Real-time Visualization of Photo-brightening in Lead Halide Perovskites using Confocal Laser Scanning Microscopy
Jigar Halpati a
a Indian Institute of Technology Madras, Sardar Patel Road, Adyar, Chennai, India
Materials for Sustainable Development Conference (MATSUS)
Proceedings of MATSUS23 & Sustainable Technology Forum València (STECH23) (MATSUS23)
#PerFut - Metal Halide Perovskites Fundamental Approaches and Technological Challenges
VALÈNCIA, Spain, 2023 March 6th - 10th
Organizers: Wang Feng, Giulia Grancini and Pablo P. Boix
Poster, Jigar Halpati, 289
Publication date: 22nd December 2022

One of the key issues with halide perovskites is the light induced structural changes and its associated instability which affects its optoelectronic properties. To understand and unravel the role of light on the properties of these materials, we systematically investigated the effect of light as a function of wavelength, time and intensity of illumination. Also, all these earlier mentioned light effects are carried out on various chemical compositions (varying A-site and X-site) and the effect on bulk/surface of perovskites is visualized with respect to the real-time changes using confocal laser scanning microscopy. The technique to study the light induced variations is inspired from bio imaging method – Fluorescence Recovery After Photobleaching (FRAP). A modified version of FRAP is applied to perovskites in-order to understand the variations due to light. This is one of the first detailed real-time microscopic investigations of halide perovskites that provides evidence for stability/instability via the observations on photoluminescence brightening and bleaching. In this work, the APbX3(A= CH3NH3+, (NH2)CH(NH2)+, Cs+; X = Br-, I- or their mix)  was subjected to variety of light conditions ( excitation wavelength, time of illumination, intensity of illumination) and their photoluminescence changes were imaged via confocal microscope and correlated with PL spectra. The study was separately conducted in these materials at three different illuminations wavelengths (488 nm, 561 nm & 633 nm) until PL saturates. Different wavelength of light induces different changes to the perovskite materials with green photons enhancing the photoluminescence more than blue or red photons, which is termed as photobrightening (PLB). The PLB saturates after certain illumination time, and intense photon illumination, tend to degrade the material. With careful confocal imaging, we could clearly identify that most of the changes that are happening reside on the surface/grain boundary and less to do with bulk. The similar enhancement in PL spectrums at various wavelengths are observed in the steady state PL. One other interesting aspect is that all these changes are very much specific to CH3NH3PbI3 and the introduction of formamidinium or cesium cations in the A site or the presence of mixed halide or bromide in the B site suppresses the photobrightening or bleaching. The structural properties under various testing conditions were investigated using quasi in-situ FT-far-IR studies. The relaxation of organic A site cation is found to be responsible for the observed changes in PL. In addition, the conductivity measured in dark conditions before and after shining lights showed an enhancement in conductivity by electrochemical impedance spectroscopy. The J-V measurements also displayed that the Jsc and Voc of the film are enhanced due to photoshining at specific wavelength. However, at high laser intensity, quenching of PL and photobleaching was observed due to the degradation of material with respect to laser intensity. Hence, the light induced photobrightening and photobleaching phenomena plays a key role and it is significant to understand its photo-physical effect on the optoelectronic and photovoltaic device performances of the material.

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