CN110041337B - Pyrrolo-pyrrole organic semiconductor material containing free radicals, preparation method and application thereof - Google Patents

Pyrrolo-pyrrole organic semiconductor material containing free radicals, preparation method and application thereof Download PDF

Info

Publication number
CN110041337B
CN110041337B CN201910398946.0A CN201910398946A CN110041337B CN 110041337 B CN110041337 B CN 110041337B CN 201910398946 A CN201910398946 A CN 201910398946A CN 110041337 B CN110041337 B CN 110041337B
Authority
CN
China
Prior art keywords
pyrrole
organic semiconductor
semiconductor material
pyrrolopyrrole
monomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910398946.0A
Other languages
Chinese (zh)
Other versions
CN110041337A (en
Inventor
郑永豪
王文翔
苗芳
葛玲兵
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Electronic Science and Technology of China
Original Assignee
University of Electronic Science and Technology of China
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Electronic Science and Technology of China filed Critical University of Electronic Science and Technology of China
Priority to CN201910398946.0A priority Critical patent/CN110041337B/en
Publication of CN110041337A publication Critical patent/CN110041337A/en
Application granted granted Critical
Publication of CN110041337B publication Critical patent/CN110041337B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • 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
    • 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
    • H10K85/653—Aromatic compounds comprising a hetero atom comprising only oxygen as heteroatom
    • 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
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • 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

Abstract

The invention discloses a pyrrolo-pyrrole organic semiconductor material containing free radicals, a preparation method and application thereof, belonging to the technical field of photoelectric materials. The preparation method comprises the following steps: mixing the halogenated derivative of the pyrrolopyrrole with the monomer I, or mixing an organic tin compound of the pyrrolopyrrole with the monomer I' to obtain the organic semiconductor material of the pyrrolopyrrole; and reacting the pyrrolopyrrole organic semiconductor material with an oxidant to obtain the pyrrolopyrrole organic semiconductor material containing free radicals. The preparation method of the invention has simple synthetic route and easy synthesis. The pyrrole and pyrrole organic semiconductor material containing free radicals prepared by the invention has high electron mobility, good molecular stability, high absorption strength and narrow absorption wave band, the absorption wavelength of the material reaches near infrared wave band, and the material can be used as free-based materials of devices such as near infrared and narrow band photoelectric detectors, organic field effect tubes and the like.

Description

Pyrrolo-pyrrole organic semiconductor material containing free radicals, preparation method and application thereof
Technical Field
The invention relates to the technical field of photoelectric materials, in particular to a pyrrolo-pyrrole organic semiconductor material containing free radicals, a preparation method and application thereof.
Background
The optical detection technology can realize accurate detection from an ultraviolet visible light region to an infrared light region, and is often applied to the fields of industrial production, military scientific research, optoelectronics and the like. With the social development, people have higher and higher requirements on the optical detection technology, so that the development of narrow-band detection needs to be emphasized besides the research on widening the detectable waveband. The narrow-band detector is also called a waveband distinguishing detector, has wavelength sensitive characteristics, can only detect light of a specific waveband, and plays an important role in biological imaging and safety monitoring.
At present, inorganic semiconductor photoelectric materials of Si, GaN or InGaAs are commonly used in optical detection, the response wave band is wide, narrow-band response is realized by means of optical filter or prism coupling in use, the manufacturing process is complex and tedious, and errors often exist in detection results. In addition, the inorganic semiconductor photoelectric material has complex process and high cost for preparing the optical detection device.
At present, the size of the inorganic thin film field effect transistor is close to the natural limit of miniaturization, a new path is needed if the circuit integration level is further improved, the manufacturing cost of the inorganic thin film field effect transistor is high, the single crystal is difficult to prepare, a high-temperature process is needed, and the substrate is made of a hard material. In the face of these problems, in recent years, with the development of organic polymers, Organic Field Effect Transistors (OFETs) are receiving more and more attention, and compared with traditional inorganic field effect transistors, OFETs have many incomparable advantages:
(1) the organic thin film has more and more film forming technologies, and the size of the device can be smaller (divided into the size), so that the integration level can be improved, and further, the operating power of the integrated circuit is reduced, and the operation speed is higher;
(2) the electrical property of the OFET can be improved by properly modifying the structure of the organic molecule, and the same purpose can be achieved by doping, so that the performance of the OFET is improved;
(3) large area can be realized;
(4) the organic material has wide sources and is easy to obtain;
(5) the organic field effect transistor prepared by the organic material has better flexibility, and the electrical characteristics of the device can not be influenced by properly bending the device.
However, the organic semiconductor material used as the organic field effect transistor needs to have stable electrochemical characteristics and also should have a conjugated system of pi bonds, and the overlapping axial direction of the pi bonds should be consistent with the shortest distance direction between the source and drain electrodes as much as possible, so as to be beneficial to the transmission of carriers. Therefore, in order to achieve the optimal morphology of crystal growth and orientation, the application of most organic materials is limited to a certain extent, and higher requirements are also put on film preparation conditions. In the prior art, the process for preparing the organic semiconductor material used as the organic field effect transistor is complex, and the obtained organic semiconductor material has low electron mobility.
Disclosure of Invention
The invention aims to provide a pyrrole-pyrrole organic semiconductor material containing free radicals, a preparation method and application thereof, and aims to solve the problems that an inorganic semiconductor photoelectric material in the existing narrow-band detection technology has a wider response wave band, a complex and tedious manufacturing process and an error exists in a detection result.
The technical scheme for solving the technical problems is as follows:
a pyrrolo-pyrrole organic semiconductor material containing free radicals has a molecular structure shown as a formula I:
Figure GDA0002461732470000021
wherein R is1Is tert-butyl, aryl or heterocyclic aryl; r2Is tert-butyl, aryl or heterocyclic aryl; r3Is an oxygen atom or a sulfur atom; r4Is H atom, straight chain alkyl or branched chain alkyl of C1-C60; r5Is an oxygen atom, a sulfur atom or an imino group; r6Is furan, bitofuran, bifuran, terthiophene, tetrafuran, thiophene, bithiophene, terthiophene, tetrathiophene, 3, 4-ethylenedioxythiophene, selenophene, bisselenophene, terselenophene, tetraselenophene, aryl, nitrile, nitro derivatives, fluorine-containing thiophene, fluorine-containing furan, fluorine-containing selenophene, phenyl, 1-naphthyl or 2-naphthyl.
It should be noted that the furan referred to above in the present invention refers to 1 oxygen-containing five-membered heterocyclic compound, and the difuran, the bifuran, the trifuran and the tetradifuran refer to 2, 3 and 4 oxygen-containing five-membered heterocyclic compounds, respectively.
Furan C4H4O (English: Furan), which has the structural formula:
Figure GDA0002461732470000031
and-difuran C6H4O2(English: Furo [3,2-b ]]furan) of the formula:
Figure GDA0002461732470000032
bidifurane C8H6O2(English: 2,2' -Bifuran), the structural formula of which is:
Figure GDA0002461732470000033
tri-furan C12H8O3(English: 2,2':5', 2' -Terfuran), the structural formula of which is:
Figure GDA0002461732470000034
tetrafuran C16H10O4(English: 2,2':5',2 ": 5", 2' "-Quaterfuran) having a structural formula:
Figure GDA0002461732470000035
similarly, the thiophene, bithiophene, terthiophene and tetrathiophene referred by the invention; and selenophene, diselenophene, biselenophene, terselenophene, tetraselenophene, as well as increasing the number of rings of thiophene and selenophene, respectively. The molecular formula and the structural formula are given below, respectively.
Thiophene C4H4S (English: Thiophene), the structural formula of which is:
Figure GDA0002461732470000041
bithiophene C6H4S2(English: Thieno [3,2-b ]]thiophene), having the formula:
Figure GDA0002461732470000042
bithiophene C8H6S2(English: 2,2' -Bithiophene), the structural formula of which is:
Figure GDA0002461732470000043
trithiophene C12H8S3(English: 2,2':5', 2' -Terthiophene) having a structural formula:
Figure GDA0002461732470000044
tetrathiophene C16H10S4(English: 2,2':5',2 ": 5", 2' "-Quaterthiophene) having a structural formula:
Figure GDA0002461732470000045
in order to simplify the description, selenophene, diselenophene, biselenophene, terselenophene and tetraselenophene are not provided one by one, and the structural formula is that the O atom or the S atom is replaced by the Se atom.
A preparation method of a pyrrolo-pyrrole organic semiconductor material containing free radicals comprises the following steps:
(1) mixing a pyrrole-pyrrole halide and a derivative thereof with a monomer I, or mixing a pyrrole-pyrrole organic tin compound with a monomer I' to obtain a pyrrole-pyrrole organic semiconductor material;
the structure of the monomer I is shown as the formula II:
Figure GDA0002461732470000051
wherein R is1Is tert-butyl, aryl or heterocyclic aryl; r2Is tert-butyl, aryl or heterocyclic aryl; r3Is hydroxyl or mercapto; r7Is aryl boric acid, alkenyl boric acid, aryl boric acid ester or alkenyl boric acid ester;
the structure of the monomer I 'is shown as the formula II':
Figure GDA0002461732470000052
wherein R is1Is tert-butyl, aryl or heterocyclic aryl; r2Is tert-butyl, aryl or heterocyclic aryl; r3Is hydroxyl or mercapto; r7' is halogen;
(2) adding an oxidant into the pyrrolo-pyrrole organic semiconductor material and mixing to obtain the pyrrolo-pyrrole organic semiconductor material containing free radicals.
Further, in a preferred embodiment of the present invention, the specific process for preparing the pyrrolopyrrole organic semiconductor material in the step (1) is as follows: adding pyrrole and pyrrole halide and derivatives thereof, monomer I, palladium catalyst, phosphine ligand, alkali solid and water, and carrying out condensation reflux reaction in a toluene or dioxane solvent for 10-14 h at a reaction temperature of 90-120 ℃ under the protection of inert gas atmosphere;
wherein the molar ratio of the pyrrole-pyrrole halide and the derivative thereof to the monomer I to the palladium catalyst to the phosphine ligand to the alkali solid is 1 (2.2-4): (0.05-0.1): (0.15-0.4): (3-4), the addition amount of water is 0.2-0.4 wt% of the pyrrole halide and the derivative thereof; the base solid comprises tetrabutylammonium hydroxide, potassium carbonate or cesium carbonate.
Preferably, the above reaction temperature is, for example, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃. The reflux reaction time is, for example, 10h, 11h, 12h, 13h or 14 h. The molar ratio between the pyrrolopyrrole halide and its derivative, monomer i, palladium catalyst, phosphine ligand and base solid is, for example, 1: 2.2: 0.15: 3. 1: 2.6: 0.075: 0.2: 3.5, 1: 3: 0.075: 0.3: 3.5 or 1: 4: 0.1: 0.4: 4. the amount of water added is 0.2 wt%, 0.25 wt%, 0.3 wt%, 0.35 wt% or 0.4 wt% of the pyrrolopyrrole halide and its derivative. In the present invention, the pyrrolopyrrole halide and the derivative thereof mean an pyrrolopyrrole halide or an pyrrolopyrrole halide derivative. Preferably, the palladium catalyst comprises tetrakis (triphenylphosphine) palladium or tris (dibenzylideneacetone) dipalladium.
Preferably, the phosphine ligand comprises tris (o-methylphenyl) phosphine.
Further, in a preferred embodiment of the present invention, the structure of the pyrrolopyrrole halide and the derivative thereof is shown in formula III:
Figure GDA0002461732470000061
wherein R is4Being H atoms, C1-C60Straight or branched chain alkyl; r5Is oxygen, sulfur or imino; r6Is furan, bitofuran, bifuran, tertiaryfuran, tetrafuran, thiophene, bithiophene, tertiarythiophene, tetrathiophene, 3, 4-ethylenedioxythiophene, selenophene, bisselenophene, tertiaryselenophene, tetraselenophene, aryl, nitrile, nitro derivatives, fluorine-containing thiophene, fluorine-containing furan, fluorine-containing selenophene, phenyl, 1-naphthyl or 2-naphthyl; x is halogen.
Further, in a preferred embodiment of the present invention, the specific process for preparing the pyrrolopyrrole organic semiconductor material in the step (1) is as follows: adding a pyrrolopyrrole organotin compound, a monomer I', a palladium catalyst and a phosphine ligand, and carrying out condensation reflux reaction for 6 to 10 hours in a solvent of dry and deoxygenated toluene or tetrahydrofuran at a reaction temperature of between 80 and 120 ℃ under the protection of inert gas atmosphere;
wherein, the mol ratio of the pyrrolopyrrole organotin compound, the monomer I', the palladium catalyst and the phosphine ligand is 1: (2-3): (0.05-0.1): (0.15-0.4).
Preferably, the reaction temperature is, for example, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃. The reaction time is, for example, 6h, 7h, 8h, 9h or 10h at reflux. The molar ratio between the pyrrolopyrrole organotin compound, monomer i', palladium catalyst and triphenylphosphine is, for example, 1: 2: 0.05: 0.15, 1: 2.6: 0.075: 0.2, 1: 2.6: 0.75: 0.3 or 1: 3: 0.1: 0.4.
preferably, the palladium catalyst comprises: tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium chloride or bis (acetonitrile) palladium dichloride.
Preferably, the phosphine ligand comprises triphenylphosphine or tri-tert-butylphosphine.
Further, in a preferred embodiment of the present invention, the structure of the pyrrolopyrrole organotin compound is shown as formula IV:
Figure GDA0002461732470000071
wherein R is4Is H atomA linear or branched alkyl group having from C1 to C60; r5Is an oxygen atom, a sulfur atom or an imino group; r6Is furan, bitofuran, bifuran, tertiaryfuran, tetrafuran, thiophene, bithiophene, tertiarythiophene, tetrathiophene, 3, 4-ethylenedioxythiophene, selenophene, bisselenophene, tertiaryselenophene, tetraselenophene, aryl, nitrile, nitro derivatives, fluorine-containing thiophene, fluorine-containing furan, fluorine-containing selenophene, phenyl, 1-naphthyl or 2-naphthyl; r8Is 3 methyl groups or 3 butyl groups.
Further, in a preferred embodiment of the present invention, the specific process of the step (2) is as follows: dissolving the pyrrolopyrrole organic semiconductor material at room temperature, adding an oxidant, and reacting for 10-20 min; wherein the mol ratio of the pyrrolopyrrole organic semiconductor material to the oxidant is 1: (50-70).
Preferably, the reaction time is 10min, 12min, 14min, 15min, 16min, 18min or 20 min. The molar ratio of the pyrrolopyrrole organic semiconductor material to the oxidizing agent is, for example, 1: 50. 1: 55. 1: 60. 1: 65 or 1: 70.
preferably, the oxidizing agent comprises lead dioxide, sodium bismuthate, periodic acid, cobalt trifluoride or sodium ferrate.
The application of the pyrrole-pyrrole organic semiconductor material containing the free radicals in the preparation of narrow-band photodetectors.
Preferably, the pyrrole and pyrrole organic semiconductor material containing the free radicals is applied to optoelectronic devices such as organic field effect transistors and organic solar cells.
The invention has the following beneficial effects:
1. the aromatic group or heteroaromatic group in the chemical structure of the pyrrolopyrrole is replaced by a five-membered heterocyclic ring containing O, S or Se, the aromatic group or heteroaromatic group reacts with a monomer I or a monomer I' containing phenol or thiophenol to generate the pyrrolopyrrole organic semiconductor material, and the hydroxyl group or the sulfhydryl group on the phenol or the thiophenol in the chemical structure of the pyrrolopyrrole organic semiconductor material is oxidized into a phenoxy radical or a thiophenol free radical under the action of an oxidant, so that the pyrrolopyrrole organic semiconductor material containing the free radical is obtained. The pyrrolo-pyrrole organic semiconductor material containing the free radicals has the advantage of stable performance, and after the pyrrolo-pyrrole organic semiconductor material is oxidized into the free radicals, the spectrum of the pyrrolo-pyrrole organic semiconductor material is red-shifted, and the molar absorption coefficient of molecules is greatly improved; the absorption is strong, the absorption waveband is narrow, the absorption wavelength can reach a near infrared waveband, and the device can be used for other devices such as a narrow-band photoelectric detector.
2. The invention introduces phenol group or thiophenol group on the pyrrole-pyrrole structure through the monomer I or the monomer I', wherein the introduced benzene ring prolongs the conjugated system of the whole structure, the electronic motion range on the free radical is enlarged, the whole molecule tends to be stable, the energy band interval is reduced, the wavelength of the absorption spectrum is increased during electronic transition, and the absorption spectrum generates red shift. In addition, R in the chemical structure of the monomer I or the monomer I1And R2And the compound can also play a role in protecting phenoxy groups or phenylthio groups, thereby improving the stability of the pyrrole and pyrrole organic semiconductor materials containing free radicals.
3. According to the invention, a five-membered heterocyclic ring containing O, S or Se is further introduced into the chemical structure of the pyrrolopyrrole, so that O, S or Se atoms are introduced into the prepared pyrrolopyrrole organic semiconductor material containing the free radicals, and the molecular accumulation is facilitated in a solid state due to the action between O, S or Se atoms, thereby improving the electron transport performance of the pyrrolopyrrole organic semiconductor material containing the free radicals.
4. The pyrrole and pyrrole organic semiconductor material containing free radicals prepared by the invention comprises an open shell state and a closed shell state, and the structure of the pyrrole and pyrrole organic semiconductor material in the closed shell state is shown as a formula V:
Figure GDA0002461732470000091
the proportion of the open shell state is 33-37% calculated according to the Density Functional Theory (DFT), and the rest is the closed shell state. Wherein the proportion of the open shell state is small (not more than 50%), the absorption spectrum of the pyrrolo-pyrrole organic semiconductor material containing free radicals can reach a near infrared band, and the stability is higher. The pyrrolopyrrole organic semiconductor material contains unpaired electrons, so that the electronic transmission is facilitated, and the detection sensitivity can be improved.
5. The pyrrole and pyrrole organic semiconductor material containing free radicals prepared by the invention has high electron mobility, good molecular stability, high absorption strength and narrow absorption wave band, the absorption wavelength of the material reaches near infrared wave band, and the material can be used as free-based materials of devices such as near infrared and narrow band photoelectric detectors, organic field effect tubes and the like.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of example 1 of the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of example 2 of the present invention;
FIG. 3 is a nuclear magnetic hydrogen spectrum of example 3 of the present invention;
FIG. 4 is a graph showing UV-VIS absorption spectra of examples 1, 2 and 3 of the present invention;
FIG. 5 is a graph of the variation of UV absorption intensity under 400w illumination for examples 1, 2 and 3 of the present invention;
FIG. 6 is a graph showing an ultraviolet-visible light absorption spectrum after 16 weeks of standing in example 1 of the present invention;
FIG. 7 is a graph showing an ultraviolet-visible light absorption spectrum after 16 weeks of standing in example 2 of the present invention;
FIG. 8 is a graph showing an ultraviolet-visible light absorption spectrum after 16 weeks of standing in example 3 of the present invention;
FIG. 9 is a graph of the photo-response current at 650nm for a photo-detector device prepared in example 2 of the present invention;
FIG. 10 is a graph of the photoresponse current at 780nm for a photodetector device prepared in accordance with example 2 of the present invention;
FIG. 11 is a graph of the photo-response current at 808nm for a photo-detector device prepared in example 2 of the present invention;
fig. 12 is a mobility test chart of example 2 of the present invention;
fig. 13 is a channel current-source-drain voltage change curve diagram in embodiment 2 of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
The preparation method comprises the steps of mixing a pyrrole-pyrrole halide and a derivative thereof with a monomer I, or mixing a pyrrole-pyrrole organic tin compound with a monomer I' to obtain a pyrrole-pyrrole organic semiconductor material, and then adding an oxidant into the pyrrole-pyrrole organic semiconductor material for mixing to obtain the pyrrole-pyrrole organic semiconductor material containing free radicals. The pyrrole and pyrrole halide and the derivative thereof, the monomer I, the pyrrole and pyrrole organic tin compound and the monomer I' finally obtain the pyrrole and pyrrole organic semiconductor material containing free radicals, and the reaction processes are respectively shown as reaction lines I and II:
reaction line I:
Figure GDA0002461732470000101
reaction line ii:
Figure GDA0002461732470000111
example 1
The preparation of this example was carried out according to the above scheme I using a halogenated pyrrolopyrrole derivative of the formula R4Is 2-octane dodecyl; r5Is an oxygen atom, R6Is furan; and X is Br. In the formula of monomer I, R1Is tert-butyl; r2Is tert-butyl; r3Is a hydroxyl group; r7Is 1,3, 2-dioxolane boron, 4,4,5, 5-tetramethyl.
The preparation method of the radical-containing pyrrolopyrrole organic semiconductor material of the embodiment includes:
(1) and adding a pyrrole halogenated derivative, a monomer I, tetrakis (triphenylphosphine) palladium, tris (o-methylphenyl) phosphine, tetrabutylammonium hydroxide and water, and carrying out condensation reflux reaction in a toluene solvent at the reaction temperature of 120 ℃ for 12h under the protection of an inert gas atmosphere to obtain the pyrrole organic semiconductor material. Wherein, the molar ratio of the halogenated pyrrole derivative to the monomer I to the palladium tetrakis (triphenylphosphine), the tris (o-methylphenyl) phosphine and the tetrabutylammonium hydroxide is 1: 2.6: 0.075: 0.2, the amount of water added is 0.3% by weight of the halogenated pyrrolopyrrole derivative.
(2) At room temperature, dissolving the pyrrolo-pyrrole organic semiconductor material in dichloromethane, and adding lead dioxide to react for 15min to obtain the pyrrolo-pyrrole organic semiconductor material containing free radicals. Wherein the molar ratio of the pyrrolopyrrole organic semiconductor material to the lead dioxide is 1: 60.
example 2
The preparation of this example was carried out according to scheme I above using the halogenated derivatives of pyrrolopyrrole of formula R4Is 2-octane dodecyl; r5Is an oxygen atom; r6Is thiophene; and X is Br. In the formula of monomer I, R1Is tert-butyl; r2Is tert-butyl; r3Is a hydroxyl group; r7Is 1,3, 2-dioxolane boron, 4,4,5, 5-tetramethyl.
The preparation method of the radical-containing pyrrolopyrrole organic semiconductor material of the embodiment includes:
(1) and adding a pyrrole halogenated derivative, a monomer I, tetrakis (triphenylphosphine) palladium, tris (o-methylphenyl) phosphine, tetrabutylammonium hydroxide and water, and carrying out condensation reflux reaction in a toluene solvent at the reaction temperature of 120 ℃ for 12h under the protection of an inert gas atmosphere to obtain the pyrrole organic semiconductor material. Wherein, the molar ratio of the pyrrolopyrrole organic semiconductor material to the monomer I, the tetrakis (triphenylphosphine) palladium, the tris (o-methylphenyl) phosphine and the tetrabutylammonium hydroxide is 1: 2.6: 0.075: 0.2, the adding amount of the water is 0.3 wt% of the pyrrolopyrrole organic semiconductor material.
(2) At room temperature, dissolving the pyrrolo-pyrrole organic semiconductor material in dichloromethane, adding lead dioxide, and reacting for 15min to obtain the pyrrolo-pyrrole organic semiconductor material containing free radicals. Wherein the molar ratio of the pyrrolopyrrole organic semiconductor material to the lead dioxide is 1: 60.
example 3
The preparation of this example was carried out according to the above scheme I using a halogenated pyrrolopyrrole derivative of the formula R4Is 2-octane dodecyl; r5Is an oxygen atom; r6Is selenophene; and X is Br. In the formula of monomer I, R1Is tert-butyl; r2Is tert-butyl; r3Is a hydroxyl group; r7Is 1,3, 2-dioxolane boron, 4,4,5, 5-tetramethyl.
The preparation method of the radical-containing pyrrolopyrrole organic semiconductor material of the embodiment includes:
(1) and adding a pyrrole halogenated derivative, a monomer I, tetrakis (triphenylphosphine) palladium, tris (o-methylphenyl) phosphine, tetrabutylammonium hydroxide and water, and carrying out condensation reflux reaction in a toluene solvent at the reaction temperature of 120 ℃ for 12h under the protection of an inert gas atmosphere to obtain the pyrrole organic semiconductor material. Wherein, the molar ratio of the halogenated pyrrole derivative to the monomer I to the palladium tetrakis (triphenylphosphine), the tris (o-methylphenyl) phosphine and the tetrabutylammonium hydroxide is 1: 2.6: 0.075: 0.2, the amount of water added is 0.3% by weight of the halogenated pyrrolopyrrole derivative.
(2) At room temperature, dissolving the pyrrolo-pyrrole organic semiconductor material in dichloromethane, and adding lead dioxide to react for 15min to obtain the pyrrolo-pyrrole organic semiconductor material containing free radicals. Wherein the molar ratio of the pyrrolopyrrole organic semiconductor material to the lead dioxide is 1: 60.
example 4
The preparation of this example was carried out as described in reaction procedure I above using a pyrrolopyrrole halide of formula R4Is an H atom; r5Is a sulfur atom; r6Is 3, 4-difluorothiophene; and X is Br. In the formula of monomer I, R1Is a benzene ring; r2Is thiophene; r3Is a hydroxyl group; r7Is 2-allyl-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborolan.
The preparation method of the radical-containing pyrrolopyrrole organic semiconductor material of the embodiment includes:
(1) and adding a pyrrole halide, a monomer I, bis (triphenylphosphine) palladium chloride, tri-tert-butylphosphine, potassium carbonate and water, and carrying out condensation reflux reaction in a toluene solvent at a reaction temperature of 90 ℃ for 14h under the protection of an inert gas atmosphere to obtain the pyrrole organic semiconductor material. Wherein, the mol ratio of the pyrrole halide, the monomer I, the bis (triphenylphosphine) palladium chloride, the tri-tert-butylphosphine and the potassium carbonate is 1: 4: 0.1: 0.4: 4, water is added in an amount of 0.4 wt% of the pyrrolopyrrole halide.
(2) Dissolving the pyrrolopyrrole organic semiconductor material in dichloromethane at room temperature, adding sodium bismuthate, and reacting for 20min to obtain the pyrrolopyrrole organic semiconductor material containing free radicals. Wherein the mol ratio of the pyrrolopyrrole organic semiconductor material to the sodium bismuthate is 1: 50.
example 5
The preparation process of this example was carried out according to the above scheme II using an organotin pyrrolopyrrole compound of the formula R4Is 2-butanedodecyl; r5Is a sulfur atom; r6Is 3, 4-difluorofuran; r8Is 3 methyl groups. In the structural formula of the monomer I', R1Is thiophene; r2Is furan; r3Is mercapto; r7' is Cl.
The preparation method of the radical-containing pyrrolopyrrole organic semiconductor material of the embodiment includes:
(1) and adding a pyrrolopyrrole organotin compound, a monomer I', tetrakis (triphenylphosphine) palladium and triphenylphosphine, and carrying out condensation reflux reaction in a toluene solvent for 12 hours at the reaction temperature of 120 ℃ in the protection of inert gas atmosphere to obtain the pyrrolopyrrole organic semiconductor material. Wherein, the mol ratio of the pyrrolopyrrole organotin compound, the monomer I', the tetrakis (triphenylphosphine) palladium and the triphenylphosphine is 1: 3: 0.1: 0.4.
(2) dissolving the pyrrolopyrrole organic semiconductor material in dichloromethane at room temperature, adding periodic acid, and reacting for 10min to obtain the pyrrolopyrrole organic semiconductor material containing free radicals. Wherein the molar ratio of the pyrrolopyrrole organic semiconductor material to the periodic acid is 1: 70.
the pyrrolopyrrole organic semiconductor material containing the free radicals prepared in the detection examples 1-5 has good molecular stability, high absorption strength and narrow absorption wavelength band, and the absorption wavelength can reach the near-infrared band.
Analysis of results
The pyrrolopyrrole-based organic semiconductor materials prepared in examples 1, 2 and 3 were subjected to performance tests and analysis.
Results analysis 1
The pyrrolopyrrole-based organic semiconductor materials containing radicals prepared in examples 1, 2 and 3 were all black solids, and were prepared as solutions, which were green in color.
The pyrrole-pyrrole organic semiconductor materials containing free radicals prepared in examples 1, 2 and 3 are analyzed by nuclear magnetic hydrogen spectroscopy, and nuclear magnetic hydrogen spectrograms of examples 1, 2 and 3 are obtained, as shown in figures 1, 2 and 3.
From fig. 1 to 3, the molecular formulae of the radical-containing pyrrolopyrrole-based organic semiconductor materials of examples 1, 2 and 3 can be confirmed, and it can be shown that the radical-containing pyrrolopyrrole-based organic semiconductor materials prepared in examples 1, 2 and 3 are consistent with the target products prepared in examples 1, 2 and 3.
Results analysis 2
The radical-containing pyrrolopyrrole organic semiconductor materials prepared in examples 1, 2 and 3 were formulated into 10-5The solution of mol/L is subjected to ultraviolet-visible light absorption spectrum test to obtain the ultraviolet-visible light absorption spectrum chart of the examples 1, 2 and 3, and the ultraviolet-visible light absorption spectrum chart is shown in figure 4.
As can be seen from FIG. 4, the radical-containing pyrrolopyrrole organic semiconductor materials λ of examples 1, 2 and 3 were obtained at the same concentrationmax749nm, 781nm and 773nm respectively, the absorption bands of the three are all between 600-800nm, the absorption bands are narrow, and the absorption attenuation is 0 at about 1000 nm. As can be seen from the figure, the radical-containing pyrrolopyrrole organic semiconductor material of example 1 has the strongest absorption strength, and the radical-containing pyrrole of example 2 has the strongest absorption strengthLambda of pyrrolopyrrole organic semiconductor materialmaxAnd max.
Results analysis 3
The radical-containing pyrrolopyrrole organic semiconductor materials of examples 1, 2 and 3 were formulated into 10-3The solution of mol/L is dripped on a glass sheet to be made into a film by spin coating. The films of examples 1, 2 and 3 were observed under a 400w light source at respective lambda by irradiating the film for 100h while being placed 20cm from the light sourcemaxThe change in UV absorption intensity was plotted as a change in UV absorption intensity under 400w illumination for examples 1, 2 and 3, as shown in FIG. 5.
As can be seen from FIG. 5, examples 1, 2 and 3 are at respective λmaxThe change of UV absorption after 100h irradiation is small, which shows that the films prepared in examples 1, 2 and 3 have good light stability, and thus also shows that the pyrrole and pyrrole organic semiconductor materials containing free radicals in examples 1, 2 and 3 have good light stability.
Results analysis 4
The radical-containing pyrrolopyrrole organic semiconductor materials of examples 1, 2 and 3 were each prepared at 10-5The solution of mol/L is dripped on a glass sheet to be made into a film by spin coating. The film was placed in the air, and after 16 weeks, uv-vis absorption spectrum test was performed on the film to obtain uv-vis absorption spectrum diagrams after 16 weeks of placing examples 1, 2 and 3, as shown in fig. 6, 7 and 8.
As can be seen from FIGS. 6, 7 and 8, the absorption spectra of the radical-containing pyrrolopyrrole organic semiconductor materials of examples 1, 2 and 3 after being left in air for 16 weeks showed little change compared with the absorption spectra tested before, indicating that the films prepared in examples 1, 2 and 3 had good air stability and thus also the radical-containing pyrrolopyrrole organic semiconductor materials of examples 1, 2 and 3 had good stability.
Analysis of results 5
The radical-containing pyrrolopyrrole organic semiconductor material of example 2 was prepared in 10-5The mol/L solution is dripped on the surface of an electrode in a photoelectric detection device, after the solvent is completely volatilized, the solution is respectively dripped at 650nm,the photoresponse currents of the photodetector devices prepared in example 2 were measured under 780nm and 808nm light sources to obtain photoresponse current graphs, as shown in fig. 9, 10 and 11.
As can be seen from FIGS. 9, 10 and 11, the photo-detector device prepared in example 2 can detect photocurrent responses under 650nm, 780nm and 808nm light sources, the magnitude of photocurrent measured at 650nm is about 17 μ a, the magnitude of photocurrent measured at 780nm is 13 μ a, and the magnitude of photocurrent measured at 808nm reaches 35 μ a. And the response wave band is narrow, so that the method can be applied to accurate detection.
Results analysis 6
The radical-containing pyrrolopyrrole organic semiconductor material of example 2 was prepared in 10-5And (4) dripping the solution of mol/L onto the surface of the transistor. Wherein the transistor structure is a bottom-gate bottom contact structure, and a layer of 285nm SiO is thermally grown on a Si substrate2As dielectric layers, 2nmCr and 30nmAu were deposited, Au as drain-source electrode, and Cr as adhesion layer.
The mobility test was performed under a bias voltage of 80V for the source-drain voltage, in which the gate voltage was swept from-10V to 60V, as shown in fig. 12, and the channel current was tested as a function of the source-drain voltage at gate voltages (Vg) of 0V, 20V, 40V and 60V, respectively, as shown in fig. 13, and the change curve was obtained as shown in fig. 13, the radical-containing pyrrolopyrrole-based organic semiconductor material of example 2 exhibited an n-type in the transistor, and was fitted to have an electron mobility of 3.36 × 10-3cm2/V·s。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (6)

1. A pyrrolo-pyrrole organic semiconductor material containing free radicals is characterized in that the molecular structure is shown as the formula I:
Figure FDA0002596744500000011
in the formula:
R1is tert-butyl, phenyl or thienyl;
R2is tert-butyl, thienyl or furyl;
R3is an oxygen atom or a sulfur atom;
R4is H atom, straight chain alkyl or branched chain alkyl of C1-C60;
R5is an oxygen atom, a sulfur atom or an imino group;
R6is furyl, difuryl, thienyl, bithiothienyl, selenophenyl, bithiophenyl, fluorine-containing thienyl, fluorine-containing furyl, fluorine-containing selenophenyl; the pyrrolo-pyrrole organic semiconductor material containing the free radicals is used for narrow-band photoelectric detection.
2. The method for producing a pyrrolopyrrole-based organic semiconductor material containing a radical according to claim 1, comprising:
(1) mixing a pyrrole-pyrrole halide and a derivative thereof with a monomer I, or mixing a pyrrole-pyrrole organic tin compound with a monomer I' to obtain a pyrrole-pyrrole organic semiconductor material;
the structure of the monomer I is shown as the formula II:
Figure FDA0002596744500000021
wherein R is1Is tert-butyl, phenyl or thienyl; r2Is tert-butyl, thienyl or furyl; r3Is hydroxyl or mercapto; r7Is aryl boric acid, alkenyl boric acid, aryl boric acid ester or alkenyl boric acid ester;
the structure of the pyrrolopyrrole halide and the derivative thereof is shown as the formula III:
Figure FDA0002596744500000022
wherein R is4Is H atom, straight chain alkyl or branched chain alkyl of C1-C60; r5Is an oxygen atom, a sulfur atom or an imino group; r6Is furyl, difuryl, thienyl, bithiothienyl, selenophenyl, bithiophenyl, fluorine-containing thienyl, fluorine-containing furyl, fluorine-containing selenophenyl; x is halogen; the structure of the monomer I 'is shown as the formula II':
Figure FDA0002596744500000023
wherein R is1Is tert-butyl, phenyl or thienyl; r2Is tert-butyl, thienyl or furyl; r3Is hydroxyl or mercapto; r7' is halogen;
the structure of the pyrrolopyrrole organotin compound is shown as a formula IV:
Figure FDA0002596744500000024
wherein R is4Is H atom, straight chain alkyl or branched chain alkyl of C1-C60; r5Is an oxygen atom, a sulfur atom or an imino group; r6Is furan, bitofuranyl, thienyl, bithiopheneyl, selenophenyl, bithiopheneyl, fluorine-containing thienyl, fluorine-containing furyl, fluorine-containing selenophenyl; r8Is 3 methyl groups or 3 butyl groups;
(2) adding an oxidant into the pyrrolo-pyrrole organic semiconductor material and mixing to obtain the pyrrolo-pyrrole organic semiconductor material containing free radicals as claimed in claim 1.
3. The method for preparing a pyrrolopyrrole organic semiconductor material containing radicals according to claim 2, wherein the specific process for preparing the pyrrolopyrrole organic semiconductor material in the step (1) is as follows: adding pyrrole-pyrrole halide and derivatives thereof, monomer I, palladium catalyst, phosphine ligand, alkali solid and water, and carrying out condensation reflux reaction in a solvent of toluene or dioxane for 10-14 h at the reaction temperature of 90-120 ℃ in an inert gas atmosphere;
wherein the molar ratio of the pyrrole-pyrrole halide and the derivative thereof to the monomer I to the palladium catalyst to the phosphine ligand to the alkali solid is 1 (2.2-4): (0.05-0.1): (0.15-0.4): (3-4), the addition amount of water is 0.2-0.4 wt% of the pyrrole halide and the derivative thereof; the base solid comprises tetrabutylammonium hydroxide, potassium carbonate or cesium carbonate.
4. The method for preparing a pyrrolopyrrole organic semiconductor material containing radicals according to claim 2, wherein the specific process for preparing the pyrrolopyrrole organic semiconductor material in the step (1) is as follows: adding a pyrrolopyrrole organotin compound, a monomer I', a palladium catalyst and a phosphine ligand, and carrying out condensation reflux reaction for 6 to 10 hours in a solvent of dry and deoxygenated toluene or tetrahydrofuran at a reaction temperature of between 80 and 120 ℃ under the protection of inert gas atmosphere;
wherein, the mol ratio of the pyrrolopyrrole organotin compound, the monomer I', the palladium catalyst and the phosphine ligand is 1: (2-3): (0.05-0.1): (0.15-0.4).
5. The method for preparing a pyrrolo-pyrrole organic semiconductor material containing free radicals according to any one of claims 2 to 4, wherein the specific process of the step (2) is as follows: dissolving the pyrrolopyrrole organic semiconductor material at room temperature, adding an oxidant, and reacting for 10-20 min; wherein the mol ratio of the pyrrolopyrrole organic semiconductor material to the oxidant is 1: (50-70).
6. Use of the radical-containing pyrrolopyrrole organic semiconductor material according to claim 1 for the preparation of narrow-band photodetectors.
CN201910398946.0A 2019-05-14 2019-05-14 Pyrrolo-pyrrole organic semiconductor material containing free radicals, preparation method and application thereof Active CN110041337B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910398946.0A CN110041337B (en) 2019-05-14 2019-05-14 Pyrrolo-pyrrole organic semiconductor material containing free radicals, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910398946.0A CN110041337B (en) 2019-05-14 2019-05-14 Pyrrolo-pyrrole organic semiconductor material containing free radicals, preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN110041337A CN110041337A (en) 2019-07-23
CN110041337B true CN110041337B (en) 2020-10-09

Family

ID=67281851

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910398946.0A Active CN110041337B (en) 2019-05-14 2019-05-14 Pyrrolo-pyrrole organic semiconductor material containing free radicals, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN110041337B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113501776B (en) * 2021-06-30 2023-08-22 华南理工大学 Near infrared luminous free radical cation compound and preparation and application thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104177365A (en) * 2013-05-27 2014-12-03 海洋王照明科技股份有限公司 Organic semiconductor material containing pyrrolopyrrolidone unit and preparation method thereof, and solar cell device
CN105860032B (en) * 2016-02-29 2019-05-14 华南理工大学 A kind of organic semiconducting materials and the preparation method and application thereof of -6- of dialkyl group containing 2,9- alkoxy phenanthridines unit
CN105622902A (en) * 2016-03-30 2016-06-01 郑州轻工业学院 Bithiophene benzothiadiazole-bithiophene pyrrolopyrrole conjugated polymer and preparation method thereof
US10950800B2 (en) * 2017-04-26 2021-03-16 Samsung Electronics Co., Ltd. Compounds for infrared light sensing devices, infrared light sensing devices, image sensors, and electronic devices including the same

Also Published As

Publication number Publication date
CN110041337A (en) 2019-07-23

Similar Documents

Publication Publication Date Title
Adam et al. Solution processed perovskite solar cells using highly conductive PEDOT: PSS interfacial layer
Liu et al. Flexible organic phototransistor array with enhanced responsivity via metal–ligand charge transfer
Chen et al. Comparison of thiophene-and selenophene-bridged donor–acceptor low band-gap copolymers used in bulk-heterojunction organic photovoltaics
Qi et al. Optimization of broad-response and high-detectivity polymer photodetectors by bandgap engineering of weak donor–strong acceptor polymers
WO2013018951A1 (en) Conductive polymer comprising 3,6-carbazole and organic solar cell using same
US7731796B2 (en) Nitrogen semiconductor compound and device fabricated using the same
Do et al. Efficient planar organic semiconductors containing fused triphenylamine for solution processed small molecule organic solar cells
Kim et al. Push-pull organic semiconductors comprising of bis-dimethylfluorenyl amino benzo [b] thiophene donor and various acceptors for solution processed small molecule organic solar cells
US20220396661A1 (en) Novel polymer and organic electronic device using same
US20210230130A1 (en) Non-fullerene acceptor compound containing benzoselenadiazole and organic optoelectronic device including the same
So et al. Novel symmetric squaraine chromophore containing triphenylamine for solution processed small molecule bulk heterojunction solar cells
TWI825908B (en) Organic semiconducting compound and organic photoelectric components using the same
Kawabata et al. Synthesis of soluble dinaphtho [2, 3-b: 2′, 3′-f] thieno [3, 2-b] thiophene (DNTT) derivatives: One-step functionalization of 2-bromo-DNTT
US20160351815A1 (en) Phenazine-Based Molecular and Polymeric Semiconductors
Lu et al. A facile strategy to enhance the fill factor of ternary blend solar cells by increasing charge carrier mobility
Lee et al. Inclusion of triphenylamine unit in dopant-free hole transport material for enhanced interfacial interaction in perovskite photovoltaics
CN110041337B (en) Pyrrolo-pyrrole organic semiconductor material containing free radicals, preparation method and application thereof
Bhat et al. Versatile aza‐BODIPY‐based low‐bandgap conjugated small molecule for light harvesting and near‐infrared photodetection
Byun et al. Full donor-type conjugated polymers consisting of alkoxy-or alkylselenophene-substituted benzodithiophene and thiophene units for organic photovoltaic devices
Kim et al. A potential naphtho [2, 1-b: 3, 4-b′] dithiophene-based polymer with large open circuit voltage for efficient use in organic solar cells
CN109749061B (en) Linked receptor type polymer photovoltaic material and preparation and application thereof
KR102167007B1 (en) Conductive polymer containing hetero cyclic compounds introducing halogen atoms and Organic semiconductor device comprising the same
Gautam et al. AD–π–A1–π–A2 push–pull small molecule donor for solution processed bulk heterojunction organic solar cells
Keshtov et al. New iridium-containing conjugated polymers for polymer solar cell applications
Patel et al. Photo-induced characteristic study of the smallest fullerene fragment, 1, 6, 7, 10-tetramethylfluoranthene as an acceptor

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant