CN115960006B - Self-separating cathode interface material, preparation method thereof and method for preparing organic solar cell by one-step method - Google Patents
Self-separating 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
- 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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Abstract
A self-separating cathode interface material, a preparation method thereof and a method for preparing an organic solar cell by one-step method relate to the field of electron transport materials in the organic solar cell, and the molecular formula of the self-separating cathode interface material is C 2n+87H124F4n+2N4O2, wherein n is an integer and n is equal to or greater than 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 invention provides a material completely different from the prior art, and the self-separating cathode interface material spontaneously forms a multi-layer film structure through vertical phase separation in the processing process of an 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 facilitated.
Description
Technical Field
The invention relates to the field of electron transport materials in organic solar cells, in particular to a design and synthesis method of a self-separation cathode interface material and a preparation method of an organic solar cell.
Background
Photovoltaic power generation is highly expected 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 for realizing efficient 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 prospect in the fields of wearable equipment, transparent photovoltaic devices and the like.
In recent years, photoelectric conversion efficiency of an organic solar cell is rapidly developed, laboratory efficiency is close to commercial requirements, however, in the preparation of the organic solar cell, the cathode interface layer, the active layer and the anode interface layer need to be respectively spin-coated, so that the preparation can be completed at least three times, and in addition, the cathode interface layer is generally thinner (the optimal thickness is usually within 30 nm), and the independent processing is unfavorable for the application of a roll-to-roll process, thus preventing the preparation of a large-area device.
In order to simplify the preparation method, a plurality of universities and research institutes at home and abroad develop related researches on self-assembled cathode interface materials/interface layers.
As ：H.Zhao,L.Wang,Y.Wang,W.Su,D.Lin,W.Cai,J.Qing,Z.Zhang,J.Zhong,L.Hou,Solvent-Vapor-Annealing-Induced Interfacial Self-Assembly for Simplified One-Step Spraying Organic Solar Cells.ACS Appl.Energy Mater.,2021,4,7316-7326., a one-step process for preparing ITO/PFN, BHJ/MoO 3/Ag is disclosed. The method specifically comprises the following steps: the ITO glass substrate was washed sequentially with acetone, detergent, deionized water and isopropyl alcohol. PFN was added to the active layer and a PFN PTB7 PC71BM or PFN PBDB-T IT-M solution was sprayed directly on top of the clean ITO substrate in one step. Finally, moO 3 (10 nm)/Ag (100 nm) was evaporated sequentially on the surface of the active layer under a pressure of 3X 10 -4 Pa. The expression is formed: the drying process is extended to form a complete self-assembled PFN cathode interface layer and an optimized donor-acceptor phase-separated Bulk Heterojunction (BHJ), which can be driven by surface energy to form a separate ultrathin PFN film layer between the active layer and Indium Tin Oxide (ITO) by downward vertical self-separation as the cathode interface layer.
Another example is: the invention patent of China 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, and the active layer is formed on the surface of the cathode interface layer, and the mixed solution comprises: polyvinylpyrrolidone; 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 one-step method.
The invention adopts the following specific scheme: a self-separating cathode interface material has a fluorine/amino-containing bi-functional side chain with a molecular formula of C 2n+87H124F4n+2N4O2, wherein n is an integer and n is equal to or greater than 1.
As a further optimization of the technical scheme, the molecular formula is C 95H124F18N4O2, and the structural formula is
As a further optimization of the technical scheme, the molecular formula is C 103H124F34N4O2, and the structural formula is
A preparation method of a self-separating cathode interface material comprises the following steps of;
S1, mixing tetrahydrofuran, 2, 7-dibromo-9, 9-di (6-bromohexyl) fluorene, tetrabutylammonium bromide and 1H, 2H-perfluoro-1-hexanol, adding sodium hydroxide aqueous solution under argon atmosphere, heating and stirring, extracting, drying, filtering, rotary evaporating and purifying to obtain an intermediate product M2;
S2, adding toluene, tetraethylammonium hydroxide, an intermediate product M2 and 2- (4, 5-tetramethyl-1, 3, 2-dioxaborane-) -9, 9-bis (6- (N, N-diethylamino) hexyl) fluorene into a pressure-resistant pipe, adding Pd (PPh 3)4) catalyst under nitrogen atmosphere, heating to 85-100 ℃ and stirring for 6-8 h, cooling, and sequentially extracting, drying, filtering, rotary evaporating and purifying to obtain the self-separating cathode interface material with the molecular formula of C 95H124F18N4O2.
As a further optimization of the technical scheme, column chromatography is adopted for both the intermediate product M2 and the purification method of the self-separating cathode interface material with the molecular formula of C 95H124F18N4O2.
A preparation method of a self-separating cathode interface material comprises the following steps of;
S1, mixing tetrahydrofuran, 2, 7-dibromo-9, 9-di (6-bromohexyl) fluorene, tetrabutylammonium bromide and 1H, 2H-perfluoro-1-decanol, adding sodium hydroxide aqueous solution under argon atmosphere, heating and stirring, extracting, drying, filtering, rotary evaporating and purifying to obtain an intermediate product M3;
s2, adding toluene, tetraethylammonium hydroxide, an intermediate product M3 and 2- (4, 5-tetramethyl-1, 3, 2-dioxaborane-) -9, 9-bis (6- (N, N-diethylamino) hexyl) fluorene into a pressure-resistant pipe, adding Pd (PPh 3)4) catalyst under nitrogen atmosphere, heating to 85-100 ℃ and stirring for 6-8 h, cooling, and sequentially extracting, drying, filtering, rotary evaporating and purifying to obtain the self-separating cathode interface material with the molecular formula of C 103H124F34N4O2.
As a further optimization of the technical scheme, column chromatography is adopted for both the intermediate product M3 and the self-separating cathode interface material with the molecular formula of C 103H124F34N4O2.
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 above technical scheme, firstly, spin-coating an anode interface layer material on the surface of an anode, and forming an anode interface layer on the surface of the anode after annealing treatment; then, spin-coating the active layer solution of 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 separating the 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-separating cathode interface material into the active layer solution for later use;
S2, spin-coating PEDOT/PSS solution on the glass substrate plated with the 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 nitrogen atmosphere, carrying out thermal annealing treatment for 8-15 minutes at 105-110 ℃, 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;
s4, preparing a cathode through a mask plate by adopting an evaporation method above the cathode interface layer.
Compared with the prior art, the invention has the following beneficial effects: according to the self-separating cathode interface material, a multilayer film structure is spontaneously formed through vertical phase separation in the processing process of an 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 large-area industrial processing is facilitated.
The amino side chain of the self-separation cathode interface material is beneficial to modifying the work function of the cathode, promoting the transmission and collection of electrons and improving 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, the self-separating cathode interface material is used as an active layer additive, and vertical phase separation can be realized through surface energy driving, so that the active layer and the cathode interface layer are prepared through a one-step method, and the preparation process is optimized. Therefore, the self-separating cathode interface material of the fluorine-containing/amino-containing double-function side chain is designed and synthesized, which is beneficial to prolonging the service life of the device, avoiding the independent spin-coating of the cathode interface layer and optimizing the preparation process of the device.
Drawings
FIG. 1 is a J-V curve of a self-dispersing polymer solar cell with PM6 as donor and Y6 as acceptor, PN8F, PN F as additive;
FIG. 2 is a graph of J-V curves for self-separating polymer solar cells with PTB7-Th as donor and PC71BM as acceptor, PN8F, PN4F as additive;
FIG. 3 is an ultraviolet-visible absorption spectrum of PN8F, PN F in CHCl 3 solution;
FIG. 4 is an ultraviolet-visible absorption spectrum of PN8F, PN F in the thin film state;
FIG. 5 is a schematic diagram showing the contact angle of PN4F with water;
fig. 6 is a schematic diagram of the contact angle of PN8F with water.
Detailed Description
The invention provides a self-separating cathode interface material, a preparation method thereof and a method for preparing an organic solar cell by one-step method, wherein the self-separating cathode interface material is provided with fluorine-containing/amino difunctional side chains, the fluorine-containing/amino difunctional side chains comprise amino side chains and fluorine-containing side chains, the molecular formula of the self-separating cathode interface material is C 2n+87H124F4n+2N4O2, wherein n is an integer and n is equal to or greater than 1.
For convenience of description, 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-bis (6-bromohexyl) fluorene;
M2 is 2, 7-dibromo-9, 9-bis (6- ((3, 4,5, 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, 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
In this embodiment, n=4, and the molecular formula of the self-separating cathode interface material C 95H124F18N4O2, abbreviated as PN4F, has the structural formula:
example 2
In this embodiment, n=8, and the molecular formula of the self-separating cathode interface material C 103H124F34N4O2, abbreviated as PN8F, has the structural formula:
Example 3
The present example provides a method for preparing the self-separating cathode interface material (PN 4F) of example 1, wherein the prepared PN4F is coupled by Suzuki, and specifically comprises the following steps:
S1, 50mL of tetrahydrofuran, 10mmol of M1, 50mg of tetrabutylammonium bromide and 24mmol of 1H, 2H-perfluoro-1-hexanol are taken and added into a 250mL two-port bottle to be mixed, 50mL of mixed solution prepared by 50% aqueous sodium hydroxide solution is added by a syringe under argon atmosphere, the mixed solution is stirred overnight at 60 ℃, the mixed solution is cooled to room temperature and then extracted by CH 2Cl2, water is used for washing twice, the extracted organic layer is dried by anhydrous MgSO 4, filtration is carried out and the filtrate is rotationally evaporated to obtain a crude product, the crude product is purified by column chromatography (SiO 2: PE/DCM is 5:1), the intermediate product M2 is obtained by purification, and the intermediate product M2 is yellow oily substance with the yield of 39%;
S2, firstly, 1.10mL of chromatographically pure toluene, 0.55mL of tetraethylammonium hydroxide, 72.1mg of intermediate M2 and 106.0mg of M4 are added into a 15mL pressure-resistant tube, nitrogen is introduced into the tube through a long needle for 15min, 5mg of Pd (PPh 3)4 catalyst is added under nitrogen atmosphere to obtain a mixed solution, the mixed solution is stirred for 8h at 100 ℃, the mixed solution is cooled to room temperature, extracted by CH 2Cl2 and washed twice by water, the extracted organic layer is dried by anhydrous MgSO 4, filtered and the filtrate is rotationally evaporated to obtain a crude product, and the crude product is purified by column chromatography (SiO 2; PE/DCM/triethylamine 100:20:5) to obtain white solid (PN 4F) with the yield of 75%.
Example 4
This example provides a method for preparing a self-separating cathode interface material (PN 4F) of example 1, wherein the PN4F is prepared by Suzuki coupling, and the method for preparing intermediate M2 of this example is the same as that of example 3, except that:
S2, firstly, 1.10mL of chromatographically pure toluene, 0.55mL of tetraethylammonium hydroxide, 72.1mg of intermediate M2 and 106.0mg of M4 are added into a 15mL pressure-resistant tube, nitrogen is introduced into the tube through a long needle for 15min, 5mg of Pd (PPh 3)4 catalyst is added under a nitrogen atmosphere to obtain a mixed solution, the mixed solution is stirred for 10h at 90 ℃, the mixed solution is cooled to room temperature, extracted by CH 2Cl2 and washed twice by water, the extracted organic layer is dried by anhydrous MgSO 4, filtered and the filtrate is rotationally evaporated to obtain a crude product, and the crude product is purified by column chromatography (SiO 2; PE/DCM/triethylamine 100:20:5) to obtain white solid (PN 4F).
Example 5
This example provides a method for preparing a self-separating cathode interface material (PN 4F) of example 1, wherein the PN4F is prepared by Suzuki coupling, and the method for preparing intermediate M2 of this example is the same as that of example 3, except that:
S2, firstly, 1.10mL of chromatographically pure toluene, 0.55mL of tetraethylammonium hydroxide, 72.1mg of intermediate M2 and 106.0mg of M4 are added into a 15mL pressure-resistant tube, nitrogen is introduced into the tube through a long needle for 15min, 5mg of Pd (PPh 3)4 catalyst is added under a nitrogen atmosphere to obtain a mixed solution, the mixed solution is stirred for 6h at 85 ℃, the mixed solution is cooled to room temperature, extracted with CH 2Cl2 and washed twice with water, the extracted organic layer is dried with anhydrous MgSO 4, filtered and the filtrate is rotationally evaporated to obtain a crude product, and the crude product is purified by column chromatography (SiO 2; PE/DCM/triethylamine 100:20:5) to obtain white solid (PN 4F).
Example 6
The embodiment provides a preparation method of a self-separating cathode interface material PN8F in embodiment 2, wherein the prepared PN8F adopts Suzuki coupling, and specifically comprises the following steps:
s1, 50mL of tetrahydrofuran, 10mmol of M1, 50mg of tetrabutylammonium bromide and 25mmol of 1H, 2H-perfluoro-1-decanol were taken, and a mixture was prepared by adding 50mL of 50% aqueous sodium hydroxide solution to a syringe under argon atmosphere and stirring overnight at 60 ℃, the mixture was cooled to room temperature and then extracted with CH 2Cl2, then washed twice with water, the extracted organic layer was dried over anhydrous MgSO 4, and then filtered and the filtrate was rotary evaporated to give a crude product, which was purified by column chromatography, siO 2 used in the column chromatography: PE/DCM 5:1, purification to give intermediate M3 as a white solid in 42% yield;
S2, 1.10mL of chromatographically pure toluene, 0.55mL of tetraethylammonium hydroxide, 104.2mg of intermediate M3 and 106.0mg of M4 were taken into a 15mL pressure-resistant tube, nitrogen was introduced with a long needle for 15min, 5mg of Pd (PPh 3)4 catalyst) was added under a nitrogen atmosphere, the mixture was stirred at 100℃for 8h, cooled to room temperature, extracted with CH 2Cl2 and washed twice with water, the extracted organic layer was dried over anhydrous MgSO 4, filtered and the filtrate was rotary evaporated to give a crude product, which was purified by column chromatography (SiO 2; PE/DCM/triethylamine 100:20:5) to give PN8F as a white solid after purification, 73% yield.
Example 7
The present example provides a method for preparing the self-separating cathode interface material PN8F in example 2, and the prepared PN8F is subjected to Suzuki coupling, and the method for preparing the intermediate product M3 in this example is the same 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 were taken, put into a 15mL pressure-resistant tube, nitrogen was introduced with a long needle for 15min, 5mg of Pd (PPh 3)4 catalyst) was added under a nitrogen atmosphere, the mixture was stirred at 85℃for 7h, cooled to room temperature, extracted with CH 2Cl2 and washed twice with water, the extracted organic layer was dried over anhydrous MgSO 4, filtered and the filtrate was rotary evaporated to give a crude product, which was purified by column chromatography (SiO 2; PE/DCM/triethylamine 100:20:5) to give PN8F as a white solid after purification.
Example 8
The present example provides a method for preparing the self-separating cathode interface material PN8F in example 2, and the prepared PN8F is subjected to Suzuki coupling, and the method for preparing the intermediate product M3 in this example is the same 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 were taken, put into a 15mL pressure-resistant tube, nitrogen was introduced with a long needle for 15min, 5mg of Pd (PPh 3)4 catalyst) was added under a nitrogen atmosphere, the mixture was stirred at 90℃for 6h, cooled to room temperature, extracted with CH 2Cl2 and washed twice with water, the extracted organic layer was dried over anhydrous MgSO 4, filtered and the filtrate was rotary evaporated to give a crude product, which was purified by column chromatography (SiO 2; PE/DCM/triethylamine 100:20:5) to give PN8F as a white solid after purification.
Example 9
The present example provides a method for preparing an organic solar cell using the self-separating cathode interface material PN4F of example 1, the organic solar cell structure prepared in this example is ITO/PEDOT: PSS/PM6: Y6: PN4F/Ag, the effective area is 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 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 1:1.2, and preparing a solution with a concentration of 6mg/mL by taking a donor PM6 as a standard to prepare an active layer solution;
S1-2, taking a donor PM6 as a standard, adding 3% by mass of self-separating cathode interface material PN4F into an active layer solution prepared by S1-1 for later use;
S2, spin-coating PEDOT/PSS solution on the glass substrate plated with the 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, spin-coating an ITO conductive glass substrate subjected to cleaning by adopting an aqueous solution of PEDOT: PSS (4083) at a rotating speed of 3500 rpm for 30S after UVO treatment, preparing 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 separating the cathode interface layer on the surface of the active layer;
S3-1, transferring the ITO conductive glass substrate subjected to the annealing treatment of the anode interface layer 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 a rotating speed of about 2000rpm in a nitrogen atmosphere, and thermally annealing for 10 minutes at 110 ℃ to form an active layer and a cathode interface layer on the surface of the anode interface layer, wherein the total thickness of the active layer and the cathode interface layer is about 100nm;
S4, preparing a cathode through a mask plate at a cathode interface layer by adopting an evaporation method, and particularly preparing an Ag electrode with the thickness of 100nm through the mask plate by adopting the evaporation method at the pressure of 10 < -7 > mbar.
Example 10
The present example provides a method for preparing an organic solar cell using the self-separating cathode interface material PN4F of example 1, the organic solar cell structure prepared in this example is ITO/PEDOT: PSS/PM6: Y6: PN4F/Ag, the effective area is 0.04cm 2. Wherein PM6 is taken as a donor, and Y6 is taken 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 into a chloroform solution added with 0.5% (volume ratio) 1-chloronaphthalene according to a mass ratio of 1:1.2, and preparing a solution with a concentration of 6mg/mL by taking a donor PM6 as a standard to prepare an active layer solution;
S1-2, taking a donor PM6 as a standard, adding 1% by mass of self-separating cathode interface material PN4F into an active layer solution prepared by S1-1 for later use;
S2, spin-coating PEDOT/PSS solution on the glass substrate plated with the 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, spin-coating an ITO conductive glass substrate subjected to cleaning by adopting an aqueous solution of PEDOT: PSS (4083) at a rotating speed of 3500 rpm for 30S after UVO treatment, preparing 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 separating the cathode interface layer on the surface of the active layer;
S3-1, transferring the ITO conductive glass substrate subjected to the annealing treatment of the anode interface layer 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 a rotating speed of about 2000rpm in a nitrogen atmosphere, and thermally annealing for 15 minutes at 105 ℃ to form an active layer and a cathode interface layer on the surface of the anode interface layer, wherein the total thickness of the active layer and the cathode interface layer is about 100nm;
S4, preparing a cathode through a mask plate at a cathode interface layer by adopting an evaporation method, and particularly preparing an Ag electrode with the thickness of 100nm through the mask plate by adopting the evaporation method at the pressure of 10 < -7 > mbar.
Example 11
The present example provides a method for preparing an organic solar cell using the self-separating cathode interface material PN4F of example 1, the organic solar cell structure prepared in this example is ITO/PEDOT: PSS/PM6: Y6: PN4F/Ag, the effective area is 0.04cm 2. Wherein PM6 is taken as a donor, and Y6 is taken 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 into a chloroform solution added with 0.5% (volume ratio) 1-chloronaphthalene according to a mass ratio of 1:1.2, and preparing a solution with a concentration of 6mg/mL by taking a donor PM6 as a standard to prepare an active layer solution;
S1-2, taking a donor PM6 as a standard, adding 10% by mass of self-separating cathode interface material PN4F into an active layer solution prepared by S1-1 for later use;
S2, spin-coating PEDOT/PSS solution on the glass substrate plated with the 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, spin-coating an ITO conductive glass substrate subjected to cleaning by adopting an aqueous solution of PEDOT: PSS (4083) at a rotating speed of 3500 rpm for 30S after UVO treatment, preparing 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 separating the cathode interface layer on the surface of the active layer;
S3-1, transferring the ITO conductive glass substrate subjected to the annealing treatment of the anode interface layer 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 a 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 total thickness of the active layer and the cathode interface layer is about 100nm;
S4, preparing a cathode through a mask plate at a cathode interface layer by adopting an evaporation method, and particularly preparing an Ag electrode with the thickness of 100nm through the mask plate by adopting the evaporation method at the pressure of 10 < -7 > mbar.
Example 12
This example is the same as the main body method of example 9, except that in step S1-2 of this example, 5% by mass of the self-separating cathode interface material PN4F is added to the active layer solution prepared in S1-1, based on the donor PM 6.
Example 13
This example is the same as the main body method of example 9, except that in step S1-2 of this example, 8% by mass of the self-separating cathode interface material PN4F is added to the active layer solution prepared in S1-1, based on the donor PM 6.
Example 14
This example provides a method for preparing an organic solar cell using the self-separating cathode interface material PN8F of example 2, the prepared organic solar cell structure being ITO/PEDOT: PSS/PM6:Y6: PN8F/Ag, 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 a donor/acceptor in a chloroform solution of 1-chloronaphthalene to prepare an active layer solution, and adding a self-separating cathode interface material PN8F 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 1:1.2, and preparing a solution with a concentration of 6mg/mL by taking donor PM6 as a standard to prepare an active layer solution;
s1-2, taking a donor PM6 as a standard, adding 3% by mass of self-separating cathode interface material PN8F into an active layer solution prepared by S1-1 for later use;
S2, spin-coating PEDOT/PSS solution on the glass substrate plated with the 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, spin-coating an ITO conductive glass substrate subjected to cleaning by adopting an aqueous solution of PEDOT: PSS (4083) at a rotating speed of 3500 rpm for 30S after UVO treatment, preparing 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 annealing treatment of the anode interface layer 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 a rotating speed of about 2000rpm in a nitrogen atmosphere, and thermally annealing for 10 minutes at 110 ℃ to form an active layer and a cathode interface layer on the surface of the anode interface layer, wherein the total thickness of the active layer and the cathode interface layer is about 100nm;
S4, preparing a cathode through a mask plate at a cathode interface layer by adopting an evaporation method, and particularly preparing an Ag electrode with the thickness of 100nm through the mask plate by adopting the evaporation method at the pressure of 10 < -7 > mbar.
Example 15
This example is the same as the main body method of example 14, except that in step S1-2 of this example, 1% by mass of the self-separating cathode interface material PN8F is added to the active layer solution prepared in S1-1, based on the donor PM6.
Example 16
This example is the same as the main body method of example 14, except that in step S1-2 of this example, 5% by mass of the self-separating cathode interface material PN8F is added to the active layer solution prepared in S1-1, based on the donor PM6.
Example 17
This example is the same as the main body method of example 14, except that in step S1-2 of this example, 8% by mass of a self-separating cathode interface material PN8F is added to the active layer solution prepared in S1-1, based on the donor PM6.
Example 18
This example is the same as the main body method of example 14, except that in step S1-2 of this example, 10% by mass of the self-separating cathode interface material PN8F is added to the active layer solution prepared in S1-1, based on the 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, the prepared organic solar cell structure being ITO/PEDOT: PSS/PTB7-Th: PC 71 BM: PN4F/Ag. This example is identical to the preparation of example 9, except that the donor in example 19 is PTB7-Th and the acceptor is: PC 71 BM. In this embodiment, the step S1-1 specifically comprises: PTB7-Th/PC 71 BM was dissolved in a chloroform solution to which 0.5% (volume ratio) 1-chloronaphthalene was added at a mass ratio of 1:1.5, and a solution of 6mg/mL was prepared based on the donor PTB7-Th, to prepare an active layer solution.
The structural formula of the PC 71 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, the prepared organic solar cell structure being ITO/PEDOT: PSS/PTB7-Th: PC 71 BM: PN8F/Ag. This example is identical to the preparation of example 14, except that the donor in example 20 is PTB7-Th and the acceptor is: PC 71 BM. In this embodiment, the step S1-1 specifically comprises: PTB7-Th/PC 71 BM was dissolved in a chloroform solution to which 0.5% (volume ratio) 1-chloronaphthalene was added at a mass ratio of 1:1.5, and a solution of 6mg/mL was prepared based on the donor PTB7-Th, to prepare an active layer solution.
Comparative example 1
The embodiment provides a preparation method of an organic solar cell, and the prepared organic solar cell has an ITO/PEDOT (indium tin oxide)/PSS/PM 6:Y6/Ag structure and 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 PM6/Y6 into a chloroform solution added with 0.5% (volume ratio) 1-chloronaphthalene according to a mass ratio of 1:1.2, and preparing a solution with a donor PM6 as a standard to prepare an active layer solution;
S2, spin-coating PEDOT/PSS solution on the glass substrate plated with the 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, spin-coating an ITO conductive glass substrate subjected to cleaning by adopting an aqueous solution of PEDOT: PSS (4083) at a rotating speed of 3500 rpm for 30S after UVO treatment, preparing 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 the 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 annealing treatment of the anode interface layer 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 thermally annealing the glass substrate with the active layer at 110 ℃ for 10 minutes;
S4, preparing a cathode through a mask plate by adopting an evaporation method on the active layer, and particularly preparing an Ag electrode with the thickness of 100nm through the mask plate by adopting the evaporation method under the condition of 10 < -7 > mbar.
Comparative example 2
The embodiment provides a preparation method of an organic solar cell, and the prepared organic solar cell has an ITO/PEDOT (indium tin oxide)/PSS/PTB 7-Th (Poly carbonate)/PC 71 BM/Ag and an effective area of 0.04cm 2. Wherein PTB7-Th is taken as a donor, PC 71 BM is taken as a receptor, and the method specifically comprises the following steps:
s1, dissolving PTB7-Th/PC 71 BM in chloroform solution added with 0.5% (volume ratio) 1-chloronaphthalene according to a mass ratio of 1:1.5, and preparing a solution with a concentration of 6mg/mL by taking donor PTB7-Th as a standard to prepare an active layer solution;
S2, spin-coating PEDOT/PSS solution on the glass substrate plated with the 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, spin-coating an ITO conductive glass substrate subjected to cleaning by adopting an aqueous solution of PEDOT: PSS (4083) at a rotating speed of 3500 rpm for 30S after UVO treatment, preparing 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 the 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 annealing treatment of the anode interface layer into a glove box protected by nitrogen;
S3-2, spin-coating the active layer solution prepared in the step S1 on the anode interface layer at a rotating speed of about 2000rpm in a nitrogen atmosphere to form an active layer, and annealing the glass substrate with the active layer;
S4, preparing a cathode through a mask plate by adopting an evaporation method on the active layer, and particularly preparing an Ag electrode with the thickness of 100nm through the mask plate by adopting the evaporation method under the condition of 10 < -7 > mbar.
< Case of energy conversion when the donor is PM6 and the acceptor is Y6 >
The solar cell devices obtained in examples 9 and 14 and comparative example 1 were subjected to performance test, and the results are shown in fig. 1 and table 1 below. It is calculated that when the donor is PM6 and the acceptor is Y6, the highest photoelectric conversion efficiency is 10.53% in the case where the active layer solution is not added with the self-separating cathode interface material, and after the self-separating cathode interface material PN4F is added, the highest photoelectric conversion efficiency is 12.05%, and after the self-separating cathode interface material PN8F is added, the highest photoelectric conversion efficiency is 11.91%. The self-separation cathode interface material PN4F, PN F is added, and after the heating annealing treatment, an active layer is formed on the surface of the anode interface layer and is separated from the cathode interface layer, so that the photoelectric conversion efficiency is improved, and the energy conversion efficiency of the organic solar cell is improved.
TABLE 1
< Case of energy conversion when the donor was PTB7-Th and the acceptor was PC 71 BM >
Analysis of examples 19, 20 and comparative example 2 in connection with fig. 2:
The solar cell devices obtained in examples 19 and 20 and comparative example 2 were subjected to performance test, and the results are shown in fig. 2 and table 2 below. According to calculation, when the donor is PTB7-Th and the receptor is PC 71 BM, under the condition that an additive is not added, the highest photoelectric conversion efficiency is 3.73%, after the self-separation cathode interface material PN4F is added, the highest photoelectric conversion efficiency is 6.93%, after the self-separation cathode interface material PN8F is added, the highest photoelectric conversion efficiency is 5.76%, and due to the addition of the self-separation cathode interface material PN4F, PN F, an active layer is formed on the surface of an anode interface layer and the self-separation cathode interface layer is formed after the heating annealing treatment, 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 can be used in organic solar cell devices of fullerene and non-fullerene materials, and has wide application range.
TABLE 2
< Analysis of ultraviolet-visible absorption Spectrometry >
As can be seen from fig. 3, PN8F and PN4F in CHCl 3 solution have similar absorption spectra, with absorption peaks around 390nm, presumably due to pi-pi transition of the intramolecular conjugated backbone, which indicates that the introduction and ratio change of the fluorine/amino-containing bifunctional side chains has little effect on the optical properties of the backbone. As can be seen from fig. 4, each small molecule also exhibits an approximate uv-vis absorption spectrum in the thin film state, and the absorption peaks in the thin film are slightly red shifted compared to the absorption spectrum in CHCl 3 solution, indicating that there is an interaction between the molecules in the thin film state and that slight aggregation results in a red shift. By the absorption edge of the polymer film, it can be calculated that each small molecule has a similar optical band gap, about 2.9eV. Therefore, it can be shown that the optical fiber has better 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. As the contact angles of PN4F and PN8F with water are larger than 90 degrees, the two materials have hydrophobicity, and can prevent water molecules from entering the activity, thereby prolonging the service life of the device and improving the stability of the device. In addition, the surface energy of PN4F and PN8F is calculated, and the calculation method is the prior art and is not described herein. The calculated surface energies of PN4F and PN8F are 37.9N/m and 34.1N/m, respectively, because the fluorine-containing side chains impart lower surface energies to the self-separating interface material, through which lower surface energies the vertical self-separation of the material is driven.
Claims (8)
1. The self-separating cathode interface material is characterized by having a fluorine/amino-containing double-function side chain, a molecular formula of C 95H124F18N4O2 and a structural formula of
Or alternatively
The molecular formula is C 103H124F34N4O2, and the structural formula is
2. A method of preparing the self-separating cathode interface material of claim 1, comprising the steps of;
S1, mixing tetrahydrofuran, 2, 7-dibromo-9, 9-di (6-bromohexyl) fluorene, tetrabutylammonium bromide and 1H, 2H-perfluoro-1-hexanol, adding sodium hydroxide aqueous solution under argon atmosphere, heating and stirring, extracting, drying, filtering, rotary evaporating and purifying to obtain an intermediate product M2; m2 is 2, 7-dibromo-9, 9-bis (6- ((3, 4,5, 6-nonafluoro) oxy) hexyl) fluorene having the structural formula
S2, adding toluene, tetraethylammonium hydroxide, an intermediate product M2 and 2- (4, 5-tetramethyl-1, 3, 2-dioxaborane-) -9, 9-bis (6- (N, N-diethylamino) hexyl) fluorene into a pressure-resistant pipe, adding Pd (PPh 3)4) catalyst under nitrogen atmosphere, heating to 85-100 ℃ and stirring for 6-8 h, cooling, and sequentially extracting, drying, filtering, rotary evaporating and purifying to obtain the self-separating cathode interface material with the molecular formula of C 95H124F18N4O2.
3. The method for preparing a self-separating cathode interface material according to claim 2, wherein the purification method of the intermediate product M2 and the self-separating cathode interface material having a molecular formula of C 95H124F18N4O2 adopts column chromatography.
4. A method of preparing the self-separating cathode interface material of claim 1, comprising the steps of;
S1, mixing tetrahydrofuran, 2, 7-dibromo-9, 9-di (6-bromohexyl) fluorene, tetrabutylammonium bromide and 1H, 2H-perfluoro-1-decanol, adding sodium hydroxide aqueous solution under argon atmosphere, heating and stirring, extracting, drying, filtering, rotary evaporating and purifying to obtain an intermediate product M3; m3 is 2, 7-dibromo-9, 9-di (6- ((3,3,4,4,5,6,7,8,9,10,10,10-heptadecafluoro) oxy) hexyl) fluorene having a structural formula of
S2, adding toluene, tetraethylammonium hydroxide, an intermediate product M3 and 2- (4, 5-tetramethyl-1, 3, 2-dioxaborane-) -9, 9-bis (6- (N, N-diethylamino) hexyl) fluorene into a pressure-resistant pipe, adding Pd (PPh 3)4) catalyst under nitrogen atmosphere, heating to 85-100 ℃ and stirring for 6-8 h, cooling, and sequentially extracting, drying, filtering, rotary evaporating and purifying to obtain the self-separating cathode interface material with the molecular formula of C 103H124F34N4O2.
5. The method for preparing a self-separating cathode interface material according to claim 4, wherein the purification method of the intermediate product M3 and the self-separating cathode interface material with a molecular formula of C 103H124F34N4O2 adopts column chromatography.
6. A method for preparing a self-separating organic solar cell, characterized in that 1-10% of the self-separating cathode interface material according to claim 1 is added into an active layer solution, and the mass fraction of the self-separating cathode interface material is based on a donor PM 6.
7. The method for preparing a self-separating organic solar cell according to claim 6, wherein first, an anode interfacial layer material is spin-coated on the surface of an anode, and an anode interfacial layer is formed on the surface of the anode after annealing treatment; next, spin-coating the active layer solution added with the self-separating cathode interface material according to 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 separating the 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.
8. The method for preparing a self-separating organic solar cell according to claim 7, 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 according to claim 1 into the active layer solution for later use;
S2, spin-coating PEDOT/PSS solution on the glass substrate plated with the 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 annealing 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 annealing;
s4, preparing a cathode through a mask plate by adopting an evaporation method above the cathode interface layer.
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| 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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| 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 |
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| Fluoro- and Amino-Functionalized Conjugated Polymers as Electron Transport Materials for Perovskite Solar Cells with Improved Efficiency and Stability;Li Tian 等;《ACS Appl. Mater. Interfaces》;20190111;第11卷(第5期);第5289-5297页 * |
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