CN115960006A - Self-separation cathode interface material, preparation method thereof and method for preparing organic solar cell by one-step method - Google Patents
Self-separation cathode interface material, preparation method thereof and method for preparing organic solar cell by one-step method Download PDFInfo
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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
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- 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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Abstract
A self-separation cathode interface material, a preparation method thereof and a method for preparing an organic solar cell by a one-step method relate to the field of electron transport materials in the organic solar cell, and the separation of the self-separation cathode interface materialSub-formula is C 2n+87 H 124 F 4n+2 N 4 O 2 Wherein n is an integer and n ≧ 1. The preparation method of the organic solar cell comprises the steps of spin-coating an active layer solution added with the self-separation cathode interface material on the surface of an anode interface layer, forming an active layer on the surface of the anode interface layer and spontaneously forming a cathode interface layer on the surface of the active layer through vertical phase separation. The self-separating cathode interface material disclosed by the invention is completely different from the materials in the prior art, and a multi-layer film structure is spontaneously formed by vertical phase separation in the processing process of an active layer, so that the active layer and the cathode interface layer are prepared by a one-step method, the processing steps are reduced, the preparation process is optimized, the application of a roll-to-roll process is promoted, and the large-area industrial processing is favorably realized.
Description
Technical Field
The invention relates to the field of electron transport materials in organic solar cells, in particular to a method for designing and synthesizing a self-separating cathode interface material and a method for preparing an organic solar cell.
Background
Photovoltaic power generation has been highly desired as a green technology that can directly convert solar energy into electric energy. The solar cell is the core of photovoltaic power generation and is the key to realizing high-efficiency photoelectric conversion. Compared with an inorganic silicon solar cell, the Organic solar cell (Organic solar cell/OSC) has the advantages of flexibility, light weight, solution processing and the like, and has wide application prospects in the fields of wearable equipment, transparent photovoltaic devices and the like.
In recent years, the photoelectric conversion efficiency of organic solar cells is rapidly developed, the laboratory efficiency is close to the commercial requirement, however, the insertion of the cathode interface layer can increase the preparation process of the device, in the preparation of the organic solar cells, the cathode interface layer, the active layer and the anode interface layer need to be respectively coated in a spin mode, so that the preparation can be completed by at least three operations, and in addition, because the cathode interface layer is generally thin (the optimal thickness is usually within 30 nm), the single processing is not favorable for the application of a roll-to-roll process, and the preparation of large-area devices is hindered.
In order to simplify the preparation method, related researches on self-assembly cathode interface materials/interface layers are carried out by a plurality of universities and research institutes at home and abroad.
Such as: H.ZHao, L.Wang, Y.Wang, W.Su, D.Lin, W.Cai, J.Qing, Z.Zhang, J.Zhong, L.Hou, solvent-Vapor-interconnecting-Induced Interfacial Self-Assembly for structured One-Step Spraying Organic Solvent cells ACS.energy. Applicator, 2021,4,7316-7326, discloses the preparation of ITO/PFN by One-Step method BHJ/MoO 3 and/Ag. The method specifically comprises the following steps: sequentially cleaning ITO glass by using acetone, detergent, deionized water and isopropanolA substrate. PFN is added to the active layer and PFN PTB7 PC71BM or PFN PBDB-T IT-M solution is sprayed directly on top of the clean ITO substrate in one step. Finally, at 3 × 10 -4 Sequentially evaporating MoO on the surface of the active layer under Pa 3 (10 nm)/Ag (100 nm). The formation expression: the drying process was extended to form a complete self-assembled PFN cathode interface layer and an optimized donor-acceptor phase-separated Bulk Heterojunction (BHJ), driven by surface energy, that can form a freestanding ultra-thin PFN film layer between the active layer and Indium Tin Oxide (ITO) by downward vertical self-separation, as the cathode interface layer.
For another example: the Chinese invention patent with the application number of 201810359288.X discloses a method for simultaneously forming a cathode interface layer and an active layer and application of the method in a reverse non-fullerene organic solar cell. The method comprises the following steps: preparing a film on a substrate containing a cathode by using a mixed solution so as to simultaneously form a cathode interface layer and an active layer, wherein the cathode interface layer is formed on the surface of the cathode, the active layer is formed on the surface of the cathode interface layer, and the mixed solution comprises: polyvinylpyrrolidone; and an active layer solution. Therefore, the reverse non-fullerene organic solar cell containing the cathode interface layer and the active layer obtained by the method has better photovoltaic performance, such as high energy conversion efficiency, and the method is simple and convenient to operate and suitable for large-scale production.
Disclosure of Invention
The invention provides a material completely different from the prior art, in particular to a self-separating cathode interface material, a preparation method thereof and a method for preparing an organic solar cell by a one-step method.
The invention adopts the specific scheme that: a self-separating cathode interface material has a fluorine/amino double-function side chain with molecular formula of C 2n+87 H 124 F 4n+2 N 4 O 2 Wherein n is an integer and n ≧ 1.
As a further optimization of the technical scheme, the molecular formula is C 95 H 124 F 18 N 4 O 2 Structural formula is
As further optimization of the technical scheme, the molecular formula is C 103 H 124 F 34 N 4 O 2 Structural formula is
A preparation method of a self-separating cathode interface material comprises the following steps;
s1, taking tetrahydrofuran, 2,7-dibromo-9,9-di (6-bromohexyl) fluorene, tetrabutylammonium bromide and 1H,2H and 2H-perfluoro-1-hexanol, mixing, adding a sodium hydroxide aqueous solution under an argon atmosphere, heating and stirring, extracting, drying, filtering, performing rotary evaporation, and purifying to obtain an intermediate product M2;
s2, adding toluene, tetraethylammonium hydroxide, an intermediate product M2 and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborane-) -9,9-bis (6- (N, N-diethylamino) hexyl) fluorene into a pressure resistant pipe, and adding Pd (PPh) under a nitrogen atmosphere 3 ) 4 Heating the catalyst to 85-100 ℃, stirring for 6-8 h, cooling, extracting, drying, filtering, rotary evaporating and purifying to obtain the compound with the molecular formula C 95 H 124 F 18 N 4 O 2 The self-separating cathode interface material of (1).
As a further optimization of the technical scheme, the intermediate product M2 and the molecular formula C 95 H 124 F 18 N 4 O 2 The purification method of the self-separating cathode interface material adopts column chromatography.
A preparation method of a self-separating cathode interface material comprises the following steps;
s1, taking tetrahydrofuran, 2,7-dibromo-9,9-di (6-bromohexyl) fluorene, tetrabutylammonium bromide and 1H,2H and 2H-perfluoro-1-decanol, mixing, adding a sodium hydroxide aqueous solution under an argon atmosphere, heating, stirring, extracting, drying, filtering, performing rotary evaporation, and purifying to obtain an intermediate product M3;
s2, adding toluene, tetraethylammonium hydroxide, an intermediate product M3 and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborane-) -9,9-bis (6- (N, N-diethylamino) hexyl) fluorene into a pressure resistant pipe, and adding Pd (PPh) under a nitrogen atmosphere 3 ) 4 Heating the catalyst to 85-100 ℃, stirring for 6-8 h, cooling, extracting, drying, filtering, rotary evaporating and purifying to obtain the compound with the molecular formula C 103 H 124 F 34 N 4 O 2 The self-separating cathode interface material of (1).
As a further optimization of the technical scheme, the intermediate product M3 and the molecular formula C 103 H 124 F 34 N 4 O 2 The purification method of the self-separation cathode interface material adopts column chromatography.
The preparation method of the self-separating organic solar cell comprises the step of adding 1-10% of the self-separating cathode interface material into an active layer solution, wherein the mass fraction of the self-separating cathode interface material is based on a donor.
As a further optimization of the technical scheme, firstly, an anode interface layer material is coated on the surface of the anode in a spin coating manner, and an anode interface layer is formed on the surface of the anode after annealing treatment; then, spin-coating an active layer solution added with the self-separating cathode interface material on the surface of the anode interface layer, forming an active layer on the surface of the anode interface layer after annealing treatment, and self-separating a cathode interface layer on the surface of the active layer; and finally, evaporating a cathode on the surface of the cathode interface layer to obtain the organic solar cell.
As a further optimization of the above technical solution, the method specifically comprises the following steps:
s1, dissolving a donor/acceptor in a chloroform solution of 1-chloronaphthalene to prepare an active layer solution, and adding the self-separation cathode interface material into the active layer solution for later use;
s2, spin-coating a PEDOT (PolyEthyleneEther phosphate) solution on a glass substrate plated with an ITO (indium tin oxide) anode, and forming an anode interface layer on the surface of the ITO anode after annealing treatment;
s3, spin-coating the active layer solution added with the self-separation cathode interface material prepared in the step S1 on an anode interface layer in a nitrogen atmosphere, carrying out thermal annealing treatment at 105-110 ℃ for 8-15 minutes, forming an active layer on the surface of the anode interface layer after annealing treatment, and spontaneously forming a cathode interface layer above the active layer through vertical phase separation;
and S4, preparing a cathode above the cathode interface layer through a mask plate by adopting a vapor deposition method.
Compared with the prior art, the invention has the following beneficial effects: the self-separation cathode interface material disclosed by the invention spontaneously forms a multilayer film structure through vertical phase separation in the processing process of the active layer, so that the active layer and the cathode interface layer are prepared through a one-step method, the processing steps are reduced, the preparation process is optimized, the application of a roll-to-roll process is promoted, and the large-area industrial processing is favorably realized.
The amino side chain of the self-separation cathode interface material is beneficial to modifying the cathode work function, promotes the transmission and collection of electrons, and can improve the energy conversion efficiency of the organic solar cell; the fluorine-containing side chain has hydrophobicity, and can prevent water molecules in the air from entering the active layer, so that the stability of the device is improved, and the service life of the device is prolonged; the fluorine-containing side chain can reduce the surface energy of the material, and the self-separation cathode interface material is used as an active layer additive, so that vertical phase separation can be realized through surface energy driving, the active layer and the cathode interface layer are prepared through a one-step method, and the preparation process is optimized. Therefore, the invention designs and synthesizes the self-separation cathode interface material containing the fluorine/amino bifunctional side chain, which is beneficial to prolonging the service life of the device, avoiding independently spin-coating the cathode interface layer and optimizing the preparation process of the device.
Drawings
FIG. 1 is a J-V curve of a self-separating polymer solar cell with PM6 as donor and Y6 as acceptor, PN8F, PN F as additive;
FIG. 2 is a J-V curve of a self-separating polymer solar cell with PTB7-Th as donor and PC71BM as acceptor, PN8F, PN F as additive;
FIG. 3 is a graph of PN8F, PN F in CHCl 3 Ultraviolet-visible absorption spectra in solution;
FIG. 4 is a UV-VIS absorption spectrum of PN8F, PN F in thin film form;
FIG. 5 is a schematic diagram of the contact angle of PN4F with water;
fig. 6 is a schematic view of the contact angle of PN8F with water.
Detailed Description
The invention provides a self-separation cathode interface material, a preparation method thereof and a method for preparing an organic solar cell by a one-step method 2n+87 H 124 F 4n+2 N 4 O 2 Wherein n is an integer and n ≧ 1.
For convenience, the reaction materials and intermediates used in the following examples are listed below, and include M1, M2, M3 and M4.
M1 is 2,7-dibromo-9,9-di (6-bromohexyl) fluorene;
m2 is 2,7-dibromo-9,9-bis (6- ((3,3,4,4,5,5,6,6,6-nonafluoro) oxy) hexyl) fluorene;
m3 is 2,7-dibromo-9,9-bis (6- ((3,3,4,4,5,6,7,8,9,10,10,10-heptadecafluoro) oxy) hexyl) fluorene;
m4 is 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborane-) -9,9-bis (6- (N, N-diethylamino) hexyl) fluorene;
the structural formulas of M1, M2, M3 and M4 are respectively as follows:
example 1
N =4 in this example, formula C of the self-separating cathode interface material 95 H 124 F 18 N 4 O 2 PN4F for short, and the structural formula is as follows:
example 2
N =8 in this example, the formula C of the self-separating cathode interface material 103 H 124 F 34 N 4 O 2 PN8F for short, and the structural formula is as follows:
example 3
This example provides a method for preparing the self-separating cathode interface material (PN 4F) in example 1, where the prepared PN4F is coupled with Suzuki, and the method specifically includes the following steps:
s1, 50mL of tetrahydrofuran, 10mmol of M1, 50mg of tetrabutylammonium bromide and 24mmol of 1H, 2H-perfluoro-1-hexanol were mixed in a 250mL two-neck flask, and a 50mL mixture of 50% aqueous sodium hydroxide was added by a syringe under an argon atmosphere, the mixture was stirred overnight at 60 ℃, cooled to room temperature, and then cooled to CH 2 Cl 2 Extracting, washing with water twice, and extracting organic layer with anhydrous MgSO 4 Drying, filtering, rotary evaporating the filtrate to obtain crude product, purifying the crude product with column chromatography (SiO 2: PE/DCM 5:1) to obtain intermediate M2, wherein the intermediate M2 is yellow oil with a yield of 39%;
s2, firstly, 1.10mL of chromatographically pure toluene, 0.55mL of tetraethylammonium hydroxide, 72.1mg of intermediate product M2 and 106.0mg of M4 are added into a 15mL pressure-resistant tube, nitrogen is introduced through a long needle for 15min, and 5mg of Pd (PPh) is added under the nitrogen atmosphere 3 ) 4 The catalyst is obtained as a mixed solution, the mixed solution is stirred for 8 hours at the temperature of 100 ℃, cooled to room temperature and then added with CH 2 Cl 2 Extracting and washing with water twice, and extracting organic layer with anhydrous MgSO 4 Drying, refiltering and rotary evaporation of the filtrate gave the crude product which was purified by column chromatography (SiO 2; PE/DCM/triethylamine 100.
Example 4
This example provides the preparation of self-detaching cathode interface material (PN 4F) from example 1, using Suzuki coupling of the prepared PN4F, and the intermediate M2 from this example was prepared as in example 3, except that:
s2, first, 1.10mL of chromatographically pure toluene, 0.55mL of tetraethylammonium hydroxide, 72.1mg of intermediate M2 and 106.0mg of M4 were placed in a 15mL pressure-resistant tube, nitrogen was introduced through a long needle for 15min, and 5mg of Pd (PPh) was added under nitrogen atmosphere 3 ) 4 The catalyst is mixed to obtain a mixed solution, the mixed solution is stirred for 10 hours at the temperature of 90 ℃, cooled to the room temperature and then added with CH 2 Cl 2 Extracting and washing with water twice, and extracting the organic layer with anhydrous MgSO 4 Drying, refiltering and rotary evaporation of the filtrate gave the crude product which was purified by column chromatography (SiO 2; PE/DCM/triethylamine 100.
Example 5
This example provides the preparation of self-detaching cathode interface material (PN 4F) from example 1, using Suzuki coupling of the prepared PN4F, and the intermediate M2 from this example was prepared as in example 3, except that:
s2, firstly, 1.10mL of chromatographically pure toluene, 0.55mL of tetraethylammonium hydroxide, 72.1mg of intermediate product M2 and 106.0mg of M4 are added into a 15mL pressure-resistant tube, nitrogen is introduced through a long needle for 15min, and 5mg of Pd (PPh) is added under the nitrogen atmosphere 3 ) 4 The catalyst is obtained into mixed liquid, the mixed liquid is stirred for 6 hours at the temperature of 85 ℃, cooled to room temperature and then added with CH 2 Cl 2 Extracting and washing with water twice, and extracting organic layer with anhydrous MgSO 4 Drying, refiltering and rotary evaporation of the filtrate gave the crude product which was purified by column chromatography (SiO 2; PE/DCM/triethylamine 100.
Example 6
The embodiment provides a preparation method of the self-separating cathode interface material PN8F in embodiment 2, where the prepared PN8F is coupled by Suzuki, and the method specifically includes the following steps:
s1, 50mL of tetrahydrofuran, 10mmol of M1, 50mg of tetrabutylammonium bromide and 25mmol of 1H, 2H-perfluoro-1-decanol were placed in a 250mL two-neck flask and the flask was filled with a syringe under an argon atmosphereThe syringe was added with 50mL of 50% aqueous sodium hydroxide solution to prepare a mixture, which was stirred at 60 ℃ overnight, cooled to room temperature, and then added with CH 2 Cl 2 Extracting, washing with water twice, and extracting organic layer with anhydrous MgSO 4 Drying, filtering, rotary evaporating the filtrate to obtain crude product, and purifying by column chromatography using SiO used in the purification 2 : the PE/DCM is 5:1, and the intermediate product M3 is obtained by purification, the intermediate product M3 is a white solid, and the yield is 42%;
s2, 1.10mL of chromatographically pure toluene, 0.55mL of tetraethylammonium hydroxide, 104.2mg of intermediate M3 and 106.0mg of M4 were taken and placed in a 15mL pressure-resistant tube, nitrogen was introduced through a long needle for 15min, and 5mg of Pd (PPh) was added under nitrogen atmosphere 3 ) 4 The mixture was stirred at 100 ℃ for 8h, cooled to room temperature and then quenched with CH 2 Cl 2 Extracting and washing with water twice, and extracting the organic layer with anhydrous MgSO 4 Drying, re-filtration and rotary evaporation of the filtrate gave a crude product which was purified by column chromatography (SiO 2; PE/DCM/triethylamine 100.
Example 7
This example provides the preparation of self-separating cathode interface material PN8F from example 2, using Suzuki coupling of the prepared PN8F, and the intermediate M3 from this example was prepared as in example 6, except that:
s2, 1.10mL of chromatographically pure toluene, 0.55mL of tetraethylammonium hydroxide, 104.2mg of intermediate M3 and 106.0mg of M4 are taken and added into a 15mL pressure-resistant tube, nitrogen is introduced through a long needle for 15min, and 5mg of Pd (PPh) is added under the nitrogen atmosphere 3 ) 4 The mixture was stirred at 85 ℃ for 7h, cooled to room temperature and then quenched with CH 2 Cl 2 Extracting and washing with water twice, and extracting organic layer with anhydrous MgSO 4 Drying, refiltering and rotary evaporation of the filtrate gave the crude product which was purified by column chromatography (SiO 2; PE/DCM/triethylamine 100.
Example 8
This example provides the preparation of self-separating cathode interface material PN8F from example 2, using Suzuki coupling of the prepared PN8F, and the intermediate M3 from this example is prepared as in example 6, except that:
s2, 1.10mL of chromatographically pure toluene, 0.55mL of tetraethylammonium hydroxide, 104.2mg of intermediate M3 and 106.0mg of M4 are taken and added into a 15mL pressure-resistant tube, nitrogen is introduced through a long needle for 15min, and 5mg of Pd (PPh) is added under the nitrogen atmosphere 3 ) 4 The mixture was stirred at 90 ℃ for 6h, cooled to room temperature and then quenched with CH 2 Cl 2 Extracting and washing with water twice, and extracting the organic layer with anhydrous MgSO 4 Drying, refiltering and rotary evaporation of the filtrate gave the crude product, which was purified by column chromatography (SiO 2; PE/DCM/triethylamine 100.
Example 9
The present example provides a method for preparing an organic solar cell by using the self-separating cathode interface material PN4F in example 1, and the structure of the organic solar cell prepared in this example is ITO/PEDOT: PSS/PM6: Y6: PN4F/Ag, effective area 0.04cm 2 . Wherein PM6 is taken as a donor, Y6 is taken as an acceptor, and the structural formulas of PM6 and Y6 are respectively as follows:
the preparation method of the organic solar cell specifically comprises the following steps:
s1, dissolving a donor/acceptor in a chloroform solution of 1-chloronaphthalene to prepare an active layer solution, and adding PN4F into the active layer solution for later use;
s1-1, dissolving PM6/Y6 into a chloroform solution added with 0.5% (volume ratio) 1-chloronaphthalene according to a mass ratio of 1.2, and preparing a solution of 6mg/mL by taking donor PM6 as a standard to prepare an active layer solution;
s1-2, adding 3% of self-separation cathode interface material PN4F in mass fraction into the active layer solution prepared by the S1-1 for later use by taking a donor PM6 as a standard;
s2, spin-coating a PEDOT (Poly ethylene glycol ether ketone) PSS solution on a glass substrate plated with an ITO anode, and forming an anode interface layer on the surface of the ITO anode after annealing treatment;
s2-1, plating an ITO anode on a glass substrate to serve as an ITO conductive glass substrate, sequentially soaking the ITO conductive glass substrate in a cleaning agent, deionized water and isopropanol, ultrasonically washing for 30min, and drying in an oven overnight;
s2-2, after the cleaned ITO conductive glass substrate is subjected to UVO treatment, spin-coating PEDOT (4083) aqueous solution for 30S at the rotating speed of 3500 rpm to prepare an anode interface layer, and annealing for 15min on a heating table at 150 ℃;
s3, spin-coating the active layer solution added with the self-separation cathode interface material prepared in the step S1 on an anode interface layer in a nitrogen atmosphere, forming an active layer on the surface of the anode interface layer after annealing treatment, and self-separating the cathode interface layer on the surface of the active layer;
s3-1, transferring the ITO conductive glass substrate subjected to the anode interface layer annealing treatment into a glove box protected by nitrogen;
s3-2, in a nitrogen atmosphere, spin-coating the active layer solution added with the self-separation cathode interface material prepared in the step S1 on an anode interface layer at the rotating speed of about 2000rpm, and thermally annealing at 110 ℃ for 10 minutes to form an active layer and a cathode interface layer on the surface of the anode interface layer, wherein the thicknesses of the active layer and the cathode interface layer are about 100nm in total;
and S4, preparing a cathode on the cathode interface layer by adopting an evaporation method through a mask plate, specifically preparing an Ag electrode with the thickness of 100nm by adopting the evaporation method under 10-7mbar through the mask plate.
Example 10
The present example provides a method for preparing an organic solar cell by using the self-separating cathode interface material PN4F of example 1, and the structure of the organic solar cell prepared in this example is ITO/PEDOT: PSS/PM6: Y6: PN4F/Ag, effective area 0.04cm 2 . Wherein PM6 is used as a donor, Y6 is used as an acceptor:
the preparation of the organic solar cell specifically comprises the following steps:
s1, dissolving a donor/acceptor in a chloroform solution of 1-chloronaphthalene to prepare an active layer solution, and adding PN4F into the active layer solution for later use;
s1-1, dissolving PM6/Y6 in a chloroform solution added with 0.5% (volume ratio) 1-chloronaphthalene according to a mass ratio of 1.2, and preparing a solution of 6mg/mL by taking donor PM6 as a standard to prepare an active layer solution;
s1-2, adding 1% mass fraction of self-separation cathode interface material PN4F into the active layer solution prepared by S1-1 by taking a donor PM6 as a standard for later use;
s2, spin-coating a PEDOT (PolyEthyleneEther phosphate) solution on a glass substrate plated with an ITO (indium tin oxide) anode, and forming an anode interface layer on the surface of the ITO anode after annealing treatment;
s2-1, plating an ITO anode on a glass substrate to serve as an ITO conductive glass substrate, sequentially soaking the ITO conductive glass substrate in a cleaning agent, deionized water and isopropanol, ultrasonically washing for 30min, and drying in an oven overnight;
s2-2, after the cleaned ITO conductive glass substrate is subjected to UVO treatment, spin-coating PEDOT (4083) aqueous solution for 30S at the rotating speed of 3500 rpm to prepare an anode interface layer, and annealing for 15min on a heating table at 150 ℃;
s3, spin-coating the active layer solution added with the self-separation cathode interface material prepared in the step S1 on an anode interface layer in a nitrogen atmosphere, forming an active layer on the surface of the anode interface layer after annealing treatment, and self-separating a cathode interface layer on the surface of the active layer;
s3-1, transferring the ITO conductive glass substrate subjected to the anode interface layer annealing treatment into a glove box protected by nitrogen;
s3-2, in a nitrogen atmosphere, spin-coating the active layer solution added with the self-separation cathode interface material prepared in the step S1 on an anode interface layer at the rotating speed of about 2000rpm, and thermally annealing at 105 ℃ for 15 minutes to form an active layer and a cathode interface layer on the surface of the anode interface layer, wherein the thicknesses of the active layer and the cathode interface layer are about 100nm in total;
and S4, preparing a cathode on the cathode interface layer by adopting an evaporation method through a mask plate, specifically preparing an Ag electrode with the thickness of 100nm by adopting the evaporation method under 10-7mbar through the mask plate.
Example 11
The present example provides a method for preparing an organic solar cell by using the self-separating cathode interface material PN4F in example 1, and the structure of the organic solar cell prepared in this example is ITO/PEDOT: PSS/PM6: Y6: PN4F/Ag, effective area 0.04cm 2 . Wherein PM6 is used as a donor, Y6 is used as an acceptor:
the preparation method of the organic solar cell specifically comprises the following steps:
s1, dissolving a donor/acceptor in a chloroform solution of 1-chloronaphthalene to prepare an active layer solution, and adding PN4F into the active layer solution for later use;
s1-1, dissolving PM6/Y6 in a chloroform solution added with 0.5% (volume ratio) 1-chloronaphthalene according to a mass ratio of 1.2, and preparing a solution of 6mg/mL by taking donor PM6 as a standard to prepare an active layer solution;
s1-2, adding 10% of self-separation cathode interface material PN4F in mass fraction into the active layer solution prepared by the S1-1 for later use by taking a donor PM6 as a standard;
s2, spin-coating a PEDOT (Poly ethylene glycol ether ketone) PSS solution on a glass substrate plated with an ITO anode, and forming an anode interface layer on the surface of the ITO anode after annealing treatment;
s2-1, plating an ITO anode on a glass substrate to serve as an ITO conductive glass substrate, sequentially soaking the ITO conductive glass substrate in a cleaning agent, deionized water and isopropanol, ultrasonically washing for 30min, and drying in an oven overnight;
s2-2, after the cleaned ITO conductive glass substrate is subjected to UVO treatment, spin-coating PEDOT (4083) aqueous solution for 30S at the rotating speed of 3500 rpm to prepare an anode interface layer, and annealing for 15min on a heating table at 150 ℃;
s3, spin-coating the active layer solution added with the self-separation cathode interface material prepared in the step S1 on an anode interface layer in a nitrogen atmosphere, forming an active layer on the surface of the anode interface layer after annealing treatment, and self-separating a cathode interface layer on the surface of the active layer;
s3-1, transferring the ITO conductive glass substrate subjected to the anode interface layer annealing treatment into a glove box protected by nitrogen;
s3-2, spin-coating the active layer solution added with the self-separation cathode interface material prepared in the step S1 on an anode interface layer at the rotating speed of about 2000rpm in a nitrogen atmosphere, and thermally annealing at 115 ℃ for 8 minutes to form an active layer and a cathode interface layer on the surface of the anode interface layer, wherein the thicknesses of the active layer and the cathode interface layer are about 100nm in total;
and S4, preparing a cathode on the cathode interface layer by adopting an evaporation method through a mask plate, specifically preparing an Ag electrode with the thickness of 100nm by adopting the evaporation method under 10-7mbar through the mask plate.
Example 12
This example is the same as the main process of example 9, except that in step S1-2 of this example, 5 mass% of self-separating cathode interface material PN4F was added to the active layer solution prepared in S1-1, based on donor PM 6.
Example 13
This example is the same as the main process of example 9, except that in step S1-2 of this example, 8 mass% of self-separating cathode interface material PN4F was added to the active layer solution prepared in S1-1, based on donor PM 6.
Example 14
This example provides a method for fabricating an organic solar cell using the self-separating cathode interface material PN8F of example 2, where the structure of the fabricated organic solar cell is ITO/PEDOT: PSS/PM6: Y6: PN8F/Ag with an effective area of 0.04cm 2 . Wherein PM6 is taken as a donor, Y6 is taken as an acceptor, and the method specifically comprises the following steps:
s1, dissolving a donor/acceptor in a chloroform solution of 1-chloronaphthalene to prepare an active layer solution, and adding a self-separation cathode interface material PN8F into the active layer solution for later use;
s1-1, dissolving PM6/Y6 in a chloroform solution added with 0.5% (volume ratio) 1-chloronaphthalene according to a mass ratio of 1.2, and preparing a solution of 6mg/mL by taking donor PM6 as a standard to prepare an active layer solution;
s1-2, adding 3% of self-separation cathode interface material PN8F in mass fraction into the active layer solution prepared by the S1-1 for later use by taking a donor PM6 as a standard;
s2, spin-coating a PEDOT (Poly ethylene glycol ether ketone) PSS solution on a glass substrate plated with an ITO anode, and forming an anode interface layer on the surface of the ITO anode after annealing treatment;
s2-1, plating an ITO anode on a glass substrate to serve as an ITO conductive glass substrate, sequentially soaking the ITO conductive glass substrate in a cleaning agent, deionized water and isopropanol, ultrasonically washing for 30min, and drying in an oven overnight;
s2-2, after the cleaned ITO conductive glass substrate is subjected to UVO treatment, spin-coating PEDOT (4083) aqueous solution for 30S at the rotating speed of 3500 rpm to prepare an anode interface layer, and annealing for 15min on a heating table at 150 ℃;
s3, spin-coating the active layer solution added with the self-separation cathode interface material PN8F prepared in the step S1 on an anode interface layer in a nitrogen atmosphere, forming an active layer on the surface of the anode interface layer after annealing treatment, and self-separating the cathode interface layer on the surface of the active layer;
s3-1, transferring the ITO conductive glass substrate subjected to the anode interface layer annealing treatment into a glove box protected by nitrogen;
s3-2, spin-coating the active layer solution added with the self-separation cathode interface material prepared in the step S1 on an anode interface layer at the rotating speed of about 2000rpm in a nitrogen atmosphere, and thermally annealing at 110 ℃ for 10 minutes to form an active layer and a cathode interface layer on the surface of the anode interface layer, wherein the thicknesses of the active layer and the cathode interface layer are about 100nm in total;
and S4, preparing a cathode on the cathode interface layer through a mask plate by adopting a vapor deposition method, specifically preparing an Ag electrode with the thickness of 100nm through the mask plate under 10-7mbar by adopting the vapor deposition method.
Example 15
This example is the same as the main process of example 14, except that in step S1-2 of this example, 1 mass% of the self-separating cathode interface material PN8F was added to the active layer solution prepared in S1-1, based on the donor PM 6.
Example 16
This example is the same as the main process of example 14, except that in step S1-2 of this example, 5 mass% of self-separating cathode interface material PN8F was added to the active layer solution prepared in S1-1, based on donor PM 6.
Example 17
This example is the same as the main process of example 14, except that in step S1-2 of this example, 8 mass% of the self-separating cathode interface material PN8F was added to the active layer solution prepared in S1-1, based on the donor PM 6.
Example 18
This example is the same as the main process of example 14, except that in step S1-2 of this example, 10 mass% of self-separating cathode interface material PN8F was added to the active layer solution prepared in S1-1, based on donor PM 6.
Example 19
This example provides a method for preparing an organic solar cell using the self-separating cathode interface material PN4F of example 1, wherein the structure of the prepared organic solar cell is ITO/PEDOT: PSS/PTB7-Th: PC 71 BM: PN4F/Ag. This example is identical to the preparation process of example 9, except that in example 19 the donor is PTB7-Th and the acceptor is: PC (personal computer) 71 And (4) BM. In this embodiment, the step S1-1 specifically includes: PTB7-Th/PC 71 BM was dissolved in a chloroform solution to which 0.5% (by volume) of 1-chloronaphthalene was added in a mass ratio of 1.5, and a solution of 6mg/mL was prepared using a donor PTB7-Th as a standard, to prepare an active layer solution.
PC 71 The structural formula of the BM receptor is as follows:
the structural formula of the donor PTB7-Th is as follows:
example 20
This example provides a method for preparing an organic solar cell using the self-separating cathode interface material PN8F of example 2, wherein the structure of the prepared organic solar cell is ITO/PEDOT: PSS/PTB7-Th:PC 71 BM: PN8F/Ag. This example is the same as the preparation procedure of example 14, except that in example 20 the donor is PTB7-Th and the acceptor is: PC (personal computer) 71 And BM. In this embodiment, step S1-1 specifically includes: PTB7-Th/PC 71 BM was dissolved in a chloroform solution to which 0.5% (by volume) of 1-chloronaphthalene was added in a mass ratio of 1.5, and a solution of 6mg/mL was prepared using a donor PTB7-Th as a standard, to prepare an active layer solution.
Comparative example 1
This example provides a method for fabricating an organic solar cell, where the structure of the fabricated organic solar cell is ITO/PEDOT: PSS/PM6: Y6/Ag, and the effective area is 0.04cm 2 . Wherein PM6 is taken as a donor, Y6 is taken as an acceptor, and the method specifically comprises the following steps:
s1, dissolving PM6/Y6 into a chloroform solution added with 0.5% (volume ratio) 1-chloronaphthalene according to a mass ratio of 1.2, and preparing a solution of 6mg/mL by taking donor PM6 as a standard to prepare an active layer solution;
s2, spin-coating a PEDOT (Poly ethylene glycol ether ketone) PSS solution on a glass substrate plated with an ITO anode, and forming an anode interface layer on the surface of the ITO anode after annealing treatment;
s2-1, plating an ITO anode on a glass substrate to serve as an ITO conductive glass substrate, sequentially soaking the ITO conductive glass substrate in a cleaning agent, deionized water and isopropanol, ultrasonically washing for 30min, and drying in an oven overnight;
s2-2, after the cleaned ITO conductive glass substrate is subjected to UVO treatment, spin-coating PEDOT (4083) aqueous solution for 30S at the rotating speed of 3500 rpm to prepare an anode interface layer, and annealing for 15min on a heating table at 150 ℃;
s3, spin-coating the active layer solution prepared in the step S1 on an anode interface layer in a nitrogen atmosphere to form an active layer, and then annealing;
s3-1, transferring the ITO conductive glass substrate subjected to the anode interface layer annealing treatment into a glove box protected by nitrogen;
s3-2, spin-coating the active layer solution prepared in the step S1 on an anode interface layer at the rotating speed of about 2000rpm in a nitrogen atmosphere to form an active layer, and then thermally annealing the glass substrate with the active layer at 110 ℃ for 10 minutes;
and S4, preparing a cathode on the active layer through a mask plate by adopting a vapor deposition method, specifically preparing an Ag electrode with the thickness of 100nm through the mask plate under 10-7mbar by adopting the vapor deposition method.
Comparative example 2
This example provides a method for fabricating an organic solar cell, which includes the steps of ITO/PEDOT: PSS/PTB7-Th: PC 71 BM/Ag, effective area of 0.04cm 2 . Wherein PTB7-Th is used as a donor, PC 71 BM is a receptor, and specifically comprises the following steps:
s1, mixing PTB7-Th/PC 71 BM is dissolved in a chloroform solution added with 0.5 percent (volume ratio) of 1-chloronaphthalene according to the mass ratio of 1.5 to prepare a solution of 6mg/mL by taking a donor PTB7-Th as a standard to prepare an active layer solution;
s2, spin-coating a PEDOT (Poly ethylene glycol ether ketone) PSS solution on a glass substrate plated with an ITO anode, and forming an anode interface layer on the surface of the ITO anode after annealing treatment;
s2-1, plating an ITO anode on a glass substrate to serve as an ITO conductive glass substrate, sequentially soaking the ITO conductive glass substrate in a cleaning agent, deionized water and isopropanol, ultrasonically washing for 30min, and drying in an oven overnight;
s2-2, after the cleaned ITO conductive glass substrate is subjected to UVO treatment, spin-coating PEDOT (4083) aqueous solution for 30S at the rotating speed of 3500 rpm to prepare an anode interface layer, and annealing for 15min on a heating table at 150 ℃;
s3, spin-coating the active layer solution prepared in the step S1 on an anode interface layer in a nitrogen atmosphere to form an active layer, and annealing;
s3-1, transferring the ITO conductive glass substrate subjected to the anode interface layer annealing treatment into a glove box protected by nitrogen;
s3-2, spin-coating the active layer solution prepared in the step S1 on an anode interface layer at a rotating speed of about 2000rpm in a nitrogen atmosphere to form an active layer, and then annealing the glass substrate with the active layer;
and S4, preparing a cathode on the active layer through a mask plate by adopting an evaporation method, specifically preparing an Ag electrode with the thickness of 100nm through the mask plate by adopting the evaporation method under 10-7 mbar.
< case of energy conversion when the donor was PM6 and the acceptor was Y6 >
The solar cell devices obtained in examples 9 and 14 and comparative example 1 were subjected to performance tests, and the results are shown in fig. 1 and table 1 below. By calculation, when the donor is PM6 and the acceptor is Y6, the maximum photoelectric conversion efficiency is 10.53% under the condition that the self-separating cathode interface material is not added in the active layer solution, the maximum photoelectric conversion efficiency is 12.05% after the self-separating cathode interface material PN4F is added, and the maximum photoelectric conversion efficiency is 11.91% after the self-separating cathode interface material PN8F is added. The self-separating cathode interface material PN4F, PN F is added, and after heating annealing treatment, an active layer is formed on the surface of the anode interface layer and the cathode interface layer is self-separated, so that the photoelectric conversion efficiency is improved, and the energy conversion efficiency of the organic solar cell is improved.
TABLE 1
<The donor is PTB7-Th and the acceptor is PC 71 Energy conversion situation at BM>
Examples 19, 20 and comparative example 2 were analyzed in conjunction with fig. 2:
the solar cell devices obtained in examples 19 and 20 and comparative example 2 were subjected to performance tests, and the results are shown in fig. 2 and table 2 below. Calculated when the donor is PTB7-Th and the acceptor is PC 71 In BM, the photoelectric conversion efficiency is 3.73% at most without adding additives, the photoelectric conversion efficiency is 6.93% at most after adding the self-separating cathode interface material PN4F, and the photoelectric conversion efficiency is 5.76% at most after adding the self-separating cathode interface material PN8F, because the self-separating cathode interface material PN4F, PN F is added, and after heating and annealing treatment, an active layer is formed on the surface of the anode interface layer and the cathode interface layer is self-separated, so that the photoelectric conversion efficiency is improved, and the energy conversion efficiency of the organic solar cell is improved. The self-separating cathode interface material of the inventionThe material can be used in organic solar cell devices made of fullerene and non-fullerene materials, and has wide application range.
TABLE 2
< UV-visible absorption Spectroscopy >
As can be seen from FIG. 3, in CHCl 3 The result that PN8F and PN4F in the solution have similar absorption spectra, the absorption peaks are both near 390nm and are presumed to be generated by pi-transition of an intramolecular conjugated main chain shows that the introduction and the proportion change of the fluorine/amino-containing bifunctional side chain have little influence on the optical property of the main chain. As can be seen from FIG. 4, each small molecule also exhibits an approximate UV-visible absorption spectrum in the thin film state, similar to CHCl 3 The absorption spectra in solution are slightly red-shifted from the absorption peaks in the film, indicating that there is an interaction between the molecules in the film state and a slight aggregation, resulting in a red-shift. The absorption edge of the polymer film can be calculated to have a similar optical band gap for each small molecule, about 2.9eV. Therefore, it can be shown that the optical waveguide has a good light transmittance in the near infrared band.
< hydrophobicity >
As shown in fig. 5 and 6, the contact angle of PN4F with water was 90.7 degrees, and the contact angle of PN8F with water was 96.3 degrees. The contact angles of PN4F and PN8F with water are larger than 90 degrees, which shows that the two materials have hydrophobicity and can prevent water molecules from entering into the active region, thereby prolonging the service life of the device and improving the stability of the device. In addition, the surface energies of PN4F and PN8F are also calculated, and the calculation method is prior art and is not described herein again. The surface energies of PN4F and PN8F were calculated to be 37.9N/m and 34.1N/m, respectively, since the fluorine-containing side chains impart a lower surface energy to the self-separating interface material, driving vertical self-separation of the material by the lower surface energy.
Claims (10)
1. A self-separating cathode interface material is characterized in that the self-separating cathode interface materialHas a side chain with double functions of fluorine and amino, and the molecular formula is C 2n+87 H 124 F 4n+2 N 4 O 2 Wherein n is an integer and n ≧ 1.
2. The self-separating cathode interface material as claimed in claim 1, wherein the formula is C 95 H 124 F 18 N 4 O 2 Structural formula is
3. The self-separating cathode interface material as claimed in claim 1, wherein the formula is C 103 H 124 F 34 N 4 O 2 Structural formula is
4. A method of making the self-separating cathode interface material of claim 2, comprising the steps of;
s1, taking tetrahydrofuran, 2,7-dibromo-9,9-di (6-bromohexyl) fluorene, tetrabutylammonium bromide and 1H,2H and 2H-perfluoro-1-hexanol, mixing, adding a sodium hydroxide aqueous solution under an argon atmosphere, heating, stirring, extracting, drying, filtering, performing rotary evaporation and purification to obtain an intermediate product M2;
s2, toluene, tetraethylammonium hydroxide, intermediate M2 and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborane-) -9,9-bis (6- (N, N-diethylamino) hexyl) fluorene were added to a pressure resistant tube, and Pd (PPh) was added under nitrogen atmosphere 3 ) 4 Heating the catalyst to 85-100 ℃, stirring for 6-8 h, cooling, extracting, drying, filtering, rotary evaporating and purifying to obtain the compound with the molecular formula C 95 H 124 F 18 N 4 O 2 The self-separating cathode interface material of (1).
5. The method of claim 4, wherein the intermediate product M2 and the compound of formula C are selected from the group consisting of 95 H 124 F 18 N 4 O 2 The purification method of the self-separation cathode interface material adopts column chromatography.
6. A process for preparing the self-separating cathode interface material of claim 3, comprising the steps of;
s1, taking tetrahydrofuran, 2,7-dibromo-9,9-di (6-bromohexyl) fluorene, tetrabutylammonium bromide and 1H,2H and 2H-perfluoro-1-decanol, mixing, adding a sodium hydroxide aqueous solution under an argon atmosphere, heating, stirring, extracting, drying, filtering, performing rotary evaporation, and purifying to obtain an intermediate product M3;
s2, adding toluene, tetraethylammonium hydroxide, an intermediate product M3 and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborane-) -9,9-bis (6- (N, N-diethylamino) hexyl) fluorene into a pressure resistant pipe, and adding Pd (PPh) under a nitrogen atmosphere 3 ) 4 Heating the catalyst to 85-100 ℃, stirring for 6-8 h, cooling, extracting, drying, filtering, rotary evaporating and purifying to obtain the compound with the molecular formula C 103 H 124 F 34 N 4 O 2 Is used to separate the cathode interface material.
7. The method of claim 6, wherein the intermediate product M3 and the compound of formula C are selected from the group consisting of 103 H 124 F 34 N 4 O 2 The purification method of the self-separation cathode interface material adopts column chromatography.
8. A method for manufacturing a self-separating organic solar cell, characterized in that the self-separating cathode interface material of claim 1 is added to an active layer solution in a mass fraction of 1% to 10%.
9. The method for preparing the self-separating organic solar cell according to claim 8, wherein the method comprises spin-coating an anode interface layer material on the surface of the anode, annealing and forming an anode interface layer on the surface of the anode; then, spin-coating an active layer solution added with the self-separating cathode interface material of claim 1 on the surface of the anode interface layer, forming an active layer on the surface of the anode interface layer after annealing treatment, and self-separating a cathode interface layer on the surface of the active layer; and finally, evaporating a cathode on the surface of the cathode interface layer to obtain the organic solar cell.
10. The method for preparing a self-separating organic solar cell according to claim 9, comprising the following steps:
s1, dissolving a donor/acceptor in a chloroform solution of 1-chloronaphthalene to prepare an active layer solution, and adding the self-separating cathode interface material as claimed in claim 1 into the active layer solution for later use;
s2, spin-coating a PEDOT (Poly ethylene glycol ether ketone) PSS solution on a glass substrate plated with an ITO anode, and forming an anode interface layer on the surface of the ITO anode after annealing treatment;
s3, spin-coating the active layer solution added with the self-separation cathode interface material prepared in the step S1 on an anode interface layer in a nitrogen atmosphere, and carrying out annealing treatment at 105-115 ℃ for 8-15 minutes to form an active layer and a cathode interface layer on the surface of the anode interface layer after the annealing treatment;
and S4, preparing a cathode above the cathode interface layer through a mask plate by adopting a vapor deposition method.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110212097A (en) * | 2019-06-21 | 2019-09-06 | 吉林大学 | A kind of cathode interface layer material and preparation method thereof, organic solar batteries and preparation method thereof |
| CN112062777A (en) * | 2020-09-08 | 2020-12-11 | 国家纳米科学中心 | Organic small-molecule photovoltaic material based on dithienylbenzodithiophene donor nucleus and preparation method and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110212097A (en) * | 2019-06-21 | 2019-09-06 | 吉林大学 | A kind of cathode interface layer material and preparation method thereof, organic solar batteries and preparation method thereof |
| CN112062777A (en) * | 2020-09-08 | 2020-12-11 | 国家纳米科学中心 | Organic small-molecule photovoltaic material based on dithienylbenzodithiophene donor nucleus and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| LI TIAN 等: "Fluoro- and Amino-Functionalized Conjugated Polymers as Electron Transport Materials for Perovskite Solar Cells with Improved Efficiency and Stability", 《ACS APPL. MATER. INTERFACES》, vol. 11, no. 5, 11 January 2019 (2019-01-11), pages 5289 - 5297 * |
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