Highly Sensitive Terahertz Thin-Film Total Internal Reflection Spectroscopy Reveals in Situ Photoinduced Structural Changes in Methylammonium Lead Halide Perovskites

• Published in: Journal of physical chemistry. C 2018-08, Vol.122 (30), p.17552-17558
• Main Authors: Sun, Qiushuo, Liu, Xudong, Cao, Jie, Stantchev, Rayko I, Zhou, Yang, Chen, Xuequan, Parrott, Edward P. J, Lloyd-Hughes, James, Zhao, Ni, Pickwell-MacPherson, Emma
• Format: Article
• Language: English
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/acs.jpcc.8b05695

Terahertz (THz) thin-film total internal reflection (TF-TIR) spectroscopy is shown to have an enhanced sensitivity to the vibrational properties of thin films in comparison with standard THz transmission spectroscopy. This increased sensitivity was used to track photoinduced modifications to the structure of thin films of methylammonium (MA) lead halide, MAPbI3–x Br x (x = 0, 0.5, 1, and 3). Initially, illumination strengthened the phonon modes around 2 THz, associated with Pb–I stretch modes coupled to the MA ions, whereas the 1 THz twist modes of the inorganic octahedra did not alter in strength. Under longer term illumination, the 1 THz phonon modes of encapsulated films slowly reduced in strength, whereas in films exposed to moisture and oxygen, these phonons weaken more rapidly and blue-shift in frequency. The rapid monitoring of environmentally induced changes to the vibrational modes afforded by TF-TIR spectroscopy offers applications in the characterization and quality control of the perovskite thin-film solar cells and other thin-film semiconductors.