CN115385382B - Preparation method of Ag and Fe co-substituted copper zinc tin sulfide nanocrystalline - Google Patents

Preparation method of Ag and Fe co-substituted copper zinc tin sulfide nanocrystalline Download PDF

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CN115385382B
CN115385382B CN202211051231.6A CN202211051231A CN115385382B CN 115385382 B CN115385382 B CN 115385382B CN 202211051231 A CN202211051231 A CN 202211051231A CN 115385382 B CN115385382 B CN 115385382B
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朱艳
董文博
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Shanghai Technical Institute of Electronics and Information
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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
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    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
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Abstract

The invention discloses a preparation method of Ag and Fe co-substituted copper zinc tin sulfur nanocrystalline, belonging to the technical field of photoelectric materials, devices and new energy. The invention adds cuprous iodide, silver acetate, anhydrous ferric chloride, stannic chloride pentahydrate and anhydrous zinc chloride into organic solvent oleylamine, and completely dissolves solute through ultrasonic and magnetic stirring. And then uniformly heating to 100-120 ℃ to obtain a precursor solution, cooling to room temperature along with a furnace, sequentially adding n-dodecyl mercaptan and carbon disulfide into the precursor solution, uniformly mixing, uniformly heating to 150-180 ℃ to react for 20-40min, uniformly heating to 220-250 ℃ to react for 20-40min to obtain a reaction product solution, cooling to room temperature, centrifuging, washing with absolute ethyl alcohol and/or n-hexane, and drying the precipitate in a heat preservation manner to finally prepare the CAFZTS nanocrystalline with different phase structures. The CAFZTS nanocrystalline prepared by the method has high yield, the used material has low price, and the product has good crystallinity. The most critical is that CAFZTS nanocrystalline with different mineral phases and different band gaps can be obtained by only adjusting the adding proportion of Ag and Fe.

Description

Preparation method of Ag and Fe co-substituted copper zinc tin sulfide nanocrystalline
Technical Field
The invention relates to a preparation method of Ag and Fe co-substituted copper zinc tin sulfur nanocrystalline, belonging to the technical field of photoelectric materials, devices and new energy.
Background
In recent years, energy crisis and environmental pollution make it urgent to develop a new environment-friendly new energy technology. Copper Zinc Tin Sulfide (CZTS) is used as an excellent P-type absorbing material, the optical band gap of the material is about 1.5 eV (direct band gap), and the material has high light absorption coefficient in the visible light range> 104 cm -1 ) CZTS is a potential candidate for solar materials because the elements of which are less toxic than other compound materials and are distributed in the crust of the earth in abundance. However, CZTS thin film solar cells are much less efficient than CIGS and CdTe solar cells, mainly because of the Cu in CZTS Zn The dislocation defect may affect the open circuit voltage of the battery to be too low, resulting in lower efficiency of the battery. At present, the highest efficiency of a thin film solar cell taking CZTS as an absorption layer reaches 12.6 percent, which is far less than the theoretical limit conversion efficiency of 32.2 percent, which shows that the research on the CZTS material is far from reaching the expected result.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of Ag and Fe co-substituted Cu-Zn-Sn-S nanocrystalline with controllable band gap and phase; the preparation method has the characteristics of simple process, mild reaction condition, short time, environmental protection and visual and controllable preparation process, has much higher single output than the existing preparation method, is favorable for large-scale production, and comprises the following specific steps:
(1) And adding the copper source, the zinc source, the tin source, the silver source and the iron source into the organic solvent oleylamine according to the molar ratio of 5.6 (0-3.8): 3.0:1.4 (0.2-4) and then dissolving, and then uniformly heating to 100-120 ℃ to obtain a precursor solution.
(2) And (3) cooling the precursor solution to room temperature under the stirring condition, sequentially adding n-dodecyl mercaptan and carbon disulfide into the precursor solution obtained in the step (1), uniformly mixing until the molar ratio of the sulfur element to the tin element is 50:3, uniformly heating to the temperature of 150-180 ℃ in the stirring process, reacting for 20-40min, uniformly heating to the temperature of 220-250 ℃ and reacting for 20-40min to obtain a reaction product, and cooling to the room temperature.
(3) And (3) carrying out multiple cleaning and centrifugal treatment on the reaction product by using an organic solvent until the supernatant of the product is clear, pouring out the suspension, collecting the product, and drying the product to finally obtain the CAFZTS nanocrystalline with different phase structures.
Preferably, in the step (1) of the invention, the copper source is cuprous iodide, the zinc source is anhydrous zinc chloride, the tin source is pentahydrate tin tetrachloride, the silver source is silver acetate, and the iron source is anhydrous ferric chloride.
Preferably, the volume ratio of the n-dodecyl mercaptan to the carbon disulfide in the step (2) is (40-35) (3-2).
Preferably, the method of the invention sets the rotating speed of the magnetic stirrer to 400-500r/min in the heating and reacting stage.
Preferably, the drying temperature of the sample is 60-80 ℃ and the drying time is 6-12 hours.
Preferably, in the step (3) of the invention, the organic solvent is absolute ethanol and/or n-hexane, and the volume ratio of the absolute ethanol to the n-hexane is (3-1).
The CAFZTS nanocrystalline prepared by the method can be used as an absorption layer material of a solar cell, and elements contained in the nanocrystalline are nontoxic, have a very high light absorption coefficient, are direct band gap semiconductor materials, have band gaps of about 1.2-1.5 eV, and have uniform particle size and good optical properties.
The invention has the beneficial effects that:
(1) In the method, the raw materials are common chemicals (metal iodide salt, metal salt, carbon disulfide, n-dodecyl mercaptan and oleylamine), the used materials are low in price, and the product crystallinity is good.
(2) The method has accurate temperature control, the temperature difference can be controlled to be +/-0.1 ℃, and the nucleation can be effectively controlled, so that the Ag and Fe co-substituted CZTS nanocrystalline with good particle size distribution, morphology and components can be obtained.
(3) The average particle size of the CAFZTS particles prepared by the method is 50-100 nm, and the particle size distribution is uniform.
(4) The method has the advantages of simple operation, visual and controllable preparation process, low equipment requirement and the like.
(5) According to the method, CAFZTS nanocrystals with different mineral phases and different band gaps can be obtained by adjusting the addition proportion of Ag and Fe.
(6) The CAFZTS particles prepared by the method have good crystallinity and good absorption in a visible light region, are beneficial to improving the photoelectric conversion efficiency, and can play an important role in the field of photovoltaic solar energy.
Drawings
FIG. 1 is an XRD pattern of the CAFZTS nanocrystals prepared in example 1;
FIG. 2 is a TEM image of the CAFZTS nanocrystals prepared in example 1;
FIG. 3 is an XRD pattern of the CAFZTS nanocrystals prepared in example 2;
fig. 4 is a TEM image of CAFZTS nanocrystals prepared in example 2.
Fig. 5 is an XRD pattern of CAFZTS nanocrystals prepared in example 3.
Fig. 6 is a TEM image of CAFZTS nanocrystals prepared in example 3.
Fig. 7 is an XRD pattern of CAFZTS nanocrystals prepared in example 4.
Fig. 8 is a TEM image of CAFZTS nanocrystals prepared in example 4.
Fig. 9 is an XRD pattern of CAZTS nanocrystals prepared in comparative example 1.
Fig. 10 is an XRD pattern of CFZTS nanocrystals prepared in example 2.
Detailed Description
The invention will be described in further detail with reference to specific embodiments, but the scope of the invention is not limited to the description.
Example 1
A preparation method of Ag and Fe co-substituted copper zinc tin sulfide (CAFZTS) nanocrystalline comprises the following specific steps:
(1) 5.6mmol of cuprous iodide, 3.8mmol of anhydrous zinc chloride, 3mmol of stannic chloride pentahydrate, 1.4mmol of silver acetate and 0.2mmol of anhydrous ferric chloride are added into 45mL of organic solvent (the organic solvent is oleylamine) according to the molar ratio of 5.6:3.8:3.0:1.4:0.2, and then are dissolved, and then are placed in a magnetic stirring heater, and the temperature is uniformly raised to 120 ℃ to obtain a precursor solution.
(2) After cooling to room temperature under stirring, sequentially adding 8mL of n-dodecyl mercaptan and 0.6mL of carbon disulfide into 45mL of the precursor solution obtained in the step (1), uniformly mixing, heating to 180 ℃ at a constant speed for reaction for 30min, heating to 250 ℃ at a constant speed for reaction for 30min to obtain a reaction system, cooling to room temperature, washing and centrifuging the reaction product with absolute ethyl alcohol for multiple times (the centrifugation speed is 10000rpm and the centrifugation speed is 5 min), clarifying the supernatant of the product, pouring out the suspension, collecting the product, and putting into a blast drying box for drying treatment, wherein the temperature of the blast drying box is set to 60 ℃, and the drying time is 10h.
As shown in the XRD chart of the CAFZTS nanocrystalline prepared in the embodiment as shown in the figure 1, when the substituted Zn amount of Fe is 5%, the crystallinity of the CAFZTS nanocrystalline is good, and other impurity phases are not generated; the TEM image of the CAFZTS nanocrystal prepared in this example is shown in fig. 2, and as can be seen from fig. 2, the lattice spacing of the CAFZTS nanocrystal is about 0.32nm, and the CAFZTS nanocrystal has a uniform particle size and a smaller particle size.
From the analysis, when the substitution ratio of Ag is 0.2 and the substitution ratio of Fe is 0.05, the synthesized CAFZTS nanocrystalline structure is more prone to wurtzite phase, and the band gap is about 1.35 eV.
Example 2
A preparation method of Ag and Fe co-substituted copper zinc tin sulfide (CAFZTS) nanocrystalline comprises the following specific steps:
(1) 5.6mmol of cuprous iodide, 3.6mmol of anhydrous zinc chloride, 3mmol of stannic chloride pentahydrate, 1.4mmol of silver acetate and 0.4mmol of anhydrous ferric chloride are added into 45mL of organic solvent (the organic solvent is oleylamine) according to the molar ratio of 5.6:3.6:3.0:1.4:0.4:0.4, and then are dissolved, and then are placed in a magnetic stirring heater, and the temperature is uniformly raised to 120 ℃ to obtain a precursor solution.
(2) After cooling to room temperature under stirring, sequentially adding 8mL of n-dodecyl mercaptan and 0.6mL of carbon disulfide into 45mL of the precursor solution obtained in the step (1), uniformly mixing, heating to 180 ℃ at a constant speed for reaction for 30min, heating to 250 ℃ at a constant speed for reaction for 30min to obtain a reaction system, cooling to room temperature, washing and centrifuging the reaction product with absolute ethyl alcohol for multiple times (the centrifugation speed is 10000rpm and the centrifugation speed is 5 min), clarifying the supernatant of the product, pouring out the suspension, collecting the product, and putting into a blast drying box for drying treatment, wherein the temperature of the blast drying box is set to 60 ℃, and the drying time is 10h.
The XRD pattern of the CAFZTS nanocrystalline prepared in the embodiment is shown in figure 3, and as can be seen from figure 3, the crystallinity of the CAFZTS nanocrystalline is good, and no other impurity phase exists; the TEM image of the CAFZTS nanocrystal prepared in this example is shown in fig. 4, and as can be seen from fig. 4, the lattice spacing of the CAFZTS nanocrystal is about 0.31nm, and the particle size is small. From the analysis, when the substitution ratio of Ag is 0.2 and the substitution ratio of Fe is 0.1, the synthesized CAFZTS nanocrystalline structure is more prone to a kesterite phase, and the band gap is about 1.3 eV.
Example 3
A preparation method of Ag and Fe co-substituted copper zinc tin sulfide (CAFZTS) nanocrystalline comprises the following specific steps:
(1) 5.6mmol of cuprous iodide, 2.0mmol of anhydrous zinc chloride, 3mmol of stannic chloride pentahydrate, 1.4mmol of silver acetate and 2.0mmol of anhydrous ferric chloride are added into 45mL of organic solvent (the organic solvent is oleylamine) according to the molar ratio of 5.6:2.0:3.0:1.4:2.0:2.0, and then are dissolved, and then are placed in a magnetic stirring heater to be heated to 120 ℃ at constant speed to obtain a precursor solution.
(2) After cooling to room temperature under stirring, sequentially adding 8mL of n-dodecyl mercaptan and 0.6mL of carbon disulfide into 45mL of the precursor solution obtained in the step (1), uniformly mixing, heating to 180 ℃ at a constant speed for reaction for 30min, heating to 250 ℃ at a constant speed for reaction for 30min to obtain a reaction system, cooling to room temperature, washing and centrifuging the reaction product with absolute ethyl alcohol for multiple times (the centrifugation speed is 10000rpm and the centrifugation speed is 5 min), clarifying the supernatant of the product, pouring out the suspension, collecting the product, and putting into a blast drying box for drying treatment, wherein the temperature of the blast drying box is set to 60 ℃, and the drying time is 10h.
The XRD pattern of the CAFZTS nanocrystalline prepared in the embodiment is shown in figure 5, and as can be seen from figure 5, the crystallinity of the CAFZTS nanocrystalline is good, and no other impurity phase exists; the TEM image of the CAFZTS nanocrystal prepared in this example is shown in fig. 6, and as can be seen from fig. 6, the lattice spacing of the CAFZTS nanocrystal is about 0.31nm, and the particle size is small. According to analysis, when the substitution ratio of Ag is 0.2 and the substitution ratio of Fe is 0.5, the synthesized CAFZTS nanocrystalline structure is a kesterite phase, and the band gap is about 1.2 eV.
Example 4
A preparation method of Ag and Fe co-substituted copper zinc tin sulfide (CAFZTS) nanocrystalline comprises the following specific steps:
(1) 5.6mmol of cuprous iodide, 3mmol of stannic chloride pentahydrate, 1.4mmol of silver acetate and 4.0mmol of anhydrous ferric chloride are added into 45mL of organic solvent (the organic solvent is oleylamine) according to the mol ratio of 5.6:3.0:1.4:4.0, and then placed in a magnetic stirring heater to uniformly heat to 120 ℃ to obtain a precursor solution.
(2) After cooling to room temperature under stirring, sequentially adding 8mL of n-dodecyl mercaptan and 0.6mL of carbon disulfide into 45mL of the precursor solution obtained in the step (1), uniformly mixing, heating to 180 ℃ at a constant speed for reaction for 30min, heating to 250 ℃ at a constant speed for reaction for 30min to obtain a reaction system, cooling to room temperature, washing and centrifuging the reaction product with absolute ethyl alcohol for multiple times (the centrifugation speed is 10000rpm and the centrifugation speed is 5 min), clarifying the supernatant of the product, pouring out the suspension, collecting the product, and putting into a blast drying box for drying treatment, wherein the temperature of the blast drying box is set to 60 ℃, and the drying time is 10h.
The XRD pattern of the CAFZTS nanocrystalline prepared in the embodiment is shown in figure 7, and as can be seen from figure 7, the crystallinity of the CAFZTS nanocrystalline is good, and no other impurity phase exists; as shown in FIG. 8, the TEM image of the CAFZTS nanocrystal prepared in this example shows that the lattice spacing of the CAFZTS nanocrystal is about 0.31nm, and the particle size is small as shown in FIG. 8. According to analysis, when the substitution ratio of Ag is 0.2 and the substitution ratio of Fe is 1, the synthesized CAFZTS nanocrystalline structure is a kesterite phase, and the band gap is about 1.1 eV.
It can be seen from examples 1 to 4 that CAFZTS nanocrystals with different mineral phases and different band gaps can be obtained by adjusting the addition ratio of Ag and Fe.
Example 5
The other conditions in this example were the same as in example 1, except that the reaction conditions in step (2) were:
(1) The reaction conditions are as follows: heating to 180 ℃ at constant speed for reaction for 30min, heating to 250 ℃ at constant speed for reaction for 30min to obtain a reaction system, cooling to room temperature, washing and centrifuging the reaction product with absolute ethyl alcohol for multiple times (the centrifuging speed is 10000rpm and centrifuging is 5 min).
(2) The reaction conditions are as follows: the temperature is increased to 150 ℃ at constant speed for reaction 40min, then the temperature is increased to 220 ℃ at constant speed for reaction 40min to obtain reaction product liquid, the reaction product liquid is cooled to room temperature, and the reaction product is washed and centrifuged for multiple times by absolute ethyl alcohol (the centrifugation speed is 10000rpm and the centrifugation is 5 min).
(3) The reaction conditions are as follows: heating to 160 ℃ at constant speed for reaction for 30min, heating to 230 ℃ at constant speed for reaction for 20min to obtain reaction product, cooling to room temperature, washing the reaction product with absolute ethyl alcohol for multiple times, and centrifuging (the centrifuging speed is 10000rpm and centrifuging for 5 min).
(4) The reaction conditions are as follows: heating to 130 ℃ at constant speed for reaction for 20min, heating to 150 ℃ at constant speed for reaction for 30min to obtain reaction product, cooling to room temperature, washing the reaction product with absolute ethyl alcohol for multiple times, and centrifuging (the centrifuging speed is 10000rpm and centrifuging for 5 min).
In the embodiment, the products obtained in (1) - (3) are similar to the product obtained in the embodiment 1, the crystallization performance of the product obtained in (4) is poor, and XRD images are displayed in disorder.
Comparative example 1
A preparation method of Ag-substituted copper zinc tin sulfide (CAZTS) nanocrystalline comprises the following specific steps:
(1) 5.6mmol of cuprous iodide, 4.0mmol of anhydrous zinc chloride, 3.0mmol of stannic chloride pentahydrate and 1.4mmol of silver acetate are added into 45mL of organic solvent (the organic solvent is oleylamine) according to the molar ratio of 5.6:4.0:3.0:1.4, and then are dissolved, and then are placed in a magnetic stirring heater to be heated to 120 ℃ at a constant speed to obtain a precursor solution.
(2) And (2) cooling to room temperature under stirring, sequentially adding 8mL of n-dodecyl mercaptan and 0.6mL of carbon disulfide into the precursor solution obtained in the step (1), uniformly mixing, uniformly heating to the temperature of 150 ℃ for reacting for 40min, uniformly heating to the temperature of 250 ℃ for reacting for 30min to obtain a reaction system, cooling to room temperature, washing and centrifuging the reaction product with absolute ethyl alcohol for multiple times, pouring out suspension after the supernatant of the product is clear, collecting the product, and drying in a blast drying box, wherein the temperature of the blast drying box is set to be 60-80 ℃ and the drying time is set to be 6-12 h.
As shown in fig. 9, the XRD pattern of the CAZTS nanocrystal prepared in this example shows that the CAZTS nanocrystal has good crystallinity but has a hetero-phase, and it can be seen from analysis that the synthesized CAZTS nanocrystal structure is more prone to wurtzite phase when the substitution ratio of Ag is 0.2 by using oleylamine as a reaction solvent. Substitution by a single metal cation makes it difficult to adjust the band structure characteristics (particularly the band gap and the band edge) and the phase change at the same time, and substitution can adjust the band structure characteristics (particularly the band gap and the band edge) and the phase change at the same time, so that the phase change is better controlled.
Comparative example 2
A preparation method of Fe-substituted copper zinc tin sulfide (CFZTS) nanocrystalline comprises the following specific steps:
(1) 7mmol of cuprous iodide, 3.6mmol of anhydrous zinc chloride, 3mmol of stannic chloride pentahydrate and 0.4mmol of anhydrous ferric chloride are added into 45mL of organic solvent (the organic solvent is oleylamine) according to the mol ratio of 7:3.6:3.0:0.4, and then placed in a magnetic stirring heater to uniformly heat to 120 ℃ to obtain precursor solution.
(2) And (2) cooling to room temperature under stirring, sequentially adding 8mL of n-dodecyl mercaptan and 0.6mL of carbon disulfide into the precursor solution obtained in the step (1), uniformly mixing, uniformly heating to 180 ℃ for reaction for 30min, uniformly heating to 250 ℃ for reaction for 30min to obtain a reaction system, cooling to room temperature, washing and centrifuging the reaction product with absolute ethyl alcohol for multiple times, pouring out the suspension after the supernatant of the product is clear, collecting the product, and drying in a blast drying box, wherein the temperature of the blast drying box is set to 60-80 ℃ and the drying time is set to 6-12 h.
The XRD pattern of the CFZTS nanocrystals prepared in this example is shown in fig. 10, and as can be seen from fig. 10, the CFZTS nanocrystals have good crystallinity but have hetero-phase formation, and analysis shows that the synthesized CFZTS nanocrystal structure is more prone to wurtzite phase when the substitution ratio of Fe is 0.1 by using oleylamine as a reaction solvent; substitution by a single metal cation makes it difficult to adjust the band structure characteristics (particularly the band gap and the band edge) and the phase change at the same time, and substitution can adjust the band structure characteristics (particularly the band gap and the band edge) and the phase change at the same time, so that the phase change is better controlled.

Claims (5)

1. The preparation method of the Ag and Fe co-substituted copper zinc tin sulfur nanocrystalline is characterized by comprising the following steps of:
(1) Adding a copper source, a zinc source, a tin source, a silver source and an iron source into organic solvent oleylamine according to the molar ratio of the copper source to the zinc source to the tin source to the silver source to the iron source of 5.6 (0-3.8) to be 3.0:1.4 (0.2-4), dissolving, and then uniformly heating to 100-120 ℃ to obtain a precursor solution;
(2) Cooling the precursor solution to room temperature under the stirring condition, sequentially adding n-dodecyl mercaptan and carbon disulfide into the precursor solution obtained in the step (1) in a molar ratio of sulfur element to tin element of 50:3, uniformly heating to 150-180 ℃ for reacting for 20-40min in the stirring process, uniformly heating to 220-250 ℃ for reacting for 20-40min to obtain a reaction product, and cooling to room temperature;
(3) Washing and centrifuging the reaction product for multiple times by using an organic solvent until the supernatant of the product is clear, pouring out the suspension, collecting the product, and drying the product to finally obtain CAFZTS nanocrystals with different phase structures;
the volume ratio of the n-dodecyl mercaptan to the carbon disulfide in the step (2) is (40-35) (3-2).
2. The method for preparing Ag and Fe co-substituted Cu-Zn-Sn-S nanocrystals according to claim 1, wherein the method comprises the following steps: in the step (1), the copper source is cuprous iodide, and the zinc source is anhydrous zinc chloride; the tin source is tin tetrachloride pentahydrate, and the silver source is silver acetate; the iron source is anhydrous ferric chloride.
3. The method for preparing Ag and Fe co-substituted Cu-Zn-Sn-S nanocrystals according to claim 1, wherein the method comprises the following steps: during the heating and reaction phases, the rotational speed of the magnetic stirrer is set to 400-500r/min.
4. The method for preparing Ag and Fe co-substituted Cu-Zn-Sn-S nanocrystals according to claim 1, wherein the method comprises the following steps: the drying temperature of the sample is 60-80 ℃ and the drying time is 6-12 h.
5. The method for preparing Ag and Fe co-substituted Cu-Zn-Sn-S nanocrystals according to claim 1, wherein the method comprises the following steps: in the step (3), the organic solvent is absolute ethyl alcohol and/or n-hexane, and the volume ratio of the absolute ethyl alcohol to the n-hexane is (3-1), namely (3-1).
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