CN116332994B - Hole transport material, synthesis method thereof and application of hole transport material in perovskite solar cell - Google Patents
Hole transport material, synthesis method thereof and application of hole transport material in perovskite solar cell Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 38
- 238000001308 synthesis method Methods 0.000 title abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000007983 Tris buffer Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000004528 spin coating Methods 0.000 claims description 9
- -1 4-bromobutyl Chemical group 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
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- 239000002904 solvent Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 claims description 3
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 3
- IQRFZFGTHZJRFV-UHFFFAOYSA-N 10,15-dihydro-5h-diindolo[3,2-a:3',2'-c]carbazole Chemical compound N1C2=CC=CC=C2C2=C1C(C1=CC=CC=C1N1)=C1C1=C2NC2=CC=CC=C12 IQRFZFGTHZJRFV-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims 2
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 abstract description 6
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- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 abstract 1
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- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 9
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
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- 230000001590 oxidative effect Effects 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
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- 239000011521 glass Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
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- 229940125904 compound 1 Drugs 0.000 description 2
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- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 230000008569 process Effects 0.000 description 2
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- 125000003003 spiro group Chemical group 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 108010038083 amyloid fibril protein AS-SAM Proteins 0.000 description 1
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- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001437 electrospray ionisation time-of-flight quadrupole detection Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
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- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
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- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
-
- 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
Abstract
A hole transport material, a synthesis method thereof and an application thereof in perovskite solar cells are disclosed, organic functional molecules with three phosphoric carbazole structures are designed and developed, dynamic self-assembly of the organic molecules in a film is realized by blending with a hole transport material solution, and the prepared composite hole transport layer passivates an upper perovskite interface and a lower hole transport layer interface simultaneously, so that the microscopic morphology of the upper surface of a perovskite layer is improved, chemical bonding action is generated between the upper hole transport layer interface and a metal electrode material by organic self-assembled small molecules, and the diffusion of electrodes into the device is slowed down. In addition, the organic self-assembled small molecules promote the chemical doping of the hole transport material and improve the conductivity of the film. The multifunctional interface modification of the organic self-assembled molecules not only enhances hole transmission and inhibits non-radiative recombination, but also greatly improves the efficiency and stability of the device.
Description
Technical Field
The invention relates to the field of solar cells, in particular to a hole transport material, a synthesis method thereof and application thereof in perovskite solar cells.
Background
Solar energy has the advantages of being green, wide, sustainable and the like, and is the renewable energy source with the most scale application at present. Photovoltaic solar cells are one of the important ways to directly convert solar energy into electric energy for efficient use of solar energy, representing one of the most potential renewable energy technologies currently used, and are being paid attention to and expected from the world. In the new generation of photovoltaics, the emerging Perovskite Solar Cell (PSC) is considered one of the most promising runners, with a high Power Conversion Efficiency (PCE) of more than 25%, comparable to the commercial c-Si counterpart (26.7%). This PSC technology has shown great commercial promise in combination with its solution processible manufacturing capability.
Although PSC has the advantages of easy manufacture, excellent flexibility, and high compatibility with serial batteries. However, their photovoltaic performance is limited by the defects of the PSC functional layers themselves and interface defects. Among other things, to address these issues between perovskite layer and hole transport layer interfaces in PSCs, researchers have used some additives to fine tune the Hole Transport Layer (HTL) bandgap structure or post-treat the HTL surface to adjust the surface properties of the perovskite. The method can improve the morphology of the perovskite film and optimize the energy level matching degree between the transmission layer and the perovskite, but has the problems of complex material synthesis, complex interface structure, high manufacturing cost and the like, and is not suitable for future large-scale application.
Over the past few years researchers have been designing and developing low cost, high performance HTLs, but the conversion efficiency and stability of materials in devices is difficult to balance. Among them, self-assembled monolayers (SAMs) have multiple advantages of low material cost, compatibility with flexible substrates, band gap adjustability, high light transmittance, and the like, and have great potential. SAMs having anchoring groups therein (e.g., carboxylic or phosphonic) spontaneously adsorb onto the surface of the substrate to form a dense and uniform monolayer coverage, greatly enhancing interfacial layer contact. The SAM-based PSC not only simplifies the device structure, but also greatly improves device efficiency and long-term stability. However, such a hierarchical SAM has a number of problems: (1) The solution spin-coated SAM layer is difficult to reach a monolayer, which increases interfacial resistance and also affects film compactness and uniformity. (2) The SAM layer is easily damaged by the solution of the overlying film, such as chlorobenzene solvents in the hole transporting material, severely affecting the microstructure and interfacial properties of the SAM layer. (3) The surface chemical structure, surface energy, wettability, etc. of the SAM layer also seriously affect the nucleation or film formation of the upper film, and thus affect the microstructure (e.g., molecular stacking orientation in the film) and conductivity of the film. These problems bring difficulty to the application of SAM materials in perovskite solar cell interfaces, and the development of novel SAM molecular structures and thin film preparation processes is an important research topic in the field.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a hole transport material, a synthesis method thereof and application thereof in perovskite solar cells.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a hole transport material has the following structural formula:
The preparation method of the hole transport material comprises the following steps:
1) Sequentially adding 10, 15-dihydro-5H-diindolo [3,2-a:3',2' -c ] carbazole (3 CZ), 1, 4-dibromobutane, tetrabutylammonium bromide and KOH aqueous solution into a reaction tube, heating for reaction overnight, cooling the reaction mixture to room temperature after the spot plate reaction is completed, washing with water, extracting, drying and purifying to obtain a compound 1;
2) Adding a compound 1 and triethyl phosphite into a reaction tube, vacuumizing and introducing nitrogen for a plurality of times, carrying out reflux reaction, cooling a reaction mixture to room temperature after the spot-plate reaction is completed, separating out at low temperature, carrying out suction filtration, and washing to obtain a compound 2;
3) Dissolving the compound 2 in anhydrous 1, 4-dioxane under nitrogen atmosphere, dropwise adding trimethyl bromosilane, reacting at room temperature, adding methanol, continuously stirring for reacting, removing part of solvent by rotary evaporation, adding methanol, dropwise adding distilled water until the solution is opaque, stirring overnight, filtering out the product, washing with water, and drying to obtain the product 3CZ-3C4PA with the structural formula.
In step 1), the reaction temperature is 50-80 ℃.
In the step 2), the reaction temperature is 150-200 ℃.
The hole transport material is applied to preparing perovskite solar cells.
In particular, it is applied to the preparation of perovskite solar cells of n-i-p structure.
The perovskite solar cell with the n-i-p structure comprises an upper electrode, a hole transport layer, a perovskite layer, an electron transport layer and a lower electrode which are sequentially arranged from top to bottom, wherein the hole transport layer comprises a compound with the structural formula as shown in claim 1.
Mixing 3CZ-3C4PA with a hole transport layer precursor solution, and spin-coating on a perovskite layer; the mass concentration of 3CZ-3C4PA in the hole transport layer precursor solution is 0.01 to 1.5mg/mL, preferably 0.01 to 0.05mg/mL.
Further, the spin coating rotating speed is 1000-5000 r/min, and more preferably, the rotating speed is 3000r/min; the duration is 15 to 50s, more preferably 30s.
The upper electrode adopts an Ag electrode, and the thickness is 10-100 nm, and more preferably 70-90 nm.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
The hole transport material 3CZ-3C4PA prepared by the invention is used as SAM molecules to be mixed with an HTL layer in a perovskite battery with an n-i-p structure, so that the multi-functional SAM designed by the invention can solve the processing challenges layer by layer. The 3CZ-3C4PA is directly added into the hole transport layer precursor solution to spin-coat the HTL, eliminating HTL annealing and interface wettability issues, and simplifying the device fabrication process. Through the studies of the present invention, organic molecules having one or two phosphate anchoring groups are not sufficiently stable themselves, and are prone to self-twisting during material blending to affect charge collection at the interface, thereby limiting the conversion efficiency of the device. Aiming at the problems, the invention synthesizes the SAM molecule with three phosphate groups and the hole material to be blended for solution spin coating, thereby realizing the dynamic self-assembly in the film. The spin-coated HTL in the self-assembly blending mode can promote the doping oxidation of the HTL, improve the doping efficiency, and further improve the stability of the HTL due to the chemical action of phosphonic acid groups in self-assembly molecules and a hole transport layer precursor solution Spiro-OMeTAD.
In addition, the diffusion of metal electrodes and defects between interfaces in perovskite solar cells are important factors affecting the performance and stability of PSCs, and in the study of the present invention, blended self-assembled molecules spontaneously migrate to interfaces during the film formation process of hole transport layers, exhibiting a tendency to anchor from the inside to the upper and lower interfaces. At room temperature, the organic SAM molecules diffuse to the interface between the metal electrode and the hole transport layer, forming stable covalent bonds with the metal silver electrode, preventing downward diffusion of the electrode. In addition, the organic SAM molecules migrate to the interface of the perovskite and the hole transport layer at the same time, so that the upper surface morphology of the perovskite layer is obviously improved, perovskite structure defects are passivated, hole transport is effectively enhanced, and non-radiative recombination loss is reduced.
The hole blending self-assembled hole transport film prepared by the invention has high efficiency of 22.4% in a front device, has excellent long-term stability (about 95% after being stored for 1500 hours in a glove box), and is one of the highest efficiency in SAM-based PSCs. This work is important to simplify the PSC (single junction and/or series device) structure and reduce the device fabrication cost.
Drawings
Fig. 1 is a graph of the results of performance testing of perovskite solar cells based on hole blending materials of different 3CZ-3C4PA mass ratios in example 2.
FIG. 2 is a graph showing the ultraviolet spectrum test results based on different intervals in example 3.
Fig. 3 is a graph of the results of the performance test of perovskite solar cell based on different time intervals in example 4.
FIG. 4 shows XPS 3d orbitals of A) Ag in example 5; b) The breakdown voltage of Ag in the device is shown.
Fig. 5 is a fluorescence imaging test chart of example 6.
FIG. 6 is a fluorescence spectrum test chart of example 6.
Fig. 7 is a J-V curve of perovskite solar cell for different hole transporting materials prepared in example 7.
Fig. 8 is the stability of perovskite solar cells of different hole transport materials prepared in example 7 in a dry cabinet.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear and obvious, the invention is further described in detail below with reference to the accompanying drawings and embodiments.
Example 1
The synthesis of the compound (5H-diindolo [3,2-a:3',2' -C ] carbazole-5, 10, 15-triyl) tris (butane-4, 1-diyl)) tris (phosphonic acid) (3 CZ-3C4 PA) of the hole transport material comprises the following three steps.
1) Synthesis of the Compound 5,10, 15-tris (4-bromobutyl) -10, 15-dihydro-5H-diindolo [3,2-a:3',2' -C ] carbazole (3 CZ-3C4 Br):
To a 100mL reaction tube were successively added 3CZ (0.85 g,2.46 mmol), 8.8mL of 1, 4-dibromobutane, and 4.2mL of tetrabutylammonium bromide (479.0 mg,1.48 mmol) as a 50% aqueous KOH solution. The reaction was then allowed to react overnight at 70 ℃. After the spot-plate reaction was complete, the reaction mixture was cooled to room temperature, washed with water, and extracted with dichloromethane. Dried over anhydrous magnesium sulfate, and purified by silica gel column chromatography (petroleum ether/dichloromethane, v/v, 1:1) to give 3CZ-3C4Br (1.52 g, 82.3%) as a pale yellow solid.
2) The compound hexaethyl ((5H-diindolo) [3,2-a:3',2' -C ] carbazole-5, 10, 15-diyl) tris (butane-4, 1-diyl)) tris (phosphonate) (3 CZ-3C 4P):
Into a 200mL reaction tube were charged 3CZ-3C4Br (1.3 g,1.73 mmol) and 15.0mL of triethyl phosphite, and the reaction was performed under vacuum with nitrogen several times in an iron sand bath at 160℃under reflux for 16h. After the completion of the spot-plate reaction, the mixture was cooled to room temperature, introduced into 200mL of petroleum ether, precipitated at low temperature, suction-filtered to give a solid, and then rinsed with petroleum ether to give the product 3CZ-3C4P (1.33 g, 83.3%).
3) Synthesis of the Compound (5H-diindolo [3,2-a:3',2' -C ] carbazole-5, 10, 15-diyl) tris (butane-4, 1-diyl)) tris (phosphonic acid) (3 CZ-3C4 PA):
3CZ-3C4P (1.1 g,1.19 mmol) was dissolved in anhydrous 1, 4-dioxane (20 mL) under nitrogen and trimethylbromosilane (5.48 g,35.48 mmol) was added dropwise. The reaction was carried out at room temperature for 24 hours. Thereafter, methanol (. About.1.5 mL) was added and stirring was continued for 3h. A portion of the solvent was removed by rotary evaporation, 8mL of methanol was added, and distilled water (20 mL) was added dropwise until the solution was opaque, and stirred overnight. Filtering out the product, washing with water, and drying to obtain solid 3CZ-3C4PA(0.52g,57.8%).1H NMR(500MHz,DMSO-d6,δ):8.29(d,3H),7.64(d,3H),7.45(t,3H),7.34(t,3H),4.92(t,6H),1.99(t,6H),1.58(m,12H).13CNMR(125MHz,DMSO-d6,δ):20.59,20.63,26.89,27.99,30.78,30.89,42.59,107.14,110.30,118.79,119.80,120.96,127.47,137.25,138.29.C36H42N3O9P3[M+]Exact Mass=753.2134,MS(ESI-QTOF)=753.2146.
Example 2
The three phosphonate containing small molecule 3CZ-3C4PA prepared in example 1 was added to a hole transporting layer precursor solution to prepare an n-i-p perovskite solar cell comprising an upper electrode, a hole transporting layer, a perovskite layer, an electron transporting layer and a lower electrode, which were sequentially disposed from top to bottom.
The preparation method comprises the following specific steps:
1) Ultrasonically treating an FTO glass substrate in deionized water, glass cleaning liquid, acetone and isopropanol for 15min in sequence, then drying the FTO glass substrate by using dry compressed air, and treating the cleaned FTO glass with ultraviolet-ozone for 15min to improve wettability; mixing SnO 2 (15 wt%) solution with deionized water at a volume ratio of 1:3, stirring for 5min, directly spin-coating the prepared SnO 2 solution on an FTO substrate for 30 seconds at 2500r/min, heating to 200 ℃ on a hot table, annealing for 40min to prepare an electron transport layer, cooling to room temperature, and treating with ultraviolet-ozone for 15min again;
2) Preparing a Cs 0.07FA0.9MA0.03Pb(I0.92Br0.08)3 perovskite precursor solution: 191.4mg of FAI, 13.5mg FABr, 24.6mg of CsI, 31.9mg MACl, 39.6mg of PbB 2, 0.64mg of MAI, 591.2mg of PbI 2 are added to 1mL of DMF/DMSO (v/v, 1:4) solution; 40. Mu.L of the perovskite precursor solution is directly spin-coated on the substrate prepared in the step 1), spin-coated for 10s at a rotation speed of 1500r/min, spin-coated for 30s at a rotation speed of 4000r/min, and then the obtained film is transferred onto a heat table and heated at 100 ℃ for 40min.
3) Preparing a hole transport layer Spiro-ome tad precursor solution: 72.3mg of Spiro-OMeTAD powder was first mixed with 17.5. Mu.L of Li-TFSI solution and 28.8. Mu.L of tBP solution, and the mixed solutions were then added together to 1mL of chlorobenzene solution; and then mixing 3CZ-3C4PA with the hole transport layer precursor solution, directly spin-coating 40 mu L of the hole transport layer precursor solution containing 3CZ-3C4PA on the perovskite substrate prepared in the step 2), spin-coating for 30s at a rotating speed of 3000r/min, and finally thermally evaporating an Ag electrode with a thickness of 80nm on the prepared film.
In the step 3), 3CZ-3C4PA of different mass is added into the hole transport layer precursor solution to be configured to be 0.01-1.5 mg/mL, and more preferably, the mass concentration is 0.01-0.05 mg/mL.
In the embodiment, the solar device is manufactured according to the 3CZ-3C4PA hole blending materials with different proportions, and as shown in figure 1, in the hole blending device with the mass proportion of 0.01-0.05 mg/mL, the battery parameters are obviously superior to those of the devices with other proportions, and the specific parameters comprise open circuit voltage, current density, filling factor and efficiency.
Example 3
Testing the Oxidation and stability of hole transport materials
Taking a hole transport layer Spiro-OMeTAD precursor solution as a blank group; taking a mixed solution of a Spiro-OMeTAD precursor solution and 3CZ-3C4PA as an experimental group; the three groups of solutions are subjected to an external visible absorption spectrum test by taking a mixed solution of a Spiro-OMeTAD precursor solution and self-assembled molecules with two phosphate groups as a control group, wherein the following structural formula is the self-assembled molecules with two phosphate groups:
As shown in fig. 2 a), it was found in the uv-vis absorption spectrum test that the oxidizing property after SAM molecule is added to the hole material Spiro was significantly improved, and at the same time, the stability of the hole material was improved due to the combination of phosphate groups and Spiro, and fig. 2B) shows that the oxidizing property of the hole material containing three phosphate groups is still very high after one month interval, while the oxidizing property of the hole material blended with few phosphate groups and no phosphate groups has been significantly reduced.
Example 4
Testing the performance of the prepared n-i-p perovskite solar cell
This example tests the performance of n-i-p perovskite solar cells prepared after 0 and 30 days of 3CZ-3C4PA blended spira-ome tad (experimental group), and n-i-p perovskite solar cells prepared after 0 and 30 days of spira-ome tad without 3CZ-3C4PA added (control group), the performance parameters including open circuit voltage, current density, fill factor and efficiency.
Referring to fig. 3, the results demonstrate that after 30 days the solution of 3CZ-3C4PA blended spira-ome tad can still be used as hole transport material, whereas the battery performance of the spira-ome tad solution without 3CZ-3C4PA has been significantly reduced, which means that the lithium salt itself in the spira-ome tad solution has been eluted and has not been used as a good hole transport material, which also corresponds to the significantly reduced oxidizing property after one month of the interval shown in fig. 2B).
Example 5
The working mechanism of the silver electrode and the blended hole is studied by X-ray photoelectron spectroscopy (XPS). The XPS 3d orbitals of Ag (different hole transport materials deposited on the Ag surface) are shown in fig. 4 a). The n-i-p perovskite solar cell prepared by the hole transport layer Spiro-OMeTAD precursor solution is used as a blank group, the n-i-p perovskite solar cell prepared by the mixed solution of the Spiro-OMeTAD precursor solution and 3CZ-3C4PA is used as an experimental group, and the n-i-p perovskite solar cell prepared by the mixed solution of the Spiro-OMeTAD precursor solution and the self-assembly molecules with two phosphate groups is used as a control group.
The results in FIG. 4A) show that the Ag3d peak in the blank Ag film appears at 367.65eV; whereas in the Ag film of the control group, ag3d appears at 367.59eV; in the Ag films of the experimental group, the peak value of Ag3d is 367.57eV, and the peak moves towards the low-energy binding direction, which indicates that the self-assembled molecules with phosphate groups are coordinated with Ag through bonds. Thereby enhancing the effect between the upper electrode and the upper interface of the blended hole transport layer and preventing or slowing down diffusion of the electrode.
In fig. 4B) shows the breakdown voltage of the Ag electrode in the device, and it is seen from the figure that the breakdown voltage of the silver electrode is smaller when the unblended hole material is used, and the breakdown voltage of the device is improved when the blended hole material is used, so that the use of the blended hole material helps to prevent the diffusion of the silver electrode, and further improves the stability of the device.
Example 6
The blank, experimental and control groups of example 5 were subjected to fluorescence test, and the results are shown in fig. 5 to 6. The highest fluorescence intensity of the non-blended hole transport material indicates that the recombination at the interface is stronger, and in the blended hole transport material, the recombination is less, the intensity is also smaller, and especially the three phosphate blended materials show lower recombination, which indicates that the lower surface of the blended hole transport layer contacted with perovskite is passivated to a certain extent, so that the hole transport is enhanced.
Example 7
Performance and stability tests were performed on the cells according to the blank, experimental and control groups in example 5. The open circuit voltage, short circuit current and fill factor of the prepared battery device were tested using a xenon lamp solar simulator with a test light source intensity of AM 1.5g,100mw cm -2. The device performance and its stability are shown in fig. 7-8. Fig. 7 is a J-V curve of the device, with an experimental device open circuit voltage V oc of 1.13V, a short circuit current J sc of 24.3mA/cm 2, a fill factor FF of 82%, and a photoelectric conversion efficiency of 22.4%. Also, the prepared device was stored in a drying cabinet for 1500 hours while maintaining 95% of the initial efficiency (fig. 8). In contrast, the photoelectric conversion efficiency of the control and blank devices was only 20.4% and 17.6%, and after 1500 hours of storage under the same conditions, the control efficiency was reduced to 40% of the initial efficiency. The above results show that the use of the 3CZ-3C4PA hole blending method improves both device efficiency and stability.
According to the invention, hole blending is carried out in the n-i-p perovskite battery for the first time, and three phosphate radical molecules are blended, so that the stability of the molecules is better, the molecules are distributed more uniformly at the upper and lower interfaces, and the effect of passivating the interfaces is improved. The invention passivates between the perovskite upper interface and the lower interface of the hole transport layer through the blended hole transport material, so that the hole transport is enhanced, the non-radiative recombination is inhibited, and the upper surface morphology of the perovskite layer is improved; meanwhile, the blended hole transport material generates bond coordination with the electrode material at the upper interface, so that the downward diffusion of the electrode is slowed down; in addition, blending the hole material also enhances the oxidizing property of the hole layer. Through the functions, the efficiency and the stability of the device are greatly improved, and ideas are provided for the research of self-assembled molecules and the commercialized road of perovskite solar cells.
Claims (13)
1. A hole transport material characterized by the following structural formula:
2. the method for preparing a hole transport material according to claim 1, comprising the steps of:
1) Sequentially adding 10, 15-dihydro-5H-diindolo [3,2-a:3',2' -c ] carbazole, 1, 4-dibromobutane, tetrabutylammonium bromide and KOH aqueous solution into a reaction tube, heating to react overnight, cooling the reaction mixture to room temperature after the spot plate reaction is completed, washing with water, extracting, drying and purifying to obtain a compound 5,10, 15-tris (4-bromobutyl) -10, 15-dihydro-5H-diindolo [3,2-a:3',2' -c ] carbazole;
2) Adding a compound of 5,10, 15-tris (4-bromobutyl) -10, 15-dihydro-5H-diindole [3,2-a:3',2' -c ] carbazole and triethyl phosphite into a reaction tube, vacuumizing and introducing nitrogen for several times, carrying out reflux reaction, cooling a reaction mixture to room temperature after the spot plate reaction is completed, precipitating at low temperature, carrying out suction filtration, and washing to obtain a compound of hexaethyl ((5H-diindole) [3,2-a:3',2' -c ] carbazole-5, 10, 15-triyl) tris (butane-4, 1-diyl)) tris (phosphonate);
3) Dissolving the compound hexaethyl ((5H-diindolophate) [3,2-a:3',2' -c ] carbazole-5, 10, 15-triyl) tris (butane-4, 1-diyl)) tris (phosphonate) in anhydrous 1, 4-dioxane, dropwise adding trimethyl bromosilane, reacting at room temperature, adding methanol, continuing stirring for reacting, removing part of the solvent by rotary evaporation, adding methanol, dropwise adding distilled water until the solution is opaque, stirring overnight, filtering out the product, washing with water, and drying to obtain the product.
3. The method for producing a hole transporting material according to claim 2, wherein: in step 1), the reaction temperature is 50-80 ℃.
4. The method for producing a hole transporting material according to claim 2, wherein: in the step 2), the reaction temperature is 150-200 ℃.
5. A hole transport material according to claim 1 and use of the hole transport material prepared by the preparation method according to any one of claims 2 to 4, characterized in that: the method is applied to the preparation of perovskite solar cells.
6. The use according to claim 5, wherein: the method is applied to the preparation of perovskite solar cells with n-i-p structures.
7. The use according to claim 6, wherein: the perovskite solar cell with the n-i-p structure comprises an upper electrode, a hole transport layer, a perovskite layer, an electron transport layer and a lower electrode which are sequentially arranged from top to bottom, wherein the hole transport layer comprises a compound with the structural formula as shown in claim 1.
8. The use according to claim 7, wherein: mixing a compound of the formula of claim 1 with a hole transport layer precursor solution and spin-coating onto a perovskite layer; the compound of the structural formula of claim 1, wherein the mass concentration of the compound in the hole transport layer precursor solution is 0.01 to 1.5mg/mL.
9. The use according to claim 8, wherein: the compound of the structural formula of claim 1, wherein the mass concentration of the compound in the hole transport layer precursor solution is 0.01 to 0.05mg/mL.
10. The use according to claim 8, wherein: the spin coating rotating speed is 1000-5000 r/min, and the duration time is 15-50 s.
11. The use according to claim 10, wherein: spin coating was carried out at a speed of 3000r/min for a duration of 30s.
12. The use according to claim 7, wherein: the upper electrode adopts an Ag electrode with the thickness of 10-100 nm.
13. The use according to claim 12, wherein: the thickness is 70-90 nm.
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WO2023038050A1 (en) * | 2021-09-13 | 2023-03-16 | 株式会社エネコートテクノロジーズ | Photoelectric conversion element and compound |
CN115819457A (en) * | 2022-12-06 | 2023-03-21 | 厦门大学 | Carbazole organic micromolecule hole transport material containing phosphonic acid and methylthio, and preparation method and application thereof |
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WO2023038050A1 (en) * | 2021-09-13 | 2023-03-16 | 株式会社エネコートテクノロジーズ | Photoelectric conversion element and compound |
CN115215901A (en) * | 2022-08-03 | 2022-10-21 | 厦门大学 | Self-assembly hole transport material based on 7H-dibenzocarbazole and synthetic method |
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