CN112661940B - Thiophene thiadiazole-based n-type water/alcohol-soluble conjugated polyelectrolyte, and preparation and application thereof - Google Patents
Thiophene thiadiazole-based n-type water/alcohol-soluble conjugated polyelectrolyte, and preparation and application thereof Download PDFInfo
- Publication number
- CN112661940B CN112661940B CN202011395222.XA CN202011395222A CN112661940B CN 112661940 B CN112661940 B CN 112661940B CN 202011395222 A CN202011395222 A CN 202011395222A CN 112661940 B CN112661940 B CN 112661940B
- Authority
- CN
- China
- Prior art keywords
- alcohol
- water
- soluble
- thienothiadiazole
- conjugated polyelectrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention belongs to the technical field of organic photoelectricity, and discloses an n-type water/alcohol-soluble conjugated polyelectrolyte based on thienothiadiazole, and preparation and application thereof. The structure of the n-type water/alcohol-soluble conjugated polyelectrolyte based on the thienothiadiazole is shown as a formula I, wherein A is a unit consisting of one or more aromatic groups; r is R A Or R is B Is a side chain with a water-alcohol-soluble strong polar group, and R A And R is B At least one of them is a side chain with a strong polar group that is water-alcohol soluble; n is a positive integer from 1 to 2000. The invention also discloses a preparation method of the conjugated polyelectrolyte. The conjugated polyelectrolyte is used for preparing organic photoelectric devices, in particular large-area photoelectric devices. The conjugated polyelectrolyte has better electron transmission performance and meets the requirements of thick film processing in an organic photoelectric device; the material has a lower benzoquinone type conversion energy barrier, and can realize higher n-type conductivity; meanwhile, the water/alcohol solubility is also achieved, and the water/alcohol solubility can be processed by using environment-friendly solution.
Description
Technical Field
The invention belongs to the field of organic photoelectricity, and particularly relates to an n-type water/alcohol-soluble conjugated polyelectrolyte based on thiophene [3,4-C ] [1,2,5] thiadiazole, and a preparation method and application thereof. The conjugated polyelectrolyte is used as an electron transport layer for organic optoelectronic devices.
Background
The photoelectric material and the semiconductor material applied by the device not only have the electronic characteristics of metal or semiconductor, but also have the characteristics of low cost, light weight, low-temperature processing, easy realization of large-area preparation and the like, meet the requirements of industrial large-scale production and large-area popularization, and have wide commercial prospect. Since the development of organic small molecule thin film electroluminescent devices [ Organic electroluminescent diodes, appli ed Physics Letters,1987,51,913 ] by the dane blue cloud research group in the united states in 1987, organic display technologies have been rapidly developed. Meanwhile, organic photoelectric fields such as organic solar cells, organic field effect transistors, organic biochemical sensors and the like are also being developed vigorously. At present, the new energy technology is one of the popular research fields of leading edge science, and is widely focused at home and abroad. Solar energy is used as an extremely important part of new energy, and has the characteristics of cleanness, reproducibility, wide coverage range and the like. And the efficiency of the organic solar cell breaks through 18%, so that the market potential is huge.
Currently, a multi-layer device structure is generally required for a high-efficiency semiconductor device, and in order to enable electrons and holes to be extracted to a cathode and an anode respectively and efficiently, a hole transport layer and an electron transport layer are often added outside an active layer. When the device is prepared, the water/alcohol-soluble conjugated polymer material is used as an electron transport layer, and the orthogonalization solvent such as methanol can be used for directly processing on the active layer film, so that the damage to the active layer is avoided. Meanwhile, researches show that the water/alcohol-soluble conjugated polymer has good interface modification performance and can improve the performance of an organic photoelectric device.
In 2004, huang et al [ Novel Electroluminescent Conjugated Polyelectrolytes Based on Polyfluorne. Chem. Mater.,2004,16,708-716.]The preparation of the conjugated polymer PFN and the quaternary ammonium salt PFN-Br with the side chains of neutral amine can adopt environment-friendly solvent processing, and the PFN can be used as an electron transport material to improve the performance of the polymer light-emitting diode. Later, PFN and PFN-Br were also used as electron transport layers in polymer solar cells and could improve the device performance of polymer solar cells [ Novel Electroluminescent Conjugated Polyelectrolytes Based on Polyfluorne. Chem Mater,2004,16:708-716; efficient electron injection from a bilayer cathode consisting of aluminum and alcohol-/water-soluble conjugated polymers.adv Mater,2004,16:1826-1830.]. He et al spin-coated a 5nm thick PFN between the active layer and the cathode material of the polymer solar cell, and the resulting device results showed that the short circuit current (J) SC ) Open circuit voltage (V) OC ) And FF are greatly improved [ Simultaneous Enhancement of Open-Circuit Voltage, short-Circuit Current Density, and Fill Factor in Polymer Solar cells. Adv Mater.2011,23 (40): 4636-4643 ].]. But is limited by its low conductivity, and can only function properly at low thicknesses (< 10 nm) in organic solar cell devices. Later, document [ n-Type Water/Alcohol-Soluble Naphthalene Diimide-Based Conjugated Polymers for High-Performance Polymer Solar cells.J.am.chem.Soc.2016,138,6,2004-2013]And patent CN104725613B reports that constructing a water/alcohol soluble conjugated polymer PF3NThNDI-Br by utilizing a naphthalene diimide unit with poor electrical property has higher electron mobility and can meet the requirement of adding a thick film deviceAnd (5) working requirements.
Most of the n-type water/alcohol soluble conjugated polymers reported at present are mainly used for improving the electron affinity and electron mobility of materials by introducing an electric absorption unit (such as naphthalimide, perylene diimide and the like). However, due to the lack of effective benzoquinone resonance transformation, electrons are mainly delocalized on the electric absorption unit, and the water/alcohol soluble conjugated polymer with high conductivity is difficult to realize effectively.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide an n-type water/alcohol-soluble conjugated polyelectrolyte based on thienothiadiazole (namely an n-type water/alcohol-soluble conjugated polyelectrolyte based on thiophene [3,4-C ] [1,2,5] thiadiazole) and a preparation method thereof.
It is another object of the present invention to provide the use of the above-described thienothiadiazole-based n-type water/alcohol soluble conjugated polyelectrolyte in photovoltaic devices, in particular as an electron transport layer in organic solar cell devices.
The technical scheme of the invention is as follows:
an n-type water/alcohol soluble conjugated polyelectrolyte based on thienothiadiazoles (i.e., an n-type water/alcohol soluble conjugated polyelectrolyte based on thiophene [3,4-C ] [1,2,5] thiadiazoles) having the structure of formula I:
wherein A is a unit consisting of one or more aromatic groups; r is R A Or R is B Is a side chain with a water-alcohol-soluble strong polar group, and R A And R is B At least one of them is a side chain with a strong polar group that is water-alcohol soluble; n is a positive integer from 1 to 2000. R is R A And R is B At least one of them has one or more water-alcohol-soluble strongly polar groups.
Preferably, R B Is hydrogen or-R 1 -R B′ ，R 1 Is alkylene or alkylene having one or more carbon atoms replaced by oxygen, amino, sulfone, carbonyl, aryl, alkenyl, alkynyl, ester, cyanoNitro-substituted, or hydrogen on alkylene substituted with halogen or hydroxy, amino, carboxyl, cyano, nitro, aryl, alkene or alkyne; r is R A Is hydrogen or-R 2 -R A′ ，R 2 Is alkylene or alkylene in which one or more carbon atoms are replaced by oxygen, amino, sulfone, carbonyl, aryl, alkenyl, alkynyl, ester, cyano, nitro, or alkylene in which hydrogen is replaced by halogen or hydroxy, amino, carboxyl, cyano, nitro, aryl, alkenyl or alkynyl; r is R A′ Or R is B′ Is hydrogen or a water-alcohol-soluble strongly polar group, and R A′ And R is B′ At least one of them is a water-alcohol-soluble strong polar group; the number of the water-alcohol-soluble strong polar groups in the formula I is 1 or more, and when the number of the water-alcohol-soluble strong polar groups is more than one, the alkylene or the substituted alkylene loses one or more hydrogen to be connected with the corresponding water-alcohol-soluble strong polar groups. The water-alcohol-soluble strong polar group is more than one of amino, quaternary ammonium salt or amino.
R 1 And R is R 2 The alkylene groups, which may be the same or different, are straight, branched or cyclic.
The said
One or a combination of several of the following structures:
the preparation method of the n-type water/alcohol-soluble conjugated polyelectrolyte based on the thienothiadiazole comprises the following steps:
coupling the unit containing A with a halogen substituted thienothiadiazole compound under the action of a palladium catalyst to obtain a polymer which is not salified; alternatively, the non-salified polymer is subjected to a quaternization reaction to obtain a conjugated polyelectrolyte containing a quaternary ammonium salt. When the non-salified polymer is free of water-alcohol-soluble strong polar groups, the non-salified polymer is subjected to a quaternization reaction. When the non-salified polymer has a water-alcohol-soluble strong polar group, the non-salified polymer is not quaternized or quaternized.
The unit containing A is a unit containing A with a palladium catalyst catalytic coupling reaction functional group.
The structure of the halogen substituted thienothiadiazole compound is
Wherein X is halogen.
The unit containing A can be a borate unit containing A, a boric acid unit containing A or a trimethyltin unit containing A.
Thiophene [3,4-C ] [1,2,5] thiadiazole has a very low benzoquinone type conversion energy barrier, can easily realize benzoquinone type interconversion of self structure, can realize benzoquinone type conversion of polymer conjugated main chains, and promotes n-type self doping:
the n-type water/alcohol-soluble conjugated polyelectrolyte based on the thienothiadiazole is used for preparing photoelectric devices, is used as an electron transport layer, and is particularly used for preparing organic solar cells.
The invention characterizes the optical property of the polymer by an ultraviolet-visible light absorption spectrometer, and characterizes the photoelectric property of the polymer by preparing a photoelectric device and testing the property of the photoelectric device. The test analysis means show that the obtained polymer material has potential application value in the field of organic photoelectricity.
The thiophene [3,4-C ] [1,2,5] thiadiazole molecule in the polymer contains a strong-electrical-absorption thiadiazole functional group, so that the lowest unoccupied orbit (LUMO) energy level of the polymer can be effectively reduced, and the electron transmission is facilitated. The low LUMO energy level is beneficial to realizing n-type doping of the polymer, and can also improve the air stability of the polymer. Meanwhile, due to the unique bonding mode between the thiadiazole unit and thiophene, the benzoquinone type energy conversion is very low, the whole polymer molecule can generate a quinoid free radical through self resonance, and the whole polymer main chain is driven to form a stable quinoid structure, so that the carrier transmission efficiency is further improved.
Compared with the prior art, the invention has the main advantages that:
1) The n-type water-alcohol-soluble conjugated polymer based on thiophene [3,4-C ] [1,2,5] thiadiazole has better electron transmission performance, has air-stable n-type conductivity, can improve the electron collection capability of an electronic device, can be applied to a photoelectric device as a thick film electron transmission layer, can meet the requirement of insensitive roll-to-roll printing technology on thickness, and is suitable for preparing a large-area photoelectric device;
2) The n-type water-alcohol-soluble conjugated polymer film based on thiophene [3,4-C ] [1,2,5] thiadiazole has high transmittance in the visible light region, and can not influence the light absorption of an active layer when being applied to an organic solar cell device as an electron transport layer;
3) The material provided by the invention has water/alcohol solubility, meets the requirement of environment-friendly chemical processing, and can realize large-area processing by means of spin coating, ink-jet printing and the like.
Drawings
FIG. 1 is a graph of the UV-visible absorption spectra of thiophene [3,4-C ] [1,2,5] thiadiazole-based n-type water-alcohol soluble conjugated polyelectrolytes prepared in example 10 and example 12;
FIG. 2 is a spin density plot of the n-type conjugated polyelectrolytes in examples 10 and 12; the upper graph is the spin density map of example 10, and the lower graph is the spin density map of example 12;
FIG. 3 is a graph showing the results of conductivity tests for the conjugated polyelectrolytes of examples 10 and 12 as conductive layers;
fig. 4 is a graph showing the performance of the conjugated polyelectrolytes of examples 10 and 12 as electron transport layers for organic solar cell devices.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but embodiments of the present invention are not limited thereto. In the following examples, the possibility of some experimental errors being present should be considered. The reagents used in the examples below, unless specifically noted, are commercially available analytically, chromatographically or chemically pure reagents. The following examples are carried out at or near atmospheric pressure unless specifically noted. All chemical reactions in the examples were carried out under nitrogen or argon protection.
Example 1
Th-NO 2 The chemical reaction equation is as follows:
taking monomer A (5.19 g), monomer B (12.8 g,2.5 eq.) and ligand tris (o-methylphenyl) phosphorus [ p (o-tol) 3 ](1.07 g) was placed in a reaction vessel equipped with a stirrer, evacuated for 5 minutes and purged with nitrogen, 100mL of toluene was added, and the atmosphere was changed 2 times, and tris (dibenzylideneacetone) dipalladium [ Pd ] was added under nitrogen 2 (dba) 3 ]36mg, stirring and heating to 100 ℃, and reacting for 48 hours; removing toluene by using a rotary evaporator after the reaction is finished to obtain a crude product; purifying the crude product by column chromatography with mixed solvent of petroleum ether and dichloromethane (3:1) as eluent to obtain target compound Th-NO 2 As yellow brown solid (87% yield). 1 H NMR(500MHz,CDCl 3 ,ppm)：7.96-7.84(d,2H),7.28-7.26(d,2H),6.98-6.94(d,2H)。
Example 2
Th-NH 2 The chemical reaction equation is as follows:
Th-NO 2 (2.4 g) was dispersed in 80ml of ethanol, 50ml of hydrochloric acid was added and nitrogen was introduced for 20 minutes, stannous chloride hydrate (30-fold equivalent) was added in portions over 20 minutes, slightly heated, and reacted at 30-35 ℃ for 30 hours at an oil temperature, the solution turned from brown to golden yellow; the reaction solution was poured into 25% by weight sodium hydroxide solution (to be requiredEnsure PH>10 A large amount of solid is instantaneously precipitated and stirred for 10 minutes at room temperature; adding a large amount of ethyl acetate, and obtaining a suspension at the moment; removing insoluble substances with diatomite column to obtain phase-separated solution, collecting organic phase, extracting and washing the organic phase with deionized water for 2-3 times, drying with anhydrous MgSO4, eluting with mixed solvent of petroleum ether and dichloromethane (1:1), and purifying crude product Th-NH by column chromatography 2 Directly used for the next reaction.
Experimental example 3
TTD is prepared by the following chemical reaction equation:
Th-NH under nitrogen 2 Dissolving with ultra-dry pyridine, adding into a reaction flask, heating the reaction solution to 85-90 ℃, adding 2 equivalents of aniline N-methylene, adding 2.5 equivalents of trimethylchlorosilane after 5 minutes, adding a great deal of smoke instantaneously to emit, continuously heating and reacting for 3 hours, and recovering the room temperature; the crude product was purified by column chromatography using a mixed solvent of petroleum ether and dichloromethane (1:1) as eluent and recrystallized from MeOH to give the product TTD (about 75% overall yield in two steps). 1 H NMR(500MHz,CDCl 3 ,ppm)：7.76-7.72(d,2H),7.32-7.28(d,2H),7.18-7.14(d,2H)。
Experimental example 4
Preparation of TTD-Br, the chemical reaction equation is as follows:
dissolving TTD in tetrahydrofuran, and ice-bathing; NBS (2.15 eq.) was dissolved in N, N-Dimethylformamide (DMF) and added slowly; the reaction was carried out at room temperature for 14 hours, and the solvent was removed by rotary evaporator to obtain a crude product. The crude product was purified by column chromatography using a mixed solvent of toluene and tetrahydrofuran (2:1) as an eluent and recrystallized from n-hexane/toluene=10:1 to give a blue precipitate (yield 37%). 1 H NMR(500MHz,CDCl 3 ,ppm)：7.32-7.28(d,2H),7.18-7.14(d,2H)。
Example 5
The preparation of IIG-C6Br, the chemical reaction equation is as follows:
under the protection of argon, the raw material (E) -6,6 '-dibromo- [3,3' -diindoline subunit]2,2' -dione (10 mmol) was dissolved in 150mL of ultra-dry N, N-dimethylformamide, potassium carbonate (25 mmol) was added, heated to 85℃and stirred for 1 hour; 1, 6-dibromohexane (60 mmol) was added and the temperature was raised to 100℃for 24 hours; the reaction solution was cooled to room temperature, N-dimethylformamide was removed by rotary evaporator to give a viscous crude product, and the crude product was purified by column chromatography using a mixed solvent of petroleum ether and methylene chloride (1:1) as an eluent to give the objective compound IIG-C6Br as a red needle-like solid (15% yield). 1 H NMR(500MHz,CDCl 3 ,ppm)：9.09-9.05(d,2H),7.20-7.16(dd,2H),6.95-6.92(d,2H),3.80-3.71(t,4H),3.44-3.37(t,4H),1.91-1.82(p,4H),1.76-1.68(p,4H),1.42-1.37(m,4H),1.32-1.21(m,4H)。
Example 6
The preparation of IIG-C6Br-BO has the following chemical reaction formula:
in a nitrogen-protected glove box, IIG-C6Br (2 mmol), potassium acetate (16 mmol), pinacol ester (6 mmol) and 1,1' -bis-diphenylphosphino ferrocene palladium dichloride (0.15 mmol) were added to a 150mL sealed reaction tube and 80mL of ultra-dry dioxane was added to dissolve the starting material. The temperature was raised to 100℃and the reaction was carried out for 24 hours. The reaction solution was cooled to room temperature, and dioxane was removed by rotary evaporator to give a viscous crude product. Purifying the crude product by column chromatography with mixed solvent of petroleum ether and ethyl acetate (3:1) as eluent to obtain the target compound IIG-C6Br-BO as red solid (21% yield))。 1 H NMR(500MHz,CDCl 3 ,ppm)：9.09-9.05(d,2H),7.20-7.16(dd,2H),7.05-7.02(d,2H),3.80-3.71(t,4H),3.44-3.37(t,4H),1.91-1.82(p,4H),1.76-1.68(p,4H),1.42-1.37(m,4H),1.32-1.21(m,4H)，1.08-1.02(s,24H)。
Example 7
The preparation of B-C6Br, the chemical reaction equation is as follows:
under the protection of argon, the raw material 2, 5-dibromo-1, 4-benzene glycol (10 mmol) is dissolved in 150mL of acetone, potassium carbonate (25 mmol) is added, heated to 85 ℃ and stirred for 1 hour; 1, 6-dibromohexane (60 mmol) was added and heated to 100℃for reaction for 24 hours, the reaction solution was cooled to room temperature, acetone was removed by a rotary evaporator to obtain a crude product, and the crude product was purified by column chromatography using a mixed solvent of petroleum ether and methylene chloride (4:1) as an eluent to obtain the objective compound B-C6Br as a white solid (25% yield). 1 H NMR(500MHz,CDCl 3 ,ppm)：7.10-7.06(s,2H),3.99-3.92(t,4H),3.45-3.40(t,4H),1.95-1.86(m,4H),1.87-1.77(m,4H),1.58-1.46(m,8H)。
Example 8
The preparation of B-C6Br-BO, the chemical reaction equation is as follows:
in a glove box protected by nitrogen, B-C6Br (2 mmol), potassium acetate (16 mmol), pinacol ester of bisboric acid (6 mmol) and 1,1' -bis-diphenylphosphino ferrocene palladium dichloride (0.15 mmol) are added into a 150mL sealed reaction tube, 80mL of ultra-dry dioxane is added for dissolving raw materials, the temperature is raised to 100 ℃ for reaction for 24 hours, the reaction solution is cooled to room temperature, the dioxane is removed by a rotary evaporator to obtain a viscous crude product, the crude product is purified by column chromatography by using a mixed solvent of petroleum ether and ethyl acetate (3:1) as eluent, and the target compound B-C6Br is obtained by methanol recrystallizationBO, as a white solid (46% yield). 1 H NMR(500MHz,CDCl 3 ,ppm)：7.10-7.06(s,2H),3.99-3.92(t,4H),3.45-3.40(t,4H),1.95-1.86(m,4H),1.87-1.77(m,4H),1.58-1.46(m,8H)，1.38-1.29(m,24H)。
Example 9
The preparation of the polymer PB-TTD has the following chemical reaction equation:
adding monomer 1 (0.15 mmol) and monomer 2 (0.15 mmol) into a reaction vessel with a stirrer, introducing nitrogen for 5 minutes, adding 2mL of chromatographic pure toluene into a reaction bottle, carrying out ultrasonic treatment for 10 minutes to completely dissolve the monomer, adding 1.5mL of potassium carbonate aqueous solution (2M) and 1mL of tetrahydrofuran, pumping and ventilating under ice bath for 4 times to remove oxygen in the system, adding 3mg of tetrakis (triphenylphosphine) palladium, introducing fast-flowing nitrogen into the reaction tube for 10 minutes, sealing the reaction tube, heating to 100 ℃ with stirring, reacting for 6 hours, precipitating the polymer with methanol after the reaction is finished, filtering, wrapping the obtained precipitate with filter paper, placing the filter paper into a Soxhlet extraction device, washing with methanol, acetone, n-hexane and chlorobenzene in sequence, collecting a chlorobenzene part, concentrating to about 5mL by a rotary evaporator, precipitating with methanol, filtering, collecting the solid, drying in a vacuum drying box, taking out after 24 hours to obtain PB green solid-TDD, and obtaining 76% yield.
Example 10
The preparation of water/alcohol-soluble conjugated polyelectrolyte PB-TTD-Br has the following chemical reaction equation:
a100 mL flask with a magnetic stirrer was charged with PB-TTD (80 mg) dissolved in 20mL Tetrahydrofuran (THF), 10mL of a tetrahydrofuran solution (1M) of trimethylamine was added to the solution, the solution was stirred in the dark at room temperature to react for 4 days, 15mL Trifluoroethanol (TFE) was added to dissolve part of the precipitate, stirring was continued for 2 days, the solvent was concentrated to about 4mL by a rotary evaporator, then the polymer was precipitated in about 100mL ethyl acetate, filtration was performed, the resulting precipitate was collected, dried in the air, washed with tetrahydrofuran a plurality of times, and then dried in a vacuum oven at 40℃for 24 hours, and the resulting conjugated polyelectrolyte PB-TTD-Br was collected as a green solid in 77% yield.
Example 11
The polymer PIIG-TTD is prepared by the following chemical reaction equation:
monomer 1 (0.15 mmol) and monomer 2 (0.15 mmol) are added into a 15mL reaction tube with a stirrer, nitrogen is introduced for 5 minutes, 2mL of chromatographic pure toluene is added into a reaction bottle, ultrasound is performed for 10 minutes to completely dissolve the monomer, 1.5mL of potassium carbonate aqueous solution (2M) and 1mL of tetrahydrofuran are added, after 4 times of pumping and air exchange are performed under an ice bath to remove oxygen in the system, 3mg of tetra (triphenylphosphine) palladium is added, and then rapidly flowing nitrogen is introduced into the reaction tube for 10 minutes. The reaction tube is closed, stirred and heated to 100 ℃, the polymer is precipitated by methanol after the reaction is finished for 6 hours, the polymer is filtered, the obtained precipitate is wrapped by filter paper and placed in a Soxhlet extraction device, the obtained precipitate is washed by methanol, acetone, normal hexane and chloroform in sequence, the chloroform part is collected, the chloroform part is concentrated to about 5mL by a rotary evaporator, the methanol is used for precipitating, the polymer is filtered, the solid is collected and placed in a vacuum drying oven for drying, and the polymer is taken out after 24 hours, so that green solid PIIG-TTD is obtained, and the yield is 66%.
Example 12
The preparation of the water/alcohol-soluble conjugated polyelectrolyte PIIG-TTD-Br has the following chemical reaction equation:
a reaction vessel equipped with a magnetic stirrer was charged with chloroform (CHCl) dissolved in 20mL 3 ) PIIG-TTD (80 mg) in solution, to which solution is addedAdding 5mL of tetrahydrofuran solution (1M) of trimethylamine, stirring the solution in the dark at room temperature for reaction for 4 days, adding 15mL of Trifluoroethanol (TFE) to dissolve partial precipitate, adding 5mL of tetrahydrofuran solution (1M) of trimethylamine, continuously stirring for 2 days, concentrating the solvent to about 4mL by a rotary evaporator, precipitating the polymer in about 100mL of ethyl acetate, filtering, collecting the obtained precipitate, drying the precipitate in the air, washing the precipitate with tetrahydrofuran for multiple times, and then drying the precipitate in a vacuum drying oven at 40 ℃ for 24 hours, and collecting the conjugated polyelectrolyte PIIG-TTD-Br as a green solid with the yield of 77%.
Example 13
The n-type conjugated polyelectrolyte alcohol phase solutions synthesized in examples 10 and 12 were directly spin-coated to form a film, and the conductivity was measured by using a four-foot probe method, to illustrate the high conductivity characteristics of the n-type conjugated polyelectrolyte based on thiophene [3,4-C ] [1,2,5] thiadiazole units according to the present invention.
And washing the quartz glass sheet sequentially by using acetone, a micron-sized semiconductor special detergent, deionized water and isopropanol as cleaning solvents in an ultrasonic cleaning instrument, drying the surface by using nitrogen after washing, drying by using an infrared lamp, and then placing in a constant-temperature oven for standby. Before use, the glass sheet was bombarded with plasma in a plasma etcher for 10 minutes.
After the preparation of the glass sheet was completed, it was placed on a spin coater, spin-coated with the n-type conjugated polyelectrolyte methanol solution (20 mg/ml) prepared in examples 10 and 12 at high speed with a spin coater (KW-4A) while monitoring the thickness of the film by actual measurement with a surface profiler, the film thickness was about 100nm, and after the completion of the film formation, the surface conductivity was measured with a four-foot probe conductivity tester (RTS-8 type four-probe tester) as shown in Table 1.
TABLE 1n Water/alcohol soluble conjugated polyelectrolyte conductivity test
| Conjugated polyelectrolytes | Sheet resistance | Conductivity of electric conductivity |
| PB-TTD-Br | 8.6MΩ/□ | 8×10 -4 S/cm |
| PIIG-TTD-Br | 0.35MΩ/□ | 9×10 -3 S/cm |
Example 14
The conjugated polyelectrolytes synthesized in examples 10 and 12 are applied to an organic solar cell, and the application of the n-type conjugated polyelectrolyte based on thiophene [3,4-C ] [1,2,5] thiadiazole units, which is provided by the invention, as a thick film electron transport layer in an organic photoelectric device is illustrated by taking the conjugated polyelectrolytes as an example.
The structure of the organic solar cell device is ITO/PEDOT: PSS/PM6: Y6/n type conjugated polyelectrolyte/silver electrode.
The glass substrate coated with Indium Tin Oxide (ITO) was washed with deionized water, acetone and isopropyl alcohol, respectively, at room temperature for 15 minutes, and then dried in an oven at 60 ℃ for 12 hours. And then spin-coating poly (3, 4-ethylenedioxythiophene) with the thickness of 40nm on the cleaned ITO glass substrate: polystyrene sulfonic acid (PEDOT: PSS, CLEVIOS PVP Al 4083) and heated in air at 150℃for 15 minutes on a heated table. After the active layer donor material conjugated polymer PM6 and acceptor material Y6 were weighed in a dry bottle (mass ratio of 1:1.5), transferred into a nitrogen protection film-forming dedicated glove box (purchased from VAC corporation), dissolved in chloroform solvent containing 1% of 1, 8-diiodooctane, and then transferred into PED0T by spin coater and surface profiler: an active layer film of 100nm thickness was spin-coated on the PSS film. The polymer materials obtained in examples 10 and 12 were prepared into a solution with a concentration of 0.5% to 5% using a polar solvent, methanol, spin-coated on the active layer,as an electron transport layer for solar cell devices. The thickness is defined as between 5-100 nm. The film was then transferred to a vacuum evaporation bin connected to a glove box and then passed through a mask at about 10 a -7 Vapor plating silver (100 nm) electrode under Pa condition, and effective area of single device is 0.04cm 2 . All processes for the preparation of solar cell devices were carried out in glove boxes with oxygen and water contents below 1 ppm.
The energy of the simulated sunlight was corrected to 100mW/cm prior to testing using a silicon photodiode calibrated by the National Renewable Energy Laboratory (NREL) and a KG5 filter 2 . The energy conversion efficiency of the device was measured under a standard solar spectrum AM1.5 solar simulator (model 91192, oriel, usa) and photon and non-illuminated carrier density-voltage (J-V) characteristics of the solar cell device were recorded using Keithley 2410 and Keithley 236 digital source tables, respectively.
The current density versus voltage relationship of the device under illumination is shown in fig. 4, and the specific device efficiency is shown in table 2.
TABLE 2 organic solar cell Performance based on different polyelectrolyte interfacial layers
FIG. 1 is a graph of the UV-visible absorption spectra of thiophene [3,4-C ] [1,2,5] thiadiazole-based n-type water-alcohol soluble conjugated polyelectrolytes prepared in example 10 and example 12. It can be seen from the figure that its absorption can extend to the near infrared region.
Fig. 2 is a spin density diagram of the n-type conjugated polyelectrolyte in examples 10 and 12, the upper diagram is example 10, and the lower diagram is example 12. To illustrate that the diradical nature of the thiophene [3,4-C ] [1,2,5] thiadiazole unit can cause quinoid resonance throughout the backbone.
Fig. 3 is a graph showing the results of conductivity tests for the conjugated polyelectrolytes of examples 10 and 12 as conductive layers.
Fig. 4 is a graph showing the performance of the conjugated polyelectrolytes of examples 10 and 12 as electron transport layers for organic solar cell devices.
Claims (9)
1. An n-type water/alcohol soluble conjugated polyelectrolyte based on thienothiadiazole, characterized in that: the structure is as formula I:
wherein A is a unit consisting of one or more aromatic groups; r is R A Or R is B Is a side chain with a water-alcohol-soluble strong polar group, and R A And R is B At least one of them is a side chain with a strong polar group that is water-alcohol soluble; n is a positive integer from 1 to 2000; r is R A And R is B At least one of the two is provided with one or more water-alcohol-soluble strong polar groups;
the water-alcohol-soluble strong polar group is more than one of amino, quaternary ammonium salt or amino.
2. The thienothiadiazole based n-type water/alcohol soluble conjugated polyelectrolyte of claim 1, wherein: r is R B Is hydrogen or-R 1 -R B′ ，R 1 Is alkylene or alkylene in which one or more carbon atoms are replaced by oxygen, amino, sulfone, carbonyl, aryl, alkenyl, alkynyl, ester, cyano, nitro, or alkylene in which hydrogen is replaced by halogen or hydroxy, amino, carboxyl, cyano, nitro, aryl, alkenyl or alkynyl; r is R A Is hydrogen or-R 2 -R A′ ，R 2 Is alkylene or alkylene in which one or more carbon atoms are replaced by oxygen, amino, sulfone, carbonyl, aryl, alkenyl, alkynyl, ester, cyano, nitro, or alkylene in which hydrogen is replaced by halogen or hydroxy, amino, carboxyl, cyano, nitro, aryl, alkenyl or alkynyl; r is R A′ Or R is B′ Is hydrogen or a water-alcohol-soluble strongly polar group, and R A′ And R is B′ At least one of them is a water-alcohol-soluble strong polar group; the number of the water-alcohol-soluble strong polar groups in the formula I is 1 or more, and when the number of the water-alcohol-soluble strong polar groups is more than one, the alkylene group or the upper groupThe substituted alkylene groups in turn lose one or more hydrogens attached to the corresponding water-alcohol soluble strongly polar group.
3. The thienothiadiazole based n-type water/alcohol soluble conjugated polyelectrolyte of claim 1, wherein: the said
One or a combination of several of the following structures:
4. the thienothiadiazole based n-type water/alcohol soluble conjugated polyelectrolyte of claim 1, wherein: facilitating the progress of n-type autodoping by benzoquinone form interconversion;
5. the method for preparing the thienothiadiazole-based n-type water/alcohol-soluble conjugated polyelectrolyte according to any one of claims 1 to 4, wherein: the method comprises the following steps:
coupling the unit containing A with a halogen substituted thienothiadiazole compound under the action of a palladium catalyst to obtain a polymer which is not salified; alternatively, the polymer which is not salified is subjected to quaternization reaction to obtain conjugated polyelectrolyte containing quaternary ammonium salt;
the unit containing A is a unit containing A with a palladium catalyst catalytic coupling reaction functional group.
6. The method for preparing the thienothiadiazole-based n-type water/alcohol-soluble conjugated polyelectrolyte according to claim 5, wherein the method comprises the following steps: when the non-salified polymer is free of water-alcohol-soluble strong polar groups, the non-salified polymer is subjected to quaternization; when the non-salified polymer has a water-alcohol-soluble strong polar group, the non-salified polymer is not subjected to quaternization or is subjected to quaternization;
the structure of the halogen substituted thienothiadiazole compound is
Wherein X is halogen;
the unit containing A is a borate unit containing A, a boric acid unit containing A and a trimethyltin unit containing A.
7. Use of a thienothiadiazole based n-type water/alcohol soluble conjugated polyelectrolyte according to any of claims 1 to 4, characterized in that: the n-type water/alcohol-soluble conjugated polyelectrolyte based on the thienothiadiazole is used for preparing photoelectric devices.
8. The use according to claim 7, characterized in that: the thienothiadiazole-based n-type water/alcohol soluble conjugated polyelectrolyte is used for preparing an organic solar cell and/or an organic light emitting diode.
9. The use according to claim 7, characterized in that: the thienothiadiazole-based n-type water/alcohol soluble conjugated polyelectrolyte is used as an electron transport layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011395222.XA CN112661940B (en) | 2020-12-03 | 2020-12-03 | Thiophene thiadiazole-based n-type water/alcohol-soluble conjugated polyelectrolyte, and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011395222.XA CN112661940B (en) | 2020-12-03 | 2020-12-03 | Thiophene thiadiazole-based n-type water/alcohol-soluble conjugated polyelectrolyte, and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112661940A CN112661940A (en) | 2021-04-16 |
| CN112661940B true CN112661940B (en) | 2023-07-04 |
Family
ID=75400952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011395222.XA Active CN112661940B (en) | 2020-12-03 | 2020-12-03 | Thiophene thiadiazole-based n-type water/alcohol-soluble conjugated polyelectrolyte, and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112661940B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI825907B (en) * | 2021-08-23 | 2023-12-11 | 天光材料科技股份有限公司 | Organic semiconducting compound and organic photoelectric components using the same |
| TWI825908B (en) * | 2021-08-27 | 2023-12-11 | 天光材料科技股份有限公司 | Organic semiconducting compound and organic photoelectric components using the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936332A (en) * | 2012-11-08 | 2013-02-20 | 华东理工大学 | Narrow band gap conjugated polymer material with side chain provided with dendritic carbazole groups, and preparation method and application thereof |
| CN106986982A (en) * | 2017-04-12 | 2017-07-28 | 华南理工大学 | The molten conjugated polymer of water alcohol of three keys connection and its application in organic electro-optic device |
| WO2019005247A1 (en) * | 2017-03-30 | 2019-01-03 | Georgia Tech Research Corporation | Conjugated polymers with multistage side-chain cleavage |
| CN109942800A (en) * | 2019-04-08 | 2019-06-28 | 苏州和颂生化科技有限公司 | Amphoteric ion conjugated polyelectrolytes boundary material with amino acid group |
-
2020
- 2020-12-03 CN CN202011395222.XA patent/CN112661940B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936332A (en) * | 2012-11-08 | 2013-02-20 | 华东理工大学 | Narrow band gap conjugated polymer material with side chain provided with dendritic carbazole groups, and preparation method and application thereof |
| WO2019005247A1 (en) * | 2017-03-30 | 2019-01-03 | Georgia Tech Research Corporation | Conjugated polymers with multistage side-chain cleavage |
| CN106986982A (en) * | 2017-04-12 | 2017-07-28 | 华南理工大学 | The molten conjugated polymer of water alcohol of three keys connection and its application in organic electro-optic device |
| CN109942800A (en) * | 2019-04-08 | 2019-06-28 | 苏州和颂生化科技有限公司 | Amphoteric ion conjugated polyelectrolytes boundary material with amino acid group |
Non-Patent Citations (1)
| Title |
|---|
| N‑Type Self-Doped Water/Alcohol-Soluble Conjugated Polymers;Jianchao Jia等;《Macromolecules》;20180306;第51卷;第2195-2202页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112661940A (en) | 2021-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10312446B2 (en) | Conductive polymers, the organic photovoltaic cell comprising the same, and the synthesis thereof | |
| CN102164926A (en) | Active materials for photoelectric devices | |
| CN108461637B (en) | Hybrid for polymer solar cell electron transport layer and preparation method thereof | |
| CN105968126B (en) | One kind is containing bipyridyl/ferrosin salt water/Alcohol-soluble conjugate small molecule and the preparation method and application thereof | |
| CN112661940B (en) | Thiophene thiadiazole-based n-type water/alcohol-soluble conjugated polyelectrolyte, and preparation and application thereof | |
| Hu et al. | Enhanced performance of inverted perovskite solar cells using solution-processed carboxylic potassium salt as cathode buffer layer | |
| CN111138640B (en) | Acceptor polymer, photoactive layer, energy device, preparation method and application | |
| CN112646129B (en) | N-type water/alcohol-soluble conjugated polyelectrolyte containing benzobisthiadiazole and preparation and application thereof | |
| CN106410042B (en) | Organic solar batteries donor material, organic solar batteries and preparation method thereof | |
| CN114507232A (en) | Perylene bisimide quaternary ammonium salt solar cell electron transport layer material and preparation and application thereof | |
| CN104693422B (en) | A kind of polymer solar battery material of doping metals complex and its application | |
| CN112646130B (en) | N-type water/alcohol-soluble conjugated polyelectrolyte based on double free radical benzobisthiadiazole, and preparation and application thereof | |
| CN110544743B (en) | Efficient porphyrin material-based ternary organic solar cell and preparation method thereof | |
| CN109749061B (en) | Linked receptor type polymer photovoltaic material and preparation and application thereof | |
| CN109776769B (en) | Terpolymer based on thiophene, perylene diimide and isoindigo units and preparation method thereof | |
| CN116375732A (en) | Non-fullerene acceptor material and preparation method and application thereof | |
| CN113956447B (en) | Electronic polymer based on condensed ring imide structure, preparation method and device application thereof | |
| CN113173936B (en) | Non-doped hole transport material based on condensed ring electron-withdrawing parent nucleus and synthesis method and application thereof | |
| CN110698654A (en) | Hyperbranched conjugated polyelectrolyte based on trimeric indole, preparation method and application thereof | |
| CN110982047B (en) | Indacarbazine difuranyl organic solar cell donor material, and preparation method and application thereof | |
| CN106977701A (en) | The n-type water alcohol solubility conjugated polymer of the ring of imidodicarbonic diamide containing benzo and its application in organic/polymer light electrical part | |
| JP5701453B2 (en) | Difluorobenzotriazolyl solar cell material, preparation method, and method of use thereof | |
| US20180033985A1 (en) | An Electron Transport Layer Material and the Application Thereof | |
| CN113666927B (en) | Compound and preparation method and application thereof | |
| CN110556482A (en) | Non-fullerene organic solar cell based on benzodithiazole |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20230329 Address after: 100020 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Applicant after: CHINA PETROLEUM & CHEMICAL Corp. Address before: 510640 No. five, 381 mountain road, Guangzhou, Guangdong, Tianhe District Applicant before: SOUTH CHINA University OF TECHNOLOGY |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |