CN106045998B - N-type semiconductor benzene-naphthalene diimide derivative compound, the preparation method and application of a kind of high stability - Google Patents
N-type semiconductor benzene-naphthalene diimide derivative compound, the preparation method and application of a kind of high stability Download PDFInfo
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- CN106045998B CN106045998B CN201610343356.4A CN201610343356A CN106045998B CN 106045998 B CN106045998 B CN 106045998B CN 201610343356 A CN201610343356 A CN 201610343356A CN 106045998 B CN106045998 B CN 106045998B
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- benzene
- nitrae
- isosorbide
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- trifluoromethylthio
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/06—Peri-condensed systems
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
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- 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
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
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- C09K2211/1007—Non-condensed systems
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
Abstract
The present invention relates to benzene-naphthalene diimide derivative compound, preparation method and as n types organic semiconductor photoelectric material application.One kind contains N, N ' [4 (trifluoromethylthio) phenyl] Isosorbide-5-Nitrae, and the compound structure of 5,8 benzene-naphthalene diimide derivatives is as follows：
Description
Technical field
The present invention relates to benzene-naphthalene diimide derivative compound.Particularly relate to N, N '-[4- (trifluoromethylthio) benzene
Base]-Isosorbide-5-Nitrae, the compounds of 5,8- benzene-naphthalene diimide derivatives, preparation method and as n-type organic semiconductor in photoelectric material
Using.
Background technology
Since organic luminescent device is released, organic electronic device is because it is inexpensive, the characteristic such as pliability and easy processing,
Have been to be concerned by more and more people, Optoelectronics Technology industry sodality (PIDA) points out, the global opto-electronics gross output value in 2014
576600000000 dollars.The minimum original paper of organic photoelectric science and technology is that organic field effect tube (OTFT) core technology is organic material
Prepare.
According to the polarity of principal carrier in device, organic field effect tube can be divided into the p-type in conducting hole and lead
Be powered the sub class of n-type two.Certainly, if using ambipolar organic semiconducting materials, device not only conduct electrons but also can turn on sky
Cave.The development of n-type material now and bipolarity organic semiconductor equipment more fall behind relative to p-type material, and for OTFT
For p-type and n-type no less important, the complementary circuit being made up of the device of two kinds of different shapeds is the basis for realizing organic circuit.
Therefore develop new particularly important with stabilized illumination performance and the material of good electronic injection and transmission.
Benzene-naphthalene diimide is a kind of typical n-type organic semiconducting materials, due to the less conjugation aromatic ring of benzene-naphthalene diimide
It is difficult to form effective pi-pi accumulation, so benzene-naphthalene diimide derivative compound is relatively low in OTFT device mobilities.By Shukla
Et al. the benzene-naphthalene diimide device mobilities of the cyclic substituents of report significantly improve and reach 6.2cm2/ (Vs), Katz etc. profits
The stability of material is set to have obtained good lifting with the introducing of fluoro substituents.(Chem.Mater.2008,20,7486；
Chem.Mater.2008,20,3609.) in order to which the n-type material of high mobility for seeking to have stability, this patent disclose not
A series of N to appear in the newspapers, N '-[4- (trifluoromethylthio) phenyl]-Isosorbide-5-Nitrae, (structure is shown in that right will to 5,8- benzene-naphthalene diimide derivatives
Ask part), and application of the portion of material in OTFT devices.This patent also reports one pot process benzene-naphthalene diimide class chemical combination
Thing, this method are applied to the synthesis of similar-benzene-naphthalene diimide derivative.
The content of the invention
Goal of the invention
Present invention aims at provide one kind to contain N, N '-[4- (trifluoromethylthio) phenyl]-Isosorbide-5-Nitrae, 5,8- benzene-naphthalene diimides
The compound of derivative.
A further object of the present invention is that providing a kind of easy synthetic method is used for above-mentioned N, N '-[4- (fluoroform sulphur
Base) phenyl]-Isosorbide-5-Nitrae, the compound of 5,8- benzene-naphthalene diimide derivatives.
The another object of this patent is to provide above-mentioned N, N '-[4- (trifluoromethylthio) phenyl]-Isosorbide-5-Nitrae, the acyl of 5,8- naphthalene two
The application of the compound of imine derivative, mainly for the preparation of organic electro-optic device.
Invention particular content
The present invention provides one kind and contains N, N '-[4- (trifluoromethylthio) phenyl]-Isosorbide-5-Nitrae, 5,8- benzene-naphthalene diimide derivatives
Compound structure is as follows：
R in formula1And R2It is independently selected from hydrogen, deuterium, C1-C3Alkyl, R1 and R2 can be with identical or differ；Preferably R1And R2
It is identical and for hydrogen, deuterium, methyl
The present invention prepares N, N '-[4- (trifluoromethylthio) phenyl] 1-1, the preparation side of 4,5,8- benzene-naphthalene diimide derivatives
Method, reaction expression are as follows：
R in formula1And R2As it was previously stated, R1And R2Can be with identical or differ；Preferably R1And R2It is identical and for hydrogen, deuterium,
Methyl.Wherein solvent is solvent, and RT represents room temperature.
The specific reactions steps of the present invention are as follows：
By Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidic acid anhydrides, zinc acetate and acetic acid are added in the reactor equipped with appropriate organic solvent.Room temperature
Stir 0.5h, by Isosorbide-5-Nitrae, the ratio 1 of 5,8- naphthalenetetracarbacidic acidic acid anhydrides and amine：Amine corresponding to 4 additions, room temperature are rising to 80 DEG C of stirring 2h
Warm to 153 DEG C stirring 10h.
Described method is carried out under the protection of nitrogen or argon gas.
The described preferred DMF of method organic solvent (DMF).
Described method products therefrom separates out in water, is recrystallized in toluene, methyl phenyl ethers anisole or chloroform, yield 80~
93%.
The product that described method obtains nuclear magnetic resoance spectrum (1H-NMR/13C-NMR), mass spectrum (MS-TOF) etc. it is a kind of or
A variety of sign structures are correct.
Synthetic method of the present invention not only has that simple step but also yield are higher, and reaction unit is simple and post processing side
Just.The cost of synthesis n-type material is so significantly reduced, there is very big commercial value.
It is a kind of to be applied to organic electroluminescence device, the n-type organic semiconducting materials of organic field effect tube device,
It is using material
The compound has 0.1cm in the organic layer semiconductor layer of organic field effect tube2/ V.s carrier mobilities.
The method for preparing above-mentioned organic field effect tube, comprises the following steps：Using the grid with insulating barrier, pass through
Vacuum heat deposition method or solution spin-coating method are on its insulating barrier covered with machine semiconductor layer；Source electricity is covered on organic semiconductor layer
Pole and drain electrode, obtain organic field effect tube.
The superiority of the present invention：Typical n-type material device is being designed as using high performance naphthalene diamides as skeleton；
Fluorine-containing molecular structure, so that stability significantly improves in the air of OTFT devices, device detection mobility base after 30 days
This does not change；Fluoro-containing group and conjugation phenyl ring between add S so that the electron mobility of device significantly improve to
0.1cm2/V.s；The structure of small molecule make it that material dissolubility is fabulous, solution spin-coating method etc. can be used to prepare OTFT, have business
The potentiality of industry application.The method for preparing the material is simple, yield is high, cost is low；With good carrier mobility, extensively should
For organic electroluminescence device, organic field effect tube.
Brief description of the drawings
Fig. 1：N, N '-[4- (trifluoromethylthio) phenyl]-Isosorbide-5-Nitrae, 5,8- benzene-naphthalene diimide hydrogen nuclear magnetic resonance spectrograms
Fig. 2：Containing N, N '-[4- (trifluoromethylthio) phenyl]-Isosorbide-5-Nitrae, the compound n-type of 5,8- benzene-naphthalene diimide derivatives
Structural representation of the semi-conducting material as the organic field effect tube of organic layer
Embodiment
Case study on implementation 1
By Isosorbide-5-Nitrae, Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidic acid anhydrides, zinc acetate and acetic acid are added be equipped with molar ratio by 5,8- naphthalenetetracarbacidic acidic acid anhydrides
In 150mlDMF reactor.0.5h is stirred at room temperature, adds 4- trifluoro-methylthio anilines, 50 DEG C of stirring 2h, then be warming up to 153 DEG C
Stir 10h.Added after being cooled to room temperature in 500ml water, have solid precipitation, filtration drying, obtained with re crystallization from toluene faint yellow
Acicular crystal.Decompression gradient sublimation can obtain high purity N, N ,-[4- (trifluoromethylthio) phenyl]-Isosorbide-5-Nitrae, the acyl of 5,8- naphthalene two Asia
Amine crystal yield 85.4%.
Checked by thermogravimetric analyzer (TGA), analysis condition is nitrogen atmosphere, and sweep speed is 10 DEG C/min, is obtained
To the decomposition temperature of the organic semiconducting materials of embodiment 1, its heat decomposition temperature is up to more than 385 DEG C (5% thermal weight losses), illustrates this
Class material has preferable heat endurance.
Case study on implementation 2
The preparation of organic field effect tube
Step 1：Wafer Cleaning
Prepare silicon chip of the one side with silica inorganic insulating barrier, be cleaned by ultrasonic 25 minutes with distilled water, isopropanol, acetone
It is cleaned by ultrasonic 15 minutes, adds the mixing mixed solution that hydrogen peroxide and the concentrated sulfuric acid (ratio 3: 7) are prepared, 90 DEG C of Ultrasonic Heatings 30 divides
Clock, then it is with distilled water that Wafer Cleaning is clean.Then ultrasound 20 minutes in isopropanol, are dried up with argon gas.
Step 2：It is prepared by device
The silicon chip after cleaning is taken, the organic semiconducting materials prepared in embodiment 1, vacuum are deposited using vacuum heat deposition method
Pressure is 6 × 10-4 pas, and heat flow rate 0.02, organic semi-conductor thickness is about 70nm.Pass through vacuum mask hot evaporation side
Method deposition drain-source electrodes, thickness 70nm, the device architecture prepared are as shown in Figure 2.
Crystal growth is carried out on substrate and be prepared by device
Cleaned silicon chip is positioned over to the crystal growth area of multi-temperature zone tube furnace, carried out using gas phase Physical (PVT)
Crystal growth, by 295 degrees Celsius of sublimation zone temperature setting by high purity N, N '-[4- (trifluoromethylthio) phenyl]-Isosorbide-5-Nitrae, 5,8-
Benzene-naphthalene diimide crystal is put into, and crystal growth area temperature setting is 245 degrees Celsius, is kept normal pressure in pipe and is passed to inert gas nitrogen
Gas or argon gas.The substrate for having grown monocrystalline is then carried out to the evaporation of metal electrode.The device architecture prepared such as Fig. 2
It is shown
Case study on implementation 3
Organic field effect tube device prepared by case study on implementation 2 carries out performance test.
Performance test is carried out to device using Keithley4200：Transfer curve and curve of output are tested respectively.Wherein, institute
State source-drain current curve of output (abbreviation curve of output) and refer to that source-drain current ISD is with source-drain voltage VSD's in certain grid voltage VG
Change curve；Wherein, the source-drain current transfer curve (abbreviation transfer curve) refers under certain source-drain voltage VSD, source
Leakage current ISD with grid voltage VG change curve.Threshold voltage produces the minimum voltage of conducting channel, Ke Yiyou for induced crystal pipe
(ISD) it is extended down to outside 1/2 pair of VG mappings institute fitting a straight line obtained by voltage when electric current is 0.Test N, N '-[4- (trifluoromethylthio)
Phenyl]-Isosorbide-5-Nitrae, 5,8- benzene-naphthalene diimide quartz crystal device electron mobilities are up to 0.1cm2/V.s.Same property is carried out after 30 days
Mobility can be tested not change.
Summarize result above and show N, N '-[4- (trifluoromethylthio) phenyl]-Isosorbide-5-Nitrae, 5,8- benzene-naphthalene diimides are organic partly to lead
Stability significantly improves in the air of body material OTFT devices, and the method for preparing the material is simple, yield is high, cost is low；And
Device has well stable carrier mobility.The N of the group containing hetero atom substituents provided above the embodiment of the present invention,
N '-[4- (trifluoromethylthio) phenyl]-Isosorbide-5-Nitrae, 5,8- benzene-naphthalene diimide organic semiconducting materials and its preparation method and application enters
Go and be discussed in detail, specific case used herein is set forth to the principle and embodiment of the present invention, and the above is implemented
The explanation of example is only intended to help the method and its core concept for understanding the present invention, and this specification content should not be construed as to this hair
Bright limitation.
Claims (7)
1. one kind contains N, N '-[4- (trifluoromethylthio) phenyl]-Isosorbide-5-Nitrae, the compound of 5,8- benzene-naphthalene diimide derivatives, structure is such as
Shown in lower：
R in formula1And R2It is independently selected from hydrogen, deuterium, C1-C3Alkyl, R1 and R2 can be with identical or differ；Work as R1And R2When identical, R1
And R2For hydrogen, deuterium, methyl.
2. one kind is prepared as contained N, N '-[4- (trifluoromethylthio) phenyl]-Isosorbide-5-Nitrae in claim 1,5,8- benzene-naphthalene diimides derive
The method of the compound of thing, preparation process are by Isosorbide-5-Nitrae, and 5,8- naphthalenetetracarbacidic acidic acid anhydrides, zinc acetate and acetic acid are added equipped with appropriate organic
In the reactor of solvent, under inert gas shielding, after stirring 30min~2h, Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidic acid anhydrides are with amine by certain
Molar ratio add30~80 DEG C of stirring 1h~4h, then be warming up to 130~160 DEG C and stir 5h~12h, it is cold
But solid product is obtained in falling back, is purified in organic solvent recrystallization.
3. according to claim 2 contain N, N '-[4- (trifluoromethylthio) phenyl]-Isosorbide-5-Nitrae, 5,8- benzene-naphthalene diimide derivatives
Compound preparation method, it is characterized in that Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidic acid anhydrides and amine ratio be less than 1: 2.
4. according to claim 2 contain N, N '-[4- (trifluoromethylthio) phenyl]-Isosorbide-5-Nitrae, 5,8- benzene-naphthalene diimide derivatives
Compound preparation method, it is characterized in that reaction when organic solvent selection for DMF, N, N- dimethyl oneself
Acid amides.
5. according to claim 2 contain N, N '-[4- (trifluoromethylthio) phenyl]-Isosorbide-5-Nitrae, 5,8- benzene-naphthalene diimide derivatives
Compound preparation method, it is characterized in that reaction inertia protection under carry out, product separates out in water, with toluene, methyl phenyl ethers anisole
Or Gossypol recrystallized from chloroform purification.
6. a kind of N as claimed in claim 1, N '-[4- (trifluoromethylthio) phenyl]-Isosorbide-5-Nitrae, 5,8- benzene-naphthalene diimide derivatives
Compound application, it is characterized in that preparing organic electronic device.
7. N according to claim 6, N '-[4- (trifluoromethylthio) phenyl]-Isosorbide-5-Nitrae, the change of 5,8- benzene-naphthalene diimide derivatives
Compound application, it is characterized in that the semiconductor active layer as organic field effect tube.
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