CN113410388B - Interface modified organic solar cell and preparation method thereof - Google Patents

Interface modified organic solar cell and preparation method thereof Download PDF

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CN113410388B
CN113410388B CN202110547016.4A CN202110547016A CN113410388B CN 113410388 B CN113410388 B CN 113410388B CN 202110547016 A CN202110547016 A CN 202110547016A CN 113410388 B CN113410388 B CN 113410388B
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solar cell
transport layer
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CN113410388A (en
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於黄忠
杨宋
孙亚鹏
黄金珍
黄承稳
王键鸣
张健开
谭靖宇
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South China University of Technology SCUT
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention discloses an interface modified organic solar cell and a preparation method thereof; the organic solar cell comprises a cathode substrate, an electron transport layer, an active layer, a hole transport layer and an anode layer which are sequentially stacked, wherein the electron transport layer is a ZnO film of which the surface is modified with a biological material; the biological material is caffeic acid C 9 H 8 O 4 Ferulic acid C 10 H 10 O 4 3, 4-Dimethoxycinnamic acid C 11 H 12 O 4 One kind of (1). After the ZnO film is modified by the biological material, the surface defect state of ZnO is reduced, the leakage current of the device is effectively reduced, and the recombination of current carriers can be effectively inhibited; the performance of the device is improved, and the short-circuit current density and the filling factor are effectively improved.

Description

Interface modified organic solar cell and preparation method thereof
Technical Field
The invention belongs to the field of solar cells, and particularly relates to an interface modified organic solar cell and a preparation method thereof.
Background
Organic solar cells have attracted much attention because of their advantages such as wide raw material sources, easy processing, easy physical and chemical modification, various cell device structures, low price, and environmental friendliness. However, compared with the conventional inorganic silicon solar cell, the organic solar cell has lower photoelectric conversion efficiency, which limits further development.
The working principle of the organic solar cell is as follows: (1) light irradiates the active layer through the ITO electrode, and the active layer absorbs photons to generate excitons; exciton diffusion to the donor/acceptor interface; (2) excitons in the acceptor transfer holes to the donor, and excitons in the donor transfer electrons to the acceptor, thereby realizing charge separation; (3) electrons and holes diffuse to the cathode and the anode along the acceptor and the donor respectively; (4) the electrons and holes are collected at the electrode/active layer interface by the cathode and anode, respectively, and a photocurrent and photovoltage are generated therefrom.
The interface layer material includes an electron transport layer material and a hole transport layer material. The most common electron transport layer material is ZnO. ZnO is an n-type semiconductor material with a wide forbidden band (3.3eV), has the advantages of high electron mobility, high light transmittance (up to 90%) in a visible light range, high stability and the like, and is a high-quality transparent electrode of a solar cell. However, the presence of intrinsic donor defects, such as interstitial Zn atoms, O vacancies, etc., in ZnO films makes ZnO films inherently weakly n-type conductive, and thus the resistivity of the ZnO films is generally high. Therefore, the method is found that the device performance can be effectively improved by doping, surface modification and other methods. For example, Mi-Hyae Park et al reported the use of Cs-doped TiO 2 Cathode interface modification layer, doping of Cs promotes TiO 2 More stable nano structure is formed, thereby improving the stability of the device and optimizing TiO 2 The work function of (2) is more favorable for the transmission of electrons; the Jen subject group uses ZnO/C60-SAMs as an electron transport layer, so that the interface exciton separation efficiency is improved, the surface defect state of a passivation material is improved, the form of an organic layer is optimized, and the cell efficiency is improved; lim subject group uses ZnO/SWCNT as electron transport layer, which improves carrier mobility and increases roughness of interfaceAnd the battery efficiency is improved. The Cao topic group uses PFN to modify ZnO on the surface, so that the work function of a cathode can be effectively reduced, the transmission and collection efficiency of electrons is improved, and the efficiency of a device is further improved; the ZHou modifies ZnO nanoparticles by using cysteine, greatly regulates the self-assembly of the ZnO nanoparticles, and forms dipoles at an interface to effectively reduce the work function of the ZnO surface.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a biological material C 9 H 8 O 4 、 C 10 H 10 O 4 、C 11 H 12 O 4 An organic solar cell with a ZnO film as an electron transmission layer and a preparation method thereof, which is an interface modified organic solar cell capable of improving photoelectric conversion efficiency.
The purpose of the invention is realized by the following technical scheme:
an interface modified organic solar cell comprises a cathode substrate 01, an electron transport layer 02, an active layer 03, a hole transport layer 04 and an anode layer 05 which are sequentially stacked, wherein the electron transport layer 02 is a ZnO film of which the surface is modified with a biological material; the biological material is caffeic acid C 9 H 8 O 4 Ferulic acid C 10 H 10 O 4 3, 4-Dimethoxycinnamic acid C 11 H 12 O 4 One kind of (1).
Preferably, the cathode substrate is indium tin oxide glass (ITO).
Preferably, the thickness of the electron transport layer is 30-40 nm.
Preferably, the active layer is P3HT: PCBM, and the thickness of the active layer is 150-200 nm.
Preferably, the hole transport layer is MoO x The thickness of the material is 1-3 nm; further preferably, the hole transport layer is MoO x The thickness of the material is 2-3 nm;
preferably, the anode layer is silver and has a thickness of 80-100 nm.
The preparation method of the interface modified organic solar cell comprises the following steps:
cleaning a cathode substrate, and carrying out surface treatment on the surface of the cathode substrate;
step two, spin-coating an electron transport layer and an active layer on the surface of the cathode substrate subjected to surface treatment in the step one in sequence; the electron transport layer comprises ZnO and a biological material;
and thirdly, sequentially evaporating a hole transport layer and an anode layer on the surface of the active layer in the second step to prepare the interface modified organic solar cell.
Preferably, in the first step, the cathode substrate cleaning includes: firstly, ultrasonic cleaning is sequentially carried out for 15-20 minutes by using liquid detergent, deionized water, acetone, absolute ethyl alcohol and isopropanol respectively; then drying in a vacuum drying oven at 80-90 ℃; the surface treatment is plasma surface treatment for 7-10 minutes.
Preferably, in the second step, the preparation of the electron transport layer comprises: dissolving zinc acetate in a mixed solution of ethylene glycol monomethyl ether and ethanolamine (a stabilizer), wherein the volume fraction of the ethanolamine in the mixed solution is 2.8-3%, and preparing a ZnO precursor solution with the mass concentration of the zinc acetate of 1 g/ml; dissolving the biological material in an ethanol solution, stirring for 2-4 hours, and filtering by using an organic filter head with the diameter of 0.22 mu m after stirring to obtain a biological material solution; spin-coating the ZnO precursor solution on the surface of the cathode substrate at the rotating speed of 4000-500 r.p.m for 40-50 s; annealing the cathode substrate which is spin-coated with the ZnO precursor solution at the temperature of 180-200 ℃ for 60-100 minutes; after the ZnO is cooled, spin-coating a biological material solution on the surface of ZnO at the rotating speed of 4000-5000 r.p.m for 40-50 s; and (3) drying the device in a vacuum drying oven at the temperature of 80-90 ℃ for 20-30 min.
Preferably, the concentration of the biological material in the biological material solution is 0.01-0.5 mg/mL.
Preferably, in the second step, the active layer is P3HT: PCBM, and the preparation of the active layer includes: dissolving P3HT and PCBM in o-dichlorobenzene, wherein the mass ratio of P3HT to PCBM is 1:1, the concentration of P3HT is 20 mg/ml, and stirring for 12-14 hours; stirring, and filtering with 0.22 μm organic filter head; finally, spin-coating an active layer solution on the surface of the electron transport layer at the rotating speed of 1000-1500 r.p.m for 40-50 s; and after the active layer is subjected to spin coating, the active layer is placed for 4 to 6 hours and naturally dried, and then annealing treatment is carried out at 120 to 130 ℃ for 7 to 10 minutes.
The interface modified organic solar cell is characterized in that a layer of biological material is modified on the surface of ZnO. First, C 9 H 8 O 4 The adhesive has good viscosity and can be well adsorbed on the surface of ZnO; secondly, C 9 H 8 O 4 、 C 10 H 10 O 4、 C 11 H 12 O 4 All containing the same functional group-COO - The carboxyl contained in the ZnO can be combined with free hydroxyl on the surface of ZnO to form an effective electronic channel, so that electrons can be transmitted from the active layer to the electronic transmission layer more conveniently, phenolic hydroxyl O atoms on the benzene ring have a large amount of negative charges, and the O atoms contribute to charge transmission, so that the carrier concentration can be effectively improved; finally, the electron donating ability of the compound is changed by changing the functional group on the benzene ring, so that the contribution of the compound to charge transfer is changed.
Compared with the prior art, the invention has the following beneficial effects:
after the ZnO film is modified by the biological material, the defect state of the ZnO surface is reduced, the leakage current of the device is effectively reduced, and the recombination of current carriers can be effectively inhibited; the performance of the device is improved, and the short-circuit current density and the filling factor are effectively improved.
Drawings
Fig. 1 is a schematic structural diagram of an interface modified organic solar cell according to the present invention.
Fig. 2 is a flow chart of a method for manufacturing an interface modified organic solar cell device according to the present invention.
FIG. 3 is a graph of current density versus voltage for the solar devices of examples 1-3 and comparative examples.
Detailed Description
The invention provides an interface modified organic solar cell, which comprises a cathode substrate 01, an electron transport layer 02, an active layer 03, a hole transport layer 04 and an anode layer 05 as shown in figure 1. The describedThe cathode substrate 01 is indium tin oxide glass (ITO). The electron transport layer 02 is formed by zinc oxide (ZnO) and C 9 H 8 O 4 、C 10 H 10 O 4 、C 11 H 12 O 4 The double-layer structure is composed of two layers, and the thickness of the double-layer structure is 30-40 nm. The active layer is P3HT/PCBM, wherein P3HT is poly 3-hexylthiophene, PCBM is [6, 6 ]]-phenyl-C61-butyric acid methyl ester; the preparation method of the electron transport layer solution comprises the following steps: dissolving zinc acetate in a mixed solution of ethylene glycol monomethyl ether and ethanolamine (a stabilizer), wherein the volume fraction of the ethanolamine is 2.8-3%, preparing into a mixed solution with the mass concentration of 1g/ml, and then adding C 9 H 8 O 4 、C 10 H 10 O 4 、C 11 H 12 O 4 Respectively dissolving the raw materials in an ethanol solution, and stirring the prepared solution for 2-4 hours; filtering with 0.22 μm organic filter head after stirring, and calculating the concentration of the filtrate; secondly, coating the ZnO precursor solution on the surface of the treated cathode substrate in a spinning way, wherein the rotating speed is 4000-5000 r.p.m, and the time is 40-50 s; annealing the cathode substrate which is spin-coated with the ZnO precursor solution at 200 ℃ for 60-100 minutes; after the ZnO is cooled, respectively spin-coating a layer of C on the surface of the ZnO 9 H 8 O 4 、 C 10 H 10 O 4 、C 11 H 12 O 4 The rotating speed of the solution is 4000-5000 r.p.m, and the time is 40-50 s; placing the device in a vacuum drying oven at 80-90 ℃ for drying for 20-30 min; the thickness of the active layer is about 200 nm. The hole transport layer is MoO x The thickness of the film is 2 to 3 nm. The anode layer is made of silver, and the thickness of the anode layer is 80-100 nm.
The preparation process of the interface modified organic solar cell is shown in fig. 2 and comprises the following steps:
step 1, sequentially ultrasonically cleaning a cathode substrate (ITO) for 20 minutes by using liquid detergent, deionized water, acetone, absolute ethyl alcohol and isopropanol respectively; the mixture is dried in a vacuum drying oven at the temperature of 80-90 ℃.
And 2, carrying out plasma surface treatment on the surface of the cleaned and dried cathode substrate (ITO) for 10 minutes, wherein the treatment method utilizes the strong oxidizing property of ozone generated under microwaves to clean residual organic matters and the like on the surface of the ITO, and can improve oxygen vacancies on the surface of the ITO and the work function of the surface of the ITO at the same time.
And 3, spin-coating a ZnO precursor solution on the ITO surface treated in the step 2, and annealing at the temperature of 200 ℃ for 1 hour to form a ZnO layer. After the ZnO is naturally cooled, the surface of the ZnO layer is spin-coated with caffeic acid C 9 H 8 O 4 A solution; the preparation process of the electron transport layer comprises the following steps: dissolving zinc acetate in a mixed solution of ethylene glycol monomethyl ether and ethanolamine (a stabilizer), wherein the volume fraction of the ethanolamine is 2.8-3%, preparing the mixed solution into a mixed solution with the mass concentration of 1g/ml, and adding C 9 H 8 O 4 、C 10 H 10 O 4 、C 11 H 12 O 4 Respectively dissolving the raw materials in an ethanol solution, and stirring the prepared solution for 2-4 hours; after stirring, filtering by using a 0.22 mu m organic filter head, and calculating the concentration of the filtrate; secondly, coating the ZnO precursor solution on the surface of the treated cathode substrate in a spinning mode, wherein the rotating speed is 4000-5000 r.p.m, and the time is 40-50 s; annealing the cathode substrate which is spin-coated with the ZnO solution at the temperature of 200 ℃ for 60-100 minutes; after the ZnO is cooled, respectively spin-coating a layer of C on the surface of the ZnO 9 H 8 O 4 、C 10 H 10 O 4 、C 11 H 12 O 4 The rotating speed of the solution is 4000-5000 r.p.m, and the time is 40-50 s; placing the device in a vacuum drying oven at 80-90 ℃ for drying for 20-30 min; the total thickness of the electron transport layer is 30-40 nm.
Step 4, spin-coating an active layer solution on the surface of the electron transport layer, wherein the revolution of the active layer is 1000-1500 r.p.m, the time is 40-50 s, and the thickness of the active layer is about 200 nm; the active layer is formed by P3 HT/PCBM; and after the spin coating is finished, the mixture is placed for 4-6 hours to be naturally dried, and then annealing treatment is carried out for 7-10 minutes at 120-130 ℃.
Step 5, evaporating a hole transport layer MoO on the surface of the active layer x The thickness of the film is 2 to 3 nm.
And 6, evaporating silver (Ag) of the anode layer on the surface of the hole transport layer, wherein the thickness of the silver (Ag) is 80-100 nm.
And obtaining the interface modified organic solar cell after the steps are finished.
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and may be carried out with reference to conventional techniques for process parameters not particularly noted.
Example 1
The structure of the interface modified organic solar cell device in this embodiment 1 is as follows: ITO/ZnO: C 9 H 8 O 4 /P3HT:PCBM/MoO x /Ag。
The preparation process flow of the interface modified organic solar cell is as follows:
step 1, sequentially ultrasonically cleaning a cathode substrate (ITO) for 20 minutes by using liquid detergent, deionized water, acetone, absolute ethyl alcohol and isopropanol respectively; this time dried in a vacuum oven at 80 ℃.
And 2, carrying out plasma surface treatment on the surface of the cleaned and dried cathode substrate (ITO) for 10 minutes, wherein the treatment method utilizes the strong oxidizing property of ozone generated under microwaves to clean residual organic matters and the like on the surface of the ITO, and can improve oxygen vacancies on the surface of the ITO and the work function of the surface of the ITO at the same time.
And 3, spin-coating a ZnO solution on the ITO surface treated in the step 2, and annealing at 200 ℃ for 1 hour to form a ZnO layer. After the ZnO is naturally cooled, spin-coating C on the surface of the ZnO layer 9 H 8 O 4 A solution; the preparation process of the electron transport layer comprises the following steps: dissolving zinc acetate in a mixed solution of ethylene glycol monomethyl ether and ethanolamine (a stabilizer), wherein the volume fraction of the ethanolamine is 2.8%, preparing a mixed solution with the mass concentration of 1g/mL, and adding C 9 H 8 O 4 Dissolving in ethanol solution, wherein C 9 H 8 O 4 The concentration of the solution is 0.1 mg/mL; stirring the prepared solution for 2 hours; stirring, and filtering with 0.22 μm organic filter head; secondly, coating the ZnO precursor solution on the surface of the treated cathode substrate in a rotating mode at the rotating speed of 4000r.p.m for 40 s; annealing the cathode substrate which is spin-coated with the ZnO precursor solution at the temperature of 200 DEG C60 minutes at the temperature; after the ZnO is cooled, a layer of C is coated on the surface of the ZnO in a spinning way 9 H 8 O 4 The rotating speed of the solution is 4000r.p.m, and the time is 40 s; drying the device in a vacuum drying oven at 80 deg.C for 20 min; the total thickness of the electron transport layer was 30 nm.
Step 4, spin-coating an active layer solution on the surface of the electron transport layer, wherein the revolution is 1000r.p.m, the time is 40s, and the thickness of the active layer is about 200 nm; after the active layer is completely spin-coated, the active layer is placed for 6 hours to be naturally dried, and then is annealed at 120 ℃ for 7 minutes.
And 5, evaporating a hole transport layer MoOx on the surface of the active layer, wherein the thickness of the hole transport layer MoOx is 2 nm.
And 6, evaporating anode layer silver on the surface of the hole transport layer, wherein the thickness of the anode layer silver is 80 nm.
And obtaining the interface modified organic solar cell after the steps are finished.
Example 2
The interface modification organic solar cell device in the embodiment has the following structure: ITO/ZnO: C 10 H 10 O 4 /P3HT:PCBM/MoO x /Ag。
The preparation process flow of the interface modified organic solar cell is as follows:
step 1, sequentially carrying out ultrasonic cleaning on a cathode substrate (ITO) for 20 minutes by using liquid detergent, deionized water, acetone, absolute ethyl alcohol and isopropanol respectively; this time dried in a vacuum oven at 80 ℃.
And 2, carrying out plasma surface treatment on the surface of the cleaned and dried cathode substrate (ITO) for 10 minutes, wherein the treatment method utilizes the strong oxidizing property of ozone generated under microwaves to clean residual organic matters and the like on the surface of the ITO, and can improve oxygen vacancies on the surface of the ITO and the work function of the surface of the ITO at the same time.
And 3, spin-coating a ZnO precursor solution on the ITO surface treated in the step 2, and annealing at 200 ℃ for 1 hour to form a ZnO layer. After the ZnO is naturally cooled, spin-coating C on the surface of the ZnO layer 10 H 10 O 4 A solution; the preparation process of the electron transport layer comprises the following steps: dissolving zinc acetate in mixed solution of ethylene glycol monomethyl ether and ethanolamine (stabilizer)Wherein the volume fraction of ethanolamine is 2.8%, preparing into mixed solution with mass concentration of 1g/ml, and mixing with C 10 H 10 O 4 Dissolving in ethanol solution, wherein C 10 H 10 O 4 The concentration of the solution is 0.1 mg/mL; stirring the prepared solution for 2 hours; stirring, and filtering with 0.22 μm organic filter head; secondly, coating the ZnO solution on the surface of the treated cathode substrate in a rotating mode at the rotating speed of 4000r.p.m for 40 s; annealing the cathode substrate which is spin-coated with the ZnO solution at 200 ℃ for 60 minutes; after the ZnO is cooled, a layer of C is coated on the surface of the ZnO in a spinning way 10 H 10 O 4 The rotating speed of the solution is 4000r.p.m, and the time is 40 s; drying the device in a vacuum drying oven at 80 deg.C for 20 min; the total thickness of the electron transmission layer is 30 nm;
step 4, spin-coating an active layer solution on the surface of the electron transport layer, wherein the revolution is 1000r.p.m, the time is 40s, and the thickness of the active layer is about 200 nm; after the active layer is completely spin-coated, the active layer is placed for 6 hours to be naturally dried, and then is annealed at 120 ℃ for 7 minutes.
Step 5, evaporating a hole transport layer MoO on the surface of the active layer x The thickness is 2 nm.
And 6, evaporating anode layer silver on the surface of the hole transport layer, wherein the thickness of the anode layer silver is 80 nm.
And obtaining the interface modified organic solar cell after the steps are finished.
Example 3
The interface modification organic solar cell device in the embodiment has the following structure: ITO/ZnO: C 11 H 12 O 4 /P3HT:PCBM/MoO x /Ag。
The preparation process flow of the interface modified organic solar cell is as follows:
step 1, sequentially carrying out ultrasonic cleaning on a cathode substrate (ITO) for 20 minutes by using liquid detergent, deionized water, acetone, absolute ethyl alcohol and isopropanol respectively; this time dried in a vacuum oven at 80 ℃.
And 2, carrying out plasma surface treatment on the surface of the cleaned and dried cathode substrate (ITO) for 10 minutes, wherein the treatment method utilizes the strong oxidizing property of ozone generated under microwaves to clean residual organic matters and the like on the surface of the ITO, and can improve oxygen vacancies on the surface of the ITO and the work function of the surface of the ITO at the same time.
And 3, spin-coating a ZnO precursor solution on the ITO surface treated in the step 2, and annealing at the temperature of 200 ℃ for 1 hour to form a ZnO layer. After the ZnO is naturally cooled, spin-coating C on the surface of the ZnO layer 11 H 12 O 4 A solution; the preparation process of the electron transport layer comprises the following steps: dissolving zinc acetate in a mixed solution of ethylene glycol monomethyl ether and ethanolamine (stabilizer), wherein the volume fraction of the ethanolamine is 2.8%, preparing into a mixed solution with the mass concentration of 1g/ml, and adding C 11 H 12 O 4 Dissolving in ethanol solution, wherein C 11 H 12 O 4 The concentration of the solution is 0.1 mg/mL; stirring the prepared solution for 2 hours; stirring, and filtering with 0.22 μm organic filter head; secondly, coating the ZnO solution on the surface of the treated cathode substrate in a rotating mode at the rotating speed of 4000r.p.m for 40 s; annealing the cathode substrate which is spin-coated with the ZnO solution at 200 ℃ for 60 minutes; after the ZnO is cooled, a layer of C is coated on the surface of the ZnO in a spinning way 11 H 12 O 4 The rotation speed of the solution is 4000r.p.m, and the time is 40 s; drying the device in a vacuum drying oven at 80 deg.C for 20 min; the total thickness of the electron transport layer was 30 nm.
Step 4, spin-coating an active layer solution on the surface of the electron transport layer, wherein the revolution is 1000r.p.m, the time is 40s, and the thickness of the active layer is about 200 nm; after the active layer is completely spin-coated, the active layer is placed for 6 hours to be naturally dried, and then is annealed at 120 ℃ for 7 minutes.
Step 5, evaporating a hole transport layer MoO on the surface of the active layer x The thickness is 2 nm.
And 6, evaporating anode layer silver on the surface of the hole transport layer, wherein the thickness of the anode layer silver is 80 nm.
And obtaining the interface modified organic solar cell after the steps are finished.
Comparative example
Organic solar cell without interface modification: ITO/ZnO/P3HT PCBM/MoO x /Ag。
The preparation method was substantially the same as in example 1 except that step (3) was not spin-coated with C 9 H 8 O 4 And (3) solution.
Example 4
Organic solar cell performance testing
FIG. 3 is a graph of current density versus voltage for three examples of the interface modified organic solar cell and the unmodified organic solar cell of the comparative example; wherein ZnO is the unmodified organic solar cell in the comparative example (the structure is ITO/ZnO/P3HT: PCBM/MoO x Ag) current density versus voltage curve, ZnO/0.1 mg/mL C 9 H 8 O 4 The interface modified organic solar cell of example 1 (structure: ITO/ZnO: C) 9 H 8 O 4 /P3HT:PCBM/MoO x Ag) current density versus voltage curve; ZnO/0.1 mg/mLC 10 H 10 O 4 The interface modified organic solar cell of example 2 (structure: ITO/ZnO: C) 10 H 10 O 4 /P3HT:PCBM/MoO x Current density versus voltage curve of/Ag); ZnO/0.1 mg/mL C 11 H 12 O 4 The interface modified organic solar cell of example 3 (structure: ITO/ZnO: C) 11 H 12 O 4 /P3HT:PCBM/MoO x Current density versus voltage curve of/Ag); as can be seen from FIG. 3, the open circuit voltage (V) of the unmodified organic solar cell of the comparative example oc ) 0.61V, short-circuit current density (J) sc ) 7.94mA/cm 2; open circuit voltage (V) of the interface modified organic solar cell of example 1 oc ) 0.62V, short-circuit current density (J) sc ) 8.89mA/cm 2; open circuit voltage (V) of the interface modified organic solar cell of example 2 oc ) 0.62V, short-circuit current density (J) sc ) It was 8.79mA/cm 2. Open circuit voltage (V) of the interface modified organic solar cell of example 3 oc ) 0.61V, short-circuit current density (J) sc ) It was 8.27mA/cm 2. This shows that the three biomaterials can effectively improve charge separation and charge transport efficiency after modification, thereby improving short-circuit current density.
TABLE 1
Figure BDA0003073886550000111
From Table 1, it can be found that the short-circuit current densities (J) in the three examples sc ) And the Filling Factor (FF) is improved to a certain extent, which shows that the organic solar cell modified by the three biological materials improves the contact between the ZnO film and the active layer, thereby enhancing the extraction of charges, and effectively improving the exciton separation efficiency and the carrier mobility.
The above-described embodiments are merely representative of several embodiments of the present invention, and the description thereof is in more detail, but not to be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various changes and modifications without departing from the spirit of the present invention, and these changes and modifications are within the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the appended claims.

Claims (10)

1. An interface modification organic solar cell is characterized by comprising a cathode substrate (01), an electron transport layer (02), an active layer (03), a hole transport layer (04) and an anode layer (05) which are sequentially stacked, wherein the electron transport layer (02) is a ZnO thin film with a surface modified with biological materials; the biological material is caffeic acid C 9 H 8 O 4 Ferulic acid C 10 H 10 O 4 3, 4-dimethoxycinnamic acid C 11 H 12 O 4 One of (1);
the modification method of the biological material comprises the following steps: annealing the cathode substrate which is spin-coated with the ZnO precursor solution at the temperature of 180-200 ℃ for 60-100 minutes; after cooling, spin-coating a biological material solution on the surface of ZnO at the rotating speed of 4000-5000 r.p.m for 40-50 s; and (3) drying the device in a vacuum drying oven at the temperature of 80-90 ℃ for 20-30 min.
2. The interface modified organic solar cell of claim 1, wherein the cathode substrate is indium tin oxide glass.
3. The interface-modified organic solar cell of claim 1, wherein the thickness of the electron transport layer is 30-40 nm.
4. The interface modified organic solar cell of claim 1, wherein the active layer is P3HT PCBM, and the thickness of the active layer is 150-200 nm.
5. The interface-modified organic solar cell of claim 1, wherein the hole transport layer is MoO x The thickness of the material is 2-3 nm; the anode layer is made of silver and has a thickness of 80-100 nm.
6. The method of any one of claims 1-5 for preparing an interface modified organic solar cell, comprising the steps of:
step one, cleaning a cathode substrate, and carrying out surface treatment on the surface of the cathode substrate;
step two, spin-coating an electron transport layer and an active layer on the surface of the cathode substrate subjected to the surface treatment in the step one in sequence; the electron transport layer comprises ZnO and a biological material;
and thirdly, sequentially evaporating a hole transport layer and an anode layer on the surface of the active layer in the second step to prepare the interface modified organic solar cell.
7. The method according to claim 6, wherein in the first step, the cathode substrate cleaning comprises: firstly, ultrasonic cleaning is sequentially carried out for 15-20 minutes by using liquid detergent, deionized water, acetone, absolute ethyl alcohol and isopropanol respectively; then drying in a vacuum drying oven at 80-90 ℃; the surface treatment is plasma surface treatment for 7-10 minutes.
8. The method according to claim 6, wherein the step two, the preparation of the electron transport layer comprises: dissolving zinc acetate in a mixed solution of ethylene glycol monomethyl ether and ethanolamine, wherein the volume fraction of the ethanolamine in the mixed solution is 2.8-3%, and preparing a ZnO precursor solution with the mass concentration of the zinc acetate of 1 g/ml; dissolving the biological material in an ethanol solution, stirring for 2-4 hours, and filtering by using an organic filter head with the diameter of 0.22 mu m after stirring to obtain a biological material solution; and spin-coating the ZnO precursor solution on the surface of the cathode substrate at the rotating speed of 4000-500 r.p.m for 40-50 s.
9. The method according to claim 8, wherein the concentration of the biomaterial in the biomaterial solution is 0.01-0.5 mg/mL.
10. The preparation method according to claim 6, wherein in the second step, the active layer is P3HT: PCBM, and the preparation of the active layer comprises: dissolving P3HT and PCBM in o-dichlorobenzene, wherein the mass ratio of P3HT to PCBM is 1:1, the concentration of P3HT is 20 mg/ml, and stirring for 12-14 hours; stirring, and filtering with 0.22 μm organic filter head; finally, spin-coating an active layer solution on the surface of the electron transport layer at the rotating speed of 1000-1500 r.p.m for 40-50 s; and after the active layer is spin-coated, the active layer is placed for 4-6 hours to be naturally dried, and then annealing treatment is carried out at 120-130 ℃ for 7-10 minutes.
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