CN109354591B - Active layer material of organic solar cell and preparation method and application thereof - Google Patents
Active layer material of organic solar cell and preparation method and application thereof Download PDFInfo
- Publication number
- CN109354591B CN109354591B CN201811376295.7A CN201811376295A CN109354591B CN 109354591 B CN109354591 B CN 109354591B CN 201811376295 A CN201811376295 A CN 201811376295A CN 109354591 B CN109354591 B CN 109354591B
- Authority
- CN
- China
- Prior art keywords
- compound
- solar cell
- active layer
- organic solar
- layer material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 63
- 150000001875 compounds Chemical class 0.000 claims description 49
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 46
- 238000001035 drying Methods 0.000 claims description 22
- -1 5- (2-ethylhexyl) -4-hexylthiophen-2-yl Chemical group 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical compound C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229940125904 compound 1 Drugs 0.000 claims description 9
- 229940126214 compound 3 Drugs 0.000 claims description 6
- 229940125782 compound 2 Drugs 0.000 claims description 5
- 229940125898 compound 5 Drugs 0.000 claims description 5
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 4
- ANVJARPTPIVPRC-UHFFFAOYSA-N 2,1,3-benzothiadiazole-4-carbaldehyde Chemical compound O=CC1=CC=CC2=NSN=C12 ANVJARPTPIVPRC-UHFFFAOYSA-N 0.000 claims description 3
- LPASVVQQHVDHIG-UHFFFAOYSA-N 3-hexyl-2-sulfanylidene-1,3-thiazolidin-4-one Chemical compound CCCCCCN1C(=O)CSC1=S LPASVVQQHVDHIG-UHFFFAOYSA-N 0.000 claims description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000011161 development Methods 0.000 abstract description 5
- 239000011149 active material Substances 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000010494 dissociation reaction Methods 0.000 abstract description 3
- 230000005593 dissociations Effects 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract 4
- 125000005842 heteroatom Chemical group 0.000 abstract 3
- 125000003118 aryl group Chemical class 0.000 abstract 2
- 229930192474 thiophene Natural products 0.000 abstract 2
- 150000003384 small molecules Chemical class 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 54
- 239000012043 crude product Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 238000010898 silica gel chromatography Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000013086 organic photovoltaic Methods 0.000 description 5
- 229920000144 PEDOT:PSS Polymers 0.000 description 4
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 229910017464 nitrogen compound Inorganic materials 0.000 description 4
- 150000002830 nitrogen compounds Chemical class 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229940117389 dichlorobenzene Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- NUGPIZCTELGDOS-QHCPKHFHSA-N N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclopentanecarboxamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CC[C@@H](C=1C=NC=CC=1)NC(=O)C1CCCC1)C NUGPIZCTELGDOS-QHCPKHFHSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000011097 chromatography purification Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- JNEBZFFTOLBIKJ-UHFFFAOYSA-N thiadiazole-4-carbaldehyde Chemical compound O=CC1=CSN=N1 JNEBZFFTOLBIKJ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention belongs to the technical field of solar cell materials, and particularly relates to an active layer material of an organic solar cell, and a preparation method and application thereof. The chemical structure general formula of the active layer material of the organic solar cell is as follows:
r1 is selected from (alkyl chain, heteroatom (O, S) -substituted alkyl chain, alkyl-substituted aromatic ring (thiophene, furan, benzene), heteroatom (O, S) -containing alkyl-substituted aromatic ring (thiophene, furan, benzene)), R2 is selected from (alkyl chain, heteroatom (O, S) -substituted alkyl chain) D is selected from small molecule acceptor materials. The active layer material of the organic solar cell does not depend on the blending ratio of the donor material to the acceptor material, the preparation method greatly simplifies the preparation process of the organic solar cell, the generation and dissociation of excitons in the active layer of the organic solar cell can occur in the same molecule, the very effective (or rapid) charge separation is ensured, and the organic solar cell has good device performance and stability, is relatively more economic compared with the existing active material of the organic solar cell, and is more beneficial to the development of the field of the organic solar cell.
Description
Technical Field
The invention belongs to the technical field of solar cell materials, and particularly relates to an active layer material of an organic solar cell, and a preparation method and application thereof.
Background
Organic Photovoltaic (OPV) solar cells are widely focused on the world due to their advantages of being lightweight, flexible, and capable of being processed in large areas. Through the development of the last 20 years, a plurality of breakthrough progresses are achieved. The maximum photoelectric conversion efficiency of the current single-layer heterojunction OPVs can reach 14.2 percent, and the single-layer heterojunction OPVs is considered to be a new generation solar cell capable of replacing the traditional silicon-based cell. However, the preparation process of the single-layer heterojunction OPVs is complex, the stability is poor, and the preparation cost is high. To solve this bottleneck problem, many research groups around the world have conducted extensive and intensive studies over the years, including the preparation of highly efficient photoactive materials, the design of novel devices, and the study of photoelectric conversion mechanisms.
Although the research at home and abroad has made great progress, the research has been greatly improved so farThe photoelectric conversion efficiency of the organic solar cell is not obvious. The reason for this is that most photoactive materials (especially, acceptor materials) in the current organic solar cell systems have low light absorption efficiency, and cannot fully and effectively utilize sunlight. The fullerene derivative is the most widely used and successful electron acceptor in the organic solar cell at present. However, due to richnessThe lexene receptor is expensive and can Weak absorption in the visible region, difficult energy level regulation, easy diffusion and aggregation and the like,severely restricting the development of the organic polymer solar cell field.
Therefore, aiming at the defects that the prior organic solar cell active layer appearance optimization process is complicated, the donor material and the acceptor material in the active layer are not uniformly mixed and are easy to excessively gather to form excessive phase separation, so that the organic solar cell has low photoelectric conversion efficiency, the active layer is unstable and the like, the design and development are carried outNovel organic solar cell active layer material for reducing excessive polymerization The method has the advantages of improving the speed of charge separation and hopefully greatly improving the high photoelectric conversion efficiency and stability of the organic solar cell.
Disclosure of Invention
In view of the above, an object of the present invention is to provide an active layer material for an organic solar cell, which is independent of a blending ratio with a donor material-acceptor material, and in which generation and dissociation of excitons in an active layer of an organic solar cell may occur in the same molecule, ensuring very efficient (or rapid) charge separation, and having good device performance and stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
an active layer material of an organic solar cell, which has a chemical structure general formula as follows:
wherein R is1One selected from the following groups:
R2one selected from the following groups:
d is a small molecule receptor material which is respectively selected from one of the following materials:
further, when R1 is
R2 is
D is
In the case, the active layer material of the organic solar cell is BTR-PCBM.
Furthermore, the active layer material BTR-PCBM of the organic solar cell has a chemical structural formula as follows:
further, when R1 is
R2 is
D is
In the case, the active layer material of the organic solar cell is BTR-IDTBR.
Furthermore, the active layer material BTR-IDTBR of the organic solar cell has a chemical structure as follows:
the second purpose of the present invention is to provide a method for preparing an active layer material of an organic solar cell.
In order to achieve the purpose, the invention adopts the following technical scheme:
an active layer material of an organic solar cell is BTR-PCBM, and the chemical structure of the BTR-PCBM is as follows:
the preparation method of the BTR-PCBM comprises the following steps:
in a round-bottom flask, under the protection of nitrogen, adding compound 3 and compound 4 (PC) in turn70BM-COOCl) and super-dry dichloromethane, heating, refluxing and stirring overnight, cooling the reaction mixture to room temperature, extracting with dichloromethane, washing with water, drying with anhydrous sodium sulfate, spin-drying the solvent to obtain a crude product, and separating and purifying by silica gel column chromatography to obtain a black solid, namely BTR-PCBM.
The compound 3 is ((E) -5- ((5 '- (4, 8-bis (5- (2-ethylhexyl) -4-hexylthiophen-2-yl) -6- (3-hexyl-5' - ((E) - (3- (6-hydroxyhexyl) -4-oxo-2-thioxothiazolidin-5-ylidene) methyl) -4 '-pentyl- [2, 2': 5', 2' -trithiophene ] -5-yl) benzo [1, 2-b: 4,5-b '] dithiophene-2-yl) -3', 3 '-hexyl- [2, 2': 5', 2' -trithiophene ] -5-yl) methylene) -3- (6-hydroxyhexyl) -2-thioxothiazolidin-2-yl -4-ketones).
Further, the preparation method of the compound 4 comprises the following steps:
sequentially adding into a round-bottom flask under the protection of nitrogenCompound 1(5 '- (4, 8-bis (5- (2-ethylhexyl) -4-hexylthiophen-2-yl) -6- (5' -formyl-3, 4 '-dihexyl- [2, 2': 5', 2' -trithiophene)]-5-yl) benzo [1, 2-b: 4,5-b']Dithiophen-2-yl) -3 "-hexyl-3 '-pentyl- [2, 12': 5', 2' -Trithiophene]-5-formaldehyde),Compound 2(3- (6-hydroxyhexyl) -2-thiazolidine-4-ketone) and super-dry chloroform, heating and refluxing the solution, stirring for 12 hours, cooling to room temperature, extracting with dichloromethane, washing with water, drying with anhydrous sodium sulfate, spin-drying the solvent to obtain a crude product, and separating and purifying by silica gel column chromatography to obtain a dark reddish brown solid, namely the compound 4.
The invention also aims to provide a preparation method of the active layer material of the organic solar cell.
In order to achieve the purpose, the invention adopts the following technical scheme:
an active layer material of an organic solar cell is BTR-IDTBR, and the chemical structure of the BTR-IDTBR is as follows:
the preparation method of the BTR-IDTBR comprises the following steps:
adding a compound 6, a compound 9 and ultra-dry chloroform into a round-bottom flask under the protection of nitrogen, heating and refluxing the solution, stirring for 12 hours, cooling to room temperature, extracting with dichloromethane, washing with water, drying with anhydrous sodium sulfate, spin-drying the solvent to obtain a crude product, and separating and purifying by silica gel column chromatography to obtain a black solid, namely BTR-IDTBR.
Further, the preparation method of the compound 6 comprises the following steps:
adding the compound 1, the compound 5 (hexane-1, 6-diyl bis (2- (4-oxo-2-thioxothiazolidin-3-yl) acetate)) and ultra-dry chloroform in turn in a round-bottom flask under the protection of nitrogen, heating and refluxing the solution, stirring for 12 hours, cooling to room temperature, extracting with dichloromethane, washing with water, drying with anhydrous sodium sulfate, spin-drying the solvent to obtain a crude product, and separating and purifying by silica gel column chromatography to obtain a black solid, namely the compound 6.
Further, the preparation method of the compound 9 comprises the following steps:
adding a compound 7(7,7'- (5,5,10, 10-tetrahexyl-5, 10-dihydro-s-benzodiindeno [2, 1-b: 6,5-b' ] dithiophene-2, 7-diyl) bis (benzo [ c ] [1,2,5] thiadiazole-4-carbaldehyde)), a compound 8 (3-hexyl-2-thioxothiazolidin-4-one) and ultra-dry chloroform into a round-bottom flask under the protection of nitrogen, heating and refluxing the solution, stirring for 12 hours, cooling to room temperature, extracting with dichloromethane, washing with water, drying with anhydrous sodium sulfate, spin-drying the solvent to obtain a crude product, and separating and purifying by using a silica gel column chromatography to obtain a black solid, namely a compound 9.
Preferably, the millimolar ratio of compound 3, compound 4 and ultra-dry dichloromethane before reaction is 0.07: 0.18: 156.
preferably, the millimolar unreacted ratio of compound 1, compound 2 and ultra-dry chloroform is 0.3: 1.3: 124.
preferably, the millimolar unreacted ratio of compound 6, compound 9 and ultra-dry chloroform is 0.1: 0.5: 124.
preferably, the millimolar unreacted ratio of compound 1, compound 5 and ultra-dry chloroform is 0.5: 0.1: 124.
preferably, the millimolar unreacted ratio of compound 7, compound 8 and ultra-dry chloroform is 0.2: 0.2: 124.
the fourth purpose of the present invention is to provide an application of an active layer material of an organic solar cell.
In order to achieve the purpose, the invention adopts the following technical scheme:
an active layer material of an organic solar cell is applied to the preparation of the organic solar cell.
The finished product can be made into a flexible solar cell panel by a large-area printing mode and used for outdoor products such as outer walls of buildings, windows, roofs, car doors and car windows of automobiles, sunshades, mobile phone shells and the like.
The invention has the beneficial effects that: 1) the active layer material of the organic solar cell and the preparation method are characterized in that the donor material and the acceptor material are connected together through an alkyl chain, and the blending ratio of the donor material to the acceptor material is not required to be adjusted when the organic solar cell is prepared, so that the preparation process of the organic solar cell is simplified;
2) the generation and dissociation of excitons in the active layer of the organic solar cell may occur in the same molecule, ensuring very effective (or rapid) charge separation, thereby improving the light-spot conversion efficiency of the organic solar cell, and simultaneously the active layer material of the organic solar cell has very high morphological stability;
3) compared with the existing organic solar cell active material (particularly fullerene), the organic solar cell active material is relatively more economic, the receptor is not easy to diffuse and gather, the efficiency is high, and the organic solar cell active material is more beneficial to the development of the field of organic solar cells.
Drawings
Fig. 1 is a synthesis route of an active layer material BTR-PCBM of an organic solar cell prepared in example 1.
Fig. 2 is a synthesis route of an active layer material BTR-IDTBR of the organic solar cell prepared in example 2.
FIG. 3 is an I-V plot of a solar cell device of the structure ITO/PEDOT: PSS/active layer/ZnO/Al.
FIG. 4 is a graph of EQE for a solar cell device of the structure ITO/PEDOT: PSS/active layer/ZnO/Al.
FIG. 5 is an I-V plot of a solar cell device of the structure ITO/PEDOT: PSS/active layer/ZnO/Al.
FIG. 6 is a graph of EQE for a solar cell device of the structure ITO/PEDOT: PSS/active layer/ZnO/Al.
Detailed Description
The examples are given for the purpose of better illustration of the invention, but the invention is not limited to the examples. Therefore, those skilled in the art should make insubstantial modifications and adaptations to the embodiments of the present invention in light of the above teachings and remain within the scope of the invention.
The petroleum ether, methylene chloride, used in the examples below was purchased from Chongqing Chuandong chemical industries, Inc.; ultra-dry chloroform was purchased from Shanghai Tantake Technique, Inc.; triethylamine was purchased from sahn chemical technology (shanghai) ltd; compounds 1,2, 4,5, 7, 8 are available from the general company of organic opto-electronic technology of Plastic (Beijing).
Example 1
Preparation of active layer material of organic solar cell the chemical structural general formula of the active layer material of an organic solar cell is:
wherein R is1One selected from the following groups:
R2one selected from the following groups:
d is a small molecule receptor material which is respectively selected from one of the following materials:
when R1 is
R2 is
D is
And then, the active layer material of the organic solar cell is BTR-PCBM, and the chemical structural formula of the active layer material of the organic solar cell is as follows:
the preparation steps of the BTR-PCBM are as follows (the preparation route is shown in figure 1):
1) synthesis of Compound 4: in a 100mL round-bottom flask, 0.3mmol is added under the protection of nitrogenCompound 1(5 '- (4, 8-bis (5- (2-ethylhexyl) -4-hexylthiophen-2-yl) -6- (5' -formyl-3, 4 '-dihexyl- [2, 2': 5', 2' -trithiophene)]-5-yl) benzo [1, 2-b: 4,5-b']Dithiophen-2-yl) -3 "-hexyl-3 '-pentyl- [2, 12': 5', 2' -Trithiophene]-5-Formaldehyde), 1.3mmolCompound 2(3- (6-hydroxyhexyl) -2-thiazolidine-4-one) and 10mL of super-dry chloroform, heating and refluxing the solution, stirring for 12 hours, cooling to room temperature, extracting with dichloromethane, washing with water, drying with anhydrous sodium sulfate, spin-drying the solvent to obtain a crude product, and separating and purifying by silica gel column chromatography to obtain a dark reddish-brown solid, namely the compound 4, wherein the yield is 88%;
2) synthesis of BTR-PCBM: 0.07mmolCompound 3((E) -5- ((5 '- (4, 8-bis (5- (2-ethylhexyl) -4-hexylthiophen-2-yl) -6- (3-hexyl-5' - ((E) - (3- (6-hydroxyhexyl) -4-oxo-2-thioxothiazolidin-5-ylidene) methyl) -4 '-pentyl- [2, 2': 5', 2' -trithiophene]-5-yl) benzo [1, 2-b: 4,5-b']Dithiophen-2-yl) -3', 3 "-hexyl- [2, 2': 5', 2' -Trithiophene]-5-yl) methylene) -3- (6-hydroxyhexyl) -2-thioxothiazolidin-4-one) and 0.18mmol of compound 4 were dissolved in 10mL of ultra dry dichloromethane, heated under reflux and stirred overnight, the reaction mixture was cooled to room temperature, then extracted with dichloromethane, washed with water, dried over anhydrous sodium sulfate, the solvent was dried by spinning to give a crude product, which was purified by silica gel column chromatography to give a black solidThe yield of the compound BTR-PCBM is 85 percent.
Example 2
Preparation of active layer material of organic solar cell
The general chemical structure formula of an active layer material of an organic solar cell is shown in example 1, when R1 is
R2 is
D is
When the organic solar cell is used, the active layer material of the organic solar cell is BTR-IDTBR, and the chemical structure of the active layer material of the organic solar cell is BTR-IDTBR:
1) synthesis of Compound 6: in a 100mL round-bottom flask, 0.5mmol is added under the protection of nitrogenCompound 1(5 '- (4, 8-bis (5- (2-ethylhexyl) -4-hexylthiophen-2-yl) -6- (5' -formyl-3, 4 '-dihexyl- [2, 2': 5', 2' -trithiophene)]-5-yl) benzo [1, 2-b: 4,5-b']Dithiophen-2-yl) -3 "-hexyl-3 '-pentyl- [2, 12': 5', 2' -Trithiophene]-5-Formaldehyde), 0.1mmolCompound 5(hexane-1, 6-diylbis (2- (4-oxo-2-thioxothiazolidin-3-yl) acetate)) and 10mL of ultra-dry chloroform, heating and refluxing the solution, stirring for 12 hours, cooling to room temperature, extracting with dichloromethane, washing with water, drying with anhydrous sodium sulfate, spin-drying the solvent to obtain a crude product, and separating and purifying by silica gel column chromatography to obtain a black solid, namely the compound 6, wherein the yield is 83%;
2) synthesis of compound 9: in a 100mL round-bottom flask, 0.2mmol is added under the protection of nitrogenCompound 7(7,7'- (5,5,10, 10-tetrahexyl-5, 10-dihydro-s-benzodiindeno [2, 1-b: 6,5-b']Dithiophenes-2, 7-diyl) bis (benzo [ c)][1,2,5]Thiadiazole-4-carbaldehyde)), 0.2mmolCompound 8(3-hexyl-2-thiazolidine-4-one) and 10mL of super-dry chloroform, heating and refluxing the solution, stirring for 12 hours, cooling to room temperature, extracting with dichloromethane, washing with water, drying with anhydrous sodium sulfate, spin-drying the solvent to obtain a crude product, and performing chromatographic separation and purification on the crude product by using a silica gel column to obtain a black solid, namely a compound 9 with the yield of 78%;
3) synthesis of Compound BTR-IDTBR: adding 0.1mmol of compound 6, 0.5mmol of compound 9 and 10mL of ultra-dry chloroform into a 100mL round-bottom flask under the protection of nitrogen, heating and refluxing the solution, stirring for 12 hours, cooling to room temperature, extracting with dichloromethane, washing with water, drying with anhydrous sodium sulfate, spinning off the solvent to obtain a crude product, and separating and purifying by silica gel column chromatography to obtain a black solid, namely the compound BTR-IDTBR with the yield of 88%.
Example 3
The performance research of the solar cell which is prepared by adopting BTR-PCBM as an active layer and adopting ITO/PEDOT, PSS/active layer/ZnO/Al as the structure of the device
The active layer material of the organic solar cell of example 1 has good solubility in several common organic solvents, such as chlorobenzene, dichlorobenzene, chloroform, toluene, trichlorobenzene.
The performance research results of the solar cell which adopts BTR-PCBM as the active layer and is made of ITO/PEDOT, PSS/active layer/ZnO/Al according to the structure of the device are shown in the table 1, the figure 3 and the figure 4, and the table 1 lists the performance parameters expressed by the solar cell which adopts BTR-PCBM as the active layer. Fig. 3 shows that the short-circuit current density, the fill factor, and the open-circuit voltage of the solar cell of this structure were 12.31mA/cm2, 54.91, and 0.98V, respectively, in the case where the active layer was BTR-PCBM. Fig. 4 shows an external quantum efficiency-wavelength curve of a solar cell with BTR-PCBM as the active layer.
TABLE 1 Performance parameters of solar cells with BTR-PCBM as the active layer
Example 4
The performance research of the solar cell which is prepared by adopting BTR-IDTBR as an active layer and adopting ITO/PEDOT, PSS/active layer/ZnO/Al as the structure of the device
The active layer material of the organic solar cell of example 2 has good solubility in several common organic solvents, such as chlorobenzene, dichlorobenzene, chloroform, toluene, trichlorobenzene.
The results of the performance study of the solar cell using BTR-IDTBR as the active layer and ITO/PEDOT/PSS/active layer/ZnO/Al as the device structure are shown in Table 2, FIG. 5 and FIG. 6, and Table 2 shows the performance parameters of the solar cell using BTR-IDTBR as the active layer. Fig. 5 shows short-circuit current density, fill factor and open-circuit voltage of 13.85mA/cm2, 60.22 and 0.77V, respectively, in the case where the active layer of the solar cell of this structure is BTR-IDTBR, and fig. 6 shows external quantum efficiency-wavelength curves of the solar cell with the BTR-IDTBR as the active layer.
TABLE 2 Performance parameters of solar cells with BTR-IDTBR as active layer
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (12)
1. The active layer material of the organic solar cell is characterized in that the active layer material of the organic solar cell is BTR-PCBM, and the chemical structural formula of the active layer material is as follows:
2. an active layer material of an organic solar cell, wherein the active layer material of the organic solar cell is BTR-IDTBR, and the chemical structure of the active layer material is as follows:
3. the preparation method of the active layer material of the organic solar cell is characterized in that the active layer material of the organic solar cell is BTR-PCBM, and the chemical structure of the BTR-PCBM is as follows:
the preparation method of the BTR-PCBM comprises the following steps:
sequentially adding a compound 3, a compound 4 and ultra-dry dichloromethane for heating reaction, and extracting, drying and concentrating by using dichloromethane to obtain the BTR-PCBM; the compound 3 is (E) -5- ((5 '- (4, 8-bis (5- (2-ethylhexyl) -4-hexylthiophen-2-yl) -6- (3-hexyl-5' - ((E) - (3- (6-hydroxyhexyl) -4-oxo-2-thioxothiazolidin-5-ylidene) methyl) -4 '-pentyl- [2, 2': 5', 2' -trithiophene]-5-yl) benzo [1, 2-b: 4,5-b']Dithiophen-2-yl) -3', 3 "-hexyl- [2, 2': 5', 2' -Trithiophene]-5-yl) methylene) -3- (6-hydroxyhexyl) -2-thioxothiazolidin-4-one, said compound 4 being PC70BM-COOCl, and the preparation method of the compound 4 comprises the following steps:
sequentially adding a compound 1, a compound 2 and ultra-dry chloroform, heating, stirring, reacting, extracting by dichloromethane, drying and concentrating to obtain a compound 4; the compound 1 is 5 "- (4, 8-bis (5- (2-ethylhexyl) -4-hexylthiophen-2-yl) -6- (5" -formyl-3, 4 '-dihexyl- [2, 2': 5', 2 "-trithiophene ] -5-yl) benzo [1, 2-b: 4,5-b' ] dithiophene-2-yl) -3" -hexyl-3 '-pentyl- [2, 12': 5', 2' -trithiophene ] -5-carbaldehyde, wherein the compound 2 is 3- (6-hydroxyhexyl) -2-thiothiazolidin-4-one.
4. The preparation method of the active layer material of the organic solar cell is characterized in that the active layer material of the organic solar cell is BTR-IDTBR, and the chemical structure of the BTR-IDTBR is as follows:
the preparation method of the BTR-IDTBR comprises the following steps:
adding a compound 6, a compound 9 and super-dry chloroform, heating, stirring, reacting, extracting by dichloromethane, drying and concentrating to obtain the BTR-IDTBR; the compound 6 is 6- (2- ((E) -5- ((5 '- (4, 8-bis (5- (2-ethylhexyl) -4-hexylthiophen-2-yl) -6- (3-hexyl-5' - ((Z) - (4-oxo-3- (2-oxo-2- ((6- (2- (4-oxo-2-thioxothiazolidin-3-yl) acetoxy) hexyl) oxy) ethyl) -2-thioxothiazolidin-5-methylene) methyl) -4 '-pentyl- [2, 2': 5', 2' -p-thiophen ] -5-yl) benzo [1, 2-b: 4,5-b ' ] dithiophen-2-yl) -3', 3 "-dihexyl- [2,2 ': 5', 2 "-p-thiophen ] -5-yl) methylene) -4-oxo-2-thioxothiazolidine-3- - (yl) acetoxy) 2- (4-oxo-2-thioxothiazolyloxazolidin-3-yl) acetic acid hexyl ester said compound 9 being (Z) -7- (5,5,10, 10-tetrahexyl-7- (7- ((3-hexyl-4-oxo-2-thioxothiazolidin-5-ylidene) methyl) benzo [ c ] [1,2,5] thiadiazol-4-yl) -5, 10-dihydro-s-benzodiindeno [2, 1-b: 6,5-b' ] dithiophen-2-yl) benzo [ c ] [1,2,5] thiadiazole-4-carbaldehyde.
5. The method according to claim 4, wherein the compound 6 is prepared by:
sequentially adding a compound 1, a compound 5 and ultra-dry chloroform, heating, stirring, reacting, extracting by dichloromethane, drying and concentrating to obtain a compound 6; said compound 5 is hexane-1, 6-diylbis (2- (4-oxo-2-thioxothiazolidin-3-yl) acetate); the compound 1 is (5 '- (4, 8-bis (5- (2-ethylhexyl) -4-hexylthiophen-2-yl) -6- (5' -formyl-3, 4 '-dihexyl- [2, 2': 5', 2' -trithiophene ] -5-yl) benzo [1, 2-b: 4,5-b '] dithiophene-2-yl) -3' -hexyl-3 '-pentyl- [2, 12': 5', 2' -trithiophene ] -5-carbaldehyde).
6. The method according to claim 4, wherein the compound 9 is prepared by:
adding a compound 7, a compound 8 and ultra-dry chloroform, heating, stirring, reacting, extracting by dichloromethane, drying and concentrating to obtain a compound 9; the compound 7 is 7,7'- (5,5,10, 10-tetrahexyl-5, 10-dihydro-s-benzodiindeno [2, 1-b: 6,5-b' ] dithiophene-2, 7-diyl) bis (benzo [ c ] [1,2,5] thiadiazole-4-carbaldehyde), and the compound 8 is 3-hexyl-2-thioxothiazolidin-4-one.
7. The method of claim 3, wherein the unreacted millimolar ratio of Compound 3, Compound 4, and ultra-dry dichloromethane is 0.07: 0.18: 156.
8. the method according to claim 3, wherein the unreacted millimolar ratio of Compound 1, Compound 2 and ultra-dry chloroform is 0.3: 1.3: 124.
9. the method of claim 4, wherein the unreacted millimolar ratio of Compound 6, Compound 9, and ultra-dry chloroform is 0.1: 0.5: 124.
10. the method according to claim 5, wherein the pre-reaction millimolar ratio of Compound 1, Compound 5 and ultra-dry chloroform is 0.5: 0.1: 124.
11. the method according to claim 6, wherein the unreacted millimolar ratio of Compound 7, Compound 8 and ultra-dry chloroform is 0.2: 0.2: 124.
12. use of the active layer material of an organic solar cell according to claim 1 or 2 for the production of an organic solar cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811376295.7A CN109354591B (en) | 2018-11-19 | 2018-11-19 | Active layer material of organic solar cell and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811376295.7A CN109354591B (en) | 2018-11-19 | 2018-11-19 | Active layer material of organic solar cell and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109354591A CN109354591A (en) | 2019-02-19 |
| CN109354591B true CN109354591B (en) | 2021-09-14 |
Family
ID=65332261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811376295.7A Active CN109354591B (en) | 2018-11-19 | 2018-11-19 | Active layer material of organic solar cell and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109354591B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112830939B (en) * | 2020-12-23 | 2021-12-10 | 中国科学院重庆绿色智能技术研究院 | Dimer small-molecule electron donor material and preparation method thereof |
| CN114891023B (en) * | 2022-06-07 | 2023-05-02 | 中国科学院重庆绿色智能技术研究院 | Double-end-capped small molecule electron donor material, and preparation and application thereof |
| CN114874205B (en) * | 2022-06-07 | 2023-06-13 | 中国科学院重庆绿色智能技术研究院 | Electron-deficient heterocyclic core small molecule electron donor material, preparation and application thereof |
| CN116375741B (en) * | 2023-03-15 | 2024-10-11 | 南方科技大学 | Organic receptor material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140020739A1 (en) * | 2011-03-29 | 2014-01-23 | The Regents Of The University Of California | Active materials for electro-optic devices and electro-optic devices |
| CN104119355A (en) * | 2014-06-27 | 2014-10-29 | 南开大学 | Organic photoelectric compounds, preparing method thereof and applications of the compounds |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101694961B1 (en) * | 2013-05-21 | 2017-01-10 | 한국화학연구원 | small molecule asymmetric organic semiconductor compounds, its manufacturing method and organic semiconductor device using the same |
-
2018
- 2018-11-19 CN CN201811376295.7A patent/CN109354591B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140020739A1 (en) * | 2011-03-29 | 2014-01-23 | The Regents Of The University Of California | Active materials for electro-optic devices and electro-optic devices |
| CN104119355A (en) * | 2014-06-27 | 2014-10-29 | 南开大学 | Organic photoelectric compounds, preparing method thereof and applications of the compounds |
Non-Patent Citations (1)
| Title |
|---|
| Graphene quantum dots as the hole transport layer material for high-performance organic solar cells;Miaomiao Li,等;《Physical Chemistry Chemical Physics》;20130926;第15卷(第43期);18973-18978页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109354591A (en) | 2019-02-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109354591B (en) | Active layer material of organic solar cell and preparation method and application thereof | |
| CN108912140B (en) | Asymmetric A-D-A type conjugated small molecule and intermediate and application thereof | |
| CN107011361A (en) | Organic photoelectric acceptor material and its preparation method and application | |
| CN107759621B (en) | Bithiophene (selenophene) -modified photoelectric compound and preparation method and application thereof | |
| CN110128633B (en) | Preparation method and application of low-HOMO energy level polymer donor material | |
| CN104177378A (en) | Tetra-substituted perylene diimide dimer, preparation method of tetra-substituted perylene diimide dimer and use of tetra-substituted perylene diimide dimer in organic photovoltaic device | |
| CN102858842A (en) | Conjugated polymer containing dithienopyrrole-quinoxaline, preparation method and uses thereof | |
| CN104045657A (en) | Five-membered heterocyclic derivative-bridged perylene diimide dipolymer and its preparation method and use in organic photovoltaic device | |
| EP2562197A1 (en) | Copolymer comprising anthracene and benzoselenadiazole, preparing method and uses thereof | |
| CN105017264A (en) | Organic small molecular photoelectric functional material, and preparation method thereof | |
| WO2011147067A1 (en) | Quinoxaline conjugated polymer containing fused-ring thiophehe unit, preparation method and uses thereof | |
| CN114621275B (en) | Benzotriazole boron nitrogen derivative and application thereof | |
| WO2011091609A1 (en) | Heterocycloquinoid thiophene organic photoelectric material, preparation method and use thereof | |
| CN102002145A (en) | Novel N-ester substituted bithiophene and pyrrole conjugated polymer | |
| CN106892917B (en) | A kind of fluoro imide derivative and its application | |
| CN113072533A (en) | Non-condensed electron acceptor material and organic solar cell constructed by same | |
| EP2573124B1 (en) | Porphyrin copolymer containing quinoxaline unit, preparation method and uses thereof | |
| CN102276801A (en) | Thienothiophene quinoid organic photoelectric material as well as preparation method and application thereof | |
| CN114621276B (en) | Benzothiadiazole boron nitrogen derivative and application thereof | |
| CN109232527B (en) | Self-doping type fullerene pyridinium electron transport material and organic solar cell formed by same | |
| CN110498793B (en) | Small-molecule photovoltaic bulk phase material based on rhodanine and application thereof | |
| JP5443655B2 (en) | Porphyrin copolymer containing thienothiadiazole unit, method for producing the copolymer and application thereof | |
| CN102234366B (en) | Thiophene-containing perylene tetracarboxylic diimide copolymer, and preparation method and application thereof | |
| Suleiman et al. | Dialkoxymethano [60] fullerenes as electron acceptors in thin-film organic solar cells | |
| CN102206328A (en) | Porphyrin copolymer containing benzothiadiazole unit, its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20190219 Assignee: Zhongjiwei (Chongqing) new material Technology Research Institute Co.,Ltd. Assignor: CHONGQING INSTITUTE OF GREEN AND INTELLIGENT TECHNOLOGY, CHINESE ACADEMY OF SCIENCES Contract record no.: X2024980012669 Denomination of invention: An active layer material for organic solar cells, its preparation method, and application Granted publication date: 20210914 License type: Common License Record date: 20240902 Application publication date: 20190219 Assignee: Chongqing Dongfang Filter Co.,Ltd. Assignor: CHONGQING INSTITUTE OF GREEN AND INTELLIGENT TECHNOLOGY, CHINESE ACADEMY OF SCIENCES Contract record no.: X2024980012528 Denomination of invention: An active layer material for organic solar cells, its preparation method, and application Granted publication date: 20210914 License type: Common License Record date: 20240902 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20190219 Assignee: CHONGQING HUAHONG INSTRUMENT Co.,Ltd. Assignor: CHONGQING INSTITUTE OF GREEN AND INTELLIGENT TECHNOLOGY, CHINESE ACADEMY OF SCIENCES Contract record no.: X2024980012973 Denomination of invention: An active layer material for organic solar cells, its preparation method, and application Granted publication date: 20210914 License type: Common License Record date: 20240903 |