CN107221603A - A kind of efficient undoped white organic light emitting device and preparation method thereof - Google Patents
A kind of efficient undoped white organic light emitting device and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of efficient undoped white light organic electroluminescent device and preparation method thereof, device architecture includes substrate, anode layer, organic function layer and cathode layer, and organic function layer includes hole injection layer, hole transmission layer, luminescent layer and electron transfer layer；Luminescent layer is made up of one of following two modes：1. by the yellow fluorescence luminous material layer (thickness is 1 10nm) with hot activation delayed fluorescence characteristic close to hole transmission layer, and close to the conventional blue fluorescence luminescent material layer composition of electron transfer layer；2. by the conventional blue fluorescence luminescent material layer close to hole transmission layer, and close to yellow fluorescence luminous material layer (thickness is 1 10nm) composition with hot activation delayed fluorescence characteristic of electron transfer layer.The present invention only realizes white light parts using a kind of blue-fluorescence luminescent material and simple device architecture, while device efficiency and reduction efficiency roll-off can be improved, and reduction production cost.
Description
Technical field
The present invention relates to the organic photoelectric technical field in electronic component, and in particular to a kind of efficient undoped white light has
Organic electroluminescence devices and preparation method thereof.
Background technology
White light organic electroluminescent device (Organic light-emitting devices, OLEDs) is a kind of new
Display Technique, because it is in solid-state illumination, FPD has wide application prospect in terms of LCD backlight source, and
It disclosure satisfy that the whole world has obtained widely studied and exploitation to saving the energy, the requirement of low-carbon environment-friendly and green living instantly.
In OLED structure, one of them most important composition is luminescent material.First generation OLED luminescent materials are organic
Fluorescent material, can only be lighted using 25% singlet exciton, and 75% triplet excitons are inactivated with unirradiated form,
Therefore theoretical luminous efficiency is relatively low.Second generation OLED luminescent materials are metal complex phosphor material, by introducing such as iridium (Ir)
With the rare precious metals such as platinum (Pt) enhancing Quantum geometrical phase, realize singlet and triplet state be between alter jump, make use of 25%
Singlet exciton and 75% triplet excitons lighted, 100% exciton utilization rate can be realized in theory, and wide
It is general to use.But, also there is the bottleneck problem of blue phosphor materials short life at present, hinder its market development.Japan in 2012
Adachi of Kyushu University et al. reports a kind of hot activation delayed fluorescence (Thermally activated delayed
Fluorescence, TADF) material, the singlet of this material molecule and the energy level difference very little of triplet state, cause at normal temperatures
Jumped with regard to that can occur triplet state to anti-channeling between the Department of Electronics of singlet, so that in theory 100% exciton utilization rate can be also reached, into
For more popular third generation OLED luminescent materials at present.Quenching effect easily occurs in the collected state for most of luminescent dyes
Should so that luminous reduction, it is therefore desirable to use physical doping method, host-guest system structure is formed, aggregation luminescence queenching is overcome
Problem.However, physical doping method also brings problems in this, such as (especially low energy is red for multiple luminescent materials
Light, orange light and Yellow light emitting material) low-doped ratio be difficult to accurate control, preparation technology is complicated, and device repeatability is low, production
Cost height etc..Therefore, scholars propose that undoped structure prepares OLED, to simplify device architecture and preparation technology.But
It is this undoped structure, is currently used primarily in the phosphorescent light-emitting materials containing heavy metal element.Although device architecture is simplified, and
And device performance can reach the high-performance of doping device, but content of beary metal is rare, expensive so that the life of OLED
Produce cost higher.Therefore, using the fluorescence luminescent material without heavy metal, by device structure design and optimization, to prepare letter
Single structure, high-performance, the white light OLED of low cost provide an effective solution.
Usually using two kinds of luminescent dyes of blue, yellow complementary colours principle, or the base of red, green, blue three in white light OLED device
Three kinds of luminescent dyes of chromogen reason.Contrast is understood, white light parts are prepared using complementary colours principle, is reduced and is used luminescent material number
Mesh, is conducive to simplifying device architecture.Because first generation fluorescence luminescent material internal quantum efficiency is relatively low, undoped white light is prepared with it
Device, device efficiency is very limited.Third generation TADF luminescent materials, most of is all to prepare high property using doped structure
Can OLED.In addition, the white light parts prepared based on whole TADF luminescent materials, with very serious efficiency roll-off, that is, are existed
Under high current, efficiency declines rapidly, because the triplet excitons of TADF luminescent materials are with caused by the longer life-span
Triplet state-triplet state and singlet-triplet excitons Quenching.Therefore, scholars propose that one kind combines first generation phosphor
Material and third generation TADF luminescent materials, the method for preparing white light OLED device.But, in order to avoid exciton formation is in poor efficiency
On first generation fluorescent material, the necessary condition that this solution needs reach is：1) control light-emitting zone is in TADF regions, this
Need to add in the middle of first generation fluorescent material and the third generation TADF luminescent materials interlayer interlayer [Adv.Mater.2015,
27,2019-2023], this introduces extra hetero-junctions；Or 2) by first generation fluorescent material with low-down doped in concentrations profiled
In third generation TADF luminescent material main bodys [Org.Electron.2015,23,138-143], this considerably increases prepare work
The difficulty and controllability of skill.Thus, it could be seen that being lighted with reference to the first generation fluorescent material of undoped and the third generation TADF of undoped
Material, material selection and device architecture by optimization are related to, and obtain high performance device, can simplify device architecture and prepare work
Skill, reduces efficiency roll-off, also helps reduction production cost, meanwhile, two undoped luminescent layer direct neighbors, it is not necessary to be spaced
Layer, while effectively using energy transmission effect, additionally it is possible to reduce the adverse effect that unnecessary hetero-junctions is brought, be to realize white light
The ideal chose of OLED, but there is presently no relevant report.
The content of the invention
In order to solve the above technical problems, it is an object of the invention to provide a kind of efficient undoped white light organic electroluminescence device
Part, it combines efficient hot activation delayed fluorescence characteristic yellow using the blue-fluorescence luminescent material of conventional, function admirable
Fluorescence luminescent material, using blue-fluorescence luminescent material and the luminescent layer of yellow fluorescence luminescent material undoped structure, the two is only
Only adjacent, the triplet excitons of blue-fluorescence luminescent material can be effectively transferred to yellow fluorescence luminescent material, so as to improve
Exciton utilization rate, improves device performance, real by only utilizing two kinds of nonmetallic fluorescence luminescent materials and simple device architecture
Existing high efficiency, it is low roll-off and low cost white light parts.
It is a further object of the present invention to provide the preparation method of above-mentioned efficient undoped white light organic electroluminescent device.
Technical problem proposed by the invention is so solved：A kind of efficient undoped white light organic electroluminescence device
Part, from bottom to top includes successively：Substrate, anode layer, organic function layer and cathode layer, it is characterised in that：Described organic functions
Layer from bottom to top includes hole injection layer, hole transmission layer, luminescent layer, electron transfer layer successively, and the luminescent layer is by following two
One of the mode of kind is constituted：1. by the yellow fluorescence luminescent material with hot activation delayed fluorescence characteristic close to hole transmission layer
Layer, and close to the conventional blue fluorescence luminescent material layer composition of electron transfer layer, the thickness of the yellow fluorescence luminous material layer
Spend for 1-10nm；2. by the conventional blue fluorescence luminescent material layer close to hole transmission layer, and close to the tool of electron transfer layer
It is made up of the yellow fluorescence luminous material layer of hot activation delayed fluorescence characteristic, the thickness of the yellow fluorescence luminous material layer is
1-10nm。
The preparation method of above-mentioned white light organic electroluminescent device, it is characterised in that comprise the following steps：
1. substrate is cleaned by ultrasonic, baking oven is put into after cleaning and is dried；
2. substrate is moved into vacuum film coating chamber, according to order from bottom to up, is prepared, divided successively by dry or wet
Anode layer, hole transmission layer, luminescent layer, electron transfer layer and cathode layer are not prepared, and white light organic electroluminescent device is made；
3. the white light organic electroluminescent device for preparing completion is packaged in nitrogen atmosphere.
Material involved in the present invention is the excellent organic semiconducting materials of traditional performance, and the range of choice of material is wide, adopts
With conventional blue fluorescence luminescent material and TADF yellow fluorescence luminescent materials, blue-fluorescence luminescent material and TADF yellow fluorescences hair
Luminescent material is tightly adjacent, and exciton forming region is predominantly located at yellow fluorescence luminescent material and blue-fluorescence luminescent material and yellow
The interface of fluorescence luminescent material, the triplet excitons energy level of blue fluorescent material higher than yellow fluorescence luminescent material singlet and
Triplet excitons energy level, can produce effective energy transmission effect so that the non-luminous triplet excitons of blue fluorescent material
It is fully utilized, and utilizes hot activation delayed fluorescence characteristic so that whole excitons are fully utilized, improves device effect
Rate.Meanwhile, using undoped luminous layer structure, asked with solving unmanageable host-guest system technique in OLED preparation process
Topic, obtains white light parts using minimum luminescent material and organic functional material, can simplify operating procedure, reduction is produced into
This.Furthermore, with all using the white light parts of TADF luminescent materials compared with, lighted material with reference to conventional fluorescent luminescent material and TADF
The white light parts of material have relatively low efficiency roll-off and high stability.The angle that the present invention is prepared from material technology and device is opened up
One approach for showing unique characteristics.The present invention provides and prepares efficient white light organic electroluminescent device, with efficiency high, knot
Structure is simple, low cost and other advantages.
Brief description of the drawings
Fig. 1 is that the high efficiency undoped white light organic electroluminescent device of the present invention and the structure of embodiment 1,2,3 are shown
It is intended to；
Fig. 2 is the structural representation of embodiment 4,5,6 provided by the present invention；
Fig. 3 is the photoelectric characteristic curve of device A in embodiment 1 provided by the present invention, wherein, solid squares curve is represented
Current density (Current density)-voltage (Voltage) characteristic curve, solid circles curve represents brightness
(Luminance)-voltage (Voltage) characteristic curve.
Fig. 4 is external quantum efficiency (the External quantum of device A in embodiment 1 provided by the present invention
Efficiency)-current density (Current density) characteristic curve.
Wherein, substrate 1, anode layer 2, hole injection layer 3, hole transmission layer 4, yellow fluorescence luminous material layer 5, blueness is glimmering
Light luminous material layer 6, electron transfer layer 7, cathode layer 8, additional power source 9.
Embodiment
The invention will be further described below in conjunction with the accompanying drawings：
As illustrated, the present invention is a kind of efficient undoped white light organic electroluminescent device, from bottom to top include successively：
Substrate 1, anode layer 2, organic function layer and cathode layer 8.Organic function layer from bottom to top includes hole injection layer 3, hole successively
Transport layer 4, luminescent layer, electron transfer layer 7.
Luminescent layer can be made up of one of following two modes：1. by prolonging with hot activation close to hole transmission layer 4
The yellow fluorescence luminous material layer 5 of slow fluorescent characteristic (TADF), and close to the conventional blue fluorescence radiation of electron transfer layer 7
Material layer 6 is constituted, and the thickness of the yellow fluorescence luminous material layer 5 is 1-10 nm；2. by the routine close to hole transmission layer 4
Blue-fluorescence luminescent material layer 6, and lighted close to the yellow fluorescence with hot activation delayed fluorescence characteristic of electron transfer layer 7
Material layer 5 is constituted, and the thickness of the yellow fluorescence luminous material layer 5 is 1-10nm.
TADF yellow fluorescences luminous material layer 5 and blue-fluorescence luminescent material layer 6, the shape under the driving of device applied voltage
Into exciton, produce luminous.It is preferred that, the triplet excitons energy level of blue-fluorescence luminescent material is higher than yellow fluorescence luminescent material
Singlet exciton and triplet excitons energy level, and blue-fluorescence luminescent material and yellow fluorescence luminescent material are tightly adjacent.Swash
Sub- forming region is predominantly located at the boundary of yellow fluorescence luminescent material and blue-fluorescence luminescent material and yellow fluorescence luminescent material
At face, when exciton formation is on the blue-fluorescence luminescent material and yellow fluorescence luminescent material, the blue luminescence
The non-luminous triplet excitons of material effectively can pass to the yellow fluorescence luminescent material by energy transmission effect
Singlet and triplet excitons.
Hole injection layer 3 polymerize good electric conductivity as anode layer 2 and the articulamentum of hole transmission layer 4, preferably organic
Conducting polymer materials are poly- (3,4- ethylenedioxy thiophenes):Poly- (styrene sulfonic acid) (PEDOT:) or metal oxide material PSS
Expect molybdenum trioxide (MoO3)。
It is preferred that, the material of hole transmission layer 4 is carbazole compound, aromatic triamine class compound or star triphen
Mixing more than one or both of aminated compounds.For example：Carbazole compound can be 1,3- bis- (carbazole -9-yl)
Benzene (MCP), 4,4 ', 4 "-three (carbazole -9-yl) triphenylamines (TCTA), 4,4 '-two (carbazole -9-yl) biphenyl (CBP) or 3,3-
Two (9H- carbazoles -9-yl) biphenyl (mCBP).Aromatic triamine class compound can be two-[4- (N, N- ditolyl-amino)-benzene
Base] hexamethylene (TAPC).Star triphenylamine compound can be that molecular center contains phenyl (TDAB series), triphenylamine
The one or more of the star triphenylamine compound of (PTDATA series) or 1,3,5- triphenylbenzenes (TDAPB series)
Mixing.
It is preferred that, in the material molecule structure with hot activation delayed fluorescence characteristic yellow fluorescence luminous material layer 5
Including electronic donor group and electron accepting groups.For example：Electronic donor group includes phenthazine group series, trianilino group
Mixing more than one or both of series, carbazole group series, acridine group series；Electron accepting groups include hexichol first
Ketone series, diphenyl sulphone (DPS) group series, benzene dicarbonitrile group series, triphen triazine group series, phenyl phosphine oxide group series, oxygen
One kind in thioxanthene oxidized series or thioxanthone group series.
It is preferred that, the conventional blue fluorescence luminescent material layer 6 is using diphenyl ethylene derivatives, triphenylethylene, four benzene second
Ene derivative, carbazole analog derivative, one kind of boron class or beryllium analog derivative.For example：Diphenyl ethylene derivatives are 4,4 '-two
(2,2- diphenylethyllenes) -1,1 '-biphenyl (DPVBi) or 1-4- bis--[4- (bis--benzene of N, N-) amido] styryl-benzene
(DSA-Ph)；Triphenylethylene or tetraphenyl ethylene derivative be 9,9'- ((2- (4'- (9 hydrogen-carbazole -9-yl)-[1,1'- biphenyl] -
4-yl) ethene -1,1-diyl) double (4,1- phenylenes)) double (9 hydrogen-carbazole) (2CzTPEPCz)；Carbazole analog derivative is 4,
4 '-bis- (9- ethyl -3- carbazoles vinyl) -1,1 '-biphenyl (BCzVBi) or 1,4- pairs [2- (3-N- ethane carbazole) vinyl]
Benzene (BCzVB)；Boron analog derivative is difluoro [the different methylene benzylacetone-N- of 6- (2- (1H)-quinolylmethyl-kN)-(the different methylene of 6-
Acetone -2- quinolylmethyls-kN1)] boron (MQAB)；Beryllium analog derivative is double (2- (2- hydroxyphenyls)-pyridine) berylliums (Bepp2).
Material used in the electron transfer layer 7 is metal complex, oxadiazole classes compound, quinoxaline chemical combination
Thing, nitrogen-containing heterocycle compound, phosphine oxo-compound, anthracene compound, organic boron material or one kind in organo-sulfur materials or
Two or more mixing.For example：Metal complex is 8-hydroxyquinoline aluminium (Alq3), double (2- methyl -8-hydroxyquinoline) it is (right
Phenylphenol) aluminium (BAlq), 8-hydroxyquinoline lithium (Liq), double (10- hydroxy benzos [h] quinoline) beryllium (Bebq2) or double [2-
(2- hydroxy phenyls -1)-pyridine] beryllium (Bepp2)；Oxadiazole class compound is 2- (4- diphenyl) -5- (4- 2-methyl-2-phenylpropanes base) -1,
3,4- oxadiazoles 18 (PBD) or 1,3- bis- [2- (4- tert-butylbenzenes) -1,3,4- oxadiazoles -5-yl] benzene (OXD-7)；It is nitrogenous
Heterocyclic compound is 1,3,5- (three N- phenyl -2- benzimidazolyl-2 radicals) benzene 41 (TPBi), the adjacent diazas of 4,7- phenylbenzenes -1,10-
Luxuriant and rich with fragrance (Bphen), 2,9- dimethyl -4,7- phenylbenzene -1,10- phenanthrolenes (BCP), the special fourths of 3- (4- hexichol) -4- benzene -5-
Base benzene -1,2,4- benzotriazoles (TAZ), 3,5,3 ", 5 "-four -3- pyridines-[1,1 '；3 ', 1 "] terphenyl (B3PyPB), 3- (two
Phosphenylic acid chlorine) double (diphenylphosphoric acid the chlorine) -9- benzene -9H- carbazoles (PPO2) of -9- benzene -9H- carbazoles (PPO1) or 3,6-；Phosphine oxygen
Based compound is two (2- (diphenylphosphino) benzene) ether oxides (DPEPO) or 2,8- bis- (diformazan benzenephosphonic acid) dibenzothiophen
(PO15)；Anthracene compound is 9,10- bis--(2- naphthyls) anthracene (AND)；Organic boron material is three (2,4,6- trimethyl -3- (pyrroles
Pyridine -3-yl) benzene) borine (3TPYMB)；Organo-sulfur materials are (diformazan benzenephosphonic acid) dibenzothiophens of 2,8- bis- (PO15) etc..
Substrate 1 is the support of electrode and organic thin film layer, and it has good light transmission in visible region, there is certain
Anti-steam and oxygen infiltration ability, have preferable profile pattern, it can be glass or flexible substrate, flexible substrate is adopted
With a kind of material or relatively thin metal in polyesters, poly- phthalimide compound.
Anode layer 2 is as the articulamentum of white light organic electroluminescent device forward voltage, and it requires there is preferable electric conductivity
Energy, visible transparent and higher work function.Generally using inorganic, metal oxide (such as tin indium oxide ITO) or high work content
Several metal materials (such as gold, copper, silver, platinum).
Cathode layer 7 is as the articulamentum of device negative voltage, and it requires there is preferable electric conductivity and relatively low work content
Number, negative electrode be usually the relatively low metal of the work function such as low workfunction metal material lithium, magnesium, calcium, strontium, aluminium, indium or they with copper,
The alloy of gold, silver；Or one layer of very thin buffer insulation layer (such as LiF, MgF2) and metal or alloy noted earlier.
Above-mentioned white light organic electroluminescent device and preparation method thereof, it comprises the following steps：
1. substrate is cleaned by ultrasonic, baking oven is put into after cleaning and is dried.
2. substrate is moved into vacuum film coating chamber, according to order from bottom to up, is prepared, divided successively by dry or wet
Anode layer, hole transmission layer, luminescent layer, electron transfer layer and cathode layer are not prepared, and white light organic electroluminescent device is made.Respectively
Layer can directly dry process successively, or be sequentially prepared after organic solvent diluting on substrate by wet processing, example
Such as by vacuum evaporation, ionized cluster beam deposition, ion plating, DC sputtering deposition, radio-frequency sputtering plated film, ion beam sputtering deposition,
Ion beam assisted depositing, plasma reinforced chemical vapour deposition, high density inductive coupling plasma source chemical vapor deposition,
One or several kinds in catalyst chemical vapor deposition, magnetron sputtering, plating, spin coating, dip-coating, inkjet printing, roller coat, LB films
Mode and formed.The technique of each layer can be with identical or different.
3. the white light organic electroluminescent device for preparing completion is packaged in nitrogen atmosphere.
The organic electro-optic device structure example prepared using the present invention is as follows：
Glass/ITO/PEDOT:PS/ hole transmission layers/TADF yellow fluorescences luminous material layer/blue-fluorescence luminescent material
Layer/electron transfer layer/cathode layer
Glass/ITO/PEDOT:PS/ hole transmission layers/blue-fluorescence luminescent material layer/TADF yellow fluorescence luminescent materials
Layer/electron transfer layer/cathode layer
Flexible substrate/ITO/PEDOT:PS/ hole transmission layers/TADF yellow fluorescences luminous material layer/blue luminescence
Material layer/electron transfer layer/cathode layer
Flexible substrate/ITO/PEDOT:PS/ hole transmission layers/blue-fluorescence luminescent material layer/TADF yellow fluorescences light
Material layer/electron transfer layer/cathode layer
The following is the specific embodiment of the present invention：
Embodiment 1
As shown in figure 1, the hole injection layer 3 in device architecture is PEDOT:PSS, hole transmission layer 4 is CBP, and TADF is yellow
Color fluorescence luminescent material layer 5 is that (wherein electronic donor group is phenthazine group to OPDPO, and electron accepting groups are benzophenone
Group), blue-fluorescence luminescent material layer 6 is triphenylethylene derivatives 2CzTPEPCz, and the material therefor of electron transfer layer 7 is TPBi,
Cathode layer 8 is Mg:Ag alloys, ratio is 10：1.Wherein, OPDPO singlet and triplet excitons energy level are respectively 2.61eV
With 2.59 eV, 2CzTPEPCz triplet excitons energy level is 2.65eV.Entirely device architecture is：
Glass substrate/ITO/PEDOT:PSS(40nm)/CBP(20nm)/OPDPO(4nm)/2CzTPEPCz (15nm)/
TPBi(40nm)/Mg:Ag(10:1,200nm), this device markings is device A.
Preparation method is as follows：
(1) ultrasound is carried out to transparent conduction base sheet ito glass with detergent, deionized water, acetone and ethanol solution respectively
Cleaning, is put into baking box after cleaning and is dried.Ito film wherein above glass substrate as device anode layer 2, ito film
Square resistance is 8 Ω/sq, and thickness is 120nm.
(2) dried substrate is moved into oxygen plasma treatment room, ITO substrates entered in air pressure 1Pa vacuum cavity
Row oxygen plasma treatment 15 minutes.
(3) on the ITO substrates after oxygen plasma treatment, with 2000rpm rotating speed spin coatings PEDOT:PSS, maintenance 60 seconds, so
Annealing 20 minutes is carried out in 150 DEG C of thermal station afterwards.
(4) by the incoming high vacuum organic vapor deposition room of transparent substrates after processing, it is evacuated to air pressure and reaches 4 × 10-3Pa with
Under, each organic function layer, including hole transmission layer 4, luminescent layer, electron transfer layer 7 are deposited successively according to order from bottom to up
With cathode layer 8.Wherein, the evaporation rate of hole transmission layer 4 (CBP) and electron transfer layer 7 (TPBi) is 1nm/s, and TADF is yellow
6 (2CzTPEPCz) of color fluorescence luminescent material 5 (OPDPO) of layer and blue-fluorescence luminescent material layer evaporation rate is 0.02-
The 0.05nm/s, (Mg of cathode layer 8:Ag) ratio is 10:1, the speed of evaporation magnesium is 10nm/s, and the speed of evaporation silver is 1nm/s,
Evaporation rate and thickness are monitored by the film thickness gauge near substrate.
(5) device for preparing completion is sent into the glove box filled with nitrogen to be packaged, and it is special to test the photoelectricity of device
The electroluminescent spectrum of property and device.
Table 1 is the photoelectric properties parameter of device A in embodiment 1 provided by the present invention.
Table 1
Embodiment 2
As shown in figure 1, the hole injection layer 3 in device architecture is PEDOT:PSS, hole transmission layer 4 is CBP, and TADF is yellow
Color fluorescence luminescent material layer 5 is that (wherein electronic donor group is phenthazine group to OPDPO, and electron accepting groups are benzophenone
Group), blue-fluorescence luminescent material layer 6 is triphenylethylene derivatives 2CzTPEPCz, and the material therefor of electron transfer layer 7 is TPBi,
Cathode layer 8 is Mg:Ag alloys, ratio is 10：1.Wherein, OPDPO singlet and triplet excitons energy level are respectively 2.61eV
With 2.59 eV, 2CzTPEPCz triplet excitons energy level is 2.65eV.Entirely device architecture is：
Glass substrate/ITO/PEDOT:PSS(40nm)/CBP(20nm)/OPDPO(10nm)/2CzTPEPCz (20nm)/
TPBi(40nm)/Mg:Ag(10:1,200nm).
The preparation process of device is similar to Example 1.
Embodiment 3
As shown in figure 1, the hole injection layer 3 in device architecture is PEDOT:PSS, hole transmission layer 4 is CBP, and TADF is yellow
Color fluorescence luminescent material layer 5 is that (wherein electronic donor group is phenthazine group to OPDPO, and electron accepting groups are benzophenone
Group), blue-fluorescence luminescent material layer 6 is triphenylethylene derivatives 2CzTPEPCz, and the material therefor of electron transfer layer 7 is
3TPYMB, cathode layer 8 is Mg:Ag alloys, ratio is 10：1.Wherein, OPDPO singlet and triplet excitons energy level difference
For 2.61eV and 2.59eV, 2CzTPEPCz triplet excitons energy level is 2.65eV.Entirely device architecture is：
Glass substrate/ITO/PEDOT:PSS(40nm)/CBP(20nm)/OPDPO(1nm)/2CzTPEPCz (14nm)/
3TPYMB(40nm)/Mg:Ag(10:1,200nm).
The preparation process of device is similar to Example 1.
Embodiment 4
As shown in Fig. 2 the hole injection layer 3 in device architecture is PEDOT:PSS, hole transmission layer 4 is MCP, and TADF is yellow
Color fluorescence luminescent material layer 5 is that (wherein electronic donor group is phenthazine group to OPDPO, and electron accepting groups are benzophenone
Group), blue-fluorescence luminescent material layer 6 is triphenylethylene derivatives 2CzTPEPCz, and the material therefor of electron transfer layer 7 is TPBi,
Cathode layer 8 is Mg:Ag alloys, ratio is 10：1.Wherein, OPDPO singlet and triplet excitons energy level are respectively 2.61eV
With 2.59 eV, 2CzTPEPCz triplet excitons energy level is 2.65eV.Entirely device architecture is：
Glass substrate/ITO/PEDOT:PSS(40nm)/CBP(20nm)/2CzTPEPCz(20nm)/ OPDPO(5nm)/
TPBi(40nm)/Mg:Ag(10:1,200nm).
The preparation process of device is similar to Example 1.
Embodiment 5
As shown in Fig. 2 the hole injection layer 3 in device architecture is MoO3, hole transmission layer 4 is MCP, TADF yellow fluorescences
Luminous material layer 5 is OPDPO (wherein electronic donor group is phenthazine group, and electron accepting groups are benzophenone groups),
Blue-fluorescence luminescent material layer 6 is triphenylethylene derivatives 2CzTPEPCz, and the material therefor of electron transfer layer 7 is TPBi, negative electrode
Layer 8 is Mg:Ag alloys, ratio is 10：1.Wherein, OPDPO singlet and triplet excitons energy level be respectively 2.61eV and
2.59eV, 2CzTPEPCz triplet excitons energy level are 2.65eV.Entirely device architecture is：
Glass substrate/ITO/MoO3(1nm)/CBP(20nm)/2CzTPEPCz(15nm)/ OPDPO(2nm)/TPBi
(40nm)/Mg:Ag(10:1,200nm).
The preparation process of device is similar to Example 1, and wherein step (3) is：
By the incoming high vacuum organic vapor deposition room of ITO substrates after oxygen plasma treatment, air pressure is 4 × 10-3Below Pa, steams
Plate MoO3, evaporation rate is 0.01nm/s.
Embodiment 6
As shown in Fig. 2 the hole injection layer 3 in device architecture is MoO3, hole transmission layer 4 is MCP, and TADF yellow is glimmering
Light luminous material layer 5 is that (wherein electronic donor group is phenthazine group to OPDPO, and electron accepting groups are benzophenone bases
Group), blue-fluorescence luminescent material layer 6 is triphenylethylene derivatives 2CzTPEPCz, and the material therefor of electron transfer layer 7 is 3TPYMB,
Cathode layer 8 is Mg:Ag alloys, ratio is 10：1.Wherein, OPDPO singlet and triplet excitons energy level are respectively 2.61eV
With 2.59 eV, 2CzTPEPCz triplet excitons energy level is 2.65eV.Entirely device architecture is：
Glass substrate/ITO/MoO3(8nm)/CBP(20nm)/2CzTPEPCz(14nm)/OPDPO(1nm)/ 3TPYMB
(40nm)/Mg:Ag(10:1,200nm).
The preparation process of device is similar to Example 5.
Claims (10)
1. a kind of efficient undoped white light organic electroluminescent device, from bottom to top includes successively：Substrate, anode layer, You Jigong
Ergosphere and cathode layer, it is characterised in that：Described organic function layer from bottom to top includes hole injection layer, hole transport successively
Layer, luminescent layer, electron transfer layer, the luminescent layer are made up of one of following two modes：1. by the tool close to hole transmission layer
There is the yellow fluorescence luminous material layer of hot activation delayed fluorescence characteristic, and close to the conventional blue fluorescence radiation of electron transfer layer
Material layer is constituted, and the thickness of the yellow fluorescence luminous material layer is 1-10nm；2. by the conventional blue close to hole transmission layer
Fluorescence luminescent material layer, and close to the yellow fluorescence luminous material layer with hot activation delayed fluorescence characteristic of electron transfer layer
Composition, the thickness of the yellow fluorescence luminous material layer is 1-10nm.
2. a kind of efficient undoped white light organic electroluminescent device according to claim 1, it is characterised in that：The indigo plant
The triplet excitons energy level of color fluorescence luminescent material swashs higher than the singlet exciton and triplet state of the yellow fluorescence luminescent material
Sub- energy level, and the blue-fluorescence luminescent material and yellow fluorescence luminescent material are tightly adjacent.
3. a kind of efficient undoped white light organic electroluminescent device according to claim 1 or 2, it is characterised in that：Institute
State hole injection layer poly- (3,4- ethylenedioxy thiophenes) for organic conductive polymer material:Poly- (styrene sulfonic acid) or metal oxygen
Compound material molybdenum trioxide.
4. a kind of efficient undoped white light organic electroluminescent device according to claim 1 or 2, it is characterised in that：Institute
It is one kind in carbazole compound, aromatic triamine class compound or star triphenylamine compound to state hole transport layer material
Or a variety of mixing, it is preferred that carbazole compound is selected from 1,3- bis- (carbazole -9-yl) benzene, 4,4 ', 4 "-three (carbazole -9-yl)
Triphenylamine, 4,4 '-two (carbazole -9-yl) biphenyl or 3,3- bis- (9H- carbazoles -9-yl) biphenyl, aromatic triamine class compound
Selected from two-[4- (N, N- ditolyl-amino)-phenyl] hexamethylenes, star triphenylamine compound contains benzene selected from molecular center
Base, triphenylamine or, one or more kinds of mixing of the star triphenylamine compound of 1,3,5- triphenylbenzenes.
5. a kind of efficient undoped white light organic electroluminescent device according to claim 1 or 2, it is characterised in that：Institute
Stating the molecular structure with hot activation delayed fluorescence characteristic yellow fluorescence luminous material layer includes electronic donor group and electronics
Acceptor groups.
6. a kind of efficient undoped white light organic electroluminescent device according to claim 5, it is characterised in that：The electricity
Sub- donor groups are in phenthazine group series, trianilino group series, carbazole group series or acridine group series
One or more mixing, electron accepting groups include benzophenone series, diphenyl sulphone (DPS) group series, benzene dicarbonitrile group system
In row, triphen triazine group series, phenyl phosphine oxide group series, phenoxathiin oxidized series or thioxanthone group series
One kind.
7. a kind of efficient undoped white light organic electroluminescent device according to claim 1 or 2, it is characterised in that：Institute
State conventional blue fluorescence luminescent material for diphenyl ethylene derivatives, triphenylethylene, tetraphenyl ethylene derivative, carbazole analog derivative,
One kind of boron class or beryllium analog derivative；It is preferred that, diphenyl ethylene derivatives be 4,4 '-two (2,2- diphenylethyllene) -1,1 ' -
Biphenyl or 1-4- bis--[4- (bis--benzene of N, N-) amido] styryl-benzene, triphenylethylene or tetraphenyl ethylene derivative are 9,9'-
((2- (4'- (9 hydrogen-carbazole -9-yl)-[1,1'- biphenyl] -4-yl) ethene -1,1-diyl) double (4,1- phenylenes)) it is double (9 hydrogen -
Carbazole), carbazole analog derivative be 4,4 '-bis- (9- ethyl -3- carbazoles vinyl) -1,1 '-biphenyl or Isosorbide-5-Nitrae-bis- [2- (3-N- second
Alkane carbazole) vinyl] benzene, boron analog derivative is difluoro [different methylene benzylacetone-N- of 6- (2- (1H)-quinolylmethyl-kN)-(6- is different
Methylene benzylacetone -2- quinolylmethyls-kN1)] boron, beryllium analog derivative is double (2- (2- hydroxyphenyls)-pyridine) berylliums.
8. a kind of efficient undoped white light organic electroluminescent device according to claim 1 or 2, it is characterised in that：Institute
State the material of electron transfer layer for metal complex, oxadiazole classes compound, quinoxaline compound, nitrogen-containing heterocycle compound,
One or both of phosphine oxo-compound, anthracene compound, organic boron material or organo-sulfur materials are mixed above；It is preferred that
, metal complex be 8-hydroxyquinoline aluminium, double (2- methyl -8-hydroxyquinoline) (p-phenyl phenol) aluminium, 8-hydroxyquinoline lithium,
Double (10- hydroxy benzos [h] quinoline) berylliums or it is double [2- (2- hydroxy phenyls -1)-pyridine] Pi , oxadiazole classes compound be 2-
(4- diphenyl) -5- (4- 2-methyl-2-phenylpropanes base) -1,3,4- oxadiazoles 18 or [2- (4- the tert-butylbenzenes) -1,3,4- Evil bis- of 1,3- bis-
Azoles -5-yl] benzene, nitrogen-containing heterocycle compound is 1,3,5- (three N- phenyl -2- benzimidazolyl-2 radicals) benzene 41,4,7- phenylbenzenes -1,10-
Phenanthrolene, 2,9- dimethyl -4,7- phenylbenzene -1,10- phenanthrolenes, 3- (4- hexichol) -4- benzene -5- tert-butylbenzenes -
1,2,4- benzotriazoles, 3,5,3 ", 5 "-four -3- pyridines-[1,1 '；3 ', 1 "] terphenyl, 3- (diphenylphosphoric acid chlorine) -9- benzene -9H-
Double (diphenylphosphoric acid the chlorine) -9- benzene -9H- carbazoles of carbazole, 3,6-, phosphine oxo-compound are two (2- (diphenylphosphino) benzene) ether oxygen
Compound or 2,8- bis- (diformazan benzenephosphonic acid) dibenzothiophen, anthracene compound are 9,10- bis--(2- naphthyls) anthracene, and organic boron material is three
(2,4,6- trimethyl -3- (pyridine -3-yl) benzene) borine, organo-sulfur materials are 2,8- bis- (diformazan benzenephosphonic acid) dibenzothiophen.
9. the preparation method of white light organic electroluminescent device described in claim 1-8, it is characterised in that comprise the following steps：
1. substrate is cleaned by ultrasonic, baking oven is put into after cleaning and is dried；
2. substrate is moved into vacuum film coating chamber, according to order from bottom to up, is prepared, made respectively successively by dry or wet
Standby anode layer, hole transmission layer, luminescent layer, electron transfer layer and cathode layer, are made white light organic electroluminescent device；
3. the white light organic electroluminescent device for preparing completion is packaged in nitrogen atmosphere.
10. the preparation method of efficient undoped white light organic electroluminescent device according to claim 9, its feature exists
In：Described step 2. in, anode layer, hole transmission layer, luminescent layer, electron transfer layer and cathode layer directly dry method system successively
It is standby, or be sequentially prepared after organic solvent diluting on substrate by wet processing；It is preferred that, the anode layer, hole
Transport layer, luminescent layer, electron transfer layer and cathode layer are plated by vacuum evaporation, ionized cluster beam deposition, ion plating, d.c. sputtering
Film, radio-frequency sputtering plated film, ion beam sputtering deposition, ion beam assisted depositing, plasma reinforced chemical vapour deposition, high density electricity
Feel coupled plasma source chemical vapor deposition, catalyst chemical vapor deposition, magnetron sputtering, plating, spin coating, dip-coating, spray
Black printing, roller coat, one or several kinds of modes in LB films and formed.
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