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CN113087725B - Benzothiadiazole deuterated derivative and application thereof in organic electronic device - Google Patents

Benzothiadiazole deuterated derivative and application thereof in organic electronic device Download PDF

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CN113087725B
CN113087725B CN202110371483.6A CN202110371483A CN113087725B CN 113087725 B CN113087725 B CN 113087725B CN 202110371483 A CN202110371483 A CN 202110371483A CN 113087725 B CN113087725 B CN 113087725B
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张曲
杨曦
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Guangzhou Zhuoguang Technology Co ltd
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Abstract

The invention discloses a diazosulfide deuterated derivative and application thereof in an organic electronic device, in particular to application in an organic solar cell. The invention also discloses an organic electronic device, in particular an organic solar cell, containing the diazosulfide deuterated derivative, and application of the organic electronic device in indoor and outdoor power supply. The invention further discloses an organic electronic device prepared by using the composition according to the invention and a preparation method. Through device structure optimization, better device performance can be achieved, particularly high-performance OPV devices can be achieved, and better materials and preparation technical options are provided for small power supply equipment of the industrial Internet of things.

Description

Diazosulfide deuterated derivative and application thereof in organic electronic device
Technical Field
The invention relates to the technical field of solar energy, in particular to diazosulfide deuterated derivatives, a mixture and a composition, and application thereof in the technical field of organic solar energy.
Background
Climate change can be said to be one of the biggest challenges facing mankind today, and replacing fossil fuels with sustainable energy in power production is an effective way to solve this problem. The installed capacity of silicon solar cells is rapidly increasing worldwide, but it is also possible that the new generation of solar cell technology will mature as a sustainable technology in the near future, thereby contributing to this transition. Organic Solar Cells (OPVs) have been intensively studied for many years and have been tried in market applications due to their translucency, flexibility, rollability, lightness in weight, portability, and designability in color and shape. In recent years, as researchers have increased laboratory cell efficiency to over 15% using novel non-fullerene acceptor materials and continue to improve large area cell fabrication processes, the competitiveness of large area organic solar cells using mature thin film technology is gradually increasing, but the challenge from the laboratory to the manufacturing plant remains the biggest barrier to marketization.
For the current development of OPV efficiency enhancement, the improvement of non-fullerene acceptor materials has become the most effective method; the efficiency (PCE) reduction caused by the membrane quality deterioration generally faced in the large-area OPV production process can also be optimized by regulating and controlling the active layer membrane morphology, the molecular arrangement and the light absorption capacity through the receptor molecular structure design.
Disclosure of Invention
Aiming at the problems, a series of A-D-A type acceptor materials with proper HOMO/LUMO energy levels are synthesized on the basis of a benzothiadiazole structure through ingenious molecular design, the A-D-A type acceptor materials have good electron transmission performance, and the A-D-A type acceptor materials matched with other group designs have a very large spectral absorption range. Their structures were confirmed by mass spectrometry and applied to organic electronic devices.
The specific technical scheme is as follows:
the invention provides a diazosulfide deuterated derivative shown as a general formula (I):
Figure BDA0003008592950000011
wherein
R001-R004Are identical or different from each other and are each independently H; d; f; cl; br; cyano (-CN); trifluoromethyl (-CF 3); substituted or unsubstituted straight-chain alkyl, alkoxy or thioalkoxy having 1 to 30C atoms; substituted or unsubstituted branched or cyclic alkyl, alkoxy or thioalkoxy having 3 to 30C atoms; substituted or unsubstituted alkenyl, alkynyl; substituted or unsubstituted aryl; a heteroaryl group of any one or more of substituted or unsubstituted N, O and S, or a combination of these systems, wherein one or more of the groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with the ring to which the groups are bonded. One or more of the H's of the various groups described above may also be further substituted by D.
And at least one of A1 and A2 is one of the structures shown by the general formulas (I-a) - (I-j), and at least one of the groups is deuterated:
Figure BDA0003008592950000021
wherein,
R101-R132are identical or different from each other and are each independently H; d; f; cl; br; cyano (-CN); trifluoromethyl (-CF 3); substituted or unsubstituted straight-chain alkyl, alkoxy or thioalkoxy having 1 to 30C atoms; substituted or unsubstituted branched or cyclic alkyl, alkoxy or thioalkoxy having 3 to 30C atoms; substituted or unsubstituted alkenyl, alkynyl; substituted or unsubstituted aryl; a heteroaryl group of any one or more of substituted or unsubstituted N, O and S, or a combination of these systems, wherein one or more groups may form a mono-or polycyclic aliphatic or aromatic ring system with each other and/or the ring to which the groups are bonded. One or more of the H's of the various groups described above may also be further substituted by D.
The dotted line represents a single bond of attachment.
The present invention also provides a polymer comprising at least one repeating unit comprising a structural unit represented by the above general formula (I) or (II-a) or (II-b) or (II-c) or (II-d) or (II-e) or (II-f) or (II-g) or (II-h) or (II-j).
The invention also provides a composition comprising at least one compound or polymer as defined in any one of the above, and at least one organic solvent.
The invention also provides the application of the compound or the high polymer in an organic electronic device.
The present invention provides an organic electronic device comprising a compound or polymer as described above.
The Organic electronic component according to the invention is characterized in that it can be selected from the group consisting of Organic photovoltaic cells (OPV), Organic Photodetectors (OPD), Organic Light Emitting Diodes (OLED), Organic light Emitting cells (OLEEC), Organic Field Effect Transistors (OFET), Organic light Emitting field effect transistors (efet), Organic lasers, Organic spintronic components, Organic sensors and Organic Plasmon Emitting diodes (Organic plasma Emitting diodes).
The organic electronic device according to the present invention is an organic solar cell device comprising at least an active layer comprising one of the above-mentioned compounds or the above-mentioned high polymer.
Has the advantages that:
a benzothiadiazole derivative according to the present invention has infrared absorption with an absorption wavelength at a long wavelength, and its absorption spectrum shows a wide absorption range and high photoelectric conversion efficiency. The organic solar cell element prepared from the diazosulfide deuterated derivative has high photoelectric conversion efficiency and long device life.
Description of the drawings: fig. 1 is a schematic diagram of a preferred solar cell device according to the present invention, in which 101 is a substrate, 102 is an anode, 103 is a Hole Transport Layer (HTL), 104 is an active layer, 105 is an Electron Transport Layer (ETL), and 106 is a cathode.
Detailed description of the invention:
to facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides a diazosulfide deuterated derivative shown as a general formula (I):
Figure BDA0003008592950000031
wherein
R001-R004Are the same or different from each other and are each independently H; d; f; cl; br; cyano (-CN); trifluoromethyl (-CF 3); substituted or unsubstituted straight-chain alkyl, alkoxy or thioalkoxy having 1 to 30C atoms; substituted or unsubstituted branched or cyclic alkyl, alkoxy or thioalkoxy having 3 to 30C atoms; substituted or unsubstituted alkenyl, alkynyl; substituted or unsubstituted aryl; a heteroaryl group of any one or more of substituted or unsubstituted N, O and S, or a combination of these systems, wherein one or more groups may form a mono-or polycyclic aliphatic or aromatic ring system with each other and/or the ring to which the groups are bonded. One or more of the H's of the various groups described above may also be further substituted by D.
In a preferred embodiment, a benzothiadiazole deuterated derivative according to the invention, at least one of A1 and A2 is one of the structures represented by formulae (I-a) to (I-j), and at least one group is deuterated:
Figure BDA0003008592950000032
Figure BDA0003008592950000041
wherein,
R101-R132are identical or different from each other and are each independently H; d; f; cl; br; cyano (-CN); trifluoromethyl (-CF 3); substituted or unsubstituted straight chain alkyl, alkoxy or thioalkoxy groups having 1 to 30C atoms; substituted or unsubstituted branched or cyclic alkyl, alkoxy or thioalkoxy having 3 to 30C atoms; substituted or unsubstituted alkenesAlkyl and alkynyl; substituted or unsubstituted aryl; a heteroaryl group of any one or more of substituted or unsubstituted N, O and S, or a combination of these systems, wherein one or more groups may form a mono-or polycyclic aliphatic or aromatic ring system with each other and/or the ring to which the groups are bonded. One or more of the H's of the various groups described above may also be further substituted by D.
The dotted line represents a single bond of attachment.
In a more preferred embodiment, a benzothiadiazole derivative according to the present invention has the structure shown by general formula (II-a) - (II-i):
Figure BDA0003008592950000042
Figure BDA0003008592950000051
Figure BDA0003008592950000061
wherein,
R011-R056，R101-R178are the same or different from each other and are each independently H; d; f; cl; br; cyano (-CN); trifluoromethyl (-CF 3); substituted or unsubstituted straight-chain alkyl, alkoxy or thioalkoxy having 1 to 30C atoms; substituted or unsubstituted branched or cyclic alkyl, alkoxy or thioalkoxy having 3 to 30C atoms; substituted or unsubstituted alkenyl, alkynyl; substituted or unsubstituted aryl; a heteroaryl group of any one or more of substituted or unsubstituted N, O and S, or a combination of these systems, wherein one or more groups may form a mono-or polycyclic aliphatic or aromatic ring system with each other and/or the ring to which the groups are bonded. One or more of the H's of the various groups described above may also be further substituted by D.
The diazosulfide deuterated derivative provided by the invention has the following specific examples, but is not limited to the following examples:
Figure BDA0003008592950000062
Figure BDA0003008592950000071
Figure BDA0003008592950000081
Figure BDA0003008592950000091
Figure BDA0003008592950000101
Figure BDA0003008592950000111
Figure BDA0003008592950000121
Figure BDA0003008592950000131
Figure BDA0003008592950000141
Figure BDA0003008592950000151
Figure BDA0003008592950000161
Figure BDA0003008592950000171
Figure BDA0003008592950000181
Figure BDA0003008592950000191
Figure BDA0003008592950000201
Figure BDA0003008592950000211
Figure BDA0003008592950000221
in a general embodiment, the compounds according to the invention have light-absorbing properties, the absorption wavelength of which is between 300 and 1100 nm.
In certain preferred embodiments, the amine compounds according to the present invention have a photoelectric conversion efficiency of 10% or more, preferably 15% or more, more preferably 17% or more, and most preferably 18% or more.
The present invention also provides a polymer comprising at least one repeating unit comprising a structural unit represented by the above general formula (I) or (II-a) or (II-b) or (II-c) or (II-d) or (II-e) or (II-f) or (II-g) or (II-h) or (II-j).
In a preferred embodiment, the mixture comprises an organic compound or polymer according to the invention and a donor material, where the organic compound according to the invention can act as an acceptor.
In a preferred embodiment, the mixture comprises an organic compound or polymer according to the invention and a further polymer donor material. In such an embodiment, the organic compound according to the invention may act as an acceptor material in a weight ratio of from 1: 99 to 99: 1 with respect to the further donor material.
The Donor material (Donor) is described in some more detail below (but not limited to):
examples of the donor material are not particularly limited, and any organic compound may be used as the host as long as the singlet energy thereof is higher than that of the light emitter, particularly, a singlet light emitter or a fluorescent light emitter.
Examples of the organic compound used as the donor material may be selected from cyclic aromatic hydrocarbon-containing compounds such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; aromatic heterocyclic compounds, such as benzodithiophene, benzodifuran, benzodiselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridine indole, pyrrole bipyridine, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuran pyridine, furan bipyridine, benzothiophene pyridine, thiophene bipyridine, benzoselenophene pyridine, and selenophene bipyridine; groups having 2 to 10 ring structures, which may be the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups, are bonded to each other directly or through at least one group selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an alicyclic group.
In a preferred embodiment, the polymer donor material may be selected from compounds comprising at least one of the following groups:
Figure BDA0003008592950000232
wherein R is1～R13Can be selected independently of one another from the following groups: hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl, and heteroaryl; y is H, D, F, Cl, etc.
Some examples of polymeric donor materials are listed in the following table:
Figure BDA0003008592950000233
Figure BDA0003008592950000241
the organic donor material publications presented above are incorporated by reference into this application for the purpose of disclosure.
It is an object of the present invention to provide a material solution for solution-type OPVs.
It is another object of the present invention to provide a material solution for the roll-to-roll production of OPVs.
In other embodiments, the compounds according to the invention have a solubility in toluene of 5mg/ml or more, preferably 15mg/ml or more, more preferably 20mg/ml or more, most preferably 50mg/ml or more at 25 ℃.
The invention also provides a composition which is characterized by comprising at least one benzothiadiazole deuterated derivative or high polymer and at least one organic solvent.
In some embodiments, the composition according to the present invention, wherein said benzothiadiazole deuterated derivative acts as an acceptor material.
In a preferred embodiment, the composition according to the invention comprises a donor material and a compound according to the invention.
In another preferred embodiment, a composition according to the invention comprises at least one donor material and one acceptor material, and one compound according to the invention.
In a preferred embodiment, the composition according to the invention is a solution.
In another preferred embodiment, the composition according to the invention is a suspension.
In some preferred embodiments, a composition according to the present invention, wherein the solvent is selected from an inorganic ester compound such as an aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefinic compound, or borate or phosphate ester, or a mixture of two or more solvents.
Examples of aromatic or heteroaromatic-based solvents according to the invention are, but not limited to: 1-tetralone, 3-phenoxytoluene, acetophenone, 1-methoxynaphthalene, p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1, 2, 3, 4-tetramethylbenzene, 1, 2, 3, 5-tetramethylbenzene, 1, 2, 4, 5-tetramethylbenzene, butylbenzene, dodecylbenzene, 1-methylnaphthalene, 1, 2, 4-trichlorobenzene, 1, 3-dipropoxybenzene, 4-difluorodiphenylmethane, diphenyl ether, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenylmethane, 4- (3-phenylpropyl) pyridine, benzyl benzoate, 1-bis (3, 4-dimethylphenyl) ethane, 2-isopropylnaphthalene, dibenzyl ether and the like.
In other embodiments, suitable and preferred solvents are aliphatic, cycloaliphatic or aromatic, amines, thiols, amides, nitriles, esters, ethers, polyethers, alcohols, diols or polyols.
In other embodiments, the alcohol represents a suitable class of solvents. Preferred alcohols include alkylcyclohexanols, particularly methylated aliphatic alcohols, naphthols, and the like.
The solvent may be a cycloalkane, such as decalin.
The solvents mentioned may be used alone or as a mixture of two or more organic solvents.
In some embodiments, the composition according to the present invention comprises an organic functional compound as described above and at least one organic solvent, and may further comprise another organic solvent, examples of which include (but are not limited to): methanol, ethanol, 2-methoxyethanol, methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1, 4-dioxane, acetone, methyl ethyl ketone, 1, 2-dichloroethane, 3-phenoxytoluene, 1, 1, 1-trichloroethane, 1, 1, 2, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydronaphthalene, decalin, indene, and/or mixtures thereof.
In some preferred embodiments, particularly suitable solvents for the present invention are those having Hansen (Hansen) solubility parameters within the following ranges:
δd(dispersion force) of 17.0 to 23.2MPa1/2In particular in the range of 18.5 to 21.0MPa1/2A range of (d);
δp(polar force) is 0.2-12.5 MPa1/2In particular in the range of 2.0 to 6.0MPa1/2A range of (d);
δh(hydrogen bonding force) of 0.9 to 14.2MPa1/2In particular in the range of 2.0 to 6.0MPa1/2In (c) is used.
In some preferred embodiments, a composition according to the invention is characterized in that
1) Having a viscosity @25 ℃ in the range of 1cPs to 100cPs, and/or
2) Its surface tension @25 ℃ is in the range of 19dyne/cm to 50 dyne/cm.
The composition according to the invention, wherein the organic solvent is selected taking into account its surface tension parameters. Suitable ink surface tension parameters are appropriate for a particular substrate and a particular printing process. For example, for ink jet printing, in a preferred embodiment, the organic solvent has a surface tension in the range of about 19dyne/cm to about 50dyne/cm at 25 ℃; more preferably in the range of 22dyne/cm to 35 dyne/cm; most preferably in the range of 25dyne/cm to 33 dyne/cm.
In a preferred embodiment, the ink according to the invention has a surface tension at 25 ℃ in the range of about 19dyne/cm to about 50 dyne/cm; more preferably in the range of 22dyne/cm to 35 dyne/cm; preferably in the range of 25dyne/cm to 33 dyne/cm.
The composition according to the invention, wherein the organic solvent is selected taking into account the viscosity parameters of the ink. The viscosity can be adjusted by different methods, such as by the selection of a suitable organic solvent and the concentration of the functional material in the ink. In a preferred embodiment, the viscosity of the organic solvent is less than 100 cps; more preferably below 50 cps; most preferably 1.5 to 20 cps. The viscosity here means the viscosity at ambient temperature at the time of printing, and is generally 15 to 30 ℃, preferably 18 to 28 ℃, more preferably 20 to 25 ℃, most preferably 23 to 25 ℃. The compositions so formulated will be particularly suitable for ink jet printing.
In a preferred embodiment, the viscosity of the composition according to the invention ranges from about 1cps to about 100cps at 25 ℃; more preferably in the range of 1cps to 50 cps; preferably in the range of 1.5cps to 20 cps.
The ink obtained from the organic solvent satisfying the above boiling point and surface tension parameters and viscosity parameters can form a functional material film having uniform thickness and composition properties.
The invention also aims to provide the application of the benzothiadiazole deuterated derivative, the high polymer and the composition thereof in organic electronic devices.
The Organic electronic device can be selected from an Organic photovoltaic cell (OPV), an Organic Photodetector (OPD), an Organic Light Emitting Diode (OLED), an Organic light Emitting cell (OLEEC), an Organic Field Effect Transistor (OFET), an Organic light Emitting field effect transistor, an Organic laser, an Organic spin electronic device, an Organic sensor and an Organic Plasmon Emitting Diode (Organic plasma Emitting Diode).
The organic electronic device further includes a hole transport layer (HTM), which is a material that receives holes from the active layer and transports the holes to the anode, and is suitable as a hole transport material for a material having a high hole mobility. By way of specific example, suitable organic HTM materials may be selected from compounds comprising the following structural units: phthalocyanines, porphyrins, amines, aromatic amines, biphenyl triarylamines, thiophenes, bithiophenes such as dithienothiophene and bithiophenes, pyrroles, anilines, carbazoles, azaindenoazafluorenes and derivatives thereof. In addition, suitable HIM also include fluorocarbon containing polymers, conductively doped containing polymers, conductive polymers, such as PEDOT: PSS.
The organic electronic device further includes an electron transport layer (ETM), which is a substance capable of receiving electrons from the active layer and transferring them to the cathode, and is suitable for a substance having a large electron mobility. Specific examples thereof include, but are not limited to, complexes of 8-hydroxyquinoline, organic radical compounds, organic polymers, and the like. The electron transport layer may be used with any desired cathode material as is conventionally used. Examples of suitable cathode materials are, in particular, the usual materials having a low work function accompanied by an aluminum or silver layer.
It is another object of the present invention to provide a method for manufacturing the above electronic device, and fig. 1 is a structure of the electronic device, but not limited thereto.
The specific technical scheme is as follows:
a method for preparing the functional layer of the present invention comprises forming a functional layer on a substrate by vapor deposition of the above compound or mixture, or forming a functional layer on a substrate by co-vapor deposition together with at least one other organic functional material, or applying the above composition onto a substrate by Printing or coating, wherein the Printing or coating method can be selected from (but not limited to) ink jet Printing, jet Printing (nozle Printing), letterpress Printing, screen Printing, dip coating, spin coating, doctor blade coating, roll Printing, twist roll Printing, offset Printing, flexo Printing, roll Printing, spray coating, brush coating or pad Printing, slit coating, etc.
The invention also relates to the use of said inks of compositions for the production of organic electronic devices, particularly preferably by printing or coating.
Suitable printing or coating techniques include, but are not limited to, ink jet printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roll printing, twist roll printing, lithographic printing, flexographic printing, rotary printing, spray coating, brush or pad printing, slot die coating, and the like. Gravure printing, screen printing and ink jet printing are preferred. Gravure printing, ink jet printing, will be used in the examples of the present invention. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, and the like, for adjusting viscosity, film forming properties, enhancing adhesion, and the like.
The method for preparing the organic electroluminescent device is characterized in that the formed functional layer has a thickness of 5nm to 1000 nm.
The invention further relates to an organic electronic component comprising at least one organic compound or polymer according to the invention or at least one functional layer, which is produced using a composition according to the invention. Generally, such an organic electronic device comprises at least a cathode, an anode and a functional layer located between the cathode and the anode, wherein the functional layer comprises at least one organic compound as described above.
In a more preferred embodiment, the organic electronic device described above is an organic solar cell device (as shown in fig. 1) comprising a substrate (101), an anode (102), at least one active layer (104), and a cathode (106).
The substrate (101) is transparent. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, Bulovic et al Nature 1996, 380, p29, and Gu et al Apbl. Phys. Lett.1996, 68, p 2606. The substrate may be rigid or flexible. The substrate may be plastic or glass. Preferably, the substrate has a smooth surface. Substrates free of surface defects are a particularly desirable choice. In a preferred embodiment, the substrate is flexible, and may be selected from polymeric films or plastics having a glass transition temperature Tg of 150 ℃ or higher, preferably above 200 ℃, more preferably above 250 ℃, and most preferably above 300 ℃. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).
The anode (102) may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily receive holes output from a Hole Transport Layer (HTL) or an active layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the donor in the active layer or the p-type semiconductor material as HTL is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. Examples of anode materials include, but are not limited to: al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is pattern structured. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.
The cathode (106) may include a conductive metal or metal oxide. The cathode can easily accept electrons output from the active layer or ETL. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO level or conduction band level of the donor or n-type semiconductor material as Electron Transport Layer (ETL) in the active layer is less than 0.5eV, preferably less than 0.3eV, and most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes for OLEDs are possible as cathode materials for the devices according to the invention. Examples of cathode materials include, but are not limited to: al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
OPVs may also contain other functional layers such as Hole Transport Layer (HTL) (103), Electron Transport Layer (ETL) (105). Suitable materials for use in these functional layers are described in detail in WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of which 3 are hereby incorporated by reference.
In a preferred embodiment, the active layer (104) of the solar cell device according to the invention is applied by solution coating, which coating comprises a compound according to the invention.
The invention also relates to the use of the organic electronic device according to the invention in various electronic devices, including, but not limited to, battery devices, detection devices, sensors, etc.
The invention also relates to electronic devices including, but not limited to, battery devices, detection devices, sensors, etc., incorporating the organic electronic device according to the invention.
The present invention will be described in connection with preferred embodiments, but the present invention is not limited to the following embodiments, and it should be understood that the appended claims outline the scope of the present invention and those skilled in the art, guided by the inventive concept, will appreciate that certain changes may be made to the embodiments of the invention, which are intended to be covered by the spirit and scope of the appended claims.
Example 1: synthesis of Compound 1
Figure BDA0003008592950000261
Figure BDA0003008592950000271
A500 mL two-necked flask was charged with 1-1(6.16g, 6mmol), 1-2(4.64g, 20mmol) and 5mL of pyridine, then purged with argon three times, added with 250mL of chloroform under argon, and reacted at 65 ℃ for 24 hours. Cooling to room temperature, extracting with dichloromethane three times, combining organic phases, drying, filtering, adding silica gel, spin-drying, and separating and purifying by column chromatography (n-hexane: dichloromethane: 3: 1) to obtain white powder 3.58g with a yield of 41%. MS (EI) m/z: [ M ] +: 1454.57.
example 2: synthesis of Compound 2
Figure BDA0003008592950000272
2-1(5.13g, 5mmol), 2-2(4.22g, 16mmol) and 5mL of pyridine were added to a 500mL two-necked flask, then argon was pumped through three times, 300mL of chloroform was added under argon, and the reaction was carried out at 65 ℃ for 24 hours. Cooling to room temperature, extracting with dichloromethane three times, combining organic phases, drying, filtering, adding silica gel, spin-drying, and separating and purifying by column chromatography (n-hexane: dichloromethane ═ 3: 1) to obtain 2.89g of white powder with a yield of 38%. MS (EI) m/z: [ M ] +: 1520.45.
example 3: synthesis of Compound 3
Figure BDA0003008592950000281
3-1(6.16g, 6mmol), 3-2(3.96g, 20mmol) and 5mL of pyridine were added to a 500mL two-necked flask, then argon was pumped through three times, 300mL of chloroform was added under argon protection, and the reaction was carried out at 65 ℃ for 24 hours. Cooling to room temperature, extracting with dichloromethane three times, combining the organic phases, drying, filtering, spin-drying with silica gel, and separating and purifying by column chromatography (n-hexane: dichloromethane ═ 3: 1) to obtain 3.08g of white powder with 37% yield. MS (EI) m/z: [ M ] +: 1386.63.
example 4: preparation and characterization of OPV devices:
materials used for the layers of OPV devices:
HTL: a water-soluble polymer;
donor: benzodithiophene polymer derivatives;
acceptor: compound 1-compound 3;
ETL: an alcohol soluble polymer.
Having an ITO/HTL (40 nm)/Donor: the preparation steps of an OPV device of Acceptor (1: 1.2, 150nm)/ETL (10nm)/Ag (100nm) are as follows:
a. cleaning the conductive glass substrate: for the first time, the cleaning agent can be cleaned by various solvents, such as chloroform, ketone and isopropanol, and then ultraviolet ozone plasma treatment is carried out;
b. HTL (40nm) is prepared by coating in air and baked at high temperature;
c. active layer (150nm) and ETL (10nm) are coated and baked in a glove box (inert gas atmosphere).
d. Cathode: ag (100nm) in high vacuum (1X 10)-6Millibar) hot evaporation coating;
e. and (3) packaging: the devices were encapsulated with uv curable resin in a nitrogen glove box.
The current-voltage (I-V) characteristics of each OPV device are characterized by characterizing the device while recording important parameters such as efficiency, lifetime and external quantum efficiency. Through detection, the efficiency of an OPV device prepared by adopting the compound 1-the compound 3 as an active layer receptor is between 15% and 18%; in terms of device lifetime, the T95 under AM G1.5 illumination of OPV devices prepared using compound 1-compound 3 as the active layer acceptor was greater than 5000 hours.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.

Claims (3)

1. A benzothiadiazole derivative, which is characterized in that: selected from the following structures:
Figure FDA0003674798630000011
2. a composition characterized by: comprising at least one benzothiadiazole derivative as claimed in claim 1, and at least one organic solvent.
3. An organic electronic device comprising a benzothiadiazole derivative according to claim 1, wherein the organic electronic device is selected from organic photovoltaic cells (OPVs).
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