CN108502918B - Synthesis method of inorganic perovskite nanowire - Google Patents

Synthesis method of inorganic perovskite nanowire Download PDF

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CN108502918B
CN108502918B CN201810377230.8A CN201810377230A CN108502918B CN 108502918 B CN108502918 B CN 108502918B CN 201810377230 A CN201810377230 A CN 201810377230A CN 108502918 B CN108502918 B CN 108502918B
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lead
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cesium
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octadecene
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CN108502918A (en
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林靖
翟伟
黄阳
何鑫
唐成春
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Hebei University of Technology
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Abstract

The invention relates to a method for synthesizing inorganic perovskite nano wires. The method utilizes solvothermal method and anion exchange method to prepare the product with length up to several millimeters at lower temperatureCsPbBr with ultra-high length-diameter ratio of about 10nm in diameter3Nanowires and CsPbI is obtained by a simple anion exchange process3And CsPbCl3A nanowire. The method has great promotion effect on the industrial mass preparation of inorganic perovskite nano wires, and is expected to further realize the application in the aspects of photoelectric detection, laser, solar cells and the like. The method is simple and controllable, high in yield, uniform in appearance, low in reaction temperature and suitable for large-scale production.

Description

Synthesis method of inorganic perovskite nanowire
Technical Field
The invention relates to a method for synthesizing an inorganic perovskite nanowire, in particular to CsPbX with ultrahigh length-diameter ratio3A method for synthesizing (X ═ Cl, Br, I) nanowires belongs to the field of new material preparation and nanotechnology.
Background
Inorganic perovskite CsPbX3The (X ═ Cl, Br, I) nanocrystals have high fluorescence quantum efficiency, adjustable emission wavelength, and excellent photoelectric properties covering the entire visible spectrum (400-. The one-dimensional inorganic perovskite nanowire has a wide application prospect in solar cells and photoelectric detection due to the unique structural characteristics, such as excellent light conductivity, good transverse conductivity and the like, so that the research on the synthesis method of the inorganic perovskite nanowire becomes the research direction of a plurality of researchers. Currently prepared inorganic perovskite CsPbX3The synthesis methods of the nanowires mainly include a thermal injection method, a recrystallization method, and a Chemical Vapor Deposition (CVD) method. The perovskite nano-wire prepared by a hot injection method (Muhammad I, France sco Di S, Zhiya Dang, et al chem. Mater.2016,28,6450) is obtained by changing reaction conditions on the basis of synthesizing inorganic perovskite quantum dots (Dandan Z, Samuel W.E, Yi Yu, et al.J.am.chem.Soc.2015,137, 9230). The synthesis method has the following limitations: the experimental operation is more complicated, dehydration and inert atmosphere are needed, and the prepared productThe yield of the nanowires is low, so that large-scale preparation is difficult to realize. Patent "a method for preparing lead-halogen perovskite nanowire by recrystallization method" (patent publication No. CN 106629835A) reports that lead-halogen perovskite CsPbI is prepared by recrystallization method3The nano wire is prepared by firstly spin-coating a precursor of the nano wire on a substrate, then adding a mixed solvent of a poor solvent and a polar aprotic solvent, and then preparing the perovskite CsPbI under the condition of high-temperature annealing3A nanowire. However, this recrystallization method did not produce CsPbBr3And CsPbCl3The preparation process needs higher annealing temperature, and the final appearance of the nano wire is affected due to uneven spin coating when the nano wire is prepared in large quantity. A perovskite nanowire preparation method (patent publication No. CN 107104357A) prepared by a chemical vapor deposition CVD method is used for preparing the perovskite nanowire with the diameter of 200-800nm and the length of 10-80 mu m and arranged in a plane in an oriented mode. The Panan exercise group also utilizes a chemical vapor deposition mode to prepare CsPbBr in planar orientation arrangement3Ultra-long nanowires (Muhammad S, Xuehong Z, xiaoxina W, et al.j.am.chem.soc,2017,139,15592) and assembled to give a photodetector with fast response. However, the method uses expensive sapphire as a substrate, and requires a high heating temperature and a high ventilation process, so the method still has certain limitation on the mass preparation of inorganic perovskite nanowires.
The patent "a synthetic method of inorganic perovskite nanosheet" (publication number CN107522225A), adopts a solvothermal method, firstly, cesium carbonate is added into a mixed solution (volume ratio of octadecene to oleic acid is 7:1) to form a precursor solution of cesium, wherein the molar concentration of cesium is 0.15-0.20 mol/L; then adding metal lead halide into the mixed solution (the volume ratio of octadecene to oleic acid to oleylamine is 7:1:1) to form a lead halide precursor solution, wherein the molar concentration of the lead halide is 0.07-0.10 mol/L; then mixing the cesium precursor and lead halide precursor solution in a volume ratio of 1:9-1:15, and reacting in a reaction kettle to obtain the flaky perovskite CsPbX3Nanosheets. Although the patent realizes CsPbX3Nano meterControlled synthesis of flakes, but CsPbX obtained3The stability of the nano-sheet is poor, and the one-dimensional CsPbX can not be realized by the existing technical parameters3Controllable synthesis of nanowires. Patent "A Cesium-lead halide Cs4PbX6The synthesis method of the nanocrystalline (application No. 201810126310.6) also adopts a solvothermal method, wherein cesium carbonate is firstly added into a mixed solution (the volume ratio of octadecene to oleic acid is 4:1) to form a precursor solution of cesium, wherein the molar concentration of cesium is 0.30-0.45 mol/L; then adding metal lead halide into the mixed solution (the volume ratio of octadecene to oleic acid to oleylamine is 10:1:1) to form a lead halide precursor solution, wherein the molar concentration of the lead halide is 0.08-0.12 mol/L; then mixing the precursor of cesium and the precursor solution of lead halide in a volume ratio of 1:4-1:2, reacting in a reaction kettle, centrifuging, washing, and drying to obtain solid powdery Cs4PbX6And (4) nanocrystals. This patent realizes to Cs4PbX6The controllable synthesis of the nano-crystal can not be realized through the prior technical parameters.
Disclosure of Invention
The invention aims at the current preparation of perovskite CsPbX3The defects of low yield, complexity of experimental process, high-temperature treatment process, high cost and the like of the nanowire method are overcome, and the inorganic perovskite CsPbX is provided3And (X ═ Cl, Br, I) nanowire synthesis method. The method utilizes a solvothermal method and an anion exchange method to prepare the nanowire with the length of several millimeters and the diameter of only about 10 nanometers and the ultrahigh length-diameter ratio at a lower temperature, and obtains the CsPbI through a simple anion exchange process3And CsPbCl3The nano-wire has great promotion effect on the industrial mass preparation of inorganic perovskite nano-wires, and is expected to further realize the application in the aspects of photoelectric detection, laser, solar cells and the like. The method is simple and controllable, high in yield, uniform in appearance, low in reaction temperature and suitable for large-scale production.
The technical scheme of the invention is as follows:
a method for synthesizing inorganic perovskite nanowires comprises the following steps:
step 1, adding cesium carbonate (Cs)2CO3) Adding the cesium into the mixed solution A, stirring the cesium for 15 to 35 minutes at the temperature of 110-160 ℃, and naturally cooling the cesium to room temperature to form a cesium precursor solution;
wherein the mixed solution A consists of oleic acid and octadecene, wherein the volume ratio of oleic acid: octadecene 1: 8; in the precursor solution of cesium, the molar concentration of cesium is 0.12-0.25 mol/L;
step 2, lead bromide (PbBr)2) Adding the mixed solution B into the mixed solution B, stirring the mixed solution B for 15 to 35min at the temperature of between 90 and 130 ℃, and then cooling the mixed solution B to room temperature under the condition of ice water bath to form a lead bromide precursor solution;
wherein, the mixed solution B consists of oleylamine, oleic acid and octadecene, wherein the volume ratio of oleylamine: oleic acid: octadecene is 1:1:8, and the molar concentration of lead bromide in a lead bromide precursor solution is 0.09-0.15 mol/L;
step 3, heating the precursor solution of cesium to 60-100 ℃, transferring the precursor solution of cesium to a reaction kettle, naturally cooling the precursor solution of cesium to room temperature, adding the precursor solution of lead bromide, and carrying out ultrasonic treatment for 15-35min at the room temperature to obtain a mixed solution D;
wherein, the volume ratio of the lead bromide precursor solution is as follows: a precursor solution of cesium in a ratio of 7:1 to 16: 1;
step 4, reacting the mixed solution D obtained in the step 3 at the temperature of 80-150 ℃ for 30-90h, and then naturally cooling to obtain a reactant solution E;
step 5, centrifuging and washing the reactant E obtained in the step to obtain the final product of inorganic perovskite CsPbBr3A nanowire.
When the product is CsPbCl3、CsPbClxBr3-x、CsPbBrxI3-xOr CsPbI3Nanowire (wherein, 0)<x<3) The method also comprises the following steps:
step 6, the CsPbBr obtained above is added3Adding the nanowire into a nonpolar solvent to obtain a dispersion liquid F; wherein the nonpolar solvent is generally toluene, n-hexane or n-octane; the concentration of the dispersion liquid F is 0.015mmol/L-0.025 mmol/L;
adding the obtained dispersion liquid F into a precursor solution of lead iodide or lead chloride at the temperature of 40-85 ℃ to obtain a mixed solution G;
wherein, the volume ratio of the precursor solution of lead iodide or lead chloride is as follows: dispersion F ═ 1: 1-5: 1;
the preparation method of the precursor solution of lead iodide or lead chloride comprises the following steps: mixing lead iodide (PbI)2) Or lead chloride (PbCl)2) Adding the mixed solution into the mixed solution C, stirring for 15-35min at the temperature of 100-170 ℃, and then cooling to room temperature under the condition of ice-water bath to form a precursor solution of lead iodide or lead chloride;
wherein, if lead iodide (PbI) is used2) When added to the mixed solution C, the solution C consists of oleylamine, oleic acid and octadecene, wherein the volume ratio of oleylamine: oleic acid: octadecene is 1:1:8, and the molar concentration of lead iodide in a precursor solution of the lead iodide is 0.09-0.15 mol/L; if lead chloride (PbCl) is added2) When added to the mixed solution C, the solution C consists of trioctylphosphine, oleic acid, oleylamine and octadecene, wherein the volume ratio of trioctylphosphine: oleic acid: oleylamine: octadecene is 1:1:1:8, and the molar concentration of lead chloride in the precursor solution of lead chloride is 0.09-0.15 mol/L;
and 7, centrifuging and washing the mixed solution G obtained in the previous step to obtain the final product inorganic perovskite CsPbCl3、CsPbClxBr3-x、CsPbBrxI3-xOr CsPbI3A nanowire;
the centrifugal rotating speed in the steps 5 and 7 is 5000-10000r/min, and the centrifugal time is 5-10 min; the washing reagent is acetone, toluene or ethyl acetate.
The nonpolar solvent is one or two of n-hexane, toluene and n-octane.
The invention has the substantive characteristics that:
the invention adopts a solvothermal method and an anion exchange mode to successfully prepare the perovskite CsPbX3(X ═ Cl, Br, I) nanowires. The precursor can fully play a role under the action of the surface ligand due to the longer reaction time at a lower temperature in the solvothermal reaction process,the nano wire can continuously grow along a specific direction, and finally the CsPbBr with better crystallization degree is obtained3A nanowire; and CsPbBr3The CsPbI with ultrahigh length-diameter ratio is prepared by taking the nano wire as a template and utilizing an anion exchange mode at a lower temperature3And CsPbCl3A nanowire.
Firstly, respectively dissolving cesium carbonate and lead bromide in a solvent of octadecene mixed with a surface ligand (steps 1 and 2), so that the surface ligand is uniformly coated on the surface of a precursor, and the reaction process can be well controlled; fully mixing a cesium carbonate precursor and a lead bromide precursor at room temperature, transferring the mixture into a reaction kettle (step 3), controlling the reaction time and the reaction temperature of solution heat to ensure that the two precursors fully nucleate and slowly grow up, centrifuging to obtain a reactant, washing redundant unreacted organic matters by using ethyl acetate to finally obtain CsPbBr3Ultra-long nanowires (steps 4, 5). CsPbBr obtained by preparation3The ultra-long nanowire is taken as a template, and CsPbBr is dispersed by an anion exchange method3Adding the dispersion liquid of the nano-wire into a lead iodide or lead chloride precursor solution continuously, controlling the anion exchange speed by using the temperature of the precursor, gradually and completely exchanging Br element into I element or Cl element (step 6), centrifuging the obtained reactant, washing the reactant by using a reagent such as acetone and the like to obtain CsPbCl3、CsPbClxBr3-x、CsPbBrxI3-xOr CsPbI3The nanowires (step 7). The method enables the oleic acid oleylamine surfactant to fully play a role by controlling the solvothermal reaction temperature and the reaction time, promotes the perovskite to grow along a specific direction, and finally generates CsPbBr with ultrahigh length-diameter ratio3Perovskite nano-wires of other halogen elements with the same appearance are obtained by using an anion exchange mode.
The invention has the beneficial effects that:
1. the diffraction peak of the XRD spectrogram of the inorganic perovskite nanowire synthesized by the method is clear, and the inorganic perovskite CsPbBr is inorganic perovskite CsPbBr3Structure, crystal structure conforming to CsPbBr3PDF #54-752, no diffraction peaks of other hetero-phases present, pureThe degree is as high as 97 percent; perovskite CsPbBr3The nano-wire SEM is shown in figure 2, and is in a superfine fiber shape, and the length can reach several millimeters; CsPbBr3The nano-wire TEM is shown in figure 3, has the diameter of 12nm and ultrahigh length-diameter ratio; CsPbBr3The fluorescence spectrum of the nanowire is shown in FIG. 8, the nanowire has a narrow half-peak width, and the maximum emission peak is 519 nm; CsPbBr3The ultraviolet-visible absorption spectrum of the nanowire is shown in FIG. 9, and the characteristic absorption peak is 508 nm.
2. According to the invention, by controlling the solvothermal reaction temperature and the reaction time, the oleic acid oleylamine surfactant can fully play a role in regulating and controlling the crystal growth, so that the perovskite can continuously grow along a specific direction, and finally the nanowire with the ultrahigh length-diameter ratio is formed.
3. The invention adopts a solvothermal method and an anion exchange mode to realize CsPbBr3，CsPbCl3And CsPbI3The perovskite nanowire is prepared and synthesized, the equipment required by experiments is simple, the strict experimental conditions are not required, the reaction controllability is strong, and the method is suitable for industrial production.
4. The inorganic perovskite nanowire prepared and synthesized by the method has the advantages of narrow half-peak width, high purity and good crystallization degree, and can be used in the fields of photoelectric detectors, solar cells and the like.
Drawings
FIG. 1 shows the inorganic perovskite CsPbBr obtained in example 13XRD pattern of the nanowires.
FIG. 2 shows the inorganic perovskite CsPbBr obtained in example 13SEM image of nanowires.
FIG. 3 shows the inorganic perovskite CsPbBr obtained in example 13TEM images of nanowires.
FIG. 4 shows CPbI, an inorganic perovskite obtained in example 23SEM image of nanowires.
FIG. 5 shows CPbI, an inorganic perovskite obtained in example 23TEM images of nanowires.
FIG. 6 shows the inorganic perovskite CsPbCl obtained in example 33SEM image of nanowires.
FIG. 7 shows CsPbCl, an inorganic perovskite obtained in example 33TEM images of nanowires.
FIG. 8 shows CsPbBr of inorganic perovskite obtained in examples 1 to 33，CsPbI3And CsPbCl3Fluorescence emission spectra of nanowires.
FIG. 9 shows the inorganic perovskites CsPbBr obtained in examples 1 to 33，CsPbI3And CsPbCl3Ultraviolet-visible absorption spectrum of the nanowires.
FIG. 10 shows the inorganic perovskite CsPbBr obtained in example 4xI3-xSEM image of nanowires.
FIG. 11 shows CsPbCl, an inorganic perovskite obtained in example 5xBr3-xSEM image of nanowires.
Detailed Description
The invention will be further explained and explained with reference to the following examples and the attached drawings
Example 1
Step 1, weighing 0.7mmol of cesium carbonate (Cs)2CO3) Added to a flask containing 1.0mL of oleic acid and 8.0mL of octadecene, stirred at 120 ℃ for 25min to completely dissolve the cesium carbonate powder, and then naturally cooled to room temperature to form a cesium precursor solution.
Step 2, weighing 2.0mmol of lead bromide, adding the lead bromide into a flask containing 2.0mL of oleic acid, 2.0mL of oleylamine and 16mL of octadecene, stirring for 25min at 110 ℃ to completely dissolve lead bromide powder, and then cooling to room temperature by using an ice water bath to form a lead bromide precursor solution.
And 3, heating the cesium oleate precursor solution obtained in the step 1 to 80 ℃, measuring 2mL of the cesium oleate precursor solution, adding the cesium oleate precursor solution into a reaction kettle, cooling to room temperature, adding 20mL of the lead bromide precursor obtained in the step 2 at room temperature, and carrying out ultrasonic treatment for 15 min.
And 4, reacting the mixed solution obtained in the step 3 at the heating temperature of 120 ℃ for 70 hours, and naturally cooling to room temperature after the reaction is finished.
Step 5, centrifuging the product obtained in the step 4 at 8000r/min for 7min, discarding the upper organic layer, washing the obtained bottom precipitate with acetone to obtain the product CsPbBr3The nanowires (0.3mmol, i.e., 0.174g) were dispersed in 20mL of n-hexane for storage.
All the operation processes are open environment, and inert protective gas and strict dehydration and deoxidation treatment are not needed.
CsPbBr obtained in example 13XRD of the nanowire is shown in figure 1, and the crystal structure of the nanowire conforms to CsPbBr3PDF #54-752, and the perovskite nanowire has better crystallinity; perovskite CsPbBr3The nano-wire SEM is shown in figure 2, and is in a superfine fiber shape, and the length can reach several millimeters; CsPbBr3The nano-wire TEM is shown in figure 3, has the diameter of 12nm and ultrahigh length-diameter ratio; CsPbBr3The fluorescence spectrum of the nanowire is shown in FIG. 8, the nanowire has a narrow half-peak width, and the maximum emission peak is 519 nm; CsPbBr3The ultraviolet-visible absorption spectrum of the nanowire is shown in FIG. 9, and the characteristic absorption peak is 508 nm.
Example 2
Step 1, weighing 0.7mmol of cesium carbonate, adding the cesium carbonate into a flask containing 1.0mL of oleic acid and 8.0mL of octadecene, stirring at 120 ℃ for 25min to completely dissolve cesium carbonate powder, and then naturally cooling to room temperature to form a cesium precursor solution.
Step 2, weighing 2.0mmol of lead bromide, adding the lead bromide into a flask containing 2.0mL of oleic acid, 2.0mL of oleylamine and 16mL of octadecene, stirring for 25min at 110 ℃ to completely dissolve lead bromide powder, and then cooling to room temperature by using an ice water bath to form a lead bromide precursor solution.
And 3, weighing 2.0mmol of lead iodide, adding the weighed lead iodide into a flask containing 2.0mL of oleic acid, 2.0mL of oleylamine and 16mL of octadecene, stirring for 25min at 110 ℃ to completely dissolve the lead iodide powder, and then cooling to room temperature by using an ice water bath to form a lead iodide precursor solution.
And 4, heating the cesium oleate precursor solution obtained in the step 1 to 80 ℃, measuring 2mL of the cesium oleate precursor solution, adding the cesium oleate precursor solution into a reaction kettle, cooling to room temperature, adding 20mL of the lead bromide precursor obtained in the step 2 at room temperature, and carrying out ultrasonic treatment for 15 min.
And 5, reacting the mixed solution obtained in the step 4 at the heating temperature of 120 ℃ for 70 hours, and naturally cooling to room temperature after the reaction is finished.
Step 6, centrifuging the product obtained in the step 5 at 8000r/min for 7min, discarding the upper organic layer, and precipitating the obtained bottom layerWashing the product with acetone to obtain CsPbBr3Nanowires (0.3mmol) were dispersed in 20mL of n-hexane.
Step 7, taking CsPbBr obtained in step 63And (3) adding 5mL of the nanowire dispersion liquid into 20mL of the lead iodide precursor solution heated to 80 ℃ obtained in the step (3), and obtaining a crude liquid after the reaction is finished.
Step 8, centrifuging the crude liquid obtained in the step 7 for 7min at 8000r/min, discarding an upper organic layer, washing the obtained bottom precipitate with acetone to obtain a CsPbI product3Nanowires were dispersed in 10mL of n-hexane. All the operation processes are open environment, and inert protective gas and strict dehydration and deoxidation treatment are not needed.
CsPbI obtained in example 23The nano-wire SEM is shown in figure 4, and is in a superfine fiber shape, and the length can reach several millimeters; CsPbI3The nanowire TEM is shown in FIG. 3, with a diameter of 12nm and an ultra-high aspect ratio. CsPbI3The fluorescence spectrum of the nanowire is shown in FIG. 8, and the maximum emission peak is 685 nm; CsPbI3The ultraviolet visible absorption spectrum of the nanowire is shown in figure 9, and the characteristic absorption peak is 678 nm.
Example 3
Step 1, weighing 0.7mmol of cesium carbonate, adding the cesium carbonate into a flask containing 1.0mL of oleic acid and 8.0mL of octadecene, stirring at 120 ℃ for 25min to completely dissolve cesium carbonate powder, and then naturally cooling to room temperature to form a cesium precursor solution.
Step 2, weighing 2.0mmol of lead bromide, adding the lead bromide into a flask containing 2.0mL of oleic acid, 2.0mL of oleylamine and 16mL of octadecene, stirring for 25min at 110 ℃ to completely dissolve lead bromide powder, and then cooling to room temperature by using an ice water bath to form a lead bromide precursor solution.
And 3, weighing 2.0mmol of lead chloride, adding the lead chloride into a flask containing 2.0mL of oleic acid, 2.0mL of oleylamine, 2.0mL of trioctylphosphine and 16mL of octadecene, stirring for 25min at 110 ℃ to completely dissolve the lead chloride powder, and then cooling to room temperature by using an ice water bath to form a lead chloride precursor solution.
And 4, heating the cesium oleate precursor solution obtained in the step 1 to 80 ℃, measuring 2mL of the cesium oleate precursor solution, adding the cesium oleate precursor solution into a reaction kettle, cooling to room temperature, adding the lead bromide precursor obtained in the step 2 at room temperature, and carrying out ultrasonic treatment for 15 min.
And 5, reacting the mixed solution obtained in the step 4 at the heating temperature of 120 ℃ for 70 hours, and naturally cooling to room temperature after the reaction is finished.
Step 6, centrifuging the product obtained in the step 5 at 8000r/min for 7min, discarding the upper organic layer, washing the obtained bottom precipitate with acetone to obtain the product CsPbBr3Nanowires (0.3mmol) were dispersed in 20mL of n-hexane.
Step 7, taking CsPbBr obtained in step 63And (3) adding 5mL of the nanowire dispersion liquid into 22mL of lead chloride precursor solution heated to 60 ℃ obtained in the step (3), and obtaining a crude liquid after the reaction is finished.
Step 8, centrifuging the crude liquid obtained in the step 7 for 7min at 8000r/min, discarding an upper organic layer, washing the obtained bottom precipitate with acetone to obtain a product CsPbCl3Nanowires were dispersed in 10mL of n-hexane. All the operation processes are open environment, and inert protective gas and strict dehydration and deoxidation treatment are not needed.
Example 3 CsPbCl was prepared3The nano-wire SEM is shown in figure 6, and is in a superfine fiber shape, and the length can reach several millimeters; CsPbCl3The nano-wire TEM is shown in figure 7, has a diameter of 12nm and an ultrahigh length-diameter ratio; CsPbCl3The fluorescence spectrum of the nanowire is shown in FIG. 8, the nanowire has a narrow half-peak width, and the maximum emission peak is 410 nm; CsPbCl3The ultraviolet-visible absorption spectrum of the nanowire is shown in FIG. 9, and the characteristic absorption peak is 404 nm.
Example 4
CsPbBr in step 7 of example 23The nanowire dispersion was changed from 5mL to 15mL, and the other operations were the same as in example 2 to obtain CsPbBrxI3-xA nanowire. Example 4 preparation of CsPbBrxI3-xThe nanowires, SEM is shown in FIG. 10, appear as ultra-fine fibers, up to several millimeters in length.
Example 5
CsPb in step 7 of example 3Br3The nanowire dispersion was changed from 5mL to 15mL, and the other operations were the same as in example 3 to obtain CsPbClxBr3-xA nanowire. Example 5 CsPbCl was preparedxBr3-xThe nanowires, SEM is shown in FIG. 11, appear as ultra-fine fibers, up to several millimeters in length.
The perovskite CsPbBr with ultrahigh length-diameter ratio is obtained by adjusting the solvothermal reaction temperature and the reaction time3Nanowires (length up to a few mm, diameter only around 10 nm), and CsPbBr3CsPbCl prepared by taking nano wire as template in ion exchange mode3、CsPbClxBr3-x、CsPbBrxI3-xAnd CsPbI3Nanowire, retains CsPbBr3Ultra-high aspect ratio characteristics of nanowires. Precursor PbI in ion exchange Process2Or PbCl2The temperature of (2) has an influence on the rate of anion exchange, and CsPbBr is dispersed3Solution of nanowire and precursor PbI2Or PbCl2The ratio of the perovskite nano-wires to the perovskite nano-wires can influence the exchange reaction, and the perovskite nano-wires with different luminescence peak positions and different components can be obtained by changing the ratio of the perovskite nano-wires to the perovskite nano-wires, so that an experimental basis is provided for the controllable synthesis of the nano-wires, and the perovskite nano-wires have an important promotion effect on the application of the perovskite nano-wires in the aspects of photoelectric detection, solar cells and the like.
The invention is not the best known technology.

Claims (2)

1. A method for synthesizing inorganic perovskite nano-wires is characterized by comprising the following steps:
step 1, adding cesium carbonate (Cs)2CO3) Adding the cesium into the mixed solution A, stirring the cesium for 15 to 35 minutes at the temperature of 110-160 ℃, and naturally cooling the cesium to room temperature to form a cesium precursor solution;
wherein the mixed solution A consists of oleic acid and octadecene, wherein the volume ratio of oleic acid: octadecene =1: 8; in the precursor solution of cesium, the molar concentration of cesium is 0.12-0.25 mol/L;
step 2, lead bromide (PbBr)2) Adding into the mixed solution B, stirring at 90-130 deg.C for 15-35min, and freezingCooling to room temperature under the condition of water bath to form a lead bromide precursor solution;
wherein, the mixed solution B consists of oleylamine, oleic acid and octadecene, wherein the volume ratio of oleylamine: oleic acid: octadecene =1:1:8, and the molar concentration of lead bromide in the lead bromide precursor solution is 0.09-0.15 mol/L;
step 3, heating the precursor solution of cesium to 60-100 ℃, transferring the precursor solution of cesium to a reaction kettle, naturally cooling the precursor solution of cesium to room temperature, adding the precursor solution of lead bromide, and carrying out ultrasonic treatment for 15-35min at the room temperature to obtain a mixed solution D;
wherein, the volume ratio of the lead bromide precursor solution is as follows: precursor solution of cesium =7:1-16: 1;
step 4, reacting the mixed solution D obtained in the step 3 at the temperature of 80-150 ℃ for 30-90h, and then naturally cooling to obtain a reactant solution E;
step 5, centrifuging and washing the reactant E obtained in the step to obtain the final product of inorganic perovskite CsPbBr3A nanowire;
when the product is CsPbCl3、CsPbClxBr3-x、CsPbBrxI3-xOr CsPbI3When the nano wire is used, the method also comprises the following steps:
step 6, the CsPbBr obtained above is added3Adding the nanowire into a nonpolar solvent to obtain a dispersion liquid F; wherein the nonpolar solvent is toluene, n-hexane or n-octane; the concentration of the dispersion liquid F is 0.015mmol/L-0.025 mmol/L;
adding the obtained dispersion liquid F into a precursor solution of lead iodide or lead chloride at the temperature of 40-85 ℃ to obtain a mixed solution G;
wherein, the volume ratio of the precursor solution of lead iodide or lead chloride is as follows: dispersion F =1: 1-5: 1;
the preparation method of the precursor solution of lead iodide or lead chloride comprises the following steps: mixing lead iodide (PbI)2) Or lead chloride (PbCl)2) Adding into the mixed solution C, stirring at 100-170 deg.C for 15-35min, cooling to room temperature in ice-water bath to obtain lead iodide or lead chloride precursor solution；
Wherein, if lead iodide (PbI) is used2) When added to the mixed solution C, the solution C consists of oleylamine, oleic acid and octadecene, wherein the volume ratio of oleylamine: oleic acid: octadecene =1:1:8, and the molar concentration of lead iodide in the lead iodide precursor solution is 0.09-0.15 mol/L; if lead chloride (PbCl) is added2) When added to the mixed solution C, the solution C consists of trioctylphosphine, oleic acid, oleylamine and octadecene, wherein the volume ratio of trioctylphosphine: oleic acid: oleylamine: octadecene =1:1:1:8, and the molar concentration of lead chloride in the lead chloride precursor solution is 0.09-0.15 mol/L;
and 7, centrifuging and washing the mixed solution G obtained in the previous step to obtain the final product inorganic perovskite CsPbCl3、CsPbClxBr3-x、CsPbBrxI3-xOr CsPbI3A nanowire; wherein, 0<x<3。
2. The method for synthesizing inorganic perovskite nanowire as claimed in claim 1, wherein the centrifugal rotation speed in step 5 and step 7 is 5000-10000r/min, and the centrifugal time is 5-10 min; the washing reagent is acetone, toluene or ethyl acetate.
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