CN111747900A - Novel electronic transmission material - Google Patents

Novel electronic transmission material Download PDF

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CN111747900A
CN111747900A CN202010696880.6A CN202010696880A CN111747900A CN 111747900 A CN111747900 A CN 111747900A CN 202010696880 A CN202010696880 A CN 202010696880A CN 111747900 A CN111747900 A CN 111747900A
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electron
electron transport
transport material
compound
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CN111747900B (en
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鲍斌
孙仲猛
石志亮
张雄飞
阮群奇
王旭亮
李文晓
张慧勤
李明政
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Yantai Shenghua Liquid Crystal Material Co ltd
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Abstract

The invention discloses a novel electron transport material, which is an organic compound with a general formula (I),

Description

Novel electronic transmission material
Technical Field
The invention relates to a novel electronic transmission material which is mainly applied to the fields of Organic Photoconductors (OPCS), organic electroluminescent diodes (OLED), organic solar cells (OPVCS), Organic Field Effect Transistors (OFETS), photoelectric detection, sensors and the like.
Background
In Organic Light Emitting Diodes (OLEDs), the property of emitting light when a material is excited by an electric current is exploited. OLEDs are particularly useful as replacements for cathode ray tubes and liquid crystal displays for the production of flat panel direct view display devices. Due to the very compact design and the inherently low power consumption, devices comprising LEDs are particularly suitable for mobile applications, such as in mobile phones, notebook computers and the like.
Since the advent of organic light emitting diodes and solar cells in 1989, elements made from organic thin films in appl.phys.lett.51 (21), 913, (1987) by c.w.tang et al have been the subject of intensive research. These films have advantageous properties for said applications, such as, for example, high-efficiency electroluminescence for organic light-emitting diodes, high absorption coefficient in the visible range for organic solar cells, inexpensive production of materials and manufacture for the elements of the simplest electronic circuits. The use of organic light emitting diodes for display applications has been of commercial significance. The performance characteristics of (opto-) electronic multilayer components depend, among other things, on the ability of said layers to transport charge carriers. In the case of light-emitting diodes, the resistance losses in the charge transport layer during operation are related to the conductivity which, on the one hand, directly influences the required operating voltage, but, on the other hand, also determines the thermal load of the component. Also, depending on the concentration of charge carriers within the organic layer, the curvature of the band near the metal contact simplifies the injection of charge carriers, and thus may reduce contact resistance. Similar considerations with respect to organic solar cells also lead to the conclusion that their efficiency also depends on the transport properties of the charge carriers. An important ring of organic semiconductors are organic charge transport materials, the properties of which determine the best performance of the device.
The organic charge transport material is an organic semiconductor material which can realize the controllable directional ordered movement of carriers under the action of an electric field when carrier electrons or holes are injected, thereby carrying out charge transport. The electronic property, the conduction mechanism and the impurity influence of the organic semiconductor material are different from the traditional inorganic semiconductor material which reveals the relationship between the chemical structure and the physical property of the organic semiconductor, and researches and prepares model devices, so that the organic semiconductor material not only has important scientific significance, but also has huge application prospect. Compared with inorganic materials, the organic charge transport material has the advantages of low cost, low toxicity, easy processing and molding, molecular tailoring for meeting different requirements, large-area and fully flexible devices and the like. In recent years, the development of organic semiconductors is very rapid, and the organic semiconductors are widely applied to many fields such as Organic Photoconductors (OPCS), organic electroluminescent diodes (OLED), organic solar cells (OPVCS), Organic Field Effect Transistors (OFETS), photodetectors, and sensors, and become one of the hot spots of domestic and foreign research.
Despite the inherent advantages of organic charge transport materials, despite the great advances currently made in organic field effect transistors, several key problems remain to be solved, such as designing and synthesizing a material that has high mobility, good stability, and is solution processable, reducing the operating voltage of devices, increasing the mobility of devices, and the like.
Organic electroluminescent devices (OLEDs) have advantages of active light emission, high energy efficiency, wide viewing angle, and high response speedThe special characteristics, especially the potential application prospect in the aspects of full-color display and light source, have more and more attracted the research interest in the scientific and commercial industries in recent years. Among all the elements, fluorine has the greatest electronegativity and a value of 4, and the bond energy of the C-F bond is 480 kJ. mol due to polarization－1. In addition, the negative inductive Effect of fluorine atoms (σ)I0.51) and positive conjugation Effect (Mesomeric Effect, σ)RThe problem of stability of organic semiconductor materials and the lack of n-type semiconductor materials are two major factors hindering commercialization of OLEDs, and recently it has been reported that halogenation is one approach to solve these problems.furthermore, C-H … F interaction in fluoro materials, similar to hydrogen bonding, has an important role in solid state stacking, which causes a typical pi-stacking arrangement, with small inter-molecular distance, thereby enhancing charge mobility, fluorine atoms block the external oxygen and water intrusion, effectively preventing the formation of molecular traps, serving as an air stability function.for example, benzene has a large quadrupole moment and is (-29.0 dipole 2-40 cm2), while hexafluorobenzene has a rectangular shape, which is a negative dipole 2-10 cm 6754, and six-fluoro-benzene has a negative electron-attracting distribution (-29.0- × -40 cm 6754), but a negative electron-six-electron-attracting density distribution of about 7.7-40 cm 42, which is a positive or more than six electron-six-electron-six-electron-six-electron-six-electron-six-electron-six-electron-six.
In addition, the fluorination can change the photophysical characteristics of the material to realize the blue shift of the emission peak of the material, and the organic iridium-phenylpyridine complex in the OLED reduces the non-radiative decay by the fluorination of the ligand, thereby improving the luminous efficiency. Fluorination can lower the sublimation temperature of the organic material and is beneficial to the purification of the material. In 2007, France co Naso et al concluded the use of fluorinated conjugated organic materials with semiconducting properties in OLEDs and Organic Field Effect Transistors (OFETs). The fluorine atom, fluoroalkyl or fluoroaryl modified organic conjugated material can significantly reduce HOMO and LUMO, the low LUMO is beneficial to electron injection, and the work function of the matched LUMO and a metal cathode can adopt durable aluminum as an electrode. At the same time, the hole-electron injection balance can increase the efficiency of the device. In addition, the reduced HOMO energy level makes the fluorinated conjugated organic material less susceptible to oxidative degradation, so that in some extent, the lifetime of the device is increased, and based on the defects of the organic electron transport material itself, the design must consider both high mobility and air stability, and the molecular design of the organic electron transport material generally follows the following two principles:
1) strong electron-withdrawing groups or nitrogen atom groups with electron deficiency are introduced, such as fluorination, nitration, cyanation, imidization and the like, to reduce the energy level of the knife, so as to be beneficial to electron injection, and meanwhile, the reduction of the energy level also avoids electron traps generated by the oxidation of organic molecules by oxygen, so that the mobility can be improved and the service life of devices can be prolonged;
2) designing and synthesizing a large conjugated system with a symmetrical structure. To meet the requirements of polarizability and dipole moment.
The carrier transport rate directly determines the exciton recombination efficiency and recombination region and thus the device efficiency, so the carrier mobility (hole mobility μ)hElectron mobility μe) Is an important index for evaluating the performance of the carrier transport material. According to the carrier transport theory of organic semiconductors, two determining factors influencing the carrier transport rate are molecular recombination energy and transfer integral, respectively. The better the planarity of the molecule, the lower the recombination energy and the more favourable the transport of charge carriers. The greater the effective orbital overlap from molecule to molecule, the greater the corresponding transfer integral, and the more favorable the charge transport. At present, the common methods for measuring the transmission rate of carriers in organic semiconductors mainly include a time of flight (TOF) method and a space charge limited current (SCL) methodC) Steady-state current-voltage method W and instant electroluminescence method.
Organic electroluminescent devices (OLEDs) are known with their unique advantages as the most promising display and lighting technology in the future. In OLEDs, balanced carrier transport is a prerequisite for high efficiency and long lifetime of devices, however, the mobility of holes (μ) in currently developed carrier transport materialsh) The mobility (mue) of the electron is higher than that of the electron by 2-3 orders of magnitude, so that the mue of the material is improved to be a core problem of the research of an Electron Transport Material (ETM). Although various ETMs have been developed in recent years and certain efficiencies have been obtained, there are few materials that can actually meet practical requirements, and thus, there is still a great need to develop new ETMs.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a novel electron transport material which has good electron accepting capacity and electron transport capacity; as the fluorine atoms in the trifluoromethyl block the attack of external oxygen and water, the formation of molecular traps is effectively prevented, and the trifluoromethyl has better chemical and physical stability.
A novel electron transport material is characterized in that the material is a compound with a general formula (I):
Figure RE-GDA0002652508770000041
wherein R is1And R2Identical or different, each independently of the others represents-H, -F, -CN, a halogenated or non-halogenated linear or branched alkyl or alkoxy group having 1 to 5 carbon atoms, or
Figure RE-GDA0002652508770000042
Z is selected from
Figure RE-GDA0002652508770000043
Figure RE-GDA0002652508770000044
Figure RE-GDA0002652508770000051
The cyclic structure of (3).
Further, R in the compound1And R2Identical or different, each independently of the others represents-H, -F, a fluorinated or non-fluorinated linear or branched alkyl or alkoxy radical having from 1 to 5 carbon atoms, or
Figure RE-GDA0002652508770000052
Further, R in the compound1And R2The same or different, or each independently represents H or-F.
Further, R in the compound1And R2The same or different, or each independently represents H or-F.
Further, Z in the compound is selected from
Figure RE-GDA0002652508770000053
Figure RE-GDA0002652508770000054
Figure RE-GDA0002652508770000055
The cyclic structure of (3).
Further, Z in the compound is selected from
Figure RE-GDA0002652508770000056
Figure RE-GDA0002652508770000057
The cyclic structure of (3).
Further, said compounds are selected from the group consisting of:
Figure RE-GDA0002652508770000058
Figure RE-GDA0002652508770000061
compared with the traditional electron transport material TAZ, the novel electron transport material containing a plurality of trifluoromethyl, a symmetrical structure and a large conjugated system of the compound has higher electron mobility and lower working voltage in devices of the same type. The material can be applied to various fields such as Organic Photoconductors (OPCS), organic light-emitting diodes (OLED), organic solar cells (OPVCS), Organic Field Effect Transistors (OFETS), photoelectric detection, sensors and the like.
Detailed Description
Example 1, preparation of 3, 3' -bis (4, 6-bis (3-trifluoromethylphenyl) -1,3, 5-triazinyl) -2', 2', 3', 5', 6' -octafluoro-1, 1':4', 1':4', 1' -tetrabiphenyl, having the structure shown in formula I-1,
Figure RE-GDA0002652508770000071
a three-neck flask of compound I-1a, 5L is synthesized by the method of references Catalysis Communications, 2019, vol.127, p.58-63, and 279g of 3-bromobenzyl alcohol, 471g of 3-trifluoromethylbenzamidine, 100g of OMS-2-SH-B and 2.5L of toluene are added, and oil bath heating stirring, oxygen protection, reflux and temperature control devices are installed. And (3) filling oxygen, evacuating for 10 times, heating in an oil bath, keeping the temperature to 70-80 ℃ for reaction for 4 hours, continuously heating to 110 ℃, refluxing for 26-32 hours, sampling and detecting that G is less than 2% of 3-bromobenzyl alcohol, stopping the reaction, recovering toluene and 3-bromobenzyl alcohol under reduced pressure, supplementing n-heptane, filtering, performing column chromatography, desolventizing and recrystallizing isopropanol to obtain 495.23G I-1a with the yield of 75.6%.
52.3g I-1a, 10.88g of 4,4' -biphenyl diboronic acid, 11g of anhydrous sodium carbonate, 100g of deionized water, 100mL of ethanol, 300mL of toluene and 0.5g of dichloro-di-tert-butyl-4-dimethylaminophenyl) phosphine palladium (II) are added into a 1L three-necked bottle, and an oil bath heating stirring device, a nitrogen protection device, a reflux device and a temperature control device are installed. And (3) filling nitrogen and evacuating for 10 times, heating in an oil bath, keeping the temperature to 65-72 ℃ for reaction for 4 hours, continuously heating to 110 ℃ for reflux for 16-20 hours, sampling, detecting HPLC, stopping the reaction when the I-1a is less than 0.1%, performing liquid separation and water washing, performing column chromatography, desolventizing and toluene recrystallization to obtain 33.8g I-1, wherein the yield is 72.2%.
By element analysis: c: 66.86%, H: 3.02%, F: 21.63%, N: 8.27%, which is substantially in accordance with the theoretical value.
Example 2, preparation of 3,3 '-bis (4, 6-bis (3-trifluoromethylphenyl) -1,3, 5-triazinylene) -1,1':4', 1':4', 1' -quaterphenyl, the structure of which is shown in general formula I-2,
Figure RE-GDA0002652508770000081
15.69g I-1a, 100mL of anhydrous ether and 200mL of dry toluene are added into a 1L tetrafluoro four-mouth bottle, and a stirring, nitrogen protection, temperature control and ultralow temperature reaction device is installed. Filling nitrogen and evacuating for 10 times, cooling to-85 ℃ under the protection of the nitrogen, controlling the temperature to be-82 to-78 ℃, dropwise adding 50ml of tert-butyl lithium (1.3M), and after dropwise adding, keeping the temperature to be-75 to-70 ℃ for reaction for 2 hours; controlling the temperature to be minus 82 to minus 78 ℃ under the protection of nitrogen, dripping 5g of perfluorobiphenyl and 50ml of toluene solution, keeping the temperature to be minus 75 to minus 70 ℃ after finishing dripping, and reacting for 4 hours; sampling and detecting HPLC, wherein the perfluorobiphenyl content is less than 0.01 percent, quenching reaction can be carried out, and 10.16g I-2 is obtained through liquid separation and water washing, column chromatography and toluene recrystallization, and the yield is 57.2 percent.
Example 3 preparation of 2, 2-bis (2- ([1,1' -biphenyl ] -3-yl) -4, 6-bis (3-trifluoromethylphenyl) -1,3, 5-triazine) yl hexafluoropropane, whose structure is represented by the general formula I-3,
Figure RE-GDA0002652508770000091
138g of 2, 2-bis (4-bromophenyl) hexafluoropropane and 2000ml of dry tetrahydrofuran are added into a 5L four-port bottle, and a stirring, nitrogen protection, temperature control and ultralow temperature reaction device is installed. Filling nitrogen and evacuating for 10 times, cooling to-85 ℃ under the protection of the nitrogen, controlling the temperature to be-80 to-75 ℃, dropwise adding 300ml of n-butyl lithium (2.5M), and preserving the temperature to be-75 to-70 ℃ for reaction for 3 hours after the dropwise adding is finished; under the protection of nitrogen, controlling the temperature to be-80 to-75 ℃, dropwise adding 130g of triisopropyl borate, and after dropwise adding, keeping the temperature to be-70 to-65 ℃ for reaction for 4 hours; sampling and detecting HPLC, wherein the content of 2, 2-bis (4-bromophenyl) hexafluoropropane is less than 0.05 percent, quenching reaction can be carried out, and 97.16g I-3b is obtained by desolventizing, washing with deionized water, washing with toluene and drying, and the yield is 82.6 percent.
116.22g I-1a, 39.2g I-3b, 23.6g of anhydrous sodium carbonate, 500g of deionized water, 500mL of ethanol, 1500mL of toluene and 1g of dichloro-di-tert-butyl- (4-dimethylaminophenyl) phosphine palladium (II) are added into a 5L three-necked bottle, and an oil bath heating stirring device, a nitrogen protection device, a reflux device and a temperature control device are installed. And (3) filling nitrogen and evacuating for 10 times, heating in an oil bath, keeping the temperature to 65-72 ℃ for reaction for 4 hours, continuously heating to 110 ℃ for reflux for 26-30 hours, sampling, detecting HPLC, stopping the reaction when the I-1a is less than 0.1%, performing liquid separation and water washing, performing column chromatography, desolventizing and toluene recrystallization to obtain 89.64g I-3, wherein the yield is 75.3%.
By element analysis: c: 61.37%, H: 2.68%, F: 28.5%, N: 7.23%, which is substantially in accordance with the theoretical value.
Example 4 preparation of N2, N9-bis (3- (4, 6-bis (3-trifluoromethylphenyl) -1,3, 5-triazin-2-yl) phenyl) -3,4,9, 10-perylenetetracarboxylic diimide having the structure shown in the general formula I-5,
Figure RE-GDA0002652508770000101
111.64g of BOC-3-aminobenzyl alcohol, 157.03g of 3-trifluoromethyl benzamidine, 50g of OMS-2-SH-B and 2.5L of toluene are added into a 5L three-necked flask, and an oil bath heating stirring device, an oxygen protection device, a reflux device and a temperature control device are installed. And (3) filling oxygen, evacuating for 10 times, heating in an oil bath, keeping the temperature to 70-80 ℃ for reaction for 4 hours, continuously heating to 110 ℃, refluxing for 26-32 hours, sampling and detecting that G is less than 2% of 3-bromobenzyl alcohol, stopping the reaction, recovering toluene and 3-bromobenzyl alcohol under reduced pressure, supplementing toluene, filtering, performing column chromatography, desolventizing and recrystallizing the toluene to obtain 121.84G I-5a-1, wherein the yield is 52.1%.
121.84g I-5a-1, 1L methyl tert-butyl ether and 0.3L dilute hydrochloric acid (6M) are added into a 2L three-neck flask, and an oil bath heating stirring, nitrogen protection, reflux and temperature control device are installed. Filling nitrogen and evacuating for 10 times, heating in oil bath, heating to 55 ℃, refluxing for 26-32h, sampling and detecting HPLC, wherein I-5a-1 is less than 2.5%, stopping the reaction, cooling under the protection of nitrogen, slowly pouring the reaction into 6M 0.6L dilute NaOH ice water, washing with liquid-separating water, desolventizing, and recrystallizing with toluene to obtain 92.28g I-5a with a yield of 92.2%.
92.28g I-5a, 31.56g of 3,4,9, 10-tetracarboxylic anhydride and 1000mL of DMF were added into a 2L three-necked flask, and an oil bath was installed for heating and stirring, nitrogen protection, reflux and temperature control. Filling nitrogen and evacuating for 10 times, heating and refluxing for 36-42h in an oil bath, sampling and detecting HPLC, stopping the reaction when the content of 3,4,9, 10-tetracarboxylic anhydride is less than 0.1%, cooling, adding water for crystallization, performing suction filtration, washing with isopropanol, and recrystallizing with toluene to obtain 70.5g I-5 with the yield of 68.8%.
By element analysis: c: 65.72%, H: 2.51%, F: 17.63%, N: 8.92%, O: 5.13%, which is substantially in accordance with the theoretical value.
To compare the operating voltages and electron mobilities, μ, of five electron transport materials (TAZ, I-1, I-2, I-3, I-5)eA group of single electron transport layer devices (ITO/LiF (1nm)/ETL (60nm)/LiF (0.5nm)/Al (120nm)) are designed and prepared. The single electron transport layer device structure comprises an ITO anode, a 1nm LiF hole blocking layer, a 60nm electron transport layer and a 0.5/120nm Li F/Al cathode.
Using TAZ as ETL, the operating voltage of the device was 8.2V, measured as μe＝1.57×10-6m2/(V·s)
Using I-1 as the ETL, the operating voltage of the device was 6.6V, measured as μe＝5.27×10-6m2/(V·s)
Using I-2 as the ETL, the operating voltage of the device was 5.1V, measured as μe＝7.32×10-6m2/(V·s)
Using I-3 as the ETL, the operating voltage of the device was 4.5V, measured as μe＝8.71×10-6m2/(V·s)
Using I-5 as the ETL, the operating voltage of the device was 3.2V, measured as μe＝9.76×10-6m2/(V·s)
Through the comparison of the devices, the novel electron transport material has higher electron mobility and lower working voltage than the traditional material TAZ, and has good application prospect in a plurality of fields such as Organic Photoconductors (OPCS), organic light-emitting diodes (OLED), organic solar cells (OPVCS), Organic Field Effect Transistors (OFETS), photoelectric detection and sensors.

Claims (6)

1. A novel electron transport material, characterized in that it is a compound having the general formula (i):
Figure RE-FDA0002652508760000011
wherein R is1And R2Identical or different, each independently of the others represents-H, -F, -CN, a halogenated or non-halogenated linear or branched alkyl or alkoxy group having 1 to 5 carbon atoms, or
Figure RE-FDA0002652508760000012
Z is selected from
Figure RE-FDA0002652508760000013
Figure RE-FDA0002652508760000014
Figure RE-FDA0002652508760000015
The cyclic structure of (3).
2. A novel electron transport material according to claim 1, wherein R in said compound is1And R2Identical or different, each independently of the others represents-H, -F, a fluorinated or non-fluorinated linear or branched alkyl or alkoxy radical having from 1 to 5 carbon atoms, or
Figure RE-FDA0002652508760000016
3. A novel electron transport material according to claim 2, wherein R in said compound is1And R2The same or different, and the same or different,or each independently represents H or-F.
4. The novel electron transport material of claim 1, wherein Z in the compound is selected from the group consisting of
Figure RE-FDA0002652508760000017
Figure RE-FDA0002652508760000021
Figure RE-FDA0002652508760000022
The cyclic structure of (3).
5. The novel electron transport material of claim 4, wherein Z in the compound is selected from the group consisting of
Figure RE-FDA0002652508760000023
Figure RE-FDA0002652508760000024
The cyclic structure of (3).
6. The novel electron transport material of claim 1, wherein the compounds are selected from the group consisting of:
Figure RE-FDA0002652508760000025
Figure RE-FDA0002652508760000031
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KR20170111802A (en) * 2016-03-29 2017-10-12 주식회사 엘지화학 Organic light emitting device
WO2020050563A1 (en) * 2018-09-03 2020-03-12 주식회사 엘지화학 Organic light emitting diode
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KR20120038032A (en) * 2010-10-07 2012-04-23 에스에프씨 주식회사 Heterocyclic com pounds and organic light-emitting diode including the same
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