Multi-component ternary copper halide nanowires, and preparation method and application thereof
The solution method for preparing multi-component ternary copper halide nanowires solves the problems of high preparation cost and cumbersome process in existing technologies, and achieves nanowires with high crystallinity and low defect density, which are suitable for semiconductor materials.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SUZHOU INST FOR ADVANCED STUDY USTC
- Filing Date
- 2025-11-19
- Publication Date
- 2026-05-29
AI Technical Summary
Existing technologies are difficult to prepare ternary copper halide nanowires with high crystallinity and low defect density at low cost and high efficiency, and existing methods are either cumbersome or costly.
Multicomponent ternary copper halide nanowires were prepared by solution method. The reaction between the copper halide film and the alkali metal halide solution at the solid-liquid interface formed a self-limiting growth kinetic, which promoted the growth of the nanowires along the main axis, resulting in a one-dimensional nanowire structure.
We have achieved low-cost and simple preparation of ternary copper halide nanowires with high crystallinity and low defect density, which have high carrier mobility and are suitable for semiconductor materials in various scenarios.
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Abstract
Description
Technical Field
[0001] This invention relates to a copper halide nanowire, specifically a multi-component ternary copper halide nanowire, its preparation method, and its application, belonging to the field of semiconductor fabrication technology. Background Technology
[0002] Against the backdrop of the increasing importance of renewable energy, scientists are searching for highly efficient optoelectronic materials to replace traditional materials. Lead-based perovskites are rapidly emerging due to their excellent light absorption coefficient, tunable bandgap, and balanced electron-hole mobility, among other superior optoelectronic properties. Perovskite materials are a class of compounds with specific crystal structures, typically possessing the general formula ABX3, where A and B are different cations and X is an anion. This structure endows perovskite materials with excellent optoelectronic properties. Lead-based perovskites not only occupy a place in traditional semiconductor devices such as solar cells and light-emitting diodes, but with the continuous advancement of research, their applications in novel devices such as X-ray imaging and X-ray detectors have also been discovered, making them a research hotspot. However, long-term exposure to lead environments may cause more serious health problems, especially damage to the nervous system and growth and development. Lead intake may lead to cognitive impairment, attention deficit, and learning difficulties, especially in children. Furthermore, lead-based perovskites undergo various phase transitions, and this instability affects their further applications. Therefore, it is necessary to develop relatively safe and stable new lead-free perovskites to gradually reduce dependence on lead-based perovskites.
[0003] In recent years, ternary copper halides have stood out among lead-free perovskites due to their abundant Cu content, excellent environmental stability, and structural diversity. In particular, certain specific structures of ternary copper halides exhibit luminescence properties similar to or even superior to lead-based perovskites, further revealing their important role in lead-free perovskites. However, current research progress is largely limited to ternary copper halide thin films. Grain boundaries, unavoidable structural defects in polycrystalline films, not only act as carrier scattering centers but can also become impurity accumulation sites, reduce material mechanical strength, increase chemical corrosion channels, and affect material stability. In contrast, single crystals exhibit periodic atomic arrangement and lack grain boundaries, while also possessing higher carrier mobility and lower defect density. Shi et al. (DOI:10.1039 / D0MH00250J) successfully prepared ternary copper halide nanowires via anti-solvent crystallization, a simple procedure, but their SEM images showed poor crystal morphology and high defect density. Xia et al. (DOI: 10.1002 / adom.202301336) successfully prepared ternary copper halide nanowires using a template method, obtaining nanowires with low defect density and high crystallinity. However, the experimental procedure was too cumbersome and the cost was high. Summary of the Invention
[0004] The main objective of this invention is to provide a low-cost and simple method for preparing multi-component ternary copper halide nanowires, while the obtained nanowires have high crystallinity and low defect density, thus overcoming the shortcomings of the prior art.
[0005] Another object of the present invention is to provide applications of the multi-component ternary copper halide nanowires.
[0006] To achieve the aforementioned objectives, the technical solution adopted by this invention includes:
[0007] This invention provides a method for preparing multi-component ternary copper halide nanowires, comprising: placing a substrate material containing a copper halide precursor in an alkali metal halide solution and allowing it to stand to obtain multi-component ternary copper halide nanowires; wherein the halogen element contained in the copper halide precursor includes one or more combinations of Cl, Br, and I; wherein the halogen element contained in the alkali metal halide solution includes one or more combinations of Cl, Br, and I; and wherein the alkali metal element contained in the alkali metal halide solution includes one or more combinations of Cs, Rb, and K.
[0008] This invention also provides multi-component ternary copper halide nanowires prepared by the aforementioned method.
[0009] Furthermore, the elements contained in the multi-component ternary copper halide nanowires include alkali metal elements, Cu, and X. The alkali metal elements include one or more combinations of Cs, Rb, and K, and X includes one or more combinations of Cl, Br, and I. The molar ratio of alkali metal elements, Cu, and X is 1:2:3 or 3:2:5.
[0010] This invention also provides the application of the multi-component ternary copper halide nanowires in the preparation of semiconductor materials.
[0011] Compared with the prior art, the beneficial effects of the present invention include at least the following:
[0012] 1) This invention provides a multi-component ternary copper halide nanowire using a solution method. The preparation method is simple and efficient. The single-crystal nanowires formed by self-limited growth have the characteristics of high crystallinity. The size of the nanowires can be controlled by changing the temperature and reaction time. By adding a mixture of different alkali metal halide precursors, the halogen ratio can be adjusted to achieve tunable light emission, so as to meet the application requirements of semiconductors in different scenarios.
[0013] 2) In this invention, the copper halide film simultaneously serves as both a copper source and a reaction template, reacting with alkali metal ions and halide ions in the solution at the solid-liquid interface. Solvent molecules preferentially adsorb onto the lateral crystal planes of the nanocrystals, forming a self-limiting growth kinetic that effectively inhibits lateral expansion and promotes axial preferential elongation. The heating stage drives the nucleation and growth of the nanowires along the main axis, while the subsequent long-term static process further promotes the growth of the nanowires along the long axis. The synergistic effect of these mechanisms ultimately guides the product to form a one-dimensional nanowire structure.
[0014] 3) Compared with the prior art, the multi-component ternary copper halide nanowires prepared by the present invention have a series of advantages such as high crystallinity, low defect density and high carrier mobility. Attached Figure Description
[0015] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0016] Figure 1 This is a flowchart illustrating the preparation process of a multi-component ternary copper halide nanowire in a typical embodiment of the present invention.
[0017] Figure 2 An optical photograph of the CsCu2I3 nanowires prepared in Example 1 of this invention;
[0018] Figure 3 An optical photograph of the CsCu2I3 nanowires prepared in Example 2 of this invention;
[0019] Figure 4 An optical photograph of the CsCu2I3 nanowires prepared in Example 3 of this invention;
[0020] Figure 5 An optical photograph of the CsCu2I3 nanowires prepared in Example 4 of this invention;
[0021] Figure 6 The image shows the XRD pattern of the CsCu2I3 nanowires prepared in Example 2 of this invention.
[0022] Figure 7 The image shows the XRD pattern of the CsCu2I3 nanowires prepared in Example 4 of this invention.
[0023] Figure 8 PL image of CsCu2I3 nanowires prepared in Example 2 of this invention;
[0024] Figure 9This is a SEM image of the CsCu2I3 nanowires prepared in Example 1 of this invention;
[0025] Figure 10 This is a SEM image of the CsCu2I3 nanowires prepared in Example 2 of this invention;
[0026] Figure 11 Optical image of the Cs3Cu2Br5 nanowires prepared in Example 5 of this invention;
[0027] Figure 12 The XRD pattern of the Cs3Cu2Br5 nanowires prepared in Example 5 of this invention;
[0028] Figure 13 PL image of Cs3Cu2Br5 nanowires prepared in Example 5 of this invention;
[0029] Figure 14 CsCu2I prepared in Example 6 of this invention 3-x Br x XRD pattern of nanowires;
[0030] Figure 15 CsCu2I prepared in Example 6 of this invention 3-x Br x PL diagram of nanowires;
[0031] Figure 16 CsCu2I prepared in Example 6 of this invention 3-x Br x SEM image of nanowires. Detailed Implementation
[0032] To address the aforementioned issues, the applicant provides a size-tunable multi-component ternary copper halide nanowire and its preparation method, which improves crystallization performance, optimizes the preparation process, reduces production costs, and enables tunable luminescence of the ternary copper halide nanowire.
[0033] The following will further explain the technical solution, its implementation process, and its principles. However, it should be understood that within the scope of this invention, the above-mentioned technical features of this invention and the technical features specifically described below (in embodiments) can be combined with each other to form new or preferred technical solutions. Due to space limitations, they will not be described in detail here.
[0034] As one aspect of the technical solution of the present invention, a method for preparing multi-component ternary copper halide nanowires includes: placing a substrate material containing a copper halide precursor in an alkali metal halide solution and allowing it to stand to obtain multi-component ternary copper halide nanowires; the halogen element contained in the copper halide precursor includes one or more combinations of Cl, Br, and I; the halogen element contained in the alkali metal halide solution includes one or more combinations of Cl, Br, and I; the alkali metal element contained in the alkali metal halide solution includes one or more combinations of Cs, Rb, and K.
[0035] The growth mechanism of copper halide nanowires in the preparation method of this invention is as follows: the copper halide film simultaneously acts as a copper source and a reaction template, reacting with alkali metal ions and halide ions contained in the alkali metal halide solution at the solid-liquid interface. Solvent molecules preferentially adsorb onto the lateral crystal planes of the nanocrystals, forming a self-limiting growth kinetic, effectively inhibiting lateral expansion and promoting axial preferential elongation. The heating stage drives the nucleation and growth of the nanowires along the main axis, while the subsequent long-term static process further promotes the growth of the nanowires along the long axis. The above mechanisms work synergistically to ultimately guide the product to form a one-dimensional nanowire structure.
[0036] In some embodiments, the copper halide precursor (i.e., CuX precursor) includes one or more combinations of CuI, CuCl, CuCl2, CuBr, CuBr2, etc., but is not limited to these.
[0037] In some embodiments, the alkali metal halide solution contains one or more combinations of CsI, CsBr, CsCl, RbCl, RbBr, RbI, KCl, KBr, KI, etc., but is not limited to these.
[0038] In some embodiments, the preparation method specifically includes: applying a copper halide precursor solution onto a substrate material, heating to evaporate the solvent, and obtaining the substrate material containing the copper halide precursor.
[0039] In some more preferred embodiments, the method for preparing the substrate material containing the copper halide precursor may specifically include:
[0040] Take an appropriate amount of CuX precursor solution and drop it onto the cleaned substrate material. Place the substrate material on a heating stage and wait for the solvent to evaporate. After cooling, remove the glass slide to obtain the substrate material containing the copper halide precursor.
[0041] Furthermore, the amount of the copper halide precursor solution applied is 10 µL to 200 µL, preferably 10 µL to 60 µL.
[0042] Furthermore, the heating temperature is 100~150℃, and the heating time is 5 min~10 min.
[0043] In some preferred embodiments, the copper halide precursor solution includes one or more combinations of CuI precursor solution, CuCl precursor solution, CuCl2 precursor solution, CuBr precursor solution, and CuBr2 precursor solution.
[0044] Furthermore, the concentration of the copper halide precursor solution is 5~80 mg / mL.
[0045] Furthermore, the concentration of the CuI precursor solution is 5~80 mg / mL.
[0046] Furthermore, the concentration of the CuCl precursor solution is 5~80 mg / mL.
[0047] Furthermore, the concentration of the CuCl2 precursor solution is 5~80 mg / mL.
[0048] Furthermore, the concentration of the CuBr precursor solution is 5~80 mg / mL.
[0049] Furthermore, the concentration of the CuBr2 precursor solution is 5~80 mg / mL.
[0050] In some preferred embodiments, the method for preparing the copper halide precursor solution includes: placing a copper halide (CuX) precursor in a first polar solvent and mixing them to obtain the copper halide precursor solution.
[0051] Furthermore, the first polar solvent may include one or more of acetonitrile, DMSO, DMF, etc., but is not limited to these.
[0052] In some preferred embodiments, the method for preparing the alkali metal halide solution includes: placing the alkali metal halide in a second polar solvent and mixing them to obtain the alkali metal halide solution.
[0053] Furthermore, the second polar solvent may include one or more of methanol, ethanol, propanol, but not limited to these.
[0054] In some preferred embodiments, the alkali metal halide solution includes one or more combinations of CsI solution, CsBr solution, CsCl solution, RbCl solution, RbBr solution, RbI solution, KCl solution, KBr solution, KI solution, etc., but is not limited thereto.
[0055] Furthermore, the concentration of the alkali metal halide solution is 0.1~32 mg / mL.
[0056] In some preferred embodiments, the substrate material includes one or more combinations of glass sheets, quartz sheets, silicon wafers, etc., but is not limited thereto.
[0057] In some implementations, the substrate material is washed multiple times with different solutions.
[0058] In some preferred embodiments, the substrate material is sequentially cleaned with a first solution, a second solution, and a third solution.
[0059] Furthermore, the first solution comprises a mixture of detergent and water.
[0060] Furthermore, the second solution includes one or a combination of two of ultrapure water and deionized water.
[0061] Furthermore, the third solution includes one or more of methanol, ethanol, isopropanol (IPA), etc.
[0062] In some embodiments, the preparation method specifically includes: placing a substrate material containing a copper halide precursor in an alkali metal halide solution, heating, and then allowing it to stand to obtain the multi-component ternary copper halide nanowires; the heating temperature is 25 ℃~100 ℃, preferably 40 ℃~100 ℃, and the heating time is 30 min~12 h. If the heating temperature is too low, it cannot provide the nucleation energy for nucleation; if the heating temperature is too high, it will reduce the yield of nanowires to some extent. The standing time is related to the growth of nanowires; a short standing time will affect the yield, while a long standing time will damage the morphology of the nanowires due to the polarity of the solvent.
[0063] In some preferred embodiments, the settling temperature is room temperature, and the settling time is 10 min to 24 h.
[0064] Please see Figure 1 As shown, a solution-based method for preparing multi-component ternary copper halide nanowires according to a typical embodiment of the present invention specifically includes the following steps:
[0065] (1) Weigh CsX powder into a clean glass bottle. The amount weighed is between 0.4 mg and 80 mg. At the same time, add an appropriate amount of alcohol solvent and shake to obtain CsX precursor solution.
[0066] (2) Take a clean glass bottle and weigh CuX or CuX2 powder, the amount of which is between 10mg and 40mg. At the same time, add an appropriate amount of one or more of the following solvents: DMSO, acetonitrile or DMF, heat and stir to obtain CuX or CuX2 precursor solution.
[0067] (3) Take a glass slide and clean it several times with a mixture of detergent solution, ultrapure water or deionized water, or a combination of methanol, ethanol or IPA, for 5 min to 1 h each time.
[0068] (4) Take the cleaned glass slide from step (3) and place it on the heating stage. Take the CuX or CuX2 precursor solution from step (2), take 10~60 µL from it and drop it onto the glass slide on the heating stage. Heat at 100~150℃ for 5~10 min. After the solvent evaporates, remove the glass slide and cool it at room temperature.
[0069] (5) Take the glass slide from step (4), put it into the CsX precursor solution, heat it at 40℃~100℃ for 30min~12h, and let it stand at room temperature for 10min~24h to obtain multi-component ternary copper halide nanowires.
[0070] In summary, this invention provides a multi-component ternary copper halide nanowire using a solution method. The preparation method is simple and efficient. The single-crystal nanowires formed by self-limiting growth have the characteristics of high crystallinity. The size of the nanowires can be controlled by changing the temperature and reaction time. By adding a mixture of different alkali metal halide precursors, the halogen ratio can be adjusted to achieve tunable luminescence, thereby meeting the application requirements of semiconductors in different scenarios.
[0071] As another aspect of the technical solution of the present invention, a multi-component ternary copper halide nanowire is prepared by the above-described preparation method.
[0072] Specifically, the multi-component ternary copper halide nanowires contain elements including alkali metals, Cu, and X. The alkali metals include one or more combinations of Cs, Rb, and K, and X includes one or more combinations of Cl, Br, and I. The molar ratio of alkali metals, Cu, and X is 1:2:3 or 3:2:5.
[0073] Furthermore, the multi-component ternary copper halide nanowires include one or more combinations of CsCu2X3, Cs3Cu2X5, RbCu2X3, Rb3Cu2X5, and KCu2X3.
[0074] Furthermore, the diameter of the multi-component ternary copper halide nanowires ranges from 200 nm to 60 µm, and the length ranges from 4 µm to 2 cm.
[0075] Compared with the traditional one-step and two-step methods for obtaining polycrystalline ternary copper halide thin films in the prior art, the ternary copper halide nanowires obtained by the present invention have high crystallinity, low defect density and high carrier mobility.
[0076] Compared with existing ternary copper halide nanowire preparation techniques, the ternary copper halide nanowires obtained by this invention have high crystallinity and low solvent toxicity, making them safer than the anti-solvent crystallization method. Compared with the template method, this invention optimizes the experimental process and reduces costs, while also ensuring that the nanowires have good crystallinity.
[0077] In summary, this invention provides a low-cost, simple, and convenient method for preparing multi-component ternary copper halide nanowires. The nanowires obtained by this method have a series of advantages such as high crystallinity, low defect density, and high carrier mobility.
[0078] As another aspect of the technical solution of the present invention, it also relates to the application of the multi-component ternary copper halide nanowires in the preparation of semiconductor materials.
[0079] To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the invention is further described in detail below. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. It should be noted that the following embodiments are intended to facilitate understanding of this invention and are not intended to limit it in any way. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions or according to the conditions recommended by the manufacturer.
[0080] Example 1
[0081] (1) Weigh 2 mg of CsI powder into a clean glass bottle and add 4 mL of ethanol and shake to obtain a CsI precursor solution.
[0082] (2) Take a clean glass bottle and weigh 20 mg of CuI powder. At the same time, add 1 mL of 99.8% DMSO and heat and stir at 70℃ for 12 h to obtain CuI precursor solution.
[0083] (3) Take a glass slide and cut it into small pieces. The resulting glass slides are ultrasonically cleaned three times each with a solution of detergent, ultrapure water, and IPA, with each cleaning time being 15 minutes.
[0084] (4) Take the cleaned glass slide from step (3) and place it on the heating stage. Take the CuI precursor solution from step (2), take 30 µL of it and drop it onto the glass slide on the heating stage. Heat at 130°C for 5 minutes. After the solvent evaporates, remove the glass slide and cool it to room temperature.
[0085] (5) Take the glass slide from step (4), put it into a 0.5 mg / ml CsI solution, heat it at 25℃ for 30 min, and let it stand at room temperature for 12 h to obtain CsCu2I3 nanowires.
[0086] Figure 2 This is an optical photograph of the CsCu2I3 nanowires prepared in this embodiment. Figure 9 Here is a SEM image of the CsCu2I3 nanowires prepared in this embodiment, by... Figure 2 and Figure 9 The optical images and SEM images demonstrate the successful fabrication of CsCu₂I₃ nanowires in this embodiment. Furthermore, the optical images and SEM images obtained from these examples confirm the successful fabrication of CsCu₂I₃ nanowires. Figure 9 It can be seen that the CsCu2I3 nanowires have high crystallinity and low defect density, which indicates that they have high carrier mobility.
[0087] Example 2
[0088] (1) Weigh 4 mg of CsI powder into a clean glass bottle and add 4 mL of ethanol and shake to obtain a CsI precursor solution.
[0089] (2) Take a clean glass bottle and weigh 20 mg of CuI powder. At the same time, add 1 mL of DMSO and heat and stir at 70°C for 12 h to obtain CuI precursor solution.
[0090] (3) Take a glass slide and cut it into small pieces. The resulting glass slides are ultrasonically cleaned three times each with a solution of detergent, ultrapure water, and IPA, with each cleaning time being 15 minutes.
[0091] (4) Take the cleaned glass slide from step (3) and place it on the heating stage. Take the CuI precursor solution from step (2), take 30 µL of it and drop it onto the glass slide on the heating stage. Heat at 130°C for 10 min. After the solvent evaporates, remove the glass slide and cool it to room temperature.
[0092] (5) Take the glass slide from step (4), put it into a 1 mg / ml CsI solution, heat it at 25℃ for 30 min, and let it stand at room temperature for 6 h to obtain CsCu2I3 nanowires.
[0093] Figure 3 This is an optical photograph of the CsCu2I3 nanowires prepared in this embodiment. Figure 6 The image shows the XRD pattern of CsCu2I3 nanowires. Figure 8 PL image of CsCu2I3 nanowires. Figure 10 Here is a SEM image of CsCu2I3 nanowires, from Figure 3 , Figure 6 , Figure 8 and Figure 10 It can be confirmed that the prepared material is CsCu₂I₃ nanowires, with its emission peak located around 575 nm. Furthermore, it is composed of... Figure 10 It can be seen that the CsCu2I3 nanowires have high crystallinity and low defect density, which indicates that they have high carrier mobility.
[0094] Example 3
[0095] (1) Weigh 4 mg of CsI powder into a clean glass bottle and add 4 mL of ethanol and shake to obtain a CsI precursor solution.
[0096] (2) Take a clean glass bottle and weigh 20 mg of CuI powder. At the same time, add 1 mL of DMSO and heat and stir at 70°C for 12 h to obtain CuI precursor solution.
[0097] (3) Take a glass slide and cut it into small pieces. The resulting glass slides are ultrasonically cleaned three times each with a solution of detergent, ultrapure water, and IPA, with each cleaning time being 15 minutes.
[0098] (4) Take the cleaned glass slide from step (3) and place it on the heating stage. Take the CuI precursor solution from step (2), take 40 µL of it and drop it onto the glass slide on the heating stage. Heat at 130°C for 7 minutes. After the solvent evaporates, remove the glass slide and cool it to room temperature.
[0099] (5) Take the glass slide from step (4), put it into a 0.5 mg / ml CsI solution, heat it at 70℃ for 4 hours, and let it stand at room temperature for 8 hours to obtain CsCu2I3 nanowires.
[0100] Figure 4 The optical photographs of the CsCu2I3 nanowires prepared in this embodiment demonstrate that the CsCu2I3 nanowires were successfully prepared using the process described in this embodiment.
[0101] Example 4
[0102] (1) Weigh 4 mg of CsI powder into a clean glass bottle and add 4 mL of ethanol and shake to obtain a CsI precursor solution.
[0103] (2) Take a clean glass bottle and weigh 20 mg of CuI powder. At the same time, add 1 mL of DMSO and heat and stir at 70°C for 12 h to obtain CuI precursor solution.
[0104] (3) Take a glass slide and cut it into small pieces. The resulting glass slides are ultrasonically cleaned three times each with a solution of detergent, ultrapure water, and IPA, with each cleaning time being 15 minutes.
[0105] (4) Take the cleaned glass slide from step (3) and place it on the heating stage. Take the CuI precursor solution from step (2), take 60 µL of it and drop it onto the glass slide on the heating stage. Heat at 130°C for 5 minutes. After the solvent evaporates, remove the glass slide and cool it to room temperature.
[0106] (5) Take the glass slide from step (4), put it into a 0.5 mg / ml CsI solution, heat it at 60℃ for 4 hours, and let it stand at room temperature for 8 hours to obtain CsCu2I3 nanowires.
[0107] Figure 5 This is an optical photograph of the CsCu2I3 nanowires prepared in this embodiment. Figure 7 The image shows the XRD pattern of CsCu2I3 nanowires. Figure 5 and Figure 7 It can be proven that the product of this embodiment is the CsCu2I3 phase, and CsCu2I3 nanowires were successfully prepared through the process of this embodiment.
[0108] Example 5
[0109] (1) Weigh 80 mg of CsBr powder into a clean glass bottle and add 4 mL of methanol and shake to obtain a CsBr precursor solution.
[0110] (2) Take a clean glass bottle and weigh 40 mg of CuBr powder. At the same time, add 1 mL of DMSO and heat and stir at 70 °C for 12 h to obtain CuBr precursor solution.
[0111] (3) Take a glass slide and cut it into small pieces. The resulting glass slides are ultrasonically cleaned three times each with a solution of detergent, ultrapure water, and IPA, with each cleaning time being 15 minutes.
[0112] (4) Take the cleaned glass slide from step (3) and place it on the heating stage. Take the CuBr precursor solution from step (2), take 60 µL of it and drop it onto the glass slide on the heating stage. Heat at 130°C for 5 minutes. After the solvent evaporates, remove the glass slide and cool it to room temperature.
[0113] (5) Take the glass slide from step (4), put it into a 20 mg / ml CsBr solution, heat it at 70℃ for 4 hours, and let it stand at room temperature for 8 hours to obtain Cs3Cu2Br5 nanowires.
[0114] Figure 12The image shows the XRD pattern of the Cs3Cu2Br5 nanowires prepared in this embodiment. Figure 13 The photoluminescence (PL) image of the Cs3Cu2Br5 nanowire confirms that it is a Cs3Cu2Br5 phase, with the emission peak around 470 nm. Figure 11 The optical photographs show that Cs3Cu2Br5 nanowires were successfully prepared in this embodiment.
[0115] Example 6
[0116] (1) Weigh 4 mg of CsBr powder and 0.4 mg of CsI powder into a clean glass bottle and shake with 4 mL of ethanol to obtain CsBr-CsI precursor solution.
[0117] (2) Take a clean glass bottle and weigh 40 mg of CuI powder. Add 2 mL of DMSO and heat and stir at 70 °C for 12 h to obtain CuI precursor solution.
[0118] (3) Take a glass slide and cut it into small pieces. The resulting glass slides are ultrasonically cleaned three times each with a solution of detergent, ultrapure water, and IPA, with each cleaning time being 15 minutes.
[0119] (4) Take the cleaned glass slide from step (3) and place it on the heating stage. Take the CuI precursor solution from step (2), take 60 µL of it and drop it onto the glass slide on the heating stage. Heat at 130°C for 5 minutes. After the solvent evaporates, remove the glass slide and cool it to room temperature.
[0120] (5) Take the glass slide from step (4), put it into the CsBr-CsI solution, heat it at 25℃ for 30 min, and let it stand at room temperature for 12 h to obtain CsCu2I. 3-x Br x Nanowires.
[0121] Figure 14 CsCu2I prepared in this embodiment 3-x Br x XRD pattern of nanowires Figure 15 CsCu2I 3-x Br x The PL pattern of the nanowires confirms that they are CsCu2I. 3-x Br x The phase composition shows an emission peak around 460 nm. Figure 16 CsCu2I 3-x Br x The SEM image of the nanowires shows that CsCu2I was successfully prepared in this embodiment. 3-x Br x Nanowires. And made of Figure 16It can be seen that the CsCu2I3 nanowires have high crystallinity and low defect density, which indicates that they have high carrier mobility.
[0122] Example 7
[0123] (1) Weigh 2 mg of RbI powder into a clean glass bottle and add 4 mL of ethanol and shake to obtain RbI precursor solution.
[0124] (2) Take a clean glass bottle and weigh 20 mg of CuI powder. At the same time, add 1 mL of 99.8% DMSO and heat and stir at 70℃ for 12 h to obtain CuI precursor solution.
[0125] (3) Take a glass slide and cut it into small pieces. The resulting glass slides are ultrasonically cleaned three times each with a solution of detergent, ultrapure water, and IPA, with each cleaning time being 15 minutes.
[0126] (4) Take the cleaned glass slide from step (3) and place it on the heating stage. Take the CuI precursor solution from step (2), take 30 µL of it and drop it onto the glass slide on the heating stage. Heat at 100°C for 5 minutes. After the solvent evaporates, remove the glass slide and cool it to room temperature.
[0127] (5) Take the glass slide from step (4), put it into a 0.5 mg / ml RbI solution, heat it at 25℃ for 12 h, and let it stand at room temperature for 24 h to obtain RbCu2I3 nanowires.
[0128] Example 8
[0129] (1) Weigh KI powder into a clean glass bottle. The amount weighed is 2 mg. At the same time, add 4 mL of ethanol and shake to obtain KI precursor solution.
[0130] (2) Take a clean glass bottle and weigh 20 mg of CuI powder. At the same time, add 1 mL of 99.8% DMSO and heat and stir at 70℃ for 12 h to obtain CuI precursor solution.
[0131] (3) Take a glass slide and cut it into small pieces. The resulting glass slides are ultrasonically cleaned three times each with a solution of detergent, ultrapure water, and IPA, with each cleaning time being 15 minutes.
[0132] (4) Take the cleaned glass slide from step (3) and place it on the heating stage. Take the CuI precursor solution from step (2), take 30 µL of it and drop it onto the glass slide on the heating stage. Heat at 150°C for 5 minutes. After the solvent evaporates, remove the glass slide and cool it to room temperature.
[0133] (5) Take the glass slide from step (4), put it into a 0.5 mg / ml KI solution, heat it at 70℃ for 30 min, and let it stand at room temperature for 10 min to obtain KCu2I3 nanowires.
[0134] In addition, the inventors of this case also conducted experiments with other raw materials, process operations, and process conditions described in this specification, referring to the aforementioned embodiments, and obtained relatively ideal results in all cases.
[0135] It should be understood that the application of the present invention is not limited to the examples above. Those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.
Claims
1. A method for preparing multi-component ternary copper halide nanowires, characterized in that, include: A substrate material containing a copper halide precursor is placed in an alkali metal halide solution and allowed to stand to obtain multi-component ternary copper halide nanowires. The halogen elements contained in the copper halide precursor include one or more combinations of Cl, Br, and I. The halogen elements contained in the alkali metal halide solution include one or more combinations of Cl, Br, and I. The alkali metal elements contained in the alkali metal halide solution include one or more combinations of Cs, Rb, and K.
2. The preparation method according to claim 1, characterized in that: The copper halide precursor includes one or more combinations of CuI, CuCl, CuCl2, CuBr, and CuBr2; And / or, the alkali metal halide solution contains one or more combinations of CsI, CsBr, CsCl, RbCl, RbBr, RbI, KCl, KBr, and KI.
3. The preparation method according to claim 1, characterized in that, include: A copper halide precursor solution is applied to a substrate material, and the solvent is evaporated by heating to obtain the substrate material containing the copper halide precursor.
4. The preparation method according to claim 3, characterized in that: The amount of copper halide precursor solution applied is 10 µL to 200 µL; And / or, the heating temperature is 100~150℃, and the heating time is 5 min~10 min.
5. The preparation method according to claim 3, characterized in that: The copper halide precursor solution includes one or more combinations of CuI precursor solution, CuCl precursor solution, CuCl2 precursor solution, CuBr precursor solution, and CuBr2 precursor solution; Preferably, the concentration of the copper halide precursor solution is 5~80 mg / mL.
6. The preparation method according to claim 3, characterized in that... include: The copper halide precursor is placed in a first polar solvent and mixed to obtain the copper halide precursor solution. Preferably, the first polar solvent includes one or more combinations of acetonitrile, DMSO, and DMF; And / or, the preparation method includes: placing an alkali metal halide in a second polar solvent, mixing them to obtain the alkali metal halide solution; Preferably, the second polar solvent includes one or more combinations of methanol, ethanol, propanol, butanol, and water; And / or, the alkali metal halide solution includes one or more combinations of CsI solution, CsBr solution, CsCl solution, RbCl, RbBr, RbI, KCl, KBr, and KI; Preferably, the concentration of the alkali metal halide solution is 0.1~32 mg / mL.
7. The preparation method according to claim 3, characterized in that: The substrate material includes one or more combinations of glass sheets, quartz sheets, and silicon wafers; And / or, the substrate material is washed multiple times with different solutions; Preferably, the substrate material is cleaned sequentially with a first solution, a second solution, and a third solution; Preferably, the first solution comprises a mixture of detergent and water; Preferably, the second solution includes one or a combination of two of ultrapure water and deionized water; Preferably, the third solution includes one or more of methanol, ethanol, and isopropanol.
8. The preparation method according to claim 1, characterized in that, include: The substrate material containing the copper halide precursor was placed in an alkali metal halide solution, heated, and then allowed to stand to obtain the multi-component ternary copper halide nanowires; the heating temperature was 25 ℃~100 ℃, and the heating time was 30 min~12 h; Preferably, the settling temperature is room temperature, and the settling time is 10 min to 24 h.
9. A multi-component ternary copper halide nanowire, characterized in that, It is prepared by the preparation method described in any one of claims 1-8; The multi-component ternary copper halide nanowires contain elements including alkali metals, Cu, and X. The alkali metals include one or more combinations of Cs, Rb, and K, and X includes one or more combinations of Cl, Br, and I. The molar ratio of alkali metals, Cu, and X is 1:2:3 or 3:2:
5. Preferably, the multi-component ternary copper halide nanowires include one or more combinations of CsCu2X3, Cs3Cu2X5, RbCu2X3, Rb3Cu2X5, and KCu2X3; Preferably, the diameter of the multi-component ternary copper halide nanowire is 200 nm to 60 µm, and the length is 4 µm to 2 cm.
10. The application of the multi-component ternary copper halide nanowires of claim 9 in the preparation of semiconductor materials.