In Situ Growth and Degradation Mechanisms in Hybrid Lead Halide Perovskite/Graphene Solar Cells
Authors: Acik Muge , Darling Seth B. 
Published: February 2020

High power conversion efficiency of perovskite-based solar cells offers promise for low-cost and scalable production of renewable energy. The need to harness solar energy has recently motivated the search to alternate ETL/HTL hybrid materials, specifically graphene/perovskite films. Hybrid organic-inorganic methylammonium lead halides, MAPbX3 (X=I, Br, Cl)/mixed-halides (I3-xClx, I3-xBrx) have been reported as light harvesting layers with their superior optoelectronic properties: tunable bandgap, long electron-hole diffusion lengths and high electron/hole mobility. Nevertheless, halide-based perovskites require in situ investigation for film growth, degradation and perovskite formation mechanisms to overcome detrimental effects of incomplete lead precursor conversion, inconsistent crystallite formation/film uniformity, and weak cation-anion-solvent coordination. Graphene-derived hybrids have recently emerged as an ETL/HTL replacement in these devices, however understanding the origin of interfacial chemical reactions between deposited perovskite films over graphene-derived materials is still lacking. Graphene/perovskite structure-property relationships are, however, not well understood due to unclear chemistry at the ETL/perovskite/HTL interfaces. Moreover, effect of film thickness, lead content, stoichiometry control, overlayer/underlayer morphology/composition, stability issues and cation-anion electrostatic interactions ought to be examined for better charge transport at the graphene/perovskite interfaces. Stability factors also need to be studied for charge mechanisms to unravel device performance challenges. Indeed, underlayer ETLs (TiO2/Al2O3) and overlayer HTLs (spiro-OMeTAD) were rarely studied with graphene. To address scalability and stability issues, we examined degradation, nucleation and growth mechanisms in reduced graphene/graphite oxide (RGO) upon halide-based (I, Cl, Br) perovskite deposition. Chemical interactions were interpreted at perovskite/RGO interfaces for the grain size, orientation, boundaries, and surface/bulk effects using variable-temperature (≤600°C, Ar(g)) in situ spectroscopy (infrared absorption, micro-Raman, UV-vis-NIR, luminescence). Controlled perovskite formation was achieved at room temperature for bromide/chloride-based perovskites resulting in improved chemical stability with heat (vs. iodide derivative). Overall, perovskite decomposition was observed at ~150°C. Oxygen-induced chemical reactions occurred at ≤150°C, eliminated hydroxyls/carboxyls in RGO, and maintained ethers/epoxides upon perovskite decomposition. Poor perovskite formation was observed on RGO due to varying electron affinity and reactivity of precursor halides, resulting in film degradation in air (O2, H2O). Film morphology was explored by characterization techniques such as SEM, XRD, XPS, TEM, and AFM.

Keywords: In situ spectroscopy, graphene/perovskite interface, perovskite-based solar cells

References: (1) M Acik, SB Darling. J. Mater. Chem. A (2016) Advance Article. Doi: 10.1039/C5TA09911K (2) J Gong, SB Darling, F You, Energy Environ. Sci. (2015) 8, 1953-1968 (3) M Acik, G Lee, C Mattevi, M Chhowalla, K Cho, YJ Chabal. Nature Mater. (2010) 9 (10), 840-845 (4) M Acik, C Mattevi, C Gong, G Lee, K Cho, M Chhowalla, YJ Chabal. Acs Nano (2010) 4 (10), 5861-5868 .

“Use of the Center for Nanoscale Materials was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. The abstract has been created by UChicago Argonne, LLC, Operator of Argonne National Laboratory (“Argonne”). Argonne, a U.S. Department of Energy Office of Science laboratory, is operated under Contract No. DE-AC02-06CH11357. The U.S. Government retains for itself, and others acting on its behalf, a paid-up nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the Government. Office of Science User Facility under Contract No. DE-AC02-06CH11357. M.A. also acknowledges support from the Joseph Katz Named Fellowship at Argonne National Laboratory.”