CN111825618B - Phenanthroimidazole-containing blue organic semiconductor material and preparation method and application thereof - Google Patents
Phenanthroimidazole-containing blue organic semiconductor material and preparation method and application thereof Download PDFInfo
- Publication number
- CN111825618B CN111825618B CN202010601059.1A CN202010601059A CN111825618B CN 111825618 B CN111825618 B CN 111825618B CN 202010601059 A CN202010601059 A CN 202010601059A CN 111825618 B CN111825618 B CN 111825618B
- Authority
- CN
- China
- Prior art keywords
- phenanthroimidazole
- semiconductor material
- organic semiconductor
- blue
- bpi
- 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
Images
Classifications
-
- 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
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- 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
- C09K2211/1007—Non-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
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses a phenanthroimidazole-containing blue organic semiconductor material and a preparation method and application thereof. The structure of the organic semiconductor material containing the phenanthroimidazole is shown as follows:
wherein R1 is different from R2, R1 is an electron donating group or an electron withdrawing group, and R2 is a large steric hindrance group; ar1 and Ar2 may be the same or different, and Ar1 and Ar2 are aggregation-induced emission groups. According to the invention, different modifying groups are connected to phenanthroimidazole to regulate the excited state property of phenanthroimidazole derivative, so that the organic semiconductor material has blue or deep blue emission in a solid state and has remarkable aggregation-induced emission performance. The organic semiconductor material prepared by the invention can be used as a luminescent layer and has the characteristics of high-efficiency solid-state luminescence and high-electric excitation exciton utilization rate, so that a blue-light organic electroluminescent device with excellent photoelectric property, simple structure and low cost is obtained, and the blue-light organic electroluminescent device can be widely applied to the field of organic electroluminescence.
Description
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a phenanthroimidazole-containing blue organic semiconductor material, and a preparation method and application thereof.
Background
The Organic Light Emitting Diode (OLED) has the characteristics of low driving voltage, high response speed, high luminous efficiency, wide color gamut, light weight, thinness, flexible folding and the like, and has wide application prospect in the fields of flat panel display and solid illumination; among them, organic light emitting materials have attracted extensive attention in academia and industry as a core technology of OLEDs. At present, compared with the development of mature green light and red light materials, an electroluminescent device prepared from a blue light material with one of three primary colors still has the defects of insufficient efficiency, poor stability and the like. How to screen out a blue light material system with high efficiency and low cost gradually becomes the focus of attention of scientists in various countries.
An excellent blue-emitting material needs to have three characteristics: high color purity blue emission, high solid state luminous efficiency, and high electron excitation exciton utilization. And the excellent blue light color purity can be well realized by selecting a proper blue light construction element. However, the conventional organic fluorescent material usually has high-brightness luminescence in a single-molecule state, but the phenomenon of fluorescence weakening or even complete disappearance occurs along with the molecular Aggregation, and the Aggregation-quenching (ACQ) effect makes the solid-state luminescence efficiency of the organic fluorescent material lower, which is not favorable for the preparation of high-efficiency OLEDs. In addition, in OLEDs based on conventional fluorescent materials, only 25% of singlet excitons may be used for light emission, while 75% of triplet excitons are white dissipated in a non-radiative form, resulting in very low device efficiency; although the Thermal Activation Delayed Fluorescence (TADF) material developed by professor Adachi at kyushu university of japan can fully utilize singlet and triplet excitons formed by electric excitation, the design concept is not favorable for the material to realize the emission of blue light, especially deep blue light, so the blue TADF material is also slow to develop, and the blue TADF device also has the troublesome problems of large roll-off, short lifetime and the like.
The phenanthroimidazole has the characteristics of large conjugation degree, good thermal stability, easy structure modification, bipolar transmission and the like, and is a typical construction element of a blue organic semiconductor material. Aggregation-induced emission (AIE) is a subversion of the traditional concept reported in the tangkui topic group 2001, and refers to a phenomenon in which a molecule hardly emits light in a single-molecule state, and the light emission is significantly enhanced in an aggregated state or under a solid film. The proposal of AIE provides a new idea for solving the ACQ problem of luminescent materials. Subsequently, more and more AIE organic light emitting materials with high solid state light emission were developed and have shown advantages in high brightness, low roll-off, undoped OLED devices. In view of the problem that 75% of triplet excitons in an OLED device cannot be utilized, 2011 has proposed a new mechanism, namely "thermal exciton" mechanism, which can also fully utilize single and triplet excitons, and the design concept of the mechanism is not in conflict with the material for realizing blue light emission. In addition, the blue light OLED device prepared based on the thermal exciton material can rapidly utilize triplet excitons, and has the advantages of low roll-off and good stability. However, although the above strategies can solve the problems faced by blue light materials separately, how to combine them organically to optimize the device still does not find a good solution.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a phenanthroimidazole-containing blue organic semiconductor material, and a preparation method and application thereof.
The invention aims to provide a phenanthroimidazole-containing blue organic semiconductor material system aiming at overcoming the defects in the prior art. The luminescent material has blue light emission and AIE characteristics, and has weak luminescence in a dilute solution, but the luminescence is obviously enhanced in an aggregation state or a solid state; the luminescent material also has the characteristic of 'heat exciton', and can break through the exciton utilization rate limit of 25% of the fluorescent material; the material has the characteristics of high solid-state luminous efficiency and high utilization rate of the electrically excited excitons, and can prepare a non-doped blue organic electroluminescent device with high efficiency and low efficiency roll-off.
The invention also aims to provide a preparation method of the phenanthroimidazole-containing blue organic semiconductor material. The method has the advantages of simple process, easily obtained raw materials and high yield.
The invention further aims to provide application of the phenanthroimidazole-containing blue organic semiconductor material in the field of organic electroluminescence, in particular application in preparing a light-emitting layer of an organic light-emitting diode.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a phenanthroimidazole-containing blue organic semiconductor material, which has a chemical structural formula as follows:
wherein R is 1 And R 2 In a different sense, R 1 Is an electron donating group or an electron withdrawing group, R 2 Is a bulky steric hindering group; ar (Ar) 1 And Ar 2 Ar1 and Ar2 may be the same or different, and are aggregation-induced emission type groups.
Said R 1 Is one of the following structures 1-6:
said R 2 Is one of the following structures 7-15:
ar is 1 、Ar 2 Is one of the following a-k structures:
the invention provides a method for preparing a phenanthroimidazole-containing blue organic semiconductor material, which comprises the following steps:
with 2, 7-dibromophenanthrene-9, 10-dione, 4-tert-butylaniline and R 1 、R 2 The benzaldehyde of a substituent group is taken as a raw material, and a corresponding intermediate is obtained through one-step ring closure; then with Ar 1 And Ar 2 And carrying out Suzuki reaction on the corresponding boric acid or boric acid ester to obtain the corresponding phenanthroimidazole-containing blue organic semiconductor material.
Further, the molar ratio of the 2, 7-dibromophenanthrene-9, 10-dione to the 4-tert-butylaniline is 1.5-1.
Further, the 2, 7-dibromophenanthrene-9, 10-dione is reacted with an R-containing compound 1 、R 2 The molar ratio of the substituted benzaldehyde is 1.
Further, the molar ratio of the 2, 7-dibromophenanthrene-9, 10-dione to ammonium acetate is 1.
The phenanthroimidazole is selected as a construction element of the material, so that the material can emit blue fluorescence; by connecting a blue light AIE group to 2,7 positions of phenanthroimidazole, under the premise of ensuring blue light emission of the material, the AIE characteristic is introduced, so that the material cannot cause fluorescence quenching phenomenon due to strong pi-pi interaction in an aggregation state, and high solid-state luminous efficiency is obtained; in addition, electron donating groups or electron withdrawing groups are connected to the para position of the C2 substituted benzene of the phenanthroimidazole, and a charge transfer excited state is introduced, so that the utilization of triplet excitons is facilitated; the ortho position of C2 substituted benzene of phenanthroimidazole is connected with large steric hindrance group so as to regulate and control the distribution of excited state energy level and make triplet state exciton be utilized by means of "thermal exciton" channel; therefore, the material of the invention has the characteristics of AIE and 'thermal exciton' while emitting blue fluorescence, thereby realizing high solid-state luminous efficiency and high utilization rate of electrically excited excitons. Based on the material, a non-doped blue organic electroluminescent device with high efficiency and low efficiency roll-off can be prepared, and the material has wide application prospect in the field of organic electroluminescence.
The organic semiconductor material can avoid the problem of fluorescence quenching in an aggregation state on the premise of ensuring blue light emission, breaks through the limit of 25 percent of exciton utilization rate of the organic fluorescent material, has simple and efficient synthesis method and excellent thermal stability and electrochemical stability, can be synthesized and purified on a large scale, and has great application prospect.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The phenanthroimidazole-containing blue organic semiconductor material has the characteristics of AIE and 'hot exciton', has the characteristics of blue light emission, high solid-state luminous efficiency and high electric excitation exciton utilization rate, and can be used for preparing a high-efficiency low-degree-efficiency roll-off non-doped organic electroluminescent device;
(2) The phenanthroimidazole-containing blue organic semiconductor material disclosed by the invention is simple in synthesis method, easy in raw material obtaining, high in yield and stable in structure;
(3) The phenanthroimidazole-containing blue organic semiconductor material is used for a light-emitting layer of an organic light-emitting diode, has excellent comprehensive performance and can be widely applied to the fields of organic electroluminescence and the like.
Drawings
FIG. 1a shows photoluminescence spectra of the phenanthroimidazole-containing blue organic semiconductor material of example 1 measured in tetrahydrofuran/water solutions in different ratios;
FIG. 1b shows photoluminescence spectra of the phenanthroimidazole-containing blue organic semiconductor material in example 2 tested in tetrahydrofuran/water solutions at different ratios;
FIG. 1c shows photoluminescence spectra of the phenanthroimidazole-containing blue organic semiconductor material in example 3 in tetrahydrofuran/water solutions at different ratios;
FIG. 1d shows the photoluminescence spectra of the phenanthroimidazole-containing blue organic semiconductor material of example 4 in tetrahydrofuran/water solutions in different ratios;
FIG. 2a is a J-V-L plot of undoped OLEDs prepared from the phenanthroimidazole-containing blue organic semiconductor material in example 1;
FIG. 2b is a graph showing the efficiency of undoped OLEDs fabricated from the phenanthroimidazole-containing blue organic semiconductor material in example 1 as a function of luminance;
FIG. 3a is a J-V-L diagram of an undoped OLEDs prepared from the phenanthroimidazole-containing blue organic semiconductor material in example 2;
FIG. 3b is a graph showing the efficiency of undoped OLEDs fabricated from the phenanthroimidazole-containing blue organic semiconductor material in example 2 as a function of luminance;
FIG. 4a is a J-V-L graph of an undoped OLEDs prepared from the phenanthroimidazole-containing blue organic semiconductor material in example 3;
FIG. 4b is a graph showing the luminance as a function of the efficiency of undoped OLEDs obtained from the blue phenanthroimidazole-containing organic semiconductor material in example 3;
FIG. 5a is a J-V-L plot of undoped OLEDs prepared from the phenanthroimidazole-containing blue organic semiconductor material of example 4;
FIG. 5b is a graph of the efficiency as a function of the luminance of undoped OLEDs produced from the phenanthroimidazole-containing blue organic semiconductor material of example 4.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1: preparation of phenanthroimidazole-containing blue organic semiconductor material (2 TriPE-BPI)
Reaction equation (one):
(1) 2, 7-dibromophenanthrene-9, 10-dione (0.73g, 2mmol), 4-tert-butylaniline (1.6 mL, 10mmol), benzaldehyde (0.2mL, 2mmol) and ammonium acetate (0.62g, 8mmol) are added into a reaction bottle, gas is pumped for three times, 30ml of glacial acetic acid is added under the protection of nitrogen, the mixture is heated to 120 ℃, and the reflux reaction is carried out for 3 hours. Adding methanol for precipitation, performing suction filtration, making powder, and passing through a column to obtain white intermediate powder with the yield of 83%;
(2) Adding the intermediate (1.17g, 2mmol), triphenylethylene boric acid (1.80g, 6mmol), tetrakis (triphenylphosphine) palladium (0.48g, 0.4 mmol) and sodium carbonate (0.54g, 6mmol) into a reaction bottle, vacuumizing three times, adding 80mL of toluene, 10mL of ethanol and 10mL of water under the protection of nitrogen, heating to 120 ℃, and carrying out reflux reaction for 12h. Extracting with dichloromethane and water, concentrating, making powder, and passing through columnTo obtain white final product 2TriPE-BPI with yield of 74%. 1 H NMR(400MHz,CD 2 Cl 2 ),δ(TMS,ppm):9.05(s,1H),8.71(dd,J＝18.0,8.8Hz,2H),7.88(d,J＝8.8Hz,1H),7.82–7.57(m,7H),7.53–7.25(m,24H),7.24–7.16(m,4H),7.14–7.06(m,3H),7.04–6.95(m,3H),1.40(s,9H).
Example 2 preparation of a phenanthroimidazole-containing blue organic semiconductor Material (2 TriPE-BPI-CN)
Reaction equation (ii):
(1) 2, 7-dibromo phenanthrene-9, 10-dione (0.73g, 2mmol), 4-tert-butyl aniline (1.6 mL, 10mmol), 4-methoxy benzaldehyde (0.27g, 2mmol) and ammonium acetate (0.62g, 8mmol) were charged into a reaction flask, the gas was purged three times, 30ml of glacial acetic acid was added under nitrogen protection, and the mixture was heated to 120 ℃ and refluxed for 3 hours. Adding methanol for precipitation, performing suction filtration, making powder, and passing through a column to obtain white intermediate powder with a yield of 85%;
(2) The intermediate (1.22g, 2mmol), triphenylethylene boric acid (1.80g, 6mmol), tetrakis (triphenylphosphine) palladium (0.48g, 0.4 mmol) and sodium carbonate (0.54g, 6mmol) were added to a reaction flask, the gas was purged three times, 80mL of toluene, 10mL of ethanol and 10mL of water were added under nitrogen protection, heated to 120 ℃ and reacted under reflux for 12h. Extracting with dichloromethane and water, concentrating, making powder, and passing through a column to obtain a white final product 2TriPE-BPI-CN with a yield of 78%. 1 H NMR(500MHz,CD 2 Cl 2 )δ(TMS,ppm):9.04(s,2H),8.75(dd,J＝22.5,9.0Hz,2H),7.92(dd,J＝8.5,1.5Hz,1H),7.83–7.59(m,10H),7.53–7.27(m,19H),7.22(dd,J＝10.0,6.6Hz,4H),7.16–7.08(m,3H),7.07–6.98(m,3H),1.43(s,9H).
Example 3 preparation of a phenanthroimidazole-containing blue organic semiconductor Material (2 TriPE-BPI-OMe)
Reaction equation (c):
(1) 2, 7-dibromo phenanthrene-9, 10-dione (0.73g, 2mmol), 4-tert-butyl aniline (1.6 mL, 10mmol), 4-methoxy benzaldehyde (0.26g, 2mmol) and ammonium acetate (0.62g, 8mmol) were charged into a reaction flask, the gas was purged three times, 30ml of glacial acetic acid was added under nitrogen protection, and the mixture was heated to 120 ℃ and refluxed for 3 hours. Adding methanol for precipitation, performing suction filtration, making powder, and passing through a column to obtain white intermediate powder with a yield of 80%;
(2) The intermediate (1.23g, 2mmol), triphenylethylene boric acid (1.80g, 6mmol), tetrakis (triphenylphosphine) palladium (0.48g, 0.4 mmol) and sodium carbonate (0.54g, 6mmol) are added into a reaction flask, the gas is pumped three times, 80mL of toluene, 10mL of ethanol and 10mL of water are added under the protection of nitrogen, the mixture is heated to 120 ℃, and the reflux reaction is carried out for 12 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain white final product 2TriPE-BPI-OMe with yield of 82%. 1 H NMR(500MHz,CD 2 Cl 2 ),δ(TMS,ppm):8.73(dd,J＝22.0,9.0Hz,2H),7.90(d,J＝8.0Hz,1H),7.80–7.71(m,3H),7.63(t,J＝11.0Hz,4H),7.51–7.16(m,25H),7.14–7.06(m,3H),7.05–6.96(m,3H),6.93–6.82(m,3H),6.59(d,J＝9.0Hz,1H),3.81(s,3H),1.41(s,9H).
Example 4 preparation of a phenanthroimidazole-containing blue organic semiconductor Material (2 TriPE-BPI-MCN)
Reaction equation (iv):
(1) 2, 7-dibromophenanthrene-9, 10-dione (0.73g, 2mmol), 4-tert-butylaniline (1.6 mL, 10mmol), 4-cyano-2-methylbenzaldehyde (0.29g, 2mmol) and ammonium acetate (0.62g, 8mmol) were charged into a reaction flask, the gas was evacuated three times, 30ml of glacial acetic acid was added under nitrogen protection, and the mixture was heated to 120 ℃ and refluxed for 3 hours. Adding methanol for precipitation, performing suction filtration, making powder, and passing through a column to obtain white intermediate powder with a yield of 80%;
(2) Adding the intermediate (1.25g, 2mmol), triphenylethylene boric acid (1.80g, 6 mmol), tetrakis (triphenylphosphine) palladium (0.48g, 0.4 mmol) and sodium carbonate (0.54g, 6 mmol) into a reaction bottle, vacuumizing three times, adding 80mL of toluene, 10mL of ethanol and 10mL of water under the protection of nitrogen, heating to 120 ℃, and carrying out reflux reaction for 12h. Extracting with dichloromethane and water, concentrating, making powder, and passing through a column to obtain a white final product 2TriPE-BPI-MCN with a yield of 82%. 1 H NMR(500MHz,CD 2 Cl 2 ),δ(TMS,ppm):8.99(s,1H),8.72(dd,J＝26.0,9.0Hz,2H),7.88(dd,J＝8.5,2.0Hz,1H),7.79(dd,J＝9.0,1.5Hz,1H),7.67(d,J＝8.5Hz,2H),7.56(s,1H),7.53–7.46(m,3H),7.44–7.23(m,22H),7.21–7.19(m,2H),7.13(dd,J＝17.0,8.0Hz,4H),7.05(s,1H),7.02–6.95(m,3H),2.41(s,3H),1.33(s,9H).
Example 5: test of aggregation-induced emission Properties of Phenanthroimidazole-containing blue organic semiconductor Material
4.68mg of 2TriPE-BPI compound was weighed out and dissolved in 5mL of ultra dry Tetrahydrofuran (THF) to a concentration of 10 -3 mol/L of test sample. 30 μ L of 2TriPE-BPI test sample was added to a 5mL centrifuge tube and repeated six times. Then, 270. Mu.L THF/2700. Mu.L H were added in sequence 2 O、570μLTHF/2400μL H 2 O、1170μL THF/1800μL H 2 O、1770μL THF/1200μL H 2 O、2370μLTHF/600μL H 2 O、2970μL THF/0μL H 2 O to six centrifuge tubes, and preparing AIE curve test samples with water contents of 90%, 80%, 60%, 40%, 20% and 0%. And testing the emission spectrum of the test sample under each water content under the corresponding excitation wavelength, and obtaining the aggregation-induced emission property curve graph of the compound 2TriPE-BPI through data processing. Aggregation-induced emission property of phenanthroimidazole-containing blue organic semiconductor materialThe test graph is shown in FIG. 1a, wherein f w The proportion of water is indicated. It can be seen from fig. 1a that the phenanthroimidazole-containing blue organic semiconductor material has significant AIE properties.
The compound 2TriPE-BPI-CN, the compound 2TriPE-BPI-OMe and the compound 2TriPE-BPI-MCN were also tested as above, and the test method was the same as that of the compound 2 TriPE-BPI. The results of the obtained aggregation-induced emission property graphs of the compound 2TriPE-BPI-CN, the compound 2TriPE-BPI-OMe and the compound 2TriPE-BPI-MCN are shown in FIG. 1b, FIG. 1c and FIG. 1d respectively. The compound 2TriPE-BPI-CN, the compound 2TriPE-BPI-OMe and the compound 2TriPE-BPI-MCN also have obvious AIE properties.
Example 6: OLEDs device performance of phenanthroimidazole-containing blue organic semiconductor material (2 TriPE-BPI)
A non-doped device is prepared by using the phenanthroimidazole-containing blue organic semiconductor material 2TriPE-BPI (blue light wavelength =462nm, solid-state fluorescence quantum yield = 62.5%) prepared in example 1 as a luminescent material, and the device performance is tested and characterized, and the result is shown in fig. 2a and fig. 2b.
Non-doped device structure: ITO/HATCN (5 nm)/TAPC (25 nm)/TCTA (15 nm)/2 TriPE-BPI (20 nm)/TPBi (40 nm)/LiF (1 nm)/Al (120 nm).
FIG. 2a is a J-V-L diagram of undoped OLEDs prepared using the blue phenanthroimidazole-containing organic semiconductor material of example 1. As can be seen from the figure, the maximum brightness of the 2TriPE-BPI based undoped device is high and the starting voltage is low, which is 8036cd/m 2 ，2.8V。
FIG. 2b is a graph of the efficiency as a function of the luminance of undoped OLEDs prepared using the blue phenanthroimidazole-containing organic semiconductor material of example 1. As can be seen from the figure, the 2TriPE-BPI based undoped device has good efficiency and reduced efficiency, and the maximum external quantum efficiency is 3.74%; when the luminance is 1000cd/m 2 The external quantum efficiency was 3.56%. The maximum electric excitation exciton utilization rate exceeds the limit value of the traditional fluorescent material and reaches 29.9 percent.
Example 7: OLEDs device performance of phenanthroimidazole-containing blue organic semiconductor material (2 TriPE-BPI-CN)
A non-doped device is prepared by using the phenanthroimidazole-containing blue organic semiconductor material 2TriPE-BPI-CN (blue light wavelength =454nm, solid-state fluorescence quantum yield = 50.2%) prepared in example 2 as a luminescent material, and the device performance is tested and characterized, and the result is shown in fig. 3a and fig. 3b.
Non-doped device structure: ITO/HATCN (5 nm)/TAPC (25 nm)/TCTA (15 nm)/2 TriPE-BPI-CN (20 nm)/TPBi (40 nm)/LiF (1 nm)/Al (120 nm).
FIG. 3a is a J-V-L diagram of undoped OLEDs prepared using the blue phenanthroimidazole-containing organic semiconductor material of example 2. As can be seen from the figure, the maximum luminance of the 2TriPE-BPI-CN based undoped device is high and the starting voltage is low, which is 5453cd/m respectively 2 ，4.2V。
FIG. 3b is a graph of the efficiency as a function of the luminance of undoped OLEDs prepared using the blue phenanthroimidazole-containing organic semiconductor material of example 2. As can be seen from the figure, the 2TriPE-BPI-CN based undoped device has good efficiency and reduced efficiency roll, and the maximum external quantum efficiency is 2.85%; when the luminance is 1000cd/m 2 When the external quantum efficiency is 2.67%. The maximum utilization rate of the electrically excited excitons exceeds the limit value of the traditional fluorescent material and reaches 28.4 percent.
Example 8: OLEDs device performance of phenanthroimidazole-containing blue organic semiconductor material (2 TriPE-BPI-OMe)
A non-doped device is prepared by using the phenanthroimidazole-containing blue organic semiconductor material 2TriPE-BPI-OMe (blue light wavelength =462nm, solid-state fluorescence quantum yield = 47.0%) prepared in example 3 as a luminescent material, and the device performance is tested and characterized, and the result is shown in fig. 4a and fig. 4b.
Non-doped device structure: ITO/HATCN (5 nm)/TAPC (25 nm)/TCTA (15 nm)/2 TriPE-BPI-OMe (20 nm)/TPBi (40 nm)/LiF (1 nm)/Al (120 nm).
FIG. 4a is a J-V-L diagram of undoped OLEDs prepared using the blue phenanthroimidazole-containing organic semiconductor material of example 3. As can be seen from the figures, it is,the maximum brightness and the starting voltage of the non-doped device based on the 2TriPE-BPI-OMe are high and low, respectively 8588cd/m 2 ，2.6V。
FIG. 4b is a graph of the efficiency as a function of the luminance of undoped OLEDs prepared using the blue phenanthroimidazole-containing organic semiconductor material of example 3. As can be seen from the figure, the 2TriPE-BPI-OMe based undoped device has good efficiency and reduced efficiency, and the maximum external quantum efficiency is 3.01%; when the luminance is 1000cd/m 2 The external quantum efficiency was 2.84%. The maximum electric excitation exciton utilization rate exceeds the limit value of the traditional fluorescent material and reaches 32.0 percent.
Example 9: OLEDs device performance of phenanthroimidazole-containing blue organic semiconductor material (2 TriPE-BPI-MCN)
A non-doped device is prepared by using the phenanthroimidazole-containing blue organic semiconductor material 2TriPE-BPI-MCN (blue light wavelength =452nm, solid-state fluorescence quantum yield = 45.8%) prepared in example 4 as a luminescent material, and the device performance is tested and characterized, and the result is shown in fig. 5a and fig. 5b.
Non-doped device structure: ITO/HATCN (5 nm)/TAPC (25 nm)/TCTA (15 nm)/2 TriPE-BPI-MCN (20 nm)/TPBi (40 nm)/LiF (1 nm)/Al (120 nm).
FIG. 5a is a J-V-L plot of undoped OLEDs prepared using the blue phenanthroimidazole-containing organic semiconducting material of example 4. As can be seen from the figure, the maximum brightness and the starting voltage of the non-doped device based on the 2TriPE-BPI-MCN are high and low, which are 6129cd/m respectively 2 ，3.8V。
Fig. 5b is a graph of the efficiency as a function of the luminance of undoped OLEDs prepared using blue phenanthroimidazole-containing organic semiconductor material from example 4. As can be seen from the figure, the 2TriPE-BPI-MCN based undoped device has good efficiency and reduced efficiency, and the maximum external quantum efficiency is 4.60%; when the luminance is 1000cd/m 2 When the external quantum efficiency is 4.52%. The maximum utilization rate of the electrically excited excitons exceeds the limit value of the traditional fluorescent material and reaches 50.2 percent.
The data show that the invention takes the phenanthroimidazole as the construction element of the material, blue light AIE group is connected to 2,7 position of the phenanthroimidazole, electron-donating group or electron-withdrawing group is connected to para position of C2 substituted benzene of the phenanthroimidazole, and large steric hindrance group is connected to ortho position of C2 substituted benzene of the phenanthroimidazole, so that blue light molecule with AIE and 'hot electron' characteristics can be obtained, and the non-doped blue light OLEDs prepared by taking the material as the luminescent layer have high efficiency and small efficiency roll-off degree. Therefore, the organic semiconductor material has wide application prospect in the field of organic electroluminescence.
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and those skilled in the art should understand that they can make various changes, substitutions, modifications, etc. without departing from the spirit of the present invention.
Claims (2)
1. The phenanthroimidazole-containing blue organic semiconductor material is characterized in that the chemical structural formula of the phenanthroimidazole-containing blue organic semiconductor material is as follows:
2. use of the phenanthroimidazole-containing blue organic semiconductor material of claim 1 in the preparation of an organic electroluminescent device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010601059.1A CN111825618B (en) | 2020-06-28 | 2020-06-28 | Phenanthroimidazole-containing blue organic semiconductor material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010601059.1A CN111825618B (en) | 2020-06-28 | 2020-06-28 | Phenanthroimidazole-containing blue organic semiconductor material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111825618A CN111825618A (en) | 2020-10-27 |
| CN111825618B true CN111825618B (en) | 2023-01-06 |
Family
ID=72898990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010601059.1A Active CN111825618B (en) | 2020-06-28 | 2020-06-28 | Phenanthroimidazole-containing blue organic semiconductor material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111825618B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112194630A (en) * | 2020-10-30 | 2021-01-08 | 南京林业大学 | Preparation and application of organic hole transport material with imidazole derivative as core |
| CN113372333B (en) * | 2021-06-17 | 2023-08-08 | 王玮铖 | Optical material containing phenanthroimidazole structure, preparation method and application |
| CN114349708A (en) * | 2021-12-31 | 2022-04-15 | 华南理工大学 | Phenanthroimidazole-containing blue organic semiconductor material, preparation method thereof and application thereof in OLED |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105777649A (en) * | 2016-03-30 | 2016-07-20 | 吉林大学 | Aggregation-induced emissive material of triphenylethenyl-substituted phenanthroimidazole derivatives and application of aggregation-induced emissive material in preparation of organic electroluminescence device |
| CN109627217A (en) * | 2019-01-23 | 2019-04-16 | 广东工业大学 | A kind of tetraphenyl ethylene-phenanthro- imdazole derivatives and its crystal, preparation method and application |
-
2020
- 2020-06-28 CN CN202010601059.1A patent/CN111825618B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105777649A (en) * | 2016-03-30 | 2016-07-20 | 吉林大学 | Aggregation-induced emissive material of triphenylethenyl-substituted phenanthroimidazole derivatives and application of aggregation-induced emissive material in preparation of organic electroluminescence device |
| CN109627217A (en) * | 2019-01-23 | 2019-04-16 | 广东工业大学 | A kind of tetraphenyl ethylene-phenanthro- imdazole derivatives and its crystal, preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| Achievement of High-Performance Nondoped Blue OLEDs Based on AIEgens via Construction of Effective High-Lying Charge-Transfer StateOLEDs;Han Zhang et al.;《Adv. Optical Mater.》;20200305;第8卷;第1-8页及SI第4-6页 * |
| Opposite ESIPT characteristic of two AIE-active isomers with different linkage sites;Yujie Dong et al.;《Tetrahedron》;20190327;第75卷;第2670-2675页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111825618A (en) | 2020-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111825618B (en) | Phenanthroimidazole-containing blue organic semiconductor material and preparation method and application thereof | |
| CN109678844B (en) | Orange red photo-thermal activation delayed fluorescence material and organic electroluminescent device | |
| CN111943961B (en) | Organic electroluminescent compound based on phenazine-thiophene-dicyano and application | |
| CN109761879B (en) | Organic blue fluorescent material, preparation method thereof and organic electroluminescent device | |
| CN112239414B (en) | Blue organic semiconductor material based on 2, 6-di-tert-butyl anthracene and preparation method and application thereof | |
| US20110263856A1 (en) | 8-hydroxyquinoline-based white-light-emitting organic electroluminescent material | |
| Liu et al. | A novel nicotinonitrile derivative as an excellent multifunctional blue fluorophore for highly efficient hybrid white organic light-emitting devices | |
| US11515488B2 (en) | Thermally activated delayed fluorescence material having red, green, or blue color, synthesis method thereof, and application thereof | |
| CN108191847B (en) | Asymmetric donor-acceptor type organic red fluorescent small molecular material and application thereof in organic electroluminescent device | |
| CN106565595A (en) | Synthesis of novel aggregation-induced emission liquid crystal materials, and applications of novel aggregation-induced emission liquid crystal materials in blue organic electroluminescent diodes | |
| CN110615783B (en) | Electroluminescent material with pyrazinoindenone as electron acceptor and application thereof | |
| CN110003115B (en) | Blue organic luminescent material, luminescent device and preparation method | |
| CN110002946B (en) | Pyrenyl blue aggregation-induced luminescent material and preparation method and application thereof | |
| CN112239470A (en) | Anthracene derivatives, preparation and application thereof | |
| CN109608403B (en) | Anthracene-tetraphenylethylene-based organic blue light small molecule and application thereof in preparation of non-doped organic electroluminescent device | |
| CN113582908A (en) | Near-ultraviolet organic electroluminescent material based on benzene cyano, preparation method thereof and application thereof in preparing OLED | |
| CN111153892A (en) | Novel D-A type TADF material, preparation method and application thereof | |
| CN114349708A (en) | Phenanthroimidazole-containing blue organic semiconductor material, preparation method thereof and application thereof in OLED | |
| CN115093363B (en) | Organic blue light small molecule and preparation and application thereof | |
| CN112707906B (en) | Novel organic electroluminescent material based on benzopyrrole diketone and application thereof | |
| CN111675709B (en) | Fluorescent material and synthetic method thereof | |
| CN113683555B (en) | D based on biphenyl derivative receptor unit 2 A-type purple light organic luminescent material and application thereof | |
| CN113292552B (en) | Benzo five-membered ring aza derivative containing benzophenone group and preparation method and application thereof | |
| CN113105382B (en) | Biphenyl modified carbazole group anthracene-based deep blue light material and preparation and application thereof | |
| WO2021103298A1 (en) | Thermally activated delayed fluorescent material, preparation method therefor and electroluminescent device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |