CN108409666A - A kind of luminous organic material and its device application - Google Patents
A kind of luminous organic material and its device application Download PDFInfo
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- CN108409666A CN108409666A CN201810123866.XA CN201810123866A CN108409666A CN 108409666 A CN108409666 A CN 108409666A CN 201810123866 A CN201810123866 A CN 201810123866A CN 108409666 A CN108409666 A CN 108409666A
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- 0 *c1c(*)c(C#N)cc(-[n]2c3ccccc3cc2-c2cccc(-c3cc(c4c(cc5)ccc(C6=CC7C=CC=CCC7C=C6)c4)c5cc3)c2)c1 Chemical compound *c1c(*)c(C#N)cc(-[n]2c3ccccc3cc2-c2cccc(-c3cc(c4c(cc5)ccc(C6=CC7C=CC=CCC7C=C6)c4)c5cc3)c2)c1 0.000 description 5
- MZBASJHBBLIDBH-UHFFFAOYSA-N Cc1ccccc1NCCN Chemical compound Cc1ccccc1NCCN MZBASJHBBLIDBH-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
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- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- 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
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- 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
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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- 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
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1011—Condensed systems
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
Abstract
The present invention relates to organic electroluminescence device technical field, more particularly to a kind of luminous organic material and its device application.The luminous organic material has structure shown in formula (I).The present invention provides a kind of completely new OLED material design schemes so that luminescent material has the function of TADF and light extraction function simultaneously in OLED device, and luminescent material is a kind of guest materials of hole transport and electron transport ability balance.Importantly, the material of the present invention does not contain the functional groups such as carbazole or triphenylamine, and the aromatic hydrocarbon for using electrochemical properties more stable is stated outside novel function as electron donating group, also improves the electrochemical stability of OLED material and device in realization.Material disclosed in this programme, acts not only as emitting layer material, is also used as hole mobile material, electron transport material or hole barrier materials or exciton-blocking material.
Description
Technical field
The present invention relates to organic electroluminescence device technical field, more particularly to a kind of luminous organic material and its device are answered
With.
Background technology
Organic electroluminescence device (OLED) comes into being as the flat panel display of a new generation and has progressed into people
The visual field, it is a kind of up-and-coming, novel flat-panel monitor.For example, the Galaxy series mobile phone of Samsung, S6 etc.
All it is OLED mobile phones.Apple Inc. will use OLED display screen configuration on its handset according to legend.
The structure of OLED is very simple at the beginning, is exactly anode/luminescent layer (with regard to a luminescent material) EML/ cathodes.In this way
Device architecture device performance it is excessively poor, for example, opening bright voltage needs 14V.This is because in general, luminescent material
HOMO and LUMO is very unmatched with anode or cathode, causes the difficulty of hole or electron injection, and therefore, opening bright voltage needs
Want very high.In addition, luminescent layer EML only has a kind of luminescent material, in electroluminescent process, luminous exciton concentration it is very high and
Cause exciton to quench, causes luminous efficiency very low.
For OLED is shown or illuminates application, such device architecture is that needs are improved, especially needs low open
Bright voltage, high-luminous-efficiency, high-quantum efficiency and long-life.
For this purpose, many device architectures are all suggested, device architecture that is relatively common and approving uses multilayered structure and host and guest
Both technological means of body doping system.For example, the basic device structure of present OLED is that anode/hole injection layer HIL/ is empty
Cave transport layer HTL/EML luminescent layers (host-guest system system)/ETL electron transfer layers/electron injecting layer EIL/ cathodes.
In such devices, each functional layer is responsible for single function, and the performance of OLED is caused to be greatly improved.
For example, HIL is hole injection, energy barrier between anode and HTL hole transmission layers is reduced, bright voltage is opened in reduction；EIL is that electronics is being noted
Enter layer, reduces the energy barrier between cathode and ETL electron transfer layers, be allowed to more match.EML uses host-guest system system, from
It anode injected holes and carries out on material of main part being compounded to form triplet state and singlet exciton from cathode injected electrons, this
Sample exciton is retransferred to the triplet state or singlet of guest materials, after the triplet state or singlet of guest materials obtain energy,
Due to unstable, light radiation is needed to carry out de excitation hair and shine.Such multilayer device structure, significantly improves OLED
Energy.
Exciton concentration quenching is to reduce a key factor of OLED device performance in luminescent layer, and exciton quenches type
Mainly by tri- kinds of STA, TTA and TPA.TTA is exactly triplet-triplet annihilation, and TPA is exactly triplet-
Polar annihilation, STA are exactly singlet-triplet annihilation.TTA and TPA occur mainly in phosphorus
In light OLED device.STA is occurred mainly in fluorescence OLED device.
But no matter phosphorescent OLED or fluorescence OLED, exciton density excessive (doping concentration is excessively high) frequently can lead to above-mentioned existing
As occurring, but if doping concentration reduces, the energy transmission between Subjective and Objective will be incomplete, and device efficiency can also reduce.
In order to further increase the luminous efficiency of OLED device, technical staff needs to extract using light outside OLED device
Technology, exactly extracts device exterior as far as possible by the light inside OLED device, and this technology generally requires device exterior system
Make or be bonded scattering layer scattering layer or micro-lens arrays, this can increase OLED complex manufacturing technology degree
With increase cost of manufacture.
In the semiconductors, if an electronics is gone on from full valence to empty conduction band, one is generated in valence band
A hole, and an electronics is generated in conduction band, to form an electron-hole pair.Hole is positively charged, and an electron is negatively charged,
Coulomb adelphotaxy between them can be such that they are spatially bound together under certain conditions, be formed in this way
Combination is known as exciton.Exciton is the electrons and holes pair being bound together each other.When electrons and holes are respectively from anode and the moon
It after the injection of pole, is moved towards other side under electric field action, close to each other under the action of Coulomb attractions, a portion electricity
Son and hole finally mutually capture and form exciton.
Energy transfer can be happened between molecule, can also be happened at intramolecule.Energy between molecule is turned
For shifting, it, either energy transfer between identical molecule, can also be the energy transfer between different molecular.From property
For upper, energy transfer is divided into radiative transfer and nonradiative transfer two major classes.
The first kind is radiation energy transfer, for example, the radiation energy transfer between a donor D and a receptor A, it can
To be expressed as：
D*→D+hv,hv+A→A*
The characteristics of this radiation energy transfer is：Receptor A absorptions in ground state are emitted in excitation state donor D*
A photon and be excited, this energy transfer is not related to being in direct contact for donor D and receptor A, and distance can be in 5-10nm.It grinds
Study carefully the transmitting quantum efficiency, receptor A that show the probability of this energy transfer and excitation state donor D* concentration absorption coefficient and
The emission spectrum of D* is related with the overlapping of the absorption spectrum of A.
Different from radiation energy transfer, radiationless energy transfer process is an a one-step process：D*+A → D+A*, this will
It asks the energy of D* → D and A* → A identical, and requires spin conservation, but this point is not stringent.Radiationless energy transfer
Process is dominated by different mechanism, such as coulomb transfer mechanism (also referred to as Forster mechanism) and exchange transfer mechanism
(Dexter mechanism).
Forster energy transfers (FET, Forster energy transfer).When Forster energy transfers occur, light
Son is sent out from a molecule (donor D) in excitation state, and the molecule (receptor A) that ground state is in by another absorbs, therefore,
Its odds is proportional to the overlapping degree of the fluorescence spectrum of donor molecule and the absorption spectrum of acceptor molecule.But with it is logical
The transmitting and absorption process difference, Forster energy here for being often happened at the photon between two molecules independent of each other turn
It moves mainly due to existing dipolar interaction between donor and receptor and makes its odds much greater, and is strong
Ground depends on the distance between donor and acceptor molecule, moreover, the de excitation hair of donor and being excited for receptor are simultaneous.
The rate of Forster energy transfers is：
Here FD(w) it is the normalized fluorescence spectrum of donor；σ A (w) are the absorption cross-section of receptor；τ D excite for donor
The natural life-span of state；R is the distance between donor and receptor, and nD is the dielectric constant of system；ω is the angular frequency of light.In order to carry
The efficiency of high Organic Light Emitting Diode is typically employed in material of main part and adulterates the mode of guest materials to obtain required wave band
High efficiency fluorescence.
Unlike FET, Dexter energy turns Dexter energy transfers (DET, Dexter Energy transfer)
The mode for not leaning on dipolar coupling is moved, with the direct transfer energy of carrier.When one in excitation state molecule and
Another molecule for being in ground state is within close proximity, so that when electron cloud overlaps each other, on the molecule in excitation state
Electrons and holes can directly migrate to that and be on the neighboring molecule of ground state, and energy is completed while completing carrier mobility
The transfer of amount.Forster energy transfers can realize in larger distance due to being acted on by the coulomb of charge, generally can be with
Reach tens angstroms, and for Dexter energy transfers, due to needing the overlapping of electron cloud, can only adjacent molecule it
Between could complete, it is intermolecular maximum spacing can only at most arrive several angstroms.It is similar with Forster energy transfers, Dexter energy occurs
Overlapping degree of the rate also proportional to the luminescent spectrum of donor molecule and the absorption spectrum of acceptor molecule of transfer is measured, i.e.,
K is one related with the overlapping situation of molecule.
It is generally believed that the singlet of main body is to the triplet state of energy transmission and main body between the singlet of object to object
The energy transmission of the singlet exciton of material is all FET type；The triplet state of material of main part is to guest materials triplet excitons
Energy transmission is DET.
In traditional TADF OLED device, material of main part and an object TADF material containing there are one, but due to TADF
The scattering direction of photon is random direction, and only the light perpendicular to ito substrate direction has an opportunity to escape out device exterior, other
The photon in direction quenches the waveguide mode in device inside by multiple reflections.In order to improve the luminous efficiency of OLED device, pass
Way of uniting is exactly that one layer of light spe membrane will be attached outside OLED device, and this way not only increases production cost, but also does not have
Have substantive close to the low problem of OLED external light emission efficiencies.Importantly, current TADF designs are required for using click
Azoles or this kind of C-N singly-bounds that contain of triphenylamine are as pushing away electronics organo-functional group, and this kind of functional group is in long-term ignition
It is easy to happen aging scission of link, leads to OLED device performance rapid degradation.
One of the easy aging of OLED device is primarily due to carrier imbalance in device and causes part small molecule
Material is easy occur chemical scission of link in long-term ignition, causes device performance rapid degradation.Typical hole mobile material
All it is the direct organo-functional group containing carbazole or fluorine-triphenylamine structure, and electron transport material is typically all to have containing electrophilic
Machine functional group.It is generally believed that the C-N keys in hole mobile material in carbazole or triphenylamine are being easily in ageing process break key
, for example, either containing in carbazole or the molecule of the organo-functional group of fluorine-triphenylamine structure or cation or anionic particles, it
C-N singly-bounds all easily scission of links, need minimum energy that can be broken, which results in OLED device hole-transporting layer or
Material of main part or luminescent material easily deteriorate in long-term ignition.
In order to improve OLED carrier balances or promoted OLED luminous efficiencies, the bipolarity OLED material proposed in recent years or
TADF (heat lag fluorescent material) scheme.However, general bipolarity OLED material, is more or less required for using above-mentioned
Carbazole or triphenylamine organo-functional group are unfavorable for OLED life-span upgradings using these bipolarity OLED materials, this is also resulted in
OLED material designs and the difficulty of selection.In addition, TADF design of material many at present, will reach HOMO-LUMO separation
Purpose just has to use the organo-functional group for containing carbazole or triphenylamine or the key containing C-N as transporting holes or formation
The organic group of HOMO, however, these groups are easy to cause follow-up OLED device aging.Finally, OLED device, in order to improve
The light-out effect of device is required for using light abstraction technique, i.e., attaches light fiber material in device exterior, this also increases
OLED production costs.
Invention content
The purpose of the present invention is to provide a kind of completely new luminous organic materials, especially a kind of material applied to OLED
Material.The material makes luminescent material in OLED device while having the function of TADF and light extraction function, and does not contain carbazole or three
The functional groups such as aniline.
The another object that this hair is is to provide a kind of above-mentioned material in Organic Light Emitting Diode, OPV, OFT or QLED etc.
Application in field.
In order to solve the above technical problems, embodiments of the present invention provide a kind of luminous organic material, it has formula (I)
Shown in structure,
Wherein,
Y1、Y2、Y4、Y5、Y6、Y7、Y11、Y12、Y13、Y14It is separately covalent bond, CH or Si,
Y3、Y8、Y10Or Y15It is separately C or Si,
Z1, Z2 or Z3 respectively constitute the hexatomic ring or five-membered ring of thick sum；
A1、A2Or A3Separately it is selected from H, C1-6Alkyl, substituted or non-substituted phenyl, substituted or non-substituted phenanthrene
It is one or more in base, substituted or non-substituted naphthalene, formula (i) group, formula (ii) group or formula (iii) group, substitution
Base is selected from：C1-6It is one or more in alkyl, phenyl, naphthalene or phenanthryl；Or A3With Y1And Y2Collectively form formula (iv) base
Group；
The integer that n or r is 1~3, the integer that m is 1~2；
Formula (i), formula (ii), formula (iii) and formula (iv) group are respectively provided with such as lower structure：
R1、R2Or R3It is separately one or more in hydrogen, cyano；
R4Or R5It is separately one or more in hydrogen, cyano, phenyl；
O, p, q are separately selected from 1~4 integer；
K1Or K2N or B atoms are separately selected from,
C1、C2、C3、C4、C5The thick sum for containing or not contain hetero atom Si or O is collectively formed with the annular atom being attached thereto
Hexatomic ring or five-membered ring；
N1、N2、N3、N4The six of the thick sum for containing or not contain hetero atom Si or O are collectively formed with the annular atom being attached thereto
Membered ring or five-membered ring；
M1、M2、M3、M4The six of the thick sum for containing or not contain hetero atom Si or O are collectively formed with the annular atom being attached thereto
Membered ring or five-membered ring；
M1、M2、M5、M6、M7And M8Collectively form the thick sum for containing or not contain hetero atom Si or O hexatomic ring or five yuan
Ring；
M3、M4、M9、M10、M11And M12Collectively form the thick sum for containing or not contain hetero atom Si or O hexatomic ring or five yuan
Ring；
Also, at least contain one kind in formula (i), formula (ii), formula (iii) and formula (iv) group in formula (I).
In formula (I) of the present invention, A1、A2Or A3It is a kind of electron attractive functional group, LUMO is distributed in A1、A2Or A3On, and HOMO
It is distributed in and removes A1、A2Or A3Outer part.
In a kind of preferred embodiment, Y1、Y2、Y4、Y5、Y6、Y7、Y11、Y12、Y13、Y14It is separately covalent bond or CH,
And Y3、Y8、Y10Or Y15It is separately C.
In another preferred embodiment, Y1、Y2、Y4、Y5、Y6、Y7、Y11、Y12、Y13Or Y14It is separately CH, Y3、
Y8、Y10Or Y15It is separately C；Correspondingly, formula (I) is
In a kind of preferred embodiment, A1、A2Or A3Separately it is selected from H, C1-6Alkyl, Formula (i) group, formula
(ii) the one or more or A in group or formula (iii) group3With Y1And Y2Collectively form formula (iv) group；Wherein R4、
R5、R6、R7、R8、R9It is hydrogen, C1-6It is one or more in alkyl, phenyl or naphthyl.
In a kind of preferred scheme, A1Selected from H,
It is one or more in formula (i) group, formula (ii) group or formula (iii) group.
In a kind of preferred scheme, A2Selected from H, C1-6Alkyl, It is one or more in formula (i) group, formula (ii) group or formula (iii) group.
In a kind of preferred scheme, A3Selected from H or A3With Y1And Y2Collectively form formula (iv) group.
C in the present invention1-6Alkyl includes but not limited to methyl, ethyl, n-propyl, isopropyl, normal-butyl, tertiary butyl, just
Amyl etc..
In a kind of preferred embodiment, formula (i), formula (ii), formula (iii) and formula (iv) group are respectively provided with such as lower structure：
In a kind of preferred embodiment, R1、R2Or R3It is separately one or more in hydrogen, cyano；The R4Or
R5It is separately one or more in hydrogen, cyano, phenyl；O, p, q are separately selected from 1~3 integer.
It needs at least to contain one kind in formula (i), formula (ii), formula (iii) and formula (iv) group in the formula (I) of the present invention, into
One step, one kind in formula (i), formula (ii), formula (iii) group is at least contained in formula (I).
The luminous organic material of the present invention specifically can be selected from following compounds：
Above-mentioned each luminous organic material provided by the present invention can be applicable to Organic Light Emitting Diode, organic photovoltaic battery
(OPV), in Organic Thin Film Transistors (OFT) or the field quantum dot diode (QLED).
The present invention provides a kind of Organic Light Emitting Diodes, it contains above-mentioned luminous organic material.The present invention's is organic
Luminescent material can be applied in luminescent layer, hole transmission layer or electron transfer layer.
The present invention provides a kind of completely new OLED material design schemes so that luminescent material has simultaneously in OLED device
TADF functions and light extract function, and luminescent material is a kind of guest materials of hole transport and electron transport ability balance.More
Importantly, the material of the present invention does not contain the functional groups such as carbazole or triphenylamine, and using the more stable virtue of electrochemical properties
Fragrant hydrocarbon is stated as electron donating group outside novel function in realization, also improves the electrochemically stable of OLED material and device
Property.Material disclosed in this programme acts not only as emitting layer material (for example, luminescent material or material of main part), can also make
For hole mobile material, electron transport material or hole barrier materials or exciton-blocking material.
Description of the drawings
Fig. 1 is the current density ＆ brightness ＆ voltage patterns of device 3；
Fig. 2 is the current efficiency ＆ external quantum efficiency ＆ voltage patterns of device 3；
Fig. 3 is the current density ＆ brightness ＆ voltage patterns of device R 2；
Fig. 4 is the current efficiency ＆ external quantum efficiency ＆ voltage patterns of device R 2.
Specific implementation mode
The preparation method of disclosed compound of present invention provided below.But present disclosure is not intended to be limited to institute herein
The method of narration it is any.Those skilled in the art can easily change described method or utilize different sides
Method prepares the one or more of disclosed compound.Following aspect is merely exemplary, and is not intended to limit in the disclosure
The range of appearance.Temperature, catalyst, concentration, reactant composition and other process conditions are changeable, and for desiredization
Object is closed, present disclosure those skilled in the art can be readily selected suitable reactant and condition.
In CDCl on Varian Liquid State NMR instruments3Or with 400MHZ record 1H figures in DMSO-d6 solution
Spectrum, is noted down with 100MHZ13C NMR spectras, chemical shift is with reference to remaining deuterated (protiated) solvent.If CDCl3 is used as
Solvent then uses tetramethylsilane (δ=0.00ppm) to note down 1H NMR spectras as internal standard；Using DMSO-d6 (δ=
77.00ppm) internal standard is used as to note down13C NMR spectras.If by H2O (δ=3.33ppm) is used as solvent, then uses remaining H2O
(δ=3.33PPM) notes down 1H NMR spectras as internal standard；It is noted down as internal standard using DMSO-d6 (δ=39.52ppm)13C NMR
Collection of illustrative plates.The multiplicity of 1H NMR is explained using following abbreviations (or combinations thereof)：S=substances, D=is dual, and T=is triple, Q=tetra-
Weight, five weights of P=, M=is multiple, BR=wide.
General synthetic routes
The part of compounds of the present invention can be synthesized by the following general formula.
Synthesize general formula 1
Synthesize general formula 2
The synthesis of compound
(1) PET-BICN-1 material numbers L1
It is put into 3- bromo phenanthrenes in there-necked flask, 4- (1- (4- cyano substituted benzene) -1-H- benzos [d] imidazoles -2-) phenyl boric acid,
Solvent 50ml installs mechanical agitation stick, is passed through nitrogen 10min, and catalyst PdCl is added under the protection of nitrogen2(dppf)
0.25mol%-3mol%, 2M aqueous slkali 0.018mol, are heated to reflux, and react 5-7 hours.It is filtered after reaction, toluene is washed, ethyl alcohol
It washes.The powder of 99% or more purity, product yield 75% are obtained after dimethylbenzene recrystallization.
Using CDCl3As solvent, tetramethylsilane (δ=0.00ppm) notes down 1H NMR spectras as internal standard.
1H NMR(400MHZ,DMSO-d6)：
7.26ppm(2H,p),7.40ppm(2H,d),7.50-7.54ppm(6H,t),7.70-7.71ppm(4H,p),
7.82-7.88ppm(2H,m),8.04 ppm(1H,d),8.12ppm(1H,d),8.18ppm(1H,d),8.93ppm(1H,d),
9.15ppm(1H,s)。
(2) PET-BICN-2 material numbers L2
3- bromo phenanthrenes, 4- (1- cyano substituted benzene -1-H- benzimidazolyl-2 radicals -) phenyl boric acid, solvent are put into there-necked flask
50ml installs mechanical agitation stick, is passed through nitrogen 10min, and catalyst PdCl is added under the protection of nitrogen2(dppf)
0.25mol%-3mol%, 2M aqueous slkali 0.018mol, are heated to reflux, and react 5-7 hours.It is filtered after reaction, toluene is washed, second
Alcohol is washed.The powder of 99% or more purity, product yield 71% are obtained after dimethylbenzene recrystallization.
Using CDCl3As solvent, tetramethylsilane (δ=0.00ppm) notes down 1H NMR spectras as internal standard.
1H NMR(400MHZ,DMSO-d6)：
7.40ppm(2H,d),7.50-7.54ppm(6H,t),7.71ppm(2H,s),7.82-7.88ppm(6H,m),
8.04ppm(1H,s),8.12ppm( 3H,d),8.18ppm(1H,d),8.93ppm(3H,d),9.15ppm(1H,s)。
(3) PET-BICN-3 material numbers L3
It is put into 3- bromo phenanthrenes in there-necked flask, 4- (1- (3,5- dicyanobenzenes) -1-H- benzos [d] imidazoles -2-) phenyl boric acid,
Solvent 50ml installs mechanical agitation stick, is passed through nitrogen 10min, and catalyst PdCl2 (dppf) is added under the protection of nitrogen
0.25mol%-3mol%, 2M aqueous slkali 0.018mol, are heated to reflux, and react 5-7 hours.It is filtered after reaction, toluene is washed, ethyl alcohol
It washes.The powder of 99% or more purity, product yield 69% are obtained after dimethylbenzene recrystallization.
Using CDCl3As solvent, tetramethylsilane (δ=0.00ppm) notes down 1H NMR spectras as internal standard.
1H NMR(400MHZ,DMSO-d6)：
7.26ppm(2H,p),7.54ppm(4H,s),7.70-7.71ppm(4H,p),7.80-7.88ppm(5H,m),
8.04ppm(1H,s),8.12ppm( 1H,d),8.18ppm(1H,d),8.93ppm(1H,d),9.15ppm(1H,s)。
(4) PET-BICN-4 material numbers L4
3- bromo phenanthrenes, 4- (1- (2,4,6- tricyano benzene) -1-H- benzos [d] imidazoles -2-) benzene boron are put into there-necked flask
Acid, solvent 50ml install mechanical agitation stick, are passed through nitrogen 10min, and catalyst PdCl is added under the protection of nitrogen2
(dppf) 0.25mol%-3mol%, 2M aqueous slkali 0.018mol, are heated to reflux, and react 5-7 hours.It is filtered after reaction, toluene
It washes, ethyl alcohol is washed.The powder of 99% or more purity, product yield 66% are obtained after dimethylbenzene recrystallization.
Using CDCl3As solvent, tetramethylsilane (δ=0.00ppm) notes down 1H NMR spectras as internal standard.
1H NMR(400MHZ,DMSO-d6)：
7.26ppm(2H,p),7.54ppm(4H,s),7.70-7.71ppm(4H,p),7.80-7.88ppm(5H,m),
8.04ppm(1H,s),8.12ppm( 1H,d),8.18ppm(1H,d),8.93ppm(1H,d),9.15ppm(1H,s)。
(5) PET-BICN-5 material numbers L5
3- bromo phenanthrenes, 4- (1- (2,4,6- tricyano benzene) -1-H- phenanthro-s [d] imidazoles -2-) benzene boron are put into there-necked flask
Acid, solvent 50ml install mechanical agitation stick, are passed through nitrogen 10min, and catalyst PdCl is added under the protection of nitrogen2
(dppf) 0.25mol%-3mol%, 2M aqueous slkali 0.018mol, are heated to reflux, and react 5-7 hours.It is filtered after reaction, toluene
It washes, ethyl alcohol is washed.The powder of 99% or more purity, product yield 56% are obtained after dimethylbenzene recrystallization.
Using CDC l3As solvent, tetramethylsilane (δ=0.00ppm) notes down 1H NMR spectras as internal standard.
1H NMR(400MHZ,DMSO-d6)：
7.54ppm(4H,s),7.71ppm(2H,s),7.82-7.88ppm(6H,m),8.0-8.04ppm(3H,t),
8.12ppm(3H,d),8.18ppm(1 H,d),8.93ppm(3H,d),9.15ppm(1H,s)。
(6) PET-BICN-6 material numbers L6
3,6-, bis- bromo phenanthrenes, 4- (1- (2,4,6- tricyano benzene) -1-H- phenanthro-s [d] imidazoles -2-) are put into there-necked flask
Phenyl boric acid, solvent 50ml install mechanical agitation stick, are passed through nitrogen 10min, and catalyst PdCl is added under the protection of nitrogen2
(dppf) 0.25mol%-3mol%, 2M aqueous slkali 0.018mol, are heated to reflux, and react 5-7 hours.It is filtered after reaction, toluene
It washes, ethyl alcohol is washed.The powder of 99% or more purity, product yield 61% are obtained after dimethylbenzene recrystallization.
Using CDCl3As solvent, tetramethylsilane (δ=0.00ppm) notes down 1H NMR spectras as internal standard.
1H NMR(400MHZ,DMSO-d6)：
7.54ppm(8H,s),7.71ppm(2H,s),7.82-7.88ppm(8H,m),8.0-8.04ppm(6H,t),
8.12ppm(4H,d),8.18ppm(2 H,d),8.93ppm(4H,d),9.15ppm(2H,s)。
(7) PET-BICN-7 material numbers L7
3,6-, bis- bromo phenanthrenes, 4- (1- (2,4,6- tricyano benzene) -1-H- phenanthro-s [d] imidazoles -2-) are put into there-necked flask
Phenyl boric acid, solvent 50ml install mechanical agitation stick, are passed through nitrogen 10min, and catalyst PdCl is added under the protection of nitrogen2
(dppf) 0.25mol%-3mol%, 2M aqueous slkali 0.018mol, are heated to reflux, and react 5-7 hours.It is filtered after reaction, toluene
It washes, ethyl alcohol is washed.The powder of 99% or more purity, product yield 65% are obtained after dimethylbenzene recrystallization.
Using CDCl3As solvent, tetramethylsilane (δ=0.00ppm) notes down 1H NMR spectras as internal standard.
1H NMR(400MHZ,DMSO-d6)：
7.26ppm(4H,p),7.54ppm(8H,s),7.70-7.71ppm(6H,q),8.0-8.04ppm(6H,t),
8.18ppm(2H,d),9.15ppm(2 H,s)。
(8) PET-BICN-8 material numbers L8
It is put into the bromo- 6- phenyl-phenanthrene of 3- in there-necked flask, 4- (1- cyano substituted benzene -1-H- benzimidazolyl-2 radicals -) phenyl boric acid,
Solvent 50ml installs mechanical agitation stick, is passed through nitrogen 10min, and catalyst PdCl is added under the protection of nitrogen2(dppf)
0.25mol%-3mol%, 2M aqueous slkali 0.018mol, are heated to reflux, and react 5-7 hours.It is filtered after reaction, toluene is washed, ethyl alcohol
It washes.The powder of 99% or more purity, product yield 73% are obtained after dimethylbenzene recrystallization.
Using CDCl3As solvent, tetramethylsilane (δ=0.00ppm) notes down 1H NMR spectras as internal standard.
1H NMR(400MHZ,DMSO-d6)：
7.22ppm(1H,t),7.32ppm(2H,t),7.40-7.54ppm(10H,m),7.71ppm(2H,s),7.82-
7.88ppm(4H,m),8.04pp m(2H,d),8.12ppm(2H,d),8.18ppm(2H,d),8.93ppm(2H,d),
9.15ppm(2H,s)。
Optical physics information：
When studying the electronic structure of fluorescent small molecule compound, influences each other and be very important between electronics, density is general
Letter theory (DFT) has been widely used for studying pi-conjugated system, and the result of the compound using the DFT method research disclosure
It is more more accurate than other methods.To the geometry under the ground state for the compound molecule studied, cation state and cloudy particle state
The optimization of structure, using the method for DFT//B3LYP/6-31G (d), the trip lake geometry of the excitation state of these compounds uses
What the method for DFT//B3LYP/6-31G (d) obtained.It is general using density containing when on the basis of ground state and excitation state geometry
Letter theory (TDDFT) method calculates the Absorption and emission spectra of these compounds.By above-mentioned computational methods, can obtain
The various properties of studied compound, including ionization energy IP, electron affinity EA, Reorganization Energy λ, highest occupied molecular orbital HOMO, most
It is low to occupy track LUMO, energy gap Eg.
For organic luminescent device, injects to hole and electronics energy active balance and transmission is very important.Molecule
Ionization energy and electron affinity be injectability for assessing hole and electronics respectively.Following table, which lists, to be calculated
The vertical and Adiabatic ionization potential of studied compound, vertical and Adiabatic electron affinity, energy is extracted in hole and electronics extracts energy.It hangs down
Straight ionization energy IP (v) refers to the energy difference of cation and molecule under neutral molecule geometric configuration；Adiabatic ionization potential IP (A) is
Refer to the energy difference under neutral and cationic geometric configuration；It refers to molecule and sun under cationic geometric configuration that energy HEP is extracted in hole
The energy difference of ion；Vertical electron affinity EA (v) refers to the energy difference under neutral and anion geometric configuration；Electronics extracts
Energy EEP refers to the energy difference of molecule and anion under anion geometric configuration.Generally for, small molecule luminous organic material,
Ionization energy is smaller, and the injection in hole is easier；And electron affinity is bigger, the injection of electronics is easier.
Usually, in terms of microcosmic angle, the transporting mechanism of charge can be described as from the process transmitted in organic film.Its
In, an electronics or hole are transferred to from a having electronic molecule on adjacent neutral molecule.It is theoretical according to Marcus, charge
Mobility can be expressed as：
Wherein, T represents temperature；V represents pre-exponential factor, is the Coupling matrix element between two kinds of particles；λ is Reorganization Energy；Kb
It is Boltzmann constant.Obviously, λ and V is to determine KetAn important factor for value.Usually, under amorphous state charge transfer range
It is limited, V values vary less.So the speed of mobility is mainly determined by the λ on index.λ is smaller, transmission speed
Rate is faster.In order to study conveniently, the influence of external environment can be ignored, what is mainly discussed is reorganization energy.
It is derived according to calculating, reorganization energy may finally be expressed as：
λhole=IP (v)-HEP
λelectron=EEP-EA (v)
The compound L 1-L10HOMO energy levels, the LUMO energy that are prepared in the specific embodiment of the invention are calculated in method as above
Grade, the Cloud Distribution and S1 energy levels and PL spectrum main peaks of HOMO and LUMO：
According to above-mentioned result of calculation, the advantages of the technical solution of the disclosure, being can be according to the practical need of OLED device
It asks, the HOMO/LUMO/S1 of entire molecule can be adjusted in turn by adjusting the type of the luxuriant and rich with fragrance substituent group in molecular structure and obtains
Preferable hole/electron injection ability/level-density parameter.For example, the HOMO=5.70eV of L1, LUMO=1.83eV, S1=
3.43eV is conducive to stop hole, but is unfavorable for electron injection, and S1 energy levels are too high, by replacing L1 China and Philippines progress phenyl
After forming L14 molecules so that the LUMO of L14 pulls down to LUMO=3.03eV, S1=2.55eV, does not influence HOMO not only in this way
Energy level (be conducive to stop hole jump), and make the LUMO of L14 facilitate electron injection (energy level with electron transfer layer more preferably
Matching), meanwhile, S1=2.55eV is conducive to obtain more preferably stable luminous organic material property.
The second advantage of disclosed technique, being can be by adjusting cyano on the imidazoles in molecular structure on A groups
Quantity and position and then adjust the HOMO/LUMO/S1 energy levels of ideal molecule.For example, by by 4- cyano benzene on L1 imidazoles
After being adjusted to the L3 MOLECULE DESIGNs of 3, the 5- dicyanobenzenes of L3 molecules, HOMO is kept approximately constant, and LUMO is by the 1.83eV of L1
It is reduced to the 2.34eV of L3, S1 is reduced to 3.03eV by the 3.43eV of L1, is conducive to the hole for keeping luminous organic material in this way
While blocking capability, electron injection and spectrum is facilitated to adjust.
The third advantage of disclosed technique, be can very simple MOLECULE DESIGN so that the disclosure material
Reach the bipolar nature of hole/electron-transport balance.It is described in detail below for the L1-L3 in disclosed compound
The technological merit that the technical program is brought.
By calculating the HOMO=5.74eV it is found that L1 molecules, relatively convenient is injected in hole, LUMO=1.83eV, electronics
It is a little to inject relative difficulty.HOMO, which is distributed mainly on luxuriant and rich with fragrance organo-functional group, benzimidazole and is directly connected to benzimidazole and phenanthrene, to be had
On the phenyl ring of machine functional group, LUMO is mainly distributed on 4- cyano benzene and is directly connected to the benzene of benzimidazole and luxuriant and rich with fragrance organo-functional group
On ring, such design effect, you can to ensure that L1 molecules have smaller Δ EST, and ensure that HOMO-LUMO has centainly
Electron exchange energy.That is, L1 molecules have most suitable TADF characteristics, while it is suitable to also ensure that L1 molecules have
Kr values.
The HOMO of L2 molecules and L3 molecules is free on the organo-functional group other than the phenyl ring that cyano replaces, and LUMO is free
On the phenyl ring of cyano substitution and/or part is free on imidazoles.
From the hole recombination of calculating can and electron recombination can judge, for L1 molecules：[hole recombination energy λ h- electronics weights
Group energy λ e]≤0.03eV, therefore, L1 molecules are bipolarity luminous organic material, i.e. cavity transmission ability in a complete meaning
It is extremely matched with electron transport ability.Such molecule benefit is the hole/electronic carrier for being conducive to balance OLED device
Transmission balance, to improve OLED luminous efficiencies and service life.
For L2 molecules：[electron recombination energy λ e- hole recombination energy λ h]0.03eV, therefore, L2 are an electron-transport energy
Bipolar materials of the power less times greater than hole transport.
For L3 molecules：[hole recombination energy λ h- electron recombination energy λ e]0.03eV, therefore, L3 molecules are hole transport energy
Power is slightly better than the bipolarity luminous organic material of electron transport ability.
The cavity transmission ability of L1 molecules is slightly better than electron transport ability, be one is closely ambipolar organic light emission material
Material.
Element manufacturing
Ito substrate is the bottom emitting glass of 30mm*30mm sizes, and there are four light-emitting zone, the areas light-emitting area AA are 2mm*
The light transmittance of 2mm, ito thin film are 90%@550nm, surface roughness Ra<1nm, ito film thickness are 1300A, and resistance per square is 10 Europe
Every square of nurse.
The cleaning way of ito substrate is first placed in the container for filling acetone soln, which is positioned over super
Sound wave cleaning machine is cleaned by ultrasonic, and scavenging period is 30 minutes, mainly dissolves the organic matter for being attached to the surfaces ITO
With dispel；Then the ito substrate taking-up that cleaning finishes is placed on hot plate and carries out the baking half an hour of high temperature 120, mainly
Remove the organic solvent and steam on ito substrate surface；Then the ito substrate that baking finishes is quickly transferred to UV-ZONE equipment
The surfaces ITO are difficult to the organic matter eliminated or foreign matter further use plasma treatment by middle progress O3Plasma processing, when processing
Between be 15 minutes, the ITO being disposed will be quickly transferred in OLED evaporated devices film forming room.
Prepare before OLED vapor depositions：Clean processing is carried out to OLED evaporated devices first, wiping film forming room is carried out using IPA
Cavity inner wall ensures that entire film forming cavity does not have foreign matter or dust.Then, by crucible and dress equipped with OLED luminous organic materials
There is the crucible of metal aluminum shot to be placed sequentially on organic evaporating source and inorganic evaporation source position.Cavity is closed, just vacuumize
With pumping high vacuum step so that vapor deposition degree reaches 10E-7Torr. inside OLED evaporated devices
OLED evaporation film-formings：OLED organic evaporatings sources is opened, 100C preheatings are carried out to OLED luminous organic materials, when preheating
Between be 15 minutes, ensure further remove OLED luminous organic materials in steam.Then organic light emission material needs being deposited
Material carries out the heat treatment that is rapidly heated, and opens the baffle above evaporation source, until the evaporation source of the material has organic light emission material
Material is run out of, while when crystal-vibration-chip detector detects evaporation rate, is then slowly heated up, increasing extent of temperature 1-5C, until
Evaporation rate was stablized at 1A/ seconds, and the baffle immediately below mask plate plate is opened, and OLED film forming was carried out, when computer end observes ITO
When organic film on substrate reaches default film thickness, baffle right over mask plate baffle and evaporation source is closed, the organic light emission is closed
The evaporation source heater of material.The evaporation process of other luminous organic materials and cathodic metal material is as described above.
OLED encapsulates flow：The cleaning treatment mode of the cap of 20mm*20mm such as ito substrate pretreatment mode.Clear
The clean cap extension surrounding finished carries out the coating of UV glue materials or then the cap for having put UV glue materials is transferred to very by dispensing
It is vacuum abutted with the ito substrate progress of film forming OLED organic films in empty abutted equipment, then, it is transferred in UV solidification cavitys, makes
Photocuring is carried out with the ultraviolet light of 365nm wave bands.The ITO devices of photocuring, it is also necessary to the rear heat treatment of 80C half an hour is carried out,
So that UV glue materials are fully cured.
Organic light emitting diode device embodiment
Device embodiments 1
We construct the multilayer device structure of ITO/HIL/HTL/ luminescent layers/ETL/EIL/ cathodes.
In order to facilitate technical staff, understand that the technical advantage of the present invention and device principle, the present invention are only with simplest
Device architecture illustrates.
ITO/MoO3(10nm)/TAPC(55nm)/TCTA(8nm)/BCPO:L2/L34-8wt% (20nm)/DPEPO (8
nm)/TmPyPB(40nm)/LiF(1nm)/Al(100nm)
Wherein, using MoO3As hole injection layer, using TAPC/TCTA as hole transmission layer, using BCPO conducts
Material of main part, L2/L3 is as guest materials, using DPEPO/TmPyPB as electron transfer layer and hole barrier layer material,
LiF is as electron injecting layer material, and Al is as cathode.
The chemical structural formula of part luminous organic material is as follows：
| Material number | S1 | The peaks PL |
| L2 | 2.82 | 440 |
| L3 | 2.80 | 442 |
In order to compare the technical advantage of the present invention, a comparative device structure I TO/HIL/HTL/BCPO is designed：
4CZIPN/ETL/EIL/ cathodes (number R1).Comparative device R1 is a traditional TADF device architecture.
The partial properties of 1. device 1 of table and parametric device R1 compare
| Device number | Maximum external quantum efficiency EQE | Efficiency roll-off * |
| 1(L2) | 8.6% | 10% |
| 2(L3) | 9.5% | 8.3% |
| R1(4CZIPN) | 8.6% | 20.7% |
* efficiency roll-off, performance change rate when efficiency when this is defined herein as 0.1mA/cm2 is to 100mA/cm2.
As shown in Table 1, the performance of traditional TADF OLED device extracts TADF materials be not as novel as we with light
Device performance.This is because traditional TADF materials 4CZIPN (Δ EST<0.2eV) by T1 excitons during electroluminescent
Energy transfer can improve the luminous efficiency of OLED to S1, still, due to 4CZIPN formed photon direction be from all directions,
Only can effectively it be shown perpendicular to the light in ito substrate direction, and the light in other directions is largely all quenched in waveguide
In pattern.The control of molecular transition dipole moment is being parallel to substrate side by novel TADF materials, the flatness carried out using phenanthrene
To so that the photon direction during mulecular luminescence is perpendicular to ito substrate so that more photons can be from ito substrate method
It projects.
The exception one of the present invention is the advantage is that the novel TADF materials that phenanthrene-benzimidizole derivatives are constituted, hole pass
Defeated and electron-transport extremely balances, and therefore, is conducive to improve exciton balance in luminescent layer, reduces the efficiency roll-off of device.Finally,
Due to not containing the organo-functional group of the C-N keys such as carbazole or triphenylamine in material, the stability of device is very good.
Embodiment of the material of the technology of the disclosure illustrated below as ETL electron transfer layers.
Using L2 as illustrating：
ITO/MoO3(10nm)/TAPC(55nm)/TCTA(8nm)/BCPO:Deep blue light emitting material 8wt% (20nm)/
L2 (10nm)/TmPyPB (40nm)/LiF (1nm)/Al (100nm), device number 3.The current density ＆ brightness ＆ voltages of device 3
Figure figure is shown in that Fig. 1, the current efficiency ＆ external quantum efficiency ＆ voltage patterns of device 3 are shown in Fig. 2.
As a comparison case with DPEPO electron transport materials：
ITO/MoO3(10nm)/TAPC(55nm)/TCTA(8nm)/BCPO:Deep blue light emitting material 8wt% (20nm)/
DPEPO (8nm)/TmPyPB (40nm)/LiF (1nm)/Al (100nm), device number R2.The current density ＆ brightness ＆ of device R 2
Voltage pattern is shown in that Fig. 3, the current efficiency ＆ external quantum efficiency ＆ voltage patterns of device R 2 are shown in Fig. 4.
By the comparison of Fig. 1-4 it is found that the OLED device 3 using L2 as electron transport material：Device cut-in voltage about 2.9V,
(cut-in voltage brightness is 1cd/m2)；Device brightness under 9V driving voltages is about 2000cd/m2；Device maximum current efficiency and
Maximum external quantum efficiency is respectively 6cd/A, and 4.4%.
OLED device R2 using DPEPO as electron transport material：Device cut-in voltage about 2.9V, (brightness 1cd/
m2)；Device brightness under 9V driving voltages is about 1000cd/m2；Device maximum current efficiency and maximum external quantum efficiency are respectively
3.3cd/A, 2.5%；The efficiency of device R 2 is relatively low compared to device architecture 3；This is because making containing L2 molecules in device architecture 3
For a kind of bipolarity electron transport material of transmission electrons balance.And DPEPO is a kind of pure electron transport material, is caused
The hole of OLED device/electron-transport is uneven.
It will be understood by those skilled in the art that the respective embodiments described above are to realize specific embodiments of the present invention,
And in practical applications, can to it, various changes can be made in the form and details, without departing from the spirit and scope of the present invention.
Claims (10)
1. a kind of luminous organic material, which is characterized in that it has structure shown in formula (I),
Wherein,
Y1、Y2、Y4、Y5、Y6、Y7、Y11、Y12、Y13、Y14It is separately covalent bond, CH or Si,
Y3、Y8、Y10Or Y15It is separately C or Si,
Z1, Z2 or Z3 respectively constitute the hexatomic ring or five-membered ring of thick sum；
A1、A2Or A3Separately it is selected from H, C1-6Alkyl, substituted or non-substituted phenanthryl, takes substituted or non-substituted phenyl
It is one or more in generation or non-substituted naphthalene, formula (i) group, formula (ii) group or formula (iii) group, substituent group choosing
From：C1-6It is one or more in alkyl, phenyl, naphthalene or phenanthryl；Or A3With Y1And Y2Collectively form formula (iv) group；
The integer that n or r is 1~3, the integer that m is 1~2；
Formula (i), formula (ii), formula (iii) and formula (iv) group are respectively provided with such as lower structure：
R1、R2Or R3It is separately one or more in hydrogen, cyano；
R4Or R5It is separately one or more in hydrogen, cyano, phenyl；
O, p, q are separately selected from 1~4 integer；
K1Or K2N or B atoms are separately selected from,
C1、C2、C3、C4、C5The hexa-atomic of the thick sum for containing or not contain hetero atom Si or O is collectively formed with the annular atom being attached thereto
Ring or five-membered ring；
N1、N2、N3、N4The hexatomic ring for the thick sum for containing or not contain hetero atom Si or O is collectively formed with the annular atom being attached thereto
Or five-membered ring；
M1、M2、M3、M4The hexatomic ring for the thick sum for containing or not contain hetero atom Si or O is collectively formed with the annular atom being attached thereto
Or five-membered ring；
M1、M2、M5、M6、M7And M8Collectively form the hexatomic ring or five-membered ring of the thick sum for containing or not contain hetero atom Si or O；
M3、M4、M9、M10、M11And M12Collectively form the hexatomic ring or five-membered ring of the thick sum for containing or not contain hetero atom Si or O；
Also, at least contain one kind in formula (i), formula (ii), formula (iii) and formula (iv) group in formula (I).
2. luminous organic material according to claim 1, which is characterized in that the Y1、Y2、Y4、Y5、Y6、Y7、Y11、Y12、
Y13Or Y14It is separately CH, Y3、Y8、Y10Or Y15It is separately C.
3. luminous organic material according to claim 1, which is characterized in that the A1、A2Or A3Independently
Ground is selected from H, C1-6Alkyl, One or more or A in formula (i) group, formula (ii) group or formula (iii) group3With Y1And Y2Altogether
Same constitutional formula (iv) group；Wherein R4、R5、R6、R7、R8、R9It is hydrogen, C1-6It is one or more in alkyl, phenyl or naphthyl.
4. luminous organic material according to claim 1, which is characterized in that the formula (i), formula (ii), formula (iii) and formula
(iv) group is respectively provided with such as lower structure：
5. luminous organic material according to claim 4, which is characterized in that the R1、R2Or R3Separately it is selected from
It is one or more in hydrogen, cyano；The R4Or R5It is separately one or more in hydrogen, cyano, phenyl；o、p、q
Separately it is selected from 1~3 integer.
6. luminous organic material according to claim 1, which is characterized in that the luminous organic material is selected from following chemical combination
Object：
7. luminous organic material described in any one of claim 1 to 6 Organic Light Emitting Diode, organic photovoltaic battery,
Application in Organic Thin Film Transistors or quantum dot diode field.
8. a kind of Organic Light Emitting Diode, which is characterized in that contain the organic light emission described in any one of claim 1 to 6
Material.
9. Organic Light Emitting Diode according to claim 8, which is characterized in that the luminous organic material is for shining
Layer.
10. Organic Light Emitting Diode according to claim 8, which is characterized in that the luminous organic material is used for hole
Transport layer or electron transfer layer.
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Application publication date: 20180817 |