Aloke Verma1* and Swapnil Jain2

1Department of Physics, Kalinga University, Naya Raipur (CG) India.

2Department of Mechanical Engineering, Kalinga University, Naya Raipur (CG) India.

Corresponding Author E-mail: alokeverma1785@gmail.com

Article Publishing History
Article Received on : 30 Apr 2024
Article Accepted on : 04 Aug 2024
Article Published : 14 Aug 2024

ABSTRACT:

This study examines the structural, optical, and morphological characteristics of Methylammonium lead halide perovskites (MAPbX3) as potential solar cell candidates. Variable band gaps, extended carrier lifetimes, high absorption coefficients, and solution-processable synthesis techniques are among the numerous advantages of these perovskites. The Hot-Injection Method (HIM) is employed in the study to further investigate the unique properties of MAPbX3 perovskites, which is cost-effective and does not require vacuum. MAPbBr3 and MAPbCl3 crystallize in a cubic phase, whereas MAPbI3 crystallizes in a tetragonal phase. The halide versions exhibit morphological differences, with MAPbCl3 exhibiting cubic nanocrystals, MAPbI3 forming a combination of rods and spherical nanocrystals, and MAPbBr3 exhibiting particulate structures. TRPL experiments indicate carrier lifetimes between 1.72 and 7.65 ns, while UV-Vis spectroscopy indicates a blue shift in absorption band edges from MAPbI3 to MAPbCl3. MAPbI3, the most promising candidate for solar cell applications, produces a PCE of 13.66% at a thickness of 250 nm, in contrast to MAPbBr3 and MAPbCl3, which produce 6.87% and 4.98% at a thickness of 500 nm, respectively. This research establishes a thorough comprehension of the structural, optical, and morphological properties of MAPbX3 perovskites, thereby facilitating the advancement of perovskite solar cell technology and the creation of more cost-effective solar energy solutions.

KEYWORDS:

Hot-Injection Method; Methylammonium; MAPbX3; Perovskites Solar Cells; Photovoltaic

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Verma A, Jain S. Advances in Methylammonium Lead Halide Perovskites Synthesis, Structural, Optical, and Photovoltaic Insights. Orient J Chem 2024;40(4).

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Verma A, Jain S. Advances in Methylammonium Lead Halide Perovskites Synthesis, Structural, Optical, and Photovoltaic Insights. Orient J Chem 2024;40(4). Available from: https://bit.ly/4dlRjth

Introduction

Methylammonium lead halide perovskites, namely MAPbX3 (X = Cl, Br, I), have demonstrated potential as hybrid organic-inorganic perovskites in solar cell technology 1. Perovskites provide appealing features such as extended carrier lifetimes, adjustable band gaps, strong absorption coefficients, and convenient synthesis processes that can be carried out using solutions. The optoelectronic characteristics of solar cells have led to a substantial increase in their power conversion efficiency (PCE), hence improving their competitiveness compared to traditional silicon-based cells. The perovskites MAPbX3 have an ABX3 crystal structure, where X represents a halogen ion (Cl, Br, or I), B represents a smaller divalent cation (often lead), and A represents a larger monovalent cation (such as methylammonium, MA+). By altering the composition of the A, B, or X sites, the flexibility of this structure allows for the adjustment of several properties, including the band gap, absorption characteristics, and lattice parameters3. The Hot-Injection Method (HIM) synthesis of MAPbX3 allows for the cost-effective and non-vacuum-based production of perovskites with distinct structural, morphological, and optical properties. This study aims to investigate the correlation between the structural characteristics of solar cells and their photovoltaic efficiency. It utilizes experimental research and device simulations to examine these attributes and their impact on the performance of solar cells. This study aims to provide a comprehensive understanding of the potential of MAPbX3 perovskites for solar cell applications by utilizing photovoltaic simulations to evaluate their structural, optical, and morphological features4. The outcomes have the potential to guide future advancements in perovskite solar cell technology, hence promoting the development of more cost-effective and efficient solar energy alternatives5.

Experimental Methods

Methylammonium lead halide perovskites (MAPbX3; X = Cl, Br, I) are synthesised using a number of important precursors to produce each variation. Lead salts, with 99.99% trace metals foundation, include lead(II) bromide (PbBr2), lead(II) iodide (PbI2), and lead(II) chloride (PbCl2). The organic component is further made up of methylammonium halides, which include methylammonium iodide (MAI), methylammonium bromide (MABr), and methylammonium chloride (MACl), all of which are more than 99% pure. Important components of the solution chemistry, the solvents octadecene (ODE), oleyl-amine (OLA), and oleic acid (OA) stabilize the perovskites throughout production. Other compounds are also used especially in the manufacture of MAPbI3, including tri-octyl phosphine (TOP). Consistency and purity in the produced perovskites are ensured by the usage of all chemicals, which are obtained from Sigma Aldrich and utilized directly 6.

The actual synthesis method is based on the controlled Hot-Injection Method (HIM). In a three-neck round-bottom flask (RBF), 1 mM of MAI is dissolved in 3 mL of OA and well swirled. The solution is next rapidly injected with 0.5 mM PbI2 dissolved in TOP after being heated to 100°C in an argon atmosphere until clear. Following a ten-minute period at 195°C, the solution is chilled, centrifuged, and toluene-washed to produce MAPbI3. With 1 mM of MABr dissolved in a mixture of OA and ODE and PbBr2 in the same mixture, the synthesis of MAPbBr3 proceeds similarly7. The remainder of the process is 200°C, same as with MAPbI3. The MAPbCl3 synthesis is repeated at 180°C, with 1 mM of MACl dissolved in the solution and PbCl2 in an ODE and OLA mixture8.

Results and Discussion

The structural, optical, and morphological characteristics of the MAPbX3 perovskites (X = Cl, Br, I) are evaluated through a thorough characterization process following their synthesis. Various techniques are employed to examine the properties of these perovskites9. X-ray diffraction (XRD) technique analyzes the crystalline structure, revealing information about each perovskite’s phase, size, and lattice planes 10.

The diffraction patterns show that MAPbBr3 and MAPbCl3 crystallize in a cubic phase, while MAPbI3 adopts a tetragonal phase 11. The crystallite sizes range from 25.77 to 38.75 nm, with lattice strains correlating with optical and photovoltaic properties. Field Emission Scanning Electron Microscopy (FE-SEM) imaging method provides insights into the surface morphology of each perovskite 12. It captures particle shapes and distributions, revealing morphological variations between halide variants 13.

For instance, MAPbI3 forms a mixture of rods and spherical nanocrystals, while MAPbCl3 shows cubic nanocrystals, with particle sizes ranging from 31.1 to 44.5 nm, in close agreement with the crystallite sizes calculated from XRD 14. Transmission Electron Microscopy (TEM) technique provides high-resolution images of the perovskite particles, enabling a nanoscale analysis of their size and distribution. The particle size distribution can be computed from these images 15.

UV-Vis Spectroscopy This technique observes the absorption spectra of the perovskites, revealing band gaps and absorption coefficients 16. The band gaps range from 1.56 to 3 eV, showing a blue shift in the absorption band edge from MAPbI3 to MAPbCl3. Photoluminescence (PL) investigations provide the emission spectra of the perovskites, showing broad peaks in the 400–800 nm range, with blue shift emission from I through Br to Cl. Time-Resolved PL (TRPL) studies show carrier lifetimes of 1.72 ns (MAPbI3), 1.87 ns (MAPbBr3), and 7.65 ns (MAPbCl3), indicating MAPbCl3 has the longest charge separation.SCAPS-1D simulations show that MAPbI3 yields a PCE of 13.66% at 250 nm thickness, while MAPbBr3 and MAPbCl3 yield 6.87% and 4.98% at 500 nm thickness, respectively 17. The combination of band gap, carrier lifetimes, and photovoltaic efficiency positions MAPbI3 as the most promising candidate for solar cells. Analysis and refinement of X-ray diffraction data (Analytical Technologies, India) using NetworkX Python library.

Figure 4: SCAPS – 1D Simulated PCE of Perovskite Materials (MAPbX3, X = Cl, I and Br) at different thicknesses.

Click here to View Figure

Conclusion

This study examines the potential application of methylaminium lead halide perovskites (MAPbX3) in solar cell technology. The perovskites form distinct phases, with MAPbI3 adopting a tetragonal morphology, while MAPbBr3 and MAPbCl3 have a cubic structure. The lattice strains are directly related to the optical and photovoltaic properties. The diameters of the crystallites vary between 25.77 and 38.75 nm. Halide variants reveal distinct morphological variations; MAPbI3 takes the shape of elongated rods and spherical nanocrystals, MAPbCl3 showcases cubic nanocrystals, and MAPbBr3 demonstrates granular structures. The UV-Vis spectroscopy revealed a blue shift in the absorption band boundaries when transitioning from MAPbI3 to MAPbCl3. The TRPL studies revealed carrier durations ranging from 1.72 to 7.65 ns, indicating that MAPbCl3 has the most extended charge separation. MAPbBr3 and MAPbCl3 exhibited photovoltaic performance of 6.87% and 4.98%, respectively, when their thickness was 250 nm. The study highlights the need of employing non-vacuum synthesis techniques, specifically the Hot-Injection Method (HIM), for cost-effective manufacturing of perovskites.

Acknowledgments

We acknowledge the support of Department of Physics and CIF Lab, Kalinga University, Naya Raipur (CG) India.

Conflict of Interest

The authors conducted ethical and transparent research, demonstrating the importance of ethical practices in scientific research.

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