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INORGANIC CHEMISTRY
DOI - 10.32 743/UniChem.2024.119.5.17229 ROOM TEMPERATURE FACILE SYNTHESES OF LEAD BROMIDE PEROVSKITES
Kodirbek Norboyev
PhD student
at Samarkand State University named after Sh. Rashidov,
Uzbekistan, Samarkand
Akhtam Samiev
PhD student
at Samarkand State University named after Sh. Rashidov,
Uzbekistan, Samarkand
Khurshid Tashpulatov
Associate professor, PhD, Samarkand State University named after Sh. Rashidov,
Uzbekistan, Samarkand E-mail: xurshiduz@yandex. ru Abdullo Nasimov Professor,
Samarkand State University named after Sh. Rashidov,
Uzbekistan, Samarkand
Alisher Nurimov
PhD student
at Samarkand State University named after Sh. Rashidov,
Uzbekistan, Samarkand
ПРОСТОЙ СИНТЕЗ ПЕРОВСКИТОВ БРОМИДА СВИНЦА ПРИ КОМНАТНОЙ ТЕМПЕРАТУРЕ
Норбоев Кодирбек
докторант
Самаркандского государственного университета
имени Ш. Рашидова, Республика Узбекистан, г. Самарканд
Самиев Ахтам
докторант
Самаркандского государственного университета
имени Ш. Рашидова, Республика Узбекистан, г. Самарканд
Ташпулатов Хуршид
PhD, доцент
Самаркандского государственного университета
имени Ш. Рашидова, Республика Узбекистан, г. Самарканд E-mail: xurshiduz@yyandex. ru
Насимов Абдулло
профессор
Самаркандского государственного университета
имени Ш. Рашидова, Республика Узбекистан, г. Самарканд
Библиографическое описание: ROOM TEMPERATURE FACILE SYNTHESES OF LEAD BROMIDE PEROVSKITES // Universum: химия и биология : электрон. научн. журн. Tashpulatov K. [и др.]. 2024. 5(119). URL: https://7univer-sum. com/ru/nature/archive/item/17229
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Нуримов Алишер
докторант
Самаркандского государственного университета
имени Ш. Рашидова, Республика Узбекистан, г. Самарканд
ABSTRACT
In this work, the bright CsPbBr3 and MAPbBr3 perovskites quantum dots quantum dots for solar cells were synthesized at room temperature in this work. The formation of quantum dots was investigated in the received perovskite CsPbBr3 and MAPbBr3. Furthermore, the quantum dots of CsPbBr3 and MAPbBr3 were studied using the electronic absorption and emission spectra.
АННОТАЦИЯ
В данной работе при комнатной температуре были синтезированы яркие квантовые точки перовскитов CsPbBr3 и MAPbBr3 — квантовые точки для солнечных элементов. Было исследовано образование квантовых точек в полученных перовскитах CsPbBr3 и MAPbBr3. Кроме того, квантовые точки CsPbBr3 и MAPbBr3 были изучены с использованием электронных спектров поглощения и эмиссии.
Keywords: CsPbBr3, MAPbBr3, perovskite, quantum dots, synthesis, absorption, emission, antisolvent.
Ключевые слова: CsPbBr3, MAPbBr3, перовскит, квантовые точки, синтез, поглощение, эмиссия, антирастворитель.
Introduction
In the recent past, all inorganic perovskite materials have become the subject of hype due to their high carrier mobility, high radiation recombination efficiency, high color purity, and a variable bandgap; as a consequence, they have become excellent candidates for next-generation light-emitting devices [1-3].
Perovskite materials are generally characterized by the generic formula ABX3, where the metallic component A is typically a monovalent organic or metal cation such as Cs+, MA+, or FA+, while B is usually a divalent metal cation, mostly Pb+2, and Sn+2. The halide anion, X, is typically Cl-, Br-, or I-. The regular octahedral per-ovskite structure is shown in Figure 1.
Figure 1. The crystal structure of perovskites
Perovskite solar cells were first reported in 2009, proving that the perovskite semiconductor presents room for applications in Nanotechnology. Currently, the power conversion efficiency of the perovskite solar cell has grown to 25.2% in the last years [4,5]. For CsPbX3 (X = Cl, Br, I) QDs, the most commonly used methods include the hot-injection method, room temperature antisolvent methods, and ion exchange methods. The hot injection method has the advantage of synthesizing high-performance perovskite nanomaterials.
Protesescu et al injected the pre-prepared cesium oleate precursor into dissolved oleic acid OAm, and oc-tadecene ODE under high temperature and nitrogen flow
conditions in the PbX2 solution, and then, the temperature of the reaction was rapidly cooled to room temperature, and the reaction solution was centrifuged to obtain the original perovskite solution. The hot-injection method introduces OA and OAm ligands, which provides the possibility for the subsequent study of ligand modification and makes it possible to introduce ions into the perovskite lattice. Since the perovskite QDs materials are essentially ionic crystals, ion migration can take place in the solution.
Since perovskite QDs materials are ionic gems, particle relocation can take put within the arrangement. By including diverse halogen components to the perovskite
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QDs arrangement arranged by warm infusion and other strategies, perovskite QDs with distinctive photoluminescence wavelength ranges can be arranged. Nedelcu et al. accomplished the preparation of perovskite QDs within the whole obvious light locale by halfway or full anion trade at room temperature [7]. Be that as it may, blending diverse incandescent lamps will lead to the stage partition of QDs causing to decrease in photosta-bility.
The main difference in solubility between materials in different solvents is mainly due to the principle that solubility is completely different in different solutions. The room temperature method uses PbX2 and CsX as material sources dissolves them in DMF (i.e. Dimethyl-formamide) and then injects them into the solution of toluene. The solvent is highly supersaturated and a large number of crystals precipitate from the solution. However, this method still needs OA (or OAm) as a surface ligand for the passivation of surface defects and to improve the stability of the QDs material. Since the entire experimental process is performed at room temperature the preparation process is very straightforward and inexpensive. However, the uniformity of QDs obtained in this way is not very appealing [9].
Schmide et al., [10] coined the term LARP (Ligand-Assisted Reprecipitation) to describe the process of preparing MAPbX3 perovskite QDs using a facile colloid strategy. They used ligands with medium-sized chains to stabilize the colloid phase. Li et al., [11], also used ligand assistance to prepare inorganic perovskites (PPs) at room temperature. Yang et al., [12], used a different approach. First, they dissolved CsBr into deionized water. Then, they dissolved PbBr2 into DMF. Finally, they mixed Oleic acid and N-Oxylamine in 10 ml hexane. In a normal process, they made the 'oil phase' by mixing oleic acid with n-octylamine in 10 mL hexane. Then, the oil phase was dropwise precipitated with a solution of CsBr • H2O + PbBr2 • DMF. The oil phase gradually changed from a clear to a pale white color, and an emulsion was formed. Acetone was then used to initiate the deemulsion process. The QDs were precipitated after centrifugation of the mixture. The mechanisms behind LARP vs. emulsion are similar, but the supersaturated environments differ. In LARP, the solvent is mixed in such a way that it changes the solubility of the solvent and nucleates the QDs. On the other hand, in emulsion methods, the solubility is changed by the microreactors resulting from solvent mixing.
Experimental part
The following reagents were used for the synthesis of perovskites: Lead (II) bromide (PbBr2 99.99%); Cesium bromide (CsBr 99.99%); methylammonium bromide (MABr); octylammonium bromide (OAmBr); dimethylformamide (DMF); dimethylsulfoxide (DMSO); oleylamine (C18H36NH2); oleic acid (C17H33COOH);
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toluene (as an antisolvent); chloroform. All reagents have been analytically graded and have not been subjected to any further purification.
The MAPbBr3 and CsPbBr3 perovskite formation process can be described as follows:
CsBr + PbBr2 ^ CsPbBr3 (in DMSO)
MABr + PbBr2 ^ MAPbBr3 (in DMF)
Synthesis of CsPbBrc. The following procedure was used to create perovskite material quantum dots: The salts CsBr and PbBr2 were measured in the proper mass at a 1:1 mol ratio. The solvent that was employed was dimethylsulfoxide (DMSO). For twelve hours, 0.1M solutions of CsBr and PbBr2 in DMSO were agitated at room temperature using a magnetic stirrer. These precursors were then combined in a single container with 1 ml. The CsBr + PbBr2 solution was supplemented with 0.1 ml of oleinamine (OAm) and 0.2 ml of oleic acid (OA) as ligands. There was no precipitation during the synthesis since the salts were all dissolved in the solvents. Using a magnetic stirrer, 0.1 ml of the produced perovskite (CsPbBn) solution was combined with 6 ml of toluene solution. A brilliant green CsPbBn perovskite quantum dot (0.000416M) was the end product. The LARP approach was used to conduct this experiment.
Synthesis of MAPbBrc. Using an analytical balance with a 1:1 mol ratio, the appropriate mass of MABr and PbBr2 salts were measured. As a solvent, 5 milliliters of dimethylformamide (DMF) were utilized. To get the salts to dissolve completely, it was heated and agitated for a long period. The resultant 0.02M MABr + PbBr2 solution was added to with 0.1 ml of oleinamine (OAm), 0.2 ml of oleic acid (OA), and 0.0001 g of octylammonium bromide (C8H20BrN) as a ligand. Using a magnetic stirrer, 0.1 ml of the resultant ligand solution was combined with 10 ml of chloroform (an antisolvent). Consequently, a vivid blue (10-6 M) MAPbBr3 perovskite quantum dot was seen to form. The previously stated LARP approach was also used to complete this synthesis.
The perovskite quantum dot samples that are produced by both techniques had their spectra examined and utilized in further experiments.
Results and discussion
A spectrophotometer (UV-2600i, Shimadzu, Japan) and a spectrofluorimeter (RF-6000, Shimadzu, Japan) were used to measure the spectra of the solutions of brilliant perovskite (CsPbBr3) and (MAPbBr3) quantum dots.
Fig. 2 shows that the fabricated CsPbBr3 perovskite has an absorption maximum of around 518 nm. In other words, spectrum research revealed that this quantum dot has a spectrum in the green region.
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0,0 И-■-1-■-1-■-1
450 500 550 600
Wavelength (nm)
Figure 2. Fluorescence emission spectrum of CsPbBr3 perovskite quantum dots
The synthesis of МЛРЪБгз perovskite involves the inclusion of octylammonium bromide (Cs^oBrN) as a ligand, together with oleic acid and oleic amine. Toluene and chloroform are used as antisolvents, and this allows us to identify the spectrum of the solution of this perovskite quantum dot in the bright blue region (Fig. 3).
The emission spectra of the yielded МЛРЬБгз perovskite quantum dots with various antisolvents can be viewed in Figure 3. The peak absorption of МЛРЬБгз perovskite may be observed at 457 nm in the case of chloroform antisolvent and 453 nm in the case of toluene antisolvent. Therefore, it is evident that the vibrant blue part of the perovskite quantum dot solution's spectrum is created when octylammonium bromide is added as a
ligand during the production process at ambient temperature. Spectral analysis was used to determine these observations.
In the MAPbBr3 synthesis, perovskite quantum dots with an apparent green emission were formed when oleic acid and oleic amine were utilized as ligands. Nevertheless, the hue turned blue when ligands such as oleic acid, oleic amine, and octylammonium bromide were added. Furthermore, it was discovered that the formation of quantum dots is impacted by the antisolvents used, which vary in composition. The spectrum of quantum dots produced by various antisolvent combinations is displayed in Figure 3.
Figure 3. Fluorescence emission spectra of MAPbBr3 perovskite quantum dots in toluene and chloroform
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Figure 4. MAPbBr3 perovskite quantum dot (antisolvent - chloroform).
When chloroform is used as an antisolvent, as can be observed in Fig. 4 above, intense blue perovskite quantum dots are formed. Using toluene as an antisolvent causes the creation of brilliant blue perovskite quantum dots, as seen in Fig. 5. The LARP technique was used to create both perovskites at room temperature.
Figure 5. MAPbBr3 perovskite quantum dot (antisolvent - toluene).
At routine temperatures, fluorescent blue MAPbBr3 and bright green CsPbBr3 perovskite quantum dots were produced. Following spectroscopic analysis, the produced perovskite compounds showed evidence of a formation of blue and green quantum dots. The occurrence of the absorption maximum of perovskite quantum dots in the bright blue region was observed to be caused by the use of octylammonium bromide as a ligand during the production of MAPbBr3, in addition to oleic acid and oleic amine.
Conclusions
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