CN113201120A - Red light polymer electroluminescent material and preparation method thereof - Google Patents
Red light polymer electroluminescent material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of photoelectric display devices, and particularly relates to a red light polymer electroluminescent material and a preparation method thereof. The invention provides a red light polymer electroluminescent material, which has a chemical formula shown in a formula (I). The invention belongs to the technical field of photoelectric display devices, and particularly relates to a red light polymer electroluminescent material and a preparation method thereof. The invention also provides a preparation method of the red light polymer electroluminescent material, which comprises the steps of carrying out Suzuki coupling reaction on 2, 7-dibromo-9, 9-dioctyl-9H-fluorene, 2' - (9, 9-dioctyl-9H-fluorene-2, 7-diyl) bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) and a compound shown in a formula (II) to prepare a polymer shown in a formula (I); the invention provides a red light polymer electroluminescent material and a preparation method thereof, and solves the technical problems of low luminous efficiency and unsatisfactory chromatographic purity of the existing red light polymer electroluminescent material.
Description
Technical Field
The invention belongs to the technical field of photoelectric display devices, and particularly relates to a red light polymer electroluminescent material and a preparation method thereof.
Background
Organic electroluminescence (O/PLED) has been produced as a new generation of flat panel display technology and gradually advanced into people's lives. Compared with the traditional cathode ray tube, the cathode ray tube has the advantages of light weight, active light emission, large visual angle and the like, and has the excellent characteristics of energy conservation, environmental protection, high-efficiency illumination, flexible display, low processing cost and the like, so that the cathode ray tube is suitable for flat panel display and white light illumination. Among red, blue and green based luminescent materials, only blue-light high molecular materials such as P-PPV and derivatives thereof have reached commercial level, while the luminescent efficiency and chromatographic purity of the existing red-light high molecular materials still need to be improved, so that the development of high-performance red-light polymer materials is urgently needed to solve the technical problem urgently needed by the technical personnel in the field.
Disclosure of Invention
The invention provides a red light polymer electroluminescent material and a preparation method thereof, and solves the technical problems of low luminous efficiency and unsatisfactory chromatographic purity of the existing red light polymer electroluminescent material.
The invention provides a red light polymer electroluminescent material, which has a chemical formula shown as a formula (I):
wherein R is aryl, triphenylamine, C1-20 linear or branched alkyl, or C1-20 alkoxy, x is 0.1-1, and n is 100-.
The invention provides a preparation method of a red light polymer electroluminescent material, which comprises the steps of carrying out Suzuki coupling reaction on 2, 7-dibromo-9, 9-dioctyl-9H-fluorene, 2' - (9, 9-dioctyl-9H-fluorene-2, 7-diyl) bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) and a compound shown in a formula (II) to prepare a polymer shown in a formula (I);
preferably, the compound of formula (II) is prepared by:
step 1: carrying out bromination reaction on 3, 4-ethylenedioxythiophene and N-bromosuccinimide to prepare a compound shown in a formula (IV);
step 2: carrying out substitution reaction on a compound shown in a formula (IV) and 4-iodophenol to obtain a compound shown in a formula (III);
and step 3: 4- (2, 7-dibromo carbazole-9-yl) aniline, a compound shown in a formula (III) and 1, 10-phenanthroline are subjected to substitution reaction to prepare a compound shown in a formula (II).
Preferably, the temperature of the Suzuki coupling reaction is 90 ℃.
Preferably, the content of the 2, 7-dibromo-9, 9-dioctyl-9H-fluorene is (0.3 to 0.9) mmol, and the content of the compound represented by the formula (II) is (0.1 to 0.7) mmol.
Preferably, the content of the 2, 7-dibromo-9, 9-dioctyl-9H-fluorene is 0.5mmol, and the content of the compound represented by the formula (II) is 0.5 mmol.
The invention has the following beneficial effects:
the electroluminescent performance data of the polymer prepared by the invention are better than that of the comparative example 1, and the optimal current efficiency is 5.8cd A-1，The light-emitting luminance was 8647cd m-2And the color coordinates are red light and are positioned near (0.66, 0.33).
Drawings
FIG. 1 is a graph showing ultraviolet-visible (UV-vis) absorption spectra of tetrahydrofuran solutions of examples 4 to 7 of the present invention and comparative example 1;
FIG. 2 is ultraviolet-visible (UV-vis) absorption spectra in thin film state of examples 4 to 7 of the present invention and comparative example 1;
FIG. 3 is fluorescence emission spectra of tetrahydrofuran solutions of examples 4 to 7 of the present invention and comparative example 1;
FIG. 4 is a fluorescence emission spectrum in a thin film state of examples 4 to 7 of the present invention and comparative example 1;
FIG. 5 is a current density-voltage curve (J-V) for the single hole device of comparative example 1;
FIG. 6 is a current density-voltage curve (J-V) for a single hole device of example 4 of the present invention;
FIG. 7 is a current density-luminance-voltage curve of examples 4 to 7 of the present invention and comparative example 1;
FIG. 8 is a graph of current density versus current efficiency for examples 4-7 of the present invention and comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are not intended to limit the present invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
3, 4-ethylenedioxythiophene (5mL,27.86mmol), glacial acetic acid (50mL) and concentrated sulfuric acid (50mL) were added to a 250mL single-neck flask at 0-5 deg.C, and stirred away from light. Then (12.3g,180mmol) N-bromosuccinimide (NBS) was added in three portions and gradually warmed to room temperature for reaction overnight. Diluting the reaction mixture with a large amount of water, separating the solid, and then reusing NaHCO3The aqueous solution and methanol were washed several times, dried and then purified using a hot chlorobenzene solvent to obtain a compound represented by the formula (IV) (4.3g, yield 70%) having the chemical reaction equation:
example 2
150ml of DMF was mixed with a compound of the formula (IV) (39.7g, 180mmol), 4-iodophenol (25.36g, 115.27mmol) and potassium carbonate (31.74g, 229.65 mmol). The reaction mixture was heated to 80 ℃ under nitrogen at reflux overnight. The mixture was then cooled to room temperature and 200ml cold water was added. The mixture was then extracted with 500ml of dichloromethane. The organic phases are combined and washed with 500ml of saturated brine, dried over magnesium sulfate and the solvent is evaporated. The obtained crude product was purified by column chromatography (petroleum ether) to obtain a compound represented by the formula (III) (46.6g, 72%) whose chemical reaction formula is:
example 3
To 4- (2, 7-dibromocarbazol-9-yl) aniline (6.24g, 15mmol), the compound represented by the formula (III) (10.08g, 28mmol), 1, 10-phenanthroline (0.09g, 0.50mmol), copper chloride (0.05g, 0.51mmol) and potassium hydroxide (4g, 71.3mmol), 50ml of toluene was added, followed by reflux reaction under argon for 48 hours. The reaction mixture is then cooled to room temperature and 200ml of water are added, extraction is then carried out 3 times with 200ml of dichloromethane, the combined organic phases are washed with water and dried over magnesium sulfate, the solvent is evaporated, and the crude product is purified by distillation over petroleum ether: purification by silica gel column chromatography using triethylamine ═ 20:1 as an eluent gave the compound represented by formula (II) (11.6g, 88%) whose chemical reaction formula was:
example 4
A100 ml three-necked flask equipped with a thermometer was charged with a magnetic stirrer, and the polymerization monomers 2, 7-dibromo-9, 9-dioctyl-9H-fluorene (0.349g, 0.9mmol), 2' - (9, 9-dioctyl-9H-fluorene-2, 7-diyl) bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) (0.64g, 1mmol) and the compound represented by the formula (II) (0.089g, 0.1mmol) were charged in the three-necked flask in this order, and 0.0045g (0.02mmol) of Pd (OAc)20.022g (0.06mmol) of P (Cy)38ml of TEAOH with the mass fraction of 25% and 6ml of toluene are stirred uniformly. Vacuumizing, introducing nitrogen, and reacting at constant temperature of 90 ℃ for 24 hours. Finally, 0.061g (0.5mmol) of phenylboronic acid is added for reaction for 4 hours, and 0.0785g (0.5mmol) of bromobenzene is further added for reaction for 6 hours. After the reaction, the reaction solution in the three-neck flask was precipitated with anhydrous methanol, the solid product was collected by filtration and dried, and then the crude product was purified by silica gel column chromatography to obtain polymer P1 with a yield of 52%.
Example 5
The difference between this example and example 4 is: a content of 2, 7-dibromo-9, 9-dioctyl-9H-fluorene (0.27g, 0.7mmol) and a content of the compound represented by the formula (II) (0.267g, 0.3mmol) were obtained, and a polymer P2 was finally obtained in a yield of 51%, which was represented by the formula:
example 6
The difference between this example and example 4 is: a content of 2, 7-dibromo-9, 9-dioctyl-9H-fluorene (0.19g, 0.5mmol) and a content of the compound represented by the formula (II) (0.445g, 0.5mmol) were respectively obtained, and a polymer P3 was finally obtained in a yield of 52%, which was represented by the formula:
example 7
The difference between this example and example 4 is: a content of 2, 7-dibromo-9, 9-dioctyl-9H-fluorene (0.11g, 0.3mmol) and a content of the compound represented by the formula (II) (0.623g, 0.7mmol) were obtained, and finally, a polymer P4 was obtained in a yield of 52%, which was represented by the formula:
example 8
Preparing an electroluminescent device: firstly, cleaning ITO glass by using an ITO cleaning agent, deionized water, acetone and isopropanol under ultrasonic waves, then purging by using nitrogen, putting the cleaned ITO glass into a constant-temperature oven at 120 ℃ for drying, treating plasma of a pure ITO sheet in an ultraviolet-ozone cleaning machine for 10 minutes, and then coating PEDOT (Poly ethylene glycol Ether-styrene) PSS (PolyEthylene Ether) water dispersion on the pure ITO sheet. Rotating at 3000r/min, placing in a 120 deg.C temperature regulator after 2 min, drying for 30 min, removing residual solvent, and forming into film with thickness of 30 nm. Subsequently, an anhydrous chloroform solution (12mg/ml) of the light-emitting polymer synthesized in examples 4 to 7 of the present invention formed a light-emitting layer on a PEDOT: PSS-modified indium tin oxide surface coating layer having a film thickness of 95 nm; and in an active area of 0.09cm2Deposition pressure of 110-4And evaporating cathode layers of 20nmCa and 100nmAl on a vacuum film coating machine of Pa in sequence to manufacture a device with an ITO/PEDOT: PSS/Polymer/Ca/Al structure. The film thickness was measured by a Tencor Alfa Step-500 Step meter, and the vacuum deposition rate of the metal electrode and its thickness were measured by a thickness/velocity meter (STM-100)And (4) determining. The encapsulation of the device is cured and encapsulated in ultraviolet light through epoxy resin and thin-layer glass, and the electroluminescence spectrum, the color coordinate and the external quantum efficiency of the device can be measured in the air after the encapsulation.
Comparative example 1
The red light-emitting material in this comparative example was Ir (piq)3。
In summary, FIGS. 1 and 2 show the ultraviolet-visible (UV-Vis) absorption spectra of the tetrahydrofuran solution (solution concentration of 0.01mg/ml) and the film of example 1 of the present invention and comparative example 1, respectively, wherein the UV absorption spectrum of the solution is measured by a UV absorption spectrophotometer model number SHIMADZU UV-3600, UV-Vis-NIR, the temperature is 25 ℃, the scanning range is 250nm-780nm, and it can be seen from FIGS. 1 and 2 that the UV absorption peak of the polymer P1-P4 prepared by example of the present invention is compared with that of Ir (piq)3The absorption peaks of (A) are all red-shifted, and the degree of red shift of the ultraviolet absorption peak of the polymer is larger with the increase of the content of the structural unit of the compound shown in the formula (II).
FIG. 3 is a fluorescence spectrum obtained when tetrahydrofuran was used as a solvent and the concentration of the solution was 0.01mg/ml, wherein the fluorescence spectrum was measured by using a HITACHI F7000 steady-state fluorescence spectrometer, and it can be seen from FIG. 3 that the luminescence wavelengths of the polymers prepared in the examples of the present invention were all in the red region, and that the higher the content of the compound represented by formula (II) was, the higher the fluorescence emission peak of P1-P4 was compared with that of Ir (piq) in the solution state3The larger the red shift occurs, the phenomenon can be attributed to the reinforced interaction of EDOT and triphenylamine with carbazole in the main chain, the more serious the distortion degree of the conjugated main chain, the shortened effective conjugation length of the main chain, and the red shift occurs to the fluorescence emission peak of the polymer.
FIG. 4 is a graph showing fluorescence emission spectra of polymers prepared in examples of the present invention and comparative example 1 in a thin film state, wherein a thin film sample was prepared by preparing a sample into a solution and spin-coating the solution on a quartz plate when measuring the thin film fluorescence spectrum of the polymer. As can be seen from FIG. 4, in the thin film state, the emission peaks of the examples of the present invention are all in the red region of 600-680nm, and the intensity is higher than that of the comparative example 1.
The current-voltage characteristics, color coordinates and brightness-voltage characteristics of the device are measured by a current voltage source-PR 655 measuring system with the instrument model of Keithley 2400. Fig. 5 is a current density-voltage curve (J-V) of the single hole device of comparative example 1, and it can be seen from fig. 5 that the current density of electrons is greater than that of holes in the operating voltage range from 0 to 10V, indicating that electron transport is dominant. Fig. 6 is a current density-voltage curve (J-V) of a polymer single-hole device prepared in example 4 of the present invention, and it can be seen from fig. 7 that the current density of the polymer P1 holes is substantially the same as that of electrons in the operating voltage range, which indicates that the injected electron hole transport is balanced, and the device performance is effectively improved.
Fig. 7 and 8 are a current density-luminance-voltage curve and a current density-current efficiency curve of examples according to the present invention and comparative examples, respectively, and it can be seen from fig. 7 that the turn-on voltage of the devices of examples 4 to 7 is reduced compared to that of the device of comparative example 1. At the same voltage (the voltage value exceeds the starting voltage), the current density and the brightness both tend to increase with the increase of the content of the compound represented by the formula (II), which indicates that more carriers are recombined in the light-emitting layer to form excitons. As can be seen from FIG. 8, the current efficiency and luminance of the devices of examples 4 to 7 were increased as compared with the device of comparative example 1, wherein the performance data of the electroluminescent diodes manufactured based on the examples of the present invention and the comparative example are shown in Table 1 (the electroluminescence spectra of the polymer devices were measured at a voltage of 10V)
TABLE 1 electroluminescent Properties of inventive examples 4-7 and comparative example 1
| Examples/comparative examples | Von | L(cd/m2) | LE(cd/A) | CIE(x，y) |
| Example 4 | 4.2 | 8647 | 3.2 | (0.66,0.33) |
| Example 5 | 3.6 | 7793 | 4.6 | (0.67,0.32) |
| Example 6 | 3.4 | 6936 | 5.8 | (0.66,0.39) |
| Example 7 | 4.2 | 6864 | 4.7 | (0.67,0.34) |
| Comparative example 1 | 5.2 | 5047 | 2.8 | (0.66,0.33) |
As can be seen from Table 1, the electroluminescent properties of the polymers prepared in examples 4 to 7 of the present invention are superior to those of the polymers prepared in examples 1Electroluminescent performance data for comparative example 1 with an optimum current efficiency of 5.8cd A-1，The light-emitting luminance was 8647cd m-2And the color coordinates are red light and are positioned near (0.66, 0.33).
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. A red light polymer electroluminescent material is characterized in that the chemical formula is shown as the formula (I):
wherein R is aryl, triphenylamine, C1-20 linear or branched alkyl, or C1-20 alkoxy, x is 0.1-1, and n is 100-.
2. A preparation method of a red light polymer electroluminescent material is characterized by comprising the steps of carrying out Suzuki coupling reaction on 2, 7-dibromo-9, 9-dioctyl-9H-fluorene, 2' - (9, 9-dioctyl-9H-fluorene-2, 7-diyl) bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) and a compound shown as a formula (II) to prepare a polymer shown as a formula (I);
3. the method of claim 2, wherein the compound of formula (II) is prepared by the following steps:
step 1: carrying out bromination reaction on 3, 4-ethylenedioxythiophene and N-bromosuccinimide to prepare a compound shown in a formula (IV);
step 2: carrying out substitution reaction on a compound shown in a formula (IV) and 4-iodophenol to obtain a compound shown in a formula (III);
and step 3: 4- (2, 7-dibromo carbazole-9-yl) aniline, a compound shown in a formula (III) and 1, 10-phenanthroline are subjected to substitution reaction to prepare a compound shown in a formula (II).
4. The method for preparing the red-light polymer electroluminescent material according to claim 2, wherein the temperature of the Suzuki coupling reaction is 90 ℃.
5. The method of claim 2, wherein the 2, 7-dibromo-9, 9-dioctyl-9H-fluorene content is (0.3-0.9) mmol, and the compound represented by the formula (II) content is (0.1-0.7) mmol.
6. The method for preparing red-light-emitting polymer electroluminescent material according to claim 5, wherein the content of 2, 7-dibromo-9, 9-dioctyl-9H-fluorene is 0.5mmol, and the content of the compound represented by formula (II) is 0.5 mmol.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1419574A (en) * | 2000-01-05 | 2003-05-21 | 剑桥显示技术有限公司 | Polymers, their preparation and uses |
| CN1702066A (en) * | 2005-06-22 | 2005-11-30 | 中国科学院长春应用化学研究所 | Hole transport materials with 9-phenyl carbazole as core and process for making same |
| CN102399359A (en) * | 2011-11-25 | 2012-04-04 | 华南理工大学 | Triphenylamine conjugated polymer containing phosphate and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1419574A (en) * | 2000-01-05 | 2003-05-21 | 剑桥显示技术有限公司 | Polymers, their preparation and uses |
| CN1702066A (en) * | 2005-06-22 | 2005-11-30 | 中国科学院长春应用化学研究所 | Hole transport materials with 9-phenyl carbazole as core and process for making same |
| CN102399359A (en) * | 2011-11-25 | 2012-04-04 | 华南理工大学 | Triphenylamine conjugated polymer containing phosphate and application thereof |
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