CN115124548A - N-type organic semiconductor capable of being electrically crosslinked, preparation method and application thereof in electrochemical polymerization - Google Patents
N-type organic semiconductor capable of being electrically crosslinked, preparation method and application thereof in electrochemical polymerization Download PDFInfo
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- CN115124548A CN115124548A CN202210394944.6A CN202210394944A CN115124548A CN 115124548 A CN115124548 A CN 115124548A CN 202210394944 A CN202210394944 A CN 202210394944A CN 115124548 A CN115124548 A CN 115124548A
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- organic semiconductor
- crosslinkable
- type organic
- electro
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- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical group CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Abstract
The invention relates to an electro-crosslinkable n-type organic semiconductor, comprising an electron-donating core structure and 4 carbazole groups, wherein the active sites of the carbazole groups enable a subsequent intramolecular or intermolecular electrochemical polymerization. The electrochemically polymerizable n-type organic semiconductor material is applied to photoelectric devices, has excellent photoelectric effect, and is obviously superior to other similar products in various indexes such as response rate, specific detection rate, adjacent pixel resistance, patterning and the like. The invention also includes related methods of making the electro-crosslinkable n-type organic semiconductors and arrays containing the products.
Description
Technical Field
The invention relates to the field of photoelectric materials, in particular to an n-type organic semiconductor capable of being electrically crosslinked, a preparation method and application thereof in electrochemical polymerization.
Background
For imaging applications of inorganic semiconductors, a patterned pixel array must be integrated with an image reading circuit to enable fast readout of each pixel element information. The general need for such devices is a compromise between miniaturization, performance and cost. However, when the size of the inorganic compound semiconductor photosensitive pixel is reduced to a size required for portable applications, the photosensitive performance is seriously affected. Surface defects at the edges of individual photosensitive pixels are the main cause of dark current rise and are a major factor in the degradation of detection sensitivity.
In recent years, research into imaging applications based on organic semiconductors has attracted considerable attention. By utilizing proper intrinsic carrier concentration and mobility of the organic semiconductor material and proper array design, crosstalk and image definition reduction can be avoided without carrying out pixel-level patterning on the organic photosensitive layer, so that the organic photodiode array is very suitable for camera application with high pixel density.
However, in addition to the organic photosensitive layer in the organic photodiode, there are usually functional layers such as a transfer layer. The transport layer is typically selected from high mobility conductive or semiconductive materials such as: zinc oxide is widely used as an electron transport layer due to its suitable energy level. However, the intrinsic carrier concentration and mobility of zinc oxide are high, and solution processed zinc oxide generally has many defect levels, having a photoconduction phenomenon. Therefore, the application of the organic imaging array technology is restricted to a certain extent.
In the prior art, the electrochemical polymerization technology is a method for preparing a functional polymer film by using a precursor molecule to perform oxidation or reduction coupling reaction at a solution/electrode interface. Compared with other film forming technologies, the electrochemical polymerization technology has the following advantages: (1) the synthesis of the polymer and the formation of the film are completed in one step; (2) the polymer film can be selectively and precisely deposited in an oriented manner, and is a preparation technology of a patterned film; (3) the properties of the polymeric film, such as structure, morphology, doping state and the like, can be regulated and controlled through parameters of electrochemical polymerization; (4) simple equipment and green preparation conditions.
In electrochemical polymerization, a precursor or a reaction substrate is required to have a crosslinkable group, and the precursor or the reaction substrate is widely applied to synthesis of polymers such as polyacetylene, polyparaphenylene vinylene, polypyrrole, polythiophene and polyaniline. The excellent performance and the convenient regulation and control method of the electropolymerization method are one of preparation methods with prospect for being applied to the field of organic electronics in the future (doctor academic thesis of Jilin university in 2018, Rong).
Therefore, there is a need to find a new class of n-type semiconductor materials that can be conveniently and efficiently fabricated in a pixel-level patterning process, thereby overcoming the above-mentioned shortcomings of inorganic materials.
Disclosure of Invention
The invention relates to an electrochemically polymerizable n-type organic semiconductor material, which contains side chains with a plurality of carbazole end groups, can induce the 3, 6-position crosslinking of two carbazoles in an electric field, and can selectively deposit patterns on an electrode; in addition, the molecule is of an A-A '-D-A' -A structure, has a deeper HOMO energy level, and has an oxidation potential after carbazole, so that the electric crosslinking process of carbazole is not influenced. Surprisingly, the active layer material obtained by blending the material serving as an n-type organic semiconductor material and a p-type material has ideal device efficiency and huge development potential and prospect in the field of organic photoelectric devices.
It is an object of the present invention to provide an electro-crosslinkable n-type organic semiconductor having the following chemical formula:
wherein br is a bridge independently selected from alkylene or alkyleneoxy;
n is a positive integer; preferably, n.gtoreq.6.
Ar is independently selected from an aromatic ring or an aromatic heterocyclic ring, and 0, 1 or several hydrogen atoms on the aromatic ring or the aromatic heterocyclic ring are substituted by substituent groups;
said E is independently selected from the following structures:
the X and X 1 Independently selected from CR 1 Or N;
y and Y 1 Independently selected from O, S, Se, C (R) 1 ) 2 、NR 1 ；
Wherein, R is 1 Independently selected from H, D, F, Cl, CN, C (═ O) R 2 、Si(R 2 ) 3 、N(R 2 ) 2 、OR 2 、SR 2 、 S(＝O)R 2 、S(＝O) 2 R 2 Straight-chain alkyl of C1-C20, branched or cyclic alkyl of C3-C20, alkenyl or alkynyl of C2-C20, aryl of C6-C60, and aryl heterocyclic of C3-C60;
R 2 independently selected from linear alkyl of C1-C60, branched or cyclic alkyl of C3-C60, alkenyl or alkynyl of C2-C20, aryl of C6-C60 and aryl heterocyclic of C3-C60.
Alternative objects of the bridge include, but are not limited to, the common alkylene or alkyleneoxy groups, which alkyl or alkoxy chains may be straight, branched or cyclic chain structures such as methyl, methoxy, ethyl, ethoxy, n-propyl, n-propoxy, isopropyl, isopropoxy, n-butyl, n-butoxy, isobutyl, isobutoxy, tert-butyl, tert-butoxy and the like.
The symbol in the above structure indicates the site of attachment of the double bond in E to other groups in the molecular structure.
Further, Ar is independently selected from benzene, furan, thiophene, selenophene, thiazole, pyridine, naphthalene, benzothiophene, benzofuran, benzoselenophene, anthracene, fluorene, indene, carbazole, and derivatives of the above alternatives, wherein 0, 1 or several of the hydrogen atoms on the derivative are substituted by a substituent.
Further, the substituent is selected from halogen atoms, alkoxy, alkylthio groups, alkenyl groups, alkynyl groups, hydroxyl groups, carbonyl groups, carboxyl groups, ester groups, nitro groups, cyano groups, amino groups and aromatic groups.
Another object of the present invention is to provide a method for preparing the above-mentioned electro-crosslinkable n-type organic semiconductor, which comprises the steps of:
s1, mixing monomer P
With a monomer Q
Reacting to obtain a precursor;
s2, performing alkyl tinning treatment on the precursor to obtain an intermediate 1;
s3, reacting the intermediate 1 with a halogenated substrate to obtain an intermediate 2;
s4, functionalizing the intermediate 2 to obtain a product;
wherein A is independently selected from halogen atoms.
The alkylstannation treatment in the present invention means that a hydrogen atom at an active site in an aromatic ring in a precursor is extracted with butyl lithium at a low temperature and substituted with an alkyltin group. Common alkyl tin groups are the trimethyltin group and the tributyltin group, with the trimethyltin group being preferred, since the precursor substituted with the trimethyltin group is usually solid and can be purified in recrystallized form.
A in the monomer Q of the present invention is preferably a bromine atom or an iodine atom because both have high reactivity with a trialkyltin group and thus Stille coupling is likely to occur.
Halogenated substrates in the context of the invention mean
Or a halogen compound of
The halogen compound of (1) as a substituent of the halogen atom, is substituted for a hydrogen atom at an active site in the aromatic ring of the above structure.
Further, the monomer Q is in excess with respect to the monomer P.
The excess means that the molar ratio of the monomer P to the monomer Q is in the range of 1:4.01 to 1: 11.0.
It is another object of the present invention to provide a method for forming a patterned film by electrochemical polymerization, which uses the above-mentioned electro-crosslinkable n-type organic semiconductor as a raw material.
Further, the method for patterning a film through electrochemical polymerization is characterized in that the deposition mode is selected from single component deposition or component blend deposition, and the film formation is selected from single-layer film formation or multi-layer film formation.
Further, the patterned film-forming method by electrochemical polymerization comprises the following steps:
l1. immersing a substrate in an electrolyte solution containing the electro-crosslinkable n-type organic semiconductor;
l2, performing electrochemical polymerization on the n-type organic semiconductor capable of being electrically crosslinked on the working electrode of the substrate by using cyclic voltammetry to form a thin film;
l3. after the deposition is complete, the film is washed with an eluent.
After electrochemical polymerization, as described above, the n-type organic semiconductor capable of electro-crosslinking is assumed to have a relatively complex bulk macromolecular structure. This is because the n-type organic semiconductor which can be electrically crosslinked has side chains having a plurality of carbazole end groups, and can induce crosslinking at the 3-and 6-positions of any two or more carbazoles in an electric field. Any two or more carbazoles may be carbazoles in the same molecule or carbazoles between different molecules. However, the bulk macromolecular structure is mainly dimeric. For simplicity, we will refer to the units in the molecule other than carbazole, all denoted by M. The structure of the electro-crosslinkable n-type organic semiconductor is then:
the crosslinking of the above-mentioned electrically crosslinkable n-type organic semiconductor can be represented by the following structure. Where the dashed lines represent the tendency of possible bonding between carbazole active sites and do not represent the number or condition of bonding shown only for the structure. As can be seen from the following structure, since the molecular structure of the n-type organic semiconductor capable of being electrically crosslinked is connected with 4 crosslinkable carbazole groups, the 3 and 6 positions of each carbazole group are active sites; and the long bridge bond can promote the carbazole group to flexibly rotate, so that the carbazole group has a high probability of forming a huge body type network structure in a short time in the electrochemical polymerization process, and the film forming property of the carbazole group is good.
Further, the solvent of the electrolyte solution is selected from solvent 1, or solvent 2, or a mixture of solvent 1 and solvent 2;
the solvent 1 is one or more selected from water, nitrile solvents, aromatic solvents, alicyclic hydrocarbon solvents, halogenated hydrocarbon solvents, alcohol solvents, ether solvents, ester solvents, sulfone solvents, ketone solvents and amide solvents;
the solvent 2 is a deuterated solvent of the solvent 1.
Preferably, the solvent is selected from the group consisting of dichloromethane, chloroform, acetonitrile, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, and a mixed solvent containing the above solvents.
The mixed solvent can be binary blending or multi-component blending in any proportion; the solvent may be the above optional solvent, or binary blend or multi-component blend with non-optional solvent, such as mixed solvent of dichloromethane/petroleum ether, mixed solvent of chloroform/petroleum ether, mixed solvent of dichloromethane/toluene/petroleum ether, etc.
Further, the eluent is selected from dichloromethane, chloroform, acetonitrile, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene and mixed solvents containing the solvents.
The mixed solvent can be binary blending or multi-component blending in any proportion; the solvent may be the above-mentioned optional solvent, or a binary blend or a multicomponent blend with a non-optional solvent, such as a mixed solvent of dichloromethane/petroleum ether, a mixed solvent of chloroform/petroleum ether, a mixed solvent of dichloromethane/toluene/petroleum ether, or the like.
Further, the patterned film forming method by electrochemical polymerization includes a method of doping or dedoping the thin film.
Further, the working electrode is selected from a metal simple substance electrode, an alloy electrode, a metal oxide, a metal nitride electrode and a composite electrode containing the electrodes;
the metal electrode includes, but is not limited to, a gold electrode, a silver electrode, a copper electrode, an aluminum electrode, a titanium electrode, a platinum electrode, and the like.
The alloy electrode includes, but is not limited to, binary or multi-element blended metal electrodes in any proportion, such as gold/silver electrodes, gold/copper electrodes, copper/silver electrodes, gold/aluminum electrodes, aluminum/silver electrodes, gold/titanium electrodes, platinum/silver electrodes, aluminum/silver/copper electrodes, gold/silver/aluminum electrodes, gold/silver/copper electrodes, and the like.
Further, the pattern formed by the electrochemical polymerization patterning film forming method is consistent with the shape of the working electrode, and the pattern formed by the electrochemical polymerization patterning film forming method completely covers the working electrode.
It is a further object of the present invention to provide the use of the above described electro-crosslinkable n-type organic semiconductor in electronic devices.
Further, the electronic deviceSelected from the group consisting of organic thin film transistors, organic solar cells, organic photodiodes, organic phototransistors, organic light emitting diodes, quantum well diodes, colloidal quantum dot transistors, organic-inorganic hybrid perovskite diodes, organic-inorganic hybrid perovskite transistors, two-dimensional material diodes of graphene-like structure, two-dimensional material transistors of graphene-like structure, group III-V compound semiconductors (e.g. InP) diodes, group II-VI compounds (e.g. CuInS) 2 、CuInSe 2 InGaZnO) semiconductor diode.
It is another object of the present invention to provide an array of electronic devices comprising the above described electro-crosslinkable n-type organic semiconductor.
Further, the n-type organic semiconductor capable of being electrically crosslinked selectively covers the lower electrode array of the array of electronic devices of the n-type organic semiconductor capable of being electrically crosslinked, and an electrode modification layer is formed.
Further, an organic semiconductor formed by an electrochemical deposition method is arranged above the lower electrode array.
Further, the electronic device is selected from the group consisting of organic thin film transistors, organic solar cells, organic photodiodes, organic phototransistors, organic light emitting diodes, quantum well diodes, colloidal quantum dot transistors, organic-inorganic hybrid perovskite diodes, organic-inorganic hybrid perovskite transistors, graphene-like two-dimensional material diodes, graphene-like two-dimensional material transistors, group III-V compound semiconductors (e.g., InP) diodes, group II-VI compounds (e.g., CuInS) 2 、CuInSe 2 InGaZnO) semiconductor diode.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention is based on a type of electrochemically polymerizable n-type organic semiconductor material, which can realize fine patterning through depositing a film through electrochemical polymerization;
(2) the molecule core of the n-type organic semiconductor material capable of being electrochemically polymerized is of an A-A '-D-A' -A structure, has a deeper HOMO energy level, and the oxidation potential of the n-type organic semiconductor material after carbazole does not influence the electric crosslinking process of carbazole;
(3) the carbazole group not only provides a cross-linked active group in the electrochemically polymerizable n-type organic semiconductor material, but also serves as an electron donor to improve the overall electron donating performance of a molecular core structure, so that a D-A system of the electrochemically polymerizable n-type organic semiconductor material is more remarkable, and more ideal device performance can be obtained when the carbazole group is applied to a photoelectric device; the bridge bond in the molecule is a long alkyl chain or an alkoxy chain, so that on one hand, the preparation method provides enough solution processability and is convenient for synthesis and post-treatment in a previous chemical synthesis stage; on the other hand, more importantly, the long-bridge bond has sufficient flexibility, and provides convenience for free rotation of the carbazole group, so that the carbazole group cannot be difficult to react with other adjacent carbazole groups due to steric effect, and excellent film-forming property of subsequent electrochemical polymerization is greatly promoted.
(4) The electrochemically polymerizable n-type organic semiconductor material is applied to photoelectric devices and related arrays thereof, has excellent photoelectric effect, and is obviously superior to other products of the same type in various indexes such as response rate, specific detection rate, adjacent pixel resistance, patterning and the like.
Drawings
Fig. 1 shows device structures of arrays of organic photodetectors of preparation examples 1 to 2 in test example 1 and comparative preparation examples 1 to 3.
Fig. 2 shows a device structure of an array of organic photodetectors of comparative example 4 in test example 1.
Fig. 3 shows graphs of voltage-current characteristics of the organic photodetector array of example 1 in test example 2 and the organic photodetector array of comparative example 4.
The attached drawings are as follows: the pixel reading circuit comprises a pixel reading circuit-201, a cathode array-202, an electrochemical polymerization layer-203, a photosensitive layer-204, a hole transport layer-205, a common anode layer-206 and an encapsulation layer-207. A pixel reading circuit-301, a cathode array-302, zinc oxide-303, a photosensitive layer-304, a hole transport layer-305, a common anode layer-306 and an encapsulation layer-307.
FIGS. 4(a) - (c) show pixel drive circuit layouts for achieving precise control of patterned thin film deposition, where:
FIG. 4(a) is a diagram of a driving circuit of a light emitting display array;
FIG. 4(b) is a driving circuit layout diagram of a Passive Pixel Sensing (PPS) array;
fig. 4(c) is a layout diagram of a driving circuit for an Active Pixel Sensing (APS) array.
Detailed Description
In order to more clearly illustrate the technical solution of the present invention, the following preparation examples and examples are listed. The starting materials, reactions and work-up procedures which are described in the preparation examples and examples are, unless otherwise stated, those which are customary on the market and are known to the person skilled in the art.
Preparation example 1
An electro-crosslinkable n-type organic semiconductor M1, prepared according to the following structure:
(1) synthesis of Compound 3
10.00g of Compound 1(37.5mmol), 134.52g of Compound 2(375.4mmol) and 27.38g (488.0mmol) of potassium hydroxide were dissolved in 200ml of dimethyl sulfoxide (DMSO) under nitrogen, stirred for 15min, added with 30mg of potassium iodide, warmed to 80 ℃ and reacted for 12 h. After the reaction is finished, the temperature is returned to the room temperature, petroleum ether and deionized water are used for extraction for 3 times, organic phase is dried, filtered, concentrated and subjected to column chromatography, and petroleum ether is used as eluent. Compound 3 was obtained in 72.9% yield.
(2) Synthesis of Compound 4
20.00g of Compound 3(14.5mmol) are dissolved in 200ml of Tetrahydrofuran (THF), the solution is cooled to-80 ℃ and 1.86g (29.1mmol) of butyllithium are added dropwise over 10 min. After the reaction mixture was stirred at this temperature for a further 1h, 5.79g (29.1mmol) of trimethyltin chloride were added dropwise. The reaction mixture was warmed to room temperature and stirred for 10 h. After the reaction was completed, it was extracted 3 times with petroleum ether and deionized water, and the organic layer was washed with deionized water and dried with magnesium sulfate, evaporated and concentrated.
Compound 4 was obtained in 73.1% yield.
(3) Synthesis of Compound M1
4.00g of Compound 4(2.35mmol) and 1.93g of Compound 5(5.0mmol) are dissolved in 200ml of toluene solution under nitrogen protection, stirred and warmed to 110 ℃ and 0.60g of tetrakis (triphenylphosphine) palladium is added and reacted at this temperature for 24 h. Cooled to room temperature and 200ml of potassium fluoride solution was added and stirred at room temperature for 12h to remove tin impurities. Extracting the mixture with chloroform and deionized water for 3 times, sequentially drying the organic phase, filtering, concentrating, and performing column chromatography, wherein the eluting agent is petroleum ether. Compound M1 was obtained in 67.9% yield.
Preparation example 2
An electro-crosslinkable n-type organic semiconductor M2, prepared according to the following structure:
synthesis of Compound M2
4.00g of Compound 4(2.3mmol) and 1.97g of Compound 6(4.7mmol) are dissolved in 200ml of toluene solution under nitrogen protection, stirred and warmed to 110 ℃ and 0.60g of tetrakis (triphenylphosphine) palladium is added and reacted at this temperature for 24 h. Cooled to room temperature and 200ml of potassium fluoride solution was added and stirred at room temperature for 12h to remove tin impurities. Extracting the mixture with chloroform and deionized water for 3 times, sequentially drying, filtering, concentrating, and performing column chromatography, wherein the eluent is petroleum ether. Compound M2 was obtained in 71.2% yield.
Preparation example 3
(1) Synthesis of Compound 8
14.00g of Compound 7(37mmol), 132.58g of Compound 2(375.4mmol) and 27.38g (488.0mmol) of potassium hydroxide were dissolved in 200ml of dimethyl sulfoxide (DMSO) under nitrogen, stirred for 15min, added with 30mg of potassium iodide, warmed to 80 ℃ and reacted for 12 h. After the reaction is finished, the temperature is returned to the room temperature, petroleum ether and deionized water are used for extraction for 3 times, organic phase is dried, filtered, concentrated and subjected to column chromatography, and petroleum ether is used as eluent. Compound 8 was obtained in 69.3% yield.
(2) Synthesis of Compound 9
20.00g of compound 8(13.4mmol) are dissolved in 200ml of Tetrahydrofuran (THF), the solution is cooled to-80 ℃ and 1.86g (29.1mmol) of butyllithium are added dropwise over 10 min. After the reaction mixture had been stirred at this temperature for a further 1h, 5.79g (29.1mmol) of trimethyltin chloride were added dropwise. The reaction mixture was warmed to room temperature and stirred for 10 h. After the reaction was completed, it was extracted 3 times with petroleum ether and deionized water, and the organic layer was washed with deionized water and dried over magnesium sulfate, and concentrated by evaporation.
Compound 9 was obtained in 75.5% yield.
(3) Synthesis of Compound M3
4.00g of compound 9(2.2mmol) and 1.82g of compound 5(4.7mmol) are dissolved in 200ml of toluene solution under nitrogen, stirred at 110 ℃ and 0.60g of tetrakis (triphenylphosphine) palladium are added and reacted at this temperature for 24 h. Cooled to room temperature and 200ml of potassium fluoride solution was added and stirred at room temperature for 12h to remove tin impurities. Extracting the mixture with chloroform and deionized water for 3 times, drying, filtering, concentrating, and performing column chromatography with organic phase sequentially, and eluting with petroleum ether. Compound M3 was obtained in 70.7% yield.
Preparation example 4
An electro-crosslinkable n-type organic semiconductor M4, prepared according to the following structure:
(1) synthesis of Compound 11
4.00g of compound 4(2.35mmol) and 1.40g of compound 10(5.0mmol) are dissolved in 200ml of toluene solution under nitrogen, stirred at 110 ℃ and 0.60g of tetrakis (triphenylphosphine) palladium are added and reacted at this temperature for 24 h. Cooled to room temperature and 200ml of potassium fluoride solution was added and stirred at room temperature for 12h to remove tin impurities. Extracting the mixture with chloroform and deionized water for 3 times, drying, filtering, concentrating, and performing column chromatography with organic phase sequentially, and eluting with petroleum ether. Compound 8 was obtained in 68.1% yield.
(2) Synthesis of Compound M4
Under nitrogen protection, 3.00g of compound 11(1.7mmol) and 645.0mg of compound 12(3.2mmol) are dissolved in 250ml of chloroform, and 15ml of triethylamine are slowly added. Stirring and heating to 60 ℃, and reacting for 2 h. After the reaction is finished, the reaction product is cooled to room temperature and extracted by petroleum ether and deionized water. The organic phase is sequentially dried, filtered, concentrated and subjected to column chromatography, and the eluent is petroleum ether. Compound M4 was obtained in 72.6% yield.
Preparation example 5
An electro-crosslinkable n-type organic semiconductor M5, prepared according to the following structure:
(1) synthesis of Compound 14
4.00g of Compound 4(2.35mmol) and 1.45g of Compound 13(5.0mmol) are dissolved in 200ml of toluene solution under nitrogen protection, stirred and warmed to 110 ℃ and 0.60g of tetrakis (triphenylphosphine) palladium is added and reacted at this temperature for 24 h. Cooled to room temperature and 200ml of potassium fluoride solution was added and stirred at room temperature for 12h to remove tin impurities. Extracting the mixture with chloroform and deionized water for 3 times, sequentially drying, filtering, concentrating, and performing column chromatography, wherein the eluent is petroleum ether. Compound 14 was obtained in 69.1% yield.
(2) Synthesis of Compound M5
2.50g of Compound 14(1.40mmol) and 584.6mg of Compound 12(4mmol) were dissolved in 200ml of a chloroform solution, and the mixture was stirred for 5min under exclusion of light, followed by addition of 0.5ml of pyridine. Heating to 65 ℃, reacting for 8h, recovering to room temperature after the reaction is finished, concentrating the solution to about 30ml, adding 500ml of anhydrous methanol, precipitating, filtering, and recrystallizing the filter residue with chloroform and methanol for 3 times. Compound M5 was obtained in 56.4% yield.
Comparative preparation example 1
The product M1 'obtained in comparative preparation example 1 has the same structure and preparation method as M1 in preparation example 1, except that the bridge of M1' in comparative preparation example 1 is not a structure in which 8 methylene groups are bonded, but a structure in which 2 methylene groups are bonded. In the preparation method, the raw material 1-bromooctane carbazole in preparation example 1 is replaced by 1-bromoethane carbazole in equal amount.
Comparative preparation example 2
The product M2 'obtained in comparative preparation 2 has the same structure and preparation method as M1 in preparation 1, except that the nucleus of M2' in comparative preparation 2 is not used
But rather that
Therefore, after the core reacts with 1-bromooctane carbazole, only 2 carbazole groups can be grafted on the active site of the core to form a product M2'.
Comparative preparation example 3
The product M3 'obtained in comparative preparation 3 has the same structure and preparation as M1 in preparation 1, except that the nucleus of M3' in comparative preparation 2 is used instead of
But rather that
Therefore, after the core reacts with 1-bromooctane carbazole, only 2 carbazole groups can be grafted on the active site of the core to form a product M3'.
Test example 1
Preparation of examples 1, 2 and comparative examples 1 to 3
The n-type organic semiconductors obtained in preparation examples 1 to 2 and comparative preparation examples 1 to 3 were applied to the field of organic photodetectors, and organic photodetector array examples 1 to 2 and comparative examples 1 to 3 were formed accordingly. The device structure of the organic photodetector array is shown in fig. 1. As can be seen from fig. 1, the photodetector array sequentially includes, from bottom to top, a pixel readout circuit 201 made of Thin Film Transistors (TFTs) fabricated on a glass substrate, each pixel readout circuit being linked to a cathode array 202 defining the size of a pixel; above the electrode array are an electrochemical polymerization layer 203, a photoactive layer 204, a hole transport layer 205, a common anode layer 206, and an encapsulation layer 207. Wherein 201 the connection contact 208 comprising the upper electrode and the picture element sensing circuit 209 are separately and independently connected to 202. From 204 to 207 are continuous structures over the entire array area, and no inter-pixel patterning is required.
The patterned lower electrode (or called bottom electrode) array is an ITO electrode (100nm), the electrochemical polymerization layer is a polymer film (30nm) of M1 (or M1 '/M2 '/M3 '), the photosensitive layer is P3HT: PC61BM (1:1.5, M/M) (200nm), the hole transport layer is a molybdenum oxide film (10nm), the common anode layer is a silver electrode (100nm), and the packaging layer is epoxy resin.
The pixel size of the array is 25 μm and the number of pixels is 1 × 256 or 1 × 512.
The preparation method of the organic photodetector array comprises the following steps:
s1, placing a pixel reading circuit substrate which is made of a Thin Film Transistor (TFT) and is manufactured on a glass substrate on a film developing frame, and ultrasonically cleaning for 1min by using an ultrasonic device, wherein a detergent is isopropanol;
s2, connecting the cleaned ITO substrate serving as a working electrode with an electrochemical workstation, wherein the counter electrode is a polished metal titanium plate, and the reference electrode is Ag/Ag + (0.01 mol/L); TBAPF with electrolyte of 0.1mol/L 6 0.5mg/mL of compound M1 (or M1 '/M2 '/M3 ') is added, and the solvent of the electrolyte is dichloromethane and acetonitrile in a volume ratio of 3: 2.
S3, scanning is carried out in a circulating mode at the scanning speed of 0.5mV/s until the thickness of the film deposited on the ITO reaches 30 nm. Keeping the voltage of-0.9V for 30 minutes to carry out the dedoping treatment on the film.
And S4, washing the substrate by using a mixed solvent of dichloromethane and acetonitrile in a volume ratio of 3: 2.
S5, spin-coating a layer of 200nm P3HT: PC on the electrochemical polymerization film 61 BM (1:1.5, m/m) in dichlorobenzene, annealed at 120 ℃ for 30 min.
And S6, sequentially depositing 10nm molybdenum oxide and 100nm silver through a patterned mask plate.
And S7, curing and packaging the device in ultraviolet light by using epoxy resin after the device is prepared.
Preparation of example 3
Meanwhile, the device structure, the materials used, and the device fabrication method in example 3, the present example were set to be the same as those in example 1. The difference is that the pixel readout circuit 201 in embodiment 1 is replaced with a pixel readout circuit composed of silicon-based complementary metal oxide semiconductor transistors (MOSFETs) on a single-crystal silicon substrate, and the material of the pixel readout circuit 202 is gold. 206 instead of ITO, the direction of the incident light is from top to bottom.
Meanwhile, comparative example 4 was set up, in which comparative example 4 the M1 of example 1 was replaced by a ZnO nanoparticle dispersion (purchased from sigma, SKU: 793361-5 ML). The structure of the photodetector array of comparative example 4 is shown in fig. 2.
Preparation of example 4
A method of making a photodetector array of comparative example 4 comprising the steps of:
s1, the same test example as above is adopted.
S2, printing a layer of ZnO nanoparticle dispersion liquid with the thickness of 30nm by using an ink-jet printer, and annealing at 100 ℃ for 10 min.
S3, spin-coating a layer of 200nm P3HT: PC on the zinc oxide film 61 BM (1:1.5, m/m) in dichlorobenzene, annealed at 120 ℃ for 30 min.
And S4, sequentially depositing 10nm molybdenum oxide and 100nm silver through a patterned mask plate.
And S5, curing and packaging the device in ultraviolet light by using epoxy resin after the device is prepared.
The test data of the resulting array device of organic photodetectors are shown in table 1 below. The test methods employed for each index are not conventional and well known to those skilled in the art.
TABLE 1 photoelectric Properties of array devices of (organic) photodetectors of examples 1 to 3 and comparative examples 1 to 4
As can be seen from table 1, the short chain of M1' in comparative example 1 did not provide sufficient solubility and the carbazole group was free to rotate to a lesser extent than in examples 1-3, resulting in poor film morphology after electropolymerization; m2' in comparative example 2 has only two crosslinking groups, and the degree of crosslinking of the formed polymer is far lower than that of the polymers in examples 1-3, and the film forming property is poor; the molecular core of M3' in comparative example 3 has a lower oxidation potential than carbazole, which interferes with the carbazole electropolymerization process and has poor film-forming properties. The various/certain indices of comparative examples 1-3 were reduced to a different extent than those of examples 1-3; in contrast, in the photodetector array in comparative example 4, the electrically crosslinkable n-type organic semiconductor of the present invention was replaced with an inorganic material, and each index showed a small decrease. The above results illustrate the advancement of the present invention.
Test example 2
Further, we performed a voltage-current characteristic curve test on adjacent pixel electrodes of the organic photodetector array of example 1 and the organic photodetector array of comparative example 4. The results are shown in FIG. 3. In the figure, a1 represents the voltage-current characteristic curve of the adjacent pixel electrodes of the organic photodetector array of example 1; a2 represents the voltage-current characteristic curve of the adjacent pixel electrodes of the organic photodetector array of comparative example 4.
As can be seen from fig. 3, in example 1, since the electrochemical polymerization modified electrode is used, the crosstalk between adjacent pixels is significantly lower than that of the conventional ZnO thin film modified electrode in comparative example 4. Therefore, the mutual interference of the electric signals among the pixels of a1 is small, and the electric signals are favorable for obtaining a clear image when used for imaging.
It is noted that the application of voltage (potential) to the bottom electrode can be precisely controlled by CMOS or TFT technology to achieve alternating intricate pattern thin film depositions. Fig. 4 shows some designs of driving circuits (corresponding to portion 209 of the substrate of fig. 1) that implement the above-described functions: fig. a is a design diagram of a driving circuit of a light emitting display array, fig. b is a design diagram of a driving circuit of a Passive Pixel Sensing (PPS) array, and fig. c is a design diagram of a driving circuit of an Active Pixel Sensing (APS) array. These designs have been widely used in advanced pixel circuits.
As shown in fig. 4, for the LED display driving circuit, a high voltage higher than Vdd may be applied to Vdata and Vselect through a Vdd line, and the transistors T1 and T2 are turned on, thereby applying cyclic voltammetry to the bottom electrode of the pixel to deposit the same thin film as the electrode pattern. Similar principles can be applied to the pixel electrodes in PPS and APS readout circuits. In the case of PPS, the potential of the pixel electrode (in this case the cathode) can be adjusted by the Vdata line, and after a voltage higher than Vdata is applied to Vselect to turn on T1, the potential of the bottom electrode of the pixel can be adjusted by Vdata. In the case of APS, the potential of the pixel electrode can be adjusted by the Vdd line, and after applying a voltage higher than Vdd to the Vreset line turns on the transistor, the pixel bottom electrode (in this case the cathode) can be adjusted by Vdd.
In addition, it is worth mentioning that the method for spontaneously forming the patterned n-type organic semiconductor thin film array on the bottom electrode provided by the invention can also be used for preparing the p-type organic semiconductor thin film array. For example, according to the document [ H.Sun et al, Chinese Journal of Polymer Science Vol.33, No.11, (2015),1527-]The electropolymerization precursor is replaced by 2' -aminomethyl-3, 4-ethylenedioxythiophene (EDOT-MeNH) from M1 2 ) Patterned p-type semiconductor (PEDOT-MeNH) can also be obtained on the bottom electrode 2 ) A film. The doping level of the formed p-type organic semiconductor film can be adjusted by a reduction process after synthesis, so that neutral PEDOT-MeNH can be obtained 2 . Therefore, by the patterned bottom electrode disclosed by the invention, self-patterned n-type, p-type and neutralized undoped organic semiconductor thin film arrays can be realized. The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention and are intended to be equivalent substitutions are included in the scope of the present invention.
Claims (19)
1. An electro-crosslinkable n-type organic semiconductor having the following chemical formula:
wherein br is a bridge independently selected from alkylene or alkyleneoxy;
n is a positive integer;
ar is independently selected from an aromatic ring or an aromatic heterocyclic ring, and 0, 1 or several hydrogen atoms on the aromatic ring or the aromatic heterocyclic ring are substituted by substituent groups;
said E is independently selected from the following structures:
said X and X 1 Independently selected from CR 1 Or N;
said Y and Y 1 Independently selected from O, S, Se, C (R) 1 ) 2 、NR 1 ；
Wherein, R is 1 Independently selected from H, D, F, Cl, CN, C (═ O) R 2 、Si(R 2 ) 3 、N(R 2 ) 2 、OR 2 、SR 2 、S(＝O)R 2 、S(＝O) 2 R 2 Straight-chain alkyl of C1-C20, branched or cyclic alkyl of C3-C20, alkenyl or alkynyl of C2-C20, aryl of C6-C60, and aryl heterocyclic of C3-C60;
R 2 independently selected from linear alkyl of C1-C60, branched or cyclic alkyl of C3-C60, alkenyl or alkynyl of C2-C20, aryl of C6-C60 and aryl heterocyclic of C3-C60.
2. The electronically crosslinkable n-type organic semiconductor of claim 1, wherein Ar is independently selected from the group consisting of benzene, furan, thiophene, selenophene, thiazole, pyridine, naphthalene, benzothiophene, benzofuran, benzoselenophene, anthracene, fluorene, indene, carbazole, and derivatives of the foregoing, wherein 0, 1, or several of the hydrogen atoms in said derivatives are substituted with substituents.
3. The electro-crosslinkable n-type organic semiconductor according to claim 2, wherein the substituent is selected from the group consisting of a halogen atom, an alkoxy group, an alkylthio group, an alkenyl group, an alkynyl group, a hydroxyl group, a carbonyl group, a carboxyl group, an ester group, a nitro group, a cyano group, an amino group, and an aryl group.
4. A method for producing an electro-crosslinkable organic semiconductor according to any one of claims 1 to 3, characterized in that the method for producing an electro-crosslinkable n-type organic semiconductor comprises the steps of:
s1, monomer
And monomer Q
Reacting to obtain a precursor;
s2, performing alkyl stannization treatment on the precursor to obtain an intermediate 1;
s3, reacting the intermediate 1 with a halogenated substrate to obtain an intermediate 2;
s4, functionalizing the intermediate 2 to obtain a product;
wherein A is independently selected from halogen atoms.
5. The method for producing an electrically crosslinkable n-type organic semiconductor according to claim 4, wherein the monomer Q is in excess with respect to the monomer P.
6. A method for patterning a film by electrochemical polymerization, which uses the n-type organic semiconductor which is electrically crosslinkable according to any one of claims 1 to 3 as a raw material.
7. The method of claim 6, wherein the electrochemically polymerized patterned film is deposited by a method selected from the group consisting of depositing a single component or a blend of components, and forming a single layer film or a multi-layer film.
8. The electrochemical polymerization patterned film forming method according to claim 6, wherein the electrochemical polymerization patterned film forming method comprises the steps of:
l1. immersing a substrate in an electrolyte solution containing the electro-crosslinkable n-type organic semiconductor;
l2, depositing the n-type organic semiconductor capable of being electrically crosslinked on the substrate by using cyclic voltammetry to perform electrochemical polymerization to form a thin film;
l3. after the deposition is complete, the film is washed with an eluent.
9. The electrochemical polymerization patterned film forming method according to claim 8, wherein the solvent of the electrolyte solution is selected from solvent 1, or solvent 2, or a mixture of solvent 1 and solvent 2;
the solvent 1 is one or more selected from water, nitrile solvents, aromatic solvents, alicyclic hydrocarbon solvents, halogenated hydrocarbon solvents, alcohol solvents, ether solvents, ester solvents, sulfone solvents, ketone solvents and amide solvents;
the solvent 2 is a deuterated solvent of the solvent 1.
10. The method of claim 8, wherein the eluent is selected from the group consisting of dichloromethane, chloroform, acetonitrile, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, and mixtures thereof.
11. The electrochemical polymerization patterning film method of claim 8, comprising doping or dedoping the thin film.
12. The method of claim 8, wherein the working electrode is selected from the group consisting of elemental metal electrodes, alloy electrodes, metal oxides, metal nitride electrodes, and composite electrodes comprising the same.
13. The method of claim 12, wherein the pattern formed by the method conforms to the shape of the working electrode and completely covers the working electrode.
14. Use of an electro-crosslinkable n-type organic semiconductor according to any one of claims 1 to 3 in an electronic device.
15. Use of an electro-crosslinkable n-type organic semiconductor in an electronic device according to claim 14, characterized in that the electronic device is selected from the group consisting of organic thin film transistors, organic solar cells, organic photodiodes, organic phototransistors, organic light emitting diodes, quantum well diodes, colloidal quantum dot transistors, organic-inorganic hybrid perovskite diodes, organic-inorganic hybrid perovskite transistors, diodes of graphene-like structured two-dimensional materials, transistors of graphene-like structured two-dimensional materials, III-V compound semiconductor diodes, II-VI compound semiconductor diodes.
16. An array of electronic devices comprising an electro-crosslinkable n-type organic semiconductor as claimed in any of claims 1 to 3.
17. The array of electronic devices of claim 16, wherein the electro-crosslinkable n-type organic semiconductor selectively overlies a lower electrode array of the array of electronic devices of the electro-crosslinkable n-type organic semiconductor, forming an electrode-modifying layer.
18. The array of electronic devices of claim 17, wherein the array of lower electrodes comprises an organic semiconductor formed by electrochemical deposition.
19. Use of an array of electronic devices of an electro-crosslinkable n-type organic semiconductor according to claim 16 in an electronic device selected from the group consisting of organic thin film transistors, organic solar cells, organic photosensitive diodes, organic photosensitive transistors, organic light emitting diodes, quantum well diodes, colloidal quantum dot transistors, organic-inorganic hybrid perovskite diodes, organic-inorganic hybrid perovskite transistors, diodes of graphene-like structured two-dimensional materials, transistors of graphene-like structured two-dimensional materials, III-V compound semiconductor diodes, II-VI compound semiconductor diodes.
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