Preparation method of diazonium cross-linking agent and application of diazonium cross-linking agent in organic photoelectric device

Abstract

The invention discloses a light or heat activated diazonium group-containing cross-linking agent, a preparation method thereof and an application of the light or heat activated diazonium group-containing cross-linking agent in an organic photoelectric device. The structural formula is shown as a general formula I, r1 and R2 are selected from hydrogen atoms, halogen atoms, C1-C20 straight-chain or fork-chain alkyl groups containing hydrogen atoms, halogen atoms, amido bonds, ether bonds, ester bonds, aryl groups or heteroaryl groups, C1-C20 straight-chain or fork-chain perfluoroalkyl groups, polysubstituted or unsubstituted aryl groups or heteroaryl groups (phenyl groups, thienyl groups, thiazolyl groups, pyridyl groups, quinolyl groups, furyl groups, pyrrolyl groups, imidazolyl groups, naphthyl groups, anthryl groups, phenanthryl groups and pyrenyl groups); the compound is a combined fragment formed by connecting one or more of the following units (R1, R2, R3, R4, R5, R6, R7, R7, R8, R7, R8, R7, R8, R8, R8, R8, R8, R8, R8, R8, R8, R8, R8, R8, R8, R8, R8, R8, R8, R8, R8, R8, R8, R8, R8, R8, R8, R8, the compound has good stability to light and heat, and patterning of the organic conjugated polymer can be efficiently achieved. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the field of chemistry, and in particular relates to a crosslinking agent containing a diazo group activated by light or heat, a preparation method thereof, and an application thereof in an organic photoelectric device. Background Art

[0002] In recent years, a series of p-type, n-type and bipolar organic semiconductor polymers with high carrier mobility have been successfully designed and developed. Due to their inherent advantages over inorganic semiconductor materials, organic polymer semiconductors have become candidate materials for wearable and implantable electronic products with great development prospects. However, there are many difficulties in applying the unique properties of organic semiconductors such as solution processing and flexibility to digital circuits. The patterning of semiconductors can reduce leakage current, avoid crosstalk between devices, and reduce the overall power consumption of the circuit, facilitating the efficient interconnection and integration between digital circuit components. At present, some patterning methods of organic / polymer semiconductors have been reported, such as physical vapor transport, solution growth, surface wettability adjustment, inkjet printing, nanoimprinting, direct writing and electron beam exposure. However, these patterning methods are incompatible with the traditional photolithography process of the microelectronics industry.

[0003] With the assistance of light / heat, the light / heat patterning of organic semiconductors is realized by chemical cross-linking reaction, which provides an effective solution. At present, the cross-reactive groups used in organic semiconductor patterning are: azido group, diaziridine group, oxetane group and o-nitrobenzyl group, etc. Among them, the azido group and diaziridine group can produce nitrene and carbene active species under ultraviolet light irradiation (Adv.Mater.2024, 36, 2309256), inducing the cross-linking of the alkyl side chain of the organic semiconductor polymer, so that the polymer semiconductor can be cured after ultraviolet light irradiation. After rinsing with an appropriate developer, a high-resolution semiconductor polymer pattern can be obtained.

[0004] Diazo (diazo) group is a linear unsaturated substituent group containing two nitrogen atoms, is an isomer of diazirine (diazirine) group, can be produced by diazirine group under ultraviolet irradiation isomerization reaction (Science 2019,366,875-878). Similar to diazirine group, diazo group can also rapidly produce carbene and nitrogen (J.Am.Chem.Soc.2021,143,10108-10119) under ultraviolet irradiation or heating conditions, and the carbene intermediate produced has high reactivity, can be inserted efficiently with the CH bond of various chemical environments adjacent to it, causing chemical crosslinking. In addition, the by-product generated after the cross-linking reaction of diazo compound is also only nitrogen, which is a kind of ideal green crosslinking agent.

[0005] At present, there have been a few studies on the use of diazo compounds as crosslinkers in non-conjugated polymers and polyfluorene compounds, but their application in the field of organic semiconductor patterning is still blank. Therefore, the design and synthesis of diazo crosslinkers suitable for organic semiconductor patterning has important research significance and practical value. Such crosslinkers have potential application advantages in the field of organic optoelectronic devices such as organic thin film transistors, organic thermoelectrics, organic solar cells, organic light-emitting diodes, and organic lasers. Summary of the invention

[0006] The object of the present invention is to provide a diazo crosslinking agent with photo / thermal crosslinking activity and a preparation method thereof.

[0007] The present invention provides a cross-linking agent containing a diazo group, the structural formula of which is shown in the following formula I:

[0008]

[0009] In the general formula I, R1 is selected from hydrogen atom, halogen atom (F, Cl, Br, I), C1~C 20 containing hydrogen atoms, halogen atoms, amide bonds, ether bonds, ester bonds, aromatic or heteroaromatic straight chain or branched chain alkyl groups, C1-C 20 One of the following: a straight-chain or branched perfluoroalkyl group, a polysubstituted or unsubstituted aryl or heteroaryl group (phenyl, thienyl, thiazolyl, pyridyl, quinolyl, furanyl, pyrrolyl, imidazolyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, pyrrolopyrroledione, isoindigotyl, naphthalimide or other aryl group), or a combination of the above units connected by single bonds, double bonds, triple bonds, or one or more of carbon, oxygen, sulfur, silicon, nitrogen or phosphorus atoms;

[0010] For example, R1 can be selected from a hydrogen atom, a halogen atom, an ester group, CH3, CF3, C2F5, C3F7, an aryl group or a heteroaryl group;

[0011] R2 is selected from C1~C 20 containing hydrogen atoms, halogen atoms, amide bonds, ether bonds, ester bonds, aromatic or heteroaromatic straight chain or branched chain alkyl groups, C1-C 20 The invention relates to a straight-chain or branched perfluoroalkyl group, a polysubstituted or unsubstituted aryl or heteroaryl group (phenyl, thienyl, thiazolyl, pyridyl, quinolyl, furyl, pyrrolyl, imidazolyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, pyrrolopyrroledione, isoindigotyl, naphthalimide or other aryl group), or a combination of the above units connected by single bonds, double bonds, triple bonds, carbon, oxygen, sulfur, silicon, nitrogen or phosphorus atoms or more.

[0012] For example, R2 can be selected from the following fragments:

[0013]

[0014] In the present invention, the R2 exemplary groups are represents the attachment position of the diazo group in the general formula I.

[0015] n is an integer between 2 and 10, such as: 2, 3, 4, 6, 8, 10.

[0016]

[0017]

[0018] In the above C-TD1, R1 may be H, CF3 or CO2CH3;

[0019] In the above C-TD2, R1 may be H, CF3 or CO2CH3;

[0020] In the above C-TD3, R1 may be H or phenyl.

[0021] The present invention also provides a method for preparing the cross-linking agent containing a diazo substituent as shown in the above general formula I.

[0022] The preparation method includes the following preparation method 1 and preparation method 2, wherein preparation method 1 is applicable to the synthesis of aromatic tetrazonium compounds C-TD1 and C-TD2, and preparation method 2 is applicable to the synthesis of aliphatic tetrazonium compound C-TD3.

[0023] Preparation method 1:

[0024] (1.1) In an organic solvent, a carbonyl compound substituted with R1 (compound represented by formula II) and p-toluenesulfonyl hydrazide are mixed and heated to react to obtain an intermediate product a (compound represented by formula III);

[0025]

[0026] Wherein, in the formula II, the definitions of R1 and n are the same as those of the general formula I; in the formula II, R2 is one of a polysubstituted or unsubstituted aryl or heteroaryl group (phenyl, thienyl, thiazolyl, pyridyl, quinolyl, furanyl, pyrrolyl, imidazolyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, pyrrolopyrroledione, isoindigotyl, naphthalimide or other aromatic group), or a combination of the above units connected by one or more of single bonds, double bonds, triple bonds, carbon, oxygen, sulfur, silicon, nitrogen or phosphorus atoms.

[0027] In the formula III, R1, R2, and n are defined the same as in formula II;

[0028] (1.2) In an organic solvent, the intermediate product a obtained in step 1.1 is mixed with a base and heated to react to obtain a diazo compound as described in general formula I;

[0029] Preparation method 2:

[0030] (2.1) In an organic solvent, a R1-substituted carbonyl compound (compound represented by Formula IV), a base and aromatic sulfonyl azide are reacted at room temperature or under heating conditions to obtain a diazo compound represented by Formula V;

[0031]

[0032] Wherein, in the formula IV, R2 and n are defined the same as in the general formula I; in the formula II, R1 is selected from one of hydrogen, polysubstituted or unsubstituted aryl or heteroaryl (phenyl, thienyl, thiazolyl, pyridyl, quinolyl, furanyl, pyrrolyl, imidazolyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, pyrrolopyrroledione, isoindigotene, naphthalimide or other aromatic groups), or a combination of the above units connected by one or more of single bonds, double bonds, triple bonds, carbon, oxygen, sulfur, silicon, nitrogen or phosphorus atoms.

[0033] In the formula V, R1, R2, and n are defined as in formula IV;

[0034] In the above-mentioned synthesis method, the organic solvent is selected from one or more mixtures of tetrahydrofuran (THF), toluene, ethanol, methanol, dichloromethane, chloroform, acetone, N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), hexamethylphosphoramide (HMP), cyclopentane, acetonitrile and benzonitrile.

[0035] In the above-mentioned synthesis method, the base is selected from a mixture of one or more of triethylamine, pyridine, N,N-diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), potassium carbonate, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, potassium fluoride and cesium fluoride.

[0036] In the above method 1, in step 1.1, the molar ratio of the R1-substituted carbonyl compound to p-toluenesulfonyl hydrazide can be 1:2-20; in step 1.2, the molar ratio of the intermediate product a to the base can be 1:2-20;

[0037] In the above method 2, in step 2.1, the molar ratio of the R1-substituted carbonyl compound to the aromatic sulfonyl azide can be 1:2-20, the molar ratio of the R1-substituted carbonyl compound to the base is 1:2-20, and the equivalents of the base and the aromatic sulfonyl azide are equal.

[0038] In the above-mentioned synthesis method, in step 1.1, the mass ratio of the volume of the organic solvent to the R1-substituted carbonyl compound is 10-400 mL: 1 g; in step 1.2, the mass ratio of the volume of the organic solvent to the intermediate product a is 10-400 mL: 1 g; in step 2.1, the mass ratio of the volume of the organic solvent to the R1-substituted carbonyl compound is 10-400 mL: 1 g.

[0039] In the above-mentioned synthesis method, in step 1.1, the conditions of the heating reaction are as follows: heating to 30 to 150 degrees Celsius in air or an inert gas atmosphere, and reacting for 1 to 24 hours; in step 1.2, the conditions of the reaction are as follows: heating to 30 to 110 degrees Celsius in air or an inert gas atmosphere, and reacting for 1 to 24 hours; in step 2.1, the conditions of the reaction are as follows: in air or an inert gas atmosphere, the reaction temperature is 20 to 80 degrees Celsius, and the reaction is carried out for 24 to 96 hours.

[0040] The inert gas is specifically nitrogen or argon.

[0041] In the present invention, the room temperature is common knowledge in the art and refers to 10 to 30 degrees Celsius.

[0042] All the steps of the above method include the step of post-treating the reaction system after the reaction is completed;

[0043] The post-treatment process is as follows: after the reaction system is cooled, the solvent is removed by rotary evaporation, the residue is extracted with dichloromethane, ethyl acetate or diethyl ether, washed with saturated sodium chloride solution, dried over anhydrous sodium sulfate or anhydrous magnesium sulfate, and concentrated under reduced pressure. In steps 1.2 and 2.1, after the post-treatment, the crude product is subjected to silica gel column chromatography or preparative thin layer chromatography to obtain the target diazo compound.

[0044] The invention also protects the application of the diazo compound.

[0045] The application provided by the present invention is the application of the diazo compound in at least one of the following 1)-3): 1) as a polymer crosslinking agent; 2) organic semiconductor patterning; 3) application in the preparation of organic photoelectric devices.

[0046] The polymer includes a non-conjugated polymer and a conjugated semiconductor polymer (such as a p-type polymer DPP4T; or an N-type polymer N2200).

[0047] In the above-mentioned application of optoelectronic devices, the organic optoelectronic device includes at least one of an organic thin film transistor, an organic digital circuit, an organic solar cell, an organic thermoelectric, an organic laser, an organic light emitting diode and an organic laser.

[0048] The present invention has the following advantages:

[0049] 1. The synthesis steps are short, the reaction conditions are mild, and the operation is simple.

[0050] 2. The raw materials used in the synthesis are readily available and easy to industrialize.

[0051] 3. The diazo compound has good chemical stability.

[0052] 4. The by-product nitrogen gas produced after the cross-linking reaction of the diazo compound is environmentally friendly.

[0053] 5. The diazo compound can undergo efficient cross-linking reaction with the conjugated polymer, and the performance of the organic semiconductor is not affected or is only slightly affected after cross-linking. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Figure 1 The tetrazo crosslinking agent C-TD2b of Example 1 of the present invention 1 H NMR spectra.

[0055] Figure 2 The tetrazo crosslinking agent C-TD2b of Example 1 of the present invention 13 C NMR spectrum.

[0056] Figure 3 The tetrazo crosslinking agent C-TD3b of Example 2 of the present invention 1 H NMR spectra.

[0057] Figure 4 The tetrazo crosslinking agent C-TD3b of Example 2 of the present invention 13 C NMR spectrum.

[0058] Figure 5 The structural formula of DPP4T polymer and the example of patterning of conjugated polymer using the tetrazo crosslinker C-TD3b of Example 2 of the present invention.

[0059] Figure 6 This is a structural diagram of a field effect transistor device prepared based on the tetrazo crosslinking agent C-TD2b of Example 1 of the present invention.

[0060] Figure 7 The output curve and transfer curve of the field effect transistor prepared based on the tetrazo crosslinking agent C-TD2b of Example 1 of the present invention.

[0061] Figure 8 The circuit diagram and output voltage curve of the inverter prepared based on the tetrazo cross-linking agent C-TD2b of Example 1 of the present invention. DETAILED DESCRIPTION

[0062] The present invention is further described below in conjunction with specific examples, but the present invention is not limited to the following examples. The methods described are conventional methods unless otherwise specified. The raw materials described can be obtained from public commercial channels unless otherwise specified.

[0063] Embodiment 1:

[0064] The synthetic route of the aromatic tetrazonium compound (denoted as C-TD1) in this embodiment is as follows:

[0065]

[0066] The specific synthesis steps are:

[0067] (1) Under nitrogen protection, add 200 mL of tetrahydrofuran and 30 mL of trifluoromethyltrimethylsilane to a reaction bottle containing 10 g of biphenyltetraaldehyde 1a. Cool the reaction solution to 0°C and slowly drop tetrabutylammonium fluoride solution (1M, 3.8 mL). After the addition is complete, react at room temperature for 48 h, add 3M HCl (500 mL), stir vigorously for 24 h, extract with dichloromethane (500 mL), wash the organic layer with water and saturated brine, remove the solvent by rotary evaporation, and purify the crude product by silica gel column chromatography to obtain compound 2.

[0068] (2) Add dichloromethane (200 mL) to the reaction bottle containing the compound 2 obtained in the above step, add 40 g of Dess-Martin periodinane under nitrogen protection, and reflux for 24 hours. After the reaction is completed, filter, wash with saturated sodium bicarbonate solution, water, and saturated brine, dry, and remove the solvent by rotary evaporation to obtain compound 1b.

[0069] (3) Add 12.8 g of p-toluenesulfonyl hydrazide to a reaction bottle containing 4.5 g of tetraaryl biphenyl ketone 1b. Under nitrogen protection, add 300 mL of toluene and stir at 80 degrees Celsius. After reacting for 12 hours, add 300 mL of methanol to the reaction solution, and a yellow solid precipitates. Filter the solid, wash with a small amount of methanol, and dry to obtain compound 3b. The synthesis method of compound 3a refers to compound 3b.

[0070] (4) Add 100 mL of methanol and 2 g of sodium hydroxide to the reaction bottle containing the compound 3b obtained in the above step, react at 70° C. for 24 h under nitrogen protection, then cool the reaction solution to room temperature, dilute with water (100 mL), extract with dichloromethane, combine the organic layers, dry over anhydrous sodium sulfate, and remove the solvent by rotary evaporation. The crude product is separated by silica gel column chromatography and recrystallized to obtain 600 mg of tetrazo compound C-TD1b. The synthesis method of compound C-TD1a refers to compound C-TD1b.

[0071] Embodiment 2:

[0072] The synthetic route of the aromatic tetrazonium compound (denoted as C-TD2) in this embodiment is as follows:

[0073]

[0074] The specific synthesis steps of tetradiazo compounds C-TD2a and C-TD2b are similar to those in Example 1 of the present invention, except that tetraaryl ketone (aldehyde) 4 is used as the starting material. The structural confirmation result of C-TD2b is: 1 H NMR spectrum is shown in Figure 1 , 13 C NMR spectrum is shown in Figure 2 .

[0075] Embodiment 3:

[0076] The synthetic route of the aliphatic tetrazonium compound (denoted as C-TD3) in this example is as follows:

[0077]

[0078] The specific synthesis steps are:

[0079] (1) 32 g of 12-bromo-1-dodecanol and 20 mL of triethylamine were dissolved in 200 mL of dichloromethane. The reaction solution was cooled to -10°C, and 19.2 mL of phenylacetyl chloride was slowly added dropwise to the reaction solution at this temperature. After constant temperature stirring for 30 min, the temperature was slowly raised to room temperature and the reaction was continued for 24 h. After the reaction was completed, 200 mL of dichloromethane was added to the mixture, and then washed three times with 200 mL of water. The organic phases were combined, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography to obtain compound 6b.

[0080] (2) 21 g of compound 6b, 8.2 g of anhydrous K2CO3, 8 g of NaI, 7.9 g of DPP-H and 100 mL of DMF were added to a reaction flask in sequence. The reaction solution was stirred at 65°C for 24 h. After cooling to room temperature, 100 mL of water was added to the reaction mixture, followed by extraction three times with 200 mL of dichloromethane. The organic phases were combined, and then washed with 200 mL of water and 200 mL of saturated NaCl aqueous solution in sequence, and dried over anhydrous Na2SO4. The solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography to obtain compound 7b.

[0081] (3) 3 g of compound 7b was dissolved in 10 mL of dichloromethane, and then a dichloromethane solution (10 mL) containing 0.16 g of N-bromosuccinimide was slowly added to the reaction solution by syringe. The reaction mixture was stirred at room temperature for 24 h. After the reaction was completed, the reaction solution was washed three times with 100 mL of water and dried over anhydrous Na2SO4. The solvent was removed by rotary evaporation, and the crude product was purified twice by silica gel column chromatography to obtain compound 8b.

[0082] (4) 202 mg of compound 8b, 156 mg of 2,2'-bipyridine, 280 mg of bis(1,5-cyclooctadiene)nickel and 20 mL of anhydrous toluene were added to a Shrek tube in sequence. After the freeze-thaw operation was repeated three times, the reaction solution was reacted at 110° C. in a nitrogen atmosphere for 12 h. After the reaction was completed, the reaction solution was diluted with 200 mL of dichloromethane, then washed with water (100 mL) three times, the solvent was removed by rotary evaporation, and compound 9b was obtained after purification by preparative thin layer chromatography (Prep-TLC).

[0083] (5) 100 mg of the compound 9b obtained in the above step, 220 mg of p-toluenesulfonyl chloride and 100 mg of pyridine were dissolved in 20 mL of dichloromethane and 10 mL of acetonitrile. The reaction mixture was stirred at room temperature for 24 h. After the reaction was completed, the reaction solution was diluted with 200 mL of dichloromethane, then washed with water (100 mL) three times, and the solvent was removed by rotary evaporation. After purification by preparative thin layer chromatography (Prep-TLC), the tetrazonium compound C-TD3b was obtained. The synthesis method of the tetrazonium compound C-TD3a refers to compound C-TD3b.

[0084] C-TD3b 1 H NMR spectrum is shown in Figure 3 , 13 C NMR spectrum is shown in Figure 4 .

[0085] Embodiment 4:

[0086] The specific steps for achieving conjugated polymer patterning based on the tetrazo crosslinker C-TD3b of Example 2 of the present invention are:

[0087] The copolymer of diketopyrrolopyrrole and bithiophene DPP4T (structural formula see Figure 5 ) and C-TD3b were dissolved in a chloroform solution at room temperature in a mass ratio of 100:10, wherein the concentration of DPP4T was 3 mg per ml. The blended solution was then spun on a silicon wafer through a gel-spinning machine at a speed of 2000 rpm and a film thickness of about 20 nanometers. The mask was covered on the film and irradiated with a 365-nanometer or 254-nanometer ultraviolet LED lamp for 40-200 seconds at a lamp power of 70 milliwatts per square centimeter. The illuminated film was then immersed in chloroform for 30 seconds, taken out and rinsed twice with 5 ml of chloroform. Patterning can be achieved after the silicon wafer is dried with nitrogen. See the patterning example. Figure 5 .

[0088] Embodiment 5:

[0089] The specific steps of applying the patterned p-type conjugated polymer film based on the tetra-diazo crosslinking agent C-TD2b of Example 1 of the present invention in a field effect transistor are:

[0090] On the prefabricated bottom electrode silicon wafer, a DPP4T pattern is first made in the electrode trench using the method in Example 4. The field effect transistor device structure is bottom gate-bottom contact. The specific structure is shown in Figure 6 : The source and drain electrodes are both gold with a thickness of 25 nanometers, the gate electrode is silicon with a thickness of 400 microns, the insulating layer is OTS (octadecyltrichlorosilane) modified silicon dioxide with a thickness of 300 nanometers, and the organic semiconductor part is patterned DPP4T with a thickness of 40-60 nanometers.

[0091] The test results show that the average hole mobility of 20 devices after annealing the patterned material at 120 degrees Celsius for 10 minutes is 2.0 cm 2 V -1 s -1 The average hole mobility of 20 unpatterned control devices is 1.9 cm 2 V -1 s -1 , representative transfer curves and output curves are shown in Figure 7 a, proving that the crosslinker does not destroy the transport properties of the p-type conjugated polymer after the crosslinking reaction, and has potential application value in organic field-effect transistors.

[0092] Embodiment 6:

[0093] The specific steps of applying the patterned n-type conjugated polymer film based on the tetra-diazo crosslinking agent C-TD2b of Example 1 of the present invention in a field effect transistor are:

[0094] According to the specific steps of Example 5, n-type polymer N2200 (structural formula see Figure 7 b) Preparation of thin film field effect transistor devices. The test results show that the average hole mobility of 20 devices after annealing the patterned material at 120 degrees Celsius for 10 minutes is 0.10 cm 2 V -1 s -1 The average hole mobility of 20 unpatterned control devices is 0.08 cm 2 V -1 s -1 , representative transfer curves and output curves are shown in Figure 7 b, proving that the crosslinker does not destroy the transport properties of the n-type conjugated polymer after the crosslinking reaction, and has potential application value in organic field-effect transistors.

[0095] Embodiment 7:

[0096] The specific steps of applying the patterned conjugated polymer film based on the tetra-diazo crosslinking agent C-TD2b of Example 1 of the present invention in the inverter are:

[0097] The steps described in Example 4 were used to prepare the two materials DPP4T and N2200. Figure 8 The circuit diagrams in the figure are used to construct a simple logic gate circuit: inverter. The specific test conditions are V dd =60V, the input and output voltage ranges are both 0-60V, and the test results show that the highest gain value is 102, proving that the cross-linking agent has potential application value in organic digital circuits.

[0098] Embodiment 8:

[0099] Application of the tetrazo crosslinking agent C-TD2b of Example 1 of the present invention in an organic solar cell device:

[0100] On a glass substrate, an indium tin oxide / PEDOT:PSS electrode is used, an organic semiconductor active layer is spin-coated thereon, and PDINN / silver is used as an electrode on top. The thickness of the PEDOT:PSS layer is about 40 nanometers, the thickness of the active layer is about 100 nanometers, the thickness of PDINN is about 10 nanometers, and the thickness of silver is about 100 nanometers. The method described in Example 4 of the present invention is used to prepare a PM6:PC based 71 BM: C-TD2b ternary blended active layer battery device, in which PM6: PC 71 The mass ratio of BM:Y6 is 0.8:0.2:1.2, and the tetrazo C-TD2b crosslinker accounts for PM6:PC 71 BM: 10% of the total mass of C-TD2b. The thermal stability of the battery performance of the cross-linked film and the control device without adding a cross-linking agent were compared and tested. The test results showed that the photoelectric conversion efficiency of the cross-linked device was 95% of that before annealing after two hours of annealing at 100 degrees Celsius, and the photoelectric conversion efficiency of the control device without adding a cross-linking agent was 90% of that before annealing after two hours of annealing at 100 degrees Celsius, proving that the material has potential application value in improving the thermal stability of organic solar cells.

Claims

1. Compounds of general formula I: In the general formula I, R1 is selected from hydrogen atom, halogen atom (F, Cl, Br, I), C1~C 20 containing hydrogen atoms, halogen atoms, amide bonds, ether bonds, ester bonds, aromatic or heteroaromatic straight chain or branched chain alkyl groups, C1-C 20 One of the following: a straight-chain or branched perfluoroalkyl group, a polysubstituted or unsubstituted aryl or heteroaryl group (phenyl, thienyl, thiazolyl, pyridyl, quinolyl, furanyl, pyrrolyl, imidazolyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, pyrrolopyrroledione, isoindigotyl, naphthalimide or other aryl group), or a combination of the above units connected by single bonds, double bonds, triple bonds, or one or more of carbon, oxygen, sulfur, silicon, nitrogen or phosphorus atoms; R2 is selected from C1~C 20 containing hydrogen atoms, halogen atoms, amide bonds, ether bonds, ester bonds, aromatic or heteroaromatic straight chain or branched chain alkyl groups, C1-C 20 The invention relates to a straight-chain or branched perfluoroalkyl group, a polysubstituted or unsubstituted aryl or heteroaryl group (phenyl, thienyl, thiazolyl, pyridyl, quinolyl, furyl, pyrrolyl, imidazolyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, pyrrolopyrroledione, isoindigotyl, naphthalimide or other aryl group), or a combination of the above units connected by single bonds, double bonds, triple bonds, carbon, oxygen, sulfur, silicon, nitrogen or phosphorus atoms or more. n is an integer between 2 and 10.

2. The compound according to claim 1, characterized in that: The aryl or heteroaryl group is selected from any one of the following: phenyl, thienyl, thiazolyl, pyridyl, quinolyl, furanyl, pyrrolyl, imidazolyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, pyrrolopyrroledione, isoindigotyl, naphthalene diimide or other aryl groups; Or, R1 is selected from a hydrogen atom, a halogen atom, an ester group, CH3, CF3, C2F5, C3F7, an aryl group or a heteroaryl group; Or, the R2 is selected from the following fragments: In the present invention, the R2 exemplary groups are represents the attachment position of the diazo group in the general formula I.

3. The compound according to claim 1 or 2, characterized in that: The compound is any one of the following: In the above C-TD1, R1 may be H, CF3 or CO2CH3; In the above C-TD2, R1 may be H, CF3 or CO2CH3; In the above C-TD3, R1 may be H or phenyl.

4. The method for preparing the compound of general formula I according to claim 1, comprising the following steps: (1.1) In an organic solvent, a carbonyl compound substituted with R1 (compound represented by formula II) and p-toluenesulfonyl hydrazide are mixed and heated to react to obtain an intermediate product a (compound represented by formula III); in, In the formula II, R1 and n are defined the same as in the general formula I; in the formula II, R2 is one of a polysubstituted or unsubstituted aryl or heteroaryl group (phenyl, thienyl, thiazolyl, pyridyl, quinolyl, furanyl, pyrrolyl, imidazolyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, pyrrolopyrroledione, isoindigotyl, naphthalimide or other aromatic group), or a combination of the above units connected by one or more of single bonds, double bonds, triple bonds, carbon, oxygen, sulfur, silicon, nitrogen or phosphorus atoms. In the formula III, R1, R2, and n are defined the same as in formula II; (1.2) In an organic solvent, the intermediate product a obtained in step 1.1 is mixed with a base and heated to react to obtain a diazo compound of formula I.

5. The method according to claim 4, characterized in that: In the above-mentioned synthesis method, the organic solvent is selected from one or more mixtures of tetrahydrofuran (THF), toluene, ethanol, methanol, dichloromethane, chloroform, acetone, N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), hexamethylphosphoramide (HMP), cyclopentane, acetonitrile and benzonitrile. In the above-mentioned synthesis method, the base is selected from a mixture of one or more of triethylamine, pyridine, N,N-diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), potassium carbonate, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, potassium fluoride and cesium fluoride. In the step 1.1, the molar ratio of the R1-substituted carbonyl compound to p-toluenesulfonyl hydrazide may be 1:2-20; in the step 1.2, the molar ratio of the intermediate product a to the base may be 1:2-20; In the step 1.1, the volume ratio of the organic solvent to the R1-substituted carbonyl compound is 10-400 mL: 1 g; in the step 1.2, the volume ratio of the organic solvent to the intermediate product a is 10-400 mL: 1 g; In the step 1.1, the conditions of the heating reaction are as follows: heating to 30 to 150 degrees Celsius in air or an inert gas atmosphere, and reacting for 1 to 24 hours; in the step 1.2, the conditions of the reaction are as follows: heating to 30 to 110 degrees Celsius in air or an inert gas atmosphere, and reacting for 1 to 24 hours; The inert gas is specifically nitrogen or argon.

6. A method for preparing the compound of general formula I according to claim 1, comprising the following steps: (2.1) In an organic solvent, a R1-substituted carbonyl compound (compound represented by Formula IV), a base and aromatic sulfonyl azide are reacted at room temperature or under heating conditions to obtain a diazo compound represented by Formula V; in, In the formula IV, R2 and n are defined the same as in the general formula I; in the formula II, R1 is selected from one of hydrogen, polysubstituted or unsubstituted aryl or heteroaryl (phenyl, thienyl, thiazolyl, pyridyl, quinolyl, furanyl, pyrrolyl, imidazolyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, pyrrolopyrroledione, isoindigotyl, naphthalimide or other aromatic groups), or a combination of the above units connected by single bonds, double bonds, triple bonds, carbon, oxygen, sulfur, silicon, nitrogen or phosphorus atoms or more. In the formula V, R1, R2, and n are defined the same as those in the formula IV.

7. The method according to claim 6, characterized in that: In the above-mentioned synthesis method, the organic solvent is selected from one or more mixtures of tetrahydrofuran (THF), toluene, ethanol, methanol, dichloromethane, chloroform, acetone, N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), hexamethylphosphoramide (HMP), cyclopentane, acetonitrile and benzonitrile. In the above-mentioned synthesis method, the base is selected from a mixture of one or more of triethylamine, pyridine, N,N-diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), potassium carbonate, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, potassium fluoride and cesium fluoride. In the step 2.1, the molar ratio of the R1-substituted carbonyl compound to the aromatic sulfonyl azide can be 1:2-20, the molar ratio of the R1-substituted carbonyl compound to the base is 1:2-20, and the equivalents of the base and the aromatic sulfonyl azide are equal. In the step 2.1, the mass ratio of the volume of the organic solvent to the mass ratio of the R1-substituted carbonyl compound is 10-400 mL: 1 g. In the step 2.1, the reaction conditions are as follows: in an air or inert gas atmosphere, the reaction temperature is 20 to 80 degrees Celsius, and the reaction time is 24 to 96 hours. The inert gas is specifically nitrogen or argon.

8. The method according to any one of claims 4 to 7, characterized in that: All steps of the method include the step of post-treating the reaction system after the reaction is completed; The post-treatment process is as follows: after the reaction system is cooled, the solvent is removed by rotary evaporation, the residue is extracted with dichloromethane, ethyl acetate or diethyl ether, washed with saturated sodium chloride solution, dried with anhydrous sodium sulfate or anhydrous magnesium sulfate, and concentrated under reduced pressure. In steps 1.2 and 2.1, after the post-treatment, the crude product is subjected to silica gel column chromatography or preparative thin layer chromatography to obtain the target diazo compound represented by general formula I.

9. Use of the compound of general formula I according to claim 1 in at least one of the following 1) to 3): 1) As a polymer cross-linking agent; 2) Patterning of organic semiconductors; 3) Application in the preparation of organic optoelectronic devices.

10. The use according to claim 9, characterized in that: The polymer includes a non-conjugated polymer and a conjugated semiconductor polymer; In the above-mentioned application of optoelectronic devices, the organic optoelectronic device includes at least one of an organic thin film transistor, an organic digital circuit, an organic solar cell, an organic thermoelectric, an organic laser, an organic light emitting diode and an organic laser.

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