International Journal of Nanoscience and Nanotechnology

International Journal of Nanoscience and Nanotechnology

Solvothermal Synthesis and Characterization of CsPbI3, CsSnI3 and CsPb1-xSnxI3 Perovskite Nanocrystals

Document Type : Research Paper

Authors
Hari Ganesha Y 1
Ramaraja Varma V 2
Gopalakrishna Naik K 1
1 Department of Studies in Physics, Mangalore University, Mangalagangothri – 574 199, India
2 Microtron Centre, Department of Studies in Physics, Mangalore University, Mangalagangothri – 574 199, India
10.22034/ijnn.2026.2068417.2695
Abstract
The solvothermal method synthesized CsPbI3, CsSnI3, and CsPb1-xSnxI3 perovskite nanoparticles. The powder X-ray diffraction (XRD) patterns of the synthesized CsPbI3 and CsSnI3 were found to be -CsPbI3 and black -CsSnI3 perovskite phases, respectively. The nanoparticles synthesized from equal molar masses of Pb and Sn indicate the formation of -CsPbI3, black -CsPbI3, and black -CsSnI3 perovskite phases instead of the formation of the intended quaternary CsPb0.5Sn0.5I3 solid solution. The field emission scanning electron microscopy (FESEM) images show the formation of nanorods for CsPbI3, nanorods and nanoplatelets for CsSnI3, and nanorods/nanowires and nanoplatelets for the intended CsPb0.5Sn0.5I3 nanostructures. The Fourier transform infrared (FTIR) spectra of the synthesized samples show the presence of the oleic acid surfactant in the synthesized nanostructures. The estimated band gaps of the synthesized -CsPbI3 and B--CsSnI3 nanostructures from the UV-visible optical absorption measurements were found to be slightly higher than the reported bulk band gap values of these materials, which may be due to the quantum confinement effect. The exciton-related absorptions were observed both in -CsPbI3 and B--CsSnI3 nanostructures. The band gaps of both -CsPbI3 and B--CsSnI3 nanostructures were found to show a blue shift with aging of the nanostructures, which may be due to the predominance of the band-to-band absorption over the excitonic absorption with aging of the nanostructures. The synthesized nanostructures appear to exhibit long-term structural stability, as confirmed by the observation of stable XRD patterns and UV-visible optical absorption spectra of the synthesized samples, which were maintained for four to six months after synthesis
Keywords
Perovskite
Solvothermal
CsPbI3
CsSnI3
Subjects
1. Dey A, Ye J, De A, Debroye E, Ha SK, Bladt E, et al. State of the Art and Prospects for Halide Perovskite Nanocrystals. ACS Nano. 2021;15(7):10775-10981. https://doi.org/10.1021/acsnano.0c08903
2. Hoefler SF, Trimmel G, Rath T. Progress on lead-free metal halide perovskites for photovoltaic applications: a review. Monatsh Chem. 2017;148(5):795-826. https://doi.org/10.1007/s00706017-1933-9 
3. Chen LJ. Synthesis and optical properties of lead-free cesium germanium halide perovskite quantum rods. RSC Adv. 2018;8(33):18396-18399. https://doi.org/10.1039/C8RA01150H
4. Kojima A, Teshima K, Shirai Y, Miyasaka T. Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells. J Am Chem Soc. 2009;131(17):6050-6051. https://doi.org/10.1021/ja809598r 
5. Kim HS, Lee CR, Im JH, Lee KB, Moehl T, Marchioro A, et al. Lead iodide perovskite sensitized all-solid-state submicron thin film mesoscopic solar cell with efficiency exceeding 9%. Sci Rep. 2012;2:591. https://doi.org/10.1038/srep00591
6. Wang R, Huang T, Xue J, Tong J, Zhu K, Yang Y. Prospects for metal halide perovskite-based tandem solar cells. Nat Photonics. 2021;15(6):411-425. https://doi.org/10.1038/s41566-02100809-8
7. Tipparak P, Passatorntaschakorn W, Khampa W, Musikpan W, Usulor CE, Bhoomanee C, et al. The Impact of MAPbI3 Quantum Dots on CsFA Perovskite Solar Cells: Interface and Hole Extraction Improvement. ACS Appl Energy Mater. 2025;8(1):355-365. https://doi.org/10.1021/acsaem.4c02474
8. Zhang Q, Yin Y. All-Inorganic Metal Halide Perovskite Nanocrystals: Opportunities and Challenges. ACS Cent Sci. 2018;4(6):668-679. 
https://doi.org/10.1021/acscentsci.8b00201
9. Protesescu L, Yakunin S, Bodnarchuk MI, Krieg F, Caputo R, Hendon CH, et al. Nanocrystals of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut. Nano Lett. 2015;15(6):3692-3696. https://doi.org/10.1021/nl5048779 
10. Chen M, Zou Y, Wu L, Pan Q, Yang D, Hu H, et al. Solvothermal Synthesis of High-Quality All-Inorganic Cesium Lead Halide Perovskite Nanocrystals: From Nanocube to Ultrathin Nanowire. Adv Funct Mater. 2017;27(23):1701121. https://doi.org/10.1002/adfm.201701121
11. Xiang W, Tress W. Review on Recent Progress of AllInorganic Metal Halide Perovskites and SolarCells.AdvMater.2019;31(44):1902851.https://doi.org/10.1002/adma.201902851
12. Chen Z, Dong L, Tang H, Yu Y, Ye L, Zang J. Direct synthesis of cubic phase CsPbI3 nanowires. CrystEngComm. 2019;21(9):13891396. https://doi.org/10.1039/C8CE02111B
13. Wang B, Novendra N, Navrotsky A. Energetics, Structures, and Phase Transitions of Cubic and Orthorhombic Cesium Lead Iodide (CsPbI3) Polymorphs. J Am Chem Soc. 2019;141(37):1450114504. https://doi.org/10.1021/jacs.9b05924
14. Idrissi S, Labrim H, Bahmad L, Benyoussef A. DFT and TDDFT studies of the new inorganic perovskite CsPbI3 for solar cell applications. Chem Phys Lett. 2021;766:138347. https://doi.org/10.1016/j.cplett.2021.138347 
15. Ke F, Wang C, Jia C, Wolf NR, Yan J, Niu S, et al. Preserving a robust CsPbI3 perovskite phase via pressure-directed octahedral tilt. Nat Commun. 2021;12:461. https://doi.org/10.1038/s41467020-20745-5 
16. Ke W, Kanatzidis MG. Prospects for low-toxicity lead-free perovskite solar cells. Nat Commun. 2019;10:965. https://doi.org/10.1038/s41467-019-08918-3
17. Ustinova MI, Mikheeva MM, Shilov GV, Dremova NN, Frolova L, Stevenson KJ, et al. Partial Substitution of Pb2+ in CsPbI3 as an Efficient Strategy to Design Fairly Stable All-Inorganic Perovskite Formulations. ACS Appl Mater Interfaces. 2021;13(4):51845194. https://doi.org/10.1021/acsami.0c18061
18. Li B, Zhang Y, Fu L, Yu T, Zhou S, Zhang L, et al. Surface passivation engineering strategy to fully-inorganic cubic CsPbI3 perovskites for high-performance solar cells. Nat Commun. 2018;9:1076. https://doi.org/10.1038/s41467-018-03169-0
19. Min X, Xie Q, Wang X, Chen M. Enhancing the stability of cesium lead iodide perovskite nanocrystals: Recent progress, challenges and opportunities. Surfaces Interfaces. 2021;22:100870. https://doi.org/10.1016/j.surfin.2020.100870
20. Li D, Chen CS, Wu YH, Zhu ZG, Shih WY, Shih WH. Improving Stability of Cesium Lead Iodide Perovskite Nanocrystals by Solution Surface Treatments. ACS Omega. 2020;5(29):1801318020. https://doi.org/10.1021/acsomega.0c01403
21. Swarnkar A, Marshall AR, Sanehira EM, Chernomordik BD, Moore DT, Christians JA, et al. Quantum dot-induced phase stabilization of α-CsPbI3 perovskite for high-efficiency photovoltaics. Science. 2016;354(6308):92-95. https://doi.org/10.1126/science.aag2700 
22. Zhao Q, Hazarika A, Schelhas LT, Liu J, Gaulding EA, Li G, et al. Size-Dependent Lattice Structure and Confinement Properties in CsPbI3 Perovskite Nanocrystals: Negative Surface Energy for Stabilization. ACS Energy Lett. 2020;5(1):238-247. https://doi.org/10.1021/acsenergylett.9b02395 
23. Le HKD, Lin CK, Jin J, Zhang Y, Lin Z, Vailionis A, et al. Quantification of strain and its impact on the phase stabilization of all-inorganic cesium lead iodide perovskites. Matter. 2023;6(7):2368-2382. https://doi.org/10.1016/j.matt.2023.05.027
24. Zhang J, Yin C, Yang F, Yao Y, Yuan F, Chen H, et al. Highly Luminescent and Stable CsPbI3 Perovskite Nanocrystals with Sodium Dodecyl Sulfate Ligand Passivation for Red-LightEmitting Diodes. J Phys Chem Lett. 2021;12(9):2437-2443. https://doi.org/10.1021/acs.jpclett.1c00008
25. Chen LC, Chang YT, Tien CH, Yeh YC, Tseng ZL, Lee KL, et al. Red Light-Emitting Diodes with All-Inorganic CsPbI3/TOPO Composite Nanowires Color Conversion Films. Nanoscale Res Lett. 2020;15:157. https://doi.org/10.1186/s11671-02003430-w 
26. Chen D, Huang D, Yang M, Xu K, Hu J, Liang S, et al. Precursor chemistry towards highly efficient and phase-stable red emitting CsPbI3 perovskite nanocrystals. Nano Res. 2022;15(1):644-652. https://doi.org/10.1007/s12274-021-3538-1
27. Wen Z, Zhai W, Liu C, Lin J, Yu C, Huang Y, et al. Controllable synthesis of CsPbI3 nanorods with tunable photoluminescence emission. RSC Adv. 2019;9(43):24928-24934. https://doi.org/10.1039/C9RA04600C 
28. Chung I, Song JH, Im J, Androulakis J, Malliakas CD, Li H, et al. CsSnI3: Semiconductor or metal? High electrical conductivity and strong near-infrared photoluminescence from a single material. J Am Chem Soc. 2012;134(20):8579-8587. https://doi.org/10.1021/ja301539s 
29. Da Silva EL, Skelton JM, Parker SC, Walsh A. Phase stability and transformations in the halide perovskite CsSnI3. Phys Rev B. 2015;91(14):144107. https://doi.org/10.1103/PhysRevB.91.144107
30. Monacelli L, Marzari N. First-Principles Thermodynamics of CsSnI3. Chem Mater. 2023;35(4):1702-1709. https://doi.org/10.1021/acs.chemmater.2c03475
31. Ali MS, Das S, Abed YF, Basith MA. Lead-free CsSnCl3 perovskite nanocrystals: Rapid synthesis, experimental characterization and DFT simulations. Phys Chem Chem Phys. 2021;23(39):2218422198. https://doi.org/10.1039/D1CP02666F
32. Adib MA, Sharmin F, Basith MA. Tuning the morphology, stability and optical properties of CsSnBr3 nanocrystals through bismuth doping for visible-light-driven applications. Nanoscale Adv. 2023;5(22):6194-6209. https://doi.org/10.1039/D3NA00309D
33. Yasmeen F, Tarek M, Basith MA. Moisture-Stable CsSnBr2Cl Halide Perovskite: Electrochemical Insights in Aqueous Environments. ACS Appl Mater Interfaces. 2024;16(35):4753547550. https://doi.org/10.1021/acsami.4c08313
34. Lin S, Zhang B, Lü TY, Zheng JC, Pan H, Chen H, et al. Inorganic Lead-Free B-γ-CsSnI3 Perovskite Solar Cells Using Diverse Electron-Transporting Materials: A Simulation Study. ACS Omega. 2021;6(41):26689-26698. https://doi.org/10.1021/acsomega.1c04096
35. Zhang M, Chen K, Wei Y, Hu W, Cai Z, Zhu J, et al. Strategies for Optimizing the Morphology of CsSnI3 Perovskite Solar Cells. Crystals (Basel). 2023;13(3):410. https://doi.org/10.3390/cryst13030410 
36. Ye T, Wang K, Hou Y, Yang D, Smith N, Magill B, et al. AmbientAir-Stable Lead-Free CsSnI3 Solar Cells with Greater than 7.5% Efficiency. J Am Chem Soc. 2021;143(11):4319-4328. https://doi.org/10.1021/jacs.0c13069 
37. Yao H, Zhou F, Li Z, Ci Z, Ding L, Jin Z. Strategies for Improving the Stability of Tin-Based Perovskite (ASnX3) Solar Cells. Adv Sci. 2020;7(10):1903540. https://doi.org/10.1002/advs.201903540
38. Cao F, Tian W, Wang M, Wang M, Li L. Stability enhancement of lead-free CsSnI3 perovskite photodetector with reductive ascorbic acid additive. InfoMat. 2020;2(3):577-584. https://doi.org/10.1002/inf2.12074 
39. Benaicha I, Amraoui S, Mhalla J, Ait-Alla Y, Diyagh H, Simassa M, et al. Enhanced structural stability and optoelectronic properties of lead-free α-phase CsSnI3 perovskite via Zn and Cu doping. Results Eng. 2025;27:106845. https://doi.org/10.1016/j.rineng.2025.106845 
40. Dilshod N, Anushervon A, Amondulloi B, Iskandar R, Kholmurodov K. Preparation of Air Stable Lead-free CsSnI3 Perovskites: Synthesis Based on CsI and SnCl2 Solutions. J Mod Nanotechnol. 2024;4:7. https://doi.org/10.53964/jmn.2024007 
41. Waleed A, Tavakoli MM, Gu L, Hussain S, Zhang D, Poddar S, et al. All inorganic cesium lead iodide perovskite nanowires with stabilized cubic phase at room temperature and nanowire array-based photodetectors. Nano Lett. 2017;17(8):4951-4957. https://doi.org/10.1021/acs.nanolett.7b02101
42. Shen Q, Ripolles TS, Even J, Ogomi Y, Nishinaka K, Izuishi T, et al. Slow hot carrier cooling in cesium lead iodide perovskites. Appl Phys Lett. 2017;111(15):153903. https://doi.org/10.1063/1.4991993 
43. Liu F, Zhang Y, Ding C, Kobayashi S, Izuishi T, Nakazawa N, et al. Highly Luminescent Phase-Stable CsPbI3 Perovskite Quantum Dots Achieving Near 100% Absolute Photoluminescence Quantum Yield. ACS Nano. 2017;11(10):10373-10383. https://doi.org/10.1021/acsnano.7b05442 
44. Farzaneh A, Abdi MR, Saraee KRE, Mostajabaldaavati M, Quaranta A. The preparation of cesium-iodide thin films via solgel method for the detection of ionizing radiation. J Solgel Sci Technol. 2016;78(2):313-321. https://doi.org/10.1007/s10971016-3959-6 
45. Burschka J, Pellet N, Moon SJ, Humphry-Baker R, Gao P, Nazeeruddin MK, et al. Sequential deposition as a route to high-performance perovskite-sensitized solar cells. Nature. 2013;499(7458):316-319. https://doi.org/10.1038/nature12340
46. Pradhan N. Growth of Lead Halide Perovskite Nanocrystals: Still in Mystery. ACS Phys Chem Au. 2022;2(4):268-276. https://doi.org/10.1021/acsphyschemau.2c00001 
47. Dutta A, Dutta SK, Das Adhikari S, Pradhan N. Phase-Stable CsPbI3 Nanocrystals: The Reaction Temperature Matters. Angew Chem Int Ed Engl. 2018;57(29):9083-9087. https://doi.org/10.1002/anie.201803701 
48. Stelmakh A, Aebli M, Baumketner A, Kovalenko MV. On the Mechanism of Alkylammonium Ligands Binding to the Surface of CsPbBr3 Nanocrystals. Chem Mater. 2021;33(15):5962-5973. https://doi.org/10.1021/acs.chemmater.1c01081
49. Zhou Y, Garces HF, Senturk BS, Ortiz AL, Padture NP. Room temperature “one-pot” solution synthesis of nanoscale CsSnI3 orthorhombic perovskite thin films and particles. Mater Lett. 2013;110:127-129. https://doi.org/10.1016/j.matlet.2013.08.011 
50. Mahesh KPO, Chang CY, Hong WL, Wen TH, Lo PH, Chiu HZ, et al. Lead-free cesium tin halide nanocrystals for light-emitting diodes and color down conversion. RSC Adv. 2020;10(60):3716137167. https://doi.org/10.1039/D0RA06139E
51. Jellicoe TC, Richter JM, Glass HFJ, Tabachnyk M, Brady R, Dutton SE, et al. Synthesis and Optical Properties of Lead-Free Cesium Tin Halide Perovskite Nanocrystals. J Am Chem Soc. 2016;138(9):2941-2944. https://doi.org/10.1021/jacs.5b13470
52. Chen LJ, Lee CR, Chuang YJ, Wu ZH, Chen C. Synthesis and Optical Properties of Lead-Free Cesium Tin Halide Perovskite Quantum Rods with High-Performance Solar Cell Application. J Phys Chem Lett. 2016;7(24):5028-5035. https://doi.org/10.1021/acs.jpclett.6b02344 
53. Triloki, Garg P, Rai R, Singh BK. Structural characterization of as-deposited cesium iodide films studied by X-ray diffraction and transmission electron microscopy techniques. Nucl Instrum Methods Phys Res A. 2014;736:128-134. https://doi.org/10.1016/j.nima.2013.10.075 
54. Sutton RJ, Filip MR, Haghighirad AA, Sakai N, Wenger B, Giustino F, et al. Cubic or Orthorhombic? Revealing the Crystal Structure of Metastable Black-Phase CsPbI3 by Theory and Experiment. ACS Energy Lett. 2018;3(8):1787-1794. https://doi.org/10.1021/acsenergylett.8b00672 
55. Dimesso L, Das C, Stöhr M, Jaegermann W. Investigation of cesium tin/lead iodide (CsSn1−xPbxI3) systems. Mater Res Bull. 2017;85:80-89. https://doi.org/10.1016/j.materresbull.2016.08.052
56. Zhang L, Zhou H, Chen Y, Zheng Z, Huang L, Wang C, et al. Spontaneous crystallization of strongly confined CsSnxPb1-xI3 perovskite colloidal quantum dots at room temperature. Nat Commun. 2024;15:905. https://doi.org/10.1038/s41467-02445945-1 
57. Bindu P, Thomas S. Estimation of lattice strain in ZnO nanoparticles: X-ray peak profile analysis. J Theor Appl Phys. 2014;8(4):123-134. https://doi.org/10.1007/s40094-014-01419 
58. Dawson M, Ribeiro C, Morelli MR. A Review of Three Dimensional Tin Halide Perovskites as Solar Cell Materials. Mater Res. 2022;25:e20210441. https://doi.org/10.1590/19805373-mr-2021-0441
59. Perez De Berti IO, Cagnoli MV, Pecchi G, Alessandrini JL, Stewart SJ, Bengoa JF, et al. Alternative low-cost approach to the synthesis of magnetic iron oxide nanoparticles by thermal decomposition of organic precursors. Nanotechnology. 2013;24(17):175601. https://doi.org/10.1088/0957-4484/24/17/175601
60. Zhao Y, Yao Z, Snow CD, Xu Y, Wang Y, Xiu D, et al. Stable fluorescence of Eu3+ complex nanostructures beneath a protein skin for potential biometric recognition. Nanomaterials (Basel). 2021;11(9):2462. https://doi.org/10.3390/nano11092462
61. Ibarra J, Melendres J, Almada M, Burboa MG, Taboada P, Juárez J, et al. Synthesis and characterization of magnetite/PLGA/chitosan nanoparticles. Mater Res Express. 2015;2(9):095010. https://doi.org/10.1088/2053-1591/2/9/095010
62. Liascukiene I, Aissaoui N, Asadauskas SJ, Landoulsi J, Lambert JF. Ordered nanostructures on a hydroxylated aluminum surface through the self-assembly of fatty acids. Langmuir. 2012;28(11):5116-5124. https://doi.org/10.1021/la2051542
63. Li G, Rivarola FWR, Davis NJLK, Bai S, Jellicoe TC, De La Peña F, et al. Highly Efficient Perovskite Nanocrystal Light-Emitting Diodes Enabled by a Universal Crosslinking Method. Adv Mater. 2016;28(18):3528-3534. https://doi.org/10.1002/adma.201600064
64. Böer KW, Pohl UW. Excitons. In: Semiconductor Physics. Springer; 2023. https://doi.org/10.1007/978-3-031-18286-0
65. Zhai W, Lin J, Li Q, Zheng K, Huang Y, Yao Y, et al. Solvothermal Synthesis of Ultrathin Cesium Lead Halide Perovskite Nanoplatelets with Tunable Lateral Sizes and Their Reversible Transformation into Cs4PbBr6 Nanocrystals. Chem Mater. 2018;30(11):3714-3721. https://doi.org/10.1021/acs.chemmater.8b00612 
66. Haryński Ł, Olejnik A, Grochowska K, Siuzdak K. A facile method for Tauc exponent and corresponding electronic transitions determination in semiconductors directly from UVVis spectroscopy data. Opt Mater (Amst). 2022;127:112205. https://doi.org/10.1016/j.optmat.2022.112205 
International Journal of Nanoscience and Nanotechnology
Volume 21, Issue 3
Summer 2025
Pages 137-148