CN113563567A - Polymer donor material based on thiophene imide as construction unit and preparation method and application thereof - Google Patents
Polymer donor material based on thiophene imide as construction unit and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an all-polymer donor material based on thiophene imide as a construction unit, and a preparation method and application thereof, wherein the all-polymer donor material has a structure shown in a formula I, and the polymer donor material prepared by the preparation method has excellent solubility, high framework planarity, excellent thermal stability, high charge transmission performance, good crystallinity and adjustable photoelectric property, can be used as a donor material to be applied to an all-polymer solar cell, has the photoelectric conversion efficiency of 15 percent, and has huge application potential and value in the field of organic solar cells.
Description
Technical Field
The invention belongs to the technical field of organic semiconductor materials, and particularly relates to a polymer donor material based on thiophene imide as a construction unit, and a preparation method and application thereof.
Background
With the rapid development of society, people have more and more demand for energy. In order to alleviate the problem of energy shortage, development of new green sustainable energy becomes a focus of attention of people. Organic solar cells are highly appreciated by researchers because of their light weight, flexibility, large-area roll-to-roll industrial production, and low manufacturing cost. The development of high-efficiency organic solar cells is expected to solve the problems of environmental pollution and energy crisis.
At present, the efficiency of the organic solar cell reaches about 18%, but the development of the all-polymer cell is relatively lagged. At present, people mainly pay attention to the development of small molecule receptors, research on all-polymer battery donors is relatively few, most of the donor materials still rely on traditional donors such as PM6 and PBDB-T, and the limited donor materials cannot meet the requirements of researchers, so that the development of new all-polymer battery donor materials is urgently needed to be solved.
An ideal all-polymer cell donor material needs to satisfy several advantages: 1. better molecular planarity; 2. complementary to the receptor material uptake; 3. high molar absorptivity; 4. the molecular energy levels are matched; 5. higher carrier mobility; 6. better solubility, etc. Therefore, these factors must be taken into account in designing new materials.
The donor used in the traditional full polymer is PM6, and the traditional full polymer has the advantages of good device performance and high synthesis and purification difficulty and cost. In recent years, the development of a bithiophene imide building unit is rapid, and the advantages of simple synthesis, adjustable structure and energy level, high carrier mobility and the like of the bithiophene imide building unit are greatly concerned in the field of organic semiconductors. Therefore, the development of novel efficient bithiophene imide building block-based all-polymer solar cell donors has great practical significance.
Disclosure of Invention
The invention aims to provide a full polymer donor material based on thiophene imide as a construction unit, and a preparation method and application thereof. The all-polymer donor material provided by the invention is a copolymer based on the combination of bithiophene imide and benzodithiophene, and has good molecular coplanarity, good solubility and high carrier mobility (mu)h＝8.8×10- 4cm2 V-1s-1) Good thermal stability and adjustable molecular energy level (HOMO ═ 5.52eV, LUMO ═-3.63 eV). The alkyl chain in the structure ensures that molecules can be subjected to solution processing, and the carbonyl in the imide has a strong electron-pulling effect, so that the HOMO energy level of the polymer can be effectively reduced, and the open-circuit voltage of the device is further improved. Meanwhile, the absorption of the donor material based on the imide is complementary to the absorption of the receptor, so that the short-circuit current is improved. Thereby achieving higher energy conversion efficiency.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
an all-polymer donor material based on thiophene imide as a building block, the all-polymer donor material having a structural formula:
wherein pi is a conjugated structural group; x is any one of C-H, N, C-Cl, C-CN or C-F; r1、R2All selected from linear alkyl or branched alkyl with 1-25 carbon atoms; n is an integer of 10 to 1000; connection R2The dotted line represents a thiophene ring surrounded by R2Monosubstituted, however R2Can be in any position of the thiophene ring.
Preferably, R1And R2Is any one of the following groups:
the structure of the all-polymer donor material is any one of structures shown in formulas II, III, IV and V:
the pi is any one of the following groups:
wherein R is a straight-chain alkyl or branched-chain alkyl with 1-25 carbon atoms.
Said pi is preferably
Wherein R is preferably C5-20 branched alkyl or linear alkyl, more preferably C5-20 branched alkyl or linear alkyl
X is preferably C-H.
R1 is preferably a branched or straight-chain alkyl group having 8 to 20 carbon atoms, more preferably a C8-20 alkyl group
R2 is preferably a branched or straight-chain alkyl group having 8 to 20 carbon atoms, more preferably a C8-20 alkyl group
The invention also provides a preparation method of the full polymer donor material based on the thiophene imide as a construction unit, and the preparation method comprises the following steps: mixing a stannized monomer, a brominated monomer, a catalyst ligand and an anhydrous solvent, and carrying out a polymerization reaction to obtain the polymer donor material based on the thiophene imide as a construction unit;
the structural formula of the stannization monomer is any one of the following formulas:
the structural formula of the brominated monomer is as follows:
the catalyst is tris (dibenzylideneacetone) dipalladium.
The catalyst ligand is tri (o-methylphenyl) phosphorus.
The anhydrous solvent is one or more of anhydrous toluene, anhydrous chlorobenzene or anhydrous DMF.
The mol ratio of the stannized monomer to the brominated monomer to the catalyst ligand is 1: (1-1.2): (0.01-0.05): (0.04-0.75); the concentration of the brominated monomer in the anhydrous solvent is 0.02-0.1M.
The conditions of the polymerization reaction are as follows: under the protection of inert gas, reacting for 1-72h at 50-170 ℃, and adding an end-capping reagent to perform end capping when the reaction is finished.
The inert gas is argon, nitrogen or helium.
The end-capping reagent is 2-tributyl tin thiophene and/or 2-bromothiophene; the temperature for blocking is 80-170 ℃, and the blocking time is 10-30 min.
The preparation method of the brominated monomer comprises the following steps:
(1) preparing a compound B by using 3, 3' -dibromo bithiophene and carbon dioxide as raw materials under the catalysis of n-butyl lithium;
(2) mixing the compound B with acetic anhydride, and heating and refluxing to obtain a compound C;
(3) reacting the compound C with alkylamine, and then adding thionyl chloride to continue to react to obtain a compound D;
(4) reacting the compound D with liquid bromine in a chloroform solution to obtain a compound E;
(5) coupling the compound E with stannated alkylthiophene to obtain a compound F;
(6) reacting the compound F with liquid bromine in a chloroform solution to obtain the brominated monomer (compound G); the preparation route of the brominated monomer is as follows:
the step (1) specifically comprises the following steps: adding n-butyllithium into anhydrous ether at the low temperature of-78 ℃, dropwise adding an ether solution of 3, 3' -dibromo bithiophene, reacting for 2 hours after complete dropwise adding, introducing carbon dioxide gas for 0.5 hour, heating to room temperature, reacting for 8-12 hours, removing the solvent after the reaction is finished, adding water to dissolve the product, adjusting the pH value to acidity, filtering, and drying to obtain a compound B.
In the step (2), the solvent for reaction is acetic anhydride, and the heating reflux condition is that the reaction is carried out for 10-12 h at 140 ℃.
In the step (3), the solvent for reaction is dichloromethane, alkylamine is added, the reaction is carried out overnight at 50 ℃, and thionyl chloride is added, and the reaction is continued for 3 hours.
In the step (4), the reaction was carried out at room temperature for 5 hours in the dark.
In the step (5), the solvent for reaction is N, N-dimethylformamide, the catalyst is palladium tetratriphenylphosphine, the reaction temperature is 130 ℃, and the reaction time is 8 hours.
In step (6), the reaction was carried out at room temperature for 5 hours in the dark.
The invention also provides application of the full polymer donor material based on the thiophene imide as a construction unit in a solar cell or an organic semiconductor material.
The invention also provides a solar cell which takes the full polymer donor material based on the thiophene imide as a construction unit as a donor material.
The preparation method of the solar cell comprises the following steps:
A. using the ITO glass as a substrate material, respectively ultrasonically cleaning the ITO glass by using deionized water, acetone and isopropanol, and then drying the ITO glass in an oven overnight;
B. PSS serving as a hole transport layer is coated on the ITO substrate treated by the UV in a spinning mode, and the ITO substrate is tempered at 150 ℃ for 15 minutes and then transferred into a glove box;
C. dispersing the polymer donor material in a chlorobenzene solution, stirring overnight at 60 ℃, then spin-coating the mixture on a hole transport layer to be used as an active layer, controlling the thickness of a blended film to be 90-110 nm, and then tempering for 5 minutes at 80 ℃;
D. spin coating PDINO with the particle size of 5nm on the surface of the active layer to serve as an electron transport layer;
E. and evaporating aluminum on the electron transport layer, and controlling the thickness of the aluminum layer to be less than 100 nm.
The solar cell provided by the invention has the highest photoelectric conversion efficiency of 14% and excellent performance.
Compared with the prior art, the invention has the following beneficial effects:
the all-polymer donor material based on the thiophene imide provided by the invention has a highly planar molecular framework and an adjustable molecular orbital energy level; good thermal stability, the decomposition temperature is higher than 350 ℃, good solubility, and can be dissolved in trichloromethane, chlorobenzene and dichlorobenzene; when it is blended with polymer acceptor, it has good intersolubility. The ultraviolet absorption wavelength of the synthesized full polymer donor material based on the thiophene imide as the construction unit is about 650nm, the ultraviolet absorption wavelength of most polymer receptors is about 900nm, and when the full polymer donor material is blended with the polymer receptors, the full polymer donor material has good absorption complementarity and has good application prospect and higher application value.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of compound B prepared in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of compound B prepared in example 1 of the present invention;
FIG. 3 is a NMR spectrum of Compound C prepared in example 1 of the present invention;
FIG. 4 is a nuclear magnetic resonance carbon spectrum of Compound C prepared in example 1 of the present invention;
FIG. 5 is a NMR chart of Compound D prepared in example 1 of the present invention;
FIG. 6 shows the NMR spectrum of Compound D obtained in example 1 of the present invention;
FIG. 7 is a NMR chart of Compound F prepared in example 1 of the present invention;
FIG. 8 is a NMR chart of Compound F prepared in example 1 of the present invention;
FIG. 9 shows a NMR spectrum of Compound G prepared in example 1 of the present invention;
FIG. 10 shows the NMR spectrum of compound G prepared in example 1 of the present invention;
FIG. 11 is a structural formula of an all-polymer donor material based on a thiophene imide as a building block in the present invention.
FIG. 12 is a GPC chart of the polymer obtained in example 2 of the present invention;
FIG. 13 is a graph showing UV absorption of a polymer solution (a) and a film (b) prepared from the polymer solution (a) according to example 2 of the present invention;
FIG. 14 is a schematic thermal decomposition diagram of a polymer produced in example 2 of the present invention;
FIG. 15 is a current-voltage curve for a solar cell made with the polymer of example 2;
fig. 16 is a graph of the external quantum efficiency of a solar cell made with the polymer in example 2.
Detailed Description
The present invention will be described in detail with reference to examples.
In the present invention, all reagents and chemicals are commercially available. If not mentioned, no further purification treatment was performed before use. The anhydrous toluene is prepared by treating with metallic sodium. All reactions were carried out under inert gas atmosphere, unless otherwise mentioned. The nuclear magnetic spectrum was performed by a Brooks 400MHz NMR spectrometer, the molecular weight measurements were performed by high temperature GPC (Agilent PL-GPC220), the UV-vis absorption spectra were measured by Shimadzu UV-3600 spectrometer, and the cyclic voltammetry was performed by CHI760 electrochemical workstation.
Example 1
A preparation method of a brominated monomer comprises the following steps:
(1) synthesis of Compound B
250mL of dehydrated ether was first added to a two-necked flask, and the flask was left at a low temperature of-78 ℃ and then charged with 17.30mL of n-butyllithium. Using another one-neck flask, the starting material A (5g,18.94mmol) was dissolved in 50mL of diethyl ether, and the solution was slowly added dropwise to the two-neck flask, reacted at low temperature for 2 hours, then introduced with carbon dioxide gas for half an hour (carbon dioxide bubbling without interruption), and allowed to warm to room temperature for 10 hours. Removing the ether solvent by a rotary evaporator, adding water for dissolution, then adjusting the pH value to 3 by hydrochloric acid, filtering and drying to obtain the compound B.
The hydrogen spectrum and the carbon spectrum nuclear magnetism are shown in FIGS. 1 and 2.
1H NMR(400MHz,DMSO)δ(ppm):7.64(d,2H),7.43(d,2H)。
13C NMR(125MHz,DMSO)δ163.97,139.51,132.68,130.12,127.14。
(2) Synthesis of Compound C
Putting the compound B (5g,19.6mmol) into a two-neck flask, adding 30mL of acetic anhydride, heating to 140 ℃, refluxing for reaction for 10 hours, cooling to room temperature, and filtering to obtain an anhydride compound C.
The hydrogen spectrum and the carbon spectrum nuclear magnetism are shown in FIGS. 3 and 4.
1H NMR(400MHz,DMSO)δ(ppm):7.65(d,2H),7.44(d,2H)。
13C NMR(125MHz,DMSO)δ163.96,139.53,132.65,130.12,127.14。
(3) Synthesis of Compound D
Compound C (500mg,2.11mmol), 2-hexyldecyl-1-amine (510mg, 2.11mmol) was dissolved in 10mL of dichloromethane, raised to 50 ℃ for overnight reaction, and then added with 10mL of thionyl chloride and allowed to react for another 3 hours. Spin-dry to give a viscous liquid, and coarse with petroleum ether: and purifying the dichloromethane (1:1) column chromatography to obtain a compound D.
The hydrogen spectrum and the carbon spectrum nuclear magnetism are shown in FIGS. 5 and 6.
1H NMR(500MHz,CDCl3)δ(ppm):7.72(d,2H),7.23(d,2H),4.24(d,2H),1.93-1.91(m,1H),1.37-1.23(m,24H),0.89-0.84(t,6H)。
13C NMR(125MHz,CDCl3)δ162.28,137.38,133.28,133.06,124.22,53.46,49.40,31.92,31.84,30.09,29.78,29.57,29.33,26.42,22.69,22.68,14.16,14.13。
(4) Synthesis of Compound E
Compound D (1.06g,2.30mmol) was placed in a single-neck flask, 20mL of chloroform was added and dissolved with stirring, 0.35mL of liquid bromine was added dropwise, and the reaction was carried out for 5 hours with exclusion of light. Adding sodium sulfite solution to quench reaction, extracting, drying and removing organic solvent, and using petroleum ether: and purifying the dichloromethane (1:1) column chromatography to obtain a compound E.
(5) Synthesis of Compound F
Compound E (1g,1.62mmol), palladium tetratriphenylphosphine (93.6mg,0.081mmol), and a thiophene π -bridge tin reagent (2.63g, 4.85mmol) were charged into a two-necked flask, 20mL of DMF solvent was added under argon protection, and the temperature was raised to 130 ℃ for 8 hours. The solvent was removed by spin-drying and the crude product was purified by petroleum ether: and purifying the dichloromethane (1:1) column chromatography to obtain a compound F.
The hydrogen spectrum and the carbon spectrum nuclear magnetism are shown in FIGS. 7 and 8.
1H NMR(500MHz,CDCl3)δ(ppm):7.75(s,2H),7.08(s,2H),6.90(s,2H),4.24(d,2H),2.60-2.57(t,4H),1.64(b,1H),1.63-1.57(m,4H),1.31-1.24(m,60H),0.89-0.84(t,12H)。
13C NMR(125MHz,CDCl3)δ161.81,144.55,136.27,135.09,134.84,133.52,128.26,126.65,121.16,77.27,77.02,76.77,49.49,36.46,31.93,31.87,31.77,31.72,30.42,30.36,30.10,29.79,29.69,29.68,29.66,29.59,29.46,29.38,29.35,29.28,26.51,26.48,22.71,22.69,14.14。
(6) Synthesis of Compound G
Compound F (1.1g,1.14mmol) was placed in a single-neck flask, 20mL of chloroform was added and dissolved with stirring, 0.18mL of liquid bromine was added dropwise, and the reaction was carried out for 5 hours with exclusion of light. Adding sodium sulfite solution to quench reaction, extracting, drying and removing organic solvent, and using petroleum ether: and purifying the dichloromethane (1:1) column chromatography to obtain a compound G.
The hydrogen spectrum and the carbon spectrum nuclear magnetism are shown in FIGS. 9 and 10.
1H NMR(500MHz,CDCl3)δ(ppm):7.66(s,2H),6.91(s,2H),4.22(d,2H),2.55-2.52(t,4H),1.88(b,1H),1.60-1.56(m,6H),1.33-1.23(m,56H),0.89-0.83(t,12H)。
13C NMR(125MHz,CDCl3)δ184.17,161.64,143.48,135.28,134.54,133.69,128.55,126.08,110.25,77.34,77.23,77.02,76.71,36.46,31.95,31.87,31.78,30.11,29.80,29.70,29.68,29.60,29.58,29.42,29.38,29.23,26.50,22.72,14.14。
Example 2
A polymer donor material based on thiophene imide as a construction unit, the structural formula of which is
The synthetic route for the polymer donor material is as follows:
the specific synthesis steps are as follows:
the stannating monomer BDT (56.61mg,0.062mmol) and brominated monomer BTI (70mg,0.062mmol) were added to a 5mL reaction tube along with the catalyst Pd2(dba)3(0.85mg,0.00093mmol), ligand P (o-tolyl)3(2.26mg,0.0074mmol), nitrogen was bubbled. Finally 2.5mL of anhydrous toluene (toluene) was added. The reaction tube was placed in a microwave (microwave) reactor and reacted at 140 ℃ for 3 hours. Cooled to room temperature, 2-tributyltin thiophene was added and capped at 100 ℃ for 20 minutes. After cooling to room temperature again, the reaction solution was added to methanol, stirred for 3 hours, precipitated, filtered and further extracted with methanol through a fat extractor to remove a low molecular weight fraction. And finally, concentrating the product, dripping the product into 5mL of methanol solution again, separating out a precipitate, and drying to obtain the target polymer. The polymer donor material prepared in this example has good solubility in chloroform, chlorobenzene, dichlorobenzene.
The GPC chart of the polymer prepared in this example is shown in FIG. 12, from which it can be seen that the molecular weight of the polymer is 81 kDa.
The UV absorption profile of the polymer prepared in this example is shown in FIG. 13, where it can be seen that the UV absorption wavelength is 650nm, while the UV absorption offset for most polymer acceptors is in the range of about 900nm, which is complementary to the absorption of most polymer acceptors.
The thermal decomposition of the polymer prepared in this example is schematically shown in FIG. 14, from which it can be seen that the thermal decomposition temperature of the polymer is above 350 ℃.
Application example 1
Preparation of a solar cell with the Polymer prepared in example 2 as donor Material for a solar cell
The preparation method of the solar cell provided by the invention comprises the following steps:
A. using ITO glass as a substrate material, respectively ultrasonically cleaning the ITO glass by deionized water, acetone and isopropanol, and then drying the ITO glass in an oven overnight;
B. PEDOT: PSS is coated on the ITO substrate treated by UV in a spinning mode, and the ITO substrate is transferred into a glove box after being tempered at 150 ℃ for 15 minutes;
C. dispersing the polymer donor material prepared in the example 2 in a chlorobenzene solution, stirring overnight at 60 ℃ to obtain a solution with the mass concentration of 4mg/mL, spin-coating the solution on a hole transport layer to serve as an active layer, controlling the thickness of a blended film to be 90-110 nm, and tempering for 5 minutes at 80 ℃;
D. spin-coating PDINO on the surface of the active layer to serve as an electron transport layer, wherein the thickness of the electron transport layer is 5 nm;
E. and evaporating aluminum on the electron transport layer, and controlling the thickness of the aluminum layer to be less than 100 nm.
The solar cell prepared in this application example was tested and the current-voltage curve was performed under simulated sunlight irradiation, as shown in fig. 15, from which the short-circuit current (J) can be seensc) Is 21.59mA cm-2Open circuit voltage (V)oc) 0.94 and a Fill Factor (FF) of 73.4, soThe resulting energy conversion efficiency (PCE) was 15.06%, with excellent performance.
The external quantum efficiency is tested by a QE-R3011 test system, the external quantum efficiency graph is shown in figure 16, and it can be seen from the graph that the polymer donor material and the acceptor material have good absorption complementation, and the maximum external quantum efficiency reaches 70%.
The above detailed description of a polymer donor material based on a thiopheneimide as building block, its preparation and its use, with reference to the examples, is illustrative and not restrictive, several examples being set forth according to the scope of the invention defined, and therefore variations and modifications thereof without departing from the general inventive concept are intended to be within the scope of the present invention.
Claims (10)
1. An all-polymer donor material based on thiophene imide as a building unit, which is characterized in that the structural formula of the all-polymer donor material is as follows:
wherein pi is a conjugated structural group; x is any one of C-H, N, C-Cl, C-CN or C-F; r1、R2All selected from linear alkyl or branched alkyl with 1-25 carbon atoms; n is an integer of 10 to 1000; the dotted line indicates the position of attachment of the group.
2. The full polymer donor material based on thiopheneimide as a building block according to claim 1, wherein pi is any one of the following groups:
wherein R is a straight-chain alkyl or branched-chain alkyl with 1-25 carbon atoms.
3. As claimed in claim1 or 2, wherein pi is
Wherein R is
X is C-H; r1Is composed of
R2Is composed of
4. The method of preparing the all-polymer donor material based on the thiopheneimide as a building block according to claim 1, wherein the method comprises the steps of: mixing a stannized monomer, a brominated monomer, a catalyst ligand and an anhydrous solvent, and carrying out a polymerization reaction to obtain the polymer donor material based on the thiophene imide as a construction unit;
the structural formula of the stannization monomer is any one of the following formulas:
the structural formula of the brominated monomer is as follows:
5. the method of claim 4, wherein: the catalyst is tris (dibenzylideneacetone) dipalladium; the catalyst ligand is tri (o-methylphenyl) phosphorus; the anhydrous solvent is one or more of anhydrous toluene, anhydrous chlorobenzene or anhydrous DMF.
6. The method of claim 4 or 5, wherein the molar ratio of the stannated monomer, brominated monomer, catalyst ligand is 1: (1-1.2): (0.01-0.05): (0.04-0.75); the concentration of the brominated monomer in the anhydrous solvent is 0.02-0.1M.
7. The process according to claim 4 or 5, wherein the polymerization conditions are: under the protection of inert gas, reacting for 1-72h at 50-170 ℃, and adding an end-capping reagent to perform end capping when the reaction is finished.
8. A method of preparing a brominated monomer according to claim 4 or claim 5, comprising the steps of:
(1) preparing a compound B by using 3, 3' -dibromo bithiophene and carbon dioxide as raw materials under the catalysis of n-butyl lithium;
(2) reacting the compound B with acetic anhydride, and heating and refluxing to obtain a compound C;
(3) reacting the compound C with alkylamine, and then adding thionyl chloride to continue to react to obtain a compound D;
(4) reacting the compound D with liquid bromine in a chloroform solution to obtain a compound E;
(5) coupling the compound E with stannated alkylthiophene to obtain a compound F;
(6) reacting the compound F with liquid bromine in a chloroform solution to obtain the brominated monomer (compound G); the preparation route of the brominated monomer is as follows:
9. use of the full polymer donor material based on thiopheneimide as building block according to any of the claims 1 to 3 in solar cells or in organic semiconductor materials.
10. A solar cell, characterized by: the solar cell takes the full polymer donor material based on the thiophene imide as a construction unit in any one of claims 1-3 as a donor material.
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| US8859714B1 (en) * | 2009-07-01 | 2014-10-14 | Northwestern University | Polymeric semiconductors and related devices |
| CN109517143A (en) * | 2017-09-20 | 2019-03-26 | 南方科技大学 | A kind of N-shaped organic semiconducting materials and the preparation method and application thereof |
| CN112794993A (en) * | 2021-01-11 | 2021-05-14 | 南方科技大学 | N-type polymer and preparation and application thereof |
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