CN107778319B - A-D-A type micromolecule compound containing hepta-fused ring structure indacene and preparation method thereof - Google Patents
A-D-A type micromolecule compound containing hepta-fused ring structure indacene and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an indacene A-D-A type conjugated micromolecule compound containing a hepta-fused ring structure, a preparation method thereof and application of the compound as an optical active layer material in an organic photovoltaic device. The compounds have the following general structure:
the photovoltaic cell is based on a hepta-fused ring as an electron supply unit (D), a thiophene ring as a bridging unit, and a thiophene 4-position as an electron pulling unit (A), and the energy level structure and the light absorption characteristic of the material are adjusted by utilizing the difference of the substitution positions of the A unit on the bridging thiophene, so that the parameters of the photovoltaic cell, such as open-circuit voltage, short-circuit current and the like, are adjusted, and the photoelectric conversion efficiency of the device is improved.
Description
Technical Field
The invention belongs to the field of organic photoelectric functional materials, and particularly relates to a derivative A-D-A type conjugated micromolecule compound containing a hepta-condensed ring structure, a preparation method thereof, and application of the molecule as an n-type material in an optical active layer in an Organic Photovoltaic (OPV) device.
Background
Among solar cells, organic solar cells have become one of the most active fields in photovoltaic research due to their advantages of light weight, low cost, simple preparation process, capability of being prepared into flexible devices, and the like. The photoactive layer material is a key photoactive layer of an organic solar cell, and its properties determine the generation and diffusion of excitons, the separation and transport of charges, and ultimately the photoelectric conversion efficiency of the cell.
The photoactive layer comprises an electron donor material and an electron acceptor material to form a bulk heterojunction, and a conjugated polymer as an electron donor and a fullerene derivative (PC)61BM、PC71BM, ICBA, etc.) as electron acceptors have made the efficiency of organic solar cells breakthrough 11% [ Nature Energy,2016,1,15027]Meaning a great potential for the application of organic solar cells. However, fullerenes and their derivatives have certain disadvantages including: harsh preparation and purification conditions, weak absorption in a visible light region, difficult energy level regulation, poor solubility in common solvents, easy aggregation and the like [ nat. photonics 2012,6,153]These disadvantages limit the further breakthrough of organic solar cell performance. In recent years, non-fullerene micromolecule electron acceptor materials attract attention of scientific researchers because of the advantages of simple preparation, strong absorption in the long wave direction, adjustable structure and energy level, excellent solubility and the like. Novel n-type electron acceptor materials based on imide, fluorenyl derivatives, benzothiazole, pyrrolopyrroledione, pentacene and the like are mainly used for photovoltaic cells. Perylene Diimides (PDI) are the first class of materials studied in solar cells, have excellent light absorption properties, broad solar spectrum, high electron mobility, tunable Highest Occupied Molecular Orbital (HOMO) and lowest unoccupied orbital (LUMO) energy levels, electron affinity comparable to fullerenes, and structurally, the imide can be modified by simple modificationAmine parent nucleus and side substituent, so as to obtain a series of n-type electron acceptor materials with excellent photoelectric property [ adv. Mater.2010,22,3876 ]]However, the wider band gap of such materials limits further improvement of device performance; pentacene and derivatives thereof are easy to regulate and control the film form through chemical modification so as to improve the charge transmission rate [ adv](ii) a Photovoltaic devices made from benzothiadiazole-based materials exhibit good electron transport properties [ adv]. Pyrrolopyrroledione (DPP) [ j]Has wide light absorption range, excellent electrochemical performance, thermodynamic stability and machining performance, and can meet the technological requirement of making organic electronic device. Zhan xiao wei et al [ j.mater.chem.a.2015,3,1910]The dithiophene indacene receptor-based molecules are developed, a pi conjugated framework is extended by fused rings, high electron mobility is obtained, in addition, due to the electron push-pull structure of the molecules, more efficient intramolecular charge transfer can be induced, so that the absorption spectrum of the material is widened, the absorption spectrum is blended with a narrow-band donor polymer material PTB7-Th, and the device efficiency reaches 6.31%. The micromolecule acceptor material generally has a penta-fused ring or hepta-fused ring structure, attracts wide attention due to excellent performance, and is used as an electron acceptor for preparing an organic photovoltaic cell, wherein the performance of the micromolecule acceptor material reaches or even exceeds that of a fullerene electron acceptor [ adv.mater.2016,28,1884; adv.mater.2016,28,4734; adv. mater.2016,28,9423]. In addition, in the reported structures, thiophene or bithiophene can be used as a bridging unit between the central condensed ring and the electricity-deficient units on two sides, and the photoelectric properties are excellent [ CN 105315298A; adv.mater.2016,28,8283; angew.chem.int.ed.2017,56,1]. The electricity-lacking units of the materials are limited to be connected to the 5-position of the thiophene bridging unit, the molecular frameworks of the materials are mostly in a planar structure, although the structure promotes the absorption spectrum of some of the materials to be red-shifted to a near infrared band, a single polymer donor material with good absorption spectrum matching property is difficult to find to form spectrum complementation with the material, and the photoelectric conversion efficiency of a binary-blended single-layer organic photovoltaic cell based on the small molecular receptors is generally less than 10%.
Disclosure of Invention
Aiming at the defects or shortcomings in the prior art, the invention provides a hepta-fused ring indacene A-D-A type micromolecule compound, wherein electricity-deficient units on two sides of the micromolecule are connected to 4-position of a thiophene bridging unit, the structure is not reported, and the structure can realize adjustment of photoelectric property so as to meet the requirement of a photovoltaic cell photoactivation layer electron acceptor material. The small molecular compound is used for a high-efficiency organic photovoltaic cell, and the energy level and the spectral range of the material are adjusted by utilizing the steric effect, the push-pull electronic characteristic of a substituent group and the like, so that the photoelectric conversion efficiency of the device is improved.
In order to realize the task, the structure of the A-D-A type micromolecule compound of the hepta-fused ring indacene designed by the invention is as follows:
wherein R is1Independently an alkyl group having 1 to 20 carbon atoms, a phenyl group substituted with an alkoxy group having 1 to 20 carbon atoms, a thienyl group substituted with an alkyl group having 1 to 20 carbon atoms, or a thienyl group substituted with an alkoxy group having 1 to 20 carbon atoms, R2Independently hydrogen atom, alkyl group with 1-20 carbon atoms, alkoxy group with 1-20 carbon atoms or alkyl ester group with 1-20 carbon atoms, wherein the electron withdrawing unit A1And A2Independently selected from one of the following structures:
A1and A2In the structure of R3Is an alkyl group having 1 to 12 carbon atoms.
The preparation method is carried out by adopting the following reaction equation:
the specific synthesis steps are as follows:
will carry R1Substituted hepta-fused ring organotin reagents, with R2Adding 5-bromo-3-thiophenecarboxaldehyde as a substituent into a reaction vessel, adding 5-10% of catalyst tetrakis (triphenylphosphine) palladium or bis (triphenylphosphine) palladium dichloride under the protection of argon, taking toluene as a solvent, carrying out micro reflux for 12-24h, stopping heating after the reaction is completed, cooling the system to room temperature, adding water to terminate the reaction, extracting an aqueous phase with toluene, carrying out liquid separation, drying and filtering on an organic layer, carrying out spin drying on the filtrate to obtain a crude product, purifying the crude product by column chromatography to obtain a corresponding hepta-condensed ring containing dialdehyde, and then mixing the aldehyde with a 4-6 times of electron withdrawing unit A1Or A2Adding pyridine into chloroform solution, refluxing for 6-12 hr, cooling, precipitating with methanol, performing silica gel column chromatography, and eluting with chloroform to obtain target product, or mixing the hepta-condensed ring containing dialdehyde with 1-1.5 times of A1Adding pyridine into chloroform solution for refluxing for 6-10 hr, purifying by column chromatography, mixing with 2-4 times of A2And adding pyridine into a chloroform solution by a unit pulling electron monomer, refluxing for 6-12 hours, extracting by chloroform, settling by methanol, carrying out silica gel column chromatography, and eluting by chloroform to obtain the A-D-A conjugated molecular product shown in the formula I.
Preferred embodiment of the invention, R1A 4-alkylphenyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a 5-alkylthienyl group having 1 to 20 carbon atoms, or a 4-alkoxyphenyl group having 1 to 20 carbon atoms; r2Is an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an alkyl ester group having 1 to 20 carbon atoms.
The indacene A-D-A type micromolecule compound containing the hepta-condensed ring structure provided by the invention can be used as an optical active layer material and applied to the preparation of organic photovoltaic cells.
The invention has the beneficial effects that: the invention introduces an electron-deficient unit to the 4-position of the thiophene ring, introduces a certain distortion on the molecular main chain, and effectively adjusts the absorption spectrum and the energy level of the material. The indacene A-D-A micromolecule compound has an absorption spectrum with adjustable width, a strong extinction coefficient, good charge transmission performance and a proper energy level structure, is mixed with a polymer electron donor with an optical band gap of 1.7-1.9 eV to manufacture a single-layer binary photovoltaic device, and the photoelectric conversion efficiency exceeds 10%. These wide-bandgap polymer electron donors include D-A type donor polymers based on difluorobenzotriazole, D-A type donor polymers based on thiazolothiazole, D-A type donor polymers based on benzo [1,2-C:4,5-C' ] dithiophene-4, 8-dione, and the like.
Drawings
FIG. 1 is a UV-VIS-NIR absorption spectrum of compound A1 of example 1 according to the invention.
FIG. 2 is a plot of the I-V curves of Compound A1 and a bis-fluorobenzotriazole polymer J52 of example 1 of the present invention.
Detailed Description
The following embodiments of the present invention are provided, and it should be noted that the present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention are within the protection scope of the present invention.
Example 1: compound A1
The synthetic route is as follows:
(1) synthesis of Compound 3:
a100 ml three-necked flask is added with 1672.5 mg/0.5mmol of compound, 478mg/1.5mmol of 2-bromo-3- (2-ethylhexyloxy) thiophene-4-formaldehyde and Pd (PPh)3)440mg of toluene 30ml, heating under nitrogen protection, refluxing for 24h, extracting, washing and performing column chromatography (n-hexane: ethyl acetate: 100:1) to obtain 550mg of compound 3 (liquid phase content)>99%) and 73.5% yield.1H NMR(500MHz,CDCl3),δ9.93(s,2H),7.94(s,2H),7.45(s,2H),7.18(d,8H),7.10(d,8H),6.88(s,2H),4.10(d,4H),2.57(t,8H),1.76(m,2H),1.66-1.58(m,16H),1.50-1.26(m,32H),0.95-0.86(m,24H).13C NMR(125MHz,CDCl3),δ181.09,164.32,157.11,153.37,146.23,142.93,141.91,139.04,137.06,135.16,129.62,128.45,127.68,126.39,122.71,119.30,117.72,111.12,74.46,63.07,39.43,35.52,31.65,31.28,30.32,29.07,29.01,23.78,22.94,22.55,14.04,14.02,11.10.Anal.Calcd for(C94H110O4S6):C 75.45,H 7.41,Found:C 75.23,H 7.27。
(2) Synthesis of A1
Placing 658mg/0.44mmol of the above compound 3, 575mg/2.5mmol of compound a in a 100ml three-necked flask, dissolving in 40ml of chloroform, adding pyridine 1.5ml, heating under reflux for 10h, stopping heating, cooling, extracting, washing, precipitating with methanol, filtering, purifying the obtained solid by column chromatography, eluting with chloroform to obtain 531mg of blue-black solid with yield of 65% and liquid phase content of liquid phase>99％。1H NMR(500MHz,CDCl3),δ9.17(s,2H)，8.66(d,2H),7.85(d,2H),7.73(m,4H),7.21(d,8H),7.14(d,8H),6.93(s,2H),4.18(q,4H),2.63(t,8H),1.91(m,2H),1.63-1.55(m,16H),1.36-1.29(m,32H),0.96-0.86(m,24H).13C NMR(125MHz,CDCl3),δ187.35,170.37,158.72,158.82,155.69,154.78,154.14,148.06,146.00,142.22,140.69,139.37,135.76,134.25,132.83,127.80,123.88,122.69,118.31,117.40,117.19,115.14,114.57,109.18,75.85,67.36,63.21,39.31,35.59,31.77,31.38,30.01,29.13,28.97,23.48,23.02,22.63,14.11,10.92.Anal.Calcd for(C118H114F4N4O4S6):C 73.79,H 5.98,Found:C 76.35,H 5.79。
The ultraviolet-visible-near infrared absorption spectra of the compound A1 solution and the film are shown in figure 1. The molar extinction coefficient of the solution of Compound A1, determined according to Lambert beer's law, was 3.94X 105M-1cm-1The optical energy gap obtained by the film absorption edge (843nm) test is 1.47 eV.
Photovoltaic performance study: adopts ITO/ZnO/J52 as receptor material/MoO3The polymer J52 and the acceptor material are made into polymer lightThe effective area of the photovoltaic cell is 0.16cm2In a simulated solar light source (Oriel model 91192; 100 mW/cm)2) Performing current-voltage test, collecting by using a Keithley 2400 source meter, and measuring the short-circuit current J of the devicescIs 21.17mA cm-2Open circuit voltage Voc0.84V, a fill factor of 66.4% and an energy conversion efficiency PCE of 11.83%. FIG. 2 shows the I-V curves of the polymer photovoltaic cells prepared from the compounds A1 and J52 according to a certain weight ratio in example 1.
The structural formula of J52 is shown below:
example 2: compound A2
The synthetic route is as follows:
placing 658mg/0.44mmol of the above compound 3, 485mg/2.5mmol of the compound b in a 100ml three-necked flask, dissolving in 40ml of chloroform, adding pyridine 1.5ml, heating and refluxing for 6h, stopping heating, cooling, extracting, washing, settling with methanol, filtering, purifying the obtained solid by column chromatography, eluting with chloroform to obtain 582mg of blue-black solid with yield of 69%, and collecting liquid phase content>99％。1H NMR(500MHz,CDCl3),δ9.17(s,2H)，8.66(d,2H),7.85(d,2H),7.72(m,4H),7.53(d,Hz,4H),7.19(d,8H),7.14(d,8H),6.93(s,2H),4.18(q,4H),2.63(t,8H),1.91(m,2H),1.62-1.55(m,16H),1.36-1.29(m,32H),0.96-0.86(m,24H).13C NMR(125MHz,CDCl3),δ187.25,170.27,158.71,158.82,154.78,154.14,145.99,142.22,140.69,139.37,137.06,135.76,134.25,132.83,128.69,127.79,123.88,122.69,118.31,117.40,117.19,115.14,114.57,109.18,75.85,67.36,63.20,39.31,35.58,31.77,31.38,30.01,29.13,28.97,23.48,23.02,22.63,14.11,10.92.Anal.Calcd for(C118H118N4O4S6):C 76.67,H 6.43,Found:C 76.15,H 6.28.
Example 3: synthesis of Compound A3
The synthetic route is as follows:
(1) synthesis of Compound 5:
in a 100ml three-necked flask, 1672.5 mg/0.5mmol of compound, 521mg/1.5mmol of 2-bromo-3-thiophenecarboxylic acid isooctyl ester-4-formaldehyde and Pd (PPh)3)440mg of toluene 30ml, heating under nitrogen protection, refluxing for 24h, extracting, washing and performing column chromatography (n-hexane: ethyl acetate: 100:1) to obtain 543mg of compound 5 (liquid phase content)>99%) and yield 70%.1H NMR(500MHz,CDCl3),δ9.93(s,2H),7.94(s,2H),7.46(s,2H),7.19(d,8H),7.11(d,8H),6.89(s,2H),4.30(d,4H),2.57(t,8H),1.81(m,2H),1.68-1.58(m,16H),1.50-1.26(m,32H),0.95-0.86(m,24H).13C NMR(125MHz,CDCl3),δ181.10,165.29,160.10,157.11,153.39,146.23,142.93,141.92,139.04,137.06,135.16,129.62,128.45,127.68,126.39,122.71,119.30,117.72,111.12,74.46,63.07,39.43,35.52,31.65,31.28,30.32,29.07,29.01,23.78,22.94,22.55,14.04,14.02,11.10.Anal.Calcd for(C96H110O6S6):C 74.28,H 7.14,Found:C 73.97,H 6.96.
(2) Synthesis of Compound A3
683mg/0.44mmol of the compound 5 and 485mg/2.5mmol of the compound b are put into a 100ml three-necked flask and dissolved in 40ml of chloroform, then 1.5ml of pyridine is added, heating reflux is carried out for 8h, heating is stopped, cooling, extraction and washing are carried out, methanol is used for sedimentation, the obtained solid is purified by column chromatography after filtration, chloroform is used for eluting and purifying562mg of bluish-black solid was obtained in 67% yield, liquid content>99％。1H NMR(500MHz,CDCl3),δ9.17(s,2H)，8.66(d,2H),7.85(d,2H),7.72(m,4H),7.53(d,Hz,4H),7.19(d,8H),7.14(d,8H),6.93(s,2H),4.31(q,4H),2.63(t,8H),2.01(m,2H),1.63-1.56(m,16H),1.38-1.30(m,32H),0.96-0.86(m,24H).13C NMR(125MHz,CDCl3),δ187.27,170.28,160.11,158.71,158.83,154.78,154.15,146.00,142.23,140.69,139.37,137.06,135.76,134.25,132.83,128.69,127.79,123.89,122.69,118.31,117.40,117.19,115.14,114.57,109.18,75.85,67.36,63.20,39.31,35.58,31.77,31.38,30.01,29.13,28.97,23.48,23.02,22.63,14.11,10.92.Anal.Calcd for(C120H118N4O6S6):C 75.67,H 6.24,Found:C 75.46,H 6.09.
Example 4: compound A4
The synthetic route is as follows:
(1) synthesis of compound 7:
a100 ml three-necked flask is added with 6520.5 mg/0.5mmol of compound, 478mg/1.5mmol of 2-bromo-3- (2-ethylhexyloxy) thiophene-4-formaldehyde and Pd (PPh)3)440mg of toluene 30ml, heating under nitrogen protection, refluxing for 24h, extracting, washing and performing column chromatography (n-hexane: ethyl acetate: 100:1) to obtain 423mg of compound 7 (liquid phase content)>99%) and yield 71%.1H NMR(500MHz,CDCl3),δ9.92(s,2H),7.91(s,2H),7.43(s,2H),6.87(s,2H),4.11(d,4H),2.57(t,8H),1.76(m,2H),1.66-1.58(m,16H),1.50-1.26(m,32H),0.95-0.86(m,24H).13C NMR(125MHz,CDCl3),δ181.09,164.32,157.11,153.37,146.23,142.93,139.04,129.62,128.45,126.39,121.76,119.30,117.72,111.12,74.46,63.07,39.43,35.52,31.65,31.28,30.32,29.07,29.01,23.78,22.94,22.55,14.04,14.02,11.10.Anal.Calcd for(C70H94O4S6):C 70.54,H 7.95,Found:C 70.32,H 7.68.
(2) Synthesis of A4
Putting 524mg/0.44mmol of the compound 7 and 575mg/2.5mmol of the compound a into a 100ml three-necked flask, dissolving in 40ml of chloroform, adding 1.5ml of pyridine, heating and refluxing for 10h, stopping heating, cooling, extracting, washing, settling with methanol, filtering, purifying the obtained solid by column chromatography, and eluting with chloroform to obtain 484mg of a bluish black solid with the yield of 68 percent and the liquid phase content of the product>99％。1H NMR(500MHz,CDCl3),δ9.17(s,2H)，8.66(d,2H),7.85(d,2H),7.73(m,4H),6.93(s,2H),4.18(q,4H),2.63(t,8H),1.91(m,2H),1.63-1.55(m,16H),1.36-1.29(m,32H),0.96-0.86(m,24H).13C NMR(125MHz,CDCl3),δ187.35,170.37,158.72,158.82,155.69,154.78,154.14,148.06,146.00,140.69,139.37,132.83,127.80,122.69,118.31,117.40,117.19,115.14,114.57,109.18,75.85,67.36,63.21,39.31,35.59,31.77,31.38,30.01,29.13,28.97,23.48,23.02,22.63,14.11,10.92.Anal.Calcd for(C94H98F4N4O4S6):C 69.86,H 6.11,Found:C 69.57,H5.92.
Example 5: compound A5
The synthetic route is as follows:
placing 658mg/0.44mmol of the above compound 3, 152mg/0.66mmol of compound a in a 100ml three-necked flask, dissolving in 40ml of chloroform, adding pyridine 1.5ml, heating and refluxing for 6h, stopping heating, stopping reaction, purifying the obtained product by column chromatography, adding 351mg/1.32mmol of compound c in a 100ml three-necked flask, adding chloroform 40ml, adding pyridine 1.5ml, heating and refluxing for 8h, stopping heating, cooling, extracting, washingWashing, precipitating with methanol, filtering, purifying the obtained solid by column chromatography, eluting with chloroform to obtain blue black solid 335mg, with yield of 39%, and liquid phase content>99％。1H NMR(500MHz,CDCl3),δ9.17(s,2H)，8.66(d,2H),7.85(d,2H),7.73(m,2H),7.21(d,8H),7.14(d,8H),6.93(s,2H),4.18(q,4H),2.63(t,8H),1.91(m,2H),1.63-1.55(m,16H),1.36-1.29(m,32H),0.96-0.86(m,24H).13C NMR(125 MHz,CDCl3),δ187.35,170.37,158.72,158.82,155.69,154.78,154.14,148.06,146.00,142.22,140.69,139.37,137.21,136.17,132.83,127.80,123.88,122.69,118.31,117.40,117.19,115.14,114.57,109.18,75.85,67.36,63.21,39.31,35.59,31.77,31.38,30.01,29.13,28.97,23.48,23.02,22.63,14.11,10.92.Anal.Calcd for(C118H112F6N4O4S6):C 72.44,H 5.77,Found:C 72.31,H 5.69.
Claims (8)
1. A kind of indacene A-D-A type micromolecule compound containing hepta-condensed ring structure is characterized in that the structural general formula is shown as formula I:
in the formula, R1Independently an alkyl group having 1 to 20 carbon atoms, a phenyl group substituted with an alkyl group having 1 to 20 carbon atoms, or a phenyl group substituted with an alkoxy group having 1 to 20 carbon atoms; r2Independently hydrogen atom, alkyl group with 1-20 carbon atoms, alkoxy group with 1-20 carbon atoms or alkyl ester group with 1-20 carbon atoms, wherein the electron withdrawing unit A1And A2Independently selected from one of the following structures:
2. the indacene a-D-a type small molecule compound containing a hepta-fused ring structure according to claim 1, whereinIn that R is1Is a 4-alkylphenyl group having 1 to 20 carbon atoms, R2Is an alkoxy group having 1 to 20 carbon atoms.
3. The indacene a-D-a type small molecule compound containing a hepta-fused ring structure according to claim 1, wherein R is1Is an alkyl group having 1 to 20 carbon atoms, R2Is an alkoxy group having 1 to 20 carbon atoms.
4. The indacene a-D-a type small molecule compound containing a hepta-fused ring structure according to claim 1, wherein R is1Is a 4-alkoxyphenyl group having 1 to 20 carbon atoms, R2Is an alkoxy group having 1 to 20 carbon atoms.
5. The indacene a-D-a type small molecule compound containing a hepta-fused ring structure according to claim 1, wherein R is1Is a 4-alkylphenyl group having 1 to 20 carbon atoms, R2Is an alkyl group having 1 to 20 carbon atoms.
6. The indacene a-D-a type small molecule compound containing a hepta-fused ring structure according to claim 1, wherein R is1Is a 4-alkylphenyl group having 1 to 20 carbon atoms, R2Is an alkyl ester group having 1 to 20 carbon atoms.
7. The indacene A-D-A type small molecule compound containing hepta-condensed ring structure of any one of claims 1-6, which is used as a photoactive layer material alone or in a blend with other materials, and is applied to the preparation of an organic photovoltaic cell.
8. A method for preparing the indacene a-D-a type small molecule compound containing a hepta-fused ring structure according to claim 1, wherein the preparation steps are performed according to the reaction formula shown in formula II:
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN105315298A (en) * | 2014-08-04 | 2016-02-10 | 中国科学院化学研究所 | A-D-A conjugated molecules based on hepta-condensed ring units and preparation method for A-D-A conjugated molecules and application of A-D-A conjugated molecules |
| CN106883247A (en) * | 2017-02-24 | 2017-06-23 | 武汉大学 | A D A conjugated molecules based on thieno cyclopentanedione derivative and preparation method thereof |
-
2017
- 2017-11-06 CN CN201711077458.7A patent/CN107778319B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150114418A (en) * | 2014-03-27 | 2015-10-12 | 주식회사 엘지화학 | Heterocyclic compound and organic solar cell comprising the same |
| CN105315298A (en) * | 2014-08-04 | 2016-02-10 | 中国科学院化学研究所 | A-D-A conjugated molecules based on hepta-condensed ring units and preparation method for A-D-A conjugated molecules and application of A-D-A conjugated molecules |
| CN106883247A (en) * | 2017-02-24 | 2017-06-23 | 武汉大学 | A D A conjugated molecules based on thieno cyclopentanedione derivative and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Energy-level modulation of non-fullerene acceptors to achieve high-efficiency polymer solar cells at a diminished energy offset;Zhongqiang Zhang;《Journal of Materials Chemistry A》;20170412(第20期);第80677-80681页 * |
| Investigating the crystalline nature, charge transport properties and photovoltaic performances of ladder-type donor based small molecules;Hua-Chun Wang;《RSC Advances》;20150915(第5期);第80677-80681页 * |
| Zhongqiang Zhang.Energy-level modulation of non-fullerene acceptors to achieve high-efficiency polymer solar cells at a diminished energy offset.《Journal of Materials Chemistry A》.2017,(第20期),第9649-9654页. * |
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