CN113061234A - Benzothiadiazole polymer, electron transport compound and perovskite photoelectric element - Google Patents
Benzothiadiazole polymer, electron transport compound and perovskite photoelectric element Download PDFInfo
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- CN113061234A CN113061234A CN202110303175.XA CN202110303175A CN113061234A CN 113061234 A CN113061234 A CN 113061234A CN 202110303175 A CN202110303175 A CN 202110303175A CN 113061234 A CN113061234 A CN 113061234A
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- substituted
- perovskite
- electron transport
- laminated
- carrier transport
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Abstract
A benzothiadiazole polymer, an electron transport complex comprising the benzothiadiazole polymer, and a perovskite photoelectric element comprising the electron transport complex are provided. The benzothiadiazole polymer contains a repeating unit represented by formula (I). The benzothiadiazole polymer can improve the energy level matching with the fullerene derivative, and can be mixed with the fullerene derivative to form an electron transport compound. When the electron transport composite is used as an up-loading current transport material of the perovskite photoelectric element, the energy conversion efficiency (PCE) and the stability of the perovskite photoelectric element can be simultaneously improved.
Description
Technical Field
The present invention relates to a polymer, an electron transport complex comprising the polymer, and a perovskite photoelectric device comprising the electron transport complex, and more particularly, to a benzothiadiazole polymer, an electron transport complex comprising the benzothiadiazole polymer, and a perovskite photoelectric device comprising the electron transport complex.
Background
Perovskite photoelectric materials have been developed rapidly in recent years, and they have excellent optical properties and electrical properties and can be used in a wet coating process, so they are used to manufacture perovskite photoelectric devices such as solar cells, light emitting diodes, or photodetectors, which are low in cost and highly functional.
Commonly used as the upper carrier transport material in perovskite optoelectronic devices are fullerene derivatives such as [6,6] -phenyl-C61-methyl butyrate { [6,6] -phenyl-C61-butyl acid methyl ester, PCBM }. However, PCBM is a small molecule material, which has poor film forming property for wet coating, often resulting in poor performance of the perovskite optoelectronic device due to leakage (shoot leakage), and may also be a cause of poor lifetime of the perovskite optoelectronic device, thus hindering the commercialization process.
CN 106449882A and CN 107994121A have disclosed improving the film forming properties of the upper carrier transport material by means of polymer doping of PCBM. However, in addition to improving film-forming properties, the role of the polymer is also important for matching the energy level of the fullerene derivative, which affects the conductivity of carriers and the electrical properties of the device. Generally, the energy of the Lowest Unoccupied Molecular Orbital (LUMO) of the doped polymer is closer to that of the fullerene derivative, which may otherwise cause the performance of the device to be low, and even charge accumulation due to energy barrier defects may adversely affect the lifetime of the device.
Therefore, how to design a polymer capable of being doped with a fullerene derivative to improve the film forming property of the fullerene derivative during wet coating, and simultaneously improve the energy level matching of the material, and improve the energy conversion efficiency (PCE) and stability of the perovskite photoelectric element is particularly important for the technical development and commercialization of the perovskite photoelectric element.
Disclosure of Invention
Accordingly, a first object of the present invention is to provide a benzothiadiazole polymer. The benzothiadiazole polymer is a copolymer, can improve the energy level matching with the fullerene derivative, and can be mixed with the fullerene derivative to form an electron transport compound. When the electron transport composite is used as an up-loading current transport material of the perovskite photoelectric element, the energy conversion efficiency (PCE) and the stability of the perovskite photoelectric element can be simultaneously improved.
Accordingly, the benzothiadiazole polymers of the present invention comprise repeating units represented by the following formula (I):
wherein the content of the first and second substances,
p and q are 0, 1 or 2 respectively;
X1and X2Are respectively H, F or Cl, and X1And X2At least one of them is F or Cl; and;
Ar1、Ar2and Ar3Respectively, arylene (arylene) or heteroarylene (heteroarylene).
Accordingly, a second object of the present invention is to provide an electron transport complex.
Thus, the electron transport complex of the present invention comprises the aforementioned benzothiadiazole polymer and fullerene derivative.
Accordingly, a third object of the present invention is to provide a perovskite photovoltaic element.
Thus, the perovskite photoelectric element of the present invention comprises the aforementioned electron transport compound.
The invention has the following effects: the benzothiadiazole polymer can control the chemical structure (Ar) of molecules in the copolymer1、Ar2、Ar3、X1And X2) To comeThe energy level of the material is properly adjusted, so that the material has better energy level matching with various fullerene derivatives.
In addition, the benzothiadiazole polymer of the present invention can obtain the required molecular ratio in the material synthesis stage, so compared with the prior art (CN 107994121A), the present invention can omit the step of mixing different polymers, which not only saves the complexity of the process, but also reduces the mismatching of the material distribution caused by the subsequent mixing.
Moreover, when the benzothiadiazole polymer and the fullerene derivative are mixed to form the electron transport compound, the upper carrier transport material prepared from the electron transport compound has better film forming property and energy level matching property, and meanwhile, the energy conversion efficiency (PCE) and the stability of the perovskite photoelectric element can be improved.
The present invention will be described in detail below:
[ benzothiadiazole Polymer ]
The benzothiadiazole polymer of the present invention comprises a repeating unit represented by the following formula (I):
wherein the content of the first and second substances,
p and q are 0, 1 or 2 respectively;
X1and X2Are respectively H, F or Cl, and X1And X2At least one of them is F or Cl; and;
Ar1、Ar2and Ar3Are each arylene or heteroarylene.
Preferably, p and q are each 0 or 1.
Preferably, Ar1Is composed of
Wherein the content of the first and second substances,
R1to R5Are respectively H,R6、-(CH2)n1OR7、-(CH2)n1SR8、
-(CH2)n1C(=O)OR9、-(CH2)n1Si(R10)3、-(CH2)n1N(CH3)2、
-(CH2)n1N+R11(CH3)2X-、-(CH2)n1N+H(CH3)2X-Or
-(C2H4O)n1R11;
R6To R10Are each unsubstituted or substituted by at least one R16Substituted C1~C40Straight-chain alkyl, unsubstituted or substituted by at least one R16Substituted C4~C40Branched alkyl, unsubstituted or substituted by at least one R16Substituted C4~C40Cyclic alkyl, unsubstituted or substituted by at least one R16Substituted C2~C40Alkenyl, or unsubstituted or substituted by at least one R16Substituted C2~C40An alkynyl group;
R11is methyl or ethyl;
x is Cl, Br or I;
R16is halogen, -CN, aryl, heteroaryl or-SiR17R18R19(ii) a And
R17to R19Are respectively C1~C40An alkyl group.
Still more preferably, R1And R2Are each R6. Still more preferably, R1And R2Are each unsubstituted or substituted by at least one R16Substituted C1~C40Straight-chain alkyl, unsubstituted or substituted by at least one R16Substituted C4~C40Branched alkyl, or unsubstituted or substituted by at least one R16Substituted C4~C40A cyclic alkyl group. Still more preferably, R1And R2Are each unsubstituted or substituted by at least one R16Substituted C1~C40A linear alkyl group. Still more preferably, R1And R2Each being unsubstituted C1~C40A linear alkyl group. Still more preferably, R1And R2Each being unsubstituted C1~C15A linear alkyl group. Still more preferably, R1And R2Each being unsubstituted C5~C13A linear alkyl group.
More preferably, Ar2And Ar3Are respectively asWherein n is2And n 31, 2 or 3 respectively; and R12To R15Are respectively H, F, Cl, Br, R6、-CN、-OR7、-SR8、-C(=O)OR9、-Si(R10)3Aryl or heteroaryl.
Still more preferably, R12And R13Are each H or R6. Still more preferably, R12And R13Are each H, unsubstituted or substituted by at least one R16Substituted C1~C40Straight-chain alkyl, unsubstituted or substituted by at least one R16Substituted C4~C40Branched alkyl, or unsubstituted or substituted by at least one R16Substituted C4~C40A cyclic alkyl group. Still more preferably, R12And R13Each is H, or unsubstituted or substituted by at least one R16Substituted C1~C40A linear alkyl group. Still more preferably, R12And R13Each is H or unsubstituted C1~C40A linear alkyl group. Still more preferably, R12And R13Each is H or unsubstituted C1~C11A linear alkyl group. Still more preferably, R12And R13Each is H or unsubstituted C3~C9A linear alkyl group.
[ Electron transport Compound ]
The electron transport compound comprises the benzothiadiazole polymer and the fullerene derivative.
Examples of fullerene derivatives include, but are not limited to, [6,6] -phenyl-C61-butyric acid methyl ester (PCBM), [6,6] -phenyl-C71-butyric acid methyl ester { [6,6] -phenyl-C71-butyl acid methyl ester, abbreviated PC71BM }, Bis [6,6] -phenyl-C62-butyric acid methyl ester { Bis (1- [3- (methoxycarboxyl) propyl ] -1-phenyl) - [6,6] C62, abbreviated Bis-PCBM }, indene-carbon sixty Bis adducts {1',1 ", 4', 4" -tetrahydro-di [1,4] methano-phthalate [5,6] fullerene-C60, abbreviated BA } or combinations thereof.
Preferably, the energy difference between the Lowest Unoccupied Molecular Orbital (LUMO) of the benzothiadiazole polymer and the Lowest Unoccupied Molecular Orbital (LUMO) of the fullerene derivative is less than 1.0 eV. More preferably, the energy difference between the Lowest Unoccupied Molecular Orbital (LUMO) of the benzothiadiazole polymer and the Lowest Unoccupied Molecular Orbital (LUMO) of the fullerene derivative is less than 0.4eV
Preferably, the diazosulfide polymer is 0.1-99 wt% based on 100 wt% of the total weight of the electron transport composite. More preferably, the diazosulfide polymer is 0.5-20 wt% based on 100 wt% of the total weight of the electron transport composite.
[ perovskite photoelectric element ]
The perovskite photoelectric element comprises the electron transport composite.
Preferably, the perovskite photoelectric element comprises a substrate, a lower electrode laminated on the substrate, a lower carrier transmission layer laminated on the lower electrode, a perovskite active layer laminated on the lower carrier transmission layer, an upper carrier transmission unit laminated on the perovskite active layer, and an upper electrode laminated on the upper carrier transmission unit, wherein the upper carrier transmission unit comprises the electron transmission composite.
Preferably, the upper carrier transport unit includes an upper carrier transport layer containing the electron transport compound.
Still more preferably, the upper carrier transport unit further comprises at least one upper carrier modification layer, the upper carrier transport layer is laminated on the perovskite active layer, the upper carrier modification layer is laminated on the upper carrier transport layer, and the upper electrode is laminated on the upper carrier modification layer.
More preferably, the thickness of the upper carrier transport layer is in the range of 0.1 to 200 nm. More preferably, the thickness of the upper carrier transport layer is in the range of 1 to 100 nm.
Drawings
Other features and effects of the present invention will become apparent from the following detailed description of the embodiments with reference to the accompanying drawings, in which:
FIG. 1 illustrates energy level diagrams of perovskites (Perovskite), PCBM, comparative example 1, and examples 1-2;
FIG. 2 is a schematic sectional view illustrating a first structure of a perovskite photovoltaic element according to the present invention;
FIG. 3 is a schematic sectional view illustrating a second structure of the perovskite photovoltaic element of the present invention; and
FIG. 4 is a graph illustrating the stability results of the perovskite photovoltaic devices of application examples 1-2 and comparative application examples 1-2 after continuous illumination for simulation.
Wherein the reference numerals are as follows:
1: substrate
2: lower electrode
3: lower carrier transport layer
4: perovskite active layer
5: upper carrier transfer unit
51: upper carrier transport layer
52: upper carrier modifying layer
6: upper electrode
Detailed Description
< comparative example 1>
Preparation of benzothiadiazole polymers
The benzothiadiazole polymer of comparative example 1 contained the repeating units shown below.
Comparative example 1
The benzothiadiazole polymer of comparative example 1 was prepared according to the following method.
A method for preparing compound 1:
fluorene (50g,300.8mmol) and N-bromosuccinimide (160.6g,902.4mmol) were dissolved in dimethylformamide (250mL) and heated to 50 ℃ and stirred for 6 hours. After the reaction was complete, the product was poured into ice water to precipitate a solid. After filtration, the product was washed with methanol and dried under vacuum to give Compound 1 as a white solid (83.7g, yield: 86%).
The preparation method of the compound 2 comprises the following steps:
compound 1(7.3g,22.5mmol) and 1-bromooctane (13.1g,67.5mmol) were dissolved in tetrahydrofuran. Subsequently, potassium tert-butoxide (12.6g.112.5mmol) was added thereto under ice bath and the mixture was allowed to react at room temperature for 1 hour. After the reaction is finished, the solution is neutralized by 1N hydrochloric acid aqueous solution, and then dichloromethane is added for extraction. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was removed by a rotary concentrator. Finally, purification was carried out by silica gel column chromatography (using n-heptane as a eluent) to obtain Compound 2(9.7g, yield: 79%) as a white solid.
A method for preparing compound 3:
after compound 2(9.6g,16.4mmol) was charged to a 250mL reaction flask, 100mL of anhydrous tetrahydrofuran was added and the temperature was reduced to-78 ℃. Next, a 2.5M n-butyllithium solution in n-hexane (22mL,54.1mmol) was added dropwise and maintained at-78 ℃ for 1 hour, and then trimethyl borate (17.0g,164mmol) was added dropwise. After the mixture was cooled to room temperature, 4N aqueous hydrochloric acid was added thereto and the mixture was stirred for 1 hour. After completion, water was added, and the mixture was extracted with n-heptane and dried over anhydrous magnesium sulfate. After filtration, the solvent was removed by concentration. The intermediate white solid is obtained by recrystallization and purification of tetrahydrofuran and n-heptane. The intermediate was then stirred overnight in a round bottom flask with pinacol (pinacol) (3.9g,32.8mmol) and toluene (100 mL). After the reaction was completed, anhydrous magnesium sulfate was added to dry, and the solvent was removed by concentration. The crude product was purified by recrystallization from toluene and methanol to give compound 3 as a white solid (4.5g, yield: 43%).
Comparative example 1
Preparation method of comparative example 1:
compound 3(500mg,0.78mmol), compound 4(229mg,0.78mmol), tris (2-furyl) phosphine (24mg,0.08mmol), Pd were added under nitrogen2(dba)3(20mg,0.02mmol)、K3PO4(1.65g,7.78mmol) and Aliquat336(1mL) were dissolved in a mixture of toluene (20mL) and water (4 mL). Then, the mixture was heated under reflux and stirred overnight. After the reaction is finished, cooling to room temperature, extracting with water and chloroform, and drying with anhydrous magnesium sulfate. After filtration, the solvent was removed by concentration. Chloroform and methanol are used for reprecipitation to separate out solid. Finally, the precipitate was collected and the solid was washed sequentially with methanol and acetone and dried under vacuum to obtain a comparativeExample 1(264mg, yield: 61%).
< example 1>
Preparation of benzothiadiazole polymers
The benzothiadiazole polymer of example 1 contains the repeating units shown below.
Example 1
The benzothiadiazole polymer of example 1 was prepared according to the following method.
Example 1
Preparation of example 1:
under nitrogen, compound 3(500mg,0.78mmol), compound 5(256mg,0.78mmol), tris (2-furyl) phosphine (24mg,0.08mmol), Pd2(dba)3(20mg,0.02mmol)、K3PO4(1.65g,7.78mmol) and Aliquat336(1mL) were dissolved in a mixture of toluene (20mL) and water (4 mL). Then, the mixture was heated under reflux and stirred overnight. After the reaction is finished, cooling to room temperature, extracting with water and chloroform, and drying with anhydrous magnesium sulfate. After filtration, the solvent was removed by concentration. Chloroform and methanol are used for reprecipitation to separate out solid. The precipitate was collected, and the solid was washed with methanol and acetone in this order and then dried in vacuo to give example 1(283mg, yield: 62%).
< example 2>
Preparation of benzothiadiazole polymers
The benzothiadiazole polymer of example 2 contains the repeating units shown below.
Example 2
The benzothiadiazole polymer of example 2 was prepared according to the following method.
A method for preparing compound 6:
3-Hexaalkylthiophene (10g,59mmol) was mixed with 150mL of anhydrous tetrahydrofuran in a round bottom flask. 2.5M n-butyllithium (26mL,65mmol) was added slowly at-10 ℃ and stirring continued for 1 h at-10 ℃. Next, trimethyltin chloride (15.4g,77mmol) was slowly added to the reaction and stirring was continued at 0 ℃ for 30 minutes. After returning to room temperature, heptane and deionized water were added and extracted three times. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated and dried by a rotary concentrator to obtain Compound 6(19.6g, yield: 99%) as a yellow liquid.
Compound 7
A method for preparing compound 7:
compound 5(8.5.g,25mmol), compound 6(19.6g,59mmol), tris (2-furyl) phosphine (840mg,2.7mmol) and Pd2(dba)3(710mg,0.7mmol) was added to a round-bottomed flask. Then 85mL of toluene was added and the mixture was stirred at 50 ℃ for 3 hours under nitrogen. After cooling, the toluene was removed using a rotary concentrator and purified by silica gel tube chromatography (petroleum ether/dichloromethane). Finally, after drying in vacuo, Compound 7 was obtained as an orange solid (8.85g, yield: 68%).
Compound 8
A method for preparing compound 8:
after compound 7(8.85g,17.6mmol) was added to a 100mL round-bottomed flask, 90mL of tetrahydrofuran was added. NBS (7,45g,41.9mmol) was added stepwise under exclusion of light, followed by heating to 55 ℃ and stirring for 1 hour. After the reaction was completed, the solvent was removed by a rotary thickener, and then purified by silica gel tube chromatography (petroleum ether/dichloromethane). Finally, vacuum drying gave Compound 8 as an orange solid (8.65g, yield: 74%).
Example 2
Preparation of example 2:
under nitrogen, compound 3(486mg,0.75mmol), compound 8(500mg,0.76mmol), tris (2-furyl) phosphine (24mg,0.08mmol), Pd2(dba)3(17mg,0.018mmol)、K3PO4(1.65g,7.78mmol) and Aliquat336(1mL) were dissolved in a mixture of toluene (15mL) and water (3 mL). Then, the mixture was heated under reflux and stirred overnight. After the reaction is finished, cooling to room temperature, extracting with water and chloroform, and drying with anhydrous magnesium sulfate. After filtration, the solvent was removed by concentration. Chloroform and methanol are used for reprecipitation to separate out solid. The precipitate was collected, and after the solid was washed with methanol and acetone in this order, it was dried in vacuo to give example 2(500mg, yield: 72%).
< level of matching between comparative example 1 and examples 1 to 2>
The energy levels of the materials of comparative example 1, example 1 and example 2 were determined by first determining the Highest Occupied Molecular Orbital (HOMO) of the material by cyclic voltammetry, and then determining the energy gap (bandgap) of the material by uv-vis spectroscopy, and calculating the LUMO of the material. FIG. 1 is a graph showing energy levels of Perovskite (Perovskite), PCBM, comparative example 1, and examples 1 to 2.
Referring to FIG. 1, the LUMO of examples 1 and 2 are-3.53 eV and-3.86 eV, respectively. Compared with comparative example 1(-3.42eV), examples 1 and 2 are closer to PCBM and the LUMO (-3.90eV) of the perovskite active layer, thereby being beneficial to reducing energy barrier defects of the material interface.
< perovskite photovoltaic device Structure >
Referring to fig. 2, a first structure of the perovskite photoelectric device of the present invention includes a substrate 1, a lower electrode 2 laminated on the substrate 1, a lower carrier transport layer 3 laminated on the lower electrode 2, a perovskite active layer 4 laminated on the lower carrier transport layer 3, an upper carrier transport unit 5 laminated on the perovskite active layer 4, and an upper electrode 6 laminated on the upper carrier transport unit 5. The upper carrier transport unit 5 includes an upper carrier transport layer 51.
Referring to fig. 3, the second structure of the perovskite photoelectric device of the present invention includes a substrate 1, a lower electrode 2 laminated on the substrate 1, a lower carrier transport layer 3 laminated on the lower electrode 2, a perovskite active layer 4 laminated on the lower carrier transport layer 3, an upper carrier transport unit 5 laminated on the perovskite active layer 4, and an upper electrode 6 laminated on the upper carrier transport unit 5. The upper carrier transport unit 5 includes an upper carrier transport layer 51 and an upper carrier modifying layer 52. The upper carrier transport layer 51 is laminated on the perovskite active layer 4, the upper carrier modifying layer 52 is laminated on the upper carrier transport layer 51, and the upper electrode 6 is laminated on the upper carrier modifying layer 52.
< comparative application examples 1 to 2 and application examples 1 to 2>
Preparation of perovskite photoelectric element
Perovskite photoelectric elements (structures shown in fig. 3) of comparative application examples 1 to 2 and application examples 1 to 2 were prepared according to the benzothiadiazole polymer contained in the electron transport compound (as an upper carrier transport material) shown in table 1 below and the following method.
TABLE 1
An Indium Tin Oxide (ITO) glass substrate (12 Ω/□) was cleaned by ultrasonic vibration using a cleaner, deionized water, acetone, and isopropyl alcohol in sequence for 15 minutes, and then the surface of the substrate was cleaned with a UV ozone cleaner for 30 minutes. Wherein, the glass substrate is the substrate 1, and Indium Tin Oxide (ITO) is the lower electrode 2.
Poly [ bis (4-phenyl) (2,4,6-trimethylphenyl) amine ] { poly [ bis (4-phenyl) (2,4,6-trimethylphenyl) amine ], PTAA } was mixed with the solvent toluene to form a solution having a solid content of 1.5% by weight. The solution is coated on the lower electrode 2 and baked at 100-120 ℃ for 10-30 minutes to form a lower carrier transport layer 3 with a thickness of about 10 nm.
The perovskite raw material component HC (NH)2)2I、CsI、PbI2、PbBr2The perovskite precursor solution was mixed with DMF/DMSO (9:1v/v) as a solvent in a molar ratio of 0.83:0.17:0.85:0.15 to form a 49 wt% solids solution. Coating the perovskite precursor solution on the lower carrier transport layer 3, removing the solvent by using a vacuum decompression method, and baking at 100-110 ℃ for 30-60 minutes to form the perovskite active layer 4 with the thickness of about 400 nm.
An electron transport complex (comprising benzothiadiazole polymer and PCBM) was mixed with chlorobenzene, a solvent, according to the benzothiadiazole polymer shown in table 1, to form a solution with a solids content of 2.5 wt%. Wherein the diazosulfide polymer is 5 wt% based on 100 wt% of the total weight of the electron transport composite. The solution is coated on the perovskite active layer 4 and baked at 80-100 ℃ for 10 minutes to form an upper carrier transport layer 51 with a thickness of about 50 nm.
PEI was mixed with the solvent dibutanol to form a solution with a solids content of 0.05% by weight. The solution is coated on the upper carrier transport layer 51 and baked at 90-100 ℃ for 6 minutes to form an upper carrier modification layer 52 with a thickness of about 2 nm.
Firstly, the obtained sample is sent into a vacuum cavity and then is put in a vacuum cavity with the volume of 1.0 multiplied by 10-6Silver metal was deposited under a torr to form an upper electrode 6 having a thickness of about 100nm, thereby obtaining a perovskite photoelectric element.
< analysis of energy conversion efficiency (PCE) of perovskite photovoltaic element >
The working area of the perovskite photovoltaic element is defined as 0.04cm by a metal mask2。KThe eitley 2400 as the power supply, controlled by Lab-View program, at a light intensity of 100mW/cm2The electrical properties of the perovskite photoelectric element were measured under irradiation of simulated AM1.5G sunlight (SAN-EI XES-40S3), and recorded by a computer program to obtain current-voltage characteristic parameters.
Electron transport composites used in perovskite photoelectric devices of application examples 1 to 2 and comparative application examples 1 to 2, and open circuit voltage (V) obtained from the results of the electrical analysisoc) Short-circuit current (short-circuit current; j. the design is a squaresc) Fill factor (fill factor; FF) and energy conversion efficiency (PCE) are collated in table 2 below, respectively. It should be noted that the fill factor FF is considered to be related to the interface defect of the element, and generally, the fewer the defects, the less the carrier transfer is, and the higher the FF value is.
TABLE 2
As can be seen from table 2, compared to the perovskite photoelectric element (comparative application example 1) in which the electron transport compound does not contain any polymer and the perovskite photoelectric element (comparative application example 2) in which the electron transport compound contains the benzothiadiazole polymer of comparative example 1 and PCBM, the perovskite photoelectric element (application examples 1 to 2) in which the electron transport compound contains the benzothiadiazole polymer of the present invention and PCBM has higher energy conversion efficiency (PCE).
Specifically, the fill factors FF of application examples 1 to 2 are significantly increased (increase by about 15 to 20%) compared to the fill factor FF of comparative application example 2, which shows that the energy barrier defects at the material interface are reduced, thereby contributing to the improvement of the carrier transport capability. The foregoing results fully demonstrate that an electron transport composite comprising the benzothiadiazole polymer of the present invention and PCBM is more suitable as an up-loading current transport material for perovskite optoelectronic devices.
< continuous irradiation stability test of perovskite photovoltaic element >
Continuous illumination of the perovskite photoelectric elements of the application examples 1-2 and the comparative application examples 1-2 is used for simulating the actual application condition, and the test result is shown in figure 4.
As can be seen from fig. 4, compared to the perovskite photoelectric device without any polymer in the electron transport composite (comparative application example 1) and the device with the electron transport composite including the perovskite photoelectric device with the benzothiadiazole polymer and the PCBM (comparative application example 2), the perovskite photoelectric devices with the electron transport composite including the benzothiadiazole polymer and the PCBM (application examples 1 to 2) have more stable energy conversion efficiency (PCE).
The foregoing is because the electron transport composite comprising the benzothiadiazole polymer of the present invention and the fullerene derivative has excellent film-forming properties, and compared with the benzothiadiazole polymer of comparative example 1, the benzothiadiazole polymer of the present invention has a better matching energy level characteristic with the fullerene derivative, thereby being beneficial to reducing the defect of material energy barrier and contributing to improving the service life of the device.
In summary, the benzothiadiazole polymer of the present invention can be obtained by controlling the chemical structure (Ar) of the molecule in the copolymer1、Ar2、Ar3、X1And X2) The energy level of the material is properly adjusted to have better energy level matching with various fullerene derivatives. In addition, the benzothiadiazole polymer of the present invention can obtain the required molecular proportion in the material synthesis stage, so compared with the prior art, the present invention can omit the step of mixing different polymers, thereby not only saving the complexity of the process, but also reducing the doubtful worry of non-uniform material distribution caused by the subsequent mixing. Moreover, when the benzothiadiazole polymer and the fullerene derivative are mixed to form the electron transport composite, the upper carrier transport material prepared from the electron transport composite has better film forming property and energy level matching property, and can improve the energy conversion efficiency (PCE) and stability of the perovskite photoelectric element, so that the purpose of the invention can be achieved.
However, the above description is only an example of the present invention, and the scope of the present invention should not be limited thereby, and all simple equivalent changes and modifications made according to the claims and the contents of the patent specification are still included in the scope of the present invention.
Claims (12)
1. A benzothiadiazole polymer comprising a repeating unit represented by the following formula (I):
Wherein the content of the first and second substances,
p and q are 0, 1 or 2 respectively;
X1and X2Are respectively H, F or Cl, and X1And X2At least one of them is F or Cl; and
Ar1、Ar2and Ar3Are arylene or heteroarylene, respectively.
2. The benzothiadiazole polymer of claim 1, wherein Ar is Ar1Is composed of
Wherein the content of the first and second substances,
R1to R5Are respectively H, R6、-(CH2)n1OR7、-(CH2)n1SR8、-(CH2)n1C(=O)OR9、-(CH2)n1Si(R10)3、-(CH2)n1N(CH3)2、-(CH2)n1N+R11(CH3)2X-、-(CH2)n1N+H(CH3)2X-Or- (C)2H4O)n1R11;
R6To R10Are each unsubstituted or substituted by at least one R16Substituted C1~C40Straight-chain alkyl, unsubstituted or substituted by at least one R16Substituted C4~C40Branched chainAlkyl, unsubstituted or substituted by at least one R16Substituted C4~C40Cyclic alkyl, unsubstituted or substituted by at least one R16Substituted C2~C40Alkenyl, or unsubstituted or substituted by at least one R16Substituted C2~C40An alkynyl group;
R11is methyl or ethyl;
n11 to 8;
x is Cl, Br or I;
R16is halogen, -CN, aryl, heteroaryl or-SiR17R18R19(ii) a And
R17to R19Are respectively C1~C40An alkyl group.
5. An electron transport complex comprising the benzothiadiazole polymer of claim 1 and a fullerene derivative.
6. The electron transport complex of claim 5, wherein the energy difference between the lowest unoccupied molecular orbital of the benzothiadiazole polymer and the lowest unoccupied molecular orbital of the fullerene derivative is less than 1.0 eV.
7. The electron transport composite of claim 5, wherein the benzothiadiazole polymer is present in an amount ranging from 0.1 to 99 wt%, based on 100 wt% of the total weight of the electron transport composite.
8. A perovskite photovoltaic element comprising the electron transport composite of claim 5.
9. The perovskite optoelectronic device as claimed in claim 8, wherein the perovskite optoelectronic device comprises a substrate, a lower electrode laminated on the substrate, a lower carrier transport layer laminated on the lower electrode, a perovskite active layer laminated on the lower carrier transport layer, an upper carrier transport unit laminated on the perovskite active layer, and an upper electrode laminated on the upper carrier transport unit, wherein the upper carrier transport unit comprises the electron transport composite.
10. The perovskite photovoltaic element of claim 9, wherein the upper carrier transport unit comprises an upper carrier transport layer comprising the electron transport composite.
11. The perovskite photovoltaic device of claim 10, wherein the upper current carrier transport unit further comprises at least one upper current carrier modification layer, the upper current carrier transport layer being laminated on the perovskite active layer, the upper current carrier modification layer being laminated on the upper current carrier transport layer, and the upper electrode being laminated on the upper current carrier modification layer.
12. The perovskite photovoltaic element according to claim 10, wherein the upper carrier transport layer has a thickness in a range of 0.1 to 200 nm.
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