CN113582991A - Amino-containing N-oxide perylene diimide micromolecule interface layer and preparation method thereof - Google Patents
Amino-containing N-oxide perylene diimide micromolecule interface layer and preparation method thereof Download PDFInfo
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- KJOLVZJFMDVPGB-UHFFFAOYSA-N perylenediimide Chemical compound C=12C3=CC=C(C(NC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)NC(=O)C4=CC=C3C1=C42 KJOLVZJFMDVPGB-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 150000001204 N-oxides Chemical class 0.000 title claims abstract description 18
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound 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 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 229910003472 fullerene Inorganic materials 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 claims description 4
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 abstract 2
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical group N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- -1 ZnO Chemical class 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000003335 secondary amines Chemical class 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical group C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000005036 potential barrier Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- CSJLBYZENVALDT-UHFFFAOYSA-N 1H-pyrrol-1-ium iodide Chemical group I.C=1C=CNC=1 CSJLBYZENVALDT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical group ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VMWJCFLUSKZZDX-UHFFFAOYSA-N n,n-dimethylmethanamine Chemical compound [CH2]N(C)C VMWJCFLUSKZZDX-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/06—Peri-condensed systems
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- 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
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- 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
- H10K30/80—Constructional details
- H10K30/81—Electrodes
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- 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
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
-
- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention discloses an amino-containing N-oxide perylene diimide micromolecule interface layer and a preparation method thereof, and the synthesis process is simple and only has two steps. The invention has strong self-doping effect due to intramolecular charge transfer of lone pair electrons on secondary amine of the side chain to the perylene diimide nucleus, and the strong self-doping effect is beneficial to forming large interface dipole and improving the electron mobility; meanwhile, the terminal nitrogen-oxygen polar group can also form a dipole and endow the material with green solvent processing. Therefore, the dipole of PDINNO can effectively reduce the work function of the Ag electrode with high stability in air by 0.6 eV. In addition, secondary amine in the side chain can form hydrogen bonds with F, H and the like in the active layer, so that interface compatibility is improved, and interface contact is improved.
Description
Technical Field
The invention relates to the technical field of organic solar cells, in particular to an amino-containing N-oxide perylene diimide micromolecule interface layer and a preparation method thereof.
Background
Current human activities and industrial development require a large amount of energy, mostly obtained by burning fossil fuels, but their use has proved to be the main cause of climate change. The solar energy has great potential to become the next generation energy source due to the advantages of huge reserves, cleanness, no pollution, no region limitation and the like. Currently, inorganic silicon solar cells have been widely used in industry because of their stable and high photoelectric conversion efficiency. However, since the silicon single crystal processing technology is complex, the purity requirement is high, the refining of the high-purity silicon easily causes environmental pollution, and the device efficiency is difficult to be improved, the cost for manufacturing the inorganic silicon solar cell is high, the energy consumption is high, the environmental protection is not facilitated, and the further popularization and application of the inorganic silicon solar cell are limited.
Organic solar cells have attracted considerable attention in recent years because of their advantages of being lightweight, inexpensive, flexible, translucent, and capable of large-area production. Although the research progress of organic solar cells has made a great breakthrough in the past decades, the photoelectric conversion efficiency is still relatively low, the theoretical device stability is relatively poor, and the research is mainly in the small area research stage of the laboratory. The introduction of an interfacial layer between the active layer and the electrode is an effective method to reduce the interfacial potential barrier and improve the charge separation and collection efficiency. The interface material plays a great role in the whole device, and the interface contact characteristics between the active layer and each electrode are closely related to the final photoelectric conversion efficiency of the organic solar cell.
The most commonly used cathode interfacial layer is currently a semiconducting metal oxide (e.g., ZnO, TiO)2) Compared with active metal Ca and the like, the electron transport layer has stronger stability, can also obviously reduce the sensitivity of the solar cell to water vapor and oxygen in air, prolongs the service life of the cell and ensures that the cell has better stability. Such semiconducting metal compounds have the function of blocking holes, influencing light distribution and self-assembling layers. However, due to its structure, the compatibility between the inorganic oxide and the organic active layer is not good, and the level controllability is small, and high-temperature annealing is generally required. Therefore, we introduce an organic conjugated compound electrolyte as the cathode interface layer of an organic solar cell. Compared with an inorganic cathode interface layer, the organic cathode interface layer has good solubility in a polar solvent, is easy for experimental and industrial device preparation, and can obtain a controllable organic material by introducing different groups, so that the controllable organic material is matched with the energy level and the crystallization property of an active layer, and the singleness of the inorganic material can be effectively avoided.
The organic polymer and the organic small molecule material have easily adjustable structures, are suitable for matching with the active layer and the cathode electrode, can adjust and control the solubility performance through structural modification, and can adjust the physical and chemical properties of the material through changing side chains. Compared with the polymer, the micromolecule has the advantages of simple manufacturing process, accurate molecular weight, monodispersity and the like, so that the organic solar cell with high batch repeatability is more attractive to prepare. One of the materials successfully applied to the cathode interface layer is a fullerene derivative, for example, fullerene derivatives modified with iodonium pyrrole salts, pyrrolidine, tertiary amines, ammonium salts and acylated alkyl groups have been successfully designed and synthesized. Another successful and more advantageous derivative of perylene diimides, perylene has excellent thermal, photo and chemical stability due to the specific structure. Meanwhile, due to good planarity of molecules, the pi-pi interaction between the molecules is greatly enhanced, and the electron transfer capability is stronger. In addition, the perylene bisimide derivative has the advantages of strong electron affinity, easy modification, adjustable energy level, simple synthesis and good alcohol and water solubility.
The invention introduces polar groups (amino and amino N-oxide) into the perylene diimide core with high yield by a simple two-step method to obtain the perylene diimide micromolecule interface layer containing amino N-oxide, so that the perylene diimide micromolecule interface layer has the dual advantages of amino and amino N-oxide. Firstly, the lone pair electrons on the secondary amine of the side chain of the perylene diimide are easy to generate intramolecular charge transfer to the perylene diimide nucleus, so that the strong autodoping effect is realized, and the strong autodoping effect is favorable for forming a large interface dipole and improving the electron mobility; at the same time, the terminal nitroxide polar groups can also form dipoles and give the material a green water/alcohol solvent processing. Therefore, the dipole of the PDINNO can effectively reduce the work function of the Ag electrode with good stability in the air. In addition, secondary amine in the side chain can form hydrogen bonds with F, H and the like in the active layer, interface compatibility and interface stability are improved, interface contact is improved, and the PDINNO can be applied to construction of a high-efficiency stable organic solar cell cathode interface layer material.
Disclosure of Invention
The invention aims to provide an amino-containing N-oxide perylene diimide micromolecule interface layer and a preparation method thereof. The non-fullerene solar cell device with the amino-containing N-oxide perylene diimide micromolecules as the cathode interface layer is applied. Compared with a blank ITO device, the efficiency is 1.11%, the efficiency of the unoptimized PDINNO-based device is improved to 6.91%, and the efficiency of the device can still be maintained above 90% after the device is placed for 30 days. Therefore, the PDINNO can be applied to the construction of a high-efficiency stable organic solar cell cathode interface layer material.
The technical scheme adopted by the invention is as follows: an amino-containing N-oxide perylene diimide micromolecule interface layer is characterized in that: has a structure shown in formula I as follows:
the invention also aims to provide a preparation method of the amino-containing N-oxide perylene diimide micromolecule interface layer, which is characterized by comprising the following steps:
the method comprises the following steps: synthesis of PDINN:
(1) adding 2mmol PDI, 4mmol N, N-dimethyl dipropylidenetriamine and 40mL methanol into a double-neck flask, vacuumizing and filling nitrogen, and circulating for three times;
(2) the mixture is reacted and refluxed for 8h at 70 ℃;
(3) after the reaction is finished, cooling to room temperature, pouring the mixture into 200mL of chloroform and 30mL of water for extraction, and then carrying out reduced pressure distillation to obtain a crude product;
(4) adding acetone into the crude product, carrying out suction filtration and purification, putting the product into a vacuum drying oven, carrying out vacuum drying for one day at 50 ℃, and finally obtaining the brownish red solid PDINN with the yield of 93%,1H NMR(500MHz,CDCl3),δ(ppm):8.43(d,4H,Ar),8.27(d,4H,Ar),4.25(t,4H,CH2(CH2)2NH(CH2)3N(CH3)2),2.75(t,CH2NH(CH2)3N(CH3)2，4H),2.69(t,4H,CH2(CH2)2N(CH3)2),2.33(t,4H,CH2N(CH3)2),2.22(s,12H,CH3),1.96(m,6H,CH2CH2NH(CH2)3N(CH3)2),1.68(m,4H,CH2CH2N(CH3)2)；
step two: synthesis of PDINNO:
(1) 0.5mmol of PDINN, 5mmol of H2O2Adding 50mL of ethanol into a double-neck flask, vacuumizing and filling nitrogen, circulating for three times, and stirring the mixture for 30min under the nitrogen atmosphere;
(2) the mixture is reacted and refluxed for 3 hours at 70 ℃;
(3) after the reaction is finished, cooling to room temperature, and performing rotary evaporation to obtain a crude product;
(4) the crude product is filtered and purified by acetone and normal hexane respectively, the product is put into a vacuum drying oven and is dried in vacuum for one day at 50 ℃, finally, brownish red powder PDINNO is obtained, the yield is 86 percent,1H NMR(500MHz,CD3OD)δ8.39(d,4H),7.49(d,4H),3.94(t,4H),3.55(t,8H),3.25(s,12H),2.81 2.45(m,4H),2.38-1.85(m,8H),1.29(s,2H)。
the other technical scheme of the invention is as follows: a preparation method of a non-fullerene solar cell device with amino N-oxide perylene diimide micromolecules as a cathode interface layer is characterized by comprising the following steps:
the solar cell comprises an ITO glass layer, a PEDOT PSS anode interface layer arranged on the ITO glass layer, an active layer arranged on the PEDOT PSS anode interface layer, a PDNNO cathode interface layer arranged on the active layer, and an Ag electrode layer arranged on the PDNNO cathode interface layer.
The other technical scheme of the invention is as follows: a synthetic method of an amino-containing N-oxide perylene diimide micromolecule interface layer is characterized by comprising the following steps: the reaction equation of the specific synthetic route is as follows:
compared with the prior art, the invention has the beneficial effects that:
the novel non-fullerene small-molecular cathode interface layer material PDNNO provided by the invention can realize water-soluble or alcohol-soluble processing in a room-temperature environment due to the amino and amino N-oxide contained in the side chain, and is beneficial to large-area commercial production;
the dipole of the PDNNO provided by the invention can effectively reduce the work function of metal Ag with good stability in air to be as high as 0.6eV, so that the interface potential barrier can be effectively reduced;
the interface layer material PDINNO provided by the invention has a strong n-type autodoping effect because lone-pair electrons on side chain secondary amine are easy to generate intramolecular charge transfer to the perylene diimide core, and the strong n-type autodoping effect is beneficial to forming large interface dipoles and improving the electron mobility so as to improve the efficiency of the device, and can also avoid external doping to reduce the stability of the device. Compared with a blank ITO device, the efficiency of the device based on PDINNO is improved from 1.11% to 6.91%, the efficiency of the device can still be maintained above 90% after the device is placed for 30 days, and the stability is high;
the invention uses Cyclic Voltammetry (CV) to test the electrochemical performance of PDINNO, and the three-electrode system comprises the following components: a glassy carbon electrode as a working electrode, a platinum sheet as an auxiliary electrode, Ag/Ag+Ferrocene is used as a reference electrode, tetrabutylammonium hexafluorophosphate/acetonitrile with the concentration of 0.1mol/L is used as an electrolyte solution. The PDNNO/methanol is prepared into a thin film to be deposited on a working electrode, and the cyclic voltammetry curve of the PDNNO is measured, as shown in figure 6, the initial reduction potential phi of the PDNNO can be obtainedredThe pdlnno has a LUMO level of-3.69 eV, calculated as-0.71 eV, close to the LUMO level of the non-fullerene acceptor in the active layer, which results in better energy-level alignment at the cathode interface, thereby enhancing electron collection and contributing to an increase in photoelectric conversion.
Secondary amine in the PDNNO side chain provided by the invention can form hydrogen bonds with F, H and the like in the active layer, so that the interface compatibility is improved, and the interface contact is improved. The device efficiency based on the blank ITO is only 1.11%, the device efficiency based on the PDINNO interface layer can be greatly improved to 6.91%, and meanwhile, the open-circuit voltage, the short-circuit current and the filling factor are greatly improved at the same time, which is specifically shown in the following table. Experiments prove that the PDINNO interface layer provided by the invention can be applied to the construction of efficient and stable organic solar cells.
Photoelectric performance parameter of device
Drawings
FIG. 1 is a structural diagram of an amino group-containing N-oxide perylene diimide micromolecule interface layer according to the present invention.
FIG. 2 is a schematic structural diagram of an organic solar cell device based on an amino group-containing N-oxide perylene diimide micromolecule interface layer.
FIG. 3 is a nuclear magnetic hydrogen spectrum diagram of an amino group-containing N-oxide perylene diimide micromolecule interface layer according to the present invention.
FIG. 4 is a reaction equation of an amino group-containing N-oxide perylene diimide micromolecule interface layer according to the present invention.
FIG. 5 is a J-V plot of a device based on ITO and PDINNO interfacial layers.
FIG. 6 PDNNO cyclic voltammogram.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
The reaction equation of the invention is shown in figure 4, and the specific reaction steps are as follows: a synthesis step of an amino-containing N-oxide perylene diimide micromolecule interface layer comprises the following steps:
(1) synthesis of PDINN:
adding 2mmol PDI, 4mmol N, N-dimethyl dipropylidenetriamine and 40mL methanol into a double-neck flask, vacuumizing and filling nitrogen, and circulating for three times; the mixture is reacted and refluxed for 8h at 70 ℃; after the reaction is finished, cooling to room temperature, pouring the mixture into 200mL of chloroform and 30mL of water for extraction, and then carrying out reduced pressure distillation to obtain a crude product; and adding acetone into the crude product, carrying out suction filtration and purification, putting the product into a vacuum drying oven, and carrying out vacuum drying at 50 ℃ for one day to finally obtain a brownish red solid PDINN with the yield of 93%.
(2) Synthesis of PDINNO:
0.5mmol of PDINN, 5mmol of H2O2Adding 50mL of ethanol into a double-neck flask, vacuumizing and filling nitrogen, circulating for three times, and stirring the mixture for 30min under the nitrogen atmosphere; the mixture is reacted and refluxed for 3 hours at 70 ℃; after the reaction is finished, cooling to room temperature, and performing rotary evaporation to obtain a crude product; the crude product is filtered and purified by acetone and normal hexane respectively, the product is put into a vacuum drying oven and is dried in vacuum for one day at 50 ℃, finally, brownish red powder PDINNO is obtained, the yield is 76 percent,1H NMR(500MHz,CD3OD)δ8.39(d,4H),7.49(d,4H),3.94(t,4H),3.55(t,8H),3.25(s,12H),2.81 2.45(m,4H),2.38-1.85(m,8H),1.29(s,2H)。
Claims (3)
1. an amino-containing N-oxide perylene diimide micromolecule interface layer is characterized in that: has a structure shown in formula I as follows:
2. the preparation method of the amine group-containing N-oxide perylene diimide micromolecule interface layer according to claim 1, characterized by comprising the following steps:
synthesis of PDINNO:
(1) 0.5mmol of PDINN, 5mmol of H2O2Adding 50mL of ethanol into a double-neck flask, vacuumizing and filling nitrogen, circulating for three times, and stirring the mixture for 30min under the nitrogen atmosphere;
(2) the mixture is reacted and refluxed for 3 hours at 70 ℃;
(3) after the reaction is finished, cooling to room temperature, and performing rotary evaporation to obtain a crude product;
(4) the crude product is filtered and purified by acetone and normal hexane respectively, the product is put into a vacuum drying oven and is dried in vacuum for one day at 50 ℃, finally, brownish red powder PDINNO is obtained, the yield is 86 percent,1H NMR(500MHz,CD3OD)δ8.39(d,4H),7.49(d,4H),3.94(t,4H),3.55(t,8H),3.25(s,12H),2.81-2.45(m,4H),2.38-1.85(m,8H),1.29(s,2H)。
3. the method of claim 1, wherein the step of preparing the non-fullerene solar cell device comprising the amino N-oxide perylene diimide micromolecule interface layer comprises the following steps: the non-fullerene solar cell device comprises an ITO glass layer, a PEDOT/PSS anode interface layer arranged on the ITO glass layer, an active layer arranged on the PEDOT/PSS anode interface layer, a PDINNO cathode interface layer arranged on the active layer, and an Ag electrode layer arranged on the PDINNO cathode interface layer.
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