CN108346751B - Electroluminescent device and its luminescent layer and application - Google Patents
Electroluminescent device and its luminescent layer and application Download PDFInfo
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- CN108346751B CN108346751B CN201710719786.6A CN201710719786A CN108346751B CN 108346751 B CN108346751 B CN 108346751B CN 201710719786 A CN201710719786 A CN 201710719786A CN 108346751 B CN108346751 B CN 108346751B
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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
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/625—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing at least one aromatic ring having 7 or more carbon atoms, e.g. azulene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
Abstract
The present invention relates to a kind of electroluminescent device and its luminescent layer and applications.The luminescent layer includes at least one nanocrystalline semiconductor material, and at least one luminous organic material；The emission spectrum of the luminous organic material and the excitation spectrum of the nanocrystalline semiconductor material are least partially overlapped；The Decay of the excitation state of the luminous organic material is greater than 1 microsecond.Novelty of the invention will have long lifetime of excited state, specially excitation state Decay is more than the luminous organic material of 1 microsecond as material of main part, thus the energy of luminous organic material can effectively pass to nanocrystalline semiconductor material, to obtain the QLED device with superperformance, the efficiency of the electroluminescent device using nanocrystalline semiconductor material as luminescence activity ingredient can be increased substantially.
Description
Technical field
The present invention relates to light emitting device technologies fields, more particularly to a kind of electroluminescent device and its luminescent layer and answer
With.
Background technique
Nanocrystalline semiconductor material, it is also known as nanocrystalline, it is made of a limited number of atom, at least two dimensions
In nanometer scale, appearance like minimum a pointing object or club/thread, internal electron movement two-dimensional space all
It is restricted, quantum confined effect is particularly significant.Excitation of the nanocrystalline semiconductor material by light or electricity, can issue half-peak
Wide very narrow spectrum (usual half-peak breadth is less than 40nm), luminescent color is mainly determined by particle size, and shining has photochromic purity
The features such as high, luminous quantum efficiency height, performance are stablized.
Nanocrystalline semiconductor material is due to its luminous efficiency height, the advantages that luminescent color is controllable and excitation purity is high,
There is huge application potential in next-generation display technology.Mode of excitation usually has luminescence generated by light and electroluminescent two ways.
Luminescence generated by light mode is applied mainly using blue-ray LED as excitation light source in lighting area and LCD backlight module shown etc..
Electroluminescent device can be applied to illumination and display field, especially show that application prospect is more broad.
The electroluminescent device made using nanocrystalline semiconductor material as the emerging luminescent device of one kind, in recent years by
Extensive concern is arrived.Electroluminescent device generally include at least first electrode layer, the second electrode lay and first electrode layer with
Luminescent layer between the second electrode lay prepares luminescent layer due to the feature of quantum confined effect with nanocrystalline semiconductor material
Electroluminescent diode, (Q represents the meaning of quantum to also referred to as QLED, and specific luminescent material may include dotted, rodlike or line
The material of shape).
Compared with traditional Organic Light Emitting Diode (OLED), QLED has more excellent excitation purity, brightness and visual
The features such as angle.Nanocrystalline semiconductor material, which is dispersed in solvent, is configured to the printing materials such as ink, is suitable for solution legal system
It is standby, the methods of printing, bat printing, spin coating, blade coating manufacture light-emitting film can be used, realize the processing of large area solution.As used and spray
Similar drop on demand ink jet (the Drop on Demand) technique of ink printing (Inkjet Printing), can be accurately by required
Luminescent material is deposited on the position of setting by amount, and deposition forms accurate pixel thin film structure, and manufacture large scale colour QLED is shown
Screen.These features make the QLED using nanocrystalline semiconductor material as luminescent layer in fields such as solid-state lighting, FPD
It is with a wide range of applications, receives the extensive concern of academia and industrial circle.
Pass through continuing to optimize for improvement to nanocrystalline semiconductor material and QLED device architecture, existing QLED device
Performance be greatly improved, but requirement of its luminous efficiency apart from industrialization production has a certain gap.
Summary of the invention
It is necessary to provide a kind of luminescent layer of electroluminescent device, which uses nanocrystalline semiconductor material, and
Luminous efficiency is high, convenient for industrialization production application.
A kind of luminescent layer of electroluminescent device includes at least one nanocrystalline semiconductor material, and at least one
Luminous organic material；
The emission spectrum of the luminous organic material and the excitation spectrum of the nanocrystalline semiconductor material are at least partly
Overlapping；The Decay of the excitation state of the luminous organic material is greater than 1 microsecond.
The principle of the present invention and advantage are as follows:
The advantages of based on nanocrystalline semiconductor material, prepares luminescent layer to improve with nanocrystalline semiconductor material
The luminous efficiency of electroluminescent diode (QLED).The present invention largely research and analyse:
It first attempts to directly arrange in pairs or groups using the luminescent layer of HTL, ETL and QLED device of OLED, discovery effect is not
Ideal analyzes its reason and is that HOMO, LUMO of nanocrystalline semiconductor material are relatively deep, hole, electron injection luminescent layer
Efficiency variance is huge, thus electronic remote leads to the unstable of material and failure far more than hole.It follows that at present
QLED device lifetime is relatively low, chief reason may just in luminescent layer carrier concentration serious unbalance.Therefore
If suitable auxiliary material is introduced in luminescent layer to receive the injection in hole and electronics, it is likely that make the sky in luminescent layer
Cave, electron amount obtain good balance, but wherein, still have a critical issue to need to solve, i.e., how to draw energy from newly
The auxiliary material entered is effectively transferred to nanocrystalline semiconductor material.
Turn in addition, nanocrystalline semiconductor material has been successfully applied to colored filter (Color filter)/colour
Film (color conversion film) is changed, illustrates that the stability of nanocrystalline semiconductor material is fine, essence is nanocrystalline
Semiconductor material body is sufficiently stable for the energy of (singlet) exciton.Therefore, if electronics and hole can be allowed in energy donor
(energydonnor) it is compounded to form exciton on material, then the exciton energy on energy donor material is passed into nanocrystal half
Conductor material, nanocrystalline semiconductor material are just hopeful to obtain efficient stable as energy acceptor (energy acceptor)
QLED device.
Based on this, it is to improve that the energy donor material of nanocrystalline semiconductor material can effectively be transferred energy to by, which finding,
The key point of QLED luminous efficiency.Inventor with analysis, has found energy donor material to nanocrystal semiconductor after study
Material withResonance energy transfer (FRET) mode carries out effective energy transmitting and needs satisfaction following
Two key conditions:
(1) emission spectra of energy donor material has biggish overlapping with the excitation spectrum of nanocrystalline semiconductor material；
(2) Decay (decay lifetime) of the excitation state (excited state) of energy donor material, needs
It is significantly longer than the Decay of the excitation state of nanocrystalline semiconductor material.
Wherein, about first condition, since nanocrystalline semiconductor material generally has wider excitation spectrum, big multipotency
The emission spectra of amount donor material can have biggish overlapping with the excitation spectrum of nanocrystalline semiconductor material.
Second condition is the key that promote QLED device performance and significant challenge.Main body material used in previously reported
Material can not effectively utilize and shift mostly all energy in electroluminescent device, and device efficiency is bad.By inventor point
Analysis discovery reason is that the Decay of the excitation state at room temperature of the material of main part used in previously reported is only tens to several
Hundred ns ranks (such as the lifetime of excited state of PVK at room temperature is 35ns or so), are unable to satisfy and carry out the second of effective energy transfer
A condition.For the luminous organic material that nature and the mankind have been found that, lifetime of excited state is generally all shorter at room temperature,
In ns rank, therefore the material of main part that most organic materials have not been for nanocrystalline semiconductor material.
Based on aforementioned research, present invention novelty will have long lifetime of excited state, and specially excitation state Decay is super
The luminous organic material of 1 μ s (1 microsecond, i.e. 1000 nanoseconds) is crossed as material of main part, thus the energy of luminous organic material can
Nanocrystalline semiconductor material effectively is passed to, to obtain the QLED device with superperformance, can be increased substantially to receive
Efficiency of the rice crystal semiconductor material as the electroluminescent device of luminescence activity ingredient.
In the present invention, when the attenuation process of the excitation state of the luminous organic material exist simultaneously comparatively fast with slower mistake
Cheng Shi, the Decay of the excitation state of the luminous organic material are greater than 1 microsecond and refer to, be not less than wherein slower process has
The Decay of 1 μ s.Preferably, when slower process therein is the major part of attenuation process, slower process is accounted for entirely
50% or more of attenuation process specific gravity.
The Emission Spectrum Peals wavelength of the luminous organic material is less than the nanocrystal in one of the embodiments,
Semiconductor material.To be further ensured that the transmission of energy.
The Decay of the excitation state of the luminous organic material is the nanocrystal half in one of the embodiments,
5 times or more of the Decay of the excitation state of conductor material.More preferably, the Decay of the former excitation state is 10 times of the latter
More than.
In general, the Decay of the excitation state of nanocrystalline semiconductor material several nanoseconds to tens nanosecond rank.
The excitation state Decay of the nanocrystalline semiconductor material is in 1~100ns model in one of the embodiments,
It encloses.The excitation state Decay of the luminous organic material with long excitation state Decay is in the 1 μ s range of μ s~100.
In the present invention, when the excitation state of the luminous organic material, nanocrystalline semiconductor material has multiple decline
When subtracting the service life, the Decay of the excitation state of the luminous organic material is longer than the excitation state of the nanocrystalline semiconductor material
Decay refer to, the Decay nanocrystalline semiconductor material of the slow decay process of luminous organic material it is fast
The Decay of attenuation process is long.
The energy level difference between the singlet and triplet state of the luminous organic material is less than in one of the embodiments,
0.5eV.The highest occupied molecular orbital(HOMO) (referred to as HOMO) of molecule has less with lowest unocccupied molecular orbital (referred to as LUMO)
Molecular orbit overlapping.Above-mentioned molecular characterization can make the energy level difference between the singlet of luminous organic material and triplet state small
In 0.5eV, it might even be possible to reach 0~0.3eV, to pass through rate between obtaining higher inverse system and be conducive to triplet energy state
It is transferred to singlet.
Contain at least a kind of electron-donating group in the molecular structure of the luminous organic material in one of the embodiments,
Group, and/or at least a kind of electron-withdrawing group.
The electron-donating group in one of the embodiments, including containing substituent group or without the carbazoles of substituent group
Group, the aromatic amine group containing substituent group or without substituent group, the phenoxazine class base containing substituent group or without substituent group
Group, the phenothiazines group containing substituent group or without substituent group, containing substituent group or without the acridan of substituent group
Class group, the indolocarbazole class group containing substituent group or without substituent group, containing substituent group or without the indeno of substituent group
Carbazoles group；The substituent group of any of the above-described group can be cyclic or not cyclic；
The electron-withdrawing group, carbonyl class group including itrile group, containing substituent group or without substituent group contain substituent group
Or the benzophenone group without substituent group, the sulphonyl class group containing substituent group or without substituent group, containing substituent group or
Phosphine oxide base class group without substituent group, the triazines group containing substituent group or without substituent group containing substituent group or are free of
The pyridines group of substituent group, the miazines group containing substituent group or without substituent group contain substituent group or are free of substituent group
Pyrazine group, the furodiazole group containing substituent group or without substituent group, three containing substituent group or without substituent group
Azole group, the xanthones group containing substituent group or without substituent group, containing substituent group or without the imidazoles of substituent group
Group, the oxazole class group containing substituent group or without substituent group, contains the thiazoles group containing substituent group or without substituent group
Substituted base or 9H- thioxanthene-9-one 10,10- titanium dioxide species group without substituent group；The substituent group of any of the above-described group can
With cyclic or not cyclic.
Preferably, the electron-donating group optionally from: carbazoles group containing substituent group or without substituent group contains
Substituted base or aromatic amine group without substituent group；The electron-withdrawing group optionally from: itrile group, containing substituent group or is free of
The carbonyl class group of substituent group, the benzophenone group containing substituent group or without substituent group, containing substituent group or without taking
The sulphonyl class group of Dai Ji, the phosphine oxide base class group containing substituent group or without substituent group contain substituent group or are free of substituent group
Triazines group, the pyridines group containing substituent group or without substituent group.
In one of the embodiments, the electron-donating group and/or electron-withdrawing group be replaced in aromatic compound it
On.
The nanocrystalline semiconductor material is optionally from II-VI group nanocrystal semiconductor in one of the embodiments,
Material, iii-v nanocrystalline semiconductor material, group IV-VI nanocrystalline semiconductor material, with perovskite crystal type
One of nanocrystalline semiconductor material, the nanocrystalline semiconductor material being made of one or more single carbon group elements are more
Kind.
In one of the embodiments, the nanocrystalline semiconductor material optionally from CdSe, CdS of II-VI group,
ZnSe、ZnS、CdTe、ZnTe、CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS、
CdZnSeS,CdZnSeTe,CdZnSTe,CdSeSTe,ZnSeSTe,CdZnSeSTe；InP, InAs, InAsP of iii-v；
PbS, PbSe, PbTe, PbSeS, PbSeTe, PbSTe of group IV-VI；Organic metal halogen with perovskite crystal structure type
Compound semiconductor material ABX3, wherein A is organic group (including but not limited to CH3NH3, CH3CH2NH3, NH2CH=NH2), B is
Metallic element, X are halogen；One of carbon nano-crystal body, si-nanocrystals, nanometer silicon carbide crystal are a variety of.
The nanocrystalline semiconductor material is hud typed in one of the embodiments, including mononuclear structure and multicore
Structure specifically includes: the mononuclear structure of uniform unitary component (refer to and be made of element) a kind of, uniform binary composition (refer to by
Two kinds of elements composition) mononuclear structure, uniform multicomponent mixture (refer to and be made of three kinds or more element) mononuclear structure,
The mononuclear structure of the concentration of element gradual change of multicomponent mixture, the discrete core-shell structure of binary composition, multicomponent mixture discrete nucleocapsid knot
The gradual change core-shell structure of structure, multicomponent mixture.
The form group that the luminous organic material is blended with nanocrystalline semiconductor material in one of the embodiments,
At the luminescent layer, the mass ratio of the nanocrystalline semiconductor material and the luminous organic material is 1:99~99:1.It is excellent
Selection of land is 10:90~60:40.
The outside of the nanocrystalline semiconductor material may include organic ligand to be dissolved in one of the embodiments,
Low polar solvent, the organic ligand is including but not limited to sour ligand, mercaptan ligand, amine ligand, (oxygen) Phosphine ligands, phosphatide, soft
One of phosphatide, polyvinylpyridine etc. are a variety of.It is described acid ligand include ten acid, undecenoic acid, tetradecylic acid, oleic acid and firmly
One of resin acid is a variety of；The mercaptan ligand includes in eight alkyl hydrosulfides, lauryl mercaptan and Stearyl mercaptan
It is one or more；The amine ligand includes one of oleyl amine, octadecylamine and eight amine or a variety of；(oxygen) Phosphine ligands include three
Octyl phosphine, trioctylphosphine oxide (TOPO) it is one or more.
The outside of the nanocrystalline semiconductor material may include organic ligand to be dissolved in one of the embodiments,
Water or other highly polar solvents, the ligand is including but not limited to sulfydryl acids, sulfydryl alcohols.The sulfydryl acids ligand packet
It includes: thioacetic acid, 2 mercaptopropionic acid, 3- mercaptopropionic acid, 3- mercaptobenzoic acid, 4- mercaptobenzoic acid, 6- mercaptohexanoic acid, sulfydryl fourth
One of diacid, 11- Mercaptoundecanoic acid, 12- sulfydryl lauric acid/dodecanoic acid, 16- mercaptohexadecanoic acid are a variety of；The sulfydryl alcohols
Ligand includes: 2 mercapto ethanol, 1- thioglycerol, 2- sulfydryl -3- butanol, 4- sulfydryl-n-butyl alcohol, 6- sulfydryl -1- hexanol, 8- mercapto
One of base -1- octanol, 9- sulfydryl -1 nonyl alcohol, 11- sulfydryl -1- undecyl alcohol are a variety of.
In one of the embodiments, the luminescent layer with a thickness of 5~150nm.
Luminescent layer of the present invention includes one layer or at least two layers of light-emitting film layer for stacking gradually；Each light-emitting film layer
It can be made of homogenous material, can also be blended and be formed by multiple material.
The luminous organic material and nanocrystalline semiconductor material can be located on the same floor in light-emitting film layer, can also be with
In the light-emitting film layer of different layers.When the luminous organic material be located at from nanocrystalline semiconductor material it is different
When light-emitting film layer, light-emitting film layer where the luminous organic material and shining where nanocrystalline semiconductor material are thin
Vertical range between film layer is no more than 10nm.It is partly led so that excited energy is transferred to nanocrystal from luminous organic material
Body material.
The nanocrystalline semiconductor material of the present invention refers to that the size at least two dimensions is 1~30nm
The crystal semiconductor material of magnitude contains dotted according to size of the nanocrystalline semiconductor material in third dimension
Quanta point material (size is all nanoscale zero dimension material in three dimensions) and rodlike quantum bar material or line
The quantum wire material (in third dimension being micron order having a size of nanoscale in two dimensions) of shape.
The present invention also provides a kind of electroluminescent devices, have the luminescent layer.
Electroluminescent device of the present invention can form energy in luminescence process and turn by using the luminescent layer
It moves, in the energy transfer process, energy effectively can be transferred to nanocrystalline semiconductor material by luminous organic material.Into
One step, the long lifetime of excited state organic material with electron-withdrawing group and electron-donating group of introducing facilitates electronics and sky
All preferably injection luminescent layer forms exciton in cave, thus hole, electron amount in balance luminescent layer have electroluminescent device
There is the advantages of efficient stable.
The electronic light emitting devices include the first electrode layer stacked gradually, luminescent layer and in one of the embodiments,
Two electrode layers.
Functional layer is additionally provided between the first electrode layer and the second electrode lay in one of the embodiments,；The function
Ergosphere is hole injection layer, hole transmission layer, electronic barrier layer, hole blocking layer, electron transfer layer, one in electron injecting layer
Kind is a variety of, and the positional relationship between the luminescent layer can be according to conventional arrangement.
The present invention also provides application of the electroluminescent device in display or lighting device.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of electroluminescent device described in one embodiment of the invention.
Specific embodiment
Electroluminescent device and its luminescent layer of the invention and application are made below in conjunction with specific embodiment further detailed
Explanation.
In the embodiment of the present invention, the Decay of the excitation state of the luminous organic material, under nitrogen atmosphere at room temperature
The Decay of the excitation state (excited state) of measurement.
In the embodiment of the present invention, the structure of electroluminescent device is as shown in Figure 1, include stacking gradually on substrate 100
First electrode layer 101, hole injection layer 104, hole transmission layer or electronic barrier layer 105, luminescent layer 103, electron transfer layer
Or hole blocking layer 106, electron injecting layer 107, the second electrode lay 102.
Used material information is as follows:
PEDOT:PSS is Poly (3,4-ethylenedioxythiophene)-poly (styrene-sulfonate)；
TFB is Poly [(9,9-dioctylfluorenyl-2,7-diyl)-co- (4,4'- (N- (4-sec-
butylphenyl)-diphenylamine)]；
CdSe/ZnS quantum dot refers to the dotted nanocrystalline semiconductor material using CdSe as core, ZnS for shell；
CdSe/ZnS quantum rod refers to the rod-like nano crystal semiconductor material using CdSe as core, ZnS for shell；
The structure of the other small organic molecules such as following figure:
Embodiment 1:
A kind of electroluminescent device of the present embodiment, structure are as follows:
ITO/PEDOT:PSS/TFB/DCzIPN:(CdSe/ZnS quantum dot)/PO-T2T/LiF/Al。
Wherein, for luminescent layer using organic material DCzIPN as energy donor material, the Decay of excitation state is 1.2 micro-
Second, Emission Spectrum Peals wavelength 447nm, the energy level difference 0.05eV between singlet and triplet state；
With CdSe/ZnS quantum dot (CdSe/ZnS quantum dot) for nanocrystalline semiconductor material, excitation state
Decay is 0.05 microsecond, Emission Spectrum Peals wavelength 626nm.
The preparation step of above-mentioned electroluminescent device is as follows:
(1) processing substrate: with glass cleaner, the successive cleaning base plate surface of pure water, to be dried at 150 DEG C after being dried with nitrogen
It is 1 hour roasting, with UV processing 5 minutes under atmospheric environment, obtain clean substrate and the surface ITO.
(2) prepared by hole injection layer: with the revolving speed spin coating PEDOT:PSS ink of 3000rpm/min, spin coating 30 seconds, then
In 110 DEG C of bakings, 15 minutes acquisition hole injection layer films.
(3) prepared by hole transmission layer: with the revolving speed spin coating TFB ink (5mg/ml) of 1500rpm/min, spin coating 30 seconds, so
Afterwards in 150 DEG C of bakings, 30 minutes acquisition hole transport layer films.
(4) prepared by luminescent layer: the mixture of DCzIPN (8mg/ml) and CdSe/ZnS quantum dot (12mg/ml) are dissolved in chlorine
Benzene forms luminescent layer ink, with the revolving speed spin coating luminescent layer ink of 1000rpm, spin coating 30 seconds, then toasts 20 minutes at 120 DEG C
Obtain the layer film that shines.
(5) electron transfer layer, electron injecting layer, cathode preparation: be successively deposited in a manner of vapor deposition PO-T2T (40nm),
LiF (1nm) and Al (150nm), sequentially forms electron transfer layer, electron injecting layer and cathode.
Embodiment 2:
A kind of electroluminescent device of the present embodiment, structure are as follows:
ITO/PEDOT:PSS/TFB/DCzTrz:(InP/ZnSeS quantum dot)/PO-T2T/LiF/Al。
Wherein, for luminescent layer using organic material DCzTrz as energy donor material, the Decay of excitation state is 3.1 micro-
Second, Emission Spectrum Peals wavelength 440nm, the energy level difference 0.25eV between singlet and triplet state；
With InP/ZnSeS quantum dot (InP/ZnSeS quantum dot) for nanocrystalline semiconductor material, excitation state
Decay be 0.03 microsecond, Emission Spectrum Peals wavelength 520nm.
The preparation similar embodiment 1 of above-mentioned electroluminescent device.
Embodiment 3:
A kind of electroluminescent device of the present embodiment, structure are as follows:
ITO/PEDOT:PSS/TFB/CPC:(CdSe/ZnS quantum dot)/PO-T2T/LiF/Al。
Wherein, for luminescent layer using organic material CPC as energy donor material, the Decay of excitation state is 47 microseconds,
Emission Spectrum Peals wavelength 490nm, the energy level difference 0.04eV between singlet and triplet state；
With (CdSe/ZnS quantum dot) for nanocrystalline semiconductor material, the Decay of excitation state is 0.05
Microsecond, Emission Spectrum Peals wavelength 626nm.
The preparation similar embodiment 1 of above-mentioned electroluminescent device.
Embodiment 4:
A kind of electroluminescent device of the present embodiment, structure are as follows:
ITO/PEDOT:PSS/TFB/PIC-TRZ:(CdSe/ZnS quantum dot)/PO-T2T/LiF/Al。
Wherein, for luminescent layer using organic material PIC-TRZ as energy donor material, the Decay of excitation state is 120
Microsecond, Emission Spectrum Peals wavelength 500nm, the energy level difference 0.11eV between singlet and triplet state；
With (CdSe/ZnS quantum dot) for nanocrystalline semiconductor material, the Decay of excitation state is 0.05
Microsecond, Emission Spectrum Peals wavelength 626nm.
The preparation similar embodiment 1 of above-mentioned electroluminescent device.
Embodiment 5:
A kind of electroluminescent device of the present embodiment, structure are as follows:
ITO/PEDOT:PSS/TFB/CZ-PS:(CsPbBr3quantum dot)/PO-T2T/LiF/Al。
Wherein, for luminescent layer using organic material CZ-PS as energy donor material, the Decay of excitation state is 540 micro-
Second, Emission Spectrum Peals wavelength 423nm, the energy level difference 0.32eV between singlet and triplet state；
With (CsPbBr3quantum dot) for nanocrystalline semiconductor material, the Decay of excitation state is 0.03 micro-
Second, Emission Spectrum Peals wavelength 510nm.
The preparation similar embodiment 1 of above-mentioned electroluminescent device.
Embodiment 6:
A kind of electroluminescent device of the present embodiment, structure are as follows:
ITO/PEDOT:PSS/TFB/CZ-PS:(CdSe/ZnS quantum rod)/PO-T2T/LiF/Al。
Wherein, for luminescent layer using organic material CZ-PS as energy donor material, the Decay of excitation state is 540 micro-
Second, Emission Spectrum Peals wavelength 423nm, the energy level difference 0.32eV between singlet and triplet state；
With CdSe/ZnS quantum rod (CdSe/ZnS quantum rod) for nanocrystalline semiconductor material, excitation state
Decay is 0.03 microsecond, Emission Spectrum Peals wavelength 625nm.
The preparation similar embodiment 1 of above-mentioned electroluminescent device.
Embodiment 7:
A kind of electroluminescent device of the present embodiment, structure are as follows:
ITO/PEDOT:PSS/TFB/CZ-PS:(InP/ZnSeS quantum dot/PO-T2T/LiF/Al。
Wherein, for luminescent layer using organic material CZ-PS as energy donor material, the Decay of excitation state is 540 micro-
Second, Emission Spectrum Peals wavelength 423nm, the energy level difference 0.32eV between singlet and triplet state；
With InP/ZnSeS quantum dot (InP/ZnSeS quantum dot) for nanocrystalline semiconductor material, excitation state
Decay be 0.03 microsecond, Emission Spectrum Peals wavelength 520nm.
The preparation similar embodiment 1 of above-mentioned electroluminescent device.
Comparative example 1:
A kind of electroluminescent device of this comparative example, raw material and preparation method similar embodiment 1, difference is: luminescent layer
Using common OLED material of main part PVK (8mg/ml) as energy donor material, instead of DCzIPN, the decaying of PVK material excitation state
Service life is 0.035 microsecond, Emission Spectrum Peals wavelength 380nm；EL device structure are as follows:
ITO/PEDOT:PSS/TFB/PVK:(CdSe/ZnS quantum dot)/PO-T2T/LiF/Al。
Comparative example 2:
A kind of electroluminescent device of this comparative example, raw material and preparation method similar embodiment 6, difference is: luminescent layer
CZ-PS is replaced using organic delayed fluorescence material PXZ-TRZ as energy donor material, the excitation state of PXZ-TRZ material decays the longevity
Life is 0.7 microsecond, Emission Spectrum Peals wavelength 545nm, the energy level difference 0.07eV between singlet and triplet state；Electroluminescent cell
Part structure are as follows:
ITO/PEDOT:PSS/TFB/PXZ-TRZ:(CdSe/ZnS quantum rod)/PO-T2T/LiF/Al。
Comparative example 3
A kind of electroluminescent device of this comparative example, raw material and preparation method similar embodiment 7, difference is: using hair
Photosphere replaces CZ-PS using organic delayed fluorescence material DCBPy as energy donor material, and the excitation state of DCBPy material decays the longevity
Life is 0.6 microsecond, Emission Spectrum Peals wavelength 490nm, the energy level difference 0.07eV between singlet and triplet state；Electroluminescent cell
Its structure of part are as follows:
ITO/PEDOT:PSS/TFB/DCBPy:(InP/ZnSeS quantum dot)/PO-T2T/LiF/Al。
Measure of merit is carried out to the electroluminescent device of embodiment and comparative example, the results are shown in Table 1:
Table 1
Energy donor material PVK in comparative example 1, the energy donor material PXZ-TRZ in comparative example 2 and comparative example 3
In energy donor material DCBPy be that lifetime of excited state less than 1 μ s is had, when it by a kind of TADF material of wide coverage
When mixing the luminescent layer as electroluminescent device with quantum dot, the promotion of device efficiency is not obvious.
Compared with comparative example, the energy donor material that embodiment has used lifetime of excited state to be greater than 1 μ s, device obtained
Efficiency is compared comparative example and is obviously improved.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of luminescent layer of electroluminescent device, which is characterized in that comprising at least one nanocrystalline semiconductor material, and
A kind of organic luminescent compounds；
The emission spectrum of the organic luminescent compounds and the excitation spectrum of the nanocrystalline semiconductor material are at least partly heavy
It is folded；The Decay of the excitation state of the organic luminescent compounds is greater than 1 microsecond, and the excitation state of the organic luminescent compounds
Decay be 103 times or more of Decay of excitation state of the nanocrystalline semiconductor material.
2. the luminescent layer of electroluminescent device according to claim 1, which is characterized in that the organic luminescent compounds
The Decay of excitation state is 103~18000 times of the Decay of the excitation state of the nanocrystalline semiconductor material.
3. the luminescent layer of electroluminescent device according to claim 1, which is characterized in that the organic luminescent compounds
Emission Spectrum Peals wavelength is less than the nanocrystalline semiconductor material.
4. the luminescent layer of electroluminescent device according to claim 1, which is characterized in that the organic luminescent compounds
Energy level difference between singlet and triplet state is less than 0.5eV.
5. the luminescent layer of electroluminescent device according to claim 4, which is characterized in that the organic luminescent compounds
Contain at least a kind of electron-donating group and/or at least a kind of electron-withdrawing group in molecular structure.
6. the luminescent layer of electroluminescent device according to claim 1-5, which is characterized in that the nanocrystal
Semiconductor material is optionally received from II-VI group nanocrystalline semiconductor material, iii-v nanocrystalline semiconductor material, group IV-VI
Rice crystal semiconductor material, the nanocrystalline semiconductor material with perovskite crystal type, by one or more single carbon group elements
One of nanocrystalline semiconductor material of composition is a variety of.
7. the luminescent layer of electroluminescent device according to claim 6, which is characterized in that the nanocrystal semiconductor material
Material optionally from CdSe, CdS of II-VI group, ZnSe, ZnS, CdTe, ZnTe, CdZnS, CdZnSe, CdZnTe, ZnSeS,
ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS、CdZnSeS、CdZnSeTe、CdZnSTe、CdSeSTe、ZnSeSTe、
CdZnSeSTe；InP, InAs, InAsP of iii-v；PbS, PbSe, PbTe, PbSeS, PbSeTe, PbSTe of group IV-VI；
Organic metal halide semiconductor material ABX with perovskite crystal structure type3, wherein A is organic group, and B is metal
Element, X are halogen；One of carbon nano-crystal body, si-nanocrystals, nanometer silicon carbide crystal are a variety of.
8. the luminescent layer of electroluminescent device according to claim 1-5, which is characterized in that the nanocrystal
The mass ratio of semiconductor material and the organic luminescent compounds is 1:99~99:1.
9. a kind of electroluminescent device, which is characterized in that have the described in any item luminescent layers of claim 1-8.
10. application of the electroluminescent device as claimed in claim 9 in display or lighting device.
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| CN117242157A (en) * | 2021-04-07 | 2023-12-15 | 浙江光昊光电科技有限公司 | Mixture and application thereof in photoelectric field |
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| WO2017037571A1 (en) * | 2015-09-04 | 2017-03-09 | Semiconductor Energy Laboratory Co., Ltd. | Compound, light-emitting element, display device, electronic device, and lighting device |
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