CN105482813B - Novel Fluorene class bipolarity fluorescent material based on anthraquinone radicals and its application in Organic Light Emitting Diode - Google Patents
Novel Fluorene class bipolarity fluorescent material based on anthraquinone radicals and its application in Organic Light Emitting Diode Download PDFInfo
- Publication number
- CN105482813B CN105482813B CN201510971202.5A CN201510971202A CN105482813B CN 105482813 B CN105482813 B CN 105482813B CN 201510971202 A CN201510971202 A CN 201510971202A CN 105482813 B CN105482813 B CN 105482813B
- Authority
- CN
- China
- Prior art keywords
- formula
- emitting diode
- organic light
- light emitting
- electron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C50/00—Quinones
- C07C50/16—Quinones the quinoid structure being part of a condensed ring system containing three rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present invention relates to Novel Fluorene class bipolarity fluorescent material of the one kind based on anthraquinone radicals and its applications in Organic Light Emitting Diode；Such material is as shown in Equation 1 with D π A types or A π A type Intramolecular electron transfer structures, general structure；Material shown in the formula 1 has bipolarity carrier transport property, organic light-emitting diode using its preparation is functional, and the synthesis of material and purification operations are easy, and yield is high, is the ideal chose as yellow light in Organic Light Emitting Diode to red light material；It is contemplated that this kind of material can become the electroluminescent organic material with some commercial potential.
Description
Technical field
The present invention relates to Novel Fluorene class bipolarity fluorescent material of the one kind based on anthraquinone radicals preparation method and its having
Application in machine light emitting diode belongs to organic electroluminescence device field.
Background technology
Organic electroluminescent LED (OLED) is due to driving voltage is low, fast response time, low in energy consumption, contrast is high
With visual angle it is wide the advantages that, had received widespread attention in flat display field；In recent years, OLED is more believed to realize flexible flat
Plate is shown, is current opto-electronic device and flat display field so as to become the developing direction of solid-state lighting light source of new generation
In most one of technology of attraction.But OLED is during industrialization is realized, however it remains yield rate is not high, shines
The problems such as efficiency is undesirable and stability is bad.
Electroluminescent organic material be determine OLED performances it is fine or not an important factor for one of, lot of domestic and international research institution and
Enterprise constantly researches and develops the luminescent material of new excellent combination property, to improve the luminous efficiency of OLED and stability.
Luminescent material species used is various in OLED, and choice is big, and its performance can also be optimized by MOLECULE DESIGN.Its
In, compound of fluorene class has the features such as preferable photo and thermal stability, higher fluorescence quantum efficiency and wide band gap and receives much attention.
But the electron affinity of such compound is relatively low, electronics is not easy to inject to it, and the injection and transmission of hole and electronics are uneven
Weighing apparatus.Luminous due to OLED is the exciton radiation transistion of composition generation of being met by injected holes in organic luminous layer and electronics
It generates, the balanced injection and transmission of the two are the key that improve OLED device luminous efficiency.So compound of fluorene class itself hole
Injection-transmittability difference with electronics can influence the performance of its OLED performance.
Strong electron-withdrawing group group is introduced into fluorenes unit, electron injection barrier is reduced, to improve the electronics of compound of fluorene class
Injection and transmission performance, are a kind of effective means for solving its hole and electron injection transmittability difference problem at present.Recently,
Adachi etc. has synthesized a series of organic fluorescences with D- π-A- π-D type Intramolecular electron transfer structures based on anthraquinone radicals
Material, and prepared high efficiency OLED device using them.Wherein, anthraquinone is as a kind of strong electron-withdrawing group group, have compared with
High electron affinity is conducive to the injection of electronics, to the balance of carrier in the above-mentioned organic fluorescent compounds haveing excellent performance
Play key effect.
The content of the invention
Technical problem：The object of the present invention is to provide Novel Fluorene class bipolarity fluorescent material of the one kind based on anthraquinone radicals and
Its application in Organic Light Emitting Diode.
Technical scheme is as follows：Anthraquinone radicals is introduced into compound of fluorene class by design, improves the injection of its electronics
With transmittability, a kind of Novel Fluorene class bipolarity fluorescent material based on anthraquinone radicals is obtained, and it is good using it to prepare performance
Good OLED device.
Above-mentioned material provided by the present invention has D- π-A types or A- π-A type Intramolecular electron transfer structures.Ladder type
Oligomerization fluorenes is in centre as pi-electron conjugated bridge, and one side is connected with electron acceptor anthraquinone, and another side then connects different electronics
It is connected to receptor or directly using pi-electron conjugated bridge as electron donor with anthraquinone, general structure is as shown in Equation 1：
Wherein R1、R2、R3、R4It is each independently selected from substituted or unsubstituted C1-C22Alkyl, substituted or unsubstituted C1-
C22Alkoxy, substituted or unsubstituted C3-C22Cycloalkyl group, substituted or unsubstituted C6-C60It is aromatic radical, substituted or unsubstituted
C6-C60Any one in aryloxy group；
Wherein X is any one in substituted or unsubstituted aromatic radical, substituted or unsubstituted heterocycle；
N, m wherein in formula 1, formula 2 are denoted as the corresponding print of molecule intermediate structure and the number of iterations of fluorenes unit, n, m
Take the integer between 1-5.
The specific X is substituted or unsubstituted aryl amine, substituted or unsubstituted carbazoles, substitution or unsubstituted
Acridine, substituted or unsubstituted phenoxazine class and substituted or unsubstituted Anthraquinones, above-mentioned substituent structure formula is as follows
One of：
One of specific described n, m are 1~2 integer, and corresponding molecule intermediate structure is following：
R in said structure1~R2It is each independently selected from substituted or unsubstituted C1-C22It is alkyl, substituted or unsubstituted
C1-C22Alkoxy, substituted or unsubstituted C3-C22Cycloalkyl group, substituted or unsubstituted C6-C60Aromatic radical, substitution do not take
The C in generation6-C60Any one in aryloxy group.
Material containing compound shown in formula 1 provided by the present invention, for example, luminescent material, carrier transmission material etc. and
Compound shown in formula 1 provided by the present invention is applied to prepare the guarantor for belonging to the present invention in organic electroluminescent LED material
Protect scope.
The present invention also provides a kind of organic electroluminescent LED, the organic electroluminescent LED puies forward the present invention
Compound is as the guest materials in organic luminous layer shown in the formula 1 of confession.
The structure of the specific organic electroluminescent LED is sequentially arranged to from bottom to up：Substrate, hole injection layer,
Organic luminous layer, electron transfer layer, electron injecting layer and cathode layer.
Wherein：
The substrate is tin indium oxide (ITO) glass substrate；
The hole injection layer is poly- 3,4- ethylenedioxy thiophenes：Poly styrene sulfonate (PEDOT:PSS), thickness exists
20-50nm；
Organic luminous layer compounds object material as shown in material of main part and formula provided by the invention 1 mutually adulterates
Composition, thickness is between 30-60nm；Wherein, material of main part preferably is selected from 4,4'- bis- (9- carbazoles) biphenyl (CBP), and 9,9'- (1,3-
Phenyl) two -9H- carbazoles (mCP), 1,3,5- tri- (9- carbazyls) benzene (TCP) and 4,4', 4 "-three (carbazole -9- bases) triphenylamines
(TCTA), structural formula is as follows：
Material of main part in the organic luminous layer has both hole transport function and electron-transport function；
The thickness of the electron transfer layer is between 30-60nm；Wherein, electron transport layer materials preferably are selected from 4,7- hexichol
Base -1,10- phenanthroline (Bphen), 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene (TPBi) and 1,3,5- tri- [(3-
Pyridyl group) -3- phenyl] benzene (TmPyPb), structural formula is as follows：
The electron injecting layer is lithium fluoride (LiF), and thickness is between 0.5-1.0nm；
The thickness of the cathode layer is between 80-120nm；Wherein, cathode layer materials are metallic aluminium (Al) or metallic silver
(Ag)。
Beneficial effects of the present invention are as follows：
The present invention improves electron injection and the transmission of such compound by introducing anthraquinone radicals into compound of fluorene class
Performance realizes the balance of its carrier, has synthesized a series of Novel Fluorene class bipolarity fluorescent materials based on anthraquinone radicals.It utilizes
The Organic Light Emitting Diode of such material preparation is functional, and the synthesis of material and purification operations simplicity, and yield is high, is
Ideal chose as yellow light in organic electroluminescent LED to red light material.There is this kind of material very big commercialization to dive
Power.
Description of the drawings
In Fig. 1 embodiments 4, the structure chart of the organic electroluminescent LED based on CzLTTPHAA
In Fig. 2 embodiments 4, the molecule of the organic material used in the organic electroluminescent LED based on CzLTTPHAA
Structural formula.
In Fig. 3 embodiments 4, the normalization electricity based on the organic electroluminescent LED of CzLTTPHAA under different voltages
Photoluminescence (EL) spectrogram.
In Fig. 4 embodiments 4, Current density-voltage-brightness of the organic electroluminescent LED based on CzLTTPHAA is special
Linearity curve.
In Fig. 5 embodiments 4, current efficiency-current density-work(of the organic electroluminescent LED based on CzLTTPHAA
Rate efficiency characteristic.
Specific embodiment
In order to be better understood from present disclosure, the technology that is further illustrated the present invention below by specific example
Scheme, these embodiments are not that the scope or spirit of the invention is limited.Raw material of the present invention are such as without spy
Bright equal can be obtained from open commercial sources is not mentionleted alone.
1 2- of embodiment (12,12', 15,15'- tetra-n-butyl -6,6'- diisooctyl -12,15- dihydro -6H- rings penta 2
Alkene [1,2-b:5,4-b'] two fluorenyl) anthracene -9,10- diketone (LTTPHAA) preparation, synthetic route is as follows：
The preparation of step 1 intermediate 1-1：1.15g (1.45mmol) LTTPH 45~75mL chloroforms dissolve, dropwise
0.23g (1.45mmol) bromine is added in, is kept for -10~10 DEG C, reaction is overnight；It is extracted with dichloromethane, dry, revolving removes molten
After agent, 1g white solids, yield 80% are obtained through dichloromethane and ethyl alcohol recrystallization.
| Sequence number | LTTPH(g) | Bromine (g) | Chloroform (mL) | Temperature (DEG C) | Product (g) |
| 1 | 1.15 | 0.23 | 45 | -10 | 0.93 |
| 2 | 1.15 | 0.23 | 55 | 0 | 1 |
| 3 | 1.15 | 0.23 | 75 | 10 | 0.96 |
The preparation of step 2 LTTPHAA：8222 by 0.36g (0.41mmol) intermediate 1-1 and 0.14g (0.41mmol) 2-
Anthraquinone pinacol borate is added in there-necked flask, vacuum nitrogen gas 3 times, adds in 20mg tetrakis triphenylphosphine palladiums；By nitrogen
5~10mL toluene/tetrahydrofuran mixed solvent (1 after bubbling deoxygenation：And 1~2mL potassium carbonate/potassium fluoride mixed solvent 1)
(2mol/L) is separately added into reaction bulb, is heated to 80~100 DEG C, be stirred to react 24~72 it is small when.After the completion of reaction, dichloro is used
Methane extracts, dry, after revolving removes solvent, purifies to obtain 0.3g yellow solids, yield 73% through silica gel column chromatography.
LTTPHAA experimental datas：
1H NMR(400MHz,CDCl3,ppm):δ 8.66 (s, 1H), 8.44-8.41 (d, J=8.4Hz, 1H), 8.40-
8.35 (m, 2H), 8.16-8.11 (d, J=8.2Hz, 1H), 7.89-7.81 (m, 3H), 7.78-7.64 (m, 7H), 7.38-7.28
(m,3H),2.20–2.00(m,12H),1.18–1.03(m,8H),0.87–0.77(m,11H),0.76–0.61(m,27H),
0.58–0.47(m,12H)。
LTTPHAA molecule exact masses：996.68；MALDI-TOF m/z:996.58[M]+。
Embodiment 22,2'- (12,12', 15,15'- tetra-n-butyl -6,6'- diisooctyl -12,15- dihydro -6H- rings penta
Diene [1,2-b:5,4-b'] two fluorenyl) connection (anthracene -9,10- diketone) (DAALTTPH) preparation, synthetic route is as follows：
The preparation of step 1 intermediate 2-1：0.92g (1.16mmol) LTTPH 45~75mL chloroforms dissolve, dropwise
0.37g (2.32mmol) bromine is added in, is kept for -10~10 DEG C, reaction is overnight；It is extracted with dichloromethane, dry, revolving removes molten
After agent, 0.93g white solids, yield 85% are obtained through dichloromethane and ethyl alcohol recrystallization.
| Sequence number | LTTPH(g) | Bromine (g) | Chloroform (mL) | Temperature (DEG C) | Product (g) |
| 1 | 0.92 | 0.37 | 45 | -10 | 0.90 |
| 2 | 0.92 | 0.37 | 55 | 0 | 0.93 |
| 3 | 0.92 | 0.37 | 75 | 10 | 0.88 |
The preparation of step 2 DAALTTPH：By 0.95g (1mmol) intermediate 2-1 and 0.67g (2mmol) 2- anthraquinone boric acid
Pinacol ester is added in there-necked flask, vacuum nitrogen gas 3 times, adds in 50mg tetrakis triphenylphosphine palladiums；By nitrogen bubbling deoxygenation
5~20mL toluene/tetrahydrofuran mixed solvent (1 afterwards：And 1.5~3mL potassium carbonate/potassium fluoride mixed solvent (2mol/L) 1)
Be separately added into reaction bulb, be heated to 80~100 DEG C, be stirred to react 24~72 it is small when.After the completion of reaction, extracted with dichloromethane
It takes, it is dry, after revolving removes solvent, purify to obtain 0.96g crocus solids, yield 80% through silica gel column chromatography.
DAALTTPH experimental datas：
1H NMR(400MHz,CDCl3,ppm):δ 8.66 (s, 2H), 8.44-8.42 (d, J=8Hz, 2H), 8.40-8.35
(m, 4H), 8.16-8.12 (d, J=8Hz, 2H), 7.90-7.82 (m, 6H), 7.79-7.72 (m, 8H), 1.19-1.09 (m,
9H),0.94–0.80(m,15H),0.79–0.63(m,30H),0.59–0.46(m,13H)。
DAALTTPH molecule exact masses：1202.72；MALDI-TOF m/z:1202.72[M]+。
3 2- of embodiment [12,12', 15,15'- tetra-n-butyl -10- (9-9H- carbazyls) -6,6'- diisooctyl -12,
15- dihydro -6H- cyclopentadiene [1,2-b:5,4-b'] two fluorenyl] anthracene -9,10- diketone (CzLTTPHAA) preparation, synthesis
Route is as follows：
The preparation of step 1 intermediate 3-1：The intermediate 2-1 and 0.4g that will be prepared in 1.14g (1.2mmol) embodiment 2
(1.2mmol) 2- anthraquinone pinacol borates are added in there-necked flask, vacuum nitrogen gas 3 times, add in tetra- (triphenyls of 50mg
Phosphine) palladium；By 5~20mL toluene/tetrahydrofuran mixed solvent (1 after nitrogen bubbling deoxygenation：And 2~4mL potassium carbonate/fluorination 1)
Potassium mixed solvent (2mol/L) is separately added into reaction bulb, is heated to 80~100 DEG C, be stirred to react 24~72 it is small when.It has reacted
Cheng Hou is extracted with dichloromethane, dry, after revolving removes solvent, purifies to obtain 0.65g yellow solids through silica gel column chromatography, is produced
Rate 50%.
The preparation of step 2 CzLTTPHAA：By 0.25g (0.23mmol) intermediates 3-1,0.08g (0.46mmol) carbazole,
0.23g (0.69mmol) cesium carbonate, 0.13g (0.69mmol) cuprous iodides and 0.14g (0.69mmol) ligand 1,10- phenanthrolines
It is added in there-necked flask, vacuum nitrogen gas 3 times；4~8mL N, N'- dimethylformamide after nitrogen bubbling deoxygenation is added in
In reaction bulb, agitating and heating flows back at 130~160 DEG C, when reaction 12~24 is small；After completion of the reaction, extracted with dichloromethane,
It is dry, after revolving removes solvent, purify to obtain 0.18g yellow solids, yield 67% through silica gel column chromatography.
CzLTTPHAA experimental datas：
1H NMR(400MHz,CDCl3,ppm):δ 8.66 (s, 1H), 8.45-8.41 (d, J=8Hz, 1H), 8.40-8.34
(m, 2H), 8.21-8.17 (d, J=7.6Hz, 2H), 8.16-8.11 (d, J=8Hz, 1H), 7.97-7.93 (d, J=7.9Hz,
1H),7.91–7.82(m,3H),7.79–7.70(m,6H),7.58–7.53(m,2H),7.50–7.42(m,4H),7.29–7.29
(t, J=7.1Hz, 2H), 2.23-2.03 (m, 12H), 1.19-1.07 (m, 8H), 0.98-0.81 (m, 12H), 0.80-0.66
(m,26H),0.63–0.47(m,13H)。
CzLTTPHAA molecule exact masses：1161.74；MALDI-TOF m/z:1161.83[M]+。
The preparation of 4 organic electroluminescent LED of embodiment
Step 1 by the ito glass substrate of the 10 Ω square resistances of attachment etched, successively with special cleaning, acetone/
After alcohol mixeding liquid and deionized water are cleaned by ultrasonic, be placed in 120 DEG C of thermostatic drying chamber dry 1 it is small when, then to its surface into
Row corona treatment 5 minutes.
Step 2 is placed in the ito glass substrate handled well in step 1 on spin coater, with 2500 turns of rotating speed/per second,
The poly- 3,4- ethylenedioxy thiophenes of spin coating on ito glass substrate：Poly styrene sulfonate (PEDOT:PSS hole injection layer) is used as,
Spin coating film thickness is 40nm；120 DEG C of warm table is subsequently placed in anneal 20 minutes.
2- [12,12', 15,15'- tetra-n-butyl -10- in step 3 preferably compound shown in formula 1 provided by the invention
(9-9H- carbazyls) -6,6'- diisooctyl -12,15- dihydro -6H- cyclopentadiene [1,2-b:5,4-b'] two fluorenyls] anthracene -9,
10- diketone (CzLTTPHAA) is as guest materials with 6wt% concentration and material of main part 4,4'- bis- (9- carbazoles) biphenyl (CBP) phase
Mutually doping is prepared into organic luminous layer by spin-coating method, and spin coating film thickness is 40nm, is subsequently placed in the sky prepared in step 2
On the implanted layer of cave.
On the organic luminous layer that step 4 is prepared in step 3,1,3,5- tri- [(3- pyridyl groups) -3- phenyl] are preferably deposited
Benzene (TmPyPb) is used as electron transfer layer, evaporation rate 0.2nm/s, and vapor deposition film thickness is 60nm；
Continue to be deposited lithium fluoride (LiF) on the electron transfer layer that step 5 is prepared in step 4 as electron injecting layer, steam
Plating speed is 0.05nm/s, and vapor deposition film thickness is 0.8nm；
On the electron injecting layer that step 6 is prepared in steps of 5, preferably evaporation metal aluminium (Al) is used as cathode layer, vapor deposition speed
It spends for 0.5nm/s, vapor deposition film thickness is 100nm, obtains organic electroluminescent LED provided by the invention.
Point of the structure chart of organic electroluminescent LED according to prepared by step 1-6 and the organic material wherein used
Subformula is as depicted in figs. 1 and 2.The test of the organic electroluminescent LED is carried out under atmosphere at room temperature environment, hair
Light area is 3mm × 4mm, and driving voltage is provided and as current source table, PR-650 using 2602 type DC power supplies of Keithley
Luminance spectral instrument measures electroluminescent (EL) spectrum and the related Electroluminescence of the supplementary instruments such as luminance parameter, optical table measurement
Matter, obtained electroluminescent (EL) spectrogram (Fig. 3), CIE chromaticity coordinates (table 1), current density of organic electroluminescent LED-
The photoelectric characteristics such as voltage-luminance characteristics curve (Fig. 4) and current efficiency-current density-power efficiency characteristic curve (Fig. 5).
From figure 3, it can be seen that with the increase of voltage, the emission peak of the Organic Light Emitting Diode based on CzLTTPHAA
Peak shape is basically unchanged, and the blue shift of very little can only occur for wavelength, in the wave-length coverage of 560nm to 556nm, illustrate applied voltage
Variation the electroluminescent of the material is influenced it is little；And the corresponding CIE chromaticity coordinates (being shown in Table 1) of different voltages varies less,
Excitation purity is more stable, can generate orange light transmitting.As shown in Figure 4 and Figure 5, which opens bright voltage
For 6V；When driving voltage is 13.88V, device reaches high-high brightness for 5565.24cdm-2；In addition, the maximum current of device
Efficiency and maximum power efficiency are respectively 2.18cdA-1And 0.60lmW-1.Data above shows using with anthraquinone radicals
Fluorenes class bipolarity fluorescent material CzLTTPHAA prepare OLED device luminescent properties it is good, operation and chromaticity stability also compared with
It is good, it is that one kind is applied in Organic Light Emitting Diode preferably orange light material.
Using above preferred embodiment as enlightenment, by the description of the present invention, relevant staff completely can be not
In the range of deviateing this invention technological thought, various changes and amendments are carried out.Meanwhile the technical scope of this invention
The content being not limited on specification, it is necessary to which its technical scope is determined according to right.
The CIE chromaticity coordinates figure tables of comparisons of organic electroluminescent LED under 1 different voltages of table
Claims (8)
1. a kind of Novel Fluorene class bipolarity fluorescent material based on anthraquinone radicals, it is characterised in that there is D- π-A types or A- π-A
Type Intramolecular electron transfer structure, ladder type oligomerization fluorenes are used as pi-electron conjugated bridge, one side and electron acceptor anthraquinone phase in centre
Connect, and another side then connects different electron donor-acceptor (EDA)s or directly connects pi-electron conjugated bridge as electron donor and anthraquinone
It connects, general structure is as shown in formula 1, formula 2：
Wherein R1、R2It is each independently selected from substituted or unsubstituted C1-C22Alkyl, substituted or unsubstituted C1-C22Alkoxy,
Substituted or unsubstituted C3-C22Cycloalkyl group, substituted or unsubstituted C6-C60Aromatic radical, substituted or unsubstituted C6-C60Fragrant oxygen
Any one in base；
X substituent structures formula is one of following：
N, m wherein in formula 1, formula 2 are denoted as the corresponding print of molecule intermediate structure and the number of iterations of fluorenes unit, n=1, and 2；m
=1；
Corresponding molecule intermediate structure is one of following：
2. the purposes of formula 1 described in claim 1, compound shown in formula 2, it is characterised in that passed applied to luminescent material, carrier
In defeated material.
3. formula 1 described in claim 1, use of a compound shown in formula 2, it is characterised in that applied to preparing Organic Light Emitting Diode material
In material.
4. a kind of Organic Light Emitting Diode, it is characterised in that the Organic Light Emitting Diode is by formula 1 described in claim 1, formula 2
Shown compound is as the guest materials in organic luminous layer.
5. according to the Organic Light Emitting Diode described in claim 4, it is characterised in that the structure of the diode is suitable from bottom to up
Sequence is arranged to：Substrate, hole injection layer, organic luminous layer, electron transfer layer, electron injecting layer and cathode layer.
6. according to the Organic Light Emitting Diode described in claim 5, it is characterised in that：The substrate is tin indium oxide
(ITO) glass substrate.
7. according to the Organic Light Emitting Diode described in claim 5, it is characterised in that：The hole injection layer is poly- 3,4-
Ethylenedioxy thiophene：Poly styrene sulfonate (PEDOT:PSS), thickness is between 20-50nm.
8. according to the Organic Light Emitting Diode described in claim 5, it is characterised in that：The organic luminous layer is by main body material
Compounds object material shown in formula 1 described in material and claim 1 or formula 2 mutually adulterates composition, and thickness is between 30-60nm；Its
In, material of main part be selected from 4,4'- bis- (9- carbazoles) biphenyl (CBP), 9,9'- (1,3- phenyl) two -9H- carbazoles (mCP), 1,3,5-
Three (9- carbazyls) benzene (TCP) and 4,4', 4 "-three (carbazole -9- bases) triphenylamines (TCTA), structural formula is as follows：
Material of main part in the organic luminous layer has both hole transport function and electron-transport function；
The thickness of the electron transfer layer is between 30-60nm；Wherein, electron transport layer materials are selected from 4,7- diphenyl -1,10-
Phenanthroline (Bphen), 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene (TPBi) and 1,3,5- tri- [(3- pyridyl groups) -
3- phenyl] benzene (TmPyPb), structural formula is as follows：
The electron injecting layer is lithium fluoride (LiF), and thickness is between 0.5-1.0nm；
The thickness of the cathode layer is between 80-120nm；Wherein, cathode layer materials are metallic aluminium (Al) or metallic silver (Ag).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510971202.5A CN105482813B (en) | 2015-12-21 | 2015-12-21 | Novel Fluorene class bipolarity fluorescent material based on anthraquinone radicals and its application in Organic Light Emitting Diode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510971202.5A CN105482813B (en) | 2015-12-21 | 2015-12-21 | Novel Fluorene class bipolarity fluorescent material based on anthraquinone radicals and its application in Organic Light Emitting Diode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105482813A CN105482813A (en) | 2016-04-13 |
| CN105482813B true CN105482813B (en) | 2018-05-18 |
Family
ID=55670097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510971202.5A Active CN105482813B (en) | 2015-12-21 | 2015-12-21 | Novel Fluorene class bipolarity fluorescent material based on anthraquinone radicals and its application in Organic Light Emitting Diode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105482813B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106083694A (en) * | 2016-05-30 | 2016-11-09 | 山西大学 | A kind of 3,6 2 (anthraquinone 2 vinyl) N ethyl carbazole and preparation method thereof |
| CN106800525B (en) * | 2016-12-14 | 2019-04-02 | 中节能万润股份有限公司 | A kind of fluorenyl Anthraquinones electroluminescent organic material and its preparation method and application |
| CN106749082B (en) * | 2016-12-14 | 2019-03-15 | 中节能万润股份有限公司 | A kind of Anthraquinones electroluminescent organic material and its preparation method and application |
| CN107162984A (en) * | 2017-05-23 | 2017-09-15 | 华南理工大学 | A kind of bipolarity small molecule emitter material using the indenes fluorenes unit of two phenanthro- 2,8 as core and preparation method and application |
| CN107573299A (en) * | 2017-07-31 | 2018-01-12 | 华南理工大学 | It is a kind of using two phenanthro- indenes fluorenes units as bipolarity small molecule emitter material of core and preparation method and application |
| CN108329419B (en) * | 2018-01-12 | 2020-01-10 | 南京邮电大学 | Temperature-sensitive water-soluble polymer based on D-pi-A structure and preparation method and application thereof |
| CN115044361B (en) * | 2022-05-15 | 2024-05-10 | 南京邮电大学 | Double-luminescence organic fluorescence temperature sensing film and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100569827C (en) * | 2002-11-08 | 2009-12-16 | 默克专利有限公司 | The poly-indenofluorene that is used for the aryl replacement of organic electroluminescence device |
| CN101624441A (en) * | 2009-07-24 | 2010-01-13 | 南京邮电大学 | Preparation method and application method of 4-9, 9-diaryl fluorene polymer material containing substituted radical |
| CN104513361A (en) * | 2013-09-26 | 2015-04-15 | 海洋王照明科技股份有限公司 | Anthraquinone based copolymer, preparation method and applications thereof |
| CN104650089A (en) * | 2013-12-26 | 2015-05-27 | 北京鼎材科技有限公司 | Fluorene derivative containing carbazole-9-yl group and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102140018B1 (en) * | 2013-12-17 | 2020-07-31 | 삼성전자주식회사 | Condensed cyclic compound and organic light emitting device including the same |
-
2015
- 2015-12-21 CN CN201510971202.5A patent/CN105482813B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100569827C (en) * | 2002-11-08 | 2009-12-16 | 默克专利有限公司 | The poly-indenofluorene that is used for the aryl replacement of organic electroluminescence device |
| CN101624441A (en) * | 2009-07-24 | 2010-01-13 | 南京邮电大学 | Preparation method and application method of 4-9, 9-diaryl fluorene polymer material containing substituted radical |
| CN104513361A (en) * | 2013-09-26 | 2015-04-15 | 海洋王照明科技股份有限公司 | Anthraquinone based copolymer, preparation method and applications thereof |
| CN104650089A (en) * | 2013-12-26 | 2015-05-27 | 北京鼎材科技有限公司 | Fluorene derivative containing carbazole-9-yl group and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Anthraquinone-Based Intramolecular Charge-Transfer Compounds:Computational Molecular Design, Thermally Activated Delayed Fluorescence, and Highly Effi cient Red Electroluminescence;Qisheng Zhang等;《J. Am. Chem. Soc.》;20141203;18070-18081 * |
| Charge Transfer Fluorescence and 34 nm Exciton Diffusion Length in Polymers with Electron Acceptor End Traps;Lori Zaikowski等;《J. Phys. Chem. B》;20141222;7231-7241 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105482813A (en) | 2016-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105482813B (en) | Novel Fluorene class bipolarity fluorescent material based on anthraquinone radicals and its application in Organic Light Emitting Diode | |
| TWI611003B (en) | Compounds for electronic devices | |
| Kotchapradist et al. | Pyrene-functionalized carbazole derivatives as non-doped blue emitters for highly efficient blue organic light-emitting diodes | |
| CN105175313B (en) | A kind of hole injection compound and its organic electroluminescence device | |
| CN102473848A (en) | Organic electroluminescent element using pyrene derivative | |
| CN106467542A (en) | A kind of compound with anthrone as core and its application | |
| CN109535131B (en) | Compound taking cyanopyridine as receptor and application thereof | |
| CN110041366B (en) | Indenonanthracene derivative compound and application thereof | |
| CN106467497A (en) | A kind of compound with anthrone as core and its application in OLED | |
| CN109608453B (en) | Compound taking 4, 7-phenanthroline as receptor and application thereof | |
| CN105418485B (en) | A kind of new green light host compound and its preparation method and application | |
| CN104513247B (en) | A kind of benzo ［ c ］ benzo ［ 3,4 ］ carbazole and carbazole derivates and application | |
| You et al. | Pyrene-cored dendrimer with carbazole derivatives as dendrons: Synthesis, properties and application in white light-emitting diode | |
| CN107216329A (en) | A kind of pyridoindole derivatives and processes and the organic electroluminescence device prepared using the compound | |
| CN104628581A (en) | 2,6,6,8-tetra-substituted-6H-benzo[cd]pyrene compound and organic electroluminescence device containing same | |
| CN107057681A (en) | A kind of photoelectric material containing xanthene structure and its application in OLED fields | |
| CN109336772A (en) | A kind of triaromatic amine compound containing spiro structure and application thereof and luminescent device | |
| CN106220649A (en) | Diaryl ketone-based compound and application thereof in organic electroluminescent device | |
| KR20150135599A (en) | Noble Organic Light-Emitting Compound and Organic Light-Emitting Device Using the Same | |
| CN111689962A (en) | Compound with benzimidazole pyridine as receptor and application thereof | |
| Chen et al. | A multifunctional bipolar host material based on phenanthroimidazole for efficient green and red PhOLEDs with low turn-on voltage | |
| CN107868030A (en) | A kind of organic compound containing fluorenes and its application on organic electroluminescence device | |
| CN107602336A (en) | A kind of anthracene derivative and its synthetic method and organic luminescent device | |
| KR20210014411A (en) | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof | |
| CN107619406A (en) | A kind of new carbazole analog derivative and preparation method thereof and application in the devices |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |