency improves about 78% compared to single layer device.
Embodiment 2 (comparative example):
This comparative example is compared with invention device, and only in luminescence unit, luminescent material is different, remaining structure is completely the same.
Comparative device structure are as follows:
Single layer device ITO (140nm)/MoO3(3nm)/NPB (40nm)/TCTA (5nm)/TCTA:Firpic (10wt%,
30nm)/TPBi(40nm)/LiF(0.6nm)/Al(120nm)
Laminated device: ITO (140nm)/MoO3(3nm)/NPB (40nm) TCTA (5nm)/TCTA:Firpic (10wt%,
30nm)/TPBi(40nm)/LiF(0.6nm)/Al(1nm)/C60(6nm)/ZnPc(6nm)/MoO3(3nm)/NPB(40nm)/
TCTA (5nm)/TCTA:Firpic (10wt%, 30nm)/TPBi (40nm)/LiF (0.6nm)/Al (120nm)
(1) processing of ito glass substrate
Ito glass substrate square resistance is about 7 Ω/, and size is about 17 × 17mm.First is successively pressed to ito glass substrate
Benzene, acetone, dehydrated alcohol, deionized water (3 times) sequence be cleaned by ultrasonic, 15mins is cleaned every time, by cleaned glass
Glass substrate is placed in 20mins in 120 DEG C of baking boxes with being dried with nitrogen, and the glass substrate of drying is carried out oxygen plasma treatment
20mins(O2Flow is 900ml/min), it is therefore an objective to improve interfacial contact angle, improves its work function.
(2) preparation of hole injection layer
After the completion of ito glass substrate processing, ITO substrate is put into the intracavitary preparation for carrying out each functional layer of vacuum evaporation.NPB
Evaporation rate control existsDuration is about 400s.
(3) preparation of hole transmission layer and exciton barrier-layer
Hole-injecting material NPB is heated to evaporating temperature, evaporation rate control existsEvaporation time is about
400s；The control of exciton-blocking material TCTA evaporation rate existsDuration is about 250s.
(4) preparation of luminescence unit
Material of main part and guest materials need to be opened simultaneously when luminescent layer is deposited, guest materials is mixed with 10wt% (mass fraction)
It is miscellaneous in material of main part.The control of material of main part TCTA evaporation rate existsThe control of guest materials Firpic evaporation rate existsDuration is about 150 seconds.
(5) preparation of electron transfer layer
The control of electron transport material TPBi evaporation rate existsEvaporation time is about 400s.
(6) preparation of CGU
CGU is mainly C60The interface /ZnPc generates charge, LiF/Al and MoO3Positioned at C60The two sides /ZnPc, it is therefore an objective to be produced
Raw charge is respectively detached effectively in real time and is injected in corresponding luminescent layer, LiF/Al/C60/ZnPc/MoO3Evaporation rate
Respectively control is per second at 0.2 angstrom.
(7) preparation of LiF/Al
The evaporation rate control of electron injecting layer LiF existsEvaporation time is about 50s；The evaporation rate of Al cathode
AboutDuration is about 330s.
Fig. 5 and Fig. 6 is respectively Current density-voltage-brightness curve of the green light OLED comparative device prepared in embodiment 2
With current density-power efficiency curve.
Green light laminated device is in 1000cd/m it can be seen from Fig. 5 and Fig. 62When driving voltage lower than single layer device
Twice, in 20mA/cm2Under luminance raising about 3 times, in 1000cd/m2When current efficiency improve 3.32 times, power effect
Rate improves about 72%.
Embodiment 3 (comparative example):
This comparative example is only that luminescent material is different in luminescence unit compared with invention device, remaining structure is completely the same.
Comparative device structure are as follows:
Single layer device ITO (140nm)/MoO3(3nm)/NPB(40nm)/TCTA(5nm)/TCTA:Ir(ppy)3(10wt%,
30nm)/TPBi(40nm)/LiF(0.6nm)/Al(120nm)
Laminated device: ITO (140nm)/MoO3(3nm)/NPB(40nm)TCTA(5nm)/TCTA:Ir(ppy)3(10wt%,
30nm)/TPBi(40nm)/LiF(0.6nm)/Al(1nm)/C60(6nm)/ZnPc(6nm)/MoO3(3nm)/NPB(40nm)/
TCTA(5nm)/TCTA:Ir(ppy)3(10wt%, 30nm)/TPBi (40nm)/LiF (0.6nm)/Al (120nm)
(1) processing of ito glass substrate
Ito glass substrate square resistance is about 7 Ω/, and size is about 17 × 17mm.First is successively pressed to ito glass substrate
Benzene, acetone, dehydrated alcohol, deionized water (3 times) sequence be cleaned by ultrasonic, 15mins is cleaned every time, by cleaned glass
Glass substrate is placed in 20mins in 120 DEG C of baking boxes with being dried with nitrogen, and the glass substrate of drying is carried out oxygen plasma treatment
20mins(O2Flow is 900ml/min), it is therefore an objective to improve interfacial contact angle, improves its work function.
(2) preparation of hole injection layer
After the completion of ito glass substrate processing, ITO substrate is put into the intracavitary preparation for carrying out each functional layer of vacuum evaporation.NPB
Evaporation rate control existsDuration is about 400s.
(3) preparation of hole transmission layer and exciton barrier-layer
Hole-injecting material NPB is heated to evaporating temperature, evaporation rate control existsEvaporation time is about
400s；The control of exciton-blocking material TCTA evaporation rate existsDuration is about 250s.
(4) preparation of luminescence unit
Material of main part and guest materials need to be opened simultaneously when luminescent layer is deposited, guest materials is mixed with 10wt% (mass fraction)
It is miscellaneous in material of main part.The control of material of main part TCTA evaporation rate existsGuest materials Ir (ppy)3Evaporation rate control
?Duration is about 150 seconds.
(5) preparation of electron transfer layer
The control of electron transport material TPBi evaporation rate existsEvaporation time is about 400s.
(6) preparation of CGU
CGU is mainly C60The interface /ZnPc generates charge, LiF/Al and MoO3Positioned at C60The two sides /ZnPc, it is therefore an objective to be produced
Raw charge is respectively detached effectively in real time and is injected in corresponding luminescent layer, LiF/Al/C60/ZnPc/MoO3Evaporation rate
Respectively control is per second at 0.2 angstrom.
(7) preparation of LiF/Al
The evaporation rate control of electron injecting layer LiF existsEvaporation time is about 50s；The evaporation rate of Al cathode
AboutDuration is about 330s.
Fig. 7 and Fig. 8 is respectively Current density-voltage-brightness curve of the green light OLED comparative device prepared in embodiment 3
With current density-power efficiency curve.
Green light laminated device is in 1000cd/m it can be seen from Fig. 7 and Fig. 82When driving voltage lower than single layer device
Twice, in 20mA/cm2Under luminance raising about 2 times, in 1000cd/m2When current efficiency improve 2.07 times, power effect
Rate only promotes 13.6%.
The comparison of the performance parameter of device of the present invention and comparative device is as shown in table 1.
By above data it can be found that the driving voltage of all laminated devices is respectively less than 2 times of single layer device, device of the present invention
Part (embodiment 1) device brightness and current efficiency promotion improve 3.27 times and 3.35 times respectively, and power efficiency improves about
78%.Blue light comparative device (embodiment 2) improves 3 times and 3.32 times, power effect respectively in terms of brightness and current efficiency
Rate promotes about 72%.Green comparative device (embodiment 3) improves 2 times and 2.07 times respectively in terms of brightness and current efficiency,
Power efficiency improves about 13.6%, and overall performance is promoted to red > blue > green.By CGU in Fig. 2 in visible-range
Absorption characteristic and luminescence unit spectrum comparison it is found that in visible-range, C60The absorption and red, green and blue of/ZnPc
The overlapping range of luminescent material is red > indigo plant > green, i.e. C60/ ZnPc is greater than blue light to the absorption of feux rouges wave crest and is greater than green light, this and reality
Result is tested to coincide.Red device improved efficiency is most, and for blue light secondly, green light improved efficiency is minimum, this shows C60/ ZnPc is visible
There is photovoltaic property in optical range.The present invention utilizes C60The CGU of the photovoltaic property preparation of/ZnPc has the electricity of " electricity+light " mode
Lotus generates ability, so that lamination red device is when driving voltage is lower than 2 times of single layer device, the brightness of device, current efficiency is mentioned
Liter is more than 3 times or more of single layer device, meanwhile, the power efficiency of device promotes about 78%, this imitates laminated device in power
Being difficult to the problem of being promoted in rate is effectively solved.
It should be noted that the organic material that the present invention uses is purchased from Guangdong Aglaia Optoelectronic Materials Co., Ltd.,
Material purity is all larger than 99.5%；Cleaning substrate solution is purchased from Chongqing Chemical Co., Ltd., and purity is greater than 95%.This invention
In used organic matter title and structural formula be as follows:
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 record of the invention, technical staff can be made 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 modified lamination red OLED based on photovoltaic type CGU, including the glass substrate to play a supportive role, feature exists
In being provided with the ito anode layer (1) for injecting hole on the substrate, be provided on the ito anode layer (1) for infusing
Enter the hole injection layer (2) in hole, the hole transmission layer (3) for being used for transmission hole, institute are provided on the hole injection layer (2)
State the exciton barrier-layer (4) being provided on hole transmission layer (3) for being limited in exciton in luminescent layer, the exciton barrier-layer
(4) it is provided on for electroluminescent emitting red light unit (5), is provided on the emitting red light unit (5) for electronics
The electron transfer layer (6) of transmission is provided with for generating electrons and holes on the electron transfer layer (6), and is injected separately into two
The charge of the neighbouring luminescence unit on side generates unit CGU (7), is also repeated on the CGU (7) and is provided with hole transmission layer
(3), helpful electronics is arranged on the electron transfer layer (6) in exciton barrier-layer (4), luminescence unit (5), electron transfer layer (6)
The electron injecting layer (8) of luminescence unit (5) is injected, the Al cathode for electron injection is provided on the electron injecting layer (8)
(9), Al cathode (9) is opaque, has the function of reflected light.
2. a kind of modified lamination red OLED based on photovoltaic type CGU according to claim 1, which is characterized in that institute
It states charge and generates unit CGU (7) using N-shaped organic semiconducting materials C60As electron acceptor material, p-type is organic partly to be led fullerene
Body material ZnPc Phthalocyanine Zinc is as donor material, and double-layer structure LiF lithium fluoride/Al aluminium is in C60Side is as electron injecting layer and electricity
Sub- extract layer；MoO3Molybdenum trioxide is in the side ZnPc as hole injection layer and hole extract layer；Double-layer structure LiF lithium fluoride/
Al aluminium) and single layer MoO3The charge that unit is generated for improving charge generates and separating capacity.
3. a kind of modified lamination red OLED based on photovoltaic type CGU according to claim 1, which is characterized in that institute
Stating luminescence unit (5) is two, and two luminescence units (5) are separated by charge generation layer (7), and the luminescence unit (5) includes master
Body material, guest materials, guest materials are entrained in material of main part with 10wt% (mass fraction), entire luminescence unit thickness 30
Nanometer.
4. a kind of modified lamination red OLED based on photovoltaic type CGU according to claim 3, which is characterized in that institute
The material of main part for stating luminescence unit (5) is phosphor material TCTA (4,4', 4 "-three -9- carbazyl triphenylamine), and guest materials is red
Color phosphor material Ir (piq)2Acac (three [1- phenyl isoquinolin quinoline-C2, N] iridium (III)).
5. a kind of modified lamination red OLED based on photovoltaic type CGU according to claim 2, which is characterized in that institute
Stating CGU (7) has photovoltaic property, C in visible light wave range60It is combined with both ZnPc, realization can not only be induced under extraneous bias
Separation of charge, while charge can be generated by illumination, realize that the charge of " electricity+light " generates mode, to improve CGU (7)
Charge generate ability.
6. a kind of preparation process based on one of claim 1-5 modified lamination red OLED, which is characterized in that including following
Technique:
The processing of step 1, ito glass substrate: toluene, acetone, dehydrated alcohol, deionized water (3 are successively pressed to ito glass substrate
It is secondary) sequence be cleaned by ultrasonic, every time cleaning 12 minutes；By cleaned glass substrate with being dried with nitrogen, it is placed in 120 DEG C of bakings
Baking 20 minutes in oven, the glass substrate of drying is carried out oxygen plasma treatment 20 minutes；
The preparation of step 2, hole injection layer: after the completion of ito glass substrate processing, by ITO substrate be put into vacuum evaporation it is intracavitary into
The preparation of each functional layer of row, the control of NPB evaporation rate is per second at 1 angstrom, and the duration is about 400 seconds；
The preparation of step 3, hole transmission layer and electronic barrier layer: being heated to evaporating temperature for hole-injecting material NPB, vapor deposition
Rate control is per second at 1 angstrom, and evaporation time is about 400 seconds；The control of electron-blocking materials TCTA evaporation rate is per second at 0.2 angstrom,
Duration is about 250 seconds；
The preparation of step 4, luminescence unit: material of main part and guest materials, material of main part need to be opened simultaneously when vapor deposition luminescent layer
TCTA evaporation rate controls, guest materials Ir (piq) per second at 1.8 angstroms2The evaporation rate control of acac is per second at 0.2 angstrom, holds
The continuous time is about 150 seconds；
The preparation of step 5, electron transfer layer: the control of electron transport material TPBi evaporation rate is per second at 1 angstrom, and evaporation time is about
400 seconds；
The preparation of step 6, CGU: CGU is mainly C60The interface /ZnPc generates charge, LiF/Al and MoO3Positioned at C60The two sides /ZnPc,
Purpose is that the charge generated is respectively detached effectively in real time and injected in corresponding luminescent layer；
The preparation of step 7, LiF/Al: the evaporation rate control of electron injecting layer LiF is per second at 0.1 angstrom, and evaporation time is about 50
Second；The evaporation rate of Al cathode is about 3 angstroms per second, and the duration is about 400 seconds.
7. the preparation process of modified lamination red OLED according to claim 6, which is characterized in that the ito glass
After Substrate treatment is complete, it is immediately placed in vacuum evaporation cavity；Using vacuum thermal evaporation method, in high vacuum conditions (~3.2 ×
10-5Pa device) is prepared, wherein vapor deposition MoO3(2) when, evaporation rate control is per second at 0.2 angstrom；TCTA and Ir in luminescence unit
(piq)2Acac is deposited forms luminescence unit simultaneously, and TCTA rate control is per second at 1.8 angstroms.
8. the preparation process of modified lamination red OLED according to claim 6, which is characterized in that the step 6
In the preparation process of CGU, LiF/Al/C60/ZnPc/MoO3Evaporation rate respectively control it is per second at 0.2 angstrom.
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| WO2024082939A1 (en) * | 2022-10-17 | 2024-04-25 | 京东方科技集团股份有限公司 | Light-emitting device, display substrate and display apparatus |
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