CN114085362B - Preparation method and application of polymer donor material containing multi-element aromatic ring thieno-thiophene diketone - Google Patents
Preparation method and application of polymer donor material containing multi-element aromatic ring thieno-thiophene diketone Download PDFInfo
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Abstract
The invention provides a preparation method and application of a polymer donor material containing multi-element aromatic ring thiophene diketone, wherein the polymer provided by the invention is a polymer with a structure shown in a formula (I), and experiments show that the polymer provided by the invention can obtain higher photoelectric conversion efficiency which can reach 15.04% when being used as an active layer component of a photoelectric conversion device.
Description
Technical Field
The invention relates to the field of solar cells, in particular to a polymer based on multi-component aromatic thienothiophene diketone and a preparation method and application thereof.
Background
Energy is a material basis and guarantee for the development of human society. With the rapid development of science and technology, the demand of human beings for energy is increasing year by year. At present, the main energy acquisition way is still fossil energy, but the energy is increasingly exhausted, and obvious environmental pollution is caused. Solar energy is an inexhaustible clean energy and is widely concerned by scientific workers, factories and enterprises in various countries.
Scientists have produced various solar cells based on the photovoltaic effect. Among them, organic solar cells (OPVs) have the outstanding advantages of light weight, low cost, and the ability to be fabricated into flexible large-area devices. Through continuous efforts of researchers, the photoelectric conversion efficiency of a single photovoltaic cell based on a polymer exceeds 18%, and the single photovoltaic cell based on the polymer has excellent performance in the field of indoor photovoltaics and has great commercial application potential.
Most important in organic solar cells are photoactive layers. The most excellent photoactive layer system is now a polymer donor/small molecule acceptor. In recent years, the structure of a high-performance small molecule acceptor is discovered, so that the photoelectric conversion efficiency of an organic solar cell is rapidly improved, and the development of a polymer donor material is slow. Obviously, the donor material and the acceptor material are equally important, and the development of the donor material is not slow to obtain a higher-performance organic solar cell.
The existing excellent polymer donor material mainly comprises a benzodithiophene derivative and a benzodithiophene diketone derivative, wherein the benzodithiophene derivative and the benzodithiophene diketone derivative bring proper energy level and good self-assembly effect due to a unique planar electron-withdrawing structure, and are one of the most excellent electron-deficient units in the donor polymer material. Therefore, it is of great importance to develop more polymer donor materials in a preferred form that can improve the photoelectric conversion efficiency of solar cells.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a polymer based on a poly-aromatic thienothiophene dione, and a preparation method and an application thereof.
The invention provides a polymer containing a multi-element aromatic ring thiophene diketone, which is a polymer with a formula (I):
wherein, R is 1-1 And R 1-2 Independently selected from oxygen, sulfur, selenium, amino, carbonyl, sulfone, sulfoxide, vinyl and imino,
said R is 2-1 、R 2-2 、R 3-1 、R 3-2 Independently selected from hydrogen, bromine, iodine, sulfuryl, sulfoxide, ester group, carbonyl, trifluoromethyl, C1-C30,
ar is 1 Selected from unsubstituted or substituted ethenylene, unsubstituted or substituted ethynylene, unsubstituted or substituted monocyclic arylene, unsubstituted or substituted bicyclic arylene, unsubstituted or substituted tricyclic arylene, unsubstituted or substituted monocyclic heteroarylene, unsubstituted or substituted bicyclic heteroarylene, or unsubstituted or substituted tricyclic heteroarylene;
ar is 2 Selected from unsubstituted or substituted fluorenes, carbazoles, dibenzofurans, silafluorenes, benzophosphinindoles, dibenzothiophenes, germanofluorenes, stannofluorenes;
n is a natural number between 5 and 1000, preferably between 10 and 100.
Preferably, said R is 2-1 、R 2-2 、R 3-1 、R 3-2 Independently selected from hydrogen or C5-C20 alkyl, chlorine, bromine, iodine, C1-C20 sulfuryl, C1-C20 sulfoxide, C2-C20 ester, C1-C20 carbonyl, trifluoromethyl or C2-C20 alkynyl.
Preferably, the heteroatoms in the monocyclic heteroarylene, bicyclic heteroarylene and tricyclic heteroarylene are nitrogen, sulfur or oxygen.
Preferably, the substituent of the substituted ethenylene group, the substituted ethynylene group, the substituted monocyclic arylene group, the substituted bicyclic arylene group, the substituted three-ring arylene group, the substituted monocyclic heteroarylene group, the substituted bicyclic heteroarylene group and the substituted three-ring heteroarylene group is a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C60 arylalkyl group, a C1-C20 alkyl group, a C1-C20 alkoxy group, an ester sulfone group, a fluoroalkyl group, a fluorinated heterocyclic group, an ethenylene group, an ethynylene group, a monocyclic arylene group, a bicyclic arylene group, a three-ring arylene group, a monocyclic heteroarylene group, a bicyclic heteroarylene group or a three-ring heteroarylene group.
Preferably, ar is 1 Selected from the following structures:
wherein R is hydrogen, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkyl-substituted C6-C30 aryl, cl-C30 alkyl-substituted C6-C60 arylalkyl, ester group, sulfone group, fluoroalkyl group, fluoroheterocyclic group, ethenylene group, ethynylene group, monocyclic arylene group, bicyclic arylene group, arylene group containing three rings, monocyclic heteroarylene group, bicyclic heteroarylene group or heteroarylene group containing three rings;
x is an chalcogen, preferably S;
y is a carbon group element.
Preferably, ar is 2 Selected from the following structures:
wherein, R is 4 、R 5 、R 6 、R 7 、R 8 、R 9 Independently selected from hydrogen or C5-C20 alkyl, C2-C20 ester group of chlorine, C1-C20 carbonyl and trifluoromethyl.
Z is selected from carbon group, nitrogen group and oxygen group.
The invention also relates to a semiconductor composition comprising the polymer having the formula (I) described above.
The invention also relates to a photoelectric conversion device, wherein the active layer material in the photoelectric conversion device is the polymer with the formula (I).
Compared with the prior art, the polymer based on the poly-aromatic thienothiophene dione provided by the invention is a polymer with a structure shown in a formula (I), and experiments show that the polymer provided by the invention can obtain higher photoelectric conversion efficiency which is up to 15.04% when being used as an active layer component of a photoelectric conversion device.
Drawings
FIG. 1 is a UV-VIS absorption spectrum of polymer P1 prepared in example 5 in chloroform solution and a thin film;
FIG. 2 is a J-V plot of a photovoltaic device made from polymer P1;
fig. 3 is a EQE curve for polymer P1 as the active layer.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only illustrative and are not intended to limit the present invention.
In general, the number average molecular weight of the polymer of the present invention is 1000 to 1,000,000, preferably 3000 to 500,000, and further preferably 20,000 to 200,000. It is understood that the molecular weight can be varied to optimize polymer properties. For example, lower molecular weights ensure solubility, while higher molecular weights ensure good film forming properties.
The preparation method of the polymer provided by the invention polymerizes the monomers of formula (II) and formula (III) into formula (I), v-Ar 1 -v (formula II),
wherein W is selected from I, br or Cl and V is selected from a boronic acid group, a boronic ester group, a zinc halide group or a trialkyltin group;
the boronic acid group is selected from the group including, but not limited to: 1,3, 2-dioxaborolan-2-yl, 4, 5-tetramethyl-1, 2, 3-dioxaborolan-2-yl or 5, 5-dimethyl-1, 3, 2-dioxaborolan-2-yl;
the magnesium halide group is selected from the group including, but not limited to: magnesium chloride, bromide or iodide; the zinc halide group is preferably: zinc chloride or bromide;
the trialkyltin group is selected from the group including, but not limited to: trimethyltin, triethyltin or tributyltin.
If a polycondensation reaction is carried out between a dimagnesium haloaromatic compound and an aromatic dihalide, the polymerization reaction is a typical "McCullough" process as reported by McCullough and Lowe [ chem. In the McCullough method, tetrahydrofuran and toluene are used as common solvents, and a mixed solvent of tetrahydrofuran and toluene may be used. Some catalysts containing Pd or Ni, such as [1, 3-bis (diphenylphosphino) propane ] dichloronickel (II) and tetrakis (triphenylphosphine) palladium (0), can be used as catalysts for this reaction, and the molar ratio between the catalyst and the starting material is 10% to 0.1%. The reaction is typically carried out at a temperature of about 10 ℃ to the reflux temperature of the solvent. The polymerization reaction may be carried out for 10 minutes to 72 hours for different reactivities of the reactants. The dimagnesium haloarene used in this reaction can be produced by the Grignard displacement reaction [ Macromolecules,2001,34,4324-4333], as reported by Loewe and McCullough, or by the reaction between an arene dihalide and magnesium. In some embodiments, the aromatic dihalide and dimagnesium haloaromatic hydrocarbon used in the "McCullough process" with the polymer of the present invention are aromatic dibromides and dimagnesium bromoaromatic hydrocarbons.
If a polycondensation reaction is carried out between a di-zinc haloaromatic compound and an aromatic dihalide, the polymerization reaction is typically the "Rieke process" as reported by Chen and Rieke [ synth. Met,1993,60,175]. In this process, tetrahydrofuran is generally used as a solvent, [1, 2-bis (diphenylphosphino) ethane ] nickel (ii) dichloride, which can be used as a catalyst for the reaction and is generally carried out at about 10 ℃ to the reflux temperature of the solvent, at a molar ratio of the catalyst to the starting materials of 10% to 0.1%. Depending on the reactivity of the reactants, the polymerization may be carried out for 10 minutes to 72 hours, in a preferred embodiment, the aromatic dihalides and zinc bis-haloarylenes used in the "Rieke process" with the polymers of the invention are aromatic dibromides and zinc bis-chloroarenes.
If a polycondensation reaction is carried out between the aromatic diboronic acid compound or the aromatic diboronate compound and the aromatic dihalide, the polymerization reaction is a typical "Suzuki reaction" as reported by Miyaura and Suzuki [ ChemRev.1995,95,2457-2483]. In this process, solvents including but not limited to many types of solvents such as tetrahydrofuran and toluene, some catalysts containing Pd such as tetrakis (triphenylphosphine) palladium (0) may be used as the catalyst for the reaction, and the molar ratio between the catalyst and the starting material is 10% to 0.1%. The reaction is typically carried out at a temperature of about 10 ℃ to the reflux temperature of the solvent. The polymerization reaction may be carried out for 10 minutes to 72 hours for different reactivities of the reactants. In some embodiments, the arene dihalide used in the polymer "Suzuki reaction" for some embodiments of the present invention is an arene diiodide, an arene dihalide, or an arene dichloride.
If the polycondensation reaction is conducted between a trialkyltin aromatic hydrocarbon compound and an aromatic hydrocarbon dihalide, the polymerization reaction is a typical "Stille reaction" as reported by John k. Stille and Luping Yu [ angelw. Chem. Int. Ed.1986,25,508-524; chem. Rev.2011,111,1493-1528], in the method, a solvent includes many types of solvents including but not limited to tetrahydrofuran, N-dimethylformamide, toluene and chlorobenzene, and a mixed solvent such as a mixed solvent of tetrahydrofuran and toluene, a mixed solvent of toluene and N, N-dimethylformamide may also be sometimes used but not limited to a mixture of these two mixed solvents. Some catalysts containing Pd, such as tetrakis (triphenylphosphine) palladium (0), palladium chloride, palladium acetate and or (dibenzylideneacetone) palladium (0), may be used as catalysts for the reaction, and the molar ratio between the catalyst and the starting material is 10% to 0.1%. The reaction is generally carried out at a temperature of between 10 and 200 ℃. The polymerization time is from 10 minutes to 72 hours. In some embodiments, the arene dihalide used in the polymer "Stille reaction" used in some embodiments of the present invention is arene diiodide, arene dihalide, or arene dichloride and bistrimethylstannic arene.
Definition and naming: unless otherwise indicated, the invention is not limited to specific starting materials, reagents or reaction conditions, but may be varied. The term "alkyl" as used herein refers to a branched or unbranched saturated alkyl group typically, but not necessarily, containing 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-octyl, isooctyl, decyl, and the like; and cycloalkyl groups such as cyclopentyl, cyclohexyl, and the like.
"arylene" has its usual meaning. The term "heteroarylene" as used herein refers to an aromatic ring of 5 or 6 atoms containing one or more "heteroatoms" (i.e., atoms other than carbon, such as nitrogen, oxygen, sulfur, silicon, selenium, phosphorus). The term "N-containing heteroarylene" as used herein refers to a heteroarylene group in which one or more "heteroatoms" as defined above is nitrogen. The "fused" rings share the same bond, and the "connected" rings are connected by a single bond.
The term "substituted" as in "substituted arylene", "substituted heteroarylene", and the like, refers to moieties in which at least one hydrogen atom bonded to a carbon or heteroatom is replaced with one or more non-hydrogen substituents, which may include, but are not limited to, alkyl or aryl groups, and functional groups such as halogen, hydroxy, alkylthio, alkoxy, aryloxy, alkylcarbonyl, acyloxy, nitro, nitrile, and the like.
In general, the polymer of the invention is selected such that the polymer of the invention is combined with the admixture in any proportion, e.g., the mass ratio of polymer to admixture1.5, and the like. The admixture is typically a compound selected such that when an excitation source comprising light or voltage is applied to the combination, charge transfer and/or energy transfer occurs between the admixture and the polymer. For example, the admixture may be a fullerene, such as: c 60 Or C 70 Or some substituted fullerene derivatives, such as PCBM ([ 6, 6)]-phenyl radical C 61 Methyl butyrate) and indene-containing fullerenes. Polymers according to some embodiments of the invention are particularly useful as photovoltaic materials in photovoltaic devices such as photodetector devices, solar cell devices, and the like.
The present invention also protects a photovoltaic device (including a solar cell device) generally comprising a hole-collecting layer, an electron-collecting layer, and a layer of photovoltaic material between the hole-collecting layer and the electron-collecting layer; the photovoltaic material layer at least comprises the polymer or semiconductor composition provided by the invention. Additional layers, elements or substrates in the photovoltaic device may or may not be present.
In describing embodiments of the invention, specific terminology is employed for the sake of clarity. However, the invention is not intended to be limited to the specific terminology so selected. It is to be understood that each specific element includes all technical equivalents which operate in a similar manner to accomplish a similar purpose.
The practice of the present invention may employ conventional techniques of polymer chemistry within the skill of the art. In the following examples, efforts are made to ensure accuracy with respect to numbers (including amounts) of temperature, reaction times, etc.) used, but some experimental errors and deviations should be accounted for. The temperatures used in the following examples are expressed in degrees Celsius and the pressures are at or near atmospheric. All solvents, reagents were commercially available and all reactions were carried out under nitrogen atmosphere. All reagents were obtained commercially unless otherwise indicated.
Example 1: synthesis of intermediate 2
Potassium tert-butoxide (2.7g, 24.1mmol,4 eq) was added in portions to a solution of fluorene (1.0g, 6.0mmol) and bromo-n-octane (3.5g, 18.1mmol, 3eq) in tetrahydrofuran (15 mL); after the addition, stirring at room temperature for 1 hour; adding 20mL of water for quenching, extracting an organic phase by using dichloromethane, washing by water to remove impurities, drying the organic phase by using anhydrous sodium sulfate, filtering and concentrating; petroleum ether is used as an eluent, and the crude product is eluted by a silica gel column to obtain colorless liquid, namely an intermediate 2; intermediate 2 was obtained in 2.0g, 85% yield; 1 h NMR analysis was consistent with literature.
Example 2: synthesis of intermediate 3
Aluminum trichloride (1.5g, 11.3mmol, 4.4eq) was added in portions to a solution of intermediate 2 (1.0g, 2.6 mmol) and compound C1 (0.94g, 2.6mmol, 1eq) in dichloromethane (20 mL) at 0 ℃; after the addition, stirring at room temperature for 3 hours; adding 20mL of ice water for quenching, extracting an organic phase by using dichloromethane, washing with water to remove impurities, drying the organic phase by using anhydrous sodium sulfate, filtering and concentrating; petroleum ether and dichloromethane are used as eluent, and the crude product is eluted by a silica gel column to obtain light yellow liquid, namely an intermediate 3; intermediate 2 was obtained in 0.5g, 28% yield;
the structure confirmation data is as follows: 1 H NMR(400MHz,CDCl 3 )δ8.59(s,1H),8.29(s,1H),7.90-7.88(d,1H),7.44–7.40(m,3H),2.14–1.96(m,4H),1.25–0.96(m,12H),0.81–0.78(t,6H)。
example 3: synthesis of intermediate 4
Intermediate 3 (0.50g, 0.73mmol), tributyltin-based thiophene (0.25g, 1.8mmol, 2.4eq), pd under inert atmosphere 2 (dba) 3 (25 mg) and P (o-tol) 3 (50 mg) was added to 15mL of toluene, and stirred at 80 ℃ for 6 hours; after cooling to room temperature, the solvent was removed and the reaction mixture was washed with petroleum ether and dichloromethaneRemoving the solvent, and eluting through a silica gel column to obtain a yellow solid, namely an intermediate 4; intermediate 4 was obtained in 0.45g, yield 90%;
the structure confirmation data is as follows: 1 H NMR(400MHz,CDCl 3 )δ8.62(s,1H),8.30(s,1H),7.88-7.86(m,3H),7.58–7.57(m,2H),7.43–7.40(m,3H),7.19–7.17(m,2H),2.14–1.96(m,4H),1.25–0.96(m,12H),0.81–0.77(t,6H)。
example 4: synthesis of intermediate M1
N-bromosuccinimide (NBS) (0.52g, 2.9mmol, 5eq) was added to a 40mL mixed solution of N, N-Dimethylformamide (DMF) and dichloromethane of intermediate 4 (0.40g, 0.58mmol) under dark conditions; stirring at 40 deg.C overnight; extracting the organic phase with dichloromethane, washing with water to remove impurities, drying the organic phase with anhydrous sodium sulfate, filtering and concentrating; eluting with petroleum ether and dichloromethane as eluent through silica gel column to obtain orange solid as intermediate M1; intermediate M2 was obtained in 0.35g, 71% yield;
the structure confirmation data is as follows: 1 H NMR(400MHz,CDCl 3 )δ8.62(s,1H),8.32(s,1H),7.89-7.87(m,1H),7.58–7.56(m,2H),7.45–7.40(m,3H),7.14–7.12(m,2H),2.14–1.99(m,4H),1.25–0.96(m,12H),0.81–0.77(t,6H)。
example 5: synthesis of Polymer P1
Under an inert atmosphere, compound M1 (84.9mg, 0.10mmol), compound M2 (94.1g, 0.10mmol) and Pd (PPh) 3 ) 4 (1.2 mg) was added to a mixed solvent of 4mL of toluene and 1mL of DMF; stirring to be viscous at 110 ℃ for about 45 minutes; the mixture was poured into 30mL of methanol and the filtrate was removed; dissolving the residue with 30mL chloroform, eluting with chloroform as eluent, and passing through silica gel column to obtain black solid, i.e. polymerA compound P1; the polymer P1 obtained was 82mg in 63% yield. Molecular weight by GPC (1,2,4-trichlorobezene, 150 ℃ C.): mw =203.7kDa, PDI =6.17.
Example 6
Physical representation of conjugated polymer organic solar cell donor material based on multi-element aromatic ring thienothiophene dione unit and manufacturing and performance test of solar cell device
1 The H NMR spectra were measured by a Bruker AV-400 instrument, the UV-Vis absorption spectra by a Shimadzu UV-2700 UV-Vis absorption spectrometer and the cyclic voltammetry by a CHI660E electrochemical workstation.
The conjugated polymer organic solar cell device based on the polycyclic aromatic benzothiophene diketone unit adopts a forward structure, and the structure is Glass/ITO/PEDOT, PSS/active layer/PNDIT-F3N/Ag. The material of the photoactive layer is a conjugated polymer donor material and a Y6 non-fullerene acceptor material, and the blending weight ratio of the materials is 1.2.
Example 7
Photophysical, electrochemical and solar cell device properties of polymer P1
The ultraviolet-visible absorption spectrum of the polymer P1 in the chloroform solution and the film is shown in FIG. 1. The specific details are tabulated in table 1.
TABLE 1 optical absorption data for Polymer P1
The maximum absorption site of the polymer P1 in the solution was 590nm, and the initial absorption site was 682nm. When polymer P1 was spin-coated into a film, its absorption maxima and absorption onset were 588nm and 685nm, respectively. The polymer P1 is illustrated in an enhanced state of aggregation between molecular chains after film formation. From the position of the initial absorption of the polymer film according to the formula
The optical band gap of the obtained polymer P1 was 1.81eV.
The solar cell device performance data for polymer P1 are summarized in table 2.
The J-V curve of the photovoltaic device with the mixing ratio of P1 and Y6 being 1.2 (w/w, 6.1 mg/mL), 0.5% CN added and chloroform as solvent is shown in fig. 2. Under this condition, the short-circuit current density of the device was 24.08mA/cm 2 The open circuit voltage was 0.86V, the fill factor was 72.5%, and the energy conversion efficiency was 15.04%.
The EQE curve of the active layer with P1 and Y6 mixed at a ratio of 1.2 (w/w, 6.1 mg/mL), 0.5% CN added and chloroform as solvent is shown in FIG. 3. The graph shows the EQE test range of 300-1000nm, with EQE values exceeding 70% in all ranges of about 500-850 nm.
TABLE 2 solar cell device Performance data for Polymer P1
While the scope of the invention has been described in connection with preferred embodiments, the invention is not limited to the embodiments described above, it being understood that the appended claims outline the scope of the invention. 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 (3)
1. A polymer comprising a polyvalent aromatic thienothiophene dione, wherein the polymer is represented by the formula:
n is a natural number between 5 and 1000.
2. A semiconducting composition comprising the polymer of claim 1.
3. A photoelectric conversion device, wherein an active layer material in the photoelectric conversion device is the polymer according to claim 1.
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