CN110165020B - Based on CdS/SnO2High efficiency Sb of mixed N type layer2Se3Thin film battery and preparation method thereof - Google Patents
Based on CdS/SnO2High efficiency Sb of mixed N type layer2Se3Thin film battery and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000010409 thin film Substances 0.000 claims abstract description 34
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- 239000010408 film Substances 0.000 claims description 78
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Abstract
The invention belongs to the field of solar cell preparation, and particularly relates to a CdS/SnO-based solar cell2High efficiency Sb of mixed N type layer2Se3Thin film battery and preparation method thereof, and CdS/SnO-based thin film battery2High efficiency Sb of mixed N type layer2Se3The thin film battery is formed by using CdS/SnO2Mixed N-type layers instead of a single SnO2Buffer layer of Sb by comparison2Se3The XRD pattern of the composition can be obviously found, and SnO is used2When used as an N-type layer, (120) is Sb2Se3And Sb can be made using a mixed N-type layer2Se3The orientation of the (120) crystal face is reduced to the lowest, the (221) is in a preferred orientation, the transmission of electrons is more facilitated, and the Sb can be induced due to the existence of the CdS thin film2Se3The columnar growth of the thin film can also improve the crystallinity of the thin film so as to improve the cell efficiency of the thin film.
Description
Technical Field
The invention belongs to the field of solar cell preparation, and particularly relates to a CdS/SnO-based solar cell2High efficiency Sb of mixed N type layer2Se3A thin film battery and a method for manufacturing the same.
Background
In recent years, with the gradual depletion of limited non-renewable resources such as petroleum and coal on the earth, the utilization and development of renewable energy sources become more and more urgent, wherein solar photovoltaic power generation converts inexhaustible solar energy radiated to the ground into electric energy through the photoelectric conversion of photovoltaic devices such as solar cells, and the electric energy has become the safest, most environment-friendly and most potential competitor among the renewable energy sources.
So far, common solar cells mainly include silicon cells, thin film cells and the like, and the thin film cells are mainly divided into perovskite cells, CIGS, CZTS and the like, however, perovskite cells have environmental instability, CIGS cost is high, Sn melting point in CZTS is low, Sn is easy to dissipate in the preparation process, and the perovskite cells are difficult to prepare. While Sb2Se3As a binary semiconductor material, due to its excellent optoelectronic properties, for example: appropriate band gap (1.1 eV), large absorption coefficient (1.1 eV)>105cm-1) High carrier mobility (10 cm)2V-1s-1Minority carrier) and long carrier life (60 ns based on transient absorption spectrum), and has extremely high vapor pressure (1200 Pa @550 ℃), so that a plurality of research institutions at home and abroad carry out more intensive research on the antimony selenide thin film battery.
However, most antimony selenide thin film batteries are based on a toxic CdS thin film as a buffer layer so far, on one hand, CdS absorbs most incident light due to a smaller band gap (about 2.4eV), and on the other hand, the device instability may be caused by the diffusion of Cd element, so that an environment-friendly buffer layer SnO is selected2Instead of the toxic CdS film, because it has wide band gap (3.6eV) and high n-type doping concentration (10 eV)19To 1020cm-3). SnO on the other hand2Its stable chemical properties, no toxicity, large band gap and high stability make SnO2Can replace CdS as buffer layer. Further, SnO2The similarity to the transparent conductive layer of the FTO will result in less lattice mismatch, resulting in better electron transport. However, SnO is used alone2There are some disadvantages to the CdS removal, because SnO2The film has lower crystallinity and larger surface roughness with Sb2Se3When the film forms a P-N junction, more interface defects and electron recombination are introduced, and Sb2Se3The growth orientation of the thin film is not good, resulting in low efficiency.
Disclosure of Invention
To further improve Sb2Se3The invention provides a CdS/SnO based thin film battery2High efficiency Sb of mixed N type layer2Se3A thin film battery and a method for manufacturing the same.
The inventors of the present invention suspected to influence SnO2/Sb2Se3The main factor of the final efficiency of the solar cellIs roughness and crystallinity of the surface of the thin film, however, SnO prepared by a low-temperature solution method2The thin film has good surface properties and crystallinity, so we hypothesize that the main reason why the efficiency is lower than other buffer layers is due to Sb2Se3The growth orientation of the film. For this purpose, the process of the invention is carried out in SnO2Adding a layer of ultrathin CdS under the film hopes to change Sb2Se3And (3) growing the film. Thereby improving the battery efficiency thereof.
The invention relates to a CdS/SnO-based catalyst2High efficiency Sb of mixed N type layer2Se3The preparation method of the thin film battery is implemented according to the following steps:
(1) cleaning the FTO substrate glass, namely respectively ultrasonically cleaning the FTO glass for 30 minutes by using foam water, acetone, ethanol and deionized water, and drying the FTO glass by using nitrogen.
(2) Preparing a CdS film by mixing 15-20 mL of CdSO4And sequentially pouring the solution (15mmol/L), 19-35 mL of ammonia water (25-28% of industrial ammonia water) and 15-20 mL of thiourea solution (75mmol/L) into a beaker filled with 250mL of deionized water to obtain a mixed solution, clamping the cleaned FTO glass by using a clamp, putting the FTO glass into the mixed solution, stirring the solution, reacting for 8-20 min at 65-80 ℃ to obtain the CdS film with the thickness of 10-40 nm.
(3)SnO2Preparing a film, namely putting the CdS film with the thickness of 10-40nm obtained in the step (2) into a spin coater, and dropwise adding prepared SnO2Aqueous solution (SnO according to mass ratio)2:H2O/1:4) on the CdS film, spin-coating for 1-4 times at a rotation speed of 5000rpm for 30s each time, and annealing at 150 ℃ for 30min to obtain SnO with a thickness of 10-40nm2A film.
The N-type layer generally has an optimal thickness, and if the thickness is too thin or too thick, the quality of a p-N junction is influenced, and the extraction and transmission of electrons are influenced, so that the open voltage of the cell is reduced, and the efficiency is reduced, therefore, the CdS film and SnO in the invention2The thickness of the film is preferably 10 to 40 nm.
SnO2The ratio of the aqueous solution can affect SnO2Thickness of the filmIf the formulation is too thin, spin coating is required several times to obtain the same thickness, which may cause an increase in the problem of the interface between layers and also cause difficulty in electron transport, thereby affecting the efficiency of the battery.
The spin coating time and speed also affect SnO2The thickness of the film, and thus the efficiency of the cell.
Annealing can increase SnO2If the crystallinity, annealing temperature and time of the film are insufficient, crystal grains are not fused together and grow large, so that a plurality of holes and grain boundary defects are generated, thereby affecting the transmission of electrons, and if the crystallinity, annealing temperature and time are too high, the film is cracked, and the holes and the grain boundary defects are generated, thereby reducing the efficiency of the battery.
(4)Sb2Se3Preparing a film, namely preparing the CdS/SnO obtained in the step (3)2The film was put into a rapid annealing furnace, and 0.4 to 0.6g of Sb produced by Jiangxi Koita Co., Ltd2Se3Placing the powder into a chamber, and depositing at 580 deg.C for 110s under 0.34Pa to obtain Sb2Se3A film.
In the annealing furnace, the pressure during annealing is the degree of vacuum of the chamber, and if the degree of vacuum is insufficient, Sb2Se3Can be oxidized at high temperature to generate Sb 203Sb is affected by over-high or over-low temperature2Se3Too high or too low of the evaporation rate of the film can result in Sb2Se3The film generates a lot of holes and defects, and too high time can affect Sb2Se3The thickness of the film, and thus a good p-n junction, is not obtained, resulting in a decrease in efficiency.
(5) Preparing a gold electrode, namely preparing Sb obtained in the step (4)2Se3The film was placed in an evaporator and a 80nm thick gold electrode was evaporated.
Compared with the prior art, the invention has the following beneficial effects: the method has the advantages of simple operation, low cost, high industrialization degree and the like. CdS/SnO-based material prepared by adopting method2High efficiency Sb of mixed N type layer2Se3The thin film battery is formed by using CdS/SnO2Mixed N-type layers instead of a single SnO2Buffer layer, Sb can be induced by the existence of CdS thin film2Se3Columnar growth of Sb2Se3The orientation of the (120) crystal face is reduced to the minimum, the (221) is preferentially oriented, the transmission of electrons is more facilitated, the antimony selenide film is induced to grow along a column, in addition, the crystallinity of the antimony selenide film can be improved, and the Sb is improved2Se3The cell efficiency of the thin film has very important scientific significance for promoting the development of the antimony selenide thin film cell.
Drawings
FIG. 1 shows CdS/SnO prepared by the invention2/Sb2Se3The structure of the thin film battery is shown schematically.
FIG. 2 shows a SnO-based catalyst prepared according to the present invention2，CdS/SnO2Sb with CdS as buffer layer2Se3XRD pattern of the film.
FIG. 3 shows a SnO-based catalyst prepared according to the present invention2，CdS/SnO2Sb with CdS as buffer layer2Se3SEM image of the film.
FIG. 4 shows a SnO-based catalyst prepared according to the present invention2，CdS/SnO2Sb with CdS as buffer layer2Se3Cross-sectional SEM image of thin film cell.
FIG. 5 shows a SnO-based catalyst prepared according to the present invention2，CdS/SnO2Sb with CdS as buffer layer2Se3Efficiency map of thin film battery.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to illustrate the invention only and not to limit the scope of the invention, the object of the invention is to provide a CdS/SnO based catalyst2High efficiency Sb of mixed N type layer2Se3The preparation method of the thin film battery comprises the following specific steps:
preparing CdS film by water bath method, and depositing a layer of SnO on the CdS film by spin coating2Film, then preparing Sb by RTE method2Se3Film, depositing a layer of gold by evaporationAnd an electrode.
These examples are intended to illustrate the invention and do not limit the scope of the invention.
Example 1
Cleaning of FTO substrate glass
The substrate is made of FTO glass, sequentially and ultrasonically cleaned for 30 minutes by using foam water, acetone, ethanol and deionized water, and dried for later use.
Preparing a CdS film:
15mL of CdSO4And sequentially pouring the solution (15mmol/L), 19mL of ammonia water (25-28% industrial ammonia water) and 15mL of thiourea solution (75mmol/L) into a beaker filled with 250mL of deionized water to obtain a mixed solution, clamping the cleaned FTO glass by using a clamp, putting the FTO glass into the mixed solution, stirring the solution, and reacting for 8min at the temperature of 70 ℃ to obtain the CdS film with the thickness of 10 nm.
SnO2Preparing a film:
putting the CdS film with the thickness of 10nm into a spin coater, and dropwise adding prepared SnO2Aqueous solution (SnO)2:H2O/1:4) on the CdS film, spin-coating for 4 times, each time spin-coating for 30s at the rotation speed of 5000rpm, and then annealing at 150 ℃ for 30min to obtain SnO with the thickness of 40nm2A film.
Sb2Se3Preparing a film:
1. the treated N-type CdS/SnO2The film is placed in a rapid annealing furnace, and the pressure of the cavity is pumped to 0.34Pa by a vacuum pump.
2. The furnace temperature is increased to 300 ℃ at the speed of 10 ℃/s and is kept for 20min, so that the substrate and Sb are mixed2Se3The source is heated sufficiently.
3. Then heating to 580 ℃ at the speed of 10 ℃/s, keeping for 110s, naturally cooling, taking out below 50 ℃, and thus obtaining Sb2Se3A film.
XRD powder diffraction analysis shows that the (120) peak is reduced to the lowest, and the (221) peak becomes the preferred orientation. The surface appearance of the film is observed by adopting a field emission scanning electron microscope to find the prepared Sb2Se3Film complete junctionAnd (4) crystallizing. And it can be seen from the cross-sectional SEM image that it induces Sb2Se3The film grows along the pillar.
Preparation of Au electrode
In the Sb obtained above2Se3Plating a layer of gold electrode with the thickness of about 80nm on the surface of the film by adopting an evaporator to obtain the CdS/SnO-based film2High efficiency Sb of mixed N type layer2Se3Thin film cell, SnO found at a CdS film thickness of 10nm2The thickness of 40nm is the highest performance parameter of the battery with the highest efficiency: open circuit voltage Voc0.36V, short-circuit current density Jsc＝27.8mA/cm2The fill factor FF is 52.7 and the cell efficiency PCE is 5.27%.
Comparative example 1
Cleaning of FTO substrate glass:
the substrate is made of FTO glass, sequentially and ultrasonically cleaned for 30 minutes by using foam water, acetone, ethanol and deionized water, and dried for later use.
SnO2Preparing a film:
putting the cleaned FTO into a spin coater, and dropwise adding prepared SnO2Aqueous solution (SnO)2:H2O/1:4) on FTO, spin-coating for 4 times, each time spin-coating for 30s at the rotation speed of 5000rpm, and then annealing at 150 ℃ for 30min to obtain SnO with the thickness of 40nm2A film.
Sb2Se3Preparing a film:
1. the treated N-type SnO2The film is placed in a rapid annealing furnace, and the pressure of the cavity is pumped to 0.34Pa by a vacuum pump.
2. The furnace temperature is increased to 300 ℃ at the speed of 10 ℃/s and is kept for 20min, so that the substrate and Sb are mixed2Se3The source is heated sufficiently.
3. Then heating to 580 ℃ at the speed of 10 ℃/s, keeping for 110s, naturally cooling, taking out below 50 ℃, and thus obtaining Sb2Se3A film.
The XRD powder diffraction analysis shows that the (120) peak is preferentially oriented and the (221) peak is lower. Using field-emission scanning electron microscopes for observing the filmSurface morphology, discovery of the prepared Sb2Se3The film was completely crystallized. And Sb can be seen from the cross-sectional SEM image2Se3The film is arranged in disorder.
Preparation of Au electrode
In the Sb obtained above2Se3Plating a layer of gold electrode with the thickness of about 80nm on the surface of the film by adopting an evaporator to obtain SnO2Sb as N-type layer2Se3The thin film battery has the following battery performance parameters: open circuit voltage Voc0.32V, short-circuit current density Jsc＝18.4mA/cm2The fill factor FF is 39.4 and the cell efficiency PCE is 2.33%.
Comparative example 2
Cleaning of FTO substrate glass:
the substrate is made of FTO glass, sequentially and ultrasonically cleaned for 30 minutes by using foam water, acetone, ethanol and deionized water, and dried for later use.
Preparing a CdS film:
mixing CdSO4Pouring 15mL of the solution, 19mL of ammonia water and 15mL of thiourea solution into a beaker filled with 250mL of deionized water in sequence, clamping the cleaned FTO glass by using a clamp, putting the FTO glass into the beaker, and stirring the solution, wherein the reaction time is 20min, and the reaction temperature is 70 ℃, so as to obtain the CdS film with the thickness of about 40 nm.
Sb2Se3Preparing a film:
1. and (3) putting the processed N-type CdS film into a rapid annealing furnace, and pumping the pressure of the cavity to 0.34Pa by using a vacuum pump.
2. The furnace temperature is increased to 300 ℃ at the speed of 10 ℃/s and is kept for 20min, so that the substrate and Sb are mixed2Se3The source is heated sufficiently.
3. Then heating to 580 ℃ at the speed of 10 ℃/s, keeping for 110s, naturally cooling, taking out below 50 ℃, and thus obtaining Sb2Se3A film.
The (221) peak was found to be its preferred orientation by XRD powder diffraction analysis. The surface appearance of the film is observed by adopting a field emission scanning electron microscope to find the prepared Sb2Se3The crystallinity of the film is inferior to that of CdS/SnO2Sb as buffer layer2Se3The film had crystallinity and many voids were present. And it can be seen from the cross-sectional SEM image that it induces Sb2Se3The film grows along the pillar.
Preparation of Au electrode
In the Sb obtained above2Se3Plating a layer of gold electrode with the thickness of about 80nm on the surface of the film by adopting an evaporator to obtain Sb with CdS as an N-type layer2Se3The thin film battery has the following battery performance parameters: open circuit voltage Voc0.36V, short-circuit current density Jsc＝26.2mA/cm2The fill factor FF is 52.2 and the cell efficiency PCE is 4.94%.
Claims (3)
1. Based on CdS/SnO2High efficiency Sb of mixed N type layer2Se3The preparation method of the thin film battery is characterized by comprising the following steps:
(1) preparing a CdS film on an FTO substrate by adopting a chemical bath deposition method;
(2) a layer of SnO is spin-coated and deposited on the CdS film obtained in the step (1) by adopting a spin coating method2A film;
putting the CdS film with the thickness of 10-40nm obtained in the step (1) into a spin coater, and dropwise adding prepared SnO2Spin coating the aqueous solution on the CdS film for 4 times, each time spin coating for 30s at the rotation speed of 5000rpm, and annealing at 150 ℃ for 30min to obtain SnO with the thickness of 10-40nm2Wherein, SnO2SnO in aqueous solution according to mass ratio2:H2Preparing (1: 4) O;
(3) CdS/SnO obtained in the step (2) by adopting a rapid thermal evaporation method2Depositing a layer of Sb on the film2Se3A film;
CdS/SnO obtained in the step (2)2Placing the film into a rapid annealing furnace, and depositing for 110s at 580 ℃ under the pressure of 0.34Pa to obtain Sb2Se3A film;
(4) sb obtained in step (3) by evaporation2Se3Preparing a layer of gold electrode on the film;
the structure of the thin film battery is as follows from bottom to top in sequence: FTO substrate, CdS layer, SnO2Layer, Sb2Se3Layer, Au.
2. CdS/SnO based on according to claim 12High efficiency Sb of mixed N type layer2Se3The preparation method of the thin film battery is characterized in that the step (1) is carried out according to the following steps: and ultrasonically cleaning the FTO glass by using foam water, acetone, ethanol and deionized water in sequence, drying, and preparing the CdS film with the thickness of 10-40nm by using a water bath method.
3. CdS/SnO based on according to claim 12High efficiency Sb of mixed N type layer2Se3The preparation method of the thin film battery is characterized in that the Sb obtained in the step (3) is used2Se3The film was placed in an evaporator and a 80nm thick gold electrode was evaporated.
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