CN109309162B - Perovskite-based thin film solar cell and preparation method thereof - Google Patents
Perovskite-based thin film solar cell and preparation method thereof Download PDFInfo
- Publication number
- CN109309162B CN109309162B CN201811186312.0A CN201811186312A CN109309162B CN 109309162 B CN109309162 B CN 109309162B CN 201811186312 A CN201811186312 A CN 201811186312A CN 109309162 B CN109309162 B CN 109309162B
- Authority
- CN
- China
- Prior art keywords
- layer
- perovskite
- solar cell
- tio
- deposition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- 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
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/10—Transparent electrodes, e.g. using graphene
- H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/10—Transparent electrodes, e.g. using graphene
- H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
- H10K2102/102—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising tin oxides, e.g. fluorine-doped SnO2
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
Abstract
A perovskite-based thin-film solar cell relates to the field of solar cells, and a composite modification layer of the perovskite-based thin-film solar cell comprises a Y-shaped layer 2 O 3 A bottom layer of a finishing layer made of ZnO or zinc tin oxide, and Al 2 O 3 And the upper layer of the decorative layer is made. Bottom layer of the decorative layer reduces TiO 2 The defect state density of the electron transport layer improves the efficiency of the battery. The upper layer of the modification layer has abundant methyl groups, which is beneficial to improving the quality of the perovskite film, thereby enhancing the photoelectric property of the device. The composite modification layer effectively prevents the titanium dioxide from contacting with the perovskite, reduces the damage of the titanium dioxide to the perovskite material under the illumination condition, improves the stability of the cell, and prolongs the service life of the solar cell. The preparation method of the perovskite-based thin-film solar cell is simple and convenient to operate, has low requirements on equipment, and can produce the thin-film solar cell efficiently and in high quality.
Description
Technical Field
The invention relates to the field of solar cells, in particular to a perovskite-based thin film solar cell and a preparation method thereof.
Background
In recent years, with the increasing exhaustion of fossil energy and the increasing severity of greenhouse effect and environmental pollution, the effective and rational utilization of solar energy has become one of the important approaches to solve these problems. In order to solve the increasingly severe energy and environmental problems, people are focusing on the development and utilization of new energy. Among various new energy technologies, photovoltaic power generation is undoubtedly one of the most promising directions. Although the traditional silicon-based solar cell realizes industrialization and has a mature market, the cost performance of the traditional silicon-based solar cell cannot compete with that of the traditional energy source, and the pollution and energy consumption problems in the manufacturing process influence the wide application of the traditional silicon-based solar cell. Therefore, it is necessary to research and develop a new solar cell with high efficiency and low cost.
Among a plurality of novel solar cells, perovskite-based thin-film solar cells have the advantages of high photoelectric conversion efficiency, low manufacturing material cost and the like, so that the perovskite-based thin-film solar cells are focused on the novel solar cells and attract the attention of a plurality of scientific researchers. The photoelectric conversion efficiency of the perovskite-based thin-film solar cell is rapidly improved from 3.8% to 23.3% after certification within 5 years (by 2018), and novel thin-film solar cells such as dye-sensitized solar cells and organic solar cells are thrown behind the solar cell. With the continuous refreshing of the efficiency record of perovskite-based thin-film solar cells, people begin to pay more attention to the researches on the stability, service life, substitution of heavy metal elements lead, preparation of large-area flexible devices and the like of the cells. The main factors influencing the efficiency and the service life of the perovskite-based thin-film solar cell are the balance of the transmission and blocking layers of carriers among layers and the prevention of the exciton recombination of a quenched electron transmission layer at an electrode interface. Among the reported high efficiency perovskite-based thin film solar cells, titanium dioxide is the most highly used electron transport layer material. However, under the ultraviolet irradiation, the titanium dioxide transmission layer prepared by the current traditional technology has unstable devices caused by oxygen molecule desorption on the surface, which will seriously restrict the large-scale application of perovskite-based thin-film solar cells, so the research of a method capable of effectively isolating the contact between titanium dioxide and perovskite is particularly important for the development of perovskite-based thin-film solar cells.
Disclosure of Invention
The invention aims to provide a perovskite-based thin film solar cell, which can effectively isolate the contact between titanium dioxide and perovskite, enhance the stability of the solar cell and prolong the service life of the solar cell.
The invention also aims to provide a preparation method of the perovskite-based thin-film solar cell, which is simple and convenient to operate, has low requirements on equipment and can produce the thin-film solar cell efficiently and high in quality.
The embodiment of the invention is realized by the following steps:
the perovskite-based thin film solar cell comprises a conductive substrate and TiO, which are sequentially stacked 2 The electronic device comprises an electron transmission layer, a composite modification layer, a perovskite light absorption layer and a carbon electrode layer;
wherein the composite modification layer comprises TiO 2 The electronic transmission layer is in contact with the bottom layer of the modification layer, and the modification layer is in contact with the perovskite light absorption layer; the bottom layer of the decorative layer is composed of Y 2 O 3 ZnO or zinc tin oxide, the upper layer of the decorative layer is made of Al 2 O 3 And (4) preparing.
The preparation method of the perovskite-based thin-film solar cell comprises the following steps:
depositing TiO on the surface of the conductive substrate by magnetron sputtering technology 2 Densifying the film, annealing to obtain TiO 2 An electron transport layer;
by atomic deposition on TiO 2 Surface deposition of electron transport layer Y 2 O 3 ZnO or zinc tin oxide to obtain a bottom layer of the composite modification layer;
depositing Al on the surface of the bottom layer of the composite modification layer by adopting an atomic deposition technology 2 O 3 And obtaining the upper layer of the composite decoration layer.
The embodiment of the invention has the beneficial effects that:
the embodiment of the invention provides a perovskite-based thin film solar cell which comprises a conductive substrate and TiO, wherein the conductive substrate and the TiO are sequentially laminated 2 Electron transport layer, compound modification layer, perovskite light absorption layer and carbon electrode layer. Wherein the composite modifying layer comprises Y 2 O 3 A bottom layer of a finishing layer made of ZnO or zinc tin oxide, and a coating layer made of Al 2 O 3 And the upper layer of the decorative layer is made. The bottom layer of the modification layer is a dense interconnected network formed by crystal grains with relatively uniform size, the appearance is relatively smooth and continuous, and TiO is reduced 2 Defect state density of electron transport layer and enables TiO 2 The conduction band of (a) is moved to a lower level, thereby resulting in an increase in electron lifetime, which increases the open circuit voltage, resulting in an increase in cell efficiency. At the same time, al 2 O 3 The upper layer of the prepared modification layer has rich methyl groups, and the wettability can be controlled by regulating the number of the methyl groups, so that TiO 2 The perovskite thin film has better contact with perovskite, and is beneficial to improving the quality of the perovskite thin film, thereby enhancing the photoelectric property of a device. The composite modification layer effectively prevents the titanium dioxide from contacting with the perovskite, reduces the damage of the titanium dioxide to the perovskite material under the illumination condition, improves the stability of the cell, and prolongs the service life of the solar cell.
The embodiment of the invention also provides a preparation method of the perovskite-based thin-film solar cell, and TiO is prepared on the surface of the conductive substrate by the magnetron sputtering technology 2 An electron transport layer; then adopting atomic deposition technique to sequentially deposit Y 2 O 3 ZnO or zinc tin oxide, and Al 2 O 3 And obtaining the composite decorative layer. The preparation method is simple and convenient to operate, has low requirements on equipment, and can produce the thin-film solar cell with high efficiency and high quality.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a current-voltage characteristic curve of a perovskite-based thin-film solar cell provided in example 1 of the present invention;
fig. 2 is a stability test curve of the perovskite-based thin film solar cell provided in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
The perovskite-based thin film solar cell and the preparation method thereof according to the embodiment of the invention are specifically described below.
A perovskite-based thin film solar cell comprises a conductive substrate and TiO which are sequentially stacked 2 The electronic device comprises an electron transmission layer, a composite modification layer, a perovskite light absorption layer and a carbon electrode layer;
wherein the composite modification layer comprises TiO 2 The electronic transmission layer is in contact with the bottom layer of the modification layer, and the modification layer is in contact with the perovskite light absorption layer; the bottom layer of the decorative layer is composed of Y 2 O 3 ZnO or zinc tin oxide, the upper layer of the decorative layer being made of Al 2 O 3 And (4) preparing.
The perovskite-based thin-film solar cell has the advantages of high photoelectric conversion efficiency, low manufacturing material cost and the like, so that the perovskite-based thin-film solar cell becomes a focused research hotspot in novel solar cells and attracts the attention of a plurality of scientific researchers. Among the reported high efficiency perovskite-based thin film solar cells, titanium dioxide is the most highly used electron transport layer material. However, in the titanium dioxide transmission layer prepared by the current traditional technology, oxygen molecules on the surface of the titanium dioxide transmission layer are desorbed and adsorbed under ultraviolet light to cause decomposition of perovskite materials, so that poor device stability is caused, and large-scale application of perovskite-based thin-film solar cells is severely restricted. Therefore, the perovskite-based thin-film solar cell interface modification method is reasonable in structural design, the modification layer is beneficial to reducing the recombination of photon-generated carriers on the interface, and the stability of the device is enhanced.
The perovskite light absorption layer adopted by the embodiment of the invention is ABX m Y 3-m A material of a type crystal structure, wherein A is CH 3 NH 3 Or C 4 H 9 NH 3 B is Pb or Sn, X is Cl, br or I, Y is Cl, br or I, and m is 1, 2 or 3.
In perovskite light-absorbing layers and TiO 2 And a composite modification layer is arranged between the electron transmission layers to play a role in isolation and protection. Wherein, tiO 2 The thickness of the electronic transmission layer is 100 to 300 nm, and the thickness of the composite modification layer is 60 to 90 nm; the thickness of the perovskite light absorption layer is 300 to 1000 nm. The composite decorative layer comprises Y 2 O 3 A bottom layer of a finishing layer made of ZnO or zinc tin oxide, and Al 2 O 3 And the upper layer of the decorative layer is made. The bottom layer of the modification layer is a dense interconnected network formed by crystal grains with relatively uniform size, the appearance is relatively smooth and continuous, and TiO is reduced 2 Defect state density of electron transport layer and enables TiO 2 The conduction band of (a) is shifted to a lower level, thereby resulting in an increase in electron lifetime, which increases the open circuit voltage, resulting in an increase in cell efficiency. At the same time, al 2 O 3 The upper layer of the prepared modification layer has rich methyl groups, and the wettability can be controlled by regulating the number of the methyl groups, so that TiO 2 The perovskite thin film has better contact with perovskite, and is beneficial to improving the quality of the perovskite thin film, thereby enhancing the photoelectric property of the device. The composite modification layer effectively prevents the titanium dioxide from contacting with the perovskite, reduces the damage of the titanium dioxide to the perovskite material under the illumination condition, improves the stability of the cell, and prolongs the service life of the solar cell.
Further, the conductive substrate employed in the embodiment of the present invention includes any one of fluorine-doped tin dioxide conductive glass, indium tin oxide conductive glass, and aluminum-doped ZnO conductive glass. Preferably, the transmittance of the conductive substrate is 85% or more. The carbon electrode layer is prepared from at least one of conductive carbon black, graphite, carbon fibers, carbon nanotubes and graphene, and preferably, the thickness of the carbon electrode layer is 5 to 20 micrometers.
The embodiment of the invention also provides a preparation method of the perovskite-based thin-film solar cell, which comprises the following steps:
s1, depositing TiO on the surface of a conductive substrate by using a magnetron sputtering technology 2 Densifying the film, annealing to obtain TiO 2 An electron transport layer.
The conductive substrate may be cleaned prior to magnetron sputtering. The cleaning method comprises the following steps: and respectively carrying out ultrasonic cleaning and drying by using liquid detergent, deionized water, ethanol, acetone and isopropanol, and carrying out ultraviolet ozone treatment to improve the work function of the substrate. The conductive substrate is cleaned, the magnetron sputtering effect can be improved, and TiO with higher compactness and stronger adhesive force can be obtained 2 A film.
Further, the temperature of magnetron sputtering is room temperature, the sputtering power is 80 to 150W, the pressure is 0.4 to 1 Pa, and the distance between the target and the conductive substrate is 10 to 20 cm. Specifically, the cleaned conductive substrate can be placed in a magnetron sputtering chamber, the door of the chamber is closed, and the chamber is evacuated to 5 × 10 by a vacuum pump -4 ~10×10 -4 And Pa, introducing argon, controlling the pressure in the chamber to be 0.4-1 Pa, setting the sputtering power, and setting the rotating speed of the sample stage to be 6-10 rpm. Starting a direct current power supply, pre-sputtering for 5-15min to remove pollutants, opening the sample plate to start sputtering, and sputtering for 30-60 min to obtain TiO with the particle size of 100-300 nm 2 And (4) compacting the film. Adding TiO into the mixture 2 Annealing the compact film at 400 to 600 ℃ for 0.5 to 5 hours to obtain TiO 2 An electron transport layer.
The preparation method of the perovskite-based thin film solar cell provided by the embodiment of the invention further comprises the following steps:
s2, adopting atomic deposition technology to deposit on TiO 2 Surface deposition of electron transport layer Y 2 O 3 And ZnO or zinc tin oxide to obtain the bottom layer of the composite modification layer.
Alternatively, in TiO 2 Surface deposition of electron transport layer Y 2 O 3 And ZnO or zinc tin oxide is finished through a plurality of deposition cycles, the deposition thickness of each deposition cycle is 0.1 to 0.2 nm, and the number of the deposition cycles is 40 to 100.
To deposit Y 2 O 3 For example, one deposition cycle includes the following steps:
a. will carry TiO 2 And (3) treating the conductive substrate of the electronic transmission layer for 20-30 min by using ultraviolet ozone. Then placing the mixture into a reaction cavity of atomic layer deposition equipment with the temperature of 100-200 ℃, and carrying out prescanning and purging for 5-10 min by using high-purity argon of 50-300sccm.
b. And (2) sending trimethyl cyclopentadienyl yttrium with the purity of more than 99% into a reaction chamber as a metal organic precursor, setting the pulse time to be 0.06-0.3s, setting the exposure time to be 6-14 s, and blowing by high-purity argon for 20-40 s.
c. Feeding deionized water into a reaction cavity in a pulse mode, wherein the pulse time is 0.06-0.3s, the exposure time is 6-14s, then blowing by using high-purity argon gas, and the blowing time is 20-40s, thereby completing one deposition cycle, namely, in TiO 2 A layer of Y is deposited on the surface of the compact film 2 O 3 。
The preparation method of the perovskite-based thin film solar cell provided by the embodiment of the invention further comprises the following steps:
s3, depositing Al on the surface of the bottom layer of the composite modification layer by adopting an atomic deposition technology 2 O 3 And obtaining the upper layer of the composite decorative layer.
Optionally, depositing Al on the surface of the bottom layer of the composite modifying layer 2 O 3 The method is completed through a plurality of deposition cycles, the deposition thickness of each deposition cycle is 0.05 to 0.15 nm, and the number of deposition cycles is 1 to 9.
One deposition cycle includes the following steps:
a. and (3) carrying out ultraviolet ozone treatment on the conductive substrate deposited with the bottom layer of the modification layer for 20-30 min. Then placing the mixture into a reaction cavity of atomic layer deposition equipment with the temperature of 100-200 ℃, and carrying out prescanning and purging for 5-10 min by using high-purity argon of 50-300sccm.
b. And (2) feeding trimethylaluminum with the purity of more than 99% as a metal organic precursor into a reaction cavity, setting the pulse time to be 0.02 to 0.1s, setting the exposure time to be 5 to 12s, and blowing by using high-purity argon for 15 to 30 s.
c. Sending deionized water into a reaction cavity in a pulse mode, wherein the pulse time is 0.04-0.2s, the exposure time is 5-12s, then blowing by using high-purity argon gas, the blowing time is 15-30s, completing a deposition cycle, namely depositing a layer of Al on the surface of the bottom layer of the modification layer 2 O 3 。
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a perovskite-based thin film solar cell, and the preparation method comprises the following steps:
s1, preparing TiO 2 Electron transport layer
S1-1, performing ultrasonic cleaning and drying on FTO glass by using acetone, detergent, deionized water, ethanol and isopropanol respectively, performing ultraviolet ozone treatment, putting the FTO glass into a magnetron sputtering chamber, and closing a cabin door;
s1-2, pumping the sputtering cavity to 7 x 10 by using a mechanical pump and a vacuum molecular pump -4 And after Pa, introducing argon to control the pressure to be 0.8 Pa. The sputtering power is set to be 120W, and the rotating speed of the sample stage is 6 rpm. Starting a direct-current power supply to glow, and pre-sputtering for 5min to remove pollutants;
s1-3, opening the sample plate to start sputtering, and sputtering for 30 min to obtain 100 nm TiO 2 Dense layer film, tiO obtained 2 Annealing the compact film at 400 ℃ for 30 min to obtain TiO 2 An electron transport layer.
S2, preparing a bottom layer of the decorative layer
S2-1, plating TiO on S1 2 Treating the conductive substrate of the electron transmission layer with ultraviolet ozone for 20min, placing the conductive substrate into a reaction cavity of atomic layer deposition equipment at the temperature of 100 ℃, and purging with high-purity argon of 50sccm for 5min;
s2-2, feeding trimethyl cyclopentadienyl yttrium with the purity of more than 99% into a reaction cavity in a pulse mode, wherein the pulse time is 0.06S, the exposure time is 6S, and then purging with high-purity argon for 20S;
s2-3, feeding deionized water into the reaction cavity in a pulse mode, wherein the pulse time is 0.08S, the exposure time is 6S, then purging with high-purity argon gas for 20S, and completing one deposition cycle, namely, in TiO 2 A layer of Y is deposited on the surface of the electron transport layer 2 O 3 ；
S2-4. The deposition cycle of steps S2-1 to S2-3 is then repeated 39 times.
S3, preparing a decorative layer upper layer
S3-1, treating the conductive substrate deposited with the bottom layer of the modification layer obtained in the S2 by ultraviolet ozone for 25 min, then placing the conductive substrate into a reaction cavity of atomic layer deposition equipment with the temperature of 150 ℃, and purging for 7 min by using high-purity argon of 50 sccm;
s3-2, feeding trimethylaluminum TMA with the purity of more than 99% into a reaction cavity in a pulse mode, wherein the pulse time is 0.05S, the exposure time is 8S, and then purging with high-purity argon gas for 20S;
s3-3, feeding deionized water into the reaction cavity in a pulse mode, wherein the pulse time is 0.1S, the exposure time is 8S, purging with high-purity argon gas for 20S, and completing one deposition cycle, namely depositing a layer of Al on the surface of the yttrium oxide compact film 2 O 3 。
S4, preparing the perovskite-based thin-film solar cell
Mixing TiO with 2 The electron transmission layer, the composite modification layer, the perovskite light absorption layer and the carbon electrode are sequentially stacked to assemble the perovskite-based thin-film solar cell. Wherein the perovskite light-absorbing layer is CH 3 NH 3 PbI 3 The carbon slurry is conductive carbon black. The photoelectric efficiency of the perovskite-based thin-film solar cell obtained by the method can reach 10.3%.
Example 2
The embodiment provides a perovskite-based thin film solar cell, and a preparation method of the perovskite-based thin film solar cell comprises the following steps:
s1, preparing TiO 2 Electron transport layer
S1-1, performing ultrasonic cleaning and drying on the ITO glass by using acetone, detergent, deionized water, ethanol and isopropanol respectively, performing ultraviolet ozone treatment, putting the ITO glass into a magnetron sputtering chamber, and closing a cabin door;
s1-2, pumping the sputtering cavity to 8 x 10 by using a mechanical pump and a vacuum molecular pump -4 And after Pa, introducing argon to control the pressure to be 1 Pa. The sputtering power is set to be 100W, and the rotating speed of the sample stage is 6 rpm. Starting a direct-current power supply to start brightness, and pre-sputtering for 10 min to remove pollutants;
s1-3, opening the sample plate to start sputtering, and sputtering for 40 min to obtain 130 nm TiO 2 Dense layer film, tiO obtained 2 Annealing the compact film at 500 ℃ for 30 min to obtain TiO 2 An electron transport layer.
S2, preparing a bottom layer of the decorative layer
S2-1, coating TiO on S1 2 Treating the conductive substrate of the electron transmission layer with ultraviolet ozone for 25 min, placing the treated conductive substrate into a reaction cavity of atomic layer deposition equipment at the temperature of 150 ℃, and purging with high-purity argon of 50sccm for 7 min;
s2-2, feeding diethyl zinc with the purity of more than 99% into a reaction cavity in a pulse mode, wherein the pulse time is 0.16S, the exposure time is 10S, and then purging with high-purity argon gas for 30S;
s2-3, feeding deionized water into the reaction cavity in a pulse mode, wherein the pulse time is 0.2S, the exposure time is 10S, then purging with high-purity argon gas for 30S, and completing one deposition cycle, namely, in TiO 2 A layer of ZnO is deposited on the surface of the electron transport layer;
s2-4, the deposition cycle of steps S2-1 to S2-3 is then repeated 59 times.
S3, preparing a decorative layer upper layer
S3-1, treating the conductive substrate deposited with the bottom layer of the modification layer obtained in the S2 by ultraviolet ozone for 25 min, then placing the conductive substrate into a reaction cavity of atomic layer deposition equipment with the temperature of 150 ℃, and purging for 7 min by using high-purity argon of 50 sccm;
s3-2, feeding trimethylaluminum TMA with the purity of more than 99% into a reaction cavity in a pulse mode, wherein the pulse time is 0.05S, the exposure time is 8S, and then purging with high-purity argon gas for 20S;
s3-3, feeding the deionized water into the reaction cavity in a pulse mode, wherein the pulse time is 0.1S, the exposure time is 8S, and then purging with high-purity argon for a purging timeFor 20s, completing one deposition cycle, namely depositing a layer of Al on the surface of the ZnO dense film 2 O 3 。
S3-4, repeating the deposition cycle of the steps S3-1 to S3-3 for 4 times.
S4, preparing the perovskite-based thin-film solar cell
Adding TiO into the mixture 2 The electron transmission layer, the composite modification layer, the perovskite light absorption layer and the carbon electrode are sequentially stacked to assemble the perovskite-based thin-film solar cell. Wherein the perovskite light-absorbing layer is CH 3 NH 3 PbI 3 The carbon slurry is conductive carbon black. The photoelectric efficiency of the perovskite-based thin-film solar cell obtained by the method can reach 9.76%.
Example 3
The embodiment provides a perovskite-based thin film solar cell, and a preparation method of the perovskite-based thin film solar cell comprises the following steps:
s1, preparing TiO 2 Electron transport layer
S1-1, ultrasonically cleaning and drying ATO glass by using acetone, detergent, deionized water, ethanol and isopropanol respectively, placing the ATO glass into a magnetron sputtering chamber after ultraviolet ozone treatment, and closing a cabin door;
s1-2, pumping the sputtering cavity to 1 x 10 by using a mechanical pump and a vacuum molecular pump -3 And after Pa, introducing argon to control the pressure to be 1 Pa. The sputtering power is set to be 80W, and the rotating speed of the sample stage is 6 rpm. Starting a direct-current power supply to start brightness, and pre-sputtering for 15min to remove pollutants;
s1-3, opening the sample plate to start sputtering, and sputtering for 60 min to obtain 190 nm TiO 2 Dense layer film, tiO obtained 2 Annealing the compact film at 600 ℃ for 30 min to obtain TiO 2 An electron transport layer.
S2, preparing a bottom layer of the decorative layer
S2-1, coating TiO on S1 2 Treating the conductive substrate of the electron transmission layer with ultraviolet ozone for 30 min, placing the conductive substrate into a reaction cavity of atomic layer deposition equipment at the temperature of 200 ℃, and purging with high-purity argon of 50sccm for 7 min;
s2-2, feeding diethyl zinc with the purity of more than 99% into a reaction cavity in a pulse mode, wherein the pulse time is 0.3S, the exposure time is 14S, and then purging with high-purity argon for 30S;
s2-3, feeding deionized water into the reaction cavity in a pulse mode, wherein the pulse time is 0.4S, the exposure time is 14S, then purging with high-purity argon gas for 30S, and completing one deposition cycle, namely, in TiO 2 A layer of ZnO is deposited on the surface of the electron transport layer;
s2-4, repeating the deposition cycle of the steps S2-1 to S2-3 for 99 times.
S2-5, feeding tetra (dimethylamino) tin with the purity of more than 99% into a reaction cavity in a pulse mode, wherein the pulse time is 0.3S, the exposure time is 14S, and then purging with high-purity argon for 40S;
s2-6, feeding deionized water into the reaction cavity in a pulse mode, wherein the pulse time is 0.4S, the exposure time is 14S, purging with high-purity argon gas for 30S, and completing one deposition cycle, namely depositing a layer of SnO on the surface of the zinc oxide film 2 And obtaining the zinc tin oxide film.
S3, preparing a decorative layer upper layer
S3-1, treating the conductive substrate deposited with the bottom layer of the modification layer obtained in the step S2 by ultraviolet ozone for 30 min, then placing the conductive substrate into a reaction cavity of atomic layer deposition equipment with the temperature of 200 ℃, and purging by using high-purity argon of 50sccm for 10 min;
s3-2, feeding trimethylaluminum TMA with the purity of more than 99% into a reaction cavity in a pulse mode, wherein the pulse time is 0.1S, the exposure time is 12S, and then purging with high-purity argon gas for 30S;
s3-3, feeding deionized water into the reaction cavity in a pulse mode, wherein the pulse time is 0.2S, the exposure time is 12S, purging with high-purity argon gas for 30S, and completing one deposition cycle, namely depositing a layer of Al on the surface of the zinc tin oxide compact film 2 O 3 。
S3-4. The deposition cycle of steps S3-1 to S3-3 is then repeated 8 times.
S4, preparing the perovskite-based thin film solar cell
Adding TiO into the mixture 2 The electron transmission layer, the composite modification layer, the perovskite light absorption layer and the carbon electrode are sequentially stacked to form the perovskite base filmA solar cell. Wherein the perovskite light-absorbing layer is CH 3 NH 3 PbI 3 The carbon slurry is conductive carbon black. The photoelectric efficiency of the perovskite-based thin-film solar cell obtained by the method can reach 9.63%.
Comparative example 1
The present comparative example provides a perovskite-based thin-film solar cell, the manufacturing method of which is described with reference to example 1, except that the perovskite-based thin-film solar cell of the present comparative example is not provided with a composite modification layer.
Test example 1
The perovskite-based thin-film solar cells provided in example 1 and comparative example 1 were used, and the photoelectric conversion efficiency thereof was measured, respectively, and the obtained voltammetry characteristics were shown in fig. 1.
As can be seen from fig. 1, the short-circuit current and the open-circuit voltage of the solar cell provided in example 1 of the present invention are both higher than those of comparative example 1, so that it can be calculated that the solar cell provided in the example of the present invention has higher photoelectric conversion efficiency.
Test example 2
The perovskite-based thin film solar cells provided in example 1 and comparative example 1 were used to test the stability performance, and the test method was as follows: the devices prepared in example 1 and comparative example 1 were placed in a constant temperature and humidity electronic storage cabinet at 25 ℃ and 30% humidity, and the photoelectric conversion efficiency of two batches of cells was measured at 48-hour intervals using an electrochemical workstation, totaling 8 time points from 0 to 400.
As shown in fig. 2, it can be seen from fig. 2 that after the solar cell provided in embodiment 1 of the present invention is used for 400 hours, the PCE value of the solar cell can still maintain more than 90% of the initial efficiency, and is reduced by less than 10%. In contrast, the solar cell provided in comparative example 1 reached a PCE value of only about 50% of the initial efficiency after 400 hours of use, which was about 50% lower. The solar cell provided by the embodiment of the invention has better stability.
In summary, embodiments of the present invention provide a perovskite-based thin film solar cell, which includes a conductive substrate, a TiO, and a plurality of layers stacked in sequence 2 Electron transport layer, compound decoration layer, perovskite light-absorbing layer and carbon electrode layer. Wherein the composite modifying layer comprises Y 2 O 3 A bottom layer of a finishing layer made of ZnO or zinc tin oxide, and Al 2 O 3 And the upper layer of the decorative layer is made. The bottom layer of the modification layer is a dense interconnected network formed by crystal grains with relatively uniform size, presents a relatively smooth and continuous appearance on the surface, and reduces TiO 2 Defect state density of electron transport layer and enables TiO 2 The conduction band of (a) is shifted to a lower level, thereby resulting in an increase in electron lifetime, which increases the open circuit voltage, resulting in an increase in cell efficiency. Meanwhile, al 2 O 3 The upper layer of the prepared modification layer has rich methyl groups, and the wettability can be controlled by regulating the number of the methyl groups, so that TiO 2 The perovskite thin film has better contact with perovskite, and is beneficial to improving the quality of the perovskite thin film, thereby enhancing the photoelectric property of a device. The composite modification layer effectively prevents the titanium dioxide from contacting with the perovskite, reduces the damage of the titanium dioxide to the perovskite material under the illumination condition, improves the stability of the cell, and prolongs the service life of the solar cell.
The embodiment of the invention also provides a preparation method of the perovskite-based thin-film solar cell, which is characterized in that TiO is prepared on the surface of the conductive substrate by the magnetron sputtering technology 2 An electron transport layer; then adopting atomic deposition technique to sequentially deposit Y 2 O 3 ZnO or zinc tin oxide, and Al 2 O 3 And obtaining the composite decorative layer. The preparation method is simple and convenient to operate, has low requirements on equipment, and can produce the thin-film solar cell efficiently and high in quality.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. Perovskite-based thin film solar cellThe preparation method of the solar cell is characterized in that the perovskite-based thin-film solar cell comprises a conductive substrate and TiO which are sequentially laminated 2 The electronic device comprises an electron transmission layer, a composite modification layer, a perovskite light absorption layer and a carbon electrode layer; the preparation method comprises the following steps:
depositing TiO on the surface of the conductive substrate by using a magnetron sputtering technology 2 Densifying the film, annealing to obtain said TiO 2 An electron transport layer;
by atomic deposition on said TiO 2 Surface deposition of electron transport layer Y 2 O 3 Or zinc tin oxide to obtain the bottom layer of the composite modification layer;
depositing Al on the surface of the bottom layer of the composite modification layer by adopting an atomic deposition technology 2 O 3 Obtaining the upper layer of the composite decorative layer;
the temperature of the magnetron sputtering is room temperature, the sputtering power is 80 to 150W, the pressure is 0.4 to 1 Pa, and the distance between the target and the conductive substrate is 10 to 20 cm;
to the TiO 2 The temperature for annealing the compact film is 400 to 600 ℃, and the time is 0.5 to 5 hours;
in the TiO 2 Surface deposition of electron transport layer Y 2 O 3 Or the zinc tin oxide is finished through a plurality of deposition cycles, the deposition thickness of each deposition cycle is 0.1 to 0.2 nm, and the number of the deposition cycles is 40 to 100;
depositing Al on the surface of the bottom layer of the composite modification layer 2 O 3 The method is completed through a plurality of deposition cycles, the deposition thickness of each deposition cycle is 0.05 to 0.15 nm, and the number of deposition cycles is 1 to 9.
2. The method of claim 1, wherein the perovskite light absorption layer is ABX-based m Y 3-m A material of a crystal structure of the form, wherein A is CH 3 NH 3 Or C 4 H 9 NH 3 B is Pb or Sn, X is Cl, br or I, Y is Cl, br or I, and m is 1, 2 or 3.
3. The method of manufacturing a perovskite-based thin film solar cell according to claim 1, wherein the TiO is 2 The thickness of the electronic transmission layer is 100 to 300 nm, and the thickness of the composite modification layer is 60 to 90 nm; the thickness of the perovskite light absorption layer is 300 to 1000 nm.
4. The method of claim 1, wherein the conductive substrate comprises any one of fluorine-doped tin dioxide conductive glass, indium tin oxide conductive glass, and aluminum-doped ZnO conductive glass.
5. The method according to claim 1, wherein the carbon electrode layer is prepared from at least one of conductive carbon black, graphite, carbon fiber, and carbon nanotubes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811186312.0A CN109309162B (en) | 2018-10-10 | 2018-10-10 | Perovskite-based thin film solar cell and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811186312.0A CN109309162B (en) | 2018-10-10 | 2018-10-10 | Perovskite-based thin film solar cell and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109309162A CN109309162A (en) | 2019-02-05 |
| CN109309162B true CN109309162B (en) | 2023-01-20 |
Family
ID=65225592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811186312.0A Active CN109309162B (en) | 2018-10-10 | 2018-10-10 | Perovskite-based thin film solar cell and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109309162B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110277498B (en) * | 2019-06-10 | 2022-08-02 | 储天新能源科技（长春）有限公司 | Preparation method of perovskite battery |
| CN112271260B (en) * | 2020-11-25 | 2023-12-01 | 昆山协鑫光电材料有限公司 | Perovskite solar cell and preparation method thereof |
| CN113540390B (en) * | 2021-06-29 | 2022-04-01 | 哈尔滨工业大学 | Preparation method and application of dynamic interface coating of metal zinc cathode of zinc ion battery |
| CN113948643A (en) * | 2021-10-19 | 2022-01-18 | 中南大学 | Low-temperature mesoporous carbon-based perovskite solar cell with simple structure |
| CN115584483B (en) * | 2022-09-23 | 2024-06-07 | 隆基绿能科技股份有限公司 | Tin dioxide film and preparation method and application thereof |
| CN117809985B (en) * | 2024-02-29 | 2024-05-10 | 山东恒嘉高纯铝业科技股份有限公司 | Thin film electrode containing calcium hexaaluminate and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101834068A (en) * | 2009-03-13 | 2010-09-15 | 中国科学院福建物质结构研究所 | Core-shell structure positive electrode for dye sensitization solar battery and preparation method thereof |
| CN103904147A (en) * | 2014-03-28 | 2014-07-02 | 中国科学院上海技术物理研究所 | Perovskite battery based on nanometer oxide electron transfer layer |
| CN104124295A (en) * | 2014-08-12 | 2014-10-29 | 中国乐凯集团有限公司 | Planar heterogeneous perovskite solar cell and preparation method thereof |
| CN104183697A (en) * | 2014-08-25 | 2014-12-03 | 常州大学 | Solar cell of perovskite structure and preparing method of solar cell |
| CN104409636A (en) * | 2014-11-18 | 2015-03-11 | 天津理工大学 | Perovskite thin-film solar cell with three-dimensional ordered mesopore support layer |
| CN104638108A (en) * | 2015-01-23 | 2015-05-20 | 华东师范大学 | Modified electron transport layer and perovskite solar cell |
| CN105280389A (en) * | 2015-10-16 | 2016-01-27 | 湖北大学 | Preparation method for dye-sensitized solar cell |
| CN105280827A (en) * | 2015-10-16 | 2016-01-27 | 湖北大学 | Preparation method for perovskite type solar battery |
| CN107482120A (en) * | 2017-07-12 | 2017-12-15 | 北京科技大学 | A kind of perovskite battery and preparation method based on composite electron transport layer |
| CN108039393A (en) * | 2017-12-07 | 2018-05-15 | 暨南大学 | A kind of full-inorganic Ca-Ti ore type solar cell and preparation method thereof |
-
2018
- 2018-10-10 CN CN201811186312.0A patent/CN109309162B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101834068A (en) * | 2009-03-13 | 2010-09-15 | 中国科学院福建物质结构研究所 | Core-shell structure positive electrode for dye sensitization solar battery and preparation method thereof |
| CN103904147A (en) * | 2014-03-28 | 2014-07-02 | 中国科学院上海技术物理研究所 | Perovskite battery based on nanometer oxide electron transfer layer |
| CN104124295A (en) * | 2014-08-12 | 2014-10-29 | 中国乐凯集团有限公司 | Planar heterogeneous perovskite solar cell and preparation method thereof |
| CN104183697A (en) * | 2014-08-25 | 2014-12-03 | 常州大学 | Solar cell of perovskite structure and preparing method of solar cell |
| CN104409636A (en) * | 2014-11-18 | 2015-03-11 | 天津理工大学 | Perovskite thin-film solar cell with three-dimensional ordered mesopore support layer |
| CN104638108A (en) * | 2015-01-23 | 2015-05-20 | 华东师范大学 | Modified electron transport layer and perovskite solar cell |
| CN105280389A (en) * | 2015-10-16 | 2016-01-27 | 湖北大学 | Preparation method for dye-sensitized solar cell |
| CN105280827A (en) * | 2015-10-16 | 2016-01-27 | 湖北大学 | Preparation method for perovskite type solar battery |
| CN107482120A (en) * | 2017-07-12 | 2017-12-15 | 北京科技大学 | A kind of perovskite battery and preparation method based on composite electron transport layer |
| CN108039393A (en) * | 2017-12-07 | 2018-05-15 | 暨南大学 | A kind of full-inorganic Ca-Ti ore type solar cell and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Enhanced Charge Collection with Passivation Layers inPerovskite Solar Cells;Yong Hui Lee等;《ADVANCED MATERIALS》;20160525;第28卷(第20期);全文 * |
| Optimization of TiO2/ZnO bilayer electron transport layer to enhance efficiency of perovskite solar cell;Nitu Kumari等;《Materials Science in Semiconductor Processing》;20180301;第75卷;摘要、2. Materials and methodology以及表1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109309162A (en) | 2019-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109309162B (en) | Perovskite-based thin film solar cell and preparation method thereof | |
| CN104183697B (en) | Solar cell of perovskite structure and preparing method of solar cell | |
| WO2016026294A1 (en) | Perovskite film photovoltaic cell based on sno2 and preparation method therefor | |
| CN107369766B (en) | Perovskite solar cell with high-quality metal oxide electron transport layer and preparation method thereof | |
| CN105280827B (en) | The preparation method of Ca-Ti ore type solar cell | |
| CN107331775B (en) | A kind of perovskite solar cell and preparation method thereof of high quality electron transfer layer | |
| CN107482122B (en) | perovskite solar cell and preparation method | |
| KR20140003776A (en) | Preparation of a high resistivity zno thin film | |
| CN108807694B (en) | Flat perovskite solar cell with ultralow temperature stability and preparation method thereof | |
| CN108389969B (en) | Green solvent system and mixed solution for preparing perovskite layer of perovskite solar cell | |
| KR101079413B1 (en) | Dye sensitized solar cell including metal oxide of core-shell structure | |
| CN112331740A (en) | Preparation method of inorganic perovskite solar cell adopting spin coating-evaporation two-step method | |
| CN105161623A (en) | Perovskite solar cell and preparation method thereof | |
| CN115020596A (en) | Double-layer electron transport layer, perovskite solar cell with double-layer electron transport layer, and preparation method and application of perovskite solar cell | |
| CN107394044B (en) | Perovskite solar cell with conductive electrode and electron transmission layer and preparation method | |
| CN1819274A (en) | Thin-film solar battery barrier with flexible substrate and production thereof | |
| CN112038490A (en) | Method for preparing perovskite solar cell by improved steam assistance | |
| CN209963073U (en) | Novel high-efficiency double-sided incident light CdTe perovskite laminated photovoltaic cell | |
| CN105280389B (en) | The preparation method of dye-sensitized solar cells | |
| CN116322072A (en) | Preparation method of semitransparent perovskite solar cell | |
| CN109888097A (en) | A kind of preparation method of perovskite thin film and the solar battery prepared based on this | |
| CN108461636A (en) | A kind of preparation method of embellishing cathode interface perovskite solar cell | |
| CN105575669B (en) | A kind of preparation method of dye-sensitized solar cells | |
| CN110190192B (en) | Preparation method of trans-organic-inorganic hybrid perovskite solar cell | |
| CN112952001A (en) | Perovskite solar cell and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |