CN105602553B - Thermally activated delayed fluorescence material and its preparation and application based on 4 fluorophenyl acetonitriles - Google Patents
Thermally activated delayed fluorescence material and its preparation and application based on 4 fluorophenyl acetonitriles Download PDFInfo
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Abstract
The invention discloses a kind of thermally activated delayed fluorescence material with blue emission wavelength, it is to be used as electron acceptor unit using 4 fluorophenyl acetonitriles, pass through the 2 of heart phenyl ring wherein, 3,5,6 connection electron donor units are obtained, and are the compounds represented by following general structural formula (I), R therein represents N carbazyls, N phenothiazinyls or N phenoxazine groups.The present invention is by the 2 of 4 fluorophenyl acetonitrile electron acceptor parent benzenes, 3,5,6 functional groups for introducing different electronegativity are chemically modified, realize blue emission, and prepared fluorescent material has typical thermally activated delayed fluorescence effect, is capable of the life-span of delayed fluorescence between 10~60 microseconds, can apply in organic electroluminescence device.
Description
Technical field
The invention belongs to organic photoelectric functional material technical field, it is related to a kind of thermally activated delayed fluorescence material, this is glimmering
The preparation method of luminescent material, and its application in organic electroluminescence device.
Technical background
Organic electroluminescence device is lightweight, fast response time, and low cost, low energy consumption is shown and solid-state illumination in plane
Field gets more and more people's extensive concerning.Counted according to Quantum Spin, electronics and hole are respectively from two in organic electroluminescence device
Pole is injected, and migrates the singlet exciton of composition generation 25% and 75% triplet excitons.
Thermally activated delayed fluorescence（Thermally Activated Delayed Fluorescence, TADF）Material
Triplet excitons by the anti-intersystem crossing of thermal excitation can be converted into singlet exciton radioluminescence, so as to break through conventional fluorescent
The theoretical limit of material exciton utilization rate 25%, luminous quantum efficiency highest can reach 100%.Due to being related to exciton from triplet state
To the process of the anti-intersystem crossing of singlet, TADF materials typically exhibit photochemical long-life phosphors phenomenon（Delayed fluorescence）,
The delayed fluorescence life-span can reach microsecond to the millisecond order of magnitude, hence it is evident that be different from conventional fluorescent material.TADF materials combine organic
The advantage that fluorescent material stability is good and transient metal complex phosphor material luminous efficiency is high, uses it for organic electroluminescence hair
In optical device, the external quantum efficiencys of some devices close to phosphorescent devices level of efficiency, it is huge prominent as organic fluorescence device
It is broken.Therefore, TADF materials cause the very big emerging of scientific research personnel as a class novel low-cost high-efficiency rate luminous organic material
Interest, is with a wide range of applications.
One of MOLECULE DESIGN principle of TADF materials is with Electron donor acceptor（D-A）Type molecular structure, molecule highest
Occupy track（HOMO）Track is not occupied with minimum（LUMO）Electron donor and electron acceptor unit are respectively distributed to, this two parts
Moderately separated in space, to realize less molecule triplet state-singlet energy level difference（∆E ST）, beneficial to the reverse of triplet excitons
Intersystem crossing.
Itrile group and N- carbazyls are respectively as effective electron acceptor and electronic donor group, in D-A type molecular structure
Relatively broad application has been obtained in TADF materials.Wherein, by electron accepting groups of dinitrile benzene, carbazole be electron donor base
The TADF molecules of group are good due to stability, and luminous efficiency is high, applied to achieving preferable effect in organic electroluminescence device.
But only drawback is that the glow color of this quasi-molecule is located at green glow to orange light wave band, it is difficult to realize blue emission.
The content of the invention
It is an object of the invention to provide a kind of thermally activated delayed fluorescence material with blue emission wavelength.
A kind of preparation method of the thermally activated delayed fluorescence material is provided, is another goal of the invention of the present invention.
The present invention also aims to provide the thermally activated delayed fluorescence material as electroluminescent organic material or
The application of material of main part.
Thermally activated delayed fluorescence material of the present invention be using 4- fluorophenyl acetonitriles as electron acceptor unit, by
Luminescent material obtained from 2,3,5,6 connection electron donor units of its center phenyl ring.
Specifically, thermally activated delayed fluorescence material of the present invention is the compound that following general structural formula (I) is represented：
Wherein, described R represents N- carbazyls, N- phenothiazinyls or N- phenoxazine groups.
The present invention be the thermally activated delayed fluorescence material of blu-ray type of the class based on 4- fluorophenyl acetonitrile electron acceptors, by
The 2,3,5,6- positions of parent benzene introduce the functional group of these different electronegativity of N- carbazoles or N- phenoxazines or N- phenthazine respectively
Be chemically modified, adjust molecule frontier molecular orbital energy levels, and then modulating compound blue region glow color with
And the triplet state of molecule-singlet energy level difference∆E ST, obtain emission wavelength and molecule∆E STAdjustable luminescent material, is realized
Blue emission.
Further, the invention provides a kind of typical preparation method of the thermally activated delayed fluorescence material, institute
The method of stating is, using phenyl-pentafluoride acetonitrile as raw material, to exist in the DMF dicyandiamide solution containing sodium hydride with heterocyclic amine
Nucleophilic substitution is carried out under normal temperature, the thermally activated delayed fluorescence material is prepared.Wherein, described heterocyclic amine be carbazole,
One kind in phenoxazine or phenthazine.
Further, in above-mentioned preparation method, the amount ratio for controlling heterocyclic amine and the material of phenyl-pentafluoride acetonitrile is 4~4.5: 1.
Thermally activated delayed fluorescence material prepared by the present invention has typical thermally activated delayed fluorescence effect, can
The life-span of delayed fluorescence is between 10~60 microseconds.It therefore, it can the fluorescent material as light emitting guest material, be entrained in energy
It is used as the luminescent layer of organic electroluminescence device in the material of main part of level matching；Or as material of main part, adulterate energy thereto
The light emitting guest material of level matching is used as the luminescent layer of organic electroluminescence device.
Closer, the invention provides a kind of organic electroluminescence device, the organic electroluminescence device has
At least one layer of luminescent layer between first electrode and second electrode, and necessary functional layer.Wherein, in the luminescent layer
In include one or more of thermally activated delayed fluorescence materials of the present invention.
The above-mentioned organic electroluminescence device of the present invention can be prepared using evaporation altogether or the process of solution spin coating.
For example, use altogether vapour deposition method prepare a kind of method of the organic electroluminescence device with typical structure for：1）
Vacuum evaporation hole transmission layer in anode ITO layer；2）By thermally activated delayed fluorescence material and small molecule host material（Thermal activation
Type delayed fluorescence material is used as light emitting guest material）Or light emitting guest material and thermally activated delayed fluorescence material of main part（Heat
Activated form delayed fluorescence material is used as material of main part）It is deposited simultaneously on hole transmission layer as luminescent layer under vacuum,
The content of luminescent material and material of main part controls respective evaporation rate to control by two independent quartz oscillators,
The weight ratio generally 1~10: 100 of luminescent material and material of main part；3）There is evaporation one to two layers hole to hinder on luminescent layer
Gear or the organic molecule of electric transmission function layer, then evaporation metal electrode, are prepared into multilayer organic electroluminescence device.Its
In, small molecule host material include 4,4 '-N,NThe carbazole biphenyl of '-two (CBP), 2- (4- diphenyl) -5- (4- tert-butyl-phenyls) -
1,3,4- oxadiazoles (PBD), (2- of 1,3,5- tri-N- phenyl benzimidazole groups) benzene (TPBI), 3- (4- diphenyl) -5- (tertiary fourths of 4-
Base phenyl) -4- (4- ethylphenyls) -, 1,2,4- triazoles (TAZ) etc.；Light emitting guest material includes organic small molecule fluorescent material
With Ir (III) complex small molecule phosphor material etc..
Use solution spin-coating method prepare the method for typical structure organic electroluminescence device for：1）Revolved in anode ITO layer
Apply poly- 3,4- ethylenedioxy thiophenes/poly styrene sulfonate（PEDOT:PSS）It is prepared into hole transmission layer；2）Prolong thermally activated
Slow fluorescent material is blended with macromolecule material of main part, is spun on hole transmission layer and is prepared into luminescent layer, thermally activated delay is glimmering
Luminescent material and the weight of material of main part ratio are 1~10: 100；3）Directly in evaporation metal electrode on luminescent layer, single-layer device is prepared into
Part, or one to two layers is introduced on luminescent layer by the method for vacuum evaporation there is having for hole barrier or electric transmission function
After machine thin layer, then evaporation metal electrode, it is prepared into multilayer device.Wherein, macromolecule material of main part includes polystyrene support, polyphenyl
Support, PVK, polycarbazole, derivative of polyfluorene or polyfluorene etc..
Brief description of the drawings
Fig. 1 is the prepare compound CyFbCz of embodiment 1 hydrogen nuclear magnetic resonance spectrogram.
Fig. 2 is the prepare compound CyFbCz of embodiment 1 carbon-13 nmr spectra figure.
Fig. 3 is ultraviolet-ray visible absorbing, luminescence generated by light and electroluminescent lights of the compound CyFbCz in dichloromethane solution
Spectrogram.
Fig. 4 is that compound CyFbCz is entrained in the transient state fluorescence decay curve figure that film is made in mCP material of main parts.
Fig. 5 is that embodiment 1 prepares electroluminescent light spectrogram of the organic electroluminescence device under different voltages.
Fig. 6 be embodiment 1 prepare organic electroluminescence device brightness and current density with voltage change curve.
Fig. 7 is that embodiment 1 prepares the current efficiency and power efficiency of organic electroluminescence device with the change of current density
Curve map.
Fig. 8 is that compound CyFbPOZ is entrained in the transient state fluorescence decay curve figure that film is made in mCP material of main parts.
Fig. 9 is that compound CyFbPTZ is entrained in the transient state fluorescence decay curve figure that film is made in mCP material of main parts.
Embodiment
Following embodiments are only the preferred technical solution of the present invention, are not used to carry out any limitation to the present invention.For
For those skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles of the invention, made
Any modification, equivalent substitution and improvements etc., should be included in the scope of the protection.
Embodiment 1
By 703mg carbazoles and 25mL N,N-dimethylformamides（DMF）Add in the three-necked flask with stirrer, often
It is gradually added into after the DMF solution 5mL containing 150mg NaH, stirring reaction 30min, is added containing 193mg phenyl-pentafluoride second under temperature
The DMF solution 5mL of nitrile, stirring reaction 3h.
After reaction terminates, reactant mixture is poured into 50mL frozen water, filtering precipitation, using silica gel as stationary phase, volume ratio
The mixed solution of petroleum ether and dichloromethane for 1~3: 1 is eluent, and column chromatography for separation obtains compound CyFbCz yellow and consolidated
Body 327mg, yield 42%.
In Fig. 1 proton nmr spectra, chemical shift be 7.84-7.59ppm, 7.49-7.28ppm, 7.15-6.99ppm,
It is the fragrant hydrogen on carbazole ring at 6.65-6.57 ppm, because product is to occur four groups of hydrogen altogether on symmetrical structure, carbazole ring, often
The number of group hydrogen is respectively 8；Because the hydrogen in parent benzene is all replaced by functional group, therefore, in proton nmr spectra
Not it was observed that hydrogen in parent benzene.In Fig. 2 carbon-13 nmr spectra, chemical shift is 141.40ppm (C4), 140.05ppm
(C2 and C6), 122.73ppm (C3 and C5), 105.65ppm (C1) place are the carbon in parent benzene, because product is symmetrical junction
Occur 4 groups of carbon in structure, parent benzene altogether, and observe at corresponding fluoro- carbon coupling division peak, 127.58ppm as on itrile group
Carbon, remaining be carbazole ring on carbon.By Fig. 1 and Fig. 2 spectral data, it can prove that the product that the present embodiment is prepared is
CyFbCz。
Fig. 3 gives ultraviolet-ray visible absorbings of the compound CyFbCz in dichloromethane solution（UV-vis）It is spectrum, photic
It is luminous（PL）Spectrum and electroluminescent（EL）Spectrum.
Wherein, compound CyFbCz absorption band edge λ=422nm is understood in uv-visible absorption spectra, according to optics
Band gap calculation formulaE g=1240/ λ, the optical band gap that can calculate CyFbCz is 2.94eV.From photoluminescence spectra and electroluminescent
In luminescent spectrum it is observed that glow peak difference positions of the CyFbCz in dichloromethane solution and in organic electroluminescence device
In 430nm and 448nm, blue emission is belonged to, it was demonstrated that CyFbCz can be applied to illumination and show as a kind of blue light material
In field.
Compound CyFbCz is entrained in mCP material of main parts（Doping concentration 10%）, prepared by the method for vacuum evaporation
Film, the transient state fluorescence decay curve for obtaining it at room temperature is tested using transient state fluorescent/phosphorescent spectrometer（Fig. 4）.By number
According to fitting, the delayed fluorescence life-span that can obtain CyFbCz is 12.8 μ s, illustrates that CyFbCz has thermally activated delayed fluorescence property.
Compound CyFbCz is entrained in 1,3- bis- (9H- carbazole -9- bases) benzene（mCP）Organic electroluminescence is prepared in material of main part
Luminescent device.First, 40nm is deposited successively in the glass surface for being coated with ITO N,N'-two (1- naphthyls)-N,N'-diphenyl-
1,1 '-diphenyl -4,4 '-diamines（NPB）As hole transmission layer, 10nm 4,4', 4''- tri- (carbazole -9- bases) triphen are deposited
Amine（TCTA）It is used as electronic barrier layer；Then mCP formation 25nm luminescent layer is deposited again, wherein the CyFbCz of doping 6%；Finally,
It is sequentially depositing (the 1- phenyl -1 of electron transfer layer 1,3,5- tri-H- benzimidazolyl-2 radicals-yl) benzene（TPBi）35nm, boundary layer LiF 1nm
With negative electrode Al 100nm.
Fig. 5 is electroluminescent spectrum of the prepared organic electroluminescence device under different voltages, it is observed that
In 9~15V voltage ranges, the emission peak of device is respectively positioned on 447nm, chromaticity coordinates CIE value X=0.18, Y=0.13, with good
Spectrum stability.
The brightness of prepared organic electroluminescence device and current density are with the change curve of voltage as shown in fig. 6, electric current
Efficiency and power efficiency are as shown in Figure 7 with the change curve of current density, it can be seen that the high-high brightness of device is 4714cd/
m2, it is 100cd/m in brightness2And current density is 100mA/cm2Under voltage be respectively 7.8V and 11.8V, it is maximum and in electric current
Density is 100mA/cm2When current efficiency be respectively 5.56cd/A and 2.15cd/A, it is maximum and be 100mA/ in current density
cm2When power efficiency be respectively 2.36lm/W and 0.58lm/W.
Embodiment 2
824mg phenoxazines and 30mL DMF are added in the three-necked flask with stirrer, be gradually added under normal temperature containing
170mg NaH DMF solution 5mL, stirring reaction 40min, add the DMF solution 5mL containing 193mg phenyl-pentafluoride acetonitriles, stir
Mix reaction 4.5h.
After reaction terminates, reactant mixture is poured into 40mL frozen water, filtering precipitation, using silica gel as stationary phase, volume ratio
The mixed solution of petroleum ether and dichloromethane for 1~4: 1 is eluent, and column chromatography for separation obtains compound CyFbPOZ yellow
Solid 313mg, yield 37%.
1H NMR (500 MHz, DMSO-d 6 ) δ (ppm): 7.33-7.29 (m, 8H), 6.98 (d, J = 7.2
Hz, 4H), 6.95-6.91 (m, 4H), 6.75-6.70 (m, 8H), 6.75-6.71 (m, 8H)。
Compound CyFbPOZ manufactured in the present embodiment is entrained in vacuum evaporation in mCP material of main parts film is made, utilized
The transient state fluorescence decay curve of transient state fluorescent/phosphorescent spectrometer test at room temperature, as shown in figure 8, obtaining CyFbPOZ through over-fitting
The delayed fluorescence life-span be 41.5 μ s, the property with thermally activated delayed fluorescence.
Compound CyFbPOZ is entrained in 1,3- bis- (9H- carbazole -9- bases) benzene（mCP）Organic Electricity is prepared in material of main part
Electroluminescence device.First, 40nm is deposited successively in the glass surface for being coated with ITO N,N'-two (1- naphthyls)-N,N'-hexichol
Base -1,1 '-diphenyl -4,4 '-diamines（NPB）As hole transmission layer, 10nm 4,4', 4''- tri- (carbazole -9- bases) three are deposited
Aniline（TCTA）It is used as electronic barrier layer；Then mCP formation 25nm luminescent layer is deposited again, wherein the CyFbPOZ of doping 8%；Most
Afterwards, it is sequentially depositing (the 1- phenyl -1 of electron transfer layer 1,3,5- tri-H- benzimidazolyl-2 radicals-yl) benzene（TPBi）35nm, boundary layer LiF
1nm and negative electrode Al 100nm.After tested, the luminous peak position of prepared organic electroluminescence device belongs to blue light hair in 460nm
Penetrate, chromaticity coordinates CIE value X=0.18, Y=0.13.The high-high brightness of device reaches 2526cd/m2, maximum current efficiency reaches
6.64cd/A, maximum power efficiency reaches 2.66 lm/W.
Embodiment 3
856mg phenthazine and 35mL DMF are added in the three-necked flask with stirrer, be gradually added under normal temperature containing
190mg NaH DMF solution 7mL, stirring reaction 1h, add the DMF solution 5mL containing 193mg phenyl-pentafluoride acetonitriles, and stirring is anti-
Answer 7h.
After reaction terminates, reactant mixture is poured into 60mL frozen water, filtering precipitation, using silica gel as stationary phase, volume ratio
The mixed solution of petroleum ether and dichloromethane for 1~2: 1 is that compound CyFbPTZ palm fibres are obtained after eluent, column chromatography for separation
Yellow solid 409mg, yield 45%.
1H NMR (500 MHz, DMSO-d 6) δ (ppm): 7.69-7.63 (m, 8H), 7.55-7.52 (m,
4H), 7.50-7.46 (m, 4H), 7.41 (d, J = 7.2 Hz, 4H), 7.36-7.33 (m, 4H), 7.29-
7.25 (m, 8H)。
Compound CyFbPTZ manufactured in the present embodiment is entrained in mCP material of main parts film is made, it is glimmering using transient state
Light/transient state the fluorescence decay curve of pectrophosphorimeter test at room temperature, as shown in figure 9, obtaining CyFbPTZ delay through over-fitting
Fluorescence lifetime is 50.4 μ s, the property with thermally activated delayed fluorescence.
Compound CyFbPTZ is entrained in 1,3- bis- (9H- carbazole -9- bases) benzene（mCP）Organic Electricity is prepared in material of main part
Electroluminescence device.First, 40nm is deposited successively in the glass surface for being coated with ITO N,N'-two (1- naphthyls)-N,N'-hexichol
Base -1,1 '-diphenyl -4,4 '-diamines（NPB）As hole transmission layer, 10nm 4,4', 4''- tri- (carbazole -9- bases) three are deposited
Aniline（TCTA）It is used as electronic barrier layer；Then mCP formation 25nm luminescent layer is deposited again, wherein the CyFbPTZ of doping 10%；
Finally, it is sequentially depositing (the 1- phenyl -1 of electron transfer layer 1,3,5- tri-H- benzimidazolyl-2 radicals-yl) benzene（TPBi）35nm, boundary layer
LiF 1nm and negative electrode Al 100nm.After tested, the luminous peak position of prepared organic electroluminescence device belongs to day in 473 nm
Blue emission, chromaticity coordinates CIE value X=0.19, Y=0.23.The high-high brightness of device reaches 2013cd/m2, maximum current efficiency reaches
To 5.19cd/A, maximum power efficiency reaches 1.16 lm/W.
Claims (6)
1. it is the heart phenyl ring wherein using 4- fluorophenyl acetonitriles as electron acceptor unit a kind of thermally activated delayed fluorescence material
The luminescent material that 2,3,5,6 connection electron donor units are obtained, the fluorescent material is represented with following general structural formula (I)：
Wherein, described R represents N- carbazyls, N- phenothiazinyls or N- phenoxazine groups.
2. the preparation method of thermally activated delayed fluorescence material described in claim 1, be using phenyl-pentafluoride acetonitrile as raw material, containing
Nucleophilic substitution preparation is carried out at normal temperatures with heterocyclic amine in the DMF dicyandiamide solution of sodium hydride, wherein,
Described heterocyclic amine is one kind in carbazole, phenoxazines or phenthazine.
3. the preparation method of thermally activated delayed fluorescence material according to claim 2, it is characterized in that the heterocyclic amine with
The amount ratio of the material of phenyl-pentafluoride acetonitrile is 4~4.5: 1.
4. application of the thermally activated delayed fluorescence material in organic electroluminescence device is prepared described in claim 1.
5. application according to claim 4, it is characterized in that regarding the thermally activated delayed fluorescence material as light-emitting guest
Material, is entrained in the luminescent layer that organic electroluminescence device is constituted in the material of main part of level-density parameter.
6. application according to claim 4, it is characterized in that using the thermally activated delayed fluorescence material as material of main part,
The light emitting guest material of doped energy-band matching constitutes the luminescent layer of organic electroluminescence device thereto.
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