CN114933609A - Isoindigo-boron-fluorine-hybridization-based n-type organic semiconductor material, preparation method thereof and organic field effect transistor - Google Patents
Isoindigo-boron-fluorine-hybridization-based n-type organic semiconductor material, preparation method thereof and organic field effect transistor Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
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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
- H10K85/30—Coordination compounds
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
- H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
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- 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
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Abstract
The invention relates to the technical field of organic semiconductor materials, and provides an isoindigo boron fluoride hybrid-based n-type organic semiconductor material, a preparation method thereof and an organic field effect transistor. The semiconductor material provided by the invention is a brand-new isoindigo derivative with multiple fluorine atoms and nitrogen atoms, has strong electron deficiency characteristics, low LUMO energy level, high stability, n-type electron transmission characteristics, high coplanarity of molecular frameworks, excellent intramolecular charge transfer characteristics and a wider spectral absorption band, and has great application potential in photovoltaic devices. The organic field effect transistor prepared by adopting the n-type organic semiconductor material as the organic layer has the n-type transmission characteristic, high electron transmission mobility and good stability in air.
Description
Technical Field
The invention relates to the technical field of organic semiconductor materials, in particular to an isoindigo boron fluoride hybrid-based n-type organic semiconductor material, a preparation method thereof and an organic field effect transistor.
Background
An Organic Field Effect Transistor (OFET) is a field effect transistor that uses an organic semiconductor to form a channel. Organic field effect transistors have attracted considerable attention over the last two decades for their excellent performance in rollable displays, smart identification cards, wearable and implantable electronic devices.
OFET is an electronic device mainly composed of a metal electrode, an insulator layer and an organic semiconductor layer, and the organic semiconductor layer is mainly a pi-conjugated organic material at present. In the past years, most of the reported semiconductors are p-type semiconductors, which can show high carrier mobility and stability, while n-type semiconductors are very little studied and have inferior performance to p-type semiconductors. In addition, since n-type and p-type properties are required to be matched within a device, the development of new n-type semiconductor dye molecules with high carrier mobility and high stability is crucial for the development of OFETs.
The conjugated semiconductor should have a suitable Lowest Unoccupied Molecular Orbital (LUMO) whose energy level should match the fermi level of the metal electrode to form an ohmic contact to facilitate electron injection from the electrode into the semiconductor and to facilitate electron transport in the semiconductor layer. However, in most cases, the LUMO level of the conjugated material is high relative to the metal electrode, which makes it difficult to ensure the carrier transport property. To reduce the LUMO level of the conjugated material, a simple and effective strategy is to introduce electron-deficient groups into the molecule. In recent years, in terms of molecular structure design, pyrrolopyrrolidinone, indigo, N' -dimethyl-3, 4,9, 10-perylenetetracarboxylic acid diimine and derivatives thereof are widely used as acceptor groups for designing N-type semiconductors; in addition, fluorine atoms, unsaturated nitrogen atoms, chlorine atoms and cyano groups (-CN) are introduced into molecules, so that the electron deficiency capability of the material is improved, and the LUMO energy level can be obviously reduced. However, a too low LUMO level often causes problems such as device instability, since it is easily attacked by weak nucleophiles. Thus, it is believed that the LUMO level of the ideal organic semiconductor layer material should be between-3.6 eV and-4.5 eV, after a great deal of practice. In view of the materials reported in recent years, it is still highly challenging to develop n-type semiconductor materials with strong electron-deficient characteristics and high electron transport capability and high stability.
Disclosure of Invention
In view of this, the invention provides an isoindigo boron hybrid-based n-type organic semiconductor material, a preparation method thereof and an organic field effect transistor. The isoindigo fluoroboron hybridization-based n-type organic semiconductor material provided by the invention is a brand-new large-pi conjugated system molecule, has strong electron deficiency characteristics and lower LUMO energy level, and shows high-stability n-type electron transmission characteristics.
In order to achieve the above object, the present invention provides the following technical solutions:
an isoindigo fluoroboron hybridization-based n-type organic semiconductor material has a structural formula shown as a formula I:
in formula I: r is
The invention also provides a preparation method of the isoindigo boron fluoride hybridization-based n-type organic semiconductor material, which comprises the following steps:
isoindigo, azaarylamine, titanium tetrachloride, triethylamine, boron trifluoride diethyl etherate and benzene solvent are mixed to carry out Schiff base reaction, so that an isoindigo fluoroboron hybridization-based n-type organic semiconductor material with a structure shown in a formula I is obtained;
the structure of the isoindigo is shown as a formula II, and the structure of the azaarylamine is shown as a formula III:
preferably, the schiff base reaction specifically comprises: the isoindigo, azaarylamine and benzene solvent are mixed and react for 1-1.5 hours under the conditions of nitrogen protection and reflux, then titanium tetrachloride is added into a reaction system, triethylamine is added after the reaction is carried out for 10-15 minutes, boron trifluoride ether is added after the reaction is continued for 1.5-2 hours, and the reaction is finished to obtain the isoindigo fluoroboron hybridization-based n-type organic semiconductor material with the structure shown in the formula I.
Preferably, the benzene solvent is toluene or xylene; and the reaction time after adding the boron trifluoride diethyl etherate is 12-15 h.
Preferably, the molar ratio of the isoindigo to the azaarylamine is (4-4.5) to 1; the molar ratio of the carbon tetrachloride to the nitrogen heterocyclic aromatic amine is (5.5-6) to 1; the molar ratio of the triethylamine to the azaarylamine is (14.5-15): 1; the molar ratio of boron trifluoride diethyl etherate to nitrogen heteroaromatic amine is (15.5-16): 1.
Preferably, the preparation method of the azaarylamine comprises the following steps:
mixing 2-amino-3-hydroxypyridine, 7- (bromomethyl) pentadecane, hydride and an organic solvent for condensation reaction to obtain nitrogen heterocyclic arylamine with a structure shown in a formula III; the condensation reaction was carried out under dark conditions.
Preferably, the hydride is sodium hydride or calcium hydride.
Preferably, after the Schiff base reaction is finished, the method further comprises the step of carrying out post-treatment on the obtained product liquid; the post-processing method comprises the following steps: and pouring the obtained product liquid into water, extracting with dichloromethane, drying the obtained organic phase, removing the solvent to obtain a crude product, and purifying the crude product by silica gel column chromatography to obtain the isoindigo fluoroboron hybridization-based n-type organic semiconductor material with the structure shown in the formula I.
The invention also provides application of the isoindigo boron fluoride hybridization-based n-type organic semiconductor material in the scheme in an organic field effect transistor and a photovoltaic device.
The invention also provides an organic field effect transistor, which is characterized in that the isoindigo fluoroboron hybridization-based n-type organic semiconductor material in claim 1 is adopted as an organic semiconductor layer.
The invention provides an isoindigo boron-fluorine hybridization-based n-type organic semiconductor material, which has a structural formula shown in a formula I. The semiconductor material provided by the invention is a brand-new isoindigo (IIDG) derivative with multiple fluorine atoms and nitrogen atoms, namely isoindigo based dimeric nitrogen fluorine hetero boron dipyrrolidine (IIDG-AB); the organic semiconductor material is a large pi conjugated system molecule constructed based on an indigo molecule, has strong electron deficiency characteristics and lower LUMO energy level, is favorable for injecting electrons from an electrode to a semiconductor layer and transferring the electrons in the semiconductor layer, and shows high-stability n-type electron transmission characteristics; in addition, the n-type organic semiconductor material with the structure shown in the formula I has high coplanarity of a molecular skeleton and excellent intramolecular charge transfer characteristics, is favorable for the transfer of electrons in molecules, and also has better molecular arrangement and stronger molecular aggregation, so that the transfer of the electrons between the molecules of the molecular semiconductor layer is facilitated; the invention provides an effective new material for designing a high-performance n-type organic field effect transistor, and meanwhile, the semiconductor material has a wider spectral absorption band and has very wide light absorption between 530nm and 850nm, so that the semiconductor material also has huge application potential in photovoltaic devices.
The invention also provides a preparation method of the isoindigo fluoroboron hybridization-based n-type organic semiconductor material in the scheme, which adopts isoindigo and azaarylamine as raw materials to prepare the n-type organic semiconductor material with the structure shown in the formula I by a simple and mild method according to the Schiff base reaction principle. The preparation method provided by the invention has simple steps, is easy to operate and is suitable for large-scale production.
The invention also provides an organic field effect transistor, and the n-type organic semiconductor material adopting the scheme is an organic layer. The organic field effect transistor constructed by the n-type organic semiconductor material with the structure shown in the formula I has n-type transmission characteristics, high electron transmission mobility and good stability in air. The embodiment result shows that the highest electron transfer mobility of the bottom-gate bottom-contact organic field effect transistor constructed by the invention reaches 8.2 multiplied by 10 –2 cm 2 V -1 s -1 Average value of 6.9X 10 –2 cm 2 V -1 s -1 Current switching ratio of 10 4 To 10 5 And the threshold voltage is 32V, so that the excellent performance is shown.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a nitrogen heteroaromatic amine;
FIG. 2 is a nuclear magnetic carbon spectrum of an azaarylamine;
FIG. 3 is a nuclear magnetic hydrogen spectrum of IIDG-AB;
FIG. 4 is a nuclear magnetic carbon spectrum of IIDG-AB;
FIG. 5 is a diagram showing UV-VIS absorption spectra of IIDG-AB chloroform solution and IIDG-AB solid film;
FIG. 6 is a graph of the electron mobility values for 8 IIDG-AB based OFET devices prepared in application example 1;
FIG. 7 is a graph of transfer characteristics of the OFET device based on IIDG-AB prepared in application example 1;
FIG. 8 Electron mobility retention in air for 7 consecutive days using the OFET device of IIDG-AB prepared in example 1;
FIG. 9 is a diagram comparing the molecular structures of isoindigo molecule IIDG and isoindigo-based dinitrodiazofluorodipyrrolidine IIDG-AB;
FIG. 10 is an XRD pattern of isoindigo molecule IIDG and isoindigo-based dinitrodiazofluorodipyrrolidine IIDG-AB;
FIG. 11 is a graph comparing the transfer transmission characteristics of organic field effect transistors fabricated using IIDG and IIDG-AB.
Detailed Description
The invention provides an isoindigo boron-fluoride-hybrid-based n-type organic semiconductor material, which has a structural formula shown as a formula I:
in formula I: r is
In the invention, the chemical name of the n-type organic semiconductor material shown in the formula I is isoindigo based dimeric nitrogen fluorine hetero boron dipyrrolidine.
The invention also provides a preparation method of the isoindigo boron fluoride hybridization-based n-type organic semiconductor material, which comprises the following steps:
isoindigo, azaarylamine, titanium tetrachloride, triethylamine, boron trifluoride diethyl etherate and benzene solvent are mixed to carry out Schiff base reaction, so that an isoindigo fluoroboron hybridization-based n-type organic semiconductor material with a structure shown in a formula I is obtained;
the structure of the isoindigo is shown as a formula II, and the structure of the azaarylamine is shown as a formula III:
in the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
Firstly, the invention explains the preparation method of raw materials isoindigo and nitrogen heterocyclic aromatic amine:
in the present invention, the method for preparing isoindigo preferably comprises the steps of:
mixing 6-bromoindole-2-ketone, 6-bromoindole-2, 3-diketone, acetic acid and hydrochloric acid, and carrying out condensation reaction under the protection of nitrogen to obtain the isoindigo.
In the invention, the mol ratio of the 6-bromoindole-2-ketone to the 6-bromoindole-2, 3-dione is preferably 1:1, and the dosage ratio of the 6-bromoindole-2-ketone, acetic acid and hydrochloric acid is preferably 4g:120mL:0.8 mL; the hydrochloric acid is concentrated hydrochloric acid, and the mass fraction of the concentrated hydrochloric acid is specifically 36.46%; the condensation reaction is preferably carried out under the reflux condition, the reflux temperature is particularly 117 ℃, and the condensation reaction time is preferably 12 hours; the condensation reaction is preferably carried out using a Dean Stark apparatus. After the condensation reaction is finished, the product is preferably washed by ethanol and water to obtain a dark red solid, namely isoindigo blue (IIDG).
In the present invention, the isoindigo is synthesized as shown in the following formula:
in the present invention, the preparation method of the azaarylamine comprises the following steps:
mixing 2-amino-3-hydroxypyridine, 7- (bromomethyl) pentadecane, hydride and an organic solvent for condensation reaction to obtain nitrogen heterocyclic arylamine with a structure shown in a formula III; the condensation reaction was carried out under dark conditions.
In the invention, the molar ratio of the 2-amino-3-hydroxypyridine to the 7- (bromomethyl) pentadecane is preferably 1 (1.1-1.2); the organic solvent is preferably N, N-dimethylformamide or dimethyl sulfoxide, and the dosage ratio of the 2-amino-3-hydroxypyridine to the organic solvent is preferably 1.9g:150 mL; the hydride is preferably sodium hydride or calcium hydride; the molar ratio of the 2-amino-3-hydroxypyridine to the hydride is preferably 1 (1.4-1.5). In the invention, the temperature of the condensation reaction is preferably room temperature, the time is preferably 24h, the condensation reaction is preferably carried out under the protection of nitrogen and under dark conditions, and the condensation reaction is preferably carried out by using a dean-Stark device; in the embodiment of the invention, preferably, the 2-amino-3-hydroxypyridine and the 7- (bromomethyl) pentadecane are firstly added into the dry organic solvent, then the hydride is added under the condition of ice-water bath, and after the hydride is added, the temperature is raised to the room temperature for reaction. After the condensation reaction is finished, preferably, the obtained product liquid is poured into water, then dichloromethane is used for extraction, and the obtained organic phase is subjected to silica gel chromatographic column purification to obtain the azaarylamine with the structure shown in the formula III; during the purification by silica gel column chromatography, it is preferable to remove the residual solvent with petroleum ether and elute with methanol.
In the present invention, the synthesis process of the azaarylamine is shown as the following formula:
after the isoindigo and the azaarylamine are obtained, the isoindigo and the azaarylamine are used as raw materials to synthesize the n-type organic semiconductor material (IIDG-AB) with the structure shown in the formula I, and the synthesis process of the n-type organic semiconductor material with the structure shown in the formula I is explained in detail below.
The method mixes isoindigo, azaarylamine, titanium tetrachloride, triethylamine, boron trifluoride diethyl etherate and benzene solvent to carry out Schiff base reaction. In the present invention, the schiff base reaction specifically comprises: the isoindigo, azaarylamine and benzene solvent are mixed and react for 1-1.5 hours under the conditions of nitrogen protection and reflux, then titanium tetrachloride is added into a reaction system, triethylamine is added after the reaction is carried out for 10-15 minutes, boron trifluoride ether is added after the reaction is continued for 1.5-2 hours, and the reaction is finished to obtain the isoindigo fluoroboron hybridization-based n-type organic semiconductor material with the structure shown in the formula I. In the present invention, the benzene-based solvent is preferably toluene or xylene; the temperature of the reflux is preferably 110-117 ℃; the reaction time after adding the boron trifluoride diethyl etherate is preferably 12-15 h; the above reaction is preferably carried out in a dean-stark apparatus.
In the invention, the molar ratio of isoindigo to azaarylamine is preferably (4-4.5): 1; the molar ratio of the carbon tetrachloride to the nitrogen heterocyclic aromatic amine is preferably (5.5-6): 1; the mol ratio of the triethylamine to the azaarylamine is preferably (14.5-15): 1; the molar ratio of boron trifluoride diethyl etherate to nitrogen heteroaromatic amine is preferably (15.5-16): 1. In the invention, the titanium tetrachloride is used for stripping hydrogen atoms in amino groups to form imine, and the triethylamine provides a proper alkaline environment for reaction.
After the Schiff base reaction is finished, the method preferably carries out post-treatment on the obtained product liquid; the post-processing method comprises the following steps: pouring the obtained product liquid into water, extracting with dichloromethane, drying the obtained organic phase, removing the solvent to obtain a crude product, and purifying the crude product by silica gel column chromatography to obtain the isoindigo fluoroboron hybridization-based n-type organic semiconductor material with the structure shown in the formula I; the eluent for silica gel column chromatography purification is preferably a mixed solvent of dichloromethane and petroleum ether, and the volume ratio of dichloromethane to petroleum ether in the mixed solvent is preferably 2: 1.
In the invention, the synthesis process of the isoindigo borofluoride hybrid-based n-type organic semiconductor material is shown as the following formula:
the invention also provides application of the isoindigo borofluoride hybridization-based n-type organic semiconductor material in organic field effect transistors and photovoltaic devices. The isoindigo boron-fluorine hybridization-based n-type organic semiconductor material provided by the invention has strong electron deficiency characteristics, low LUMO energy level (-4.21 eV), high stability, n-type electron transmission characteristics, high coplanarity of molecular frameworks and excellent intramolecular charge transfer characteristics, and can be used for designing high-performance n-type organic field effect transistors; meanwhile, the n-type organic semiconductor material also has a wider spectral absorption band and has very wide light absorption between 530nm and 850nm, so that the n-type organic semiconductor material also has huge application potential in photovoltaic devices.
The invention also provides an organic field effect transistor, which adopts the isoindigo boron fluoride hybridization-based n-type organic semiconductor material as an organic semiconductor layer; the invention has no special requirements on the specific structure of the organic field effect transistor, and the structure of the organic field effect transistor known by the technicians in the field can be adopted, and can be specifically a bottom gate bottom contact type, a top gate top contact type, a top gate bottom contact type or a bottom gate top contact type. The method for preparing the organic semiconductor layer is not particularly required by the present invention, and a method well known to those skilled in the art can be adopted, and in the specific embodiment of the present invention, the isoindigo-boron hybrid-based n-type organic semiconductor material is preferably dissolved in chloroform, the obtained solution is dripped on the surface of a substrate, and then the chloroform solvent is removed by heating, so that the organic semiconductor layer can be obtained.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Reagents used in the following examples, such as 6-bromoindole-2-one, 6-bromoindole-2, 3-dione, 2-amino-3-hydroxypyridine, 7- (bromomethyl) pentadecane, boron trifluoride etherate, sodium hydride, hydrochloric acid, acetic acid, N-dimethylformamide and the like, are commercially available products and are available from Aniki chemical.
Example 1
Isoindigo (IIDG) synthesis in the first step: a mixture of 6-bromoindol-2-one (4.0g, 18.8mmol) and 6-bromoindol-2, 3-dione (4.24g, 18.8mmol) was added to acetic acid (120mL) in a 250mL three-necked flask with a Dean-Stark apparatus, 0.8mL hydrochloric acid (36.46%), nitrogen blanketed, and refluxed at 117 ℃ for 24 h. After the reaction was completed, the reaction was washed with a large amount of ethanol and water to obtain a dark red isoindigo (IIDG) solid (6.3g, 79%).
A second step of synthesizing azaarylamine: in a 250mL three-necked flask, using a Dean Stark apparatus, a mixture of 2-amino-3-hydroxypyridine (1.9g, 18mmol) and 7- (bromomethyl) pentadecane (6.42g, 21mmol) was added to dry N, N-dimethylformamide (150mL) and sodium hydride (0.58g, 26mmol) was added under an ice-water bath, and the reaction was stirred at room temperature in the dark for 24h under nitrogen. The reaction mixture was poured into water and extracted with dichloromethane, and the organic phase was purified by silica gel column chromatography (petroleum ether to remove residual solvent, then methanol elution) to give an azaarylamine (4.17g, 69%).
Nuclear magnetic hydrogen spectrum of nitrogen heterocyclic aromatic amineAs shown in FIG. 1, the nuclear magnetic carbon spectrum is shown in FIG. 2, and the results of the nuclear magnetic resonance spectroscopy are as follows: 1 H NMR(CDCl 3 ,500MHz,295K):δppm:7.52(d,1H),6.79(d, 1H),6.52(d,1H),4.65(br,2H),2.84(d,2H),1.76-1.73(m,1H),1.28-1.22 (m,24H),0.85-0.81(m,6H). 13 C NMR(500MHz,CDCl3)δ150.19,142.00, 138.36,115.87,113.61,70.90,37.87,31.88,31.82,31.49,29.98,29.64, 29.56,29.30,26.87,26.84,22.65,14.08.
thirdly, synthesizing the isoindigo boron fluoride hybrid-based n-type organic semiconductor material with the structure shown in the formula I: azaarylamine (0.84g, 2.0mmol) and isoindigo (2.7g, 8.0mmol) were added to dry toluene (45mL) in a 100mL three-necked flask with Dean-Stark apparatus and the mixture was refluxed under nitrogen for 1 h. Titanium tetrachloride (1.2mL, 11mmol) was then added to the reaction mixture, and after 10min of reaction triethylamine (4.0mL, 29mmol) was added. After a further reaction time of about 1.5h, boron trifluoride diethyl etherate (3.8mL, 31mmol) was added and the mixture was refluxed at 117 ℃ for 12 h. The reaction mixture was poured into water (100mL) and extracted with dichloromethane, and the resulting organic phase solution was dried over anhydrous magnesium sulfate and the solvent removed by rotary evaporation to give a green solid. The crude product was finally purified by silica gel column chromatography (dichloromethane/petroleum ether ═ 2:1v/v) to give the product as a green solid (0.53g, 23%) noted IIDG-AB.
The nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum of IIDG-AB are shown in FIG. 3 and FIG. 4, respectively. The results of nuclear magnetic resonance spectroscopy were as follows: 1 H NMR(500MHz,CHCl 3 )δppm:9.43(s,2H),8.09(s,2H), 7.59(s,2H),7.4(s,2H)7.27(s,2H)7.13(s,2H)1.88(s,2H)1.61(s,2H)v 1.16-1.25(m,50H)0.84(s,12H). 13 C NMR(500MHz,CDCl 3 )δ159.93,159.76, 151.63,146.83,139.34,130.44,129.84,126.91,126.00,124.09,121.11,119.48, 116.59,73.71,37.59,31.84,30.95,30.03,29.69,29.59,29.30,26.56,22.65, 22.63,14.09,14.06.MS(MALDI-TOF)m/z:calculated for C 55 H 80 B 2 Br 2 O 2 F 4 N 6 1148.48；found:1171.47[Na + ].Elemental microanalysis found C,60.42％；H, 6.92％；N 7.35％(C,60.54％；H,7.01％；N,7.30％).Extinction coefficient at 718nm＝5.7×10 4 L mol -1 cm -1 .
the optical and electrochemical properties of IIDG-AB were analyzed by UV-visible absorption spectrometry and electrochemical cyclic voltammetry, the data are shown in Table 1, the UV-visible absorption spectrometry is shown in FIG. 5, wherein the concentration of chloroform solution is 1 × 10 -5 mol/L, and the thickness of the solid film is 48 nm.
TABLE 1 optical and electrochemical Properties of IIDG-AB
As can be seen from table 1 and fig. 5: IIDG-AB has a wide spectral absorption band and has wide light absorption between 530nm and 850nm, so that the IIDG-AB also has great application potential in photovoltaic devices; as can be seen from table 1, having a lower lowest unoccupied orbital level, i.e., a LUMO level as low as-4.21 eV, can facilitate electron injection and stabilize electron transport, thereby improving durability of the device.
Application example 1
Preparing an organic field effect transistor by adopting a bottom-gate bottom-contact field effect transistor structure: the N-type doped Si (n) produced by Silicon Quest International company is selected ++ ) The wafer was used as a substrate (with 300nm SiO attached to it) 2 Layer) with the silicon layer as the gate, SiO 2 The layer acts as a dielectric layer. The substrate material is sequentially etched with piranha etching solution (H) 2 SO 4 /H 2 O 2 3/1, vol), deionized water, acetone, and immersed in a 5% solution of Octadecyltrichlorosilane (OTS) in toluene at room temperature under argon for 1 h. And forming a gold source electrode and a gold drain electrode on the silicon wafer by a mask plate gold spraying method, wherein the thickness of the electrodes is 50nm, and the length and the width of the conductive groove are 50 micrometers and 1000 micrometers respectively. Then 7mg/mL of IIDG-AB solution in chloroform was dripped on the surface of the treated substrate under the protection of argon, and the substrate was heated at 50 ℃ for 0.5h to remove the chloroform solvent, and finally an IIDG-AB-based n-type organic field effect transistor (described as IIDG-AB-based) was obtainedOFET devices).
A total of 8 OFET devices were prepared according to the above method and the electron mobility values of the 8 OFET devices were tested, and the results are shown in fig. 6. As can be seen from FIG. 6, the average electron mobility μ for eight OFETs based on IIDG-AB e The average value is 6.9 multiplied by 10 –2 cm 2 V -1 s -1 Up to 8.2X 10 –2 cm 2 V -1 s -1 。
FIG. 7 is a graph of the transfer characteristics of OFET devices based on IIDG-AB, and it can be seen from FIG. 7 that the current on-off ratio of OFET is 10 4 To 10 5 In between, the threshold voltage is 32V.
The charge mobility performance was measured continuously daily and the OFET devices described above were exposed to air for one week, and the results are shown in fig. 8. As can be seen from fig. 8, after four days, the electron mobility of the OFET device was reduced by 30% compared to the initial result, after which the electron mobility remained substantially unchanged.
Comparative example
The traditional isoindigo molecule IIDG and isoindigo base dimeric nitrogen fluorine hetero boron dipyrrolidine IIDG-AB are adopted for performance comparison, and the molecular structure comparison chart of the two is shown in figure 9.
The molecular orbital levels of IIDG and IIDG-AB are shown in Table 2.
TABLE 2 molecular orbital energy levels of isoindigo molecule IIDG and isoindigo-based dinitrodiazofluorodipyrrolidine IIDG-AB
As can be seen from the data in Table 2, IIDG-AB has a HOMO level of-5.24 eV, similar to IIDG (-5.25eV), and the LUMO level of IIDG-AB is significantly lower than IIDG, IIDGA-AB is-4.21 eV, and IIDG is-3.78 eV. The presence of fluorine and unsaturated nitrogen atoms in IIDG-AB increases its electron-deficient capacity. For an n-type semiconductor, a low LUMO energy level may facilitate electron injection and stabilize electron transport, thereby improving durability of the device. The LUMO energy level of the IIDG-AB is very low, which indicates that the IIDG-AB is an n-type semiconductor molecule with a good application prospect and has good environmental stability.
The XRD patterns of IIDG and IIDG-AB are shown in figure 10. The HOMO level of IIDG-AB is-5.24 eV, similar to IIDG (-5.25eV), both materials show intermolecularly coplanar pi-pi stacking peaks at 2 theta 23.2 ° for IIDG-AB and 21.7 ° for IIDG, corresponding to pi-pi stacking with d-spacings of 0.408nm and 0.419nm, respectively. The d-spacing of the IIDG-AB thin film is slightly shorter, which indicates that the pi stacking of the IIDG-AB is tighter than that of the solid IIDG, which means that the IIDG-AB has better long-range order, stronger pi-pi stacking and better molecular stacking of the long-range order are beneficial to realizing more effective intermolecular charge transfer, thereby providing higher charge mobility in a corresponding OFET device.
IIDG is adopted as an organic semiconductor material, the method in application example 1 is adopted to prepare the OFET device based on the IIDG, other preparation conditions are consistent with those in application example 1, and only IIDG-AB in the OFET device is replaced by the IIDG.
A comparison of the transfer transmission curves of the organic field effect transistors prepared using IIDG and IIDG-AB is shown in FIG. 11, where (a) is an OFET device based on IIDG-AB and (b) is an OFET device based on IIDG. As can be seen from fig. 11, the IIDG based OFET devices exhibit p-type behavior, while the IIDG-AB based OFET devices exhibit n-type behavior. Average mu of OFET device based on IIDG-AB e Is 6.9X 10 –2 cm 2 V -1 s -1 (wherein the maximum is 8.2X 10 –2 cm 2 V -1 s -1 ) And average μ of IIDG h Is only 1.3X 10 –4 cm 2 V -1 s -1 (maximum μ) h Is 1.7X 10 –2 cm 2 V -1 s -1 ). This is because the ultra-low LUMO level of IIDG-AB facilitates electron injection from the electrode, and the strong electron-deficient nature of IIDG-AB helps stabilize the electron transport process within the semiconductor layer. In addition, IIDG-AB has a large pi-conjugated system, a stronger intramolecular charge transfer effect and high coplanarity of the skeleton structure, and the IIDG-AB thin film has stronger aggregation and long-range ordered accumulation, which are beneficial to charge transmission between adjacent molecules, so that the mobility ratio of IIDG-AB is higher than that of IIDG-ABIIDG is two orders of magnitude greater.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. An isoindigo fluoroboron hybridization-based n-type organic semiconductor material has a structural formula shown as a formula I:
in formula I: r is
2. A process for the preparation of isoindigo borofluoride hybrid-based n-type organic semiconductor material as claimed in claim 1, comprising the steps of:
isoindigo, azaarylamine, titanium tetrachloride, triethylamine, boron trifluoride diethyl etherate and benzene solvent are mixed to carry out Schiff base reaction, so that an isoindigo fluoroboron hybridization-based n-type organic semiconductor material with a structure shown in a formula I is obtained;
the structure of the isoindigo is shown as a formula II, and the structure of the azaarylamine is shown as a formula III:
3. the preparation method according to claim 2, wherein the Schiff base reaction specifically comprises: the isoindigo, azaarylamine and benzene solvent are mixed and react for 1-1.5 hours under the conditions of nitrogen protection and reflux, then titanium tetrachloride is added into a reaction system, triethylamine is added after the reaction is carried out for 10-15 minutes, boron trifluoride ether is added after the reaction is continued for 1.5-2 hours, and the reaction is finished to obtain the isoindigo fluoroboron hybridization-based n-type organic semiconductor material with the structure shown in the formula I.
4. The production method according to claim 2 or 3, wherein the benzene-based solvent is toluene or xylene; and the reaction time after adding the boron trifluoride diethyl etherate is 12-15 h.
5. The preparation method according to claim 2 or 3, wherein the molar ratio of the isoindigo to the azaarylamine is (4-4.5): 1; the molar ratio of the carbon tetrachloride to the nitrogen heterocyclic aromatic amine is (5.5-6) to 1; the molar ratio of the triethylamine to the azaarylamine is (14.5-15) to 1; the molar ratio of boron trifluoride diethyl etherate to nitrogen heteroaromatic amine is (15.5-16): 1.
6. A process according to claim 2 or 3, wherein the process for the preparation of azaarylamine comprises the steps of:
mixing 2-amino-3-hydroxypyridine, 7- (bromomethyl) pentadecane, hydride and an organic solvent for condensation reaction to obtain nitrogen heterocyclic arylamine with a structure shown in a formula III; the condensation reaction was carried out under dark conditions.
7. The method according to claim 6, wherein the hydride is sodium hydride or calcium hydride.
8. The preparation method according to claim 2 or 3, wherein after the Schiff base reaction is completed, the method further comprises performing post-treatment on the obtained product feed liquid; the post-processing method comprises the following steps: and pouring the obtained product liquid into water, extracting with dichloromethane, drying the obtained organic phase, removing the solvent to obtain a crude product, and purifying the crude product by silica gel column chromatography to obtain the isoindigo fluoroboron hybridization-based n-type organic semiconductor material with the structure shown in the formula I.
9. Use of isoindigo fluoroboron hybridization based n-type organic semiconductor material according to claim 1 in organic field effect transistors and photovoltaic devices.
10. An organic field effect transistor, characterized in that the isoindigo fluoroboron hybridization-based n-type organic semiconductor material of claim 1 is used as an organic semiconductor layer.
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