CN113527641A - Polymer material based on ester side chain substituted quinoxaline derivative and application thereof - Google Patents
Polymer material based on ester side chain substituted quinoxaline derivative and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of organic photovoltaic solar cells, and particularly relates to a quinoxaline derivative polymer material based on ester side chain substitution and an application thereof. The quinoxaline derivative substituted by the ester side chain has simple synthetic route, high yield and good stability; the introduction of the ester side chain can effectively increase the solubility of the material, reduce the highest occupied molecular orbital energy level, broaden the absorption, ensure the good phase separation of the active layer and simultaneously achieve the effects of improving the open-circuit voltage, the short-circuit current and the filling factor of the polymer solar cell. The polymer material is used as an electron donor, Y6 is used as an electron acceptor, and the energy conversion efficiency of the solution processing type polymer solar cell reaches 15.80%. The invention proves that the ester side chain quinoxaline derivative polymer can effectively improve the photovoltaic performance of the polymer solar cell, and realizes the high-efficiency energy conversion of the polymer material constructed by the side chain ester group substituted quinoxaline derivative in the polymer solar cell.
Description
Technical Field
The invention belongs to the field of Polymer Solar Cells (PSCs), and particularly relates to a polymer material based on ester side chain substituted quinoxaline derivatives and application thereof. Grafting an esterthiophene or an esterbenzene side chain on the quinoxaline conjugated side chain, and polymerizing the esterthiophene or the esterbenzene side chain with a benzodithiophene derivative as a receptor unit to obtain a D-A type conjugated polymer material; and the material and a non-fullerene small molecule acceptor material are used for preparing a photoactive layer, and the photoactive layer is applied to the research of polymer solar cell devices.
Background
Since the industrial revolution, the use of fossil energy has made great progress in human society, but it also causes problems such as environmental pollution and energy crisis. Solar energy is an inexhaustible clean energy which becomes an important choice of novel energy. Organic Solar Cells (OSCs) have the unique advantages of low preparation cost of organic materials, solution processing operation, realization of large-area manufacturing by reel-to-reel solution processing and the like, and become a hotspot for research and development and application of new energy resources in various countries in the world.
Compared to silicon-based solar cells, bulk heterojunction organic solar cells have their own unique advantages: 1) the organic material has low preparation cost and easy molecular modification of functions and structures; 2) the solution processing operation can be carried out, and light, flexible and semitransparent solar cell devices can be prepared; 3) and large-area printing and manufacturing are easy to realize. Based on the above characteristics, organic solar cells have been rapidly developed on a global scale. In bulk heterojunction organic solar cells, photoactive layers with excellent performance are key materials for obtaining high-efficiency organic solar cells. With the continuous innovation of polymer molecular structure design and the optimization of device preparation technology, the efficiency of the organic solar photovoltaic device is continuously refreshed. However, based on the high-efficiency polymer donor materials, the molecular structures of the materials have few modifiable sites, and the materials are difficult to synthesize and high in cost; particularly, the preparation process of the laminated device is complex and has poor repeatability. Therefore, the development of efficient polymer donor materials with simple molecular structure, easily modified molecules and low cost is still the focus of research in the field.
The quinoxaline derivative is a C ═ N heterocyclic molecule, is composed of two imine nitrogen atom rings consisting of two fused six-membered rings (benzene and pyrazine), is synthesized by a simple polycondensation method (Macromolecules,1993,26, 3464-; secondly, the quinoxaline unit has a quinoid resonance structure, and the quinoxaline unit has good stability in air due to the characteristic; finally, quinoxaline units can be modified at multiple sites, and various substituents can be easily introduced at multiple sites to finely adjust the solubility, aggregation tendency, energy level and other properties of the polymer (Macromolecules 2018,51, 2838-19146; mater. chem. front.2021,5, 1906-1916). Obviously, the branch engineering of quinoxaline is taken as an important modification strategy, and has a great influence on the molecular photoelectric property of the polymer derivative, at present, most of conjugated side chain groups based on the quinoxaline derivative are concentrated on alkyl, alkoxy, alkylthio and halogen atom groups, and the quinoxaline derivative copolymer containing ester side chain thiophene and ester side chain benzene is not reported.
Disclosure of Invention
Aiming at the problem of few types of the prior high-performance polymer donor materials, the invention provides a novel polymer photovoltaic donor material containing ester group thiophene and ester group benzene side chain substituted quinoxaline derivatives. The molecular construction characteristics of the material are as follows: the side chain ester substituted quinoxaline derivative has the advantages of simple synthetic route, high yield, low cost and good stability; due to the introduction of the ester side chain, the solubility of the material can be effectively increased, the HOMO energy level can be reduced, the absorption can be broadened, the active layer can be ensured to have good phase separation, and the effects of simultaneously improving the open-circuit voltage, the short-circuit current and the filling factor of the polymer solar cell can be achieved. The quinoxaline derivative polymer is used as a donor material, small molecules with matched energy levels are selected as an acceptor material, and a polymer non-fullerene solar cell device is prepared under the solution processing condition, so that the high-efficiency photoelectric conversion of the quinoxaline derivative polymer is realized.
The invention aims to provide a novel polymer donor material with high mobility, simple structure, good solubility and good film forming property, and a high-efficiency organic solar cell is obtained through simple solution processing. The material has strong and wide absorption in the range of 300-800nm and has lower highest occupied molecular orbital energy level (HOMO). The PSCs photovoltaic devices are prepared by blending with a non-fullerene receptor Y6 and solution processing, and a high-efficiency PCE value of 15.8% is obtained.
The conjugated polymer based on the ester group thiophene and the ester group benzene side chain substituted quinoxaline derivative has a molecular structure shown in formula I
Wherein R is1Independently selected from C8～C24One of alkyl groups; x is independently selected from one of H, F and Cl groups; y is independently selected from one of O, S and Se atoms;
the D unit is one of the following groups;
in the formula II, R2Independently selected from C8～C24One of alkyl groups; z is independently selected from H, F, Cl, OCH3,SCH3One of the groups; w is independently selected from one of C, Si and Ge atoms.
The constructed polymer derivative material is one of molecular structures shown in a formula III.
In the formula III, R2Independently selected from C8～C24One of alkyl groups; z is independently selected from H, F, Cl, OCH3,SCH3One of the groups.
The preferred molecular structure of the D-A type polymer donor material may be any of the following molecular structures.
Bis (2-butyloctyl) 5,5'- (5, 8-bis (5-bromothiophene-2-yl) -6, 7-difluoroquinoxaline-2, 3-diyl) bis (thiophene-2-carboxylate) (DFQxTA) is used as an electron-withdrawing unit, and 4, 8-bis (5- (ethylhexylthio) thienyl) benzo [1,2-b:4,5-b' ] dithienyl) bis (trimethyltin) (BDTTSn) is used as an electron-donating unit, so that the polymer donor material PBDTTS-DFQxTA with the D-A structure is constructed.
Polymer one: PBDTTS-DFQxTA
Bis (2-butyloctyl) 4,4'- (5, 8-bis (5-bromothiophene-2-yl) -6, 7-difluoroquinoxaline-2, 3-diyl) dibenzoate (DFQxBA) is used as an electron-withdrawing unit, and (4, 8-bis (5- (ethylhexylthio) thienyl) benzo [1,2-b:4,5-b' ] dithienyl) bis (trimethyltin) (BDTSn) is used as an electron-donating unit, so that the polymer donor material PBDTTS-DFQxBA with a D-A structure is constructed.
Polymer II: PBDTTS-DFQxBA
Synthesis of acceptor unit bis (2-butyloctyl) 5,5' - (5, 8-bis (5-bromothien-2-yl) -6, 7-difluoroquinoxaline-2, 3-diyl) bis (thiophene-2-carboxylate) (DFQxTA): 5-bromo-2-carboxythiophene is used as an initial raw material, esterification reaction is carried out to obtain 5-bromothiophene-2-carboxylic acid 2-ethylhexyl ester (SM1), a compound SM1 and oxalyl chloride react to obtain a compound bis (2-butyloctyl) 5,5 '-oxalyl bis (thiophene-2-carboxylate) (SM3), a compound SM3 and 3, 6-dibromo-4, 5-difluorobenzene-1, 2-diamine react to obtain bis (2-butyloctyl) 5,5' - (5, 8-dibromo-6, 7-difluoroquinoxaline-2, 3-diyl) bis (thiophene-2-carboxylate) (SM5) through ring closure reaction, a compound SM5 and 2-tributylstanniocentene react to obtain an intermediate bis (2-butyloctyl) 5 through still coupling reaction, 5' - (6, 7-difluoro-5, 8-bis (thien-2-yl) quinoxaline-2, 3-diyl) bis (thiophene-2-carboxylate) (SM 7). Dichloromethane and DMF are used as solvents, compounds SM7 and NBS are used as raw materials, the raw materials react for 2 hours in ice-water bath under the condition of keeping out of the sun, and then the raw materials are moved to normal temperature to react overnight to obtain bis (2-butyl octyl) 5,5' - (5, 8-bis (5-bromothiophene-2-yl) -6, 7-difluoro quinoxaline-2, 3-diyl) bis (thiophene-2-carboxylate) (DFQxTA).
Synthesis of the acceptor unit bis (2-butyloctyl) 4,4' - (5, 8-bis (5-bromothien-2-yl) -6, 7-difluoroquinoxaline-2, 3-diyl) dibenzoate (DFQxBA): p-iodobenzoic acid is taken as an initial raw material, esterification reaction is carried out to obtain 2-ethylhexyl 4-iodobenzoate (SM2), a compound SM2 and oxalyl chloride react through Grignard reaction to obtain a compound bis (2-butyloctyl) -4,4' -oxalyl dibenzoate (SM4), a compound SM4 and 3, 6-dibromobenzene-1, 2-diamine (1) react through Schiff base reaction to obtain bis (2-butyloctyl) 5,5' - (5, 8-dibromo-6, 7-difluoroquinoxaline-2, 3-diyl) bis (thiophene-2-carboxylate) (SM6), a compound SM6 and 2-tributyltin thiophene, and a classical still coupling reaction is carried out to obtain an intermediate bis (2-butyloctyl) 5,5' - (6, 7-difluoro-5, 8-bis (thien-2-yl) quinoxaline-2, 3-diyl) bis (thiophene-2-carboxylate) (SM 8). THF and DMF are used as solvents, compounds SM8 and NBS are used as raw materials, the raw materials are firstly reacted for 2 hours in an ice-water bath and then moved to normal temperature for reaction overnight, and a bis (2-butyloctyl) 4,4' - (5, 8-bis (5-bromothiophene-2-yl) -6, 7-difluoroquinoxaline-2, 3-diyl) dibenzoate (DFQxBA) receptor unit (DFQxBA) is obtained.
Synthesis of D-A type Polymer Donor Material PBDTTS-DFQxTA: the monomer DFQxTA (M1) and (4, 8-bis (5- (ethylhexylthio) thienyl) benzo [1,2-b:4,5-b' ] dithienyl) bis (trimethyltin) (BDTTSn) are synthesized to obtain a crude product PBDTTS-DFQxTA through classical still polymerization reaction, the crude product is subjected to chromatographic grade methanol sedimentation and Soxhlet extraction (methanol-acetone-n-hexane-dichloromethane-trichloromethane are adopted in sequence), and the crude product is purified and concentrated by column chromatography, then is subjected to chromatographic grade methanol sedimentation, filtered and dried to obtain a pure polymer PBDTTS-DFQxTA polymer product.
Synthesis of D-A type Polymer Donor Material PBDTTS-DFQxBA: the monomer DFQxBA (M2) and (4, 8-bis (5- (ethylhexylthio) thienyl) benzo [1,2-b:4,5-b' ] dithienyl) bis (trimethyltin) (BDTTSn) are synthesized to obtain a crude product PBDTTS-DFQxBA through classical still polymerization, the crude product is subjected to chromatographic grade methanol sedimentation and Soxhlet extraction (methanol-acetone-n-hexane-dichloromethane-trichloromethane are adopted in sequence), and the crude product is purified and concentrated by column chromatography, and then is subjected to chromatographic grade methanol sedimentation, filtration and drying to obtain a pure PBDTTS-DFQxBA polymer product.
The application of the invention is that: the organic polymer donor material which is designed and developed is used as an active layer donor material and is blended with a non-fullerene acceptor material Y6 in different proportions to manufacture a polymer solar cell device, so that high-efficiency photoelectric conversion efficiency is obtained. The molecular structure of Y6 is shown by the following formula:
the organic polymer solar cell device comprises an Indium Tin Oxide (ITO) conductive glass anode, an anode modification layer, an active layer and a cathode. Wherein the anode modification layer is PEDOT, PSS; the cathode is a deposited layer of PDINO (5nm)/Al (100 nm); the active layer material is the polymer donor material and Y6, and the blending mass ratio of the polymer donor material to the Y6 is 1: 1.
Compared with most of reported acceptor units, the novel acceptor electron-withdrawing unit derivative has the following characteristics: (1) compared with a quinoxaline receptor unit substituted by an alkyl side chain with an electron donating property, the receptor unit has stronger electron withdrawing property, so that Intramolecular Charge Transfer (ICT) is stronger and absorption is better; (2) the acceptor unit adopts an ester alkyl chain with electron-withdrawing capability, which is favorable for reducing the HOMO energy level of the polymer, thereby being favorable for obtaining high V of the deviceoc(ii) a (3) The acceptor unit can select alkyl chains with different lengths to adjust the solubility of the polymer and the molecular packing; (4) the ester alkyl chain with electron withdrawing can induce the nonpolar bonding effect in the chain and among the chains, and is beneficial to forming an ideal active layer shape, thereby improving the PCE of the device; (4) in addition, the non-covalent interaction of fluorine atoms and hydrogen atoms or sulfur atoms, such as F.H.F.S, is beneficial to improving the charge mobility of the polymer, and (5) different donor units are selected, so that the spectral absorption and HOMO and LUOMO energy levels can be effectively adjusted. Therefore, the material is a polymer donor material with great development prospect and application potential.
Drawings
FIG. 1 is a diagram showing the UV-VIS absorption spectrum of the PBDTTS-DFQxTA chloroform solution of the present invention;
FIG. 2 is a UV-VISIBLE absorption spectrum of a PBDTTS-DFQxTA solid film of the present invention;
FIG. 3 is a cyclic voltammogram of a PBDTTS-DFQxTA solid film of the present invention;
FIG. 4 is a J-V curve of a PBDTTS-DFQxTA polymer solar cell device of the present invention;
FIG. 5 is an EQE curve of the PBDTTS-DFQxTA polymer solar cell device of the present invention;
FIG. 6 is a graph of hole mobility for PBDTTS-DFQxTA polymers of the present invention;
FIG. 7 is a UV-VISIBLE absorption spectrum of a PBDTTS-DFQxBA chloroform solution of the present invention;
FIG. 8 is a UV-VISIBLE absorption spectrum of a PBDTTS-DFQxBA solid film of the present invention;
FIG. 9 is a cyclic voltammogram of a PBDTTS-DFQxBA solid film of the present invention;
FIG. 10 is a J-V curve of a PBDTTS-DFQxBA polymer solar cell device of the present invention;
FIG. 11 is an EQE curve of the PBDTTS-DFQxBA polymer solar cell device of the present invention;
FIG. 12 is a graph showing hole mobility curves of PBDTTS-DFQxBA polymers of the present invention.
Detailed Description
The invention is further illustrated by the following specific examples, which are not intended to limit the scope of the invention in any way.
Example 1
Synthesis of acceptor units bis (2-butyloctyl) 5,5'- (5, 8-bis (5-bromothien-2-yl) -6, 7-difluoroquinoxaline-2, 3-diyl) bis (thiophene-2-carboxylate) (DFQxTA) and bis (2-butyloctyl) 4,4' - (5, 8-bis (5-bromothien-2-yl) -6, 7-difluoroquinoxaline-2, 3-diyl) dibenzoate (DFQxBA). The synthetic routes for DFQxTA and DFQxBA are as follows:
1.1.5 Synthesis of 2-ethylhexyl bromothiophene-2-carboxylate (SM1)
In a 250mL three-necked flask, 5-bromo-2-carboxythiophene (8.28g,40mmol), 1- (3-dimethylamino) were added in sequencePropyl) -3-ethylcarbodiimide hydrochloride (8.43g,44mmol), 4-dimethylaminopyridine (1.46g,12mmol), 2-butyl-1-n-octanol (8.18g,44mmol) and anhydrous 120mL of dichloromethane were reacted under nitrogen at room temperature for 48 h. The reaction was stopped, the reaction was poured into 120mL of water, extracted 3 times with dichloromethane (3 × 25mL), dried over anhydrous magnesium sulfate, filtered, and the low boiling point organic solvent was removed by rotary column chromatography, and the residue was subjected to column chromatography using PE: DCM (V/V ═ 10:1) as an eluent, to give 12.12g of a colorless liquid with a yield of 95%.1H NMR(400MHz,CDCl3)δ7.56(d,J＝3.9Hz,1H),7.09(d,J＝4.0Hz,1H),4.20(d,2H),1.74(m,1H),1.41-1.26(m,16H),0.91-0.88(m,6H).
Synthesis of 2-ethylhexyl 1.2.4-iodobenzoate (SM2)
The procedure for the synthesis of compound SM2 was the same as that for the synthesis of compound SM1, except that compound 5-bromothiophene-2-carboxylic acid was replaced with compound 4-iodobenzoic acid to give product SM2 as a colorless liquid (93% yield).1H NMR(400MHz,CDCl3)δ8.19(d,J＝8.4Hz,2H),8.07(d,J＝8.4Hz,2H),4.29(d,J＝5.7Hz,2H),1.88-1.72(m,1H),1.50-1.21(m,16H),0.93-0.88(m,6H).
1.3. Synthesis of bis (2-butyloctyl) 5,5' -oxalyl bis (thiophene-2-carboxylate) (SM3)
Under the protection of nitrogen, a compound SM1(9.57g,30mmol) and 50mL of anhydrous THF are sequentially added into a 250mL three-necked flask, the flask is moved to-78 ℃ and stirred for 30min, isopropyl magnesium chloride lithium chloride complex (23.07mL,30mmol) is slowly dripped into a reaction system from a constant-pressure dropping funnel, the reaction is carried out for 2h at-78 ℃, a mixed solution of 40mL of THF containing LiBr (5.2g,60mmol) and CuBr (4.3g,30mmol) is continuously dripped into the reaction system from the constant-pressure dropping funnel, and the reaction is continuously carried out for 30min at-78 ℃. Oxalyl chloride (1.71g,13.5mmol) was added dropwise thereto, and after reacting at this temperature for 1 hour, the reaction mixture was allowed to warm to room temperature for 12 hours. After quenching with water, the reaction mixture was poured into 100mL of water, extracted 3 times with dichloromethane (3 × 30mL), dried over anhydrous magnesium sulfate, filtered, and the low boiling point organic solvent was removed by rotation, and the residue was separated by column chromatography using PE: DCM (V/V ═ 8:1) as an eluent, to give 2.23g of a yellow viscous liquid with a yield of 25.2%.1H NMR(400MHz,CDCl3)δ8.08(d,J＝4.1Hz,1H),7.83(d,J＝4.1Hz,1H),4.27(d,J＝5.6Hz,2H),1.83–1.74(m,1H),1.48–1.25(m,16H),0.97–0.86(m,6H).
1.4. Synthesis of bis (2-butyloctyl) -4,4' -oxalyl dibenzoate (SM4)
The procedure for the synthesis of compound SM4 was the same as that for the synthesis of compound SM3, except that compound SM1 was changed to compound SM2, to give a yellow viscous liquid (yield 28.5%).1H NMR(400MHz,CDCl3)δ8.07(d,J＝8.3Hz,2H),7.73(d,J＝8.3Hz,2H),4.27(d,J＝5.6Hz,2H),1.85–1.76(m,1H),1.49–1.28(m,16H),0.97–0.84(m,6H).
1.1. Synthesis of bis (2-butyloctyl) 5,5' - (5, 8-dibromo-6, 7-difluoroquinoxaline-2, 3-diyl) bis (thiophene-2-carboxylate) (SM5)
The commercial compounds 3, 6-dibromo-4, 5-difluorobenzene-1, 2-diamine and the compound SM3(1.37g,2.32mmol) were added to a 100mL three-necked flask and reacted at 120 ℃ for 24h under nitrogen. The reaction was stopped, cooled to room temperature, extracted with dichloromethane (3 × 25mL), dried over anhydrous magnesium sulfate, filtered, the low boiling organic solvent was removed, and the residue was separated by column chromatography using PE: DCM (V/V ═ 4:1) as eluent to give 1.45g of a yellow viscous liquid with a yield of 68.5%.1H NMR(400MHz,CDCl3)δ7.71(d,J＝3.0Hz,1H),7.40(d,J＝3.3Hz,1H),4.27(d,J＝5.2Hz,2H),1.81(m,1H),1.49–1.28(m,16H),0.93–0.88(m,6H).
1.5. Synthesis of bis (2-butyloctyl) 4,4' - (5, 8-dibromo-6, 7-difluoroquinoxaline-2, 3-diyl) dibenzoate (SM6)
The procedure for the synthesis of compound SM6 was the same as that for the synthesis of compound SM5, except that compound SM3 was changed to compound SM4, to give a yellow viscous liquid (yield 65.3%).1H NMR(400MHz,CDCl3)δ7.82(d,J＝8.5Hz,2H),7.75(d,J＝8.5Hz,2H),4.23(d,J＝5.7Hz,2H),1.83–1.74(m,1H),1.45–1.21(m,8H),0.91-0.87(m,6H).
1.6. Synthesis of bis (2-butyloctyl) 5,5' - (6, 7-difluoro-5, 8-di (thien-2-yl) quinoxaline-2, 3-diyl) bis (thiophene-2-carboxylate) (SM7)
Under the protection of nitrogen, the compound SM5(1.45g,1.59mmol), 2-tributyltin thiophene (1.26g,3.33mmol) and methyl are added into a 100mL three-necked bottle in sequenceBenzene (50mL), tris (dibenzylideneacetone) dipalladium (37.33mg,0.04mmol), tris (o-methylphenyl) phosphine (49.3mg,0.16mmol) were reacted at 110 ℃ for 12 hours, the reaction was stopped, the reaction solution was poured into 50mL of water, extracted with dichloromethane (3 × 20mL), dried over anhydrous magnesium sulfate, filtered, and the low-boiling organic solvent was removed by rotation, and the residue was separated by column chromatography using PE: DCM (V/V ═ 5:1) as an eluent to give 1.29g of a viscous liquid in orange yellow with a yield of 88.4%.1H NMR(400MHz,CDCl3)δ8.01(d,J＝0.7Hz,1H),7.69(dd,J＝8.6,2.4Hz,2H),7.40(d,J＝4.0Hz,1H),7.29–7.25(m,1H),4.27(d,J＝5.6Hz,2H),1.85-1.75(m,1H),1.50–1.24(m,16H),0.91–0.87(m,6H).
1.7. Synthesis of bis (2-butyloctyl) 4,4' - (6, 7-difluoro-5, 8-di (thien-2-yl) quinoxaline-2, 3-diyl) dibenzoate (SM8)
The procedure for the synthesis of compound SM8 was the same as that for the synthesis of compound (SM7), except that compound SM5 was changed to compound SM6 to give an orange-red oily liquid (yield 85%).1H NMR(400MHz,CDCl3)δ8.09(s,1H),8.07(d,J＝3.8Hz,2H),7.81(d,J＝8.4Hz,2H),7.70–7.66(m,1H),7.30-7.27(s,1H),4.28(d,J＝5.6Hz,2H),1.80(m,1H),1.37(m,16H),0.97–0.85(m,6H).
1.8. Synthesis of bis (2-butyloctyl) 5,5' - (5, 8-bis (5-bromothien-2-yl) -6, 7-difluoroquinoxaline-2, 3-diyl) bis (thiophene-2-carboxylate) (DFQxTA)
In a 100mL single-neck flask, compound (SM7) (1.29g,1.4mmol), dichloromethane (40mL) and dimethylformamide (15mL) were sequentially added, placed in an ice-water bath and protected from light, NBS (523mg,2.94mmol) was added in portions, reacted for 2 hours, then moved to room temperature for overnight reaction, the reaction was stopped, the reaction solution was poured into 50mL of water, extracted with dichloromethane (3 × 20mL), dried over anhydrous magnesium sulfate, filtered, the low-boiling organic solvent was removed by spinning, and the crude product was subjected to column chromatography using PE: DCM (V/V ═ 6:1) as an eluent to obtain 1.22g of an orange-red solid with a yield of 82%.1H NMR(400MHz,CDCl3)δ7.80(d,J＝4.1Hz,1H),7.75(d,J＝4.0Hz,1H),7.40(d,J＝4.0Hz,1H),7.22(d,J＝4.2Hz,1H),4.29(d,J＝5.5Hz,2H),1.88–1.77(m,1H),1.52–1.28(m,16H),0.94–0.88(m,6H).13C NMR(101MHz,CDCl3)δ161.96,145.85,143.98,137.67,134.05,133.23,131.64,131.53,131.45,131.37,130.55,129.59,119.14,117.28,68.38,37.44,31.87,31.50,31.08,29.66,29.02,26.80,22.96,22.70,14.14.MALDI-MS(m/z)of C54H62Br2F2N2O4S2 for[M+]:calcd.1062.25；found,1065.29.
1.9. Synthesis of bis (2-butyloctyl) 4,4' - (5, 8-bis (5-bromothien-2-yl) -6, 7-difluoroquinoxaline-2, 3-diyl) dibenzoate (DFQxBA)
The procedure for the synthesis of monomeric DFQxBA was the same as that for the synthesis of monomeric DFQxTA, except that compound SM7 was replaced with compound SM8, to give a dark red solid (85% yield).1H NMR(400MHz,CDCl3)δ7.80(d,J＝4.1Hz,2H),7.75(d,J＝4.0Hz,2H),7.40(d,J＝4.0Hz,2H),7.22(d,J＝4.2Hz,2H),4.29(d,J＝5.6Hz,4H),1.88–1.76(m,2H),1.54–1.24(m,32H),0.93-0.88(m,12H).13C NMR(101MHz,CDCl3)δ166.27,150.79,141.35,134.44,132.04,131.44,131.34,131.25,130.49,129.73,129.54,119.26,117.37,68.42,37.43,31.84,31.43,31.13,29.62,29.01,26.75,23.02,22.68,14.11.MALDI-MS(m/z)of C50H58Br2F2N2O4S2 for[M+]:calcd.1077.07；found,1077.21.
Example 2
Synthesis of Polymer PBDTTS-DFQxTA
(DFQxTA) (159.75mg,0.15mmol), 4, 8-bis (5- (ethylhexylthio) thienyl) benzo [1,2-b:4,5-b' ] dithienyl) bis (trimethyltin) (BDTTSn) (159.7mg,0.15mmol), tetrakis (triphenylphosphine) palladium (6mg), HPLC toluene (6 mL) were added sequentially in a 10mL single-neck flask, oxygen was evacuated by freezing with liquid nitrogen, thawing was carried out after each freezing, the reaction was repeated three times, the reaction was placed in a 110 ℃ thermostat, and the change in reaction was observed at each time. After the reaction is stopped, the reaction solution is diluted by chlorobenzene, settled in methanol, filtered, soxhlet extracted to wash a crude product (methanol-acetone-n-hexane-dichloromethane-trichloromethane), and a collected solution of the trichloromethane is concentrated, purified by flash column chromatography, concentrated, settled in methanol, filtered and dried in vacuum to obtain a black solid product (195.7mg, the yield is 84.2%).
EXAMPLE 3 Synthesis of Polymer PBDTTS-DFQxBA
The procedure for synthesizing and purifying the polymer PBDTTS-DFQxBA was the same as that for the polymer PBDTTS-DFQxTA. The final product was obtained as a black solid (188.1mg, 80.3% yield).
Example 4
The performance characterization of a D-A type polymer donor material constructed based on quinoxaline substituted by thiophene ester and phenyl alkyl side chains and the preparation and test of a photovoltaic device.
Of novel acceptor units and all intermediates of the synthesis1H NMR spectrum and13c NMR was measured by a Bruker Dex-400 NMR instrument and the UV-visible absorption spectrum of the novel acceptor unit type D-A polymeric material was measured by an HP-8453 UV-visible spectrometer.
The organic solar cell device based on the D-A type polymer material comprises: indium Tin Oxide (ITO) conductive glass anode, anode modification layer, optical activity layer, negative pole. Wherein the anode modification layer is PEDOT, PSS (100 nm); the cathode is a deposited layer of PDINO (5nm)/Al (100 nm); the active layer material (70nm) was a polymer donor material according to the present invention and Y6 in a blend mass ratio of 1: 1.
Example 5
Photophysical properties, electrochemical and polymer solar cell device properties of PBDTTS-DFQxTA.
The ultraviolet absorption spectrum of the polymer PBDTTS-DFQxTA in chloroform solution is shown in FIG. 1. PBDTTS-DFQxTA has strong absorption at 300-700nm, and pi-pi of polymer main chain at absorption peak of 400-500nm*The absorption peak at 500-600nm is attributed to the charge transfer (ICT) function from the BDTTS donor unit to the DFQxTA acceptor unit in the molecule. PBDTTS-DFQxTA is inUV absorption spectra in bulk films As shown in FIG. 2, the absorption of the film is significantly red-shifted with respect to the solution, with the absorption wavelength (λ) of the film being sidebandonset) At 764nm, calculated by the formula Eg＝1240/λonsetThe optical band gap of the material was found to be 1.62 eV.
The cyclic voltammogram of the polymer PBDTTS-DFQxTA in solid films is shown in FIG. 3. By the calculation of formula EHOMO＝-(Eox-E1/2,Fc/Fc++4.80) eV, giving them a HOMO energy level of-5.32 eV. By the calculation of formula ELUMO＝-(Ered-E1/2,Fc/Fc++4.80) eV, giving them a LUMO level of-3.57 eV. The electrochemical band gap of PBDTTS-DFQxTA was then calculated to be 1.75 eV.
The J-V curves of their photovoltaic devices are shown in FIG. 4 for the polymers PBDTTS-DFQxTA blended with Y6. When the doping ratio is 1:1 and CS2When the solvent annealing treatment is carried out for 2min, the open-circuit voltage of the device based on PBDTTS-DFQxTA: Y6 is 0.87V, and the short-circuit current is 23.3mA/cm2The fill factor was 71.8%, and the photoelectric conversion efficiency was 14.45%.
Under the condition that the blend of the PBDTTS-DFQxTA and the Y6 is optimal, the EQE of the photovoltaic device has a relation shown in FIG. 5, and the short-circuit current value obtained by the integral calculation of the EQE curve is 22.95mA cm-2This is consistent with the results obtained for the J-V curves (error at 5%), indicating that the device data is authentic.
The structure of the device is ITO/PEDOT (40 nm)/PSS (1200rpm)/MoO3(10nm)/Al (100nm) the hole mobility of the PBDTTS-DFQxTA blended with Y6 under optimum conditions was tested and, as shown in FIG. 6, it was 1.81X 10-4cm2 V-1s-1。
Example 6
Photophysical properties, electrochemical and polymer solar cell device properties of PBDTTS-DFQxBA.
The ultraviolet absorption spectrum of the polymer PBDTTS-DFQxBA in chloroform solution is shown in FIG. 7. PBDTTS-DFQxBA has strong absorption at 710nm of 300-*The absorption peak at 500-700nm is attributed to the charge transfer (ICT) function from the BDTTS donor unit to the DFQxBA acceptor unit in the molecule. Ultraviolet absorption spectra in solid films the film absorption is significantly red-shifted relative to the solution as shown in FIG. 8, with the film having a sideband absorption wavelength (λ @)onset) At 710nm, according to the formula Eg＝1240/λonsetThe optical band gap of the material was found to be 1.75 eV. The cyclic voltammogram of the polymer PBDTTS-DFQxBA in the solid film is shown in FIG. 9. By the calculation of formula EHOMO＝-(Eox-E1/2,Fc/Fc++4.80) eV, giving them a HOMO energy level of-5.30 eV. By the calculation of formula ELUMO＝-(Ered-E1/2,Fc/Fc++4.80) eV, giving them a LUMO level of-3.58 eV. The electrochemical band gap of PBDTTS-DFQxBA was then calculated to be 1.72 eV.
The J-V curves of the photovoltaic devices of the polymers PBDTTS-DFQxBA (8mg/mL) and Y6 when blended are shown in FIG. 10. When the doping ratio is 1:1 and CS2When the PBDTTS-DFQxBA device is subjected to solvent annealing treatment for 2min, the best photovoltaic performance is realized, the open-circuit voltage is 0.85V, and the short-circuit current is 25.6mA/cm2The fill factor was 74.0% and the photoelectric conversion efficiency was 15.8%.
Under the condition that the blend of the PBDTTS-DFQxBA and Y6 is optimal, the EQE of the photovoltaic device has a relation shown in FIG. 11, and the short-circuit current value obtained by the integral calculation of the EQE curve is 23.48mA cm-2This is consistent with the results obtained for the J-V curves (error at 5%), indicating that the device data is authentic.
The structure of the device is ITO/PEDOT (40 nm)/PSS (active layer/MoO)3(10nm)/Al (100nm) the hole mobility of the polymer PBTOSR-FBTA blended with Y6 was tested under optimum conditions, as shown in FIG. 12, and their hole mobility was 2.17X 10-4cm2 V-1s-1。
While the present invention has been described in connection with the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. In light of the present inventive concept, those skilled in the art will recognize that certain changes may be made in the embodiments of the invention to which the invention pertains without departing from the spirit and scope of the claims.
Claims (6)
1. A polymer material based on ester side chain substituted quinoxaline derivative is characterized in that the polymer material has a molecular structure shown in formula I
Wherein X in the formula I is one of H, F and Cl atoms, Y is one of O, S and Se atoms, and R1Independently selected from C8～C20One of alkyl groups;
d is one of the groups in the following formula II
In the formula II, R2Independently selected from C8～C24One of alkyl groups; z is independently selected from H, F, Cl, CN, OCH3,SCH3One of the groups; w is independently selected from one of C, Si and Ge atoms.
2. The polymeric material of claim 1, wherein the polymeric material is one of the following molecular structures
3. Use of a polymeric material according to claim 1 or 2, wherein the polymeric material is used as a donor material and is blended with a non-fullerene derivative (Y6) acceptor material to form a photoactive layer of a polymer solar cell.
4. The use of the polymer material according to claim 3, wherein the polymer material is blended with Y6 in a mass ratio of 1:1 in the photoactive layer of the polymer solar cell.
5. Use of a polymeric material according to claim 3, wherein the active layer has a thickness of between 20 nm and 300 nm.
6. Use of a polymeric material according to claim 4 or 5, wherein said active layer is obtained by solution processing methods comprising spin coating, brushing, spraying, dipping, roller coating, screen printing, printing or ink jet printing methods; wherein the solvent is organic solvent.
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