CN109802011B - Method for preparing copper-zinc-tin-sulfur film through sulfurization annealing in air - Google Patents
Method for preparing copper-zinc-tin-sulfur film through sulfurization annealing in air Download PDFInfo
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Abstract
The invention discloses a method for preparing a copper-zinc-tin-sulfur film by sulfurization annealing in air. The method is to mix CuO, ZnO and SnO2The mixed slurry is coated on a cleaned glass substrate to form an oxide precursor film; sealing the oxide precursor film and sulfur powder in a container resistant to the vulcanization reaction in an air environment; and finally, placing the sealed container into a tubular furnace or a muffle furnace, and heating for annealing treatment to obtain the copper-zinc-tin-sulfur film. The method has the advantages of simple high-temperature vulcanization annealing process, cheap preparation equipment, high utilization rate of sulfur powder raw materials, environmental protection and the like, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of solar cell materials and devices, in particular to a method for preparing a copper-zinc-tin-sulfur film through sulfurization annealing in air.
Background
With the growing world population and the increasing pressure of environmental pollution on energy sources, the energy problems are attracting more and more attention. Therefore, it is important to find a clean and renewable new energy source to replace the traditional fossil energy source. Compared with other renewable energy sources, the solar energy has the advantages of being universal in source, safe, pollution-free, renewable for a long time and the like, and is naturally a more appropriate alternative energy source. Solar cells are an efficient way to convert solar energy directly into electrical energy.
Among the numerous solar cells, the compound thin-film solar cell has been widely developed in recent years as a low-cost solar cell. The copper indium gallium selenide series thin-film solar cell is taken as a compound thin-film solar cell which is successful, and is commercially produced. However, the expensive indium gallium limits its further development. Copper zinc tin sulfide is expected to replace copper indium gallium selenide thin filmThe material of the absorbing layer of the film is attracting much attention. It has a suitable band gap (1.5 eV), a high absorption coefficient (10)5cm-1) High theoretical conversion efficiency, rich raw material sources and the like.
At present, the method for preparing the copper-zinc-tin-sulfur film mainly comprises a vacuum method and a non-vacuum method. In order to obtain high-quality copper zinc tin sulfide films, the introduction of the sulfurizing annealing is inevitable in both methods. The high-temperature vulcanization annealing can promote the growth of film crystal grains, reduce the defects of the film and improve the efficiency of the solar cell. Currently, the sulfur source can be divided into hydrogen sulfide gas and solid sulfur powder for vulcanization annealing. Annealing in hydrogen sulfide atmosphere has better reactivity, but hydrogen sulfide has toxicity, and large-scale production has potential safety hazard and tail gas emission and other problems. The annealing in sulfur steam means that solid sulfur powder is heated to form steam pressure and then reacts with a precursor film to form copper-zinc-tin-sulfur. When the high temperature reaction is finished, the sulfur steam can be condensed again to form solid sulfur. Therefore, the sulfur powder vulcanization has the advantages of safety, no toxicity, low cost, easiness in large-scale production and the like, and more attention and research are paid.
The patent application documents in the prior art are searched, and a lot of patent applications are found in the aspect of annealing the copper-zinc-tin-sulfur thin film by taking solid sulfur as a sulfur source, for example, a compact copper-zinc-tin-sulfur precursor thin film is obtained by electrodeposition coating, and then the precursor thin film and 100-2000 mg of sulfur powder are put under a vacuum condition for vulcanization annealing treatment to obtain the copper-zinc-tin-sulfur absorption layer thin film (application number 201410021101.7); and then preparing a copper-tin-sulfur and zinc sulfide prefabricated layer by adopting multi-target double-target co-sputtering, then carrying out alloy treatment on the prefabricated layer, finally putting the prefabricated layer subjected to alloy treatment into a vulcanizing furnace, carrying out vulcanization annealing (570-590 ℃, 25-35 minutes) under the protection of normal pressure nitrogen, and naturally cooling to obtain the copper-zinc-tin-sulfur film (application No. 201510612081.5). Meanwhile, the existing documents are searched, and the current method for preparing the copper-zinc-tin-sulfur film by vulcanizing the solid sulfur powder is to anneal the sample and the sulfur powder in a vacuum or inert atmosphere. If the Cu/Sn/Zn laminated film obtained by thermal evaporation is put into a nitrogen protective atmosphere, and is subjected to 560 ℃ sulfuration annealing for 2 hours by using sulfur powder, a copper-zinc-tin-sulfur film can be obtained (Thin Solid Films 517 (2008) (1457) 1457-; then, for example, the oxide nanoparticle precursor film and the sulfur powder are placed in a vacuum tube furnace at the same time, a vacuum pump is used to obtain a background vacuum of 1Pa, and finally, the sulfur vapor and the oxide precursor film are reacted under a vacuum environment to obtain the copper-zinc-tin-sulfur thin film (Journal of Power Sources 276 (2015) 145-152).
However, the existing solid sulfur powder vulcanization annealing technology all involves vacuum or inert atmosphere (nitrogen or argon), has extremely high requirements on annealing equipment and relatively high cost, and is not beneficial to large-scale production of copper-zinc-tin-sulfur films.
Disclosure of Invention
The invention aims to provide a method for preparing copper-zinc-tin-sulfur (Cu) by sulfuration annealing in air, which is simple to operate2ZnSnS4) A method of making a thin film. The method is to use low cost oxide nanoparticles, namely CuO, ZnO and SnO2The mixed slurry is a precursor, and a uniform and high-quality copper-zinc-tin-sulfur film of the solar cell absorption layer is prepared by carrying out sulfurization annealing in air.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing a copper-zinc-tin-sulfur film by sulfurization annealing in air comprises the following steps:
1) mixing CuO, ZnO and SnO2The mixed slurry is coated on a cleaned glass substrate to form an oxide precursor film;
2) sealing the oxide precursor film and sulfur powder in a container resistant to a vulcanization reaction in an air environment;
3) and (3) putting the sealed container into a tubular furnace or a muffle furnace, and heating for annealing treatment to obtain the copper-zinc-tin-sulfur film.
The molar ratio of elements in the mixed slurry in the step 1) is as follows: n (cu)/n (Sn + Zn) =0.8, n (Zn)/n (Sn) = 1.2.
The concentration of the mixed slurry in the step 1) is 200-220 mg/ml.
The coating method in the step 1) is a knife-scraping method or a spin-coating method, and the thickness of the oxide precursor film is 1-5 microns.
The glass substrate in the step 1) is a molybdenum-plated glass substrate or a soda-lime glass substrate, and is pretreated as follows: sequentially immersing the molybdenum-plated glass into a common detergent, deionized water, ethanol and an acetone solution, and then ultrasonically treating and washing the molybdenum-plated glass by using the deionized water.
The container resistant to the vulcanization reaction in the step 2) is a quartz glass tube or a stainless steel tube, the inner diameter is 1-5 cm, and the length is 5-25 cm.
The minimum usage amount of the sulfur powder in the step 2) is determined according to the volume of a container resistant to the vulcanization reaction.
The annealing temperature in the step 3) is 400-600 ℃, and the annealing time is 10-300 min.
Step 3) in the annealing process, the oxide precursor film and the sulfur powder are heated from room temperature at the same time, and the heating rate is 40-50 ℃/min
By adopting the technical scheme, the invention has the advantages of simple annealing process, uncomplicated equipment, low raw material cost, high material utilization rate and the like, and is suitable for large-scale industrial production. The principle of the invention is as follows:
1) the oxide precursor film and the solid sulfur powder are sealed in a container in an air environment to be completely isolated from the external environment, and a vacuum pump or an inert atmosphere is not needed to be used for manufacturing an oxygen-free and water-free environment in the process.
2) The sealing system is heated to a high temperature, and since sulphur sublimes above 120 ℃, the sulphur vapour obtained can preferentially react with 21% of the oxygen in the air to form sulphur dioxide, which can be considered as an inert gas during the subsequent sulphiding process. In addition, 78% of nitrogen gas in the air is inert gas, so that the high-temperature vulcanization is completely carried out to obtain a high-quality copper-zinc-tin-sulfur film.
The invention has the following outstanding advantages: the invention provides a method for obtaining a copper-zinc-tin-sulfur film by sulfurization in an air atmosphere, which has low cost and simple preparation process. According to the reports of relevant patent documents, other annealing methods for preparing the copper-zinc-tin-sulfur thin film generally need to be carried out in a high vacuum environment or an inert atmosphere, the process is complex, and the required equipment is expensive. Therefore, the invention adopts the simple closed air atmosphere to carry out vulcanization to obtain the copper-zinc-tin-sulfur film of the solar cell absorption layer, and the specific beneficial effects are embodied in the following points: 1) the invention firstly adopts a closed space in the air to carry out high-temperature vulcanization annealing on an oxide precursor to obtain the copper-zinc-tin-sulfur film; 2) vulcanization in an air atmosphere has two benefits: firstly, the vulcanizing annealing device does not need expensive high-vacuum equipment; secondly, the sulfur powder in the closed container can be recycled, and no pollution is caused.
Drawings
The invention will be further explained with reference to the drawings.
FIG. 1 is a view showing an air-vulcanizable sealed silica glass device according to example 1 of the present invention.
FIG. 2 is an XRD pattern of a CZTS film prepared in example 1 of the present invention.
FIG. 3 is an SEM image of a CZTS film prepared in example 1 of the present invention.
Detailed Description
The present invention will now be further described by way of examples for a better understanding of the invention.
A method for preparing a copper-zinc-tin-sulfur film by sulfurization annealing in air comprises the following steps:
1) sequentially immersing the glass substrate into a common detergent, deionized water, ethanol and an acetone solution, and then ultrasonically cleaning and washing the glass substrate by using the deionized water for later use;
mixing CuO, ZnO and SnO2The mixed slurry (concentration is 200-;
2) sealing the oxide precursor film and sulfur powder in a quartz glass tube or a stainless steel tube with the inner diameter of 1-5 cm and the length of 5-25 cm in an air environment;
3) and (3) carrying out high-temperature annealing treatment on the sealed container, selecting a tubular furnace or a muffle furnace as a heating source, heating the oxide precursor film and the sulfur powder from room temperature at the same time, wherein the heating rate is 40-50 ℃/min, finally keeping the temperature at 400-600 ℃, preserving the heat for 10-300 min, and then slowly cooling to room temperature to obtain the copper-zinc-tin-sulfur film.
The chemical reagents related to the invention are purchased from chemical reagent companies of the national medicine group, the sulfur powder is purchased from Aladdin Chemistry co.ltd, and the molybdenum-plated glass or the soda-lime glass is purchased from new yang generation material science and technology (Ningbo) company and Luoyang Longyao glass company.
Example 1
A method for preparing a copper-zinc-tin-sulfur film by sulfurization annealing in air comprises the following steps:
1. sequentially immersing the molybdenum-plated glass substrate into a common detergent, deionized water, ethanol and acetone solution, then ultrasonically treating and washing the substrate by the deionized water, and completely washing CuO, ZnO and SnO2Coating the mixed slurry (with the concentration of 200mg/ml, n (Cu)/n (Sn + Zn) =0.8, n (Zn)/n (Sn) = 1.2)) on the surface of the molybdenum-plated glass by a knife scraping method to obtain an oxide precursor film;
2. sealing the oxide precursor film and 0.3g of sulfur powder in a quartz tube with the inner diameter of 2.5cm and the length of 15cm in an air environment;
3. and sealing the quartz tube, performing high-temperature thermal treatment, selecting a tube furnace as a heating source, heating the sulfur powder and the oxide precursor film from room temperature at the same time at a heating rate of 40 ℃/min, finally keeping the temperature at 580 ℃, preserving the temperature for 30min, and then slowly cooling to room temperature to obtain the copper-zinc-tin-sulfur film.
The film prepared in this example was tested by XRD, and as can be seen from fig. 2, the obtained film was pure phase copper zinc tin sulfide; the film prepared in this example was tested by SEM, and as can be seen from fig. 3, the obtained cu-zn-sn-s film was dense, flat and highly uniform.
Example 2
A method for preparing a copper-zinc-tin-sulfur film by sulfurization annealing in air comprises the following steps:
1. sequentially immersing the soda-lime glass substrate into a common detergent, deionized water, ethanol and acetone solution, then ultrasonically treating and washing the substrate by the deionized water, and adding CuO, ZnO and SnO2Coating the mixed slurry (with the concentration of 200mg/ml, n (Cu)/n (Sn + Zn) =0.8, n (Zn)/n (Sn) = 1.2)) on the surface of the soda-lime glass by a knife-scraping method to obtain an oxide precursor film;
2. sealing the oxide precursor film and 0.2g of sulfur powder in a quartz tube with the inner diameter of 2cm and the length of 10cm in an air environment;
3. and sealing the quartz tube, performing high-temperature heat treatment, selecting a tube furnace as a heating source, heating the sulfur powder and the oxide film from room temperature at the same time at a heating rate of 40 ℃/min, finally keeping the temperature at 530 ℃, preserving the temperature for 60min, and then slowly cooling to room temperature to obtain the copper-zinc-tin-sulfur film.
Example 3
A method for preparing a copper-zinc-tin-sulfur film by sulfurization annealing in air comprises the following steps:
1. sequentially immersing the molybdenum-plated glass substrate into a common detergent, deionized water, ethanol and acetone solution, then ultrasonically treating and washing the substrate by the deionized water, and completely washing CuO, ZnO and SnO2Coating the mixed slurry (with the concentration of 200mg/ml, n (Cu)/n (Sn + Zn) =0.8, n (Zn)/n (Sn) = 1.2)) on the surface of the molybdenum-plated glass by a knife scraping method to obtain an oxide precursor film;
2. sealing the oxide precursor film and 0.6g of sulfur powder in a quartz tube with the inner diameter of 3cm and the length of 25cm in an air environment;
3. and sealing the quartz tube and then performing high-temperature heat treatment. And selecting a tubular furnace as a heating source, heating the sulfur powder and the oxide film from room temperature at the same time, keeping the temperature at 600 ℃ for 120min at the heating rate of 40 ℃/min, and then slowly cooling to room temperature to obtain the copper-zinc-tin-sulfur film.
Example 4
A method for preparing a copper-zinc-tin-sulfur film by sulfurization annealing in air comprises the following steps:
1. sequentially immersing the molybdenum-plated glass substrate into a common detergent, deionized water, ethanol and acetone solution, then ultrasonically treating and washing the substrate by the deionized water, and completely washing CuO, ZnO and SnO2The mixed slurry (concentration of 200mg/ml, n (Cu)/n (Sn + Zn) =0.8, n (Zn)/n (Sn) = 1.2)) was coated on the surface of the molybdenum-plated glass by a knife-blade method to obtain an oxidized molybdenum-plated glassA precursor film;
2. sealing the oxide precursor film and 0.6g of sulfur powder in a quartz tube with the inner diameter of 3cm and the length of 25cm in an air environment;
3. and sealing the quartz tube and then performing high-temperature heat treatment. And selecting a tubular furnace as a heating source, heating the sulfur powder and the oxide film from room temperature at the same time, keeping the temperature at 400 ℃ for 300min at the heating rate of 5 ℃/min, and then slowly cooling to room temperature to obtain the copper-zinc-tin-sulfur film.
Example 4
A method for preparing a copper-zinc-tin-sulfur film by sulfurization annealing in air comprises the following steps:
1. sequentially immersing the molybdenum-plated glass substrate into a common detergent, deionized water, ethanol and acetone solution, then ultrasonically treating and washing the substrate by the deionized water, and completely washing CuO, ZnO and SnO2Coating the mixed slurry (with the concentration of 220mg/ml, n (Cu)/n (Sn + Zn) =0.8, n (Zn)/n (Sn) = 1.2)) on the surface of the molybdenum-plated glass by a knife scraping method to obtain an oxide precursor film;
2. sealing the oxide precursor film and 0.5g of sulfur powder in a quartz tube with the inner diameter of 3cm and the length of 25cm in an air environment;
3. and sealing the quartz tube and then performing high-temperature heat treatment. And selecting a tubular furnace as a heating source, heating the sulfur powder and the oxide film from room temperature at the same time, keeping the temperature at 600 ℃ for 10min at the heating rate of 5 ℃/min, and then slowly cooling to room temperature to obtain the copper-zinc-tin-sulfur film.
Claims (4)
1. A method for preparing a copper-zinc-tin-sulfur film by sulfurization annealing in air is characterized by comprising the following steps: which comprises the following steps
1) Mixing CuO, ZnO and SnO2The mixed slurry is coated on a cleaned glass substrate to form an oxide precursor film;
the molar ratio of elements in the mixed slurry is as follows: n (Cu)/n (Sn + Zn) =0.8, n (Zn)/n (Sn) =1.2, and the concentration of the mixed slurry is 200-;
2) sealing the oxide precursor film and sulfur powder in a container resistant to a vulcanization reaction in an air environment;
3) putting the sealed container into a tube furnace or a muffle furnace, and heating for annealing treatment to obtain the copper-zinc-tin-sulfur film;
in the annealing process, the oxide precursor film and the sulfur powder are heated from room temperature at the same time, the heating rate is 40-50 ℃/min, the temperature is raised to 400-600 ℃, and the annealing time is 10-300 min.
2. The method for preparing the copper-zinc-tin-sulfur film by the sulfuration annealing in the air as claimed in claim 1, wherein: the coating method in the step 1) is a knife-scraping method or a spin-coating method, and the thickness of the oxide precursor film is 1-5 microns.
3. The method for preparing the copper-zinc-tin-sulfur film by the sulfuration annealing in the air as claimed in claim 1, wherein: the glass substrate in the step 1) is a molybdenum-plated glass substrate or a soda-lime glass substrate, and is pretreated as follows: sequentially immersing the molybdenum-plated glass into a common detergent, deionized water, ethanol and an acetone solution, and then ultrasonically treating and washing the molybdenum-plated glass by using the deionized water.
4. The method for preparing the copper-zinc-tin-sulfur film by the sulfuration annealing in the air as claimed in claim 1, wherein: the container resistant to the vulcanization reaction in the step 2) is a quartz glass tube or a stainless steel tube, the inner diameter is 1-5 cm, and the length is 5-25 cm.
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| CN112225244A (en) * | 2020-10-13 | 2021-01-15 | 江曙 | Preparation method of monodisperse nano copper-zinc-tin-sulfur for solar cell |
| CN114447128B (en) * | 2022-01-29 | 2024-04-23 | 江西理工大学 | Method for preparing zinc yellow tin ore structure thin film solar cell absorption layer based on sulfur-free source precursor |
| CN114988715B (en) * | 2022-05-25 | 2023-06-27 | 中南大学 | Preparation method of copper zinc tin sulfide film |
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