CN112635674B - Organic solar cell with ZnO film doped with biological material GHK-Cu as electron transport layer and preparation method thereof - Google Patents

Organic solar cell with ZnO film doped with biological material GHK-Cu as electron transport layer and preparation method thereof Download PDF

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CN112635674B
CN112635674B CN202011488757.1A CN202011488757A CN112635674B CN 112635674 B CN112635674 B CN 112635674B CN 202011488757 A CN202011488757 A CN 202011488757A CN 112635674 B CN112635674 B CN 112635674B
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CN112635674A (en
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於黄忠
黄金珍
黄承稳
侯春利
王键鸣
张健开
孙亚鹏
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South China University of Technology SCUT
South China Institute of Collaborative Innovation
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/152—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising zinc oxide, e.g. ZnO
    • H—ELECTRICITY
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Abstract

The invention discloses an organic solar cell taking a ZnO film doped with a biological material GHK-Cu as an electron transport layer and a preparation method thereof. The organic solar cell device comprises a cathode substrate, an electron transport layer, an active layer, a hole transport layer and an anode layer which are sequentially stacked; the electron transmission layer is a ZnO film doped with GHK-Cu. In the organic solar cell, the ZnO modified by the biological material GHK-Cu can reduce the defects on the surface of ZnO, effectively reduce charge recombination, improve charge transmission and collection, improve the conductivity of a film and optimize the performance of the organic solar cell; and GHK-Cu is doped into ZnO, so that the crystallization quality and the carrier concentration of the ZnO nanoparticles are effectively improved, and the transmission efficiency of carriers is improved. According to the invention, the GHK-Cu powder is mixed with ethylene glycol monomethyl ether and ethanolamine to prepare a solution, and then the solution is doped into the ZnO solution for blending, and then spin coating is carried out to form a film, so that the operation is simple.

Description

Organic solar cell with ZnO film doped with biological material GHK-Cu as electron transport layer and preparation method thereof
Technical Field
The invention relates to the field of solar cells, in particular to an organic solar cell taking a ZnO film doped with a biological material GHK-Cu as an electron transport layer and a preparation method thereof.
Background
Polymer solar cells have become one of the approaches to address energy shortages, including polymer solar cells and Inverted Polymer Solar Cells (IPSCs). However, the stability of the polymer solar cell is relatively low compared to the inverted polymer solar cell. IPSCs have been receiving wide attention in the renewable energy field because of their advantages of flexibility, bright color, various battery device configurations, low cost, and environmental stability. According to previous reports, the energy conversion efficiency of inverted polymer solar cells is close to 18%. The structure of the inverted polymer solar cell device includes a cathode electrode, an Electron Transport Layer (ETL), an active layer, a Hole Transport Layer (HTL), and an anode electrode. Among other things, the physical and chemical properties of ETL directly affect the electron transfer and extraction processes, which are critical to the performance of IPSCs.
Among IPSCs, znO has been widely used as ETL because IPSCs with ZnO as ETL have a higher ratio of TiO x And Cs 2 CO, better conductivity as ETL. However, the ZnO surface has oxygen vacancy defects, resulting in the presence of many zinc dangling bonds, which act as recombination centers to trap photogenerated carriers and reduce electron transport efficiency, thereby limiting the efficiency of the polymer solar cell. Furthermore, O absorbed by ions on the surface of ZnO nanoparticles 2 The transport of electrons is hindered, which results in a so-called light absorption effect. Therefore, it is very important to prepare a highly conductive ZnO ETL having good electron transport and hole blocking properties.
By doping ZnO with metal oxides (including doping with alkali metals, e.g. Sn) 4+ ，Mg 2+ And Al 3+ ) This problem can be solved or eliminated to passivate surface defects, enhance charge transport and improve device performance. Self-assembled monolayers (SAMs), surface small molecule or polymer modification, and organic-inorganic composites have been used for modified surfaces of ZnO. The improvement of the hydrophobicity of the surface of ZnO and the smoothness of the surface roughness are advantageous to enhance the electrical conductivity of the device. As reported by Pu Fan et al, the polymer polystyrene modified ZnO nanoparticles can be used as an electron transport layer of polymer solar cells. But the prepared ZnO electron transport layer is oppositeThe roughness is not good for the compatibility of the electron transport layer and the active layer and the inhibition effect on the surface defects of ZnO, which can prevent the effective improvement of the conductivity of the electron transport layer.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide an organic solar cell taking a ZnO film doped with a biological material GHK-Cu as an electron transport layer and a preparation method thereof.
Based on the organic solar cell, the invention provides the organic solar cell which takes the ZnO film doped with the biological material GHK-Cu as the electron transport layer.
The purpose of the invention is realized by at least one of the following technical solutions.
The organic solar cell taking the ZnO film doped with the biological material GHK-Cu as the electron transmission layer is an organic solar cell taking the ZnO film doped with the biological material blue copper peptide (Gly-His-Lys-Cu, GHK-Cu) as the electron transmission layer.
In the organic solar cell provided by the invention, the biological material GHK-Cu modified ZnO can reduce the defects on the surface of ZnO, effectively reduce charge recombination, improve charge transmission and collection, improve the conductivity of a film and optimize the performance of the organic solar cell; and GHK-Cu doped in ZnO effectively improves the crystallization quality and the carrier concentration of ZnO nanoparticles and improves the transmission efficiency of carriers.
The organic solar cell with the ZnO film doped with the biological material GHK-Cu as the electron transport layer comprises a cathode substrate, the electron transport layer, an active layer, a hole transport layer and an anode layer which are sequentially stacked; the electron transport layer is a ZnO film doped with GHK-Cu.
Further, the cathode substrate is indium tin oxide glass (ITO); the thickness of the electron transmission layer is 20-40nm;
further, the material of the active layer is PBDB-T: ITIC (Poly [ [4,8-bis [5- (2-ethylhexyl) -2-thienyl ] benzol [1,2-b:4,5-b '] dithiophene-2,6-diyl ] -2,5-thiophene [5,7-bis (2-ethylhexyl) -4,8-dioxo-4H, 8H-benzole [1,2-c:4,5-c' ] dithiophene-1, 3-diyl ] ] Propanetinitrile, 2'- [6, 12-tetrakis (4-hydroxyphenyl) -6, 12-dihydrodithiophene [2,3-d:2',3'-d' ] dithiophene-2,8-diyl ] bis [ hydroxynaphthalene (6-oxo-4H-cyclophenone [ 5H-5H ] -biphenyl [4, 4-c-1, 2-b ] ];
further, the thickness of the active layer is 80-120nm;
further, the hole transport layer is MoO 3 The thickness of the hole transport layer is
Figure BDA0002840121870000031
Further, the anode layer is silver and has a thickness of
Figure BDA0002840121870000032
Preferably, the thickness of the electron transport layer is 30nm.
Preferably, the thickness of the active layer is 100nm.
Preferably, the electron transport layer has a thickness of
Figure BDA0002840121870000033
Preferably, the anode layer is silver and has a thickness of
Figure BDA0002840121870000034
The invention provides a method for preparing an organic solar cell with a ZnO film doped with a biological material GHK-Cu as an electron transmission layer, which comprises the following steps:
(1) Cleaning a cathode substrate, and carrying out surface oxygen Plasma treatment on the surface of the cathode substrate;
(2) Blending the GHK-Cu solution and the ZnO solution, and uniformly mixing to obtain a blended solution; spin-coating the co-mixed solution on the cathode substrate subjected to surface treatment in the step (1), and performing annealing treatment to obtain an electron transport layer;
(3) And (3) spin-coating an active layer on the electron transport layer in the step (2), and then evaporating a hole transport layer and an anode layer on the active layer by one time to obtain the organic solar cell taking the ZnO & GHK-Cu thin film as the electron transport layer.
Further, the step (1) of cleaning the cathode substrate comprises: sequentially carrying out ultrasonic cleaning on the cathode substrate by using liquid detergent, deionized water, acetone, absolute ethyl alcohol and isopropanol for 15-20 minutes respectively, and then drying in a vacuum drying oven at 80-90 ℃ to obtain a cleaned cathode substrate; the time of the surface oxygen Plasma treatment is 13 to 15 minutes.
Further, the preparation of the GHK-Cu solution in the step (2) comprises: dissolving GHK-Cu powder in ethylene glycol monomethyl ether, carrying out primary stirring treatment, then adding ethanolamine, and carrying out secondary stirring treatment to obtain a GHK-Cu solution; the time of the first stirring treatment is 1-2 hours, and the time of the second stirring treatment is 11-13 hours; in the GHK-Cu solution, the concentration of GHK-Cu powder is 1-5mg/mL, and the volume percentage concentration of ethanolamine is 2.6-3.0%.
Preferably, in the preparation process of the GHK-Cu solution in the step (2), the time of the second stirring treatment is 12 hours; in the GHK-Cu solution, the volume percentage concentration of ethanolamine is 2.8%.
Further, the preparation of the ZnO solution in the step (2) comprises: dissolving zinc acetate in an ethylene glycol monomethyl ether solvent, carrying out first stirring treatment, then adding ethanolamine, and carrying out second stirring treatment to obtain the ZnO solution (the zinc acetate is dissolved in the ethylene glycol monomethyl ether solvent to react to generate ZnO, and the ethanolamine is used as a stabilizer); the time of the first stirring treatment is 1-2 hours, and the time of the second stirring treatment is 11-13 hours; the mass volume ratio of the zinc acetate to the glycol methyl ether solvent is 1/0.8-1g/mL; in the ZnO solution, the volume percentage concentration of the ethanolamine is 2.6-3.0%.
Preferably, in the preparation process of the ZnO solution in the step (2), the time of the second stirring treatment is 12 hours, and the mass volume ratio of the zinc acetate to the ethylene glycol monomethyl ether solvent is 1.
Further, the weight of the GHK-Cu solution in the step (2) is 0.03-0.3 wt% of the weight of the ZnO solution.
Preferably, the mass of the GHK-Cu solution in the step (2) is 0.03%, 0.05%, 0.1% or 0.3% of the mass of the ZnO solution.
Preferably, the uniform mixing manner in the step (2) is magnetic stirring, and the magnetic stirring time is 2 hours.
Further, the rotation speed of the spin coating of the blend solution in the step (2) is 3000-5000rpm, and the spin coating time of the blend solution is 30-50s; the temperature of the annealing treatment is 180-220 ℃, and the time of the annealing treatment is 40-80 minutes.
Preferably, the rotation speed of the co-mixing solution spin-coating in the step (2) is 4000rpm, and the time of the co-mixing solution spin-coating is 40s; the temperature of the annealing treatment is 200 ℃, and the time of the annealing treatment is 60 minutes.
Further, the preparation of the active layer in the step (3) comprises: PBDB-T and ITIC are dissolved in chlorobenzene for primary stirring treatment, 1, 8-diiodo zinc alkane is added for secondary stirring treatment to obtain an active layer solution; carrying out plasma surface treatment on the surface of the electron transport layer; spin coating an active layer solution on the surface of the electron transport layer; and after the active layer is subjected to spin coating, the active layer is placed in a glove box for self-assembly treatment and annealing treatment.
Further, the mass ratio of the PBDB-T to the ITIC is 0.8-1.2/1; the mass volume ratio of the PBDB-T to chlorobenzene is 8-12/1mg/ml; the time of the first stirring treatment is 1-2 hours, and the time of the second stirring treatment is 12-24 hours; the volume ratio of the 1, 8-diiodo zinc alkane (DIO) to the chlorobenzene is 99-100:0.5; the plasma surface treatment time is 13-15 minutes; the rotating speed of the active layer solution spin-coated on the surface of the electron transport layer is 2000-3000rpm, and the time of the active layer solution spin-coated on the surface of the electron transport layer is 30-50s; the self-assembly time is 5-7 hours; the temperature of the annealing treatment is 120-130 ℃, and the time of the annealing treatment is 7-10 minutes.
Preferably, the mass ratio of the PBDB-T to the ITIC in the preparation process of the active layer is 1; the mass volume ratio of the PBDB-T to chlorobenzene is 10:1mg/ml; the time of the first stirring treatment is 1 hour; the rotating speed of the active layer solution spin-coated on the surface of the electron transport layer is 2500rpm, and the time of spin-coating the active layer solution on the surface of the electron transport layer is 40s; the self-assembly time was 6 hours. Compared with the prior art, the invention has the following advantages and beneficial effects:
according to the organic solar cell with the ZnO & GHK-Cu composite film as the electron transmission layer, firstly, the GHK-Cu can modify the surface defects of ZnO, and can effectively reduce charge recombination and improve charge transmission and collection, so that the conductivity of the film is improved; and secondly, the GHK-Cu doped in the ZnO can effectively improve the crystallization quality and the carrier concentration of the ZnO nanoparticles, improve the transmission efficiency of carriers and optimize the performance of the organic solar cell. Finally, according to the invention, the GHK-Cu powder is mixed with ethylene glycol monomethyl ether and ethanolamine to prepare a solution, and the solution is doped into the ZnO solution for blending, and then spin-coating is carried out to form a film, so that the method is simple to operate and has good application panorama.
Drawings
Fig. 1 is a schematic structural diagram of an organic solar cell using a ZnO thin film doped with GHK-Cu as an electron transport layer according to an embodiment of the present invention;
FIG. 2 is a flow chart of a method for manufacturing an organic solar cell device with a ZnO thin film doped with GHK-Cu as an electron transport layer;
FIG. 3 is a graph of current density versus voltage for the solar devices of example 1 and comparative example;
FIG. 4 is a PL spectrum of GHK-Cu% by weight of ZnO and ZnO &0.03wt% of samples in examples;
FIG. 5 is a graph of current density versus voltage for the ITO/ZnO (or ZnO &0.03wt% GHK-Cu)/Ag device of the examples under light conditions.
Detailed Description
The following examples are included to further illustrate the practice of the invention, but are not intended to limit the practice or protection of the invention. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
The present invention provides an organic solar cell using a ZnO thin film doped with GHK — Cu as an electron transport layer, which includes a cathode substrate 1, an electron transport layer 2, an active layer 3, a hole transport layer 4, and an anode layer 5, which are sequentially stacked, as shown in fig. 1.
The preparation process of the organic solar cell with the GHK-Cu doped ZnO film as the electron transport layer is shown in figure 2 and comprises the following steps:
step 1, cleaning a cathode substrate ITO;
step 2, carrying out surface oxygen Plasma treatment on the cleaned and dried ITO surface of the cathode substrate;
step 3, spin-coating a ZnO solution doped with GHK-Cu on the ITO surface treated in the step 2, and then annealing to prepare an electron transmission layer;
step 4, spin coating on the surface of the electron transport layer to prepare an active layer;
step 5, evaporating a hole transport layer MoO on the surface of the active layer 3 ；
Step 6, evaporating an anode layer Ag on the surface of the hole transport layer;
and (4) obtaining the organic solar cell taking the ZnO film doped with the GHK-Cu as the electron transport layer after the steps are finished.
Example 1
The organic solar cell device in this example, which uses a 0.03wt% ghk-Cu-doped ZnO thin film as an electron transport layer, has the following structure:
ITO/ZnO&0.03wt％GHK-Cu/PBDB-T:ITIC/MoO 3/ Ag。
the above organic solar cell using the ZnO thin film doped with 0.03wt% GHK-Cu as the electron transport layer was prepared by the following process:
step 1, sequentially carrying out ultrasonic cleaning for 20 minutes by using liquid detergent, deionized water, acetone, absolute ethyl alcohol and isopropanol respectively; then drying in a vacuum drying oven at 80 ℃;
step 2, carrying out plasma surface treatment on the surface of the cleaned and dried cathode substrate (ITO) for 13 minutes, wherein the treatment method utilizes the strong oxidizing property of ozone generated under microwave to clean residual organic matters and the like on the surface of the ITO, and simultaneously can improve the oxygen vacancy on the surface of the ITO and improve the work function of the surface of the ITO;
step 3, spin-coating a blend solution of GHK-Cu and ZnO on the ITO surface treated in the step 2:
1) And preparing a GHK-Cu solution: dissolving GHK-Cu powder in glycol methyl ether solution, magnetically stirring for 1 hour, adding ethanolamine, and continuously stirring for 12 hours to obtain the required GHK-Cu solution. Ethanolamine as a stabilizer; in the GHK-Cu solution, the volume fraction of ethanolamine is 2.8%, and the mass concentration of GHK-Cu powder is 3mg/ml.
2) And preparing a ZnO solution: dissolving zinc acetate in ethylene glycol monomethyl ether, magnetically stirring for 1 hour, adding ethanolamine, and stirring at room temperature for 12 hours to obtain the ZnO solution. The mass volume ratio of the zinc acetate to the ethylene glycol monomethyl ether is 1:9g/ml. In the ZnO solution, the volume fraction of ethanolamine was 2.8%.
3) And blending the prepared GHK-Cu solution with a ZnO solution. Wherein the weight of the GHK-Cu solution is 0.03wt% of that of the ZnO solution, and the GHK-Cu solution is magnetically stirred for 2 hours. Spin-coating the blend solution of GHK-Cu solution and ZnO solution on the surface of the treated cathode substrate at 4000rpm for 40s and 30nm; and annealing the cathode substrate which is coated with the indium tin oxide in a spinning way at the temperature of 200 ℃ for 60 minutes.
Step 4, spin-coating an active layer solution on the surface of the electron transport layer; the active layer is PBDB-T/ITIC. The preparation process of the active layer comprises the following steps: dissolving PBDB-T and ITIC in chlorobenzene, wherein the mass ratio of PBDB-T to ITIC is 1, the mass volume ratio of PBDB-T to chlorobenzene is 10:1mg/ml; stirring for 1 hr, adding 5 μ l of 1, 8-diiodo-zinc alkane (DIO), and stirring for 12 hr; carrying out plasma surface treatment on the surface of the annealed electron transport layer for 14 minutes; finally, spin-coating an active layer solution on the surface of the electron transport layer at the rotating speed of 2500rpm for 40s, wherein the thickness of the active layer is 100nm; after the active layer is spin-coated, the active layer is placed in a glove box for self-assembly for 6 hours, and then annealing treatment is carried out for 7 minutes at 120 ℃;
step 5, evaporating a hole transport layer MoO on the surface of the active layer 3 With a thickness of
Figure BDA0002840121870000091
Step 6, evaporating an anode layer Ag on the surface of the hole transport layer, wherein the thickness of the anode layer Ag is
Figure BDA0002840121870000092
After the above steps were completed, an organic solar cell having ZnO doped with 0.03wt% GHK-Cu as an electron transport layer was obtained.
Comparative example
The comparative example was prepared under substantially the same conditions as in example 1, except that the electron transport layer was ZnO without doping with GHK — Cu.
Example 2
The organic solar cell device in this example, which uses ZnO doped with 0.05wt% ghk-Cu as an electron transport layer, has the following structure:
ITO/ZnO&0.05wt％GHK-Cu/PBDB-T:ITIC/MoO 3 and/Ag. Symbol&Meaning doping.
The preparation process of the organic solar cell taking the ZnO thin film doped with 0.05wt% of GHK-Cu as the electron transport layer comprises the following steps:
step 1, sequentially carrying out ultrasonic cleaning for 20 minutes by using liquid detergent, deionized water, acetone, absolute ethyl alcohol and isopropanol respectively; then drying in a vacuum drying oven at 80 ℃;
step 2, carrying out plasma surface treatment on the surface of the cleaned and dried cathode substrate (ITO) for 13 minutes, wherein the treatment method utilizes the strong oxidizing property of ozone generated under microwave to clean residual organic matters and the like on the surface of the ITO, and simultaneously can improve the oxygen vacancy on the surface of the ITO and improve the work function of the surface of the ITO;
step 3, spin-coating a blend solution of GHK-Cu and ZnO on the ITO surface treated in the step 2:
1) And preparing a GHK-Cu solution: and dissolving the upper GHK-Cu powder in an ethylene glycol monomethyl ether solution, magnetically stirring for 1 hour, adding ethanolamine, and continuously stirring for 12 hours to obtain the required GHK-Cu solution. Ethanolamine is used as a stabilizer, the volume fraction of ethanolamine in the GHK-Cu solution is 2.8%, and the mass concentration of GHK-Cu powder is 3mg/ml.
2) And preparing a ZnO solution: dissolving zinc acetate in ethylene glycol monomethyl ether, magnetically stirring for 1 hour, adding ethanolamine, and stirring at room temperature for 12 hours to obtain the ZnO solution. The mass volume ratio of the zinc acetate to the ethylene glycol monomethyl ether is 1:9g/ml. In the ZnO solution, the volume fraction of ethanolamine was 2.8%.
3) And blending the prepared GHK-Cu solution with a ZnO solution. Wherein the weight of the GHK-Cu solution is 0.05wt% of that of the ZnO solution, and the GHK-Cu solution is magnetically stirred for 2 hours. Spin-coating the blend solution of GHK-Cu solution and ZnO solution on the surface of the treated cathode substrate at 4000rpm for 40s and 30nm; and annealing the cathode substrate which is coated with ZnO in a spinning way at the temperature of 200 ℃ for 60 minutes.
Step 4, spin-coating an active layer solution on the surface of the electron transport layer; the active layer is PBDB-T/ITIC. The preparation process of the active layer comprises the following steps: dissolving PBDB-T and ITIC in chlorobenzene, wherein the mass ratio of PBDB-T to ITIC is 1, the mass volume ratio of PBDB-T to chlorobenzene is 10:1mg/ml; stirring for 1 hour, adding 5 μ l of 1, 8-diiodo-zinc alkane (DIO), and stirring for 12 hours; carrying out plasma surface treatment on the surface of the annealed electron transport layer for 14 minutes; finally, spin-coating an active layer solution on the surface of the electron transport layer at the rotating speed of 2500r.p.m for 40s, wherein the thickness of the active layer is about 100nm; after the active layer is subjected to spin coating, the active layer is placed in a glove box for self-assembly for 6 hours, and then annealing treatment is carried out for 7min at 120 ℃;
step 5, evaporating a hole transport layer MoO on the surface of the active layer 3 With a thickness of
Figure BDA0002840121870000111
Step 6, evaporating an anode layer Ag on the surface of the hole transport layer, wherein the thickness of the anode layer Ag is
Figure BDA0002840121870000112
After the above steps were completed, an organic solar cell having ZnO doped with 0.05wt% GHK-Cu as an electron transport layer was obtained.
Example 3
The organic solar cell device in this example, which had ZnO doped with 0.1wt% GHK-Cu as an electron transport layer, had the following structure:
ITO/ZnO&0.1wt％GHK-Cu/PBDB-T:ITIC/MoO 3 and/Ag. Symbol(s)&Meaning doping.
The above process flow for preparing an organic solar cell having ZnO doped with 0.1wt% GHK-Cu as an electron transporting layer is as follows:
step 1, ultrasonic cleaning is sequentially carried out for 20 minutes by using liquid detergent, deionized water, acetone, absolute ethyl alcohol and isopropanol respectively; then drying in a vacuum drying oven at 80 ℃;
step 2, carrying out plasma surface treatment on the surface of the cleaned and dried cathode substrate (ITO) for 13 minutes, wherein the treatment method utilizes the strong oxidizing property of ozone generated under microwave to clean residual organic matters and the like on the surface of the ITO, and simultaneously can improve the oxygen vacancy on the surface of the ITO and improve the work function of the surface of the ITO;
step 3, spin-coating a blend solution of GHK-Cu and ZnO on the ITO surface treated in the step 2:
1) And preparing a GHK-Cu solution: and dissolving the upper GHK-Cu powder in an ethylene glycol monomethyl ether solution, magnetically stirring for 1 hour, adding ethanolamine, and continuously stirring for 12 hours to obtain the required GHK-Cu solution. Ethanolamine is used as a stabilizer, and in the GHK-Cu solution, the volume fraction of ethanolamine is 2.8%, and the mass concentration of GHK-Cu powder is 1mg/ml.
2) And preparing a ZnO solution. Dissolving zinc acetate in ethylene glycol monomethyl ether, magnetically stirring for 1 hour, adding ethanolamine, and stirring at room temperature for 12 hours to obtain the ZnO solution. The mass volume ratio of the zinc acetate to the ethylene glycol monomethyl ether is 1:9g/ml. In the ZnO solution, the volume fraction of ethanolamine was 2.8%.
3) And blending the prepared GHK-Cu solution and the ZnO solution. Wherein the weight of the GHK-Cu solution is 0.1wt% of that of the ZnO solution, and the GHK-Cu solution is magnetically stirred for 2 hours. Spin-coating the mixed solution of GHK-Cu solution and ZnO solution on the surface of the treated cathode substrate at 4000r.p.m for 40s and thickness of 30nm; and annealing the cathode substrate which is coated with the indium tin oxide in a spinning way at the temperature of 200 ℃ for 60 minutes.
Step 4, spin-coating an active layer solution on the surface of the electron transport layer; the active layer is PBDB-T/ITIC. The preparation process of the active layer comprises the following steps: dissolving PBDB-T and ITIC in chlorobenzene, wherein the mass ratio of PBDB-T to ITIC is 1, the mass volume ratio of PBDB-T to chlorobenzene is 10:1mg/ml; stirring for 1 hour, adding 5 μ l of 1, 8-diiodo-zinc alkane (DIO), and stirring for 12 hours; carrying out plasma surface treatment on the surface of the annealed electron transport layer for 14 minutes; finally, spin-coating an active layer solution on the surface of the electron transport layer at the rotating speed of 2500r.p.m for 40s, wherein the thickness of the active layer is about 100nm; after the active layer is subjected to spin coating, the active layer is placed in a glove box for self-assembly for 6 hours, and then annealing treatment is carried out for 7 minutes at 120 ℃;
step 5, evaporating a hole transport layer MoO on the surface of the active layer 3 With a thickness of
Figure BDA0002840121870000131
Step 6, evaporating an anode layer Ag on the surface of the hole transport layer, wherein the thickness of the anode layer Ag is
Figure BDA0002840121870000132
And obtaining the organic solar cell with the ZnO doped with the GHK-Cu as the electron transport layer after the steps are finished.
Example 4
The organic solar cell device in this example, which had ZnO doped with 0.3wt% GHK-Cu as an electron transport layer, had a structure of:
ITO/ZnO&0.3wt％GHK-Cu/PBDB-T:ITIC/MoO 3 and/Ag. Symbol&Meaning doping.
The process flow of the preparation process of the organic solar cell taking ZnO doped with 0.3wt% GHK-Cu as the electron transport layer is as follows:
step 1, ultrasonic cleaning is sequentially carried out for 20 minutes by using liquid detergent, deionized water, acetone, absolute ethyl alcohol and isopropanol respectively; then drying in a vacuum drying oven at 80 ℃;
step 2, carrying out plasma surface treatment on the surface of the cleaned and dried cathode substrate (ITO) for 13 minutes, wherein the treatment method utilizes the strong oxidizing property of ozone generated under microwave to clean residual organic matters and the like on the surface of the ITO, and simultaneously can improve the oxygen vacancy on the surface of the ITO and improve the work function of the surface of the ITO;
step 3, spin-coating a blend solution of GHK-Cu and ZnO on the ITO surface treated in the step 2:
1) And preparing a GHK-Cu solution: and dissolving the upper GHK-Cu powder in an ethylene glycol monomethyl ether solution, magnetically stirring for 1 hour, adding ethanolamine, and continuously stirring for 12 hours to obtain the required GHK-Cu solution. Ethanolamine is used as a stabilizer, and in the GHK-Cu solution, the volume fraction of ethanolamine is 2.8%, and the mass concentration of GHK-Cu powder is 3mg/ml.
2) And preparing a ZnO solution: dissolving zinc acetate in ethylene glycol monomethyl ether, magnetically stirring for 1 hour, adding ethanolamine, and stirring at room temperature for 12 hours to obtain the ZnO solution. The mass volume ratio of the zinc acetate to the ethylene glycol monomethyl ether is 1:9g/ml. In the ZnO solution, the volume fraction of ethanolamine was 2.8%.
3) And blending the prepared GHK-Cu solution with a ZnO solution. Wherein the weight of the GHK-Cu solution is 0.3wt% of that of the ZnO solution, and the GHK-Cu solution is magnetically stirred for 2 hours. Spin-coating the blend solution of GHK-Cu solution and ZnO solution on the surface of the treated cathode substrate at 4000rpm for 40s and 30nm; and annealing the cathode substrate which is spin-coated with ZnO at 200 ℃ for 60 minutes.
Step 4, spin-coating an active layer solution on the surface of the electron transport layer; the active layer is PBDB-T/ITIC. The preparation process of the active layer comprises the following steps: dissolving PBDB-T and ITIC in chlorobenzene, wherein the mass ratio of PBDB-T to ITIC is 1, and the mass volume ratio of PBDB-T to chlorobenzene is 10 mg/ml; stirring for 1 hr, adding 5 μ l of 1, 8-diiodo-zinc alkane (DIO), and stirring for 12 hr; carrying out plasma surface treatment on the surface of the annealed electron transport layer for 14 minutes; finally, spin-coating an active layer solution on the surface of the electron transport layer, wherein the rotating speed is 2500rpm, the time is 40s, and the thickness of the active layer is about 100nm; after the active layer is subjected to spin coating, the active layer is placed in a glove box for self-assembly for 6 hours, and then annealing treatment is carried out for 7 minutes at 120 ℃;
step 5, evaporating a hole transport layer MoO on the surface of the active layer 3 With a thickness of
Figure BDA0002840121870000141
Step 6, evaporating an anode layer Ag on the surface of the hole transport layer, wherein the thickness of the anode layer Ag is
Figure BDA0002840121870000142
And (4) obtaining the organic solar cell taking the ZnO doped with the GHK-Cu as the electron transport layer after the steps are finished. As shown in fig. 3, current density-voltage (J-V) characteristics of IPSC were measured using a computer controlled Keithley 2400 source table under illumination calibrated to AM 1.5G (100 mW/cm 2), and the parameter pairs for the organic solar cells prepared in examples 1-4 and comparative example are shown in table 1.
TABLE 1 comparison of the parameters of examples 1-4 with comparative examples
Figure BDA0002840121870000151
From Table 1 and FIG. 3, it can be found that the short-circuit current density of example 1 is from 16.91mA/cm 2 The temperature is increased to 18.33mA/cm 2 The open circuit voltage and the fill factor are slightly improved compared with the comparative example, and the same is true for the example 2 and the example 3, so that the final photoelectric conversion efficiency is improved by 10.48 percent compared with the comparative example. The organic solar cell using 0.1wt% of GHK-Cu-doped ZnO as the electron transport layer has a higher transport ability for carriers, and thus the energy conversion efficiency of the organic solar cell using 0.1wt% of GHK-Cu-doped ZnO as the electron transport layer is improved as compared with the organic solar cell using ZnO as the electron transport layer.
To understand the effect of the incorporation of GHK-Cu in ZnO on the extraction efficiency of photo-generated carriers in ETL, PL test was performed on the sample (where the steady-state photoluminescence spectrum (PL) of the composite film was measured with an auto-spectrofluorometer (SPEX 1681) with an excitation wavelength of 340 nm) and the sample had mainly three emission peaks as shown in fig. 4. The two emission peaks in the blue region are mainly due to the defects on the surface of the ZnO electron transport layer, the surface defects of ZnO can cause the generation of deep energy level, and electrons on the deep energy level can generate blue-green fluorescence with longer wavelength after being excited and transited to a valence band. The GHK-Cu is doped into ZnO, so that the photoluminescence intensity of defects can be obviously reduced, and the charge transfer rate is improved. The ultraviolet region has an emission peak, the fluorescence comes from intrinsic exciton recombination of ZnO, and the stronger the fluorescence intensity of the region is, the higher the crystallization quality of the nano-particle is, the exciton separation is promoted; the sample ZnO &0.03wt% GHK-Cu has obviously higher fluorescence intensity at the position than ZnO, and the fact that the ZnO is doped with GHK-Cu proves that the crystallization quality of ZnO nanoparticles can be effectively improved. Therefore, znO doped with 0.1wt% GHK-Cu is an electron transport layer, which can increase the open circuit voltage and fill factor of the organic solar cell slightly more than the comparative examples. The open circuit voltage and fill factor of the organic solar cell in example 4 are reduced compared to the comparative example because GHK-Cu can absorb visible light, thereby limiting the absorption of light by the active layer. Furthermore, znO doping with GHK-Cu resulted in a blue shift in defect peak positions, with defect peaks for ZnO at 426nm and 470.5nm, while sample ZnO &0.1wt% GHK-Cu resulted in defect peaks at 423.5nm and 460 nm. This is because the doping of GHK — Cu causes an increase in the carrier concentration in the thin film, so that the fermi level enters the conduction band, the fermi level is in the conduction band and the band gap width is increased, resulting in the morse-boolean effect.
To further understand the reasons for the performance variation of a solar cell device, the present invention addresses ITO/ZnO/Ag or ITO/(ZnO)&0.1wt% GHK-Cu)/Ag device was subjected to I-V characteristic test under light condition. According to FIG. 5, the DC conductivity σ 0 Equation I = σ may be used 0 Ad -1 V is estimated from the slope of the I-V plot. Wherein d is the film thickness (30 nm), A is the effective area of the sample (0.16 cm) 2 ). Sample ZnO (the ITO/ZnO/Ag device) and ZnO&0.1wt% GHK-Cu (the ITO/(ZnO))&0.1wt% GHK-Cu)/Ag device) of the substratePermeability of 2.10X 10 -4 Sm -1 、 3.00×10 -4 Sm -1 。
In conclusion, the ZnO is doped with a proper amount of GHK-Cu, so that the photoelectric conversion efficiency of the organic solar cell can be effectively improved. The GHK-Cu doped ZnO can passivate the surface defects of ZnO, so that the conductivity of the film is improved, the crystallization quality of the device and the concentration of free carriers can be effectively improved, and the performance of the organic solar cell is optimized. In addition, the method uses the solution to spin-coat the blending solution of GHK-Cu and ZnO, and the selected solution has higher safety and is more environment-friendly and convenient.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.

Claims (8)

1. An organic solar cell taking a ZnO film doped with a biological material GHK-Cu as an electron transport layer is characterized by comprising a cathode substrate, the electron transport layer, an active layer, a hole transport layer and an anode layer which are sequentially stacked; the cathode substrate is indium tin oxide glass; the electron transmission layer is a ZnO film doped with GHK-Cu, and the thickness of the electron transmission layer is 20-30nm; the active layer is made of PBDB-T: the thickness of the active layer is 100-120nm; the hole transport layer is MoO 3 The thickness of the hole transport layer is
Figure FDA0003715838020000011
The anode layer is silver and has a thickness of
Figure FDA0003715838020000012
2. The preparation method of the organic solar cell which takes the ZnO film doped with the biological material GHK-Cu as the electron transmission layer as claimed in claim 1 is characterized by comprising the following steps:
(1) Cleaning a cathode substrate, and carrying out surface oxygen Plasma treatment on the surface of the cathode substrate to obtain a surface-treated cathode substrate;
(2) Blending the GHK-Cu solution and the ZnO solution, and uniformly mixing to obtain a co-mixed solution; spin-coating the blended solution on the cathode substrate with the surface treated in the step (1), and annealing to obtain an electron transport layer, wherein the preparation of the GHK-Cu solution comprises the following steps: dissolving GHK-Cu powder in ethylene glycol monomethyl ether, carrying out primary stirring treatment, then adding ethanolamine, and carrying out secondary stirring treatment to obtain a GHK-Cu solution; the time of the first stirring treatment is 1-2 hours, and the time of the second stirring treatment is 12-13 hours; in the GHK-Cu solution, the concentration of the GHK-Cu is 1-5mg/mL, and the volume percentage concentration of the ethanolamine is 2.8% -3%;
(3) And (3) spin-coating an active layer on the electron transport layer in the step (2), and then evaporating a hole transport layer and an anode layer on the active layer to obtain the organic solar cell taking the ZnO thin film doped with the biological material GHK-Cu as the electron transport layer.
3. The method as claimed in claim 2, wherein the step (1) of cleaning the cathode substrate comprises: sequentially carrying out ultrasonic cleaning on the cathode substrate by using liquid detergent, deionized water, acetone, absolute ethyl alcohol and isopropanol for 15-20 minutes respectively, and then drying under the vacuum condition of 80-90 ℃ to obtain the cleaned cathode substrate; the time of the surface oxygen Plasma treatment is 13 to 15 minutes.
4. The method for preparing an organic solar cell using a ZnO thin film doped with a biomaterial GHK-Cu as an electron transport layer according to claim 2, wherein the preparing of the ZnO solution in the step (2) comprises: dissolving zinc acetate in an ethylene glycol monomethyl ether solvent, carrying out primary stirring treatment, then adding ethanolamine, and carrying out secondary stirring treatment to obtain a ZnO solution; the time of the first stirring treatment is 1-2 hours, and the time of the second stirring treatment is 11-13 hours; the mass volume ratio of the zinc acetate to the ethylene glycol monomethyl ether solvent is 1:0.8-1g/mL; in the ZnO solution, the volume percentage concentration of the ethanolamine is 2.6-3%.
5. The method for preparing an organic solar cell using a ZnO thin film doped with a biological material GHK-Cu as an electron transport layer according to claim 2, wherein the GHK-Cu solution in the step (2) has a mass of 0.03wt% to 0.3wt% of the mass of the ZnO solution.
6. The method for preparing an organic solar cell with a ZnO film doped with a biological material GHK-Cu as an electron transport layer according to claim 2, wherein the spin coating speed of the blend solution in the step (2) is 4000-5000rpm, and the spin coating time of the blend solution is 30-50s; the temperature of the annealing treatment is 180-220 ℃, and the time of the annealing treatment is 60-80 minutes.
7. The method as claimed in claim 2, wherein the step (3) of preparing the active layer comprises: PBDB-T and ITIC are dissolved in chlorobenzene for primary stirring treatment, and after 1, 8-diiodo zinc alkyl is added, secondary stirring treatment is carried out to obtain an active layer solution; carrying out plasma surface treatment on the surface of the electron transport layer; spin coating an active layer solution on the surface of the electron transport layer; and after the active layer is subjected to spin coating, placing the active layer in a glove box for self-assembly treatment and annealing treatment to obtain the active layer.
8. The method for preparing an organic solar cell with the ZnO thin film doped with the biological material GHK-Cu as the electron transport layer as claimed in claim 7, wherein the mass ratio of PBDB-T to ITIC is 0.8-1.2; the mass volume ratio of the PBDB-T to chlorobenzene is 8-12:1mg/ml; the time of the first stirring treatment is 40-80min, and the time of the second stirring treatment is 12-24 hours; the volume ratio of the 1, 8-diiodo-zinc alkane to the chlorobenzene is 99-100; the plasma surface treatment time is 13-15 minutes; the rotating speed of the active layer solution spin-coated on the surface of the electron transport layer is 2000-3000rpm, and the time of the active layer solution spin-coated on the surface of the electron transport layer is 30-50s; the self-assembly time is 5-7 hours; the temperature of the annealing treatment is 120-130 ℃, and the time of the annealing treatment is 7-10 minutes.
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