CN116801691A - Electrode-interface layer composite structure with network body contact, preparation method and application thereof - Google Patents
Electrode-interface layer composite structure with network body contact, preparation method and application thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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Abstract
The invention discloses a network-contacting electrode-interface layer composite structure, a preparation method and application thereof. The preparation method of the electrode-interface layer composite structure comprises the following steps: providing a metal nanowire network, wherein the metal nanowire network is arranged on the active layer; and injecting the fluid interface buffer layer material from the top of the metal nanowire network serving as the top electrode, so that the interface layer forms a through structure in the metal nanowire network, and an electrode-interface layer composite structure in which the interface layer is in contact with the metal nanowire network is constructed. The preparation method provided by the invention utilizes the characteristic of the wired network accumulation of the metal nanowire, improves the contact between the metal nanowire and the interface buffer layer by a simple method of injecting the interface buffer layer, has sufficient contact area, can form better interface contact, greatly reduces interface contact resistance, improves the charge extraction capacity of the top electrode of the metal nanowire, and has strong practicability.
Description
Technical Field
The invention relates to a photoelectric device, in particular to an electrode-interface layer composite structure with network-shaped body contact and a preparation method thereof, and a photoelectric device based on the electrode-interface layer composite structure, belonging to the technical field of photoelectric semiconductor materials and devices.
Background
Organic solar cells are receiving wide attention in the field of new generation photovoltaic cells due to their advantages of flexibility, light weight, color richness, suitability for roll-to-roll processes, etc. Along with the continuous development of organic semiconductor photoelectric materials and the continuous development of interface engineering, the photoelectric conversion efficiency of the organic solar cell exceeds 18%, and the organic semiconductor photoelectric material has good application prospect.
Typical organic solar cells are prepared from a blend of photoactive layers of donor and acceptor components sandwiched between two electrodes (cathode and anode) and corresponding interfacial buffer layers. During the preparation process, each functional layer is deposited layer by layer. The bottom electrode is usually a prefabricated patterned electrode such as ITO or FTO, the electron transport layer is made of ZnO, tiO2 or other metal oxides, the photoactive layer is formed by blending and depositing a donor-acceptor material, and finally the MoO3 hole transport layer and the metal top electrode Al are evaporated. In the commercialization of organic solar cells, large-area fabrication of the cells is a fundamental requirement. However, the MoO3 hole transport layer and the metal top electrode are prepared by adopting vacuum evaporation, so that the material utilization rate is low and the energy consumption is high. Compared with the method, the organic solar cell is prepared by adopting a solution method printing process, and large-area continuous production of the organic solar cell can be realized. For the existing organic solar cell technology, the solution processing of the top electrode has great significance in the process of preparing the organic solar cell by the printing technology because the pre-prepared patterned electrode adopted by the bottom electrode, and the electron transport layer, the photoactive layer and the hole transport layer are all subjected to solution processing.
Currently, the top electrodes prepared by the common solution method are of the following types: 1. polymer PEDOT: PSS top electrode; 2. a carbon material top electrode such as graphene, carbon nanotubes, etc.; 3. metal nanoparticles/wire top electrodes, such as Ag, cu nanoparticles, and Ag, cu nanowires, etc.
In practical applications, the conductivity of the top electrode has a great influence on the cell performance. In the top electrode prepared by the above solution method, polymer PEDOT: the PSS top electrode typically requires a protonation treatment with a strong acid to increase its conductivity. However, the electrode has poor stability. In addition, the conductivity of the top electrode of carbon materials such as graphene, carbon nanotubes, etc. is still low. In contrast, metal nano-particles/wire top electrodes have great advantages in terms of conductivity due to their metal-based material properties. However, the metal nanoparticle top electrode generally needs to be sintered at a high temperature to obtain good conductivity, and the metal nanowire can be used for preparing the thin film photovoltaic top electrode at a lower temperature, so that the metal nanoparticle top electrode has a great application prospect.
However, the metal nanowire is a one-dimensional material, in the preparation process of the top electrode, the contact between the metal nanowire and the interface buffer layer is line/surface contact, and a plane contact mode is adopted, so that the effective contact area at the interface of the contact mode is smaller, and large contact resistance is caused, and the charge extraction capability of the high-conductivity metal nanowire top electrode cannot be fully exerted because the nanowire is a one-dimensional material with a large length-diameter ratio and the stacking direction of the one-dimensional material is random.
Disclosure of Invention
The invention mainly aims to provide an electrode-interface layer composite structure with a network-shaped body in contact and a preparation method thereof, so as to overcome the defects of the prior art.
It is also an object of the present invention to provide the use of the electrode-interfacial layer composite structure in contact with the network.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of an electrode-interface layer composite structure with a network-shaped body in contact, which comprises the following steps:
providing a metal nanowire network, wherein the metal nanowire network is arranged on the active layer;
providing a material comprising a fluid interface buffer layer;
and injecting the fluid interface buffer layer material from the top of the metal nanowire network serving as the top electrode, so that the interface layer forms a through structure in the metal nanowire network, and an electrode-interface layer composite structure in which the interface layer is in contact with the metal nanowire network is constructed.
Wherein the interface layer comprises a hole transport layer or an electron transport layer in the photoelectric device.
In some embodiments, the fluid interface buffer layer material includes polymers, metal oxide particles, sol-gel precursors, and the like.
The embodiment of the invention also provides an electrode-interface layer composite structure with the network body in contact, which is prepared by the method.
The embodiment of the invention also provides an optoelectronic device, which comprises the electrode-interface layer composite structure with the network-shaped body contacted.
Further, the photovoltaic device may be an organic solar cell, a perovskite solar cell, or the like, but is not limited thereto.
Compared with the prior art, the invention has the beneficial effects that:
1) The preparation method of the electrode-interface layer composite structure with the network-shaped body contact, provided by the invention, utilizes the characteristic of the networking accumulation of the metal nanowire, improves the contact between the metal nanowire and the interface buffer layer by a simple injection method of the interface buffer layer, has a sufficient contact area, can form better interface contact, greatly reduces the interface contact resistance, and improves the charge extraction capacity of the top electrode of the metal nanowire;
2) The preparation method is suitable for modification of various interface buffer layers on the metal nanowire electrode, is compatible with various solution processing methods, and has strong practicability.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is a schematic plan view of a process for preparing a network-contacting electrode-interfacial layer composite structure in accordance with an exemplary embodiment of the present application;
FIG. 2 is a schematic cross-sectional view of a process for preparing a network-contacting electrode-interfacial layer composite structure in accordance with an exemplary embodiment of the present application;
FIG. 3 is a bulk contact structure (ITO/ZnO/PM 6:Y 6/AgNWs-MoO) in example 1 of the present application x ) IV curve of organic solar cell and IV curve of cell contacted with reference sample plane;
FIG. 4 shows the bulk contact structure (ITO/ZnO/PM 6:Y 6/AgNWs-NiO) in example 2 of the present application x ) IV curve of organic solar cell and IV curve of cell contacted with reference sample plane.
Detailed Description
In view of the shortcomings of the prior art, the inventor of the present application has provided a technical scheme through long-term research and a great deal of practice, mainly according to the characteristics of metal nanowire network chemical accumulation and a certain gap in the middle of a network, a longitudinal network-shaped interface buffer layer is constructed by adopting a method of injecting interface buffer layer ink through the top of a metal nanowire by adopting fluid interface buffer layer materials such as polymers, metal oxide particles, sol-gel and the like, the interface buffer layer is filled in the metal nanowire, a through structure is formed, and an interface layer is also formed at the bottom of the metal nanowire network. The electrode-interface layer structure with the network-shaped body contact increases the contact between the metal nanowire and the interface buffer layer, and improves the charge extraction capacity of the top electrode of the metal nanowire.
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The preparation method of the electrode-interface layer composite structure with the network-shaped body contact provided by one aspect of the embodiment of the invention comprises the following steps:
providing a metal nanowire network, wherein the metal nanowire network is arranged on the active layer;
providing a material comprising a fluid interface buffer layer;
and injecting the fluid interface buffer layer material from the top of the metal nanowire network serving as the top electrode, so that the interface layer forms a through structure in the metal nanowire network, and an electrode-interface layer composite structure in which the interface layer is in contact with the metal nanowire network is constructed.
In some embodiments, the interfacial layer may be a hole transport layer, an electron transport layer, and the like in an optoelectronic device, such as a solar cell.
In some embodiments, the fluid interface buffer layer material comprises an ink comprising an interface buffer layer material, the ink comprising a fluid interface buffer layer material and a solvent.
Wherein the concentration of the ink is different for different fluid interface buffer layer materials. For example, moO x The concentration of the ink is 2-10 mg/ml; the concentration of PCBM ink is 10-20 mg/ml.
Wherein the solvent includes water and/or alcohol, and the alcohol includes any one or a combination of two or more of alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, etc., but is not limited thereto.
In some implementations, the fluid interface buffer layer material includes polymers, metal oxide particles, sol-gel precursors, and the like. The material of the fluid interface buffer layer is the same as that of the hole transport layer or the electron transport layer. When the electron transport layer or the hole transport layer is a polymer, the injected fluid interface buffer layer material is the polymer; when the electron transport layer or the hole transport layer is metal oxide particles, the injected fluid interface buffer layer material is the metal oxide particles.
In some embodiments, the metal nanowires contained in the metal nanowire network include any one or a combination of a plurality of silver nanowires, copper nanowires, and the like, but are not limited thereto.
Further, the diameter of the metal nanowire contained in the metal nanowire network is 10 nm-100 nm, and the length is 10 mu m-100 mu m. Preferably, the diameter of the metal nanowire is 30 nm-50 nm, and the length is 30 μm-50 μm.
In some embodiments, the metal nanowire network is formed using any one of spin coating, spray coating, inkjet printing, doctor blading, slot die coating, and the like.
In some embodiments, the interfacial layer is formed by any one of spin coating, spray coating, ink jet printing, blade coating, slot coating, and the like, i.e., the method of filling the interfacial layer includes spin coating, spray coating, ink jet printing, blade coating, slot coating, and the like.
In some more specific embodiments, the principle of the preparation process of the electrode-interface layer structure of the silver nanowire electrode contacted with the network-shaped body of the transmission layer provided by the invention can be briefly expressed as follows in fig. 1 and fig. 2:
1. injecting ink containing interface buffer layer material into the metal nanowire electrode network to construct a structure of contact between the interface layer and the metal nanowire network;
2. and forming the organic or perovskite solar cell by utilizing the metal nanowire wrapped by the network-shaped interface buffer layer.
In another aspect of the invention, there is provided a network-contacting electrode-interfacial layer composite structure prepared by the foregoing method. The thickness of the electrode-interface layer composite structure is basically consistent with that of the silver nanowire, and the electrode-interface layer composite structure is formed by filling a fluid interface buffer layer material which is the same as the material of the electron/hole transport layer in a metal nanowire network.
Compared with the prior structure that the metal nanowire is in plane contact with the interface layer, the nanowire is a one-dimensional material with a large length-diameter ratio, the stacking direction of the one-dimensional material is random, and the effective contact area at the interface is small by adopting a plane contact mode, so that large contact resistance is caused. And the metal nanowire and the interface buffer layer have sufficient contact area through the contact, so that better interface contact can be formed, and interface contact resistance is greatly reduced.
Another aspect of the present invention also provides an optoelectronic device based on such an electrode-interface layer composite structure, comprising the electrode-interface layer composite structure in contact with the network.
Further, the photovoltaic device may be an organic solar cell, a perovskite solar cell, or the like, but is not limited thereto.
Specifically, for a perovskite battery, the structure of the positive battery sequentially comprises: bottom electrode/electron transport layer/perovskite layer/network contact electrode-interface composite structure (the interface is a hole transport layer material, such as MoO 3 NiO, etc.); the inverted structure is as follows: bottom electrode/hole transport layer/perovskite layer/network contact electrode-interface composite structure (the interface is electron transport layer material, such as SnO 2 ZnO, etc.).
For an organic solar cell, the structure of the positive cell is as follows: bottom electrode/hole transport layer/photoactive layer/network contact electrode-interface composite structure (the interface is electron transport layer material such as ZnO, PFN-Br, etc.); the inverted structure is as follows: bottom electrode/electron transport layer/photoactive layer/network contact electrode-interface composite structure (the interface is a hole transport layer material, such as MoO 3 PEDOT: PSS, etc.).
Furthermore, the preparation method is suitable for modification of various interface buffer layers on the metal nanowire electrode, is compatible with various solution processing methods, and has strong practicability.
The technical solution of the present invention will be further described with reference to the accompanying drawings and several preferred embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are merely illustrative of the present invention, and the experimental conditions and setting parameters thereof should not be construed as limiting the basic technical scheme of the present invention. And the scope of the present invention is not limited to the following examples. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Example 1
AgNWS-MoO based x A method for preparing a network electrode with body contact and a device thereof:
ITO/ZnO/PM6：Y6/AgNWs-MoO x inverted structure organic solar cell, wherein AgNWs-MoO x MoO with bulk contact electrode-interface layer structure x Is a hole transport layer material, and comprises the following specific steps:
firstly, sequentially using a detergent, deionized water, acetone and isopropanol to ultrasonically clean a substrate formed by a transparent substrate and an Indium Tin Oxide (ITO) transparent conductive bottom electrode, wherein the cleaning time is 30min each time, and then using nitrogen to blow dry, and then using a UVO ozone cleaner to treat the substrate for 30min;
and preparing an electron transport layer on the bottom electrode: the ethanol dispersion of ZnO nano-particles adopts a spin coating method, a ZnO film with the thickness of 30nm is spin-coated on the bottom electrode, the spin coating rotating speed is 3000rpm, and the ZnO film is dried for 10min at 130 ℃;
preparation of the organic active layer: the organic active layer is prepared by mixing and dissolving an electron donor PM6 and an electron acceptor Y6 in chloroform, wherein the mass percent of PM6 and Y6 is 1:1.2, the concentration of PM6 is 7mg/mL, and then chloronaphthalene with the volume percent of 0.5% of the volume of chloroform is added into the mixed solution as an additive, and the solution is stirred for 3 hours for standby. Spin-coating the mixed solution of the active layers on the surface of the electron transport layer to obtain an organic active layer film, annealing at 100deg.C for 10min, wherein the active area of the battery active layer is 0.0625cm 2 ；
Preparation of the top electrode: adopting a mode of spraying AgNWs, and spraying and depositing an AgNWs top electrode with the thickness of 200nm on the organic active layer;
preparation of interface layer hole transport layer: collectingMoO prepared by spin coating method x A hole transport layer, wherein MoO x The ink concentration was 10mg/mL. MoO is carried out x The ink drops on the AgNWs electrode, and spin coating to obtain MoO x A hole transport layer spin coated at 3000rpm; based on the above, agNWs-MoO is obtained x Is a bulk contact electrode-interfacial layer structure. The organic solar cell of the system is prepared.
For the preparation of the battery with the electrode-interface layer 'line-surface' contact structure, moO is firstly deposited on the active layer x Hole transport layer, followed by MoO x And depositing an AgNWs electrode on the hole transport layer to obtain the target device. The preparation process of each functional layer is the same.
In FIG. 3, I-V curves of an electro-organic solar cell prepared based on different electrode-interfacial layers, which are hole transport layers, are shown, from which it is known that AgNWs-MoO is based on bulk contact x The organic solar cell with the electrode-interface layer structure has optimal performance. Specific battery performance parameters are listed in table 1.
TABLE 1 inverted organic solar cell Performance with different electrode-interface contact structures
Example 2
AgNWS-NiO-based x A method for preparing a network electrode in body contact and a device thereof:
ITO/ZnO/PM6：Y6/AgNWs-NiO x inverted structure organic solar cell wherein AgNWs-NiO x NiO is in bulk contact electrode-interface layer structure x Is a hole transport layer material, and comprises the following specific steps:
firstly, sequentially using a detergent, deionized water, acetone and isopropanol to ultrasonically clean a substrate formed by a transparent substrate and an Indium Tin Oxide (ITO) transparent conductive bottom electrode, wherein the cleaning time is 30min each time, and then using nitrogen to blow dry, and then using a UVO ozone cleaner to treat the substrate for 30min;
and preparing an electron transport layer on the bottom electrode: the ethanol dispersion of ZnO nano-particles adopts a spin coating method, a ZnO film with the thickness of 30nm is spin-coated on the bottom electrode, the spin coating rotating speed is 3000rpm, and the ZnO film is dried for 10min at 130 ℃;
preparation of the organic active layer: the organic active layer is prepared by mixing and dissolving an electron donor PM6 and an electron acceptor Y6 in chloroform, wherein the mass percent of PM6 and Y6 is 1:1.2, the concentration of PM6 is 7mg/mL, and then chloronaphthalene with the volume percent of 0.5% of the volume of chloroform is added into the mixed solution as an additive, and the solution is stirred for 3 hours for standby. Spin-coating the mixed solution of the active layers on the surface of the electron transport layer to obtain an organic active layer film, annealing at 100deg.C for 10min, wherein the active area of the battery active layer is 0.0625cm 2 ；
Preparation of the top electrode: spin-coating an AgNWs top electrode with the thickness of 200nm on the organic active layer by adopting a spin-coating mode;
preparation of interface layer hole transport layer: niO prepared by adopting spraying method x A hole transport layer, wherein NiO x The ink concentration was 2mg/mL. NiO is sprayed by using spraying equipment x The ink is sprayed on the AgNWs electrode to obtain NiO x A hole transport layer; based on the above, agNWs-NiO is obtained x Is a bulk contact electrode-interfacial layer structure. The organic solar cell of the system is prepared.
For the preparation of the battery with the electrode-interface layer 'line-surface' contact structure, niO is firstly sprayed and deposited on the active layer x Hole transport layer, followed by NiO x And spin-coating and depositing an AgNWs electrode on the hole transport layer to obtain the target device.
In FIG. 4, I-V curves of an electro-organic solar cell prepared based on different electrode-interfacial layers, which are hole transport layers, are shown, from which it is known that AgNWs-NiO is based on bulk contact x The organic solar cell of the electrode-interfacial layer structure performs optimally, and specific cell performance parameters are listed in table 2.
TABLE 2 inverted organic solar cell Performance with different electrode-interface contact structures
Example 3
Based on AgNWs-PEDOT: method for preparing network electrode contacted with PSS and device thereof:
ITO/ZnO/PM6: Y6/AgNWs-PEDOT: PSS cell, wherein AgNWs-PEDOT: PSS is bulk contact electrode-interface layer structure, PEDOT: PSS is a hole transport layer material, and comprises the following specific steps:
firstly, sequentially using a detergent, deionized water, acetone and isopropanol to ultrasonically clean a substrate formed by a transparent substrate and an Indium Tin Oxide (ITO) transparent conductive bottom electrode, wherein the cleaning time is 30min each time, and then using nitrogen to blow dry, and then using a UVO ozone cleaner to treat the substrate for 30min;
and preparing an electron transport layer on the bottom electrode: the ethanol dispersion of ZnO nano-particles adopts a spin coating method, a ZnO film with the thickness of 30nm is spin-coated on the bottom electrode, the spin coating rotating speed is 3000rpm, and the ZnO film is dried for 10min at 130 ℃;
preparation of the organic active layer: the organic active layer is prepared by mixing and dissolving an electron donor PM6 and an electron acceptor Y6 in chloroform, wherein the mass percent of PM6 and Y6 is 1:1.2, the concentration of PM6 is 7mg/mL, and then chloronaphthalene with the volume percent of 0.5% of the volume of chloroform is added into the mixed solution as an additive, and the solution is stirred for 3 hours for standby. Spin-coating the mixed solution of the active layers on the surface of the electron transport layer to obtain an organic active layer film, annealing at 100deg.C for 10min, wherein the active area of the battery active layer is 0.0625cm 2 ；
Preparation of the top electrode: spin-coating an AgNWs top electrode with the thickness of 200nm on the organic active layer by adopting a spin-coating mode;
preparation of interface layer hole transport layer: PEDOT prepared by spin coating: PSS hole transport layer. PEDOT: and (3) PSS is dripped on the AgNWs electrode, and the PEDOT is obtained through spin coating: the PSS hole transport layer is spin-coated at 3000rpm; based on this, agNWs-PEDOT is obtained: PSS is a bulk contact electrode-interfacial layer structure. The organic solar cell of the system is prepared.
For cell preparation of electrode-interface layer "line-side" contact structures, PEDOT is first deposited on the active layer: PSS hole transport layer, then at PEDOT: and spin-coating and depositing an AgNWs electrode on the PSS hole transport layer to obtain the target device. The preparation process of each functional layer is the same, and specific battery performance parameters are listed in table 3.
TABLE 3 different electrode-interface contact Structure inverted organic solar cell Performance
Example 4
Preparation method of network electrode based on AgNWS-ZnO body contact and device thereof:
ITO/MoO x PM6: the Y6/AgNWS-ZnO organic solar cell with a positive structure, wherein AgNWS-ZnO is of a bulk contact electrode-interface layer structure, znO is an electron transport layer material, and the specific steps are as follows:
Firstly, sequentially using a detergent, deionized water, acetone and isopropanol to ultrasonically clean a substrate formed by a transparent substrate and an Indium Tin Oxide (ITO) transparent conductive bottom electrode, wherein the cleaning time is 30min each time, and then using nitrogen to blow dry, and then using a UVO ozone cleaner to treat the substrate for 30min;
preparing a hole transport layer on the bottom electrode: moO (MoO) x Ethanol dispersion of nanoparticles was spin-coated with MoO having a thickness of 20nm on the bottom electrode by spin-coating x The film is dried for 10min at 130 ℃ with the rotating speed of 3000 rpm;
preparation of the organic active layer: the organic active layer is prepared by mixing and dissolving an electron donor PM6 and an electron acceptor Y6 in chloroform, wherein the mass percent of PM6 and Y6 is 1:1.2, the concentration of PM6 is 7mg/mL, and then chloronaphthalene with the volume percent of 0.5% of the volume of chloroform is added into the mixed solution as an additive, and the solution is stirred for 3 hours for standby. Spin-coating the mixed solution of the active layers on the surface of the hole transport layer to obtain an organic active layer film, annealing at 100deg.C for 10min, wherein the active area of the active layer is 0.0625cm 2 ；
Preparation of the top electrode: adopting a mode of spraying AgNWs, and spraying and depositing an AgNWs top electrode with the thickness of 200nm on the organic active layer;
Preparation of an interfacial layer electron transport layer: the ZnO electron transport layer is prepared by adopting a spraying method, wherein the concentration of ZnO ink is 5mg/mL. Spraying ZnO ink on the AgNWs electrode to obtain a ZnO electron transport layer; based on the method, the AgNWS-ZnO bulk contact electrode-interface layer structure is obtained. The organic solar cell of the system is prepared.
And for the preparation of the battery with the electrode-interface layer line-surface contact structure, firstly spraying and depositing a ZnO electron transport layer on the active layer, and then spraying and depositing an AgNWs electrode on the ZnO electron transport layer to obtain the target device. The preparation process of each functional layer was the same, and specific battery performance parameters are listed in table 4.
TABLE 4 different electrode-interface contact Structure Performance of organic solar cells
Example 5
Preparation method of network electrode based on AgNWS-PFN-Br body contact and device thereof:
the present embodiment is based on ITO/PEDOT: PSS/PM6: the Y6/AgNWS-PFN-Br positive structure organic solar cell, wherein AgNWS-PFN-Br is a bulk contact electrode-interface layer structure, PFN-Br is an electron transport layer material, and the specific steps are as follows:
firstly, sequentially using a detergent, deionized water, acetone and isopropanol to ultrasonically clean a substrate formed by a transparent substrate and an Indium Tin Oxide (ITO) transparent conductive bottom electrode, wherein the cleaning time is 30min each time, and then using nitrogen to blow dry, and then using a UVO ozone cleaner to treat the substrate for 30min;
Preparing a hole transport layer on the bottom electrode: hole transport layer PEDOT: PSS spin coating method was used to spin coat PEDOT with a thickness of 20nm on top of the bottom electrode: PSS film is spin-coated at 3000rpm and dried at 130 ℃ for 10min;
preparation of the organic active layer: the organic active layer is composed of electronsAnd (3) mixing and dissolving a donor PM6 and an electron acceptor Y6 in chloroform to prepare active layer ink, wherein the mass percent of the PM6 to the mass percent of the Y6 are 1:1.2, the concentration of the PM6 is 7mg/mL, and then adding chloronaphthalene with the volume percent of 0.5% of the volume of chloroform into the mixed solution as an additive, and stirring the solution for 3 hours for later use. Spin-coating the mixed solution of the active layers on the surface of the hole transport layer to obtain an organic active layer film, annealing at 100deg.C for 10min, wherein the active area of the active layer is 0.0625cm 2 ；
Preparation of the top electrode: adopting a mode of spraying AgNWs, and spraying and depositing an AgNWs top electrode with the thickness of 200nm on the organic active layer;
preparation of an interfacial layer electron transport layer: the PFN-Br electron transport layer is prepared by a doctor blade method, wherein the concentration of PFN-Br ink is 0.5mg/mL, and the dispersing agent is methanol. Dropping PFN-Br ink on the AgNWs electrode, and carrying out blade coating to obtain a PFN-Br electron transport layer; based on the method, agNWs-PFN-Br is obtained as a bulk contact electrode-interface layer structure. The organic solar cell of the system is prepared.
For the preparation of the battery with the electrode-interface layer line-surface contact structure, a PFN-Br electron transport layer is firstly deposited on an active layer by knife coating, and then an AgNWs electrode is deposited on the PFN-Br electron transport layer, so that the target device is obtained. The preparation process of each functional layer was the same, and specific battery performance parameters are listed in table 5.
TABLE 5 Positive organic solar cell Performance for different electrode-interface contact structures
Example 6
AgNWs-NDIB body contact-based network electrode preparation method and device thereof:
the present embodiment is based on ITO/PEDOT: PSS/PM6: the Y6/AgNWS-NDIB positive structure organic solar cell, wherein AgNWS-NDIB is a bulk contact electrode-interface layer structure, NDIB is an electron transport layer material, and the specific steps are as follows:
firstly, sequentially using a detergent, deionized water, acetone and isopropanol to ultrasonically clean a substrate formed by a transparent substrate and an Indium Tin Oxide (ITO) transparent conductive bottom electrode, wherein the cleaning time is 30min each time, and then using nitrogen to blow dry, and then using a UVO ozone cleaner to treat the substrate for 30min;
preparing a hole transport layer on the bottom electrode: hole transport layer PEDOT: PSS spin coating method was used to spin coat PEDOT with a thickness of 20nm on top of the bottom electrode: PSS film is spin-coated at 3000rpm and dried at 130 ℃ for 10min;
Preparation of the organic active layer: the organic active layer is prepared by mixing and dissolving an electron donor PM6 and an electron acceptor Y6 in chloroform, wherein the mass percent of PM6 and Y6 is 1:1.2, the concentration of PM6 is 7mg/mL, and then chloronaphthalene with the volume percent of 0.5% of the volume of chloroform is added into the mixed solution as an additive, and the solution is stirred for 3 hours for standby. Spin-coating the mixed solution of the active layers on the surface of the hole transport layer to obtain an organic active layer film, annealing at 100deg.C for 10min, wherein the active area of the active layer is 0.0625cm 2 ；
Preparation of the top electrode: a AgNWs top electrode with the thickness of 200nm is deposited on the organic active layer in a blade coating mode;
preparation of an interfacial layer electron transport layer: and an NDIB electron transport layer prepared by adopting a spin coating method, wherein the concentration of NDIB ink is 0.5mg/mL, and the dispersing agent is trifluoromethyl alcohol. Dropping NDIB ink on the AgNWs electrode, and spin-coating to obtain an NDIB electron transport layer, wherein the spin-coating rotating speed is 3000rpm; based on the method, the AgNWs-NDIB is a bulk contact electrode-interface layer structure. The organic solar cell of the system is prepared.
For the preparation of the battery with the electrode-interface layer line-surface contact structure, an NDIB electron transport layer is firstly deposited on an active layer, and then an AgNWs electrode is deposited on the NDIB electron transport layer by knife coating, so that the target device is obtained. The preparation process of each functional layer was the same, and specific battery performance parameters are listed in table 6.
TABLE 6 Positive organic solar cell Performance with different electrode-interface contact structures
Example 7
Based on CuNWS-MoO x A method for preparing a network electrode with body contact and a device thereof:
the present embodiment is based on ITO/ZnO/PM6: Y6/CuNWs-MoO x Inverted structure organic solar cell wherein CuNWs-MoO x MoO with bulk contact electrode-interface layer structure x Is a hole transport layer material, and comprises the following specific steps:
firstly, sequentially using a detergent, deionized water, acetone and isopropanol to ultrasonically clean a substrate formed by a transparent substrate and an Indium Tin Oxide (ITO) transparent conductive bottom electrode, wherein the cleaning time is 30min each time, and then using nitrogen to blow dry, and then using a UVO ozone cleaner to treat the substrate for 30min;
and preparing an electron transport layer on the bottom electrode: the ethanol dispersion of ZnO nano-particles adopts a spin coating method, a ZnO film with the thickness of 30nm is spin-coated on the bottom electrode, the spin coating rotating speed is 3000rpm, and the ZnO film is dried for 10min at 130 ℃;
preparation of the organic active layer: the organic active layer is prepared by mixing and dissolving an electron donor PM6 and an electron acceptor Y6 in chloroform, wherein the mass percent of PM6 and Y6 is 1:1.2, the concentration of PM6 is 7mg/mL, and then chloronaphthalene with the volume percent of 0.5% of the volume of chloroform is added into the mixed solution as an additive, and the solution is stirred for 3 hours for standby. Spin-coating the mixed solution of the active layers on the surface of the electron transport layer to obtain an organic active layer film, annealing at 100deg.C for 10min, wherein the active area of the battery active layer is 0.0625cm 2 ；
Preparation of the top electrode: a CuNWs top electrode with the thickness of 200nm is sprayed and deposited on the organic active layer by adopting a mode of spraying the CuNWs;
preparation of interface layer hole transport layer: moO prepared by spin coating method x A hole transport layer, wherein MoO x The ink concentration was 10mg/mL. MoO is carried out x The ink drops on the CuNWs electrode, and spin coating to obtain MoO x A hole transport layer spin coated at 3000rpm; based on this, it is obtainedCuNWs-MoO x Is a bulk contact electrode-interfacial layer structure. The organic solar cell of the system is prepared.
For the preparation of the battery with the electrode-interface layer 'line-surface' contact structure, moO is firstly deposited on the active layer x Hole transport layer, followed by MoO x And depositing a CuNWs electrode on the hole transport layer to obtain the target device. The preparation process of each functional layer was the same, and specific battery performance parameters are listed in table 7.
TABLE 7 inverted organic solar cell Performance with different electrode-interface contact structures
Example 8
Based on CuNWS-NiO x A method for preparing a network electrode with body contact and a device thereof:
the present embodiment is based on ITO/ZnO/PM6: Y6/CuNWs-NiO x Inverted structure organic solar cell wherein CuNWs-NiO x NiO is in bulk contact electrode-interface layer structure x Is a hole transport layer material, and comprises the following specific steps:
Firstly, sequentially using a detergent, deionized water, acetone and isopropanol to ultrasonically clean a substrate formed by a transparent substrate and an Indium Tin Oxide (ITO) transparent conductive bottom electrode, wherein the cleaning time is 30min each time, and then using nitrogen to blow dry, and then using a UVO ozone cleaner to treat the substrate for 30min;
and preparing an electron transport layer on the bottom electrode: the ethanol dispersion of ZnO nano-particles adopts a spin coating method, a ZnO film with the thickness of 30nm is spin-coated on the bottom electrode, the spin coating rotating speed is 3000rpm, and the ZnO film is dried for 10min at 130 ℃;
preparation of the organic active layer: the organic active layer is prepared by mixing and dissolving an electron donor PM6 and an electron acceptor Y6 in chloroform, wherein the mass percent of PM6 and Y6 is 1:1.2, the concentration of PM6 is 7mg/mL, and then chloronaphthalene with the volume percent of 0.5% of the volume of chloroform is added into the mixed solution as an additive, and the solution is stirred for 3 hours for standby. Spin-coating the active layer mixed solution onThe organic active layer film obtained on the surface of the electron transport layer is annealed at 100 ℃ for 10min, and the active area of the battery active layer is 0.0625cm 2 ；
Preparation of the top electrode: spin-coating a layer of CuNWs top electrode with the thickness of 200nm on the organic active layer by adopting a spin-coating mode;
Preparation of interface layer hole transport layer: niO prepared by adopting spraying method x A hole transport layer, wherein NiO x The ink concentration was 2mg/mL. NiO is treated by x The ink is sprayed on the CuNWs electrode to obtain NiO x A hole transport layer; based on the above, cuNWS-NiO is obtained x Is a bulk contact electrode-interfacial layer structure. The organic solar cell of the system is prepared.
For the preparation of the battery with the electrode-interface layer 'line-surface' contact structure, niO is firstly sprayed and deposited on the active layer x Hole transport layer, followed by NiO x And depositing a CuNWs electrode on the hole transport layer to obtain the target device. The preparation process of each functional layer was the same, and specific battery performance parameters are listed in table 8.
TABLE 8 inverted organic solar cell Performance with different electrode-interface contact structures
Example 9
Based on CuNWs-PEDOT: method for preparing network electrode contacted with PSS and device thereof:
the present embodiment is based on ITO/ZnO/PM6: Y6/CuNWs-PEDOT: PSS cell, wherein CuNWs-PEDOT: PSS is bulk contact electrode-interface layer structure, PEDOT: PSS is a hole transport layer material, and comprises the following specific steps:
firstly, sequentially using a detergent, deionized water, acetone and isopropanol to ultrasonically clean a substrate formed by a transparent substrate and an Indium Tin Oxide (ITO) transparent conductive bottom electrode, wherein the cleaning time is 30min each time, and then using nitrogen to blow dry, and then using a UVO ozone cleaner to treat the substrate for 30min;
And preparing an electron transport layer on the bottom electrode: the ethanol dispersion of ZnO nano-particles adopts a spin coating method, a ZnO film with the thickness of 30nm is spin-coated on the bottom electrode, the spin coating rotating speed is 3000rpm, and the ZnO film is dried for 10min at 130 ℃;
preparation of the organic active layer: the organic active layer is prepared by mixing and dissolving an electron donor PM6 and an electron acceptor Y6 in chloroform, wherein the mass percent of PM6 and Y6 is 1:1.2, the concentration of PM6 is 7mg/mL, and then chloronaphthalene with the volume percent of 0.5% of the volume of chloroform is added into the mixed solution as an additive, and the solution is stirred for 3 hours for standby. Spin-coating the mixed solution of the active layers on the surface of the electron transport layer to obtain an organic active layer film, annealing at 100deg.C for 10min, wherein the active area of the battery active layer is 0.0625cm 2 ；
Preparation of the top electrode: spin-coating a layer of CuNWs top electrode with the thickness of 200nm on the organic active layer by adopting a spin-coating mode;
preparation of interface layer hole transport layer: PEDOT prepared by spin coating: PSS hole transport layer. PEDOT: and PSS is dripped on the CuNWs electrode, and the PEDOT is obtained through spin coating: the PSS hole transport layer is spin-coated at 3000rpm; based on the method, cuNWs-PEDOT is obtained: PSS is a bulk contact electrode-interfacial layer structure. The organic solar cell of the system is prepared.
For cell preparation of electrode-interface layer "line-side" contact structures, PEDOT is first deposited on the active layer: PSS hole transport layer, then at PEDOT: and spin-coating and depositing a CuNWs electrode on the PSS hole transport layer to obtain the target device. The preparation process of each functional layer was the same, and specific battery performance parameters are listed in table 9.
TABLE 9 inverted organic solar cell Performance with different electrode-interface contact structures
Example 10
Preparation method of network electrode based on CuNWS-ZnO body contact and device thereof:
the embodiment is based on ITO/MoO x PM6: the Y6/CuNWS-ZnO organic solar cell with a positive structure, wherein the CuNWS-ZnO is of a bulk contact electrode-interface layer structure, and the ZnO is of an electron transport layer material, and the specific steps are as follows:
firstly, sequentially using a detergent, deionized water, acetone and isopropanol to ultrasonically clean a substrate formed by a transparent substrate and an Indium Tin Oxide (ITO) transparent conductive bottom electrode, wherein the cleaning time is 30min each time, and then using nitrogen to blow dry, and then using a UVO ozone cleaner to treat the substrate for 30min;
preparing a hole transport layer on the bottom electrode: moO (MoO) x Ethanol dispersion of nanoparticles was spin-coated with MoO having a thickness of 20nm on the bottom electrode by spin-coating x The film is dried for 10min at 130 ℃ with the rotating speed of 3000 rpm;
Preparation of the organic active layer: the organic active layer is prepared by mixing and dissolving an electron donor PM6 and an electron acceptor Y6 in chloroform, wherein the mass percent of PM6 and Y6 is 1:1.2, the concentration of PM6 is 7mg/mL, and then chloronaphthalene with the volume percent of 0.5% of the volume of chloroform is added into the mixed solution as an additive, and the solution is stirred for 3 hours for standby. Spin-coating the mixed solution of the active layers on the surface of the hole transport layer to obtain an organic active layer film, annealing at 100deg.C for 10min, wherein the active area of the active layer is 0.0625cm 2 ；
Preparation of the top electrode: a CuNWs top electrode with the thickness of 200nm is sprayed and deposited on the organic active layer by adopting a mode of spraying the CuNWs;
preparation of an interfacial layer electron transport layer: the ZnO electron transport layer is prepared by adopting a spraying method, wherein the concentration of ZnO ink is 5mg/mL. Spraying ZnO ink on the CuNWs electrode to obtain a ZnO electron transport layer; based on the method, the CuNWs-ZnO bulk contact electrode-interface layer structure is obtained. The organic solar cell of the system is prepared.
And for the preparation of the battery with the electrode-interface layer line-surface contact structure, firstly spraying and depositing a ZnO electron transport layer on the active layer, and then spraying and depositing a CuNWs electrode on the ZnO electron transport layer to obtain the target device. The preparation process of each functional layer was the same, and specific battery performance parameters are listed in table 10.
TABLE 10 Positive organic solar cell Performance with different electrode-interface contact structures
Example 11
Preparation method of network electrode based on CuNWS-PFN-Br body contact and device thereof:
the present embodiment is based on ITO/PEDOT: PSS/PM6: the Y6/CuNWS-PFN-Br positive structure organic solar cell, wherein CuNWS-PFN-Br is a bulk contact electrode-interface layer structure, PFN-Br is an electron transport layer material, and the specific steps are as follows:
firstly, sequentially using a detergent, deionized water, acetone and isopropanol to ultrasonically clean a substrate formed by a transparent substrate and an Indium Tin Oxide (ITO) transparent conductive bottom electrode, wherein the cleaning time is 30min each time, and then using nitrogen to blow dry, and then using a UVO ozone cleaner to treat the substrate for 30min;
preparing a hole transport layer on the bottom electrode: hole transport layer PEDOT: PSS spin coating method was used to spin coat PEDOT with a thickness of 20nm on top of the bottom electrode: PSS film is spin-coated at 3000rpm and dried at 130 ℃ for 10min;
preparation of the organic active layer: the organic active layer is prepared by mixing and dissolving an electron donor PM6 and an electron acceptor Y6 in chloroform, wherein the mass percent of PM6 and Y6 is 1:1.2, the concentration of PM6 is 7mg/mL, and then chloronaphthalene with the volume percent of 0.5% of the volume of chloroform is added into the mixed solution as an additive, and the solution is stirred for 3 hours for standby. Spin-coating the mixed solution of the active layers on the surface of the hole transport layer to obtain an organic active layer film, annealing at 100deg.C for 10min, wherein the active area of the active layer is 0.0625cm 2 ；
Preparation of the top electrode: a layer of CuNWs top electrode with the thickness of 200nm is deposited on the organic active layer in a knife coating manner;
preparation of an interfacial layer electron transport layer: the PFN-Br electron transport layer is prepared by a doctor blade method, wherein the concentration of PFN-Br ink is 0.5mg/mL, and the dispersing agent is methanol. Dropping PFN-Br ink on the CuNWs electrode, and scraping to obtain a PFN-Br electron transport layer; based on the method, the CuNWs-PFN-Br is a bulk contact electrode-interface layer structure. The organic solar cell of the system is prepared.
For the preparation of the battery with the electrode-interface layer line-surface contact structure, a PFN-Br electron transport layer is firstly deposited on an active layer by knife coating, and then a CuNWs electrode is deposited on the PFN-Br electron transport layer, so that the target device is obtained. The preparation process of each functional layer was the same, and specific battery performance parameters are listed in table 11.
TABLE 11 Positive organic solar cell Performance with different electrode-interface contact structures
Example 12
Preparation method of network electrode based on CuNWs-NDIB body contact and device thereof:
the present embodiment is based on ITO/PEDOT: PSS/PM6: the Y6/CuNWS-NDIB positive structure organic solar cell, wherein the CuNWS-NDIB is of a bulk contact electrode-interface layer structure, and the NDIB is an electron transport layer material, and the specific steps are as follows:
Firstly, sequentially using a detergent, deionized water, acetone and isopropanol to ultrasonically clean a substrate formed by a transparent substrate and an Indium Tin Oxide (ITO) transparent conductive bottom electrode, wherein the cleaning time is 30min each time, and then using nitrogen to blow dry, and then using a UVO ozone cleaner to treat the substrate for 30min;
preparing a hole transport layer on the bottom electrode: hole transport layer PEDOT: PSS spin coating method was used to spin coat PEDOT with a thickness of 20nm on top of the bottom electrode: PSS film is spin-coated at 3000rpm and dried at 130 ℃ for 10min;
preparation of the organic active layer: the organic active layer is prepared by mixing and dissolving an electron donor PM6 and an electron acceptor Y6 in chloroform, wherein the mass percent of PM6 and Y6 is 1:1.2, the concentration of PM6 is 7mg/mL, and then adding chloroform into the mixed solutionChloronaphthalene with the concentration of 0.5% is taken as an additive, and the solution is stirred for 3 hours for standby. Spin-coating the mixed solution of the active layers on the surface of the hole transport layer to obtain an organic active layer film, annealing at 100deg.C for 10min, wherein the active area of the active layer is 0.0625cm 2 ；
Preparation of the top electrode: a layer of CuNWs top electrode with the thickness of 200nm is deposited on the organic active layer in a knife coating manner;
Preparation of an interfacial layer electron transport layer: and the NDIB electron transport layer is prepared by a doctor blade method, wherein the concentration of the NDIB ink is 0.5mg/mL, and the dispersing agent is trifluoromethyl alcohol. Dropping NDIB ink on the CuNWs electrode, and scraping to obtain an NDIB electron transport layer; based on the method, the CuNWs-NDIB is a bulk contact electrode-interface layer structure. The organic solar cell of the system is prepared.
For the preparation of the battery with the electrode-interface layer line-surface contact structure, an NDIB electron transport layer is firstly deposited on an active layer by knife coating, and then a CuNWs electrode is deposited on the NDIB electron transport layer, so that the target device is obtained. The preparation process of each functional layer was the same, and specific battery performance parameters are listed in table 12.
TABLE 12 Positive organic solar cell Performance with different electrode-interface contact structures
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
The various aspects, embodiments, features and examples of the invention are to be considered in all respects as illustrative and not intended to limit the invention, the scope of which is defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
While the invention has been described with reference to an illustrative embodiment, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (10)
1. A method for preparing a network-contacting electrode-interface layer composite structure, comprising the steps of:
providing a metal nanowire network, wherein the metal nanowire network is arranged on the active layer;
providing a material comprising a fluid interface buffer layer;
and injecting the fluid interface buffer layer material from the top of the metal nanowire network serving as the top electrode, so that the interface layer forms a through structure in the metal nanowire network, and an electrode-interface layer composite structure in which the interface layer is in contact with the metal nanowire network is constructed.
2. The method of manufacturing according to claim 1, characterized in that: the interface layer includes a hole transport layer or an electron transport layer.
3. The method of manufacturing according to claim 1, characterized in that: the fluid interface buffer layer material comprises ink containing the interface buffer layer material, the ink comprises the fluid interface buffer layer material and a solvent, the solvent comprises water and/or alcohol, and the alcohol comprises any one or more of methanol, ethanol, isopropanol and n-butanol.
4. A method of preparation according to claim 3, characterized in that: the fluid interface buffer layer material comprises a polymer, metal oxide particles or a sol-gel precursor, and is the same as the hole transport layer or the electron transport layer in material.
5. The method of manufacturing according to claim 1, characterized in that: the metal nanowire contained in the metal nanowire network comprises any one or a combination of a plurality of silver nanowires and copper nanowires.
6. The method of manufacturing according to claim 1, characterized in that: the diameter of the metal nanowire contained in the metal nanowire network is 10 nm-100 nm, and the length is 10 mu m-100 mu m.
7. The method of manufacturing according to claim 1, characterized in that: the metal nanowire network is formed by adopting any one of spin coating, spray coating, ink-jet printing, doctor blade coating and slit coating.
8. The method of manufacturing according to claim 1, characterized in that: the interface layer is formed by any one of spin coating, spray coating, ink-jet printing, doctor blade coating and slit coating.
9. An electrode-interfacial layer composite structure contacted by a network prepared by the method of any one of claims 1-8.
10. An optoelectronic device comprising the network-contacting electrode-interface layer composite structure of claim 9, preferably comprising an organic solar cell or a perovskite solar cell.
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