CN109802010B - Solar cell absorption layer Sb prepared by recyclable chemical bath method2S3Method for making thin film - Google Patents

Abstract

The invention discloses a method for preparing the Sb ₂ S ₃ thin film of the solar cell absorption layer by a cyclic chemical bath method. The method is to pour a certain amount of antimony sulfide precipitate into a mixed solution of ammonia water and an appropriate solvent, and then ultrasonically vibrate it to dissolve the antimony sulfide in the solution to form a deposition solution; soak the cleaned substrate in In the deposition solution, the Sb ₂ S ₃ film of the solar cell absorption layer of the present invention is grown by chemical bath deposition at a certain temperature; the precipitate product formed after the film is grown is centrifuged, washed, and dried to obtain the following: Reactants for a chemical bath. The method has the advantages of simple deposition process, cheap preparation equipment, high utilization rate of raw materials, environmental protection, easy control of film thickness and the like, and is suitable for large-scale industrial production.

Description

A method for preparing Sb2S3 thin film of solar cell absorber layer by a recyclable chemical bath method

technical field

The invention relates to the technical field of solar cell materials and devices, in particular to a method for preparing an Sb ₂ S ₃ thin film of a solar cell absorption layer by a cyclic chemical bath method.

Background technique

With the rapid development of social economy, people's demand for fossil energy is increasing, which has caused two major problems: energy crisis and environmental pollution. Therefore, in order to develop an environment-friendly economy and solve the energy crisis, it is particularly important to find a new type of alternative energy. Solar energy is a kind of renewable energy with abundant reserves, clean and pollution-free. An efficient way to convert this energy directly into electrical energy is photovoltaic power generation, or solar cells.

So far, there are many kinds of solar cells. Among them, Sb ₂ S ₃ -based thin-film solar cells have the advantages of high theoretical conversion efficiency, low cost, good stability and non-toxicity, and are regarded as a type of thin-film solar cells with great development potential. The current Sb ₂ S ₃ -based solar cell structures mainly include: flat-panel solar cells and dye-sensitized solar cells. The core material of these two types of solar cells is the absorption layer Sb ₂ S ₃ thin film, which has a band gap width (1.7 eV) that matches the solar spectrum, a large absorption coefficient (10 ⁵ cm ^-1 ), and cheap raw materials, etc. It has the advantages of good industrialization development prospects. At present, an organic-inorganic hybrid solar cell with an efficiency of 7.5% has been obtained by preparing the Sb _{2 S 3} thin film as the absorber layer based _on the chemical bath method. Therefore, this new type of inorganic thin-film solar cells has great application prospects and business opportunities.

At present, there are many methods for preparing Sb ₂ S ₃ solar cell absorber layer materials, which can be divided into two categories: vacuum method and non-vacuum method. Among them, vacuum methods mainly include magnetron sputtering, thermal evaporation, rapid thermal evaporation, near-space sublimation and other methods. These methods require a high vacuum environment, require expensive equipment, and have high production costs; non-vacuum methods can be divided into For electrodeposition, sol-gel method and chemical bath deposition method, these methods have many advantages such as simple preparation process, cheap preparation cost, easy mass production, etc., and have received more attention and research. Among them, the chemical bath deposition method has the characteristics of simple process and low cost, which is conducive to the realization of large-scale production. After searching the prior art patents, it is found that there are many patent applications for the preparation of the Sb ₂ S ₃ thin film by chemical bath method of the absorption layer. Between 4 and 4.5, the Sb ₂ S ₃ film with good adhesion can be directly prepared on the ITO glass substrate (application number 201610190103.8); for another example, antimony chloride SbCl ₃ and thiourea SC(NH ₂ ) ₂ Dissolve in distilled water to prepare antimony chloride and thiourea solution, then mix the two to make a growth solution, and finally place the SC(NH ₂ ) ₂ treated substrate in the growth solution for 12-36 hours, take out and dry , to obtain a Sb ₂ S ₃ film (application number 200610043156.3). At the same time, after searching the existing literature, it is found that the current chemical bath method for preparing Sb ₂ S ₃ films is based on antimony compound salts and sulfur salts as starting reactants, and reacts to form Sb ₂ S ₃ films at a certain temperature. For example, SbCl ₃ was dissolved in acetone solvent, Na ₂ S ₂ O ₃ was dissolved in deionized water, and then the two were mixed and placed at 10 °C as a reaction solution, and then Sb ₂ S ₃ film was grown (Applied Surface Science254 (2008) 3200–3206); for example, using SbCl ₃ and Na ₂ S ₂ O ₃ as antimony source and sulfur source respectively, and introducing EDTA as complexing agent can greatly shorten the time for growing Sb ₂ S ₃ film in chemical bath (Applied Surface Science 451 (2018) 272-279). However, the existing technologies for preparing Sb ₂ S ₃ thin films by chemical bath method all involve salts of antimony and sulfur. After one reaction deposition, only a very small amount of Sb and S are effectively grown on the substrate to form Sb ₂ S ₃ thin films. Most of the remaining Sb ions and S ions will be combined into Sb ₂ S ₃ particles in the solution, which will settle to the bottom of the reaction vessel, and finally be discharged as reaction by-products, thereby polluting the environment. The traditional chemical bath method has the characteristics of low utilization rate of raw materials and high cost.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a simple, safe and non-toxic method for preparing the Sb ₂ S ₃ thin film of the solar cell absorber layer by a cyclic chemical bath method. In this method, ammonia water and a suitable solvent are used to dissolve the precipitated product Sb ₂ S ₃ particles in the chemical bath, and the Sb ₂ S ₃ film is prepared by chemical bath deposition. The by-product of Sb ₂ S ₃ particles deposited by the method can be used as the starting material for the next chemical bath growth, so as to realize the recycling of antimony ions and sulfide ions in the solution.

For achieving the above object, the technical scheme adopted in the present invention is:

A method for preparing a Sb ₂ S ₃ thin film of a solar cell absorber layer by a cyclic chemical bath method, comprising the following steps:

1) Pour the antimony sulfide precipitate into the mixed solution of ammonia water and solvent, and then perform ultrasonic vibration treatment to dissolve the antimony sulfide precipitate to form a deposit solution;

2) Immerse the cleaned substrate in the above-mentioned deposition solution, and use the chemical bath deposition method at a certain temperature to grow the Sb ₂ S ₃ thin film of the solar cell absorption layer after a certain period of time;

3) Centrifuge, wash and dry the precipitate formed after the growth of the Sb ₂ S ₃ film to obtain the reactant of the next chemical bath, that is, the antimony sulfide precipitate.

Step 1) The dosage ratio of the antimony sulfide precipitate and the ammonia water is 0.01~0.05g:5~50ml, and the volume ratio of the ammonia water and the solvent is 5~50:10~100.

The solvent described in step 1) is one of ethanol, glycerol, ethylene glycol or water, or a mixture of any of them.

The ultrasonic frequency of the ultrasonic vibration treatment in step 1) is 4-4.5KHZ, and the ultrasonic time is 1-5 hours.

Step 2) The temperature of the chemical bath deposition is 40-90° C., and the time is 30-600 min.

Step 2) The substrate is one of soda-lime glass, soda-lime glass, ITO or FTO conductive glass coated with molybdenum film.

The substrate is subjected to the following pretreatment: the substrate is immersed in ordinary detergent, deionized water, ethanol and acetone solution in sequence, then ultrasonicated and rinsed with deionized water, dried with nitrogen, and ready for use.

Step 3) The washing of the precipitate includes deionized water and ethanol washing three times each, and the drying temperature is 40-90 °C.

The principle of the present invention is:

1) Using ammonia water as a dissolving agent for antimony sulfide, the ammonium ion and the trace amount of sulfur ion ionized by antimony sulfide are combined to form ammonium sulfide, and the ammonium sulfide further dissolves the antimony sulfide reactant until the antimony sulfide precipitate is completely dissolved, forming a mixture containing antimony and sulfur. ionic solution.

2) The substrate is placed in the above-mentioned deposition solution, chemical bath growth is carried out at a certain temperature, and antimony ions and sulfide ions are grown on the substrate in an ion-ion deposition mode to obtain a corresponding absorption layer Sb ₂ S ₃ film.

3) The Sb ₂ S ₃ particle precipitate after the chemical bath is collected can be used as a reactant for the next thin film deposition.

The invention has the following outstanding beneficial effects: the invention provides a low cost, simple preparation process, green and recyclable chemical bath method to prepare the Sb ₂ S ₃ thin film of the thin film solar cell. According to the prior related patent application, other chemical baths for the deposition of Sb ₂ S ₃ thin film materials all use compound salts of antimony and sulfur, and only a small amount of reactants can be deposited on the substrate, while other precipitates are wasted , the material utilization rate is low. Therefore, the present invention adopts Sb ₂ S ₃ precipitation as the reactant, ammonia water as the dissolving agent, and forms a stable deposition solution with other solvents, and finally adopts the chemical bath method to successfully synthesize the Sb ₂ S ₃ absorbing layer film. The specific beneficial effects are as follows:

1) The present invention uses Sb ₂ S ₃ as a low-cost chemical bath deposition reactant for the first time, and uses a new type of deposition solution to prepare Sb ₂ S ₃ thin films;

2) The preparation of Sb _{2 S 3} films by the chemical bath method has two advantages. First, the reaction raw materials can be used repeatedly, which is conducive to reducing the preparation cost _; Environmental protection, suitable for industrial large-scale preparation requirements;

3) The cyclic chemical bath deposition method adopted in the invention has the advantages of simple equipment, low preparation cost, large area preparation and deposition, easy control of composition and film thickness, and the like.

Description of drawings

The present invention will be further described below in conjunction with the accompanying drawings.

Figure 1 is a schematic diagram of the preparation process of the present invention.

FIG. 2 is a SEM image of the Sb ₂ S ₃ thin film of the absorbing layer prepared for the first time in the present invention.

FIG. 3 is a SEM image of the Sb ₂ S ₃ thin film of the absorbing layer prepared by recycling according to the present invention.

Detailed ways

In order to have a better understanding of the present invention, the present invention will now be further described by way of examples.

A method for preparing a Sb ₂ S ₃ thin film of a solar cell absorber layer by a cyclic chemical bath method, comprising the following steps:

1) Pour 0.01~0.05g of antimony sulfide precipitate into a mixed solution of 10~100ml solvent and 5~50ml ammonia water (26% molar concentration), and then perform ultrasonic vibration treatment (frequency 4~4.5KHZ, ultrasonic time 1~ 5 hours) to dissolve the antimony sulfide precipitate to form a deposit solution;

Wherein, the solvent is a kind of ethanol, glycerol, ethylene glycol or water, or a mixture of any of them;

2) Immerse the substrate in ordinary detergent, deionized water, ethanol, and acetone solution in sequence, then ultrasonically and rinse it with deionized water, and blow dry with nitrogen; The solar cell absorber layer Sb ₂ S ₃ thin film was grown by chemical bath deposition at 90°C for 30-600 min;

Wherein, the substrate is one of soda-lime glass, soda-lime glass, ITO or FTO conductive glass coated with molybdenum film;

3) Centrifuge the precipitate formed after the growth of the Sb ₂ S ₃ film, wash with deionized water and ethanol, and dry at 40-90° C. to obtain the reactant of the next chemical bath, that is, the antimony sulfide precipitate.

The chemical reagents involved in the present invention are all purchased from Sinopharm Group Chemical Reagent Company, and the molybdenum-coated glass and soda-lime glass involved in the substrate are respectively purchased from Shengyang New Material Technology (Ningbo) Co., Ltd. and Luoyang Longyao Glass Co., Ltd., ITO and FTO glass are purchased from Yaoke Technology Co., Ltd.

Example 1

A method for preparing the Sb ₂ S ₃ thin film of the solar cell absorber layer by a cyclic chemical bath method:

1. Immerse the ITO glass substrate in ordinary detergent, deionized water, ethanol, and acetone solution in sequence, then ultrasonically rinse with deionized water, and dry it with nitrogen for use;

2. Mix 0.05g of Sb ₂ S ₃ , 8ml of ammonia water and 10ml of ethylene glycol, and place it in an ultrasonic cleaning machine to ultrasonicate for 5 hours to completely dissolve the Sb ₂ S ₃ particles to obtain a sedimentation solution;

3. Pour the above-mentioned deposition solution into an empty bottle with a substrate inserted, and grow it in a constant temperature water bath at 70°C for 120 minutes to obtain a Sb ₂ S ₃ film with a certain film thickness. After taking it out, rinse it with deionized water and dry it at 60° C. Dry in the box for 1h;

4. Centrifuge the sediment in the reaction flask at a speed of 5000 r/min. After three washings with deionized water and ethanol, the sediment was obtained, and placed in a vacuum drying box at 80°C for 5 hours to obtain Sb ₂ S ₃ particles, as a reactant for the next deposition;

5. Using the Sb ₂ S ₃ particles obtained in step 4 as an initial reactant, repeat steps 1 to 3 to obtain a Sb ₂ S ₃ film.

The Sb ₂ S ₃ film prepared for the first time in this example is tested by scanning electron microscope SEM, as shown in FIG. 2 , and FIG. 3 is an SEM image of the Sb ₂ S ₃ film prepared by recycling in this example. It can be seen from FIG. 2 that the Sb ₂ S ₃ film has good compactness, high flatness and uniformity. By comparing Fig. 2 and Fig. 3, it can be seen that the Sb ₂ S ₃ films prepared by the cyclic method have good repeatability.

Example 2

A method for preparing the Sb ₂ S ₃ thin film of the solar cell absorber layer by a cyclic chemical bath method:

1. Immerse the FTO substrate in ordinary detergent, deionized water, ethanol, and acetone solution in sequence, then ultrasonically rinse with deionized water, and dry it with nitrogen for use;

2. Mix 0.04g of Sb ₂ S ₃ , 15ml of ammonia water and 20ml of ethylene glycol, and place it in an ultrasonic cleaning machine to ultrasonicate for 3 hours to completely dissolve the Sb ₂ S ₃ particles to obtain a sedimentation solution;

3. Pour the above-mentioned deposition solution into an empty bottle with a substrate inserted, and grow it in a constant temperature water bath at 60°C for 60 minutes to obtain a Sb ₂ S ₃ film with a certain film thickness. After taking it out, rinse it with deionized water and dry it at 60° C. Dry in the box for 1h;

4. Centrifuge the sediment in the reaction flask at a speed of 5000 r/min. After three washings with deionized water and ethanol, the sediment was obtained, and placed in a vacuum drying box at 80°C for 5 hours to obtain Sb ₂ S ₃ particles, as a reactant for the next deposition;

5. Using the Sb ₂ S ₃ particles obtained in step 4 as an initial reactant, repeat steps 1 to 3 to obtain a Sb ₂ S ₃ film.

Example 3

A method for preparing the Sb ₂ S ₃ thin film of the solar cell absorber layer by a cyclic chemical bath method:

1. Immerse the FTO substrate in ordinary detergent, deionized water, ethanol, and acetone solution in sequence, then ultrasonically rinse with deionized water, and dry it with nitrogen for use;

2. Mix 0.04g of Sb ₂ S ₃ , 20ml of ammonia water and 20ml of ethylene glycol, and place it in an ultrasonic cleaner for 3 hours to sonicate to completely dissolve the Sb ₂ S ₃ particles;

3. Pour the above solution into an empty bottle with a substrate inserted, and grow it in a constant temperature water bath at 60°C for 180 minutes to obtain a Sb ₂ S ₃ film with a certain film thickness. After taking it out, rinse it with deionized water and dry it in a drying oven at 60° C. Dry for 1h;

4. Centrifuge the sediment in the reaction flask at a speed of 5000 r/min. After three washings with deionized water and ethanol, the sediment was obtained, and placed in a vacuum drying box at 80°C for 5 hours to obtain Sb ₂ S ₃ particles, as a reactant for the next deposition;

5. Using the Sb ₂ S ₃ particles obtained in step 4 as an initial reactant, repeat steps 1 to 3 to obtain a Sb ₂ S ₃ film.

Example 4

A method for preparing the Sb ₂ S ₃ thin film of the solar cell absorber layer by a cyclic chemical bath method:

1. Immerse the molybdenum-coated soda-lime glass substrate in ordinary detergent, deionized water, ethanol, and acetone solution in sequence, then ultrasonically rinse with deionized water, and dry with nitrogen for use;

2. Mix 0.01g of Sb ₂ S ₃ , 5ml of ammonia water and 20ml of glycerol, and place it in an ultrasonic cleaning machine to ultrasonicate for 1 hour, with an ultrasonic frequency of 4KHZ, to completely dissolve the Sb ₂ S ₃ particles to obtain a sedimentation solution;

3. Pour the above-mentioned deposition solution into an empty bottle with a substrate inserted, and grow it in a constant temperature water bath at 40°C for 600 minutes to obtain a Sb ₂ S ₃ film with a certain film thickness. After taking it out, rinse it with deionized water and dry it at 60° C. Dry in the box for 1h;

4. Centrifuge the sediment in the reaction flask at a speed of 5000 r/min. After washing with deionized water and ethanol for three times, the sediment is obtained, and it is placed in a vacuum drying box at 40 °C for drying for 8 hours to obtain Sb ₂ S ₃ particles, as a reactant for the next deposition;

5. Using the Sb ₂ S ₃ particles obtained in step 4 as an initial reactant, repeat steps 1 to 3 to obtain a Sb ₂ S ₃ film.

Example 5

A method for preparing the Sb ₂ S ₃ thin film of the solar cell absorber layer by a cyclic chemical bath method:

1. Immerse the molybdenum-coated soda-lime glass substrate in ordinary detergent, deionized water, ethanol, and acetone solution in sequence, then ultrasonically rinse with deionized water, and dry with nitrogen for use;

2. Mix 0.05g of Sb ₂ S ₃ , 50ml of ammonia water and 100ml of ethanol, place it in an ultrasonic cleaning machine for 5 hours, and the ultrasonic frequency is 4KHZ to completely dissolve the Sb ₂ S ₃ particles to obtain a sedimentation solution;

3. Pour the above-mentioned deposition solution into an empty bottle with a substrate inserted, and grow it in a constant temperature water bath at 90°C for 30 minutes to obtain a Sb ₂ S ₃ film with a certain film thickness. After taking it out, rinse it with deionized water and dry it at 60° C. Dry in the box for 1h;

4. Centrifuge the sediment in the reaction flask at a speed of 5000 r/min. After three washings with deionized water and ethanol, the sediment is obtained, and it is placed in a vacuum drying box at 90°C for drying for 3 hours to obtain Sb ₂ S ₃ particles, as a reactant for the next deposition;

5. Using the Sb ₂ S ₃ particles obtained in step 4 as an initial reactant, repeat steps 1 to 3 to obtain a Sb ₂ S ₃ film.

Example 6

A method for preparing the Sb ₂ S ₃ thin film of the solar cell absorber layer by a cyclic chemical bath method:

1. Immerse the ITO glass substrate in ordinary detergent, deionized water, ethanol, and acetone solution in sequence, then ultrasonically rinse with deionized water, and dry it with nitrogen for use;

2. Mix 0.03g of Sb ₂ S ₃ , 25ml of ammonia water and 40ml of water, place it in an ultrasonic cleaning machine for 2.5 hours, and ultrasonic frequency 4.5KHZ to completely dissolve the Sb ₂ S ₃ particles to obtain a sedimentation solution;

3. Pour the above-mentioned deposition solution into an empty bottle with a substrate inserted, and grow it in a constant temperature water bath at 70°C for 300 minutes to obtain a Sb ₂ S ₃ film with a certain film thickness. After taking it out, rinse it with deionized water and dry it at 60° C. Dry in the box for 1h;

4. Centrifuge the sediment in the reaction flask at a speed of 5000 r/min. After three washings with deionized water and ethanol, the sediment was obtained, and then placed in a vacuum drying box at 70°C for drying for 5 hours to obtain Sb ₂ S ₃ particles, as a reactant for the next deposition;

5. Using the Sb ₂ S ₃ particles obtained in step 4 as an initial reactant, repeat steps 1 to 3 to obtain a Sb ₂ S ₃ film.

Claims (8)

1. Solar cell absorption layer Sb prepared by recyclable chemical bath method₂S₃A method of making a film, comprising: which comprises the following steps:

1) pouring the antimony sulfide precipitate into a mixed solution of ammonia water and a solvent, and then carrying out ultrasonic oscillation treatment to dissolve the antimony sulfide precipitate to form a deposition solution;

2) soaking the cleaned substrate in the deposition solution, and growing at 40-90 ℃ for 30-600 min by using a chemical bath method to obtain the solar cell absorption layer Sb₂S₃A film;

3) sb₂S₃And centrifuging, cleaning and drying the precipitate formed after the film growth to obtain a reactant of the next chemical bath method, namely the antimony sulfide precipitate.

2. The recyclable chemical bath method for preparing the solar cell absorption layer Sb as claimed in claim 1₂S₃A method of making a film, comprising: the dosage ratio of the antimony sulfide precipitate in the step 1) to ammonia water is 0.01-0.05 g: 5-50 ml.

3. The recyclable chemical bath method for preparing the solar cell absorption layer Sb as claimed in claim 2₂S₃A method of making a film, comprising: the volume ratio of the ammonia water to the solvent in the step 1) is 5-50: 10-100.

4. The recyclable chemical bath method for preparing the solar cell absorption layer Sb as claimed in claim 1₂S₃A method of making a film, comprising: the solvent in the step 1) is one of ethanol, glycerol, glycol or water, or a mixture of any of ethanol, glycerol, glycol and water.

5. The recyclable chemical bath method for preparing the solar cell absorption layer Sb as claimed in claim 1₂S₃A method of making a film, comprising: the ultrasonic frequency of the ultrasonic vibration treatment in the step 1) is 4-4.5 KHZ, and the ultrasonic time is 1-5 hours.

6. The recyclable chemical bath method for preparing the solar cell absorption layer Sb as claimed in claim 1₂S₃A method of making a film, comprising: and 2) the substrate is one of sodium calcium glass, ITO (indium tin oxide) or FTO (fluorine-doped tin oxide) conductive glass plated with a molybdenum film.

7. The recyclable chemical bath method for preparing the solar cell absorption layer Sb as claimed in claim 6₂S₃A method of making a film, comprising: the substrate is pretreated as follows: and sequentially immersing the substrate into a common detergent, deionized water, ethanol and an acetone solution, then ultrasonically treating and washing the substrate by using the deionized water, and blow-drying the substrate by using nitrogen for later use.

8. The recyclable chemical bath method for preparing the solar cell absorption layer Sb as claimed in claim 1₂S₃A method of making a film, comprising: and 3) washing the precipitate by using deionized water and ethanol, wherein the drying temperature is 40-90 ℃.

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