CN114551725A - Interface doped double-layer plane heterojunction organic solar cell and preparation method thereof - Google Patents
Interface doped double-layer plane heterojunction organic solar cell and preparation method thereof Download PDFInfo
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Abstract
一种界面掺杂双层平面异质结有机太阳能电池及其制备方法，有机太阳能电池包括由下至上依次设置的导电玻璃基底、电子传输层、活性层、空穴传输层以及金属电极，活性层为双层平面异质结Y6/J71与BCF或硼酸盐界面掺杂而成。本发明还提供一种所述有机太阳能电池的界面掺杂方法以及该界面掺杂双层平面异质结有机太阳能电池的制备方法，制备方法包括在涂有电子传输层的导电玻璃基底表面旋涂受体材料Y6溶液，在涂有水溶性PEDOT:PSS的空白玻璃基底表面旋涂给体材料J71溶液；在涂有给体材料J71溶液的空白玻璃基底表面旋涂掺杂剂溶液，通过进行水转印制备得到活性层。本发明能大幅度提高电池的光电转化效率，工艺简单，成本低。
An interface-doped double-layer planar heterojunction organic solar cell and a preparation method thereof. The organic solar cell comprises a conductive glass substrate, an electron transport layer, an active layer, a hole transport layer and a metal electrode, which are sequentially arranged from bottom to top, and the active layer It is made of double-layer planar heterojunction Y6/J71 and BCF or borate interface doping. The present invention also provides an interface doping method of the organic solar cell and a preparation method of the interface-doped double-layer planar heterojunction organic solar cell. The preparation method includes spin coating on the surface of a conductive glass substrate coated with an electron transport layer The acceptor material Y6 solution was spin-coated with the donor material J71 solution on the surface of the blank glass substrate coated with water-soluble PEDOT:PSS; the dopant solution was spin-coated on the surface of the blank glass substrate coated with the donor material J71 solution. The transfer preparation yielded the active layer. The invention can greatly improve the photoelectric conversion efficiency of the battery, the process is simple, and the cost is low.
Description
Technical Field
The invention belongs to the field of organic solar cells, and particularly relates to an interface doped double-layer plane heterojunction organic solar cell and a preparation method thereof.
Background
In order to cope with global warming and the increasing exhaustion of fossil energy, the development and utilization of renewable energy are increasingly receiving attention from the society. Solar energy is considered as one of the most important methods for solving the increasing global energy demand and the environmental pollution by using renewable resources with the remarkable advantages of no geographical restriction, no noise, no pollution, low utilization cost, etc. Driven by technological progress, large-scale economy, increasingly competitive supply chains, and increasing developer experience, the cost of renewable energy generation has dropped dramatically over the past decade. In the period from 2010 to 2019, the solar photovoltaic power generation cost is reduced by 82%.
Currently, the conventional solar cells commercialized in the market are mainly inorganic semiconductor solar cells such as monocrystalline silicon and polycrystalline silicon. Inorganic semiconductor solar cells have been widely used in the fields of photovoltaic power stations and aerospace. However, the inorganic solar cell has limited its wide application in life due to problems of serious pollution of industrial chain, huge energy consumption, etc.
The organic solar cell is a novel photovoltaic technology developed in recent years, and has the unique advantages of flexibility, wearability, building integrated photovoltaic, indoor light application and the like. At present, the highest single-unit efficiency of a small area breaks through 18.2%, and the highest single-unit efficiency reaches the standard of commercial application, so that the organic solar cell has a good development prospect, and the device structure of the organic solar cell consists of Indium Tin Oxide (ITO) conductive glass, an electron transport layer, a hole transport layer, an active layer and a metal electrode.
The organic solar cell works on the principle that excitons (electron-hole pairs) can be generated in the donor-acceptor region in the active layer under the condition of illumination, when the excitons are diffused to the interface of the donor-acceptor material, electrons are transferred from the donor LUMO to the acceptor LUMO under the action of extremely poor energy of the donor-acceptor material, holes left in the donor HOMO and electrons of the acceptor LUMO form excitons, the excitons overcome coulomb force, namely dissociation barrier, and then generate free electrons and holes, and then the holes and the electrons are respectively transmitted to corresponding electrodes along the donor region and the acceptor region and collected. The process of exciton generation, exciton dissociation and charge collection determines the photoelectric conversion efficiency of the organic solar cell. The main bottlenecks of the organic solar cell are insufficient exciton transmission and dissociation, charge transmission and charge recombination, and the charge recombination rate of the active layer is too high, so that the hole-charge separation degree is insufficient when the cell works, and the performance of the device is reduced. How to promote exciton separation and reduce charge recombination rate so as to improve the efficiency of the organic solar cell is an urgent problem to be solved.
At present, for a planar heterojunction, energy loss caused by charge recombination is usually reduced, an interface dipole layer can be added to regulate and control an interface electric field, and the intensity and the direction of interface dipole moment are regulated through an interface monomolecular layer, so that the energy level of the planar heterojunction is regulated, the charge recombination is reduced, the charge separation degree is enhanced, and the Voc is improved. But also by optimizing the interface topography. The molecular orientation and crystallinity are controlled by heat treatment and different solvents, thereby reducing energy loss and realizing high open-circuit voltage.
However, in practical application of the two existing technologies, due to the toggle of the process and the representation, the process of regulating and controlling the interface electric field by the interface dipole layer is difficult to control, the material selectivity is low, the process is complicated due to heat treatment, the standard of the appearance optimization is fuzzy, and the device performance is not stable. There is a need for a method with simple process and a well-defined mechanism to improve the efficiency of organic solar cells.
Disclosure of Invention
The present invention is directed to solve the above problems in the prior art, and an object of the present invention is to provide an interface-doped double-layer planar heterojunction organic solar cell and a method for manufacturing the same, which can greatly improve the photoelectric conversion efficiency of the double-layer planar heterojunction organic solar cell, reduce the variable control factors, simplify the process, and reduce the cost.
In order to achieve the purpose, the invention has the following technical scheme:
in a first aspect, an embodiment of the present invention provides an interface-doped double-layer planar heterojunction organic solar cell, including a conductive glass substrate, an electron transport layer, an active layer, a hole transport layer, and a metal electrode, which are sequentially disposed from bottom to top, where the active layer is formed by doping a double-layer planar heterojunction Y6/J71 and a BCF or borate interface;
the donor material J71 of the double-layer planar heterojunction Y6/J71 has the following structural formula:
the acceptor material Y6 of the double-layer planar heterojunction Y6/J71 has the following structural formula:
the structural formula of BCF is as follows:
the borate salt has the following structure:
as a preferred embodiment:
the conductive glass substrate is made of transparent glass and a transparent indium tin oxide film plated on the transparent glass;
the electron transport layer is made of zinc oxide;
the hole transport layer is made of metal molybdenum oxide;
the metal electrode is made of metal aluminum.
Preferably, the interface doped BCF or borate in the active layer adopts a solution with the concentration of 0.01 mg/ml.
In a second aspect, an embodiment of the present invention further provides an interface doping method for an interface-doped double-layer planar heterojunction organic solar cell, including:
dissolving BCF or borate powder in absolute ethyl alcohol, and stirring at normal temperature to obtain a BCF or borate solution;
diluting BCF or borate solution to an intermediate concentration, stirring at normal temperature, and diluting to a target concentration;
the BCF or borate solution diluted to the target concentration is stirred for use.
As a preferred scheme of the interface doping method, 1mg of BCF or borate powder is weighed and dissolved in 1ml of absolute ethyl alcohol, and the mixture is stirred for 24 hours at a normal temperature of 300r/min on a hot bench to obtain 1mg/ml BCF or borate solution;
the intermediate concentration is 0.1 mg/ml;
stirring for 6h at the normal temperature of 300r/min by using a hot bench, wherein the target concentration is 0.01 mg/ml;
and stirring the BCF or borate solution diluted to the target concentration at the normal temperature of 300r/min by using a hot bench for later use.
In a third aspect, an embodiment of the present invention further provides a method for preparing the interface-doped double-layer planar heterojunction organic solar cell, including:
cleaning a conductive glass substrate and a blank glass substrate, spin-coating an electron transport layer on the surface of the cleaned conductive glass substrate, and spin-coating water-soluble PEDOT (PSS);
weighing a donor material J71 and an acceptor material Y6, respectively dissolving in chloroform CF, and preparing a single-component solution for later use;
spin-coating an acceptor material Y6 solution on the surface of a conductive glass substrate coated with an electron transport layer, and spin-coating a donor material J71 solution on the surface of a blank glass substrate coated with water-soluble PEDOT, PSS; spin-coating a dopant solution on the surface of a blank glass substrate coated with a donor material J71 solution, wherein the dopant solution is a BCF or borate solution diluted to a target concentration;
placing the blank glass substrate coated with the donor material J71 solution and the dopant solution on the surface of deionized water for water transfer printing, and performing surface lamination by using a conductive glass substrate coated with the receptor material Y6 solution to prepare an active layer;
evaporating a hole transport layer on the surface of the prepared active layer;
evaporating a metal electrode on the surface of the hole transport layer;
and obtaining the interface doped double-layer plane heterojunction organic solar cell after the steps are finished.
As a preferable scheme of the preparation method, in the step of weighing the donor material J71 and the acceptor material Y6, respectively dissolving the donor material J71 and the acceptor material Y6 which are 2.25mg in chloroform CF respectively, and respectively dissolving the donor material J71 and the acceptor material Y6 which are 2.70mg in chloroform CF, respectively, the solution concentration of the donor material J71 and the solution concentration of the acceptor material Y6 in the single-component solution are 5mg/ml and 6mg/ml respectively, and the single-component solution is stirred for 8 hours at the temperature of 50 ℃ by using a hot bench at 300r/min for later use.
As a preferred scheme of the preparation method, in the step of cleaning the conductive glass substrate and the blank glass substrate, the conductive glass substrate and the blank glass substrate are respectively and sequentially ultrasonically cleaned twice with liquid detergent, deionized water, acetone, absolute ethyl alcohol and isopropanol for 30 minutes each time, and then dried by using nitrogen;
and respectively carrying out plasma surface treatment on the conductive glass substrate and the blank glass substrate for 20 minutes.
PSS step includes, in conductive glass substrate surface after cleaning with 4500r/min zinc oxide to prepare electron transport layer, 200 ℃ anneal for 30 min; spin-coating water-soluble PEDOT (PSS) on the surface of the cleaned blank glass substrate at 1500r/min, and annealing at 140 ℃ for 3 min; and placing the conductive glass substrate and the blank glass substrate both of which the surfaces are subjected to spin coating in a glove box in a nitrogen atmosphere for later use.
Further, as a preferable scheme of the preparation method of the invention, the electron transport layer is coated on the surface of the conductive glass substrate by spin coating the receptor material Y6 solution, the water soluble PEDOT: PSS is coated on the surface of the blank glass substrate by spin coating the donor material J71 solution; the method comprises the steps of spin-coating a dopant solution on the surface of a blank glass substrate coated with a donor material J71 solution, wherein the step of spin-coating an acceptor material Y6 solution on the surface of a conductive glass substrate coated with an electron transport layer at 3000r/min for 30 s; PSS is coated on the surface of a blank glass substrate, the donor material J71 solution is spin-coated at 1300r/min for 30 s; spin-coating a dopant solution with the concentration of 0.01mg/ml on the surface of a blank glass substrate coated with a donor material J71 solution at 5000r/min for 30 s;
and placing the blank glass substrate coated with the donor material J71 solution and the dopant solution on the surface of deionized water for water transfer printing, performing surface bonding by using a conductive glass substrate coated with the receptor material Y6 solution, blow-drying by using nitrogen, placing the blank glass substrate in a glove box, vacuumizing for 8 hours, and completely removing the solvent and residual deionized water in water transfer printing to obtain the active layer.
Compared with the prior art, the invention has the following beneficial effects:
the double-layer plane heterojunction organic solar cell adopting BCF or borate as a dopant for interface doping has the advantages that the dopant and a donor material J71 are subjected to interface doping, an electronic structure can be directly adjusted, a charge transfer reaction is carried out, carriers are generated, the activation energy of the generated carriers is reduced, exciton separation can be promoted, energy loss caused by charge recombination is reduced, the interface doping is also beneficial to keeping better intermolecular stacking and built-in potential of the device, and the appearance of an active layer is not influenced. Both BCF and borate can enhance the light absorption of the donor material J71 in the active layer, and finally improve the photoelectric conversion efficiency of the organic solar cell. According to the invention, 17% of photoelectric conversion efficiency of the device can be improved only by spin-coating the BCF interface doping layer with trace concentration, the process is simple, and the efficiency improvement range is large.
Drawings
FIG. 1 is a schematic diagram of a reverse device structure of an interface doped double-layer planar heterojunction organic solar cell of the present invention;
FIG. 2 is a graph of current density versus voltage for the two-layer planar heterojunction organic solar cell of example 1, example 2 and comparative example 1 of the present invention;
FIG. 3 is an AFM of a thin film of organic solar cell active layer donor material J71 in an undoped state;
FIG. 4 is an AFM of a thin film of organic solar cell active layer donor material J71 under BCF doping;
FIG. 5 is an AFM of a thin film of organic solar cell active layer donor material J71 under doped borate;
FIG. 6 is a two-dimensional GIWAXS diagram of a thin film of organic solar cell active layer donor material J71 in an undoped state;
FIG. 7 is a two-dimensional GIWAXS plot of a thin film of organic solar cell active layer donor material J71 doped with BCF;
fig. 8 is a two-dimensional GIWAXS plot of thin films of organic solar cell active layer donor material J71 under doped borate.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
The invention provides an interface doped double-layer plane heterojunction organic solar cell, the device structure of which is shown in figure 1 and comprises a conductive glass substrate 1, an electron transport layer 2, an active layer 3, a hole transport layer 4 and a metal electrode 5 which are sequentially arranged from bottom to top. The conductive glass substrate 1 is made of transparent glass and a transparent indium tin oxide film plated on the transparent glass, the electron transmission layer 2 is made of zinc oxide, the active layer 3 is formed by doping a double-layer plane heterojunction Y6/J71 and a BCF or borate interface, and a donor material J71 of the double-layer plane heterojunction Y6/J71 has the following structural formula:
the acceptor material Y6 of the double-layer planar heterojunction Y6/J71 has the following structural formula:
the structural formula of BCF is as follows:
the borate salt has the following structure:
wherein, the doping concentrations of the BCF solution and the borate solution are both 0.01mg/ml, and the preparation method of the dopant solution comprises the following steps: weighing 1mg of dopant BCF or borate powder, dissolving in 1ml of absolute ethyl alcohol, heating the mixture at normal temperature of 300r/min, stirring for 24h to obtain 1mg/ml BCF or borate solution, diluting to 0.1mg/ml, heating the mixture at normal temperature of 300r/min, stirring for 6h to 0.01mg/ml, and stirring at normal temperature of 300r/min for later use. The thickness of the active layer 3 obtained was about 60 nm. The hole transport layer 4 was MoOx and its thickness was 10 nm. The metal electrode 5 is made of metal Al and has a thickness of 100 nm.
The preparation method of the interface doped double-layer plane heterojunction organic solar cell comprises the following steps:
s1: weighing 2.25mg of donor material J71 and 2.70mg of acceptor material Y6, respectively dissolving in chloroform CF to obtain a single-component solution, wherein the concentration of the donor material J71 solution in the obtained single-component solution is 5mg/ml, the concentration of the acceptor material Y6 solution is 6mg/ml, and stirring for 8 hours at 50 ℃ at 300r/min by using a hot bench for later use.
S2: cleaning a conductive glass substrate 1 and a blank glass substrate, sequentially and respectively ultrasonically cleaning the conductive glass substrate 1 twice by using detergent, deionized water, acetone, absolute ethyl alcohol and isopropanol for 30 minutes each time, then blow-drying by using nitrogen, and cleaning the blank glass substrate by using the same method for deionized water transfer printing for later use.
S3: the surface of the cleaned and dried conductive glass substrate 1 is subjected to plasma surface treatment for 20 minutes, the treatment method utilizes the strong oxidizing property of ozone generated under microwave to clean residual organic matters and the like on the ITO surface in the conductive glass substrate 1, simultaneously, the oxygen vacancy on the ITO surface can be improved, the work function of the ITO surface is improved, and the blank glass substrate is treated in the same way.
S4: spin-coating zinc oxide on the surface of the cleaned conductive glass substrate 1 at 4500r/min to prepare an electron transport layer 2, and annealing at 200 ℃ for 30 min; spin-coating water-soluble PEDOT (PSS) on the surface of the cleaned blank glass substrate at 1500r/min, and annealing at 140 ℃ for 3 min; and placing the conductive glass substrate 1 with the finished surface spin coating and the blank glass substrate in a glove box in a nitrogen atmosphere for later use.
S5: spin-coating receptor material Y6 solution on the surface of the conductive glass substrate 1 coated with the electron transport layer 2 at 3000r/min for 30 s; PSS is coated on the surface of a blank glass substrate, and the donor material J71 solution is spin-coated on the surface of the blank glass substrate at 1300r/min for 30 s; spin-coating a dopant solution with the concentration of 0.01mg/ml on the surface of a blank glass substrate coated with a donor material J71 solution at 5000r/min for 30s, wherein the dopant solution is a BCF or borate solution diluted to a target concentration;
s6: placing a blank glass substrate coated with a donor material J71 and a dopant solution on the surface of deionized water for water transfer printing, slowly attaching a conductive glass substrate 1 coated with an acceptor material Y6 to the surface of the donor material J71, then slightly drying the substrate with nitrogen, placing the substrate in a glove box large bin, vacuumizing for 8 hours, and ensuring that the solvent and the residual deionized water in the water transfer printing are completely removed to prepare an active layer 3;
s7: the hole transport layer 4 was formed by depositing MoOx on the surface of the active layer 3, and the thickness thereof was 10 nm.
S8: a metal electrode 5 was formed by depositing Al on the surface of the hole transport layer 4, and the thickness thereof was 100 nm.
And obtaining the interface-doped double-layer plane heterojunction organic solar cell after the steps are finished.
The film morphology characterization of the interface doped double-layer plane heterojunction organic solar cell comprises AFM and GIWAXS tests.
The sample preparation conditions for AFM test are as follows: and cleaning the conductive glass substrate 1, and sequentially cleaning with deionized water and ethanol twice. And drying the cleaned ITO wafer by using a nitrogen gun, carrying out UVO treatment for 20min to improve the surface activity, preparing a sample by using a spin coating film forming mode, and carrying out 1300r/min dynamic throwing on a donor material J71 and 5000r/min dynamic throwing on a dopant.
The sample preparation conditions for the GIWAXS test are as follows: cutting the silicon wafer into a proper size, and sequentially cleaning the silicon wafer with deionized water and ethanol twice. And drying the cleaned silicon wafer by using a nitrogen gun, carrying out UVO treatment for 20min to improve the surface activity, preparing a sample by using a spin coating film forming mode, and dynamically throwing the donor material J71 at 1300r/min and the dopant at 5000 r/min.
The present invention will be described in further detail with reference to specific examples and comparative examples, but the embodiments of the present invention are not limited thereto, and the process parameters not particularly specified may be performed by referring to the conventional techniques.
Example 1
The device structure of the interface doped double-layer plane heterojunction organic solar cell in the embodiment is as follows:
ITO/ZnO/Y6/BCF/J71/MoOx/Al。
the preparation process flow of the interface doped double-layer plane heterojunction organic solar cell is as follows:
s1: weighing 2.25mg of donor material J71 and 2.70mg of acceptor material Y6, respectively dissolving in chloroform CF to obtain a single-component solution, wherein the concentration of the donor material J71 solution in the obtained single-component solution is 5mg/ml, the concentration of the acceptor material Y6 solution is 6mg/ml, and stirring for 8 hours at 50 ℃ at 300r/min by using a hot bench for later use.
S2: cleaning a conductive glass substrate 1 and a blank glass substrate, sequentially and respectively ultrasonically cleaning the conductive glass substrate 1 twice by using detergent, deionized water, acetone, absolute ethyl alcohol and isopropanol for 30 minutes each time, then blow-drying by using nitrogen, and cleaning the blank glass substrate by using the same method for deionized water transfer printing for later use.
S3: the surface of the cleaned and dried conductive glass substrate 1 is subjected to plasma surface treatment for 20 minutes, the treatment method utilizes the strong oxidizing property of ozone generated under microwave to clean residual organic matters and the like on the ITO surface in the conductive glass substrate 1, simultaneously, the oxygen vacancy on the ITO surface can be improved, the work function of the ITO surface is improved, and the blank glass substrate is treated in the same way.
S4: spin-coating zinc oxide on the surface of the cleaned conductive glass substrate 1 at 4500r/min to prepare an electron transport layer 2, and annealing at 200 ℃ for 30 min; spin-coating water-soluble PEDOT (PSS) on the surface of the cleaned blank glass substrate at 1500r/min, and annealing at 140 ℃ for 3 min; and placing the conductive glass substrate 1 with the finished surface spin coating and the blank glass substrate in a glove box in a nitrogen atmosphere for later use.
S5: spin-coating receptor material Y6 solution on the surface of the conductive glass substrate 1 coated with the electron transport layer 2 at 3000r/min for 30 s; PSS is coated on the surface of a blank glass substrate, the donor material J71 solution is spin-coated at 1300r/min for 30 s; spin coating BCF solution on the surface of the blank glass substrate coated with the donor material J71 solution at 5000r/min for 30s, namely the step of doping the active layer interface. The preparation process of the BCF solution comprises the following steps: weighing 1mg of BCF powder in advance, dissolving the powder in 1ml of absolute ethyl alcohol, heating the mixture at the normal temperature of 300r/min, stirring the mixture for 24 hours to obtain 1mg/ml BCF solution, diluting the solution to 0.1mg/ml, heating the solution at the normal temperature of 300r/min, stirring the solution for 6 hours to dilute the solution to 0.01mg/ml, and stirring the solution at the normal temperature of 300r/min for later use.
S6: and placing the blank glass substrate coated with the donor material J71 solution and the BCF solution on the surface of deionized water for water transfer printing, slowly attaching the conductive glass substrate 1 coated with the receptor material Y6 solution to the surface of the donor material J71, then lightly drying the conductive glass substrate by using nitrogen, placing the conductive glass substrate in a glove box large warehouse, vacuumizing the glove box large warehouse for 8 hours, and ensuring that the residual deionized water in the solvent and the water transfer printing is completely removed to prepare the active layer 3.
S7: the hole transport layer 4 was formed by depositing MoOx on the surface of the active layer 3, and the thickness thereof was 10 nm.
S8: a metal electrode 5 was formed by depositing Al on the surface of the hole transport layer 4, and the thickness thereof was 100 nm.
And obtaining the interface doped double-layer plane heterojunction organic solar cell after the steps are finished.
The film morphology characterization of the present example for the above-described interface doped double-layer planar heterojunction organic solar cell includes AFM and GIWAXS tests.
The sample preparation conditions for AFM test are as follows: and cleaning the conductive glass substrate 1, and sequentially cleaning with deionized water and ethanol twice. And drying the cleaned ITO wafer by using a nitrogen gun, carrying out UVO treatment for 20min to improve the surface activity, preparing a sample by using a spin coating film forming mode, carrying out melt spinning on a donor material J71 solution for 1300r/min and 30s, and carrying out melt spinning on a dopant BCF solution for 0.01mg/ml for 5000r/min and 30 s.
The sample preparation conditions for the GIWAXS test are as follows: cutting the silicon wafer into a proper size, and sequentially cleaning the silicon wafer with deionized water and ethanol twice. And drying the cleaned silicon wafer by using a nitrogen gun, carrying out UVO treatment for 20min to improve the surface activity, preparing a sample by using a spin coating film forming mode, and carrying out melt spinning on a donor material J71 solution for 1300r/min and 30s, and carrying out melt spinning on a dopant BCF solution for 0.01mg/ml for 5000r/min and 30 s.
Example 2
The device structure of the interface doped double-layer plane heterojunction organic solar cell in the embodiment is as follows:
ITO/ZnO/Y6/Borate/J71/MoOx/Al。
the preparation process flow of the doped double-layer plane heterojunction organic solar cell is as follows:
s1: weighing 2.25mg of donor material J71 and 2.70mg of acceptor material Y6, respectively dissolving in chloroform CF to obtain a single-component solution, wherein the concentration of the donor material J71 solution in the obtained single-component solution is 5mg/ml, the concentration of the acceptor material Y6 solution is 6mg/ml, and stirring for 8 hours at 50 ℃ at 300r/min by using a hot bench for later use.
S2: cleaning a conductive glass substrate 1 and a blank glass substrate, sequentially and respectively ultrasonically cleaning the conductive glass substrate 1 twice by using detergent, deionized water, acetone, absolute ethyl alcohol and isopropanol for 30 minutes each time, then blow-drying by using nitrogen, and cleaning the blank glass substrate by using the same method for deionized water transfer printing for later use.
S3: the surface of the cleaned and dried conductive glass substrate 1 is subjected to plasma surface treatment for 20 minutes, the treatment method utilizes the strong oxidizing property of ozone generated under microwave to clean residual organic matters and the like on the ITO surface in the conductive glass substrate 1, simultaneously, the oxygen vacancy on the ITO surface can be improved, the work function of the ITO surface is improved, and the blank glass substrate is treated in the same way.
S4: spin-coating zinc oxide on the surface of the cleaned conductive glass substrate 1 at 4500r/min to prepare an electron transport layer 2, and annealing at 200 ℃ for 30 min; spin-coating water-soluble PEDOT (PSS) on the surface of the cleaned blank glass substrate at 1500r/min, and annealing at 140 ℃ for 3 min; and placing the conductive glass substrate 1 with the finished surface spin coating and the blank glass substrate in a glove box in a nitrogen atmosphere for later use.
S5: spin-coating receptor material Y6 solution on the surface of the conductive glass substrate 1 coated with the electron transport layer 2 at 3000r/min for 30 s; PSS was spin-coated onto the surface of a blank glass substrate coated with water-soluble PEDOT at 1300r/min for 30s with a solution of donor material J71. And spin-coating a Borate Borate solution on the surface of the blank glass substrate coated with the donor material J71 solution at 5000r/min for 30s, namely the step of doping the active layer interface. The preparation process of the borate solution comprises the following steps: weighing 1mg of borate powder in advance, dissolving the borate powder in 1ml of absolute ethyl alcohol, stirring the borate powder for 24 hours at the normal temperature of 300r/min on a hot bench, namely obtaining 1mg/ml borate solution, diluting the borate solution to 0.1mg/ml, stirring the borate solution for 6 hours at the normal temperature of 300r/min on the hot bench, diluting the borate solution to 0.01mg/ml, and stirring the borate solution for later use at the normal temperature of 300r/min on the hot bench.
S6: placing a blank glass substrate coated with donor material J71 solution and borate solution on the surface of deionized water for water transfer printing, slowly attaching a conductive glass substrate 1 coated with receptor material Y6 solution on the surface of donor material J71, then lightly drying the substrate with nitrogen, placing the substrate in a glove box large bin, vacuumizing for 8 hours, and ensuring that the solvent and the residual deionized water in the water transfer printing are completely removed to prepare the active layer 3.
S7: and evaporating MoOx on the surface of the prepared active layer 3 to prepare a hole transport layer 4 with the thickness of 10 nm.
S8: a metal electrode 5 was formed by depositing Al on the surface of the hole transport layer 4, and the thickness thereof was 100 nm.
And obtaining the interface doped double-layer plane heterojunction organic solar cell after the steps are finished.
The film morphology characterization of the present example for the above-described interface doped double-layer planar heterojunction organic solar cell includes AFM and GIWAXS tests.
The sample preparation conditions for AFM test are as follows: and cleaning the conductive glass substrate 1, and sequentially cleaning with deionized water and ethanol twice. And drying the cleaned ITO wafer by using a nitrogen gun, carrying out UVO treatment for 20min to improve the surface activity, preparing a sample by using a spin coating film forming mode, carrying out melt spinning on a donor material J71 solution for 1300r/min and 30s, and carrying out melt spinning on a dopant borate solution for 0.01mg/ml for 5000r/min and 30 s.
The sample preparation conditions for the GIWAXS test are as follows: cutting the silicon wafer into a proper size, and sequentially cleaning the silicon wafer with deionized water and ethanol twice. And drying the cleaned silicon wafer by using a nitrogen gun, carrying out UVO treatment for 20min to improve the surface activity, preparing a sample by using a spin coating film forming mode, and carrying out liquid throwing on the donor material J71 solution for 1300r/min and 30s, and carrying out liquid throwing on the donor material J71 solution for 5000r/min and 30s by using a dopant borate solution for 0.01 mg/ml.
Comparative example 1
The structure of the double-layer plane heterojunction organic solar cell device without the doped layer in the comparative example is as follows:
ITO/ZnO/Y6/J71/MoOx/Al。
the preparation process flow of the double-layer plane heterojunction organic solar cell is as follows:
s1: weighing 2.25mg of donor material J71 and 2.70mg of acceptor material Y6, respectively dissolving in chloroform CF to obtain a single-component solution, wherein the concentration of the donor material J71 in the single-component solution is 5mg/ml, the concentration of the acceptor material Y6 in the single-component solution is 6mg/ml, and stirring the single-component solution for 8 hours at 50 ℃ at 300r/min by using a hot bench for later use.
S2: cleaning a conductive glass substrate 1 and a blank glass substrate, sequentially and ultrasonically cleaning the conductive glass substrate 1 twice with detergent, deionized water, acetone, absolute ethyl alcohol and isopropanol for 30 minutes each time, blow-drying with nitrogen, cleaning the blank glass substrate by the same method, and transferring with the deionized water for later use.
S3: the surface of the cleaned and dried conductive glass substrate 1 is subjected to plasma surface treatment for 20 minutes, the treatment method utilizes the strong oxidizing property of ozone generated under microwave to clean residual organic matters and the like on the ITO surface in the conductive glass substrate 1, simultaneously, the oxygen vacancy on the ITO surface can be improved, the work function of the ITO surface is improved, and the blank glass substrate is treated in the same way.
S4: spin-coating zinc oxide on the surface of the cleaned conductive glass substrate 1 at 4500r/min to prepare an electron transport layer 2, and annealing at 200 ℃ for 30 min; spin-coating water-soluble PEDOT (PSS) on the surface of the cleaned blank glass substrate at 1500r/min, and annealing at 140 ℃ for 3 min; and placing the conductive glass substrate 1 with the finished surface spin coating and the blank glass substrate in a glove box in a nitrogen atmosphere for later use.
S5: spin-coating receptor material Y6 solution on the surface of the conductive glass substrate 1 coated with the electron transport layer 2 at 3000r/min for 30 s; PSS was spin-coated onto the surface of a blank glass substrate coated with water-soluble PEDOT at 1300r/min for 30s with a solution of donor material J71. The surface of the blank glass substrate coated with the donor material J71 solution was spin-coated with absolute ethanol at 5000r/min for 30s to eliminate the effect of the dopant solvent on the device.
S6: and placing the blank glass substrate coated with the donor material J71 solution on the surface of deionized water for water transfer printing, slowly attaching the conductive glass substrate 1 coated with the receptor material Y6 solution on the surface of the donor material J71, slightly drying the substrate by using nitrogen, placing the substrate in a glove box large bin, vacuumizing for 8 hours, and completely removing the solvent and the residual deionized water in the water transfer printing to prepare the active layer 3.
S7: a hole transport layer MoOx was deposited on the surface of the active layer treated in S6 to a thickness of 10 nm.
S8: and evaporating metal electrode Al on the surface of the hole transport layer subjected to the S7 treatment, wherein the thickness of the metal electrode Al is 100 nm.
After the above steps are finished, the double-layer planar heterojunction organic solar cell device without the doped layer in the comparative example 1 is obtained.
The film morphology characterization of the present example for the above-described double-layer planar heterojunction organic solar cell device without the doped layer included AFM and GIWAXS tests.
The sample preparation conditions for the AFM test are as follows: and cleaning the conductive glass substrate 1, and sequentially cleaning with deionized water and ethanol twice. And drying the cleaned ITO wafer by using a nitrogen gun, carrying out UVO treatment for 20min to improve the surface activity, preparing a sample by using a spin coating film forming mode, carrying out melt spinning for 1300r/min and 30s by using a donor material J71 solution, and carrying out melt spinning for 5000r/min and 30s by using absolute ethyl alcohol to eliminate the influence of a dopant solvent on the surface roughness.
The sample preparation conditions for the GIWAXS test are as follows: cutting the silicon wafer into a proper size, and sequentially cleaning the silicon wafer with deionized water and ethanol twice. And drying the cleaned silicon wafer by using a nitrogen gun, carrying out UVO treatment for 20min to improve the surface activity, preparing a sample by using a spin coating film forming mode, and dynamically throwing 1300r/min and 30s by using a donor material J71 solution, and 5000r/min and 30s by using absolute ethyl alcohol to eliminate the influence of a dopant solvent on the appearance.
FIG. 2 is a graph showing the relationship between the open-circuit voltage (Voc) of the undoped double-layer planar heterojunction organic solar cell of comparative example 1 and the doped double-layer planar heterojunction organic solar cell of example 1, and the medium current density and voltage, and it can be seen from Table 1 that the open-circuit voltage (Voc) and the short-circuit current density (Jsc) of the undoped organic solar cell of comparative example 1 are 0.86V and 7.00mA/cm2B, carrying out the following steps of; the BCF-doped organic solar cell of example 1 had an open circuit voltage (Voc) of 0.85V and a short circuit current density (Jsc) of 8.20mA/cm2The borate-doped organic solar cell of example 2 had an open circuit voltage (Voc) of 0.85V and a short circuit current density (Jsc) of 7.63mA/cm2This shows that after the interface doping, the charge separation efficiency can be effectively improved, and the light absorption of the active layer is increased, so that the short-circuit current density is improved.
The results of the AFM tests show that the surface roughness of the BCF-doped or borate-doped J71 films does not change much compared to the undoped films. The results of the GIWAXS test show that the crystallinity and molecular orientation of the BCF-or borate-doped J71 films do not change much, i.e. the surface morphology does not change much, compared to the undoped films. This indicates that the interface doping of BCF or borate did not affect the morphology of J71 in the active layer.
TABLE 1
As can be seen from Table 1, the short-circuit current density (Jsc) of the BCF-doped double-layer planar heterojunction organic solar cell of example 1 of the present invention is from 7.00mA/cm2Is increased to 8.20mA/cm2In the embodiment 2 of the invention, the short-circuit current density (Jsc) of the borate-doped double-layer planar heterojunction organic solar cell is improved to 7.63mA/cm2Both of the two dopantsThe open circuit voltage (Voc) Fill Factor (FF) can be kept at a good level. The Photoelectric Conversion Efficiency (PCE) of the BCF-doped double-layer planar heterojunction organic solar cell in the embodiment 1 of the invention is improved from 4.06% to 4.75%, and the Photoelectric Conversion Efficiency (PCE) of the borate-doped double-layer planar heterojunction organic solar cell in the embodiment 2 of the invention is improved from 4.06% to 4.42%, which shows that the interface-doped double-layer planar heterojunction organic solar cell has effectively improved light absorption capability, exciton separation efficiency and carrier mobility without affecting the morphology of an active layer. Compared with the prior art, the BCF doping improves the performance of the device by a larger range, so that the photoelectric conversion efficiency of the solar cell is improved from 4.06% to 4.75%, and the photoelectric conversion efficiency of the device is improved by 17%.
The above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the technical solution of the present invention, and it should be understood by those skilled in the art that the technical solution can be modified and replaced by a plurality of simple modifications and replacements without departing from the spirit and principle of the present invention, and the modifications and replacements also fall into the protection scope covered by the claims.
Claims (10)
1. The interface-doped double-layer planar heterojunction organic solar cell is characterized by comprising a conductive glass substrate (1), an electron transport layer (2), an active layer (3), a hole transport layer (4) and a metal electrode (5) which are sequentially arranged from bottom to top, wherein the active layer (3) is formed by doping a double-layer planar heterojunction Y6/J71 and a BCF or borate interface;
the donor material J71 of the double-layer planar heterojunction Y6/J71 has the following structural formula:
the acceptor material Y6 of the double-layer planar heterojunction Y6/J71 has the following structural formula:
the structural formula of BCF is as follows:
the borate salt has the following structure:
2. the interface-doped double-layer planar heterojunction organic solar cell of claim 1, wherein:
the conductive glass substrate (1) is made of transparent glass and a transparent indium tin oxide film plated on the transparent glass;
the electron transport layer (2) is made of zinc oxide;
the hole transport layer (4) is made of metal molybdenum oxide;
the metal electrode (5) is made of metal aluminum.
3. The interface-doped double-layer planar heterojunction organic solar cell of claim 1, wherein: BCF or borate doped at the interface in the active layer (3) adopts a solution with the concentration of 0.01 mg/ml.
4. An interface doping method of the interface doped double-layer planar heterojunction organic solar cell of claim 1, comprising:
dissolving BCF or borate powder in absolute ethyl alcohol, and stirring at normal temperature to obtain a BCF or borate solution;
diluting BCF or borate solution to an intermediate concentration, stirring at normal temperature, and diluting to a target concentration;
the diluted BCF or borate solution to the target concentration is stirred for use.
5. The interface doping method of claim 4, wherein: weighing 1mg of BCF or borate powder, dissolving the powder in 1ml of absolute ethyl alcohol, and stirring the solution for 24 hours at the normal temperature of 300r/min on a hot bench to obtain 1mg/ml BCF or borate solution;
the intermediate concentration is 0.1 mg/ml;
stirring for 6h at the normal temperature of 300r/min by using a hot bench, wherein the target concentration is 0.01 mg/ml;
and stirring the BCF or borate solution diluted to the target concentration at the normal temperature of 300r/min by using a hot bench for later use.
6. A method for preparing the interface doped double-layer planar heterojunction organic solar cell as claimed in any one of claims 1 to 3, comprising:
cleaning a conductive glass substrate (1) and a blank glass substrate, spin-coating an electron transport layer (2) on the surface of the cleaned conductive glass substrate (1), and spin-coating water-soluble PEDOT (PSS);
weighing a donor material J71 and an acceptor material Y6, respectively dissolving in chloroform CF, and preparing a single-component solution for later use;
spin-coating an acceptor material Y6 solution on the surface of a conductive glass substrate (1) coated with an electron transport layer (2), and spin-coating a donor material J71 solution on the surface of a blank glass substrate coated with water-soluble PEDOT, PSS; spin-coating a dopant solution on the surface of a blank glass substrate coated with a donor material J71 solution, wherein the dopant solution is a BCF or borate solution diluted to a target concentration;
placing the blank glass substrate coated with the donor material J71 solution and the dopant solution on the surface of deionized water for water transfer printing, and performing surface lamination by using a conductive glass substrate (1) coated with the receptor material Y6 solution to prepare an active layer (3);
evaporating a hole transport layer (4) on the surface of the prepared active layer (3);
metal electrodes (5) are evaporated on the surface of the hole transport layer (4);
and obtaining the interface doped double-layer plane heterojunction organic solar cell after the steps are finished.
7. The method of claim 6, wherein: in the step of weighing the donor material J71 and the acceptor material Y6, respectively dissolving the donor material J71 and the acceptor material Y6 which are respectively 2.25mg in chloroform CF to prepare a single-component solution for later use, respectively dissolving the donor material J71 and the acceptor material Y6 which are respectively 2.70mg in chloroform CF to prepare the single-component solution, wherein the concentration of the donor material J71 solution in the single-component solution is 5mg/ml, the concentration of the acceptor material Y6 solution is 6mg/ml, and stirring the single-component solution for 8h at 50 ℃ at 300r/min by using a hot bench for later use.
8. The method of claim 6, wherein: in the step of cleaning the conductive glass substrate (1) and the blank glass substrate, the conductive glass substrate (1) and the blank glass substrate are respectively and sequentially ultrasonically cleaned twice with liquid detergent, deionized water, acetone, absolute ethyl alcohol and isopropanol for 30 minutes each time, and then dried by using nitrogen;
and respectively carrying out plasma surface treatment on the conductive glass substrate (1) and the blank glass substrate for 20 minutes.
9. The method of claim 6, wherein: PSS comprises the steps of spin-coating zinc oxide on the surface of the cleaned conductive glass substrate (1) at 4500r/min to prepare an electron transport layer (2), and annealing at 200 ℃ for 30 min; spin-coating water-soluble PEDOT (PSS) on the surface of the cleaned blank glass substrate at 1500r/min, and annealing at 140 ℃ for 3 min; and (3) placing the conductive glass substrate (1) with the finished surface spin coating and the blank glass substrate in a glove box in a nitrogen atmosphere for standby.
10. The method of claim 9, wherein:
spin-coating an acceptor material Y6 solution on the surface of a conductive glass substrate (1) coated with an electron transport layer (2), and spin-coating a donor material J71 solution on the surface of a blank glass substrate coated with water-soluble PEDOT, PSS; the step of spin-coating the dopant solution on the surface of the blank glass substrate coated with the donor material J71 solution specifically comprises spin-coating the acceptor material Y6 solution on the surface of the conductive glass substrate (1) coated with the electron transport layer (2) at 3000r/min for 30 s; PSS is coated on the surface of a blank glass substrate, the donor material J71 solution is spin-coated at 1300r/min for 30 s; spin-coating a dopant solution with the concentration of 0.01mg/ml on the surface of a blank glass substrate coated with the donor material J71 solution at 5000r/min for 30 s;
and placing the blank glass substrate coated with the donor material J71 solution and the dopant solution on the surface of deionized water for water transfer printing, performing surface bonding by using the conductive glass substrate (1) coated with the receptor material Y6 solution, drying by using nitrogen, placing in a glove box, vacuumizing for 8h, and completely removing the solvent and residual deionized water in the water transfer printing to obtain the active layer (3).
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