CN110137272B - Preparation method of solar cell with antimony sulfide-based thin film subjected to alcohol steam post-annealing treatment - Google Patents

Preparation method of solar cell with antimony sulfide-based thin film subjected to alcohol steam post-annealing treatment Download PDF

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CN110137272B
CN110137272B CN201910398353.4A CN201910398353A CN110137272B CN 110137272 B CN110137272 B CN 110137272B CN 201910398353 A CN201910398353 A CN 201910398353A CN 110137272 B CN110137272 B CN 110137272B
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李炫华
韩剑
王双洁
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Northwestern Polytechnical University
Shenzhen Institute of Northwestern Polytechnical University
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Abstract

The invention relates to a preparation method of a solar cell with an antimony sulfide-based film subjected to alcohol vapor post-annealing treatment, which is characterized in that for an antimony sulfide light absorption layer, the alcohol vapor post-annealing treatment is adopted: spin coating antimony precursor solution on TiO2And (3) after preparing the antimony sulfide film on the electron transmission layer, carrying out post-annealing treatment on the antimony sulfide film by adopting an alcohol vapor post-annealing treatment method. Compared with the traditional preparation method, the method ensures that the surface of the film is smoother, and meanwhile, in the alcohol molecules, hydroxyl hydrogen in the alcohol and Sb are2S3The lone pair electrons of the end S interact, and the alcohol vapor can partially dissolve the grain boundary of the film, so that the grain growth of the film is caused, and the crystallization quality is improved. The 'alcohol steam post-annealing treatment method' obviously improves the short open-circuit voltage (V) of the antimony sulfide-based thin-film solar cellOC) Road current density (J)SC) Fill Factor (FF) and energy conversion efficiency (PCE). Compared with the traditional annealing treatment method, the photoelectric conversion efficiency of the antimony sulfide-based thin-film solar cell prepared by the method is improved from 4.01% to 5.27%, and the photoelectric conversion efficiency is increased by 31.42% on a same scale.

Description

Preparation method of solar cell with antimony sulfide-based thin film subjected to alcohol steam post-annealing treatment
Technical Field
The invention belongs to the field of solar cell devices, and relates to a preparation method of a solar cell with an antimony sulfide-based film subjected to alcohol vapor post-annealing treatment.
Background
Environmental pollution and energy shortage are main reasons for restricting the development of the current socioeconomicThe ever-increasing demand for renewable, sustainable energy has become a driving force for the development of low-cost, stable, efficient solar cells. Therefore, various semiconductors such as copper zinc tin selenide, copper indium gallium selenide, lead sulfide, organic-inorganic hybrid perovskite, and antimony sulfide are used as the absorption layer, and excellent device conversion efficiency is obtained. Of these materials, antimony sulfide (Sb)2S3) Is a V-VI family direct band gap semiconductor material with stable properties, is the main component of stibnite, has rich crustal content, low material cost, no toxicity and higher absorption coefficient (alpha is 10)5cm-1) The band gap width is moderate and easy to regulate (1.5-2.2eV), covers most of visible light spectrum, and therefore, the solar cell material is regarded as one of the most promising solar cell materials.
However, in the process of preparing the antimony sulfide-based thin-film solar cell, the photoelectric property of the antimony sulfide-based thin-film solar cell is greatly influenced by the small grain size and poor crystallinity of the antimony sulfide-based thin-film solar cell. For the antimony sulfide photoactive layer, annealing treatment is an important means for regulating and controlling the crystallinity and the grain size of the thin film, so that the selection of a proper annealing treatment method is helpful for improving the photoelectric characteristics of the cell. At present, the annealing modes adopted mainly comprise a traditional mode and a program mode, but the two methods cannot effectively solve the problems of small grain size and poor crystallinity of the antimony sulfide thin film, so that the improvement of the photoelectric conversion efficiency of the antimony sulfide-based thin film solar cell and large-scale industrial application are limited. Therefore, a processing method applied to the photoactive layer of the antimony sulfide-based thin-film solar cell is developed, and the grain size and crystallinity of the antimony sulfide thin film are improved at the same time, so that the high-efficiency antimony sulfide-based thin-film solar cell is obtained.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a preparation method of a solar cell for post-annealing an antimony sulfide-based film by alcohol steam, which selects alcohols (isopropanol, ethanol and methanol) with different polarities by an alcohol steam post-annealing treatment method and applies the alcohols in the post-annealing process of the antimony sulfide film.
Technical scheme
A preparation method of a solar cell with an antimony sulfide-based film subjected to alcohol vapor post-annealing treatment is characterized by comprising the following steps:
step 1, FTO glass treatment: performing conventional pretreatment on the FTO glass;
step 2, preparing an electron transport layer: by using TiO2Preparing an electron transport layer on FTO glass as an electron transport material;
and 3, alcohol steam post-annealing treatment of the antimony sulfide light absorption layer: spin coating antimony precursor solution on TiO2On the electron transmission layer, after preparing the antimony sulfide film, carrying out post-annealing treatment on the antimony sulfide film by adopting an alcohol vapor post-annealing treatment method: placing the substrate of the precursor solution of the spin-coated antimony on a heating table of a small crucible, respectively dropping 10-200 μ l of isopropanol, ethanol and methanol into the crucible, simultaneously quickly covering with a culture dish, annealing at 400 ℃ for 1-5min at 100-;
step 4, preparing a hole transport layer: applying a Spiro-OMeTAD solution to a Spiro-OMeTAD layer on the antimony sulfide film;
and 5, electrode evaporation: and (3) evaporating and plating a layer of Au back electrode with the thickness of 100-120nm on the hole transport layer by adopting a thermal evaporation instrument to obtain the antimony sulfide-based thin-film solar cell.
Conventional pretreatment of the step 1: cleaning FTO glass by using cleaning powder, then respectively carrying out ultrasonic treatment on the FTO glass by using deionized water, acetone and absolute ethyl alcohol for 5-15min, blow-drying by using nitrogen, and finally carrying out UV treatment on the FTO glass for 5-20 min.
Step 2 of preparing TiO on FTO glass2Electron transport layer: spin coating TiO at the speed of 1000-2Annealing the solution in air at 100-500 deg.C for 10-60min, and cooling to room temperature to obtain compact TiO2An electron transport layer.
The precursor solution of antimony in the step 3 is as follows: 1.0-2.0mmol of Sb2O3Powder, 1.0-2.5m diluted in 1.0-3.0mL ethanolCS of L2And 1.0-2.5mL of n-butylamine are mixed and stirred to obtain the precursor solution of antimony.
Preparing an antimony sulfide film in the step 3: transferring the FTO glass substrate treated in the step 2 into a glove box protected by nitrogen, and dropwise adding the precursor solution of antimony into TiO2On the layer, spin-coating at 3000-9000rpm/min for 20-80s, and heating at 100-400 deg.C for 1-10min to obtain antimony sulfide film.
The Spiro-OMeTAD solution in the step 4 is as follows: adding 28. mu.l of 4-tert-butylpyridine and 17. mu.l of lithium bis (trifluoromethanesulfonylimide), Li-TFSI, to 1mL of chlorobenzene to obtain a Spiro-OMeTAD solution; the lithium bis (trifluoromethanesulfonyl) imide Li-TFSI is prepared by dissolving 520mg of Li-TFSI in 1ml of acetonitrile; the content of the components is measured in each part.
The Spiro-OMeTAD layer on the antimony sulfide film of step 4: spin-coating the Spiro-OMeTAD solution on the antimony sulfide film at the speed of 3000-9000rpm/min for 20-80s, and finally annealing in the air at the temperature of 50-200 ℃ for 10-30min to obtain the Spiro-OMeTAD layer.
The Sb2O3Powder, CS2And n-butylamine were used analytically.
The ethanol adopts super-grade pure.
Advantageous effects
The invention provides a preparation method of a solar cell for carrying out alcohol steam post-annealing treatment on an antimony sulfide-based film, and provides a method named as an alcohol steam post-annealing treatment method. According to the method, alcohols (isopropanol, ethanol and methanol) with different polarities are selected and applied to the post-annealing process of the antimony sulfide film, and as for the alcohol vapor post-annealing treatment method, on one hand, lattice distortion at a grain boundary is large, grain boundary energy exists, atoms have high energy, and at a certain temperature, the activity of the grain boundary atoms in the antimony sulfide film is strong, so that the grain boundary migration is facilitated, and the growth of grains is carried out through the migration of the grain boundary, so that the growth of the grains is caused. On the other hand, in the alcohol molecule, the less hydrocarbon groups on the carbon atoms directly bonded to the hydroxyl groups, the weaker the electron-pushing action, the stronger the polarity of the hydroxyl bonds, and the stronger the reactivity of the hydroxyl hydrogenSo that the hydroxyl hydrogen in methanol is reacted with Sb2S3The middle terminal S is most potent, ethanol second, isopropanol second. As mentioned above, the hydroxyl hydrogen in the alcohol is reacted with Sb2S3The lone pair electrons of the end S interact with each other, and at a certain temperature, the alcohol vapor can partially dissolve the grain boundary of the film, so that a liquid phase or a quasi-liquid phase is formed, the liquid phase or the quasi-liquid phase plays a role of 'sewing adhesive', the growth of film grains is caused, the crystallization quality is improved, and the photoelectric performance of the antimony sulfide-based film solar cell is effectively improved.
Compared with the traditional preparation method, the alcohol steam post-annealing treatment method provided by the invention adopts alcohols (isopropanol, ethanol and methanol) with different polarities to carry out post-annealing treatment on the antimony sulfide film, so that the surface of the film is smoother, and meanwhile, in an alcohol molecule, hydroxyl hydrogen in the alcohol and Sb are in contact with each other2S3The lone pair electrons of the end S interact, and alcohol vapor can partially dissolve the crystal boundary of the film at a certain temperature, so that the crystal grain growth of the film is finally caused, and the crystallization quality is improved. The 'alcohol steam post-annealing treatment method' obviously improves the short open-circuit voltage (V) of the antimony sulfide-based thin-film solar cellOC) Road current density (J)SC) Fill Factor (FF) and energy conversion efficiency (PCE). Compared with the traditional annealing treatment method, the photoelectric conversion efficiency of the antimony sulfide-based thin-film solar cell prepared by the method is improved from 4.01% to 5.27%, and the photoelectric conversion efficiency is increased by 31.42% on a same scale.
Drawings
FIG. 1 is a schematic structural diagram of an antimony sulfide-based thin-film solar cell prepared by the alcohol vapor post-annealing treatment method of the invention.
FIG. 2(a) is a scanning electron microscope top view of a standard antimony sulfide film, FIGS. 2(b), (c) and (d) are scanning electron microscope top views of antimony sulfide-based films prepared by an alcohol vapor post-annealing treatment method, wherein FIGS. (b), (c) and (d) are scanning electron microscope top views of antimony sulfide films subjected to isopropanol vapor post-annealing treatment, ethanol vapor post-annealing treatment and methanol vapor post-annealing treatment, respectively. FIGS. 2(e), (f), (g) and (h) are all statistical distribution diagrams of grain size of antimony sulfide-based films prepared by the alcohol vapor post-annealing treatment method, wherein the graphs (e), (f), (g) and (h) are statistical distribution diagrams of grain size of antimony sulfide-based films of a standard part, isopropanol vapor post-annealing treatment, ethanol vapor post-annealing treatment and methanol vapor post-annealing treatment, respectively.
FIG. 3 shows the solar energy spectrum energy AM 1.5G, 100mW/cm2Under illumination, the current density-voltage (J-V) characteristic curve diagram of the antimony sulfide-based thin-film solar cell is shown.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
an antimony sulfide-based thin-film solar cell structurally comprises fluorine-doped tin oxide conductive glass (FTO), an electron transport layer, an antimony sulfide light absorption layer, a hole transport layer and a back electrode which are sequentially stacked.
The preparation method of the solar cell adopting the alcohol steam post-annealing treatment antimony sulfide-based film is characterized by comprising the following steps of:
1) and (3) processing of FTO glass: cleaning FTO glass by using cleaning powder, performing ultrasonic treatment on the FTO glass by using deionized water, acetone and absolute ethyl alcohol for 5 to 15min respectively, drying the FTO glass by using nitrogen, and performing UV treatment on the FTO glass for 5 to 20 min;
2) preparation of an electron transport layer: the invention adopts TiO2As an electron transport material, spin-coating the solution on the FTO glass treated in the step 1) for 20-80s at the speed of 1000-2A layer;
3) preparation of antimony sulfide light absorption layer: transferring the substrate treated in the step 2) into a glove box protected by nitrogen. Sb2O3CS diluted in powder (1.0-2.0mmol, AR analytically pure), ethanol (1.0-3.0mL, super grade pure GR)2(1.0-2.5mL, AR) and n-butylamine (1.0-2.5mL, AR) are fully mixed and stirred to obtain a precursor solution of antimony. Then dripping the precursor solution into TiO2Spin coating on the layer at the speed of 3000-9000rpm/min for 20-80s, heating at 100-400 deg.C for 1-10min, post-annealing the antimony sulfide film by alcohol vapor post-annealing treatment,moving the substrate to a heating table with a small crucible, respectively dripping 10-200 μ l of isopropanol, ethanol and methanol into the crucible, simultaneously quickly covering with a culture dish, annealing at 400 ℃ for 1-5min, and performing solvent-free annealing treatment on the standard antimony sulfide film to obtain the antimony sulfide light absorption layer.
4) Preparation of hole transport layer: adding 28 mu.l of 4-tert-butylpyridine (4-tert-butyl pyridine) and 17 mu.l of lithium bistrifluoromethanesulfonylimide (Li-TFSI) (520mg of Li-TFSI dissolved in 1mL of acetonitrile) into 1mL of chlorobenzene to obtain a Spiro-OMeTAD solution, spin-coating the solution on the antimony sulfide film prepared in the step 3) at the speed of 3000-9000rpm/min for 20-80s, and finally annealing in the air at 50-200 ℃ for 10-30min to obtain the Spiro-OMeTAD layer.
5) Electrode evaporation: and (3) evaporating and plating a layer of Au back electrode with the thickness of 100-120nm on the hole transport layer by adopting a thermal evaporation instrument to obtain the antimony sulfide-based thin-film solar cell.
For ease of understanding, the technical solution of the present invention is further described in the following exemplary examples and comparative examples:
comparative example one: compared with the examples, the comparative example adopts the 'alcohol-free steam post-annealing treatment method' to carry out post-annealing treatment on the antimony sulfide film, and concretely operates as follows,
1) and (3) processing of FTO glass: firstly, cleaning FTO glass with the size of 15mm multiplied by 15mm and the impedance of 14 omega/sq by using cleaning powder, then respectively carrying out ultrasonic treatment on the FTO glass for 10min by using deionized water, acetone and absolute ethyl alcohol, drying the FTO glass by using nitrogen, and finally carrying out UV treatment on the FTO glass for 15 min;
2) preparation of an electron transport layer: prepared TiO2Spin-coating the solution on the FTO glass treated in the step 1) for 60s at the speed of 4000rpm/min, then annealing the solution in the air at the temperature of 400 ℃ for 40min, and then slowly cooling the solution to the room temperature to obtain compact TiO2A layer;
3) preparing an antimony sulfide light absorption layer: transferring the substrate treated in the step 2) into a glove box protected by nitrogen. Sb2O3CS diluted in powder (1.0mmol, AR), EtOH (2mL, GR)2(2mL, AR) and n-butylamine (1.5mL, AR) were thoroughly mixed and stirred to give a precursor of antimonyA precursor solution is dripped into the TiO2Spin-coating on the layer at 8000rpm/min for 40s, heating at 250 deg.C for 3min, and annealing the substrate at 300 deg.C for 3min to obtain antimony sulfide light-absorbing layer;
4) preparation of hole transport layer: adding 28 mu.l of 4-tert-butylpyridine (4-tert-butyl pyridine) and 17 mu.l of lithium bistrifluoromethanesulfonylimide (Li-TFSI) (520mg of Li-TFSI dissolved in 1mL of acetonitrile) into 1mL of chlorobenzene to obtain a Spiro-OMeTAD solution, spin-coating the solution on the antimony sulfide film prepared in the step 3) at the speed of 6000rpm/min for 60s, and finally annealing in the air at 120 ℃ for 20min to obtain a Spiro-OMeTAD layer;
5) electrode evaporation: and (3) evaporating and plating a layer of Au back electrode with the thickness of 110nm on the hole transport layer by adopting a thermal evaporation plating instrument to obtain the antimony sulfide-based thin-film solar cell.
The photoelectric performance test result of the battery is as follows: vOC、JSCFF and PCE are respectively 0.57V +/-0.01 and 14.45mA/cm2±0.25、48.67％±0.49、4.01％±0.14。
The embodiment adopting the method of the invention comprises the following steps:
the first embodiment is as follows:
1) and (3) processing of FTO glass: firstly, cleaning FTO glass with the size of 15mm multiplied by 15mm and the impedance of 14 omega/sq by using cleaning powder, then respectively carrying out ultrasonic treatment on the FTO glass for 10min by using deionized water, acetone and absolute ethyl alcohol, drying the FTO glass by using nitrogen, and finally carrying out UV treatment on the FTO glass for 15 min;
2) preparation of an electron transport layer: prepared TiO2Spin-coating the solution on the FTO glass treated in the step 1) for 60s at the speed of 4000rpm/min, then annealing the solution in the air at the temperature of 400 ℃ for 40min, and then slowly cooling the solution to the room temperature to obtain compact TiO2A layer;
3) preparing an antimony sulfide light absorption layer: transferring the substrate treated in the step 2) into a glove box protected by nitrogen. Sb2O3CS diluted in powder (1.0mmol, AR), EtOH (2mL, GR)2(2mL, AR) and n-butylamine (1.5mL, AR) were thoroughly mixed and stirred to give a precursor solution of antimony, which was added dropwise to TiO2And spin-coating the layer at 8000rpm/min for 40s, and heating at 250 deg.C for 3min to obtain antimony sulfide light-absorbing layer. And then carrying out post-annealing treatment on the antimony sulfide film by adopting an alcohol vapor post-annealing treatment method, moving the substrate to a heating table with a small crucible, dripping 81 mu l of isopropanol into the crucible, simultaneously quickly covering the crucible with a culture dish, and carrying out annealing treatment at 300 ℃ for 3min to obtain an antimony sulfide light absorption layer subjected to post-annealing treatment by using isopropanol vapor.
4) Preparation of hole transport layer: adding 28 mu.l of 4-tert-butylpyridine (4-tert-butyl pyridine) and 17 mu.l of lithium bistrifluoromethanesulfonylimide (Li-TFSI) (520mg of Li-TFSI dissolved in 1mL of acetonitrile) into 1mL of chlorobenzene to obtain a Spiro-OMeTAD solution, spin-coating the solution on the antimony sulfide film prepared in the step 3) at the speed of 6000rpm/min for 60s, and finally annealing in the air at 120 ℃ for 20min to obtain a Spiro-OMeTAD layer;
5) electrode evaporation: and (3) evaporating and plating a layer of Au back electrode with the thickness of 110nm on the hole transport layer by adopting a thermal evaporation plating instrument to obtain the antimony sulfide-based thin-film solar cell annealed by isopropanol vapor.
The photoelectric performance test result of the battery is as follows: vOC、JSCFF and PCE are respectively 0.58V +/-0.03 and 15.72mA/cm2±0.28、50.08％±0.50、4.57％±0.13；
Example two:
1) and (3) processing of FTO glass: firstly, cleaning FTO glass with the size of 15mm multiplied by 15mm and the impedance of 14 omega/sq by using cleaning powder, then respectively carrying out ultrasonic treatment on the FTO glass for 10min by using deionized water, acetone and absolute ethyl alcohol, drying the FTO glass by using nitrogen, and finally carrying out UV treatment on the FTO glass for 15 min;
2) preparation of an electron transport layer: prepared TiO2Spin-coating the solution on the FTO glass treated in the step 1) for 60s at the speed of 4000rpm/min, then annealing the solution in the air at the temperature of 400 ℃ for 40min, and then slowly cooling the solution to the room temperature to obtain compact TiO2A layer;
3) preparing an antimony sulfide light absorption layer: transferring the substrate treated in the step 2) into a glove box protected by nitrogen. Sb2O3Powder (1.0mmol, AR) and ethanol (2mL, GR)Diluted CS2(2mL, AR) and n-butylamine (1.5mL, AR) were thoroughly mixed and stirred to give a precursor solution of antimony, which was added dropwise to TiO2And spin-coating the layer at 8000rpm/min for 40s, and heating at 250 deg.C for 3min to obtain antimony sulfide light-absorbing layer. And then carrying out post-annealing treatment on the antimony sulfide film by adopting an alcohol vapor post-annealing treatment method, moving the substrate to a heating table with a small crucible, dripping 40 mu l of ethanol into the crucible, simultaneously quickly covering the crucible with a culture dish, and carrying out annealing treatment at 300 ℃ for 3min to obtain an antimony sulfide light absorption layer subjected to ethanol vapor post-annealing treatment.
4) Preparation of hole transport layer: adding 28 mu.l of 4-tert-butylpyridine (4-tert-butyl pyridine) and 17 mu.l of lithium bistrifluoromethanesulfonylimide (Li-TFSI) (520mg of Li-TFSI dissolved in 1mL of acetonitrile) into 1mL of chlorobenzene to obtain a Spiro-OMeTAD solution, spin-coating the solution on the antimony sulfide film prepared in the step 3) at the speed of 6000rpm/min for 60s, and finally annealing in the air at 120 ℃ for 20min to obtain a Spiro-OMeTAD layer;
5) electrode evaporation: electrode evaporation: and (3) evaporating and plating a layer of Au back electrode with the thickness of 110nm on the hole transport layer by adopting a thermal evaporation plating instrument to obtain the antimony sulfide-based thin-film solar cell annealed after ethanol vapor.
The photoelectric performance test result of the battery is as follows: vOC、JSCFF and PCE are respectively 0.59V +/-0.02 and 16.03mA/cm2±0.26、51.63％±0.52、4.88％±0.12。
Example three:
1) and (3) processing of FTO glass: firstly, cleaning FTO glass with the size of 15mm multiplied by 15mm and the impedance of 14 omega/sq by using cleaning powder, then respectively carrying out ultrasonic treatment on the FTO glass for 10min by using deionized water, acetone and absolute ethyl alcohol, drying the FTO glass by using nitrogen, and finally carrying out UV treatment on the FTO glass for 15 min;
2) preparation of an electron transport layer: prepared TiO2Spin-coating the solution on the FTO glass treated in the step 1) for 60s at the speed of 4000rpm/min, then annealing the solution in the air at the temperature of 400 ℃ for 40min, and then slowly cooling the solution to the room temperature to obtain compact TiO2A layer;
3) antimony sulfide light absorbing layerThe preparation of (1): transferring the substrate treated in the step 2) into a glove box protected by nitrogen. Sb2O3CS diluted in powder (1.0mmol, AR), EtOH (2mL, GR)2(2mL, AR) and n-butylamine (1.5mL, AR) were thoroughly mixed and stirred to give a precursor solution of antimony, which was added dropwise to TiO2And spin-coating the layer at 8000rpm/min for 40s, and heating at 250 deg.C for 3min to obtain antimony sulfide light-absorbing layer. Then carrying out post-annealing treatment on the antimony sulfide film by adopting an alcohol vapor post-annealing treatment method, moving the substrate to a heating table with a small crucible, dripping 42 mu l of methanol into the crucible, simultaneously quickly covering the crucible with a culture dish, and carrying out annealing treatment at 300 ℃ for 3min to obtain an antimony sulfide light absorption layer subjected to methanol vapor post-annealing treatment;
4) preparation of hole transport layer: adding 28 mu.l of 4-tert-butylpyridine (4-tert-butyl pyridine) and 17 mu.l of lithium bistrifluoromethanesulfonylimide (Li-TFSI) (520mg of Li-TFSI dissolved in 1mL of acetonitrile) into 1mL of chlorobenzene to obtain a Spiro-OMeTAD solution, spin-coating the solution on the antimony sulfide film prepared in the step 3) at the speed of 6000rpm/min for 60s, and finally annealing in the air at 120 ℃ for 20min to obtain a Spiro-OMeTAD layer;
5) electrode evaporation: and (3) evaporating and plating a layer of Au back electrode with the thickness of 110nm on the hole transport layer by adopting a thermal evaporation plating instrument to obtain the antimony sulfide-based thin-film solar cell annealed by isopropanol vapor.
The photoelectric performance test result of the battery is as follows: vOC、JSCFF and PCE are respectively 0.60V +/-0.02 and 16.61mA/cm2±0.28、52.86％±0.65、5.27％±0.14。

Claims (8)

1. A preparation method of a solar cell with an antimony sulfide-based film subjected to alcohol vapor post-annealing treatment is characterized by comprising the following steps:
step 1, FTO glass treatment: performing conventional pretreatment on the FTO glass; the conventional pretreatment comprises the following steps: cleaning FTO glass by using cleaning powder, performing ultrasonic treatment on the FTO glass for 5 to 15min by using deionized water, acetone and absolute ethyl alcohol respectively, drying the FTO glass by using nitrogen, and finally performing UV treatment on the FTO glass for 5 to 20 min;
step 2, preparing an electron transport layer: by using TiO2Preparing an electron transport layer on FTO glass as an electron transport material;
and 3, alcohol steam post-annealing treatment of the antimony sulfide light absorption layer: spin coating antimony precursor solution on TiO2On the electron transmission layer, after preparing the antimony sulfide film, carrying out post-annealing treatment on the antimony sulfide film by adopting an alcohol vapor post-annealing treatment method: then placing the antimony sulfide film on a heating table containing a small crucible, respectively dropping 10-200 μ l of isopropanol, ethanol and methanol into the crucible, simultaneously quickly covering with a culture dish, annealing at 400 ℃ for 1-5min at 100-;
step 4, preparing a hole transport layer: spin-coating a Spiro-OMeTAD solution on the antimony sulfide film to prepare a Spiro-OMeTAD layer;
and 5, electrode evaporation: and (3) evaporating and plating a layer of Au back electrode with the thickness of 100-120nm on the hole transport layer by adopting a thermal evaporation instrument to obtain the antimony sulfide-based thin-film solar cell.
2. The method of claim 1 for preparing a solar cell by post-annealing antimony sulfide-based thin film with alcohol vapor, comprising: step 2 of preparing TiO on FTO glass2Electron transport layer: spin coating TiO at the speed of 1000-2Annealing the solution in air at 100-500 deg.C for 10-60min, and cooling to room temperature to obtain compact TiO2An electron transport layer.
3. The method of claim 1 for preparing a solar cell by post-annealing antimony sulfide-based thin film with alcohol vapor, comprising: the precursor solution of antimony in the step 3 is as follows: 1.0-2.0mmol of Sb2O3Powder, 1.0-2.5mL of CS diluted in 1.0-3.0mL of ethanol2And 1.0-2.5mL of n-butylamine are mixed and stirred to obtain the precursor solution of antimony.
4. Alcohol vapor post-annealing antimony sulfide according to claim 1 or 3The preparation method of the solar cell based on the thin film is characterized by comprising the following steps: preparing an antimony sulfide film in the step 3: transferring the FTO glass substrate treated in the step 2 into a glove box protected by nitrogen, and dropwise adding the precursor solution of antimony into TiO2On the layer, spin-coating at 3000-9000rpm/min for 20-80s, and heating at 100-400 deg.C for 1-10min to obtain antimony sulfide film.
5. The method of claim 1 for preparing a solar cell by post-annealing antimony sulfide-based thin film with alcohol vapor, comprising: the Spiro-OMeTAD solution in the step 4 is as follows: adding 28. mu.l of 4-tert-butylpyridine and 17. mu.l of lithium bis (trifluoromethanesulfonylimide), Li-TFSI, to 1mL of chlorobenzene to obtain a Spiro-OMeTAD solution; the lithium bis (trifluoromethanesulfonyl) imide Li-TFSI is prepared by dissolving 520mg of Li-TFSI in 1ml of acetonitrile; the content of the components is measured in each part.
6. The method for manufacturing a solar cell by post-annealing an antimony sulfide-based thin film using alcohol vapor according to claim 1 or 5, wherein: preparing a Spiro-OMeTAD layer on the antimony sulfide film in the step 4: spin-coating the Spiro-OMeTAD solution on the antimony sulfide film at the speed of 3000-9000rpm/min for 20-80s, and finally annealing in the air at the temperature of 50-200 ℃ for 10-30min to obtain the Spiro-OMeTAD layer.
7. The method of claim 3 for preparing a solar cell by post-annealing antimony sulfide-based thin film with alcohol vapor, comprising: the Sb2O3Powder, CS2And n-butylamine were used analytically.
8. The method of claim 3 for preparing a solar cell by post-annealing antimony sulfide-based thin film with alcohol vapor, comprising: the ethanol adopts super-grade pure.
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