CN113130763B - Inverted organic solar cell with double hole transport layers deposited based on solution method and preparation method thereof - Google Patents

Inverted organic solar cell with double hole transport layers deposited based on solution method and preparation method thereof Download PDF

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CN113130763B
CN113130763B CN202110309159.1A CN202110309159A CN113130763B CN 113130763 B CN113130763 B CN 113130763B CN 202110309159 A CN202110309159 A CN 202110309159A CN 113130763 B CN113130763 B CN 113130763B
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王磊
韦拢
叶轩立
陈震
张桂传
薛启帆
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South China University of Technology SCUT
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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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    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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Abstract

The invention discloses a flip organic solar cell with a double hole transport layer deposited based on a solution method and a preparation method thereof. The flip organic solar cell comprises a transparent conductive substrate, an electron transport layer, an active layer, a double-hole transport layer and a metal electrode layer which are sequentially arranged from bottom to top; wherein the double hole transport layer comprises PEDOT: PSS layer, and deposited on PEDOT: a NiOx layer on the PSS layer. The invention relates to a method for preparing a compound of PEDOT: and (3) modifying the PSS solution, spin-coating the modified PSS solution on an organic active layer to form a film, and then spin-coating the diluted NiOx nano-particle solution on a PEDOT: the double-hole transport layer (PEDOT: PSS layer + NiOx layer) is obtained on the PSS layer, the double-hole transport layer is prepared by a solution method, the organic solar cell is more suitable for large-area printing production in the future, and the flip organic solar cell adopting the double-hole transport layer has higher energy conversion efficiency.

Description

Inverted organic solar cell with double hole transport layers deposited based on solution method and preparation method thereof
Technical Field
The invention relates to the technical field of organic photoelectric devices, in particular to a flip organic solar cell with a double-hole transport layer deposited based on a solution method and a preparation method thereof.
Background
With the gradual depletion of non-renewable energy and the continuous increase of human energy demand, energy problems become more and more the objects of human attention, and clean renewable energy also becomes an important part for solving the energy problems. Solar energy is an environment-friendly renewable energy source, and can be converted into usable electric energy through a solar cell, compared with the traditional silicon-based solar cell, the organic solar cell has the advantages of light weight, solution processability, translucency and the like, and can be prepared into a flexible large-area solar cell, so that the organic solar cell has wider application field and more profound development prospect. At present, the maximum efficiency of a single organic solar cell can reach more than 18%, and the organic solar cell is hopefully developed further, so that the industrial production of the organic solar cell is realized.
Most of the existing high-efficiency organic solar cells stay in a laboratory preparation stage, and the process for preparing the organic solar cells by a solution processing method is not mature, so that the preparation cost of the organic solar cells is still higher, the preparation procedures are more complex, and the development and the application of the organic solar cells are hindered. Currently, PEDOT: PSS as a hole transport layer is in direct contact with ITO, whereas PEDOT: PSS is acidic and can corrode ITO to affect the stability of the device, and in order to make up for the lack of stability, flip-chip devices are often fabricated. However, in the flip-chip structure adopted by the organic solar cell, since PEDOT: PSS is an aqueous solution, which cannot be spread to form a film on an oily organic active layer. Therefore, PEDOT was developed: PSS is an excellent hole transport layer material, enables film formation on an organic active layer, and provides a solution-processable hole transport layer preparation scheme with good performance.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a flip-chip organic solar cell with a double hole transport layer deposited based on a solution method and a preparation method thereof. The invention mainly solves the problem of preparing the hole transport layer by a solution method, optimizes the hole transport layer and enables the battery to keep higher energy conversion efficiency.
The purpose of the invention is realized by the following technical scheme.
A flip organic solar cell with a double-hole transport layer deposited based on a solution method comprises a transparent conductive substrate, an electron transport layer, an active layer, the double-hole transport layer and a metal electrode layer which are sequentially arranged from bottom to top; wherein the double hole transport layer comprises PEDOT: PSS layer, and deposited on PEDOT: NiOx layer on the PSS layer.
Preferably, the transparent conductive substrate is a conductive glass sheet covered by ITO;
preferably, the electron transport layer is a ZnO layer, and the thickness of the electron transport layer is 30-40 nm;
preferably, the active layer is a mixture of a donor material PBDB-T-2F and an acceptor material BTP-eC9, the thickness is 100-110nm, and the mass ratio of the donor material to the acceptor material is 1: 1.2-1.3;
preferably, the PEDOT: the thickness of the PSS layer is 10-12 nm;
preferably, the thickness of the NiOx layer is 3-6 nm;
preferably, the metal electrode layer is silver and has a thickness of 100-120 nm.
The preparation method of the flip-chip organic solar cell based on the solution method for depositing the double-hole-transport-layer comprises the following steps:
(1) cleaning and drying the transparent conductive substrate;
(2) spin-coating the electron transport material precursor solution on a transparent conductive substrate at the rotation speed of 3000-;
(3) dissolving an active layer material in chlorobenzene, stirring for 8-10 hours at 50-70 ℃ and at a stirring speed of 150-;
(4) spinning modified PEDOT on the active layer: PSS solution, the rotating speed is 2500-: a PSS layer;
(5) in the PEDOT: the NiOx nano-particle solution is spin-coated on the PSS layer to form a NiOx layer, the rotating speed is 2500-; and then carrying out high-temperature annealing to obtain a NiOx layer, PEDOT: the PSS layer and the NiOx layer form a double-hole transmission layer;
(6) and evaporating silver on the NiOx layer to form a metal electrode layer.
Preferably, the precursor liquid of the electron transport material in the step (2) is a ZnO precursor liquid; further preferably, the preparation method of the ZnO precursor solution comprises the following steps: dissolving zinc acetate particles in a monomethyl ether solution, and then adding ethanolamine, wherein the ratio of zinc acetate to monomethyl ether to ethanolamine is 1: 9-11: 0.276-0.280 (g: mL: mL), and then stirring at the normal temperature for 12-16 hours at the stirring speed of 150-. More preferably, the ratio of the zinc acetate, the monomethyl ether and the ethanolamine is 1: 10: 0.276-0.280 (g: mL: mL).
Preferably, the concentration of the active layer material in the active layer material solution in the step (3) is 17.5-18 mg/mL.
Preferably, the modified PEDOT of step (4): the preparation method of the PSS solution comprises the following steps: and (3) mixing PEDOT: and (3) mixing PSS and isopropanol, performing ultrasonic dispersion for 15-20min, adding n-butanol, and continuing performing ultrasonic dispersion for 15-20min to obtain modified PEDOT: PSS solution.
Further preferably, the PEDOT: the volume ratio of PSS, isopropanol and n-butanol is 1: 1.5-2.5: 0.5-1.5; the PEDOT: PSS is Clevios P VP AI 4083. More preferably, the PEDOT: the volume ratio of PSS, isopropanol and n-butanol is 1: 2: 1.
preferably, the preparation method of the NiOx nanoparticle solution in the step (5) comprises the following steps: mixing Ni (NO) 3 ) 2 ·6H 2 Dispersing O in water, adding NaOH solution, adjusting the pH value of the solution to 9-11, stirring, washing with deionized water, drying and calcining to obtain black NiOx powder; dispersing the NiOx in an ethanol solution, and performing ultrasonic dispersion for 8-10 hours to obtain a NiOx solution; and mixing the NiOx solution and the isopropanol solution according to a certain proportion, and performing ultrasonic dispersion for 2-5 hours to obtain a diluted NiOx nano-particle solution with the concentration range of 3.5-7.5 mg/mL.
Further preferably, the Ni (NO) 3 ) 2 ·6H 2 The molar volume ratio of O to water is 0.5-1.5: 200 mol/mL; the concentration of the NaOH solution is 9-11 mol/L; the stirring time is 5-10 min; washing with deionized water for 2-5 times; the drying temperature is 80-100 ℃, and the drying time is 6-8 hours; the calcining temperature is 240-300 ℃, and the time is 1-3 hours; the mass-volume ratio of the black NiOx powder to the ethanol is 13-17: 1 mg/ml; adjusting the pH value of the solution to 10, and performing ultrasonic treatmentThe wave dispersion time was 2 hours. More preferably, the Ni (NO) 3 ) 2 ·6H 2 The molar volume ratio of O to water is 1: 200 mol/mL; the concentration of the NaOH solution is 10 mol/L; the stirring time is 5 min; the calcining temperature is 270 ℃, and the calcining time is 2 hours; the mass volume ratio of the black NiOx powder to the ethanol is 15: 1 mg/ml.
Preferably, the temperature of the high-temperature annealing in the step (5) is 110-120 ℃, and the time of the high-temperature annealing is 10-15 minutes.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention relates to a method for preparing a compound by mixing PEDOT: and (3) mixing the PSS with isopropanol and n-butanol in sequence to prepare modified PEDOT: PSS solution, modified PEDOT: the PSS solution can form a uniform thin film on the organic active layer, so that a hole transport layer can be prepared on the active layer by adopting a solution spin coating method.
The invention adopts modified PEDOT: PSS is used for preparing a hole transport layer, and a NiOx layer is additionally added to the hole transport layer, and the thickness of the NiOx layer is equal to that of PEDOT: the PSS layer forms a double-hole transport layer, so that the open-circuit voltage and the energy conversion efficiency of the prepared battery are improved.
Drawings
Fig. 1 is a schematic structural diagram of a flip-chip organic solar cell device with a double hole transport layer deposited by a solution method according to embodiments 1 to 3 (1 is a substrate, 2 is a transparent conductive layer, 3 is an electron transport layer, 4 is an active layer, 5 is a PEDOT: PSS layer, 6 is a NiOx layer, and 7 is a silver electrode).
Fig. 2 is a schematic diagram of the structure of a flip-chip organic solar cell device provided in comparative examples 1-2, in which a hole transport layer (PEDOT: PSS layer or NiOx layer) is deposited based on a solution method (1 is a substrate, 2 is a transparent conductive layer, 3 is an electron transport layer, 4 is an active layer, 5 is a PEDOT: PSS layer (corresponding to comparative example 1) or a NiOx layer (corresponding to comparative example 2), and 6 is a silver electrode).
Fig. 3 is a current density-voltage characteristic curve diagram of the flip-chip organic solar cells provided in examples 1 to 3 and comparative examples 1 to 2.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following specific examples, but the scope and implementation of the present invention are not limited thereto.
Example 1
(1) Ultrasonically cleaning the ITO-covered glass substrate by using a detergent, deionized water and isopropanol in sequence, and then drying the glass substrate in an oven for later use;
(2) dissolving 1.0g of zinc acetate in 10mL of monomethyl ether solution, adding 276 g of ethanolamine solution, stirring at room temperature at 200 rpm for 12 hours, and spin-coating the obtained ZnO precursor solution on an ITO layer as an electron transport layer at the rotating speed of 3000rpm and the thickness of 30 nm; then annealing for 60min at 200 ℃;
(3) the donor material PBDB-T-2F and the acceptor material BTP-eC9 were mixed according to the following ratio of 1: 1.2, dissolving in chlorobenzene, stirring at 60 ℃ and a stirring speed of 200 r/min for 10 hours to prepare a mixture solution of PBDB-T-2F and BTP-eC9, wherein the concentration of the mixture is 17.6 mg/mL;
(4) spin-coating the mixture solution on a ZnO layer at 2000 rpm, and annealing at 100 deg.C for 10min to obtain an active layer with a thickness of 100 nm;
(5) 100 μ L of PEDOT: PSS (Clevios P VP AI 4083) and 200 mu L of isopropanol are mixed and ultrasonically dispersed for 20min, then 100 mu L of n-butanol is added, and the ultrasonic dispersion is continued for 20min, so that the modified PEDOT: PSS solution is ready for use;
(6) spin-coating modified PEDOT on the active layer: PSS solution, spin speed 2500rpm, spin time 30s, to yield 10nm PEDOT: a PSS layer;
(7) mixing Ni (NO) 3 ) 2 ·6H 2 O (0.5mol) is dispersed in 100mL of deionized water to obtain a dark green solution; then adding 10mol/L NaOH solution, adjusting the pH value of the solution to 10, stirring for 5min, thoroughly washing twice with deionized water, drying for 6 hours at 80 ℃ to obtain dark green powder, and calcining for 2 hours at 270 ℃ to obtain black NiOx powder; the mixture is mixed with a stirring liquid of 15: 1 (mg: mL) in ethanol solution, and ultrasonically dispersing for 9 hours to obtain 15mg/mL NiOx solution;
(8)15mg/mL NiOx solution with isopropanol solution at a ratio of 1: 1, obtaining a diluted NiOx nano-particle solution of 7.5 mg/mL;
(9) in the PEDOT: spin-coating 7.5mg/mL diluted NiOx nanoparticle solution on the PSS layer to obtain a NiOx layer with the thickness of about 6nm, wherein the rotating speed is 3000rpm, the spin-coating time is 30s, and then annealing at 120 ℃ for 10 min;
(10) silver was deposited on the NiOx layer to a thickness of 100nm as an electrode. The structure of the resulting flip-chip organic solar cell device is shown in fig. 1.
Example 2
(1) Ultrasonically cleaning the ITO-covered glass substrate by using a detergent, deionized water and isopropanol in sequence, and then drying the glass substrate in an oven for later use;
(2) dissolving 1.0g of zinc acetate in 10mL of monomethyl ether solution, adding 276 mu l of ethanolamine solution, stirring at room temperature for 12 hours at 200 revolutions per minute, and spin-coating the obtained ZnO precursor solution on an ITO layer as an electron transport layer at the rotation speed of 3000rpm and the thickness of 30 nm; then annealing for 60min at 200 ℃;
(3) the donor material PBDB-T-2F and the acceptor material BTP-eC9 were mixed according to the following ratio of 1: 1.2, dissolving in chlorobenzene, stirring at 60 ℃ and a stirring speed of 200 r/min for 10 hours to prepare a mixture solution of PBDB-T-2F and BTP-eC9, wherein the concentration of the mixture is 17.6 mg/mL;
(4) spin-coating the mixture solution on a ZnO layer at 2000 rpm, and annealing at 100 deg.C for 10min to obtain an active layer with a thickness of 100 nm;
(5) 100 μ L of PEDOT: PSS (4083) and 200 mu L of isopropanol are mixed and ultrasonically dispersed for 20min, then 100 mu L of n-butanol is added, and the ultrasonic dispersion is continued for 20min, so that the modified PEDOT: PSS solution is ready for use;
(6) spin-coating modified PEDOT on the active layer: PSS solution, spin speed 2500rpm, spin time 30s, to yield 10nm PEDOT: a PSS layer;
(7) mixing Ni (NO) 3 ) 2 ·6H 2 O (0.5mol) is dispersed in 100mL of deionized water to obtain a dark green solution; then adding 10mol/L NaOH solution, adjusting the pH of the solution to 10, stirring for 5min, thoroughly washing twice with deionized water, and drying at 80 deg.CDrying for 6 hours to obtain dark green powder, and calcining for 2 hours at 270 ℃ to obtain black NiOx powder; mixing the raw materials in a ratio of 15: 1 (mg: mL) in ethanol solution, and ultrasonically dispersing for 9 hours to obtain 15mg/mL NiOx solution;
(8)15mg/mL NiOx solution with isopropanol solution at a ratio of 1: 2, obtaining a diluted NiOx nano-particle solution of 5 mg/mL;
(9) in the PEDOT: spin-coating 5mg/mL diluted NiOx nanoparticle solution on the PSS layer to obtain a NiOx layer with the thickness of about 4nm, wherein the rotating speed is 3000rpm, the spin-coating time is 30s, and then annealing at 120 ℃ for 10 min;
(10) silver was deposited on the NiOx layer to a thickness of 100nm as an electrode. The structure of the resulting flip-chip organic solar cell device is shown in fig. 1.
Example 3
(1) Ultrasonically cleaning the ITO-covered glass substrate by using a detergent, deionized water and isopropanol in sequence, and then drying the glass substrate in an oven for later use;
(2) dissolving 1.0g of zinc acetate in 10mL of monomethyl ether solution, adding 276 mu l of ethanolamine solution, stirring at room temperature at 200 rpm for 12 hours, and spin-coating the obtained ZnO precursor solution on an ITO layer as an electron transport layer at the rotating speed of 3000rpm and the thickness of 30 nm; then annealing for 60min at 200 ℃;
(3) the donor material PBDB-T-2F and the acceptor material BTP-eC9 were mixed according to the following ratio of 1: 1.2, dissolving in chlorobenzene, stirring at 60 ℃ and a stirring speed of 200 r/min for 10 hours to prepare a mixture solution of PBDB-T-2F and BTP-eC9, wherein the concentration of the mixture is 17.6 mg/mL;
(4) spin-coating the mixture solution on a ZnO layer at 2000 rpm, and annealing at 100 deg.C for 10min to obtain an active layer with a thickness of 100 nm;
(5) 100 μ L of PEDOT: PSS (Clevios P VP AI 4083) and 200 mu L of isopropanol are mixed and ultrasonically dispersed for 20min, then 100 mu L of n-butanol is added, and the ultrasonic dispersion is continued for 20min, so that the modified PEDOT: PSS solution is ready for use;
(6) spin-coating modified PEDOT on the active layer: PSS solution, spin speed 2500rpm, spin time 30s, to yield 10nm PEDOT: a PSS layer;
(7) mixing Ni (NO) 3 ) 2 ·6H 2 O (0.5mol) is dispersed in 100mL of deionized water to obtain a dark green solution; then adding 10mol/L NaOH solution, adjusting the pH value of the solution to 10, stirring for 5min, thoroughly washing twice with deionized water, drying for 6 hours at 80 ℃ to obtain dark green powder, and calcining for 2 hours at 270 ℃ to obtain black NiOx powder; the mixture is mixed with a stirring liquid of 15: 1 (mg: mL) in ethanol solution, and ultrasonically dispersing for 9 hours to obtain 15mg/mL NiOx solution;
(8)15mg/mL NiOx solution with isopropanol solution at a ratio of 1: 3, obtaining diluted NiOx nano-particle solution of 3.75 mg/mL;
(9) in the PEDOT: 3.75mg/mL diluted NiOx nano-particle solution is spin-coated on the PSS layer to obtain a NiOx layer with the thickness of about 3nm, the rotating speed is 3000rpm, the spin-coating time is 30s, and then annealing is carried out for 10min at 120 ℃;
(10) silver was deposited on the NiOx layer to a thickness of 100nm as an electrode. The structure of the resulting flip-chip organic solar cell device is shown in fig. 1.
Comparative example 1
(1) Ultrasonically cleaning the ITO-covered glass substrate by using a detergent, deionized water and isopropanol in sequence, and then drying the glass substrate in an oven for later use;
(2) dissolving 1.0g of zinc acetate in 10mL of monomethyl ether solution, adding 276 mu l of ethanolamine solution, stirring at room temperature at 200 rpm for 12 hours, and spin-coating the obtained ZnO precursor solution on an ITO layer as an electron transport layer at the rotating speed of 3000rpm and the thickness of 30 nm; then annealing for 60min at 200 ℃;
(3) the donor material PBDB-T-2F and the acceptor material BTP-eC9 are mixed according to the proportion of 1: 1.2, dissolving in chlorobenzene, stirring at 60 ℃ and a stirring speed of 200 r/min for 10 hours to prepare a mixture solution of PBDB-T-2F and BTP-eC9, wherein the concentration of the mixture is 17.6 mg/mL;
(4) spin-coating the mixture solution on a ZnO layer at 2000 rpm, and annealing at 100 deg.C for 10min to obtain an active layer with a thickness of 100 nm;
(5) 100 μ L of PEDOT: PSS (Clevios P VP AI 4083) and 200 mu L of isopropanol are mixed and ultrasonically dispersed for 20min, then 100 mu L of n-butanol is added, and the ultrasonic dispersion is continued for 20min, so that the modified PEDOT: PSS solution is ready for use;
(6) spin-coating modified PEDOT on the active layer: PSS solution, spin speed 2500rpm, spin time 30s, to yield 10nm PEDOT: a PSS layer;
(7) in the PEDOT: silver with a thickness of 100nm was vapor-deposited on the PSS layer as an electrode. The structure of the resulting flip-chip organic solar cell device is shown in fig. 2.
Comparative example 2
(1) Ultrasonically cleaning the ITO-covered glass substrate by using a detergent, deionized water and isopropanol in sequence, and then drying the glass substrate in an oven for later use;
(2) dissolving 1.0g of zinc acetate in 10mL of monomethyl ether solution, adding 276 mu l of ethanolamine solution, stirring at room temperature for 12 hours at 200 revolutions per minute, and spin-coating the obtained ZnO precursor solution on an ITO layer as an electron transport layer at the rotation speed of 3000rpm and the thickness of 30 nm; then annealing for 60min at 200 ℃;
(3) the donor material PBDB-T-2F and the acceptor material BTP-eC9 were mixed according to the following ratio of 1: 1.2, dissolving in chlorobenzene, stirring at 60 ℃ and a stirring speed of 200 r/min for 10 hours to prepare a mixture solution of PBDB-T-2F and BTP-eC9, wherein the concentration of the mixture is 17.6 mg/mL;
(4) spin-coating the mixture solution on a ZnO layer at 2000 rpm, and annealing at 100 deg.C for 10min to obtain an active layer with a thickness of 100 nm;
(5) mixing Ni (NO) 3 ) 2 ·6H 2 O (0.5mol) is dispersed in 100mL of deionized water to obtain a dark green solution; then adding 10mol/L NaOH solution, adjusting the pH value of the solution to 10, stirring for 5min, thoroughly washing twice with deionized water, drying for 6 hours at 80 ℃ to obtain dark green powder, and calcining for 2 hours at 270 ℃ to obtain black NiOx powder; the mixture is mixed with a stirring liquid of 15: 1 (mg: mL) in ethanol solution, and ultrasonically dispersing for 9 hours to obtain 15mg/mL NiOx solution;
(6)15mg/mL NiOx solution with isopropanol solution at a ratio of 1: 2, obtaining a diluted NiOx nano-particle solution of 5 mg/mL;
(7) spin-coating 5mg/mL diluted NiOx nanoparticle solution on the active layer to obtain a NiOx layer with about 4nm, wherein the rotation speed is 3000rpm, the spin-coating time is 30s, and then annealing at 120 ℃ for 10 min;
(8) silver was deposited on the NiOx layer to a thickness of 100nm as an electrode. The structure of the resulting flip-chip organic solar cell device is shown in fig. 2.
Example 4
The flip-chip organic solar cell devices of examples 1 to 3 and comparative examples 1 to 2 were tested by a solar analog lamp device system (manufactured by taiwan light edge science and technology limited, china) respectively, and the obtained device performance data are shown in table 1:
TABLE 1
Figure BDA0002988952080000121
From table 1, it can be seen that the PEDOT: PSS/NiOx double hole transport layer was formed by deposition such that the efficiency of the solar cell was greater than 14%, and the solar cell efficiency was up to 15.05% when the NiOx nanoparticle solution concentration was (5mg/ml) (as in example 2). By comparing single-layer PEDOT PSS and PEDOT PSS/NiOx double-hole transport layers, the PEDOT PSS/NiOx double-hole transport layers can remarkably improve voltage and keep higher current, and therefore energy conversion efficiency of the solar cell is improved.
In order to illustrate the technical effects of the present invention, examples 1 to 3 provided a flip-chip organic solar cell with a double hole transport layer deposited based on a solution method to perform a test of photoelectric conversion efficiency performance, and comparative examples 1 to 2 provided an organic solar cell to perform a performance test, as shown in fig. 3. FIG. 3 is a graph of current density versus voltage curves for examples 1-3 and comparative examples 1-2.
From examples 1 to 3, in example 2, when the concentration of the NiOx nanoparticle solution is 5mg/mL, the performance of the prepared organic solar cell is optimal, and the thickness of the NiOx layer is about 4 nm. As can be seen from fig. 3, the NiOx layer alone in comparative example 2 did not have a good effect as a hole transport layer, mainly because the NiOx layer alone had a poor film-forming effect and hole transport properties, resulting in a lower Jsc of the cell; comparative example 1 provided a solar cell that was not superior in performance to example 2, and taken together with all examples, using the modified PEDOT of the present invention: the PSS can be used as a good hole transport layer, but the problem of large voltage loss still exists, and the addition of the NiOx layer with the thickness of 4nm can enhance the collection and transport of holes and the blocking effect of electrons, so that the energy conversion efficiency of the solar cell is improved. And too high concentration NiOx nano particle solution can cause thicker spin-coated NiOx layer and worse photoelectric property, and the organic solar cell with the best performance can be obtained by regulating the thickness of the NiOx layer.
Although the embodiments of the present invention have been shown and described above, it should not be construed that the present invention is limited thereto, and those skilled in the art can make variations, modifications, substitutions and alterations to the above embodiments within the scope of the present invention.

Claims (8)

1. A flip organic solar cell with a double-hole transport layer deposited based on a solution method is characterized by comprising a transparent conductive substrate, an electron transport layer, an active layer, the double-hole transport layer and a metal electrode layer which are sequentially arranged from bottom to top; wherein the double hole transport layer comprises PEDOT: PSS layer, and deposited on PEDOT: a NiOx layer on the PSS layer; the PEDOT: the thickness of the PSS layer is 10-12nm, and the thickness of the NiOx layer is 3-6 nm;
the PEDOT: PSS layer modified PEDOT: obtaining a PSS solution;
the modified PEDOT: the preparation method of the PSS solution comprises the following steps: and (3) mixing PEDOT: and (3) mixing PSS and isopropanol, performing ultrasonic dispersion for 15-20min, adding n-butanol, and continuing performing ultrasonic dispersion for 15-20min to obtain modified PEDOT: a PSS solution; the PEDOT: the volume ratio of PSS, isopropanol and n-butanol is 1: 1.5-2.5: 0.5-1.5;
the NiOx layer is formed by depositing a layer of NiOx on a substrate at PEDOT: the PSS layer is obtained by spin-coating a NiOx nano-particle solution;
the NiOx nanoparticlesThe preparation method of the solution comprises the following steps: mixing Ni (NO) 3 ) 2 ·6H 2 Dispersing O in water, adding NaOH solution, adjusting the pH value of the solution to 9-11, stirring, washing with deionized water, drying and calcining to obtain black NiOx powder; dispersing the NiOx in an ethanol solution, and performing ultrasonic dispersion for 8-10 hours to obtain a NiOx solution; and mixing the NiOx solution with the isopropanol solution, and performing ultrasonic dispersion for 2-5 hours to obtain a diluted NiOx nanoparticle solution with the concentration range of 3.5-7.5 mg/mL.
2. The flip-chip organic solar cell based on the solution method for depositing the double hole transport layer according to claim 1, wherein the ratio of PEDOT: PSS is Clevios P VP AI 4083.
3. The flip-chip organic solar cell based on solution deposition of double hole transport layer according to claim 1, characterized in that the Ni (NO) is 3 ) 2 ·6H 2 The molar volume ratio of O to water is 0.5-1.5: 200 mol/mL; the concentration of the NaOH solution is 9-11 mol/L; the stirring time is 5-10 min; washing with deionized water for 2-5 times; the drying temperature is 80-100 ℃, and the drying time is 6-8 hours; the calcining temperature is 240-300 ℃, and the time is 1-3 hours; the mass-volume ratio of the black NiOx powder to the ethanol is 13-17: 1 mg/ml.
4. The flip-chip organic solar cell based on the solution method for depositing a double hole transport layer according to claim 1, wherein the transparent conductive substrate is an ITO coated conductive glass sheet; the electron transmission layer is a ZnO layer with the thickness of 30-40 nm; the active layer is a mixture of a donor material PBDB-T-2F and an acceptor material BTP-eC9, the thickness is 100-110nm, and the mass ratio of the donor material to the acceptor material is 1: 1.2-1.3; the PEDOT: PSS layer modified PEDOT: and (4) obtaining the PSS solution.
5. The method for preparing a flip-chip organic solar cell based on the solution method for depositing the double hole transport layer according to any one of claims 1 to 4, is characterized by comprising the following steps:
cleaning and drying the transparent conductive substrate;
spin-coating the electron transport material precursor solution on a transparent conductive substrate at the rotation speed of 3000-;
dissolving an active layer material in chlorobenzene, stirring for 8-10 hours at 50-70 ℃ and at a stirring speed of 150-;
spin-coating modified PEDOT on the active layer: PSS solution, the rotating speed is 2500-: a PSS layer;
in the PEDOT: the NiOx nano-particle solution is spin-coated on the PSS layer to form a NiOx layer, the rotating speed is 2500-; and then carrying out high-temperature annealing to obtain a NiOx layer, PEDOT: the PSS layer and the NiOx layer form a double-hole transmission layer;
and evaporating silver on the NiOx layer to form a metal electrode layer.
6. The preparation method of the flip-chip organic solar cell based on the solution method for depositing the double hole transport layer is characterized in that the electron transport material precursor solution in the step (2) is a ZnO precursor solution; the preparation method of the ZnO precursor solution comprises the following steps: dissolving zinc acetate particles in a monomethyl ether solution, and then adding ethanolamine, wherein the ratio of zinc acetate to monomethyl ether to ethanolamine is 1: 9-11: 0.276-0.280 g: mL: mL, and then stirring at the normal temperature for 12-16 hours at the stirring speed of 150-200 rpm.
7. The method for preparing the flip-chip organic solar cell based on the solution method for depositing the double hole transport layer according to the claim 5, wherein the concentration of the active layer mixed material in the solution of the active layer material in the step (3) is 17.5-18 mg/mL.
8. The method as claimed in claim 5, wherein the temperature of the high temperature annealing in step (5) is 110-120 ℃, and the time of the high temperature annealing is 10-15 minutes.
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