CN107464884B - A kind of laminated organic electroluminescent device - Google Patents

A kind of laminated organic electroluminescent device Download PDF

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CN107464884B
CN107464884B CN201610391496.9A CN201610391496A CN107464884B CN 107464884 B CN107464884 B CN 107464884B CN 201610391496 A CN201610391496 A CN 201610391496A CN 107464884 B CN107464884 B CN 107464884B
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organic electroluminescent
transport material
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CN107464884A (en
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段炼
宾正杨
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Tsinghua University
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14Carrier transporting layers
    • H10K50/16Electron transporting layers
    • H10K50/165Electron transporting layers comprising dopants
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14Carrier transporting layers
    • H10K50/15Hole transporting layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14Carrier transporting layers
    • H10K50/16Electron transporting layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30Coordination compounds

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Abstract

The present invention relates to a kind of laminated organic electroluminescent devices, including substrate, and sequentially form luminescent device on the substrate, the luminescent device includes first electrode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electronics generating layer, hole injection layer, hole transmission layer, luminescent layer and electron transfer layer the second electrode lay, and the electronics generating layer includes the electron transport material with coordination ability and the inertia transition metal being entrained in the electron transport material;Electron transport material and inert metal ion with coordination ability are capable of forming complex, reduce the work function of inert metal, achieve the similar n-type doping effect in active metal, improve free carrier concentration, the lumo energy of electron transport material is reduced, the electronics generating layer as laminated device promotes the generation of electronics and enhances the separation of electronics, so as to significantly reduce the driving voltage of device, device efficiency is improved.

Description

A kind of laminated organic electroluminescent device
Technical field
The present invention relates to laminated organic electroluminescent device technical field, especially a kind of electron-transport for having coordination ability Doping inert metal realizes the laminated organic electroluminescent device of n-type doping effect in layer.
Background technique
Lamination OLED structure includes multiple luminescence units, and is folded different luminescence units by charge generating layers It adds and sets, charge generating layers are by electronics or hole transport to adjacent luminescence unit.This structure can significantly improve device Performance, be effectively reduced electric current Quenching generation, improve the working time of device.
In laminated device, good separation of charge effect is realized, usually using n-type dopant, with electron-transport material Expect codope, improves free carrier concentration, promote the separation of electronics.The n-type dopant that tradition uses be active alkali metal and Its compound, active alkali metal is unstable in air, is oxidized easily.Pass through heat point in a vacuum using alkali metal compound Solution, the method in situ for generating active alkali metal and realizing n-type doping, although avoiding directly in air using active alkali gold Belong to, enhances its aerial stability, however this method meeting for passing through the presoma decomposition active n-type dopant of generation in situ Lead to serious phenomenon of deflation, influences the vapor deposition atmosphere of chamber, in the industrial production, it is difficult to be applied.In addition, inert metal Since its work function is bigger, energy gap is larger between electron transport material, is not to realize good electric charge transfer, therefore can not use Make n-type dopant.
Summary of the invention
For this purpose, being passed the present invention provides a kind of laminated organic electroluminescent device using in the electronics with coordination ability Inert metal is adulterated in defeated material, complexation reaction is occurred by electron transport material and inert metal cation, promotes inertia gold The process that category loses electronics makes inert metal also be able to achieve the n similar with active metal to reduce the work function of inert metal Type adulterates effect, on the one hand realizes that efficiently electronics tells on, and on the other hand reduces potential barrier, enhances the separation of electronics, thus It significantly reduces device drive voltage, improve device efficiency.
In order to solve the above technical problems, the present invention adopts the following technical scheme:
A kind of laminated organic electroluminescent device, including substrate, and stack the first electrode layer of setting, the n lists that shine Member, n-1 electronics generating layer and the second electrode lay, the luminescence unit and electronics generating layer are arranged alternately, the luminescence unit The first organic function layer, luminescent layer and electron transfer layer including stacking setting, the electron transfer layer and/or electronics generating layer It is to be made of the electron transport material with coordination ability and the inertia transition metal being entrained in the electron transport material;
The n is the integer more than or equal to 2;
The electron transport material has the adjacent heterocyclic containing N, O or S, can form preferable coordination structure, molecular formula As shown in formula (1) to formula (4), formula (6) to formula (12):
Wherein R1To R8It is identical or different, it is selected from alkyl (CnHm), conjugation aromatic group, be conjugated heterocycle, methoxyl group (OCH3)、 Amino and alkyl-substituted amino (NRxH2-x), cyano (CN), halogen family base (X), aldehyde radical and ketone group (CHO, COR2), ester group (COOR) and levulinic ketone group (COCH2COR)。
The doping ratio of the inert metal is 1vol%-99vol%, preferably 5vol%-30vol%.
The inert metal is metal stable in the air and with preferable coordination ability, specially titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), lead (Pb), silver-colored (Ag), cadmium (Cd), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), gold (Au), one of platinum (Pt), mercury (Hg) or in which several mixtures.
The inert metal is the stronger metallic atom of coordination ability, the preferably described stronger metallic atom of coordination ability For cobalt (Co), nickel (Ni), copper (Cu), ruthenium (Ru), silver-colored (Ag), iridium (Ir), golden (Au) or platinum (Pt).
The conjugation aromatic group is phenyl (Ph), naphthalene or anthryl;The conjugation heterocycle is pyridyl group (Py) or quinoline Quinoline base.
The electron transport material with coordination property is formula (2-1) to formula (4-18), formula (6-1) to formula (10-5) institute The structural formula shown:
First organic function layer includes hole injection layer and/or hole transmission layer.
The above technical solution of the present invention has the following advantages over the prior art:
Electronics generating layer of the invention and electron transfer layer are that inert metal can be promoted to realize n-type doping based on coordination Effect is specially passed through using inert metal M with electron transport material ETM (such as Bphen) codope of coordination property ETM can be with Mn+Coordination, which occurs, promotes inert metal M to lose electronics, reduces its work function, so that inert metal is realized and lives The similar n-type doping effect of alkali metal is sprinkled, the free carrier number of electron transport material is improved, reduces electronics generating layer Lumo energy improves transmission and the separating effect of electronics.By inert metal and with the ETM codope of coordination ability, so that lazy Property metal be also able to achieve the similar n-type dopant in active metal, be a kind of new n-type doping thinking, prepare it is cheap, stablize and Efficient OLED device.Simultaneously as there is very strong complexing, therefore big between inert metal ion and electron transport material The migration characteristic for reducing metal ion greatly, improves the efficiency and stability of device.
It generates the very strong inert metal complex of reproducibility in situ in electronics generating layer, improves the number of free electron, The lumo energy of electron transport material is reduced to realize efficient electronics generation and separating effect.Even if larger using work function Inert metal (such as Ag, Au), the n-type doping effect similar with active metal still may be implemented, prepare low driving electricity The laminated device of pressure and high-luminous-efficiency.Therefore preparation cost and behaviour can be reduced using stability in the air of inert metal Make complexity, is more able to achieve the n-type doping performance similar with active metal.
Applicant tests discovery: inert metal M and ETM codope being formed x%M:ETM composite material and is being formed efficiently While n-type doping effect, the stability of ETM is also greatly improved.
The material that the present invention uses is stable in the air, stores and easy to use, can recycle, be conducive to industrial life It produces;There is no phenomenon of deflation, and vapor deposition atmosphere is relatively stable, can be produced in batches;Inert metal ion and electron-transport material There is very strong complexing between material, reduce the migration characteristic of metal ion, improve the efficiency and stability of device;Inertia gold After belonging to doping electron transport material, the lumo energy of electron transport material is reduced, can preferably be matched with cathode, reduces electronics Injection barrier improves the injection efficiency of electronics;Inert metal is more, can choose the lower inert metal of some vapor deposition temperature, Selection face is than wide;Electron transport material is organic material, and thermal stability is poor, adulterates inorganic inert metal and forms complex Afterwards, its thermal stability is significantly improved.
Detailed description of the invention
In order that the present invention can be more clearly and readily understood, it below according to specific implementation case of the invention and ties Attached drawing is closed, the present invention is described in further detail, wherein
Fig. 1 is the structural schematic diagram of laminated organic electroluminescent device of the invention;
Fig. 2 is the current density voltage curve figure of the device 1-7 of embodiment 1;
Fig. 3 is current density-brightness curve figure of the device 1-7 of embodiment 1;
Fig. 4 is power efficiency-brightness curve figure of the device 1-7 of embodiment 1;
Fig. 5 is the electron transfer layer mass spectrogram of the invention doped with many types of metal.
1- substrate, 2- first electrode layer, 3- hole injection layer, 4- hole transmission layer, 5- luminescent layer, 6- electron transfer layer, 7- electronics generating layer, 8- the second electrode lay.
Specific embodiment
The present invention can be embodied in many different forms, and should not be construed as limited to embodiment set forth herein. On the contrary, providing these embodiments, so that the disclosure will be thorough and complete, and design of the invention will be fully conveyed to Those skilled in the art, the present invention will only be defined by the appended claims.In the accompanying drawings, for clarity, the area Ceng He can be exaggerated The size and relative size in domain.It should be understood that when element such as layer, region or substrate are referred to as " being formed in " or " setting " another element "upper" when, which can be arranged directly on another element, or there may also be intermediary elements. On the contrary, intermediary element is not present when element is referred to as on " being formed directly into " or " being set up directly on " another element.
A kind of laminated organic electroluminescent device of the invention, including substrate, and stack the first electrode layer of setting, n A luminescence unit, n-1 electronics generating layer and the second electrode lay, the luminescence unit and electronics generating layer are arranged alternately, described Luminescence unit includes the first organic function layer, luminescent layer and the electron transfer layer for stacking setting, the electron transfer layer and/or electricity Sub- generating layer is by the electron transport material with coordination ability and the inertia transition gold being entrained in the electron transport material Belong to and constituting;The n is the integer more than or equal to 2.
As shown in Figure 1, laminated organic electroluminescent device of the invention includes substrate 1, and it is sequentially formed at the base Luminescent device on plate 1, the luminescent device include first electrode layer 2 (anode), 2 luminescence units, an electronics generating layer 7 Be electronics generating layer 7 between two luminescence units with the second electrode lay 8, each luminescence unit include hole injection layer 3, Hole transmission layer 4, luminescent layer 5 and electron transfer layer 6 are followed successively by first electrode layer 2 (anode), hole injection layer from substrate 1 3, hole transmission layer 4, luminescent layer 5 and electron transfer layer 6, electronics generating layer 7, hole injection layer 3, hole transmission layer 4, luminescent layer 5 and electron transfer layer 6 and the second electrode lay 8;
Similarly, if the luminescent layer of laminated device of the present invention is 3,2 electronics generating layers 7, arrangement mode are needed To be followed successively by first electrode layer 2 (anode), hole injection layer 3, hole transmission layer 4, luminescent layer 5 and electron-transport from substrate 1 Layer 6, electronics generating layer 7, hole injection layer 3, hole transmission layer 4, luminescent layer 5 and electron transfer layer 6, electronics generating layer 7, hole Implanted layer 3, hole transmission layer 4, luminescent layer 5 and electron transfer layer 6 and the second electrode lay 8, when n is 4 and integer greater than 4, The arrangement and so on of each layer.
The electron transfer layer 6 and/or electronics generating layer 7 include electron transport material and are entrained in the electron-transport material Inert metal in material;The electron transport material is the electron transport material with coordination property.
The doping ratio of the inert metal is 1vol%-99vol%, preferably 5vol%-30vol%.
The inert metal is metal stable in the air and with stronger coordination ability, specially titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), lead (Pb), silver-colored (Ag), cadmium (Cd), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), gold (Au), one of platinum (Pt) or in which several mixtures.
Preferably, the inert metal be cobalt (Co), nickel (Ni), copper (Cu), ruthenium (Ru), silver-colored (Ag), iridium (Ir), golden (Au) Or platinum (Pt).
The electron transport material has the adjacent heterocyclic containing N, O or S, can form preferable coordination structure, molecular formula As shown in formula (1) to formula (4), formula (6) to formula (12):
Wherein R1To R8It is identical or different, it may be selected from but not limited to alkyl (CnHm), conjugation aromatic group, be conjugated heterocycle, first Oxygroup (OCH3), amino and alkyl-substituted amino (NRxH2-x), cyano (CN), halogen family base (X), aldehyde radical and ketone group (CHO, COR2), ester group (COOR) and levulinic ketone group (COCH2COR)。
The conjugation aromatic group is phenyl (Ph), naphthalene or anthryl;The conjugation heterocycle is pyridyl group (Py) or quinoline Quinoline base.
The electron transport material with coordination property is formula (2-1) to formula (4-18), formula (6-1) to formula (10-5) institute The structural formula shown:
The preparation process of laminated organic electroluminescent device of the invention is wherein golden in electronics generating layer 7 compared with technology The evaporation rate of category should be relatively slow, is 0.1 angstroms per second, under this rate, the material of main part with coordination property of electronics generating layer with It is contacted between dopant material inert metal more sufficiently, inert metal M disperses more uniform in material of main part ETM, is conducive to The two is compound.
Embodiment 1
The structure of device:
ITO/HATCN/NPB/Alq3/Bphen (20nm)/x%Ag:Bphen (10nm)/HATCN/NPB/Alq3/ Bphen/Mg:Ag/Ag;
First electrode layer 2 (ITO, anode), hole injection layer 3 (HATCN), hole transmission layer 4 (NPB), luminescent layer 5 (Alq3), electron transfer layer 6 (Bphen), electronics generating layer 7 (x%Ag:Bphen), hole injection layer 3 (HATCN), hole pass Defeated layer 4 (NPB), 5 (Alq of luminescent layer3), electron transfer layer 6 (Bphen), the second electrode lay 8 (Mg:Ag/Ag)
The material of main part of electronics generating layer 7 in the present embodiment is Bphen, and the inert metal of doping is Ag, as shown in Figure 2 For the voltage-brightness curve graph of device 1 to device 7, wherein device 1 is the corresponding curve of single, and device 2 is corresponding for 1nm Mg Curve, device 3 be the corresponding curve of 1nm Ag, device 4 be the corresponding curve of 10%-20nm, device 5 be 30%-10nm pairs The curve answered, device 6 are the corresponding curve of 30%-5nm, and device 7 is the corresponding curve of 20%-10nm.Wherein:
Device 1 is single layer device, is comparative device;
Device 2: electronics generating layer is the magnesium that Bphen is followed by 1nm thickness, is comparative device;
Device 3: electronics generating layer is the silver that Bphen is followed by 1nm thickness, is comparative device;
The electronics generating layer of device 4 uses Bphen and Ag codope, and doping ratio is 10vol% (i.e. evaporation thickness 100 10 angstroms of Ag of evaporation thickness simultaneously when angstrom Bphen), doped layer is with a thickness of 20nm.
The electronics generating layer of device 5 uses Bphen and Ag codope, and doping ratio is 30vol% (i.e. evaporation thickness 100 30 angstroms of Ag of evaporation thickness simultaneously when angstrom Bphen), doped layer is with a thickness of 10nm.
The electronics generating layer of device 6 uses Bphen and Ag codope, and doping ratio is 30vol% (i.e. evaporation thickness 100 30 angstroms of Ag of evaporation thickness simultaneously when angstrom Bphen), doped layer is with a thickness of 5nm.
The electronics generating layer of device 7 is using Bphen and Ag codope, and doping ratio is 20vol% (i.e. evaporation thickness When 100 angstroms of Bphen simultaneously 20 angstroms of Ag of evaporation thickness), doped layer is with a thickness of 10nm.
Efficient electronics may be implemented as electronics generating layer in inert metal Ag and Bphen codope as seen from Figure 2 It tells on.Wherein shown in Bphen such as formula (1-1):
Fig. 5 explanation tests the molecular composition in doping film by Mardi-Tof, it can be found that the ontology of Bphen+H The single coordination structure or Ag and two Bphen that peak, an Ag and unimolecule Bphen are formed form double coordination structures, such as Under:
Embodiment 2
Device 8 to device 33 structure with device 1, wherein the composition of electron transfer layer and electronics generating layer is as follows:
The electron transfer layer of the invention of table 1 and the composition for being electronically generated layer
Embodiment 3
Device 32 to device 35 structure with device 12, wherein electron transfer layer and the EMT being electronically generated in layer distinguish Using the compound of structure shown in formula (6-1), formula (6-2), formula (6-3), the metal M of doping is respectively ruthenium Ru, rhodium Rh, lead Pb, Doping ratio is respectively 20vol%, 30vol% and 40vol%.
Embodiment 4
Device 36 to device 38 structure with device 12, wherein electron transfer layer and the EMT being electronically generated in layer distinguish Using the compound of structure shown in formula (7-1), formula (7-2), formula (7-3), the metal M of doping is respectively silver Ag, cadmium Cd, tantalum Ta, Doping ratio is respectively 22vol%, 25vol% and 28vol%.
Embodiment 5
Device 39 to device 109 structure with device 12, wherein electron transfer layer and the EMT being electronically generated in layer distinguish Using the compound of structure shown in formula (8-1) to formula (8-71), the metal M that device 49 to device 60 adulterates is silver-colored Ag, doping Ratio is 22vol%;Device 61 is cadmium Cd to the metal M that device 80 adulterates, and doping ratio is 25vol%;Device 81 The metal M adulterated to device 100 is tantalum Ta, and doping ratio is 28vol%;The metal M that device 101 is adulterated to device 119 It is platinum Pt, doping ratio is 30vol%.
Note: EMT is electron transport material in upper table;
M represents inertia transition metal;
It mixes than vol%: referring to doping ratio of the inert metal in electron transport material, as 15vol% refers to inertia gold Belonging to doping ratio in electron transport material is 15vol%, i.e., doped with 15 angstroms of inertia in 100 angstroms of electron transport material Metal.
Obviously, above-mentioned case study on implementation is only intended to clearly illustrate example, and does not limit the embodiments. For those of ordinary skill in the art, other various forms of variations can also be made on the basis of the above description Or it changes.There is no necessity and possibility to exhaust all the enbodiments.And obvious variation extended from this Or it changes still within the protection scope of the invention.

Claims (10)

1. a kind of laminated organic electroluminescent device, including substrate, and stack the first electrode layer of setting, n luminescence unit, N-1 electronics generating layer and the second electrode lay, the luminescence unit and electronics generating layer are arranged alternately, and the luminescence unit includes Stack the first organic function layer, luminescent layer and the electron transfer layer of setting, which is characterized in that
The electron transfer layer and electronics generating layer are by the electron transport material with coordination ability and to be entrained in the electronics Inertia transition metal in transmission material constitutes or the electronics generating layer is by the electron transport material with coordination ability It is constituted with the inertia transition metal being entrained in the electron transport material;
The n is the integer more than or equal to 2;
The electron transport material has the adjacent heterocyclic containing N, O or S, can form preferable coordination structure, molecular formula such as formula (1) to formula (4), formula (6) to shown in formula (12):
Wherein R1To R8It is identical or different, it is selected from alkyl (CnHm), conjugation aromatic group, be conjugated heterocycle, methoxyl group (OCH3), amino And alkyl-substituted amino (NRxH2-x), cyano (CN), halogen family base (X), aldehyde radical and ketone group (CHO, COR2), ester group (COOR) and Levulinic ketone group (COCH2COR)。
2. laminated organic electroluminescent device according to claim 1, which is characterized in that the inertia transition metal is mixed Miscellaneous ratio is 1vol%-99vol%.
3. laminated organic electroluminescent device according to claim 2, which is characterized in that the inertia transition metal is mixed Miscellaneous ratio is 5vol%-30vol%.
4. laminated organic electroluminescent device according to claim 1-3, which is characterized in that the inertia transition Metal is stable in the air and has preferable coordination ability.
5. laminated organic electroluminescent device according to claim 4, which is characterized in that the inertia transition metal is titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), one of golden (Au), platinum (Pt), mercury (Hg) or in which several mixtures.
6. laminated organic electroluminescent device according to claim 5, which is characterized in that the inertia transition metal be with The stronger metallic atom of capability.
7. laminated organic electroluminescent device according to claim 6, which is characterized in that the stronger gold of coordination ability Category atom is cobalt (Co), nickel (Ni), copper (Cu), ruthenium (Ru), silver-colored (Ag), iridium (Ir), golden (Au) or platinum (Pt).
8. according to the described in any item laminated organic electroluminescent devices of claim 1-3, which is characterized in that the conjugation aromatic radical Group is phenyl (Ph), naphthalene or anthryl;The conjugation heterocycle is pyridyl group (Py) or quinolyl.
9. laminated organic electroluminescent device according to claim 8, which is characterized in that the electron transport material is formula Structural formula shown in (2-1) to formula (4-18), formula (6-1) to formula (10-5):
10. laminated organic electroluminescent device according to claim 1, which is characterized in that first organic functions Layer includes hole injection layer and/or hole transmission layer.
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