CN113603688B - N-type organic interface material and preparation method and application thereof - Google Patents

N-type organic interface material and preparation method and application thereof Download PDF

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CN113603688B
CN113603688B CN202110698072.8A CN202110698072A CN113603688B CN 113603688 B CN113603688 B CN 113603688B CN 202110698072 A CN202110698072 A CN 202110698072A CN 113603688 B CN113603688 B CN 113603688B
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赖文勇
闵洁
李祥春
刘芳
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Nanjing University of Posts and Telecommunications
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Abstract

The invention discloses an n-type organic interface material and a preparation method and application thereof. The n-type organic interface material based on perylene diimide is obtained by taking perylene diimide as a center and introducing an amphiphilic group at the gulf site or the shoulder site of the perylene diimide. The material improves the electron transport performance and solves the problem that the electron transport layer material has poor solubility in polar solvents, can be used as an electron transport layer material or an interface modification material, and is widely applied to organic photoelectric devices with high stability and high efficiency.

Description

N-type organic interface material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of photoelectric materials and application, and particularly relates to an n-type organic interface material and a preparation method and application thereof.
Background
The high-efficiency n-type interface material can not only greatly improve the efficiency of the organic photoelectric device, but also ensure the long-term stable work of the device. For example, in the field of organic solar cells, an n-type interface material plays a dual role of transporting electrons and blocking holes, and can prevent photo-generated electron-hole pairs from being recombined in the cell. In recent years, organic photoelectric functional materials have been developed very rapidly. One of the key factors for achieving the performance improvement of the organic solar cell device is to achieve efficient and balanced carrier injection and transport.
Research finds that the perylene diimide derivative shows good photoelectric property in the field of organic solar cells among a plurality of non-fullerene materials. The material is simple to synthesize, low in price, excellent in light/chemical stability, thermal stability and film-forming property, and the organic solar cell device prepared based on the material has high photoelectric conversion efficiency. Recently, amphiphilic n-type interface material containing hydrogen bonds, namely aliphatic amine functionalized perylene diimide, is constructed, the amphiphilic n-type interface material has proper dipole moment to reduce the work function of air-stabilized metals Ag and Cu, and secondary amine in a side chain of the n-type interface material can form hydrogen bonds with photovoltaic materials in an active layer and form good contact with the active layer. The obtained amphiphilic structure material has the advantages of definite small molecular structure, excellent film-forming property of polymer and solution-processing property, and has important application value as an organic photoelectric functional material.
Disclosure of Invention
The technical problem is as follows:
the invention aims to provide an n-type organic interface material, a preparation method and application thereof, which can be used for preparing organic solar cells, organic electroluminescent devices, positive device structures and negative device structures of organic field effect transistors by adopting a solution processing method such as spin coating, silk screen printing or ink jet printing. The excellent photoelectric characteristics are realized by optimizing the structure and implementation conditions of the device, and the technical problems of insufficient electron transmission capability, poor solubility and the like of the organic semiconductor material can be solved.
The technical scheme is as follows:
the invention provides an n-type organic interface material, which takes a perylene diimide n-type structure framework as a core unit, a nitrogen position is connected with a flexible alkyl chain, and a gulf position or a shoulder position is connected with an amphiphilic group, and the material has a structure shown as the following formula I:
Figure BDA0003129333930000021
wherein Ar is 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 、Ar 7 And Ar 8 Is hydrogen or an amphiphilic group; r is a linear or branched alkyl group.
In one embodiment, the amphiphilic group is a structural unit containing an amine group, a secondary amine group, a quaternary amine group, a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
In one embodiment, ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 、Ar 7 And Ar 8 Independently selecting the following groups Am-1, am-2, am-3, am-4, am-5, am-6 and Am-7:
Figure BDA0003129333930000022
Figure BDA0003129333930000031
wherein R is a linear or branched alkyl group.
In one embodiment, the organic material has the following structure:
Figure BDA0003129333930000032
Figure BDA0003129333930000041
Figure BDA0003129333930000051
Figure BDA0003129333930000061
Figure BDA0003129333930000071
Figure BDA0003129333930000081
Figure BDA0003129333930000091
the application also provides a preparation method of the amphiphilic perylene diimide n-type organic interface material, which comprises the following steps:
bromo perylene diimide and Ar containing amphiphilic group 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 、Ar 7 And Ar 8 Carrying out coupling reaction on the borate monomer under the condition of a catalyst to prepare an n-type organic interface material; the reaction process is shown as the following formula:
Figure BDA0003129333930000101
wherein Ar is Ar 1 -Ar 8 But Ar is 1 -Ar 8 Not both hydrogen.
In one embodiment, the preparation method of the n-type organic interface material specifically comprises the following steps:
(1) Bromo perylene diimide and amphiphilic group-containing Ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 、Ar 7 And Ar 8 The borate monomer and the phase transfer catalyst were added to the reaction flask. Adding a catalyst in the inert gas protection, then adding toluene and an alkaline solution, and reacting for 12-48 hours in a dark place under the condition of controlling the temperature to be 80-110 ℃.
(2) After the reaction is finished, quenching the reaction by water, cooling to room temperature, extracting by dichloromethane, filtering, performing column chromatography, and drying to obtain a target product.
The invention also provides an application method of the perylene diimide-based n-type organic interface material, and the material is applied to the fields of organic electroluminescent devices, organic solar cells, electronic paper, organic field effect transistors, organic lasers, energy storage devices, sensors and the like as an electron transport layer material or an interface modification layer material.
Has the advantages that:
the invention provides an n-type organic interface material, a preparation method and application thereof, which can be used as an electron transport layer material or an interface modification layer material to be applied to an organic electroluminescent device, an organic solar cell, electronic paper, an organic field effect transistor, organic laser, an energy storage device, a sensor and the like. The amphiphilic group is introduced to the perylene diimide which is lack of electrons, so that the electron transmission performance is improved, and the technical problems of poor solubility and poor film forming property in a polar solvent are solved. The material has excellent thermal stability, electron transport property, solubility and film forming property, and is an electron transport layer material with important application potential.
Drawings
Fig. 1 is a mass spectrum of an n-type organic interface material XVII provided in an embodiment of the present application.
Fig. 2 is a current-voltage density curve for an organic solar cell prepared based on the n-type organic interface material of XVII.
FIG. 3 is a graph of the measured external quantum efficiency of an n-type organic interface material provided in an embodiment of the present application
Detailed Description
The present invention is further illustrated by the following specific examples. The following merely illustrates the principles of the invention. Therefore, although not explicitly described or shown in the present specification, those skilled in the art can implement the principle of the invention and invent various devices included in the concept and scope of the invention. Further, it should be understood that all the terms and embodiments of the appended claims are specifically and principally intended to be used for understanding the concept of the invention, and are not intended to limit the scope of the invention to the specific embodiments and conditions specifically recited.
The n-type organic interface material provided in this embodiment may have the following structure:
Figure BDA0003129333930000111
Figure BDA0003129333930000121
example 1-1:
preparation of compound of material IX:
Figure BDA0003129333930000131
1-bromo-N, N' -bis (undecyl) perylene-3, 4,9, 10-tetracarboxylic acid diimine (1.15g, 1.5mmol), 4- (3- (1-imidazolyl) propylaminomethyl) phenylboronic acid pinacol ester (1.53g, 4.5mmol) and TBAB (0.28g, 0.86mmol) were placed in a 100mL two-neck reaction flask, nitrogen was purged three times, and Pd (PPh) was added to the reaction flask 3 ) 4 (0.5g, 0.43mmol) and sealed, and the nitrogen gas was purged three times. Into a reaction flask were charged 45mL of deoxygenated toluene and 2mol/L of K 2 CO 3 The solution was 15mL, reacted at 95 ℃ for 24 hours. After the reaction was completed, the reaction was quenched with water, cooled to room temperature, extracted with dichloromethane, suction-filtered, column-chromatographed, and dried to obtain the objective product material IX (0.36 g, yield 21.4%).
Examples 1 to 2:
preparation of compound of material XVII:
Figure BDA0003129333930000132
1, 7-dibromo-N, N' -bis (undecyl) perylene-3, 4,9, 10-tetracarboxylic acid diimine (0.9g, 1mmol), 4- (3- (1-imidazolyl) propylaminomethyl) phenylboronic acid pinacol ester (1.3g, 12mmol), tetrabutylammonium bromide (TBAB) (0.27g, 0.8mmol) were placed in a 150mL two-necked flask, which was sealed with a rubber stopper, and N was withdrawn 2 Three times. Then Pd (PPh) was added rapidly 3 ) 4 Catalyst (0.49mg, 0.43mmol) and N was replaced by another 2 Three times. Finally, deoxygenated toluene (40 mL) and 2M K were bubbled 2 CO 3 The aqueous solution (15 mL) was poured into each reaction flask and reacted at 95 ℃ for 24 hours. After the reaction is finished, extracting for 3 times by DCM solvent and saturated NaCl solution, and separating out an organic layer through MgSO 4 Drying, suction filtration and concentration of the solution the crude product obtained is purified by column chromatography (washing)DCM = 4) and dried in a vacuum oven to give pure product XVII (1.18 g, 42% yield).
Examples 1 to 3:
preparation of material XXV compound:
Figure BDA0003129333930000141
1,5, 7-tribromo-N, N' -bis (undecyl) perylene-3, 4,9, 10-tetracarboxylic acid diimine (0.47g, 0.5 mmol) and 4- (3- (1-imidazolyl) propylaminomethyl) phenylboronic acid pinacol ester (0.51g, 1.5 mmol) and TBAB (0.09g, 0.28mmol) were placed in a 100mL two-neck reaction flask, nitrogen was purged three times, and Pd (PPh) was added to the reaction flask 3 ) 4 (0.5g, 0.43mmol) and sealed, and the nitrogen gas was purged three times. Into the reaction flask were charged 45mL of deoxygenated toluene and 2mol/L of K 2 CO 3 The solution was 15mL, reacted at 95 ℃ for 24 hours. After the reaction was completed, the reaction was quenched with water, cooled to room temperature, extracted with dichloromethane, suction-filtered, column-chromatographed, and dried to obtain the objective product material XXV (0.45 g, yield 33.4%).
Examples 1 to 4:
materials preparation of xxxxxii compounds:
Figure BDA0003129333930000142
1,6,7, 12-tetrabromo-N, N' -bis (undecyl) perylene-3, 4,9, 10-tetracarboxylic acid diimine (0.20g, 0.2mmol), 3- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenoxy) propane-1-sodium sulfonate (0.51g, 1.2mmol) and TBAB (0.07g, 0.22mmol) were put into a 100mL two-port reaction flask, nitrogen gas was evacuated three times, and Pd (PPh) was added into the reaction flask 3 ) 4 (0.25g, 0.22mmol) and sealed, and the nitrogen was purged three times. Into the reaction flask were charged 45mL of deoxygenated toluene and 2mol/L of K 2 CO 3 The solution was 15mL, reacted at 95 ℃ for 24 hours. After the reaction is finished, quenching the reaction by water, cooling to room temperature, extracting by dichloromethane, filtering, carrying out column chromatography, and drying to obtain the target productThe title product material XXXXII (0.09 g, 21.7% yield).
Examples 1 to 5:
preparation of material LV compounds:
Figure BDA0003129333930000151
1,5,6,7, 12-pentabromo-N, N' -bis (undecyl) perylene-3, 4,9, 10-tetracarboxylic acid diimine (0.22g, 0.2mmol) and N-butyl-N-ethyl-4- (4, 5-tetramethyl-1, 3, 2-dioxobenzofuran-2-yl) aniline (0.45g, 1.5 mmol) and TBAB (0.07g, 0.22mmol) were placed in a 100mL two-necked reaction flask, nitrogen was purged three times, and Pd (PPh) was added to the reaction flask 3 ) 4 (0.25g, 0.22mmol) and sealed, and the nitrogen was purged three times. Into a reaction flask were charged 45mL of deoxygenated toluene and 2mol/L of K 2 CO 3 The solution was 15mL, reacted at 95 ℃ for 24 hours. After the reaction was completed, the reaction was quenched with water, cooled to room temperature, extracted with dichloromethane, filtered with suction, subjected to column chromatography, and dried to obtain the objective product material LV (0.074 g, yield 23.4%).
Examples 1 to 6:
materials preparation of LXXII compounds:
Figure BDA0003129333930000161
1,2,5,6,8, 11-hexabromo-N, N' -bis (undecyl) perylene-3, 4,9, 10-tetracarboxylic acid diimine (0.23g, 0.2 mmol) and ((3- (4, 5-tetramethyl-1, 3, 2-dioxabenzaldehyde-2-yl) phenyl) propyl) azaalkynyl) dimethanol (0.57g, 1.8 mmol) and TBAB (0.07g, 0.22mmol) were placed in a 100mL two-necked reaction flask, nitrogen was purged three times, and Pd (PPh) was added to the reaction flask 3 ) 4 (0.25g, 0.22mmol) and sealed, and the nitrogen was purged three times. Into the reaction flask were charged 45mL of deoxygenated toluene and 2mol/L of K 2 CO 3 A solution (15mL) was reacted at 95 ℃ for 24 hours. After the reaction is finished, quenching the reaction by water, cooling to room temperature, extracting by dichloromethane, filtering, performing column chromatography, and drying to obtain a target product material LXXII (0.1)4g, 37.4% yield).
Examples 1 to 7:
preparation of material LXXIII compound:
Figure BDA0003129333930000162
1,2,5,6,7,8, 12-heptabromo-N, N' -bis (undecyl) perylene-3, 4,9, 10-tetracarboxylic acid diimine (0.25g, 0.2mmol) and diethyl phosphate (0.80g, 2.1mmol) and TBAB (0.11g, 0.34mmol) were put into a 100mL two-necked reaction flask, nitrogen was purged three times, and Pd (PPh) was further added into the reaction flask 3 ) 4 (0.5g, 0.43mmol) and sealed, and the nitrogen was again purged three times. Into a reaction flask were charged 45mL of deoxygenated toluene and 2mol/L of K 2 CO 3 The solution was 15mL, reacted at 95 ℃ for 24 hours. After the reaction was completed, the reaction was quenched with water, cooled to room temperature, extracted with dichloromethane, suction-filtered, column-chromatographed, and dried to obtain the objective product LXXIII (0.21 g, yield 41.4%).
Examples 1 to 8:
preparation of material LXXV compounds:
Figure BDA0003129333930000171
1,2,5,6,7,8,11, 12-octabromo-N, N' -bis (undecyl) perylene-3, 4,9, 10-tetracarboxylic acid diimine (0.27g, 0.2mmol), diethyl phosphate (0.92g, 2.4 mmol) and TBAB (0.111g, 0.34mmol) were placed in a 100mL two-necked flask, nitrogen gas was purged three times, and Pd (PPh) was added to the flask 3 ) 4 (0.5g, 0.43mmol) and sealed, and the nitrogen gas was purged three times. Into the reaction flask were charged 45mL of deoxygenated toluene and 2mol/L of K 2 CO 3 The solution was 15mL, reacted at 95 ℃ for 24 hours. After the reaction, the reaction was quenched with water, cooled to room temperature, extracted with dichloromethane, filtered, column chromatographed, and dried to give the target product material LXXV (0.17 g, 31.4% yield).
Example 2-1:
preparing an organic solar cell device:
the preparation process of the organic solar cell device comprises the following steps: the device structure was ITO (indium tin oxide)/PEDOT: PSS (poly 3, 4-ethylenedioxythiophene: polystyrene sulfonate)/PBDB-T-2F (poly [ (2, 6- (4, 8-bis (5- (2-ethylhexyl-3-fluoro) thiophen-2-yl) -benzo [1,2-b:4,5-b '']Dithiophenes]) -alt- (5,5- (1 ',3' -di-2-thiophene-5 ',7' -bis (2-ethylhexyl) benzo [1',2' -c:4',5' -c ']Dithiophene-4, 8-diones)]3,9-bis (2-methylene- ((3- (1, 1-dicyanomethylene) -5, 6-difluoro) -indolone)) -5,5, 11-tetrakis (4-hexylphenyl) -dithio-heterocycle [2,3-d:2',3' -d ']-s-indole heterocycle [1,2-b:5,6-b']Dithio-heterocycle/n-type organic interface/Ag. The specific preparation method of the device is as follows: and (3) cleaning the ITO substrate by ultraviolet and ozone treatment for 15min, and then carrying out ultrasonic cleaning for 20min according to the sequence of acetone, a detergent, deionized water and isopropyl ketone. Spin-coating a PEDOT: PSS (4083) solution onto the treated ITO substrate at 3000r/min by spin-coating, annealing at 150 ℃ for 10min in air, and then transferring into a nitrogen-filled glove box; an active layer PBDB-T-2F (donor and acceptor are mixed according to the proportion of 1; n-type organic interface material (dissolved in methanol at concentration of 0.5 mg/mL) is spin-coated on the active layer at a rotation speed of 3000 r/min; finally, transferring the vapor deposition chamber for vacuum pumping, and when the pressure intensity in the chamber is less than 1 multiplied by 10 -5 The evaporation is started at bar, the thickness of Ag is 100nm, the current-voltage density curve of the organic solar cell device prepared on the basis of the n-type organic interface material XVII is shown in figure 2, and according to the shown results, the device prepared by the method has high-efficiency and stable photoelectric conversion performance.
Examples 2-2 to 2-8:
testing of organic solar cell devices:
an organic solar cell device was produced in the same manner as in example 2-1, except that each compound described in table 1 was used instead of the compound IX as an electron transporting material. With respect to the obtained organic solar cell device, the short-circuit current (J) was measured in the same manner as in example 2-1 sc ) Open circuit voltage (V) oc ) A Fill Factor (FF),the Photoelectric Conversion Efficiency (PCE) results are shown in table 1, and the photoelectric conversion efficiencies are all above 6%, which indicates that the n-type organic interface material has good electron transport characteristics when applied to an organic solar cell as an electron transport layer.
Table 1:
Figure BDA0003129333930000181
Figure BDA0003129333930000191
example 3-1:
preparation of organic light emitting diode device:
the preparation process of the organic light-emitting diode device comprises the following steps: the device structure is ITO/IX/Alq 3 (8-hydroxyquinolinylaluminum)/NPB ((N-N '-diphenyl-N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine)/Al) ITO substrate is cleaned by ultraviolet and ozone treatment for 15min, then is ultrasonically cleaned for 20min in sequence according to the sequence of acetone, detergent, deionized water and isopropyl alcohol, an electron transport layer IX solution is spin-coated on the treated ITO substrate at the speed of 3000r/min by a spin coating method, is annealed at the temperature of 150 ℃ in the air for 10min, then is transferred to a glove box filled with nitrogen, a luminescent layer Alq3 is spin-coated on IX at the rotating speed of 2400r/min in the glove box, then is annealed at the temperature of 100 ℃ for 10min, a hole transport layer NPB is coated on the luminescent layer at the rotating speed of 3000r/min, finally is transferred to an evaporation box for vacuumizing, and when the pressure in the cabin is less than 1 x 10 -5 The evaporation was started at bar and the thickness of Al was 100nm.
Examples 3-2 to 3-8:
preparation of organic light-emitting diode device:
an organic light-emitting diode device was produced in the same manner as in example 3-1, except that each compound described in table 2 was used instead of the compound IX as the electron transport layer. With respect to the obtained organic light emitting diode device, the lighting voltage (V) and the fluorescence luminance (cd/m) were measured in the same manner as in example 3-1 2 ) The results are shown in the table2, the fluorescent luminances were all over 3000cd/m 2 It is fully demonstrated that the n-type organic interface material has good electron transport properties when applied to an organic light emitting diode device as an electron transport layer.
Table 2:
Figure BDA0003129333930000192
Figure BDA0003129333930000201
example 4
For measuring the external quantum efficiency of the n-type organic interface material provided in examples 1 to 2 of the present application
By measuring the external quantum efficiency of the n-type organic interface material XVII prepared in examples 1-2, the test results are shown in fig. 3, in which the integrated area corresponds to the short-circuit current of the device. As can be seen from FIG. 3, the n-type organic interface material prepared by the present application has excellent short-circuit current performance.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Those skilled in the art can modify or change the above-described embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims (6)

1. An n-type organic interface material is characterized in that the material is specifically represented by a general structural formula shown in a formula I:
Figure FDA0003856582670000011
ar is 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 、Ar 7 And Ar 8 Each independently selected from the group consisting of: H.
Figure FDA0003856582670000012
2. the n-type organic interface material of claim 1, having the structure:
Figure FDA0003856582670000021
Figure FDA0003856582670000031
3. a process for the preparation of an n-type organic interface material according to claim 1, comprising the reaction steps of:
reacting bromoperylene diimide with amphiphilic group Ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 、Ar 7 And Ar 8 Carrying out coupling reaction on the borate monomer under the condition of a catalyst to prepare an n-type organic interface material; the reaction process is shown as the following formula:
Figure FDA0003856582670000032
wherein Ar is Ar 1 -Ar 8 But Ar is 1 -Ar 8 Not both hydrogen.
4. The method of preparing an n-type organic interface material of claim 1, comprising the steps of:
(1) Bromo perylene diimide and amphiphilic group-containing Ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5、 Ar 6 、Ar 7 And Ar 8 Adding raw materials and a phase transfer catalyst into a reaction bottle, adding the catalyst in the protection of inert gas, then adding toluene and an alkaline solution, controlling the temperature to be 80-110 ℃, and reacting for 12-48 hours in a dark place;
(2) After the reaction is finished, quenching the reaction by water, cooling to room temperature, extracting by dichloromethane, filtering, performing column chromatography, and drying to obtain a target product.
5. The method for preparing an n-type organic interface material according to claim 3, wherein in the reaction step (1), the bromoperylene diimide and the amphiphilic group-containing Ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6、 Ar 7 And Ar 8 In a molar ratio of 1.
6. Use of an n-type organic interface material according to claim 1, wherein the material is used as an electron transport layer or an interface modification layer in an organic electroluminescent device, an organic solar cell, electronic paper, an organic field effect transistor, an organic laser, an energy storage device, or a sensor.
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