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Auger Electron Spectroscopy Analysis of the Thermally Induced Degradation of MAPbI₃ Perovskite Films.

ABSTRACT: Organometal halide perovskites are highly promising materials for photovoltaic applications due to the rapid growth of power conversion efficiency in recent years. However, thermal stability is still a major hurdle for perovskite solar cells toward commercialization. Herein, we first explore the slow thermal response of the CH₃NH₃PbI₃ perovskite crystal investigated via Auger electron spectroscopy (AES). AES image mapping directly observes the evolution of morphology and elemental distribution over time. The AES small spot analysis demonstrates the precise initial degradation position of perovskite with both information regarding physical changes in crystals and chemical changes in elemental bonding at the nanometer scale. X-ray photoelectron spectroscopy (XPS) was used to confirm the surface chemical bonding and composition of the perovskite crystals. This work provides the first insights into the physical and chemical changes of perovskites investigated by AES upon long-term exposure to heat under ambient conditions.

SUBMITTER: Lin WC

PROVIDER: S-EPMC8697411 | biostudies-literature | 2021 Dec

REPOSITORIES: biostudies-literature

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Auger Electron Spectroscopy Analysis of the Thermally Induced Degradation of MAPbI3 Perovskite Films.

Lin Wei-Chun WC Lo Wei-Chun WC Li Jun-Xian JX Huang Pei-Chen PC Wang Man-Ying MY

ACS omega 20211129 50

Organometal halide perovskites are highly promising materials for photovoltaic applications due to the rapid growth of power conversion efficiency in recent years. However, thermal stability is still a major hurdle for perovskite solar cells toward commercialization. Herein, we first explore the slow thermal response of the CH3NH3PbI3 perovskite crystal investigated via Auger electron spectroscopy (AES). AES image mapping directly observes the evolution of morpho ...[more]

PMID: 34963945

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Project description:Organic-inorganic halide perovskites are interesting candidates for solar cell and optoelectronic applications owing to their advantageous properties such as a tunable band gap, low material cost, and high charge carrier mobilities. Despite making significant progress, concerns about material stability continue to impede the commercialization of perovskite-based technology. In this article, we investigate the impact of environmental parameters on the alteration of structural properties of MAPbI3 (CH3NH3PbI3) thin films using microscopy techniques. These characterizations are performed on MAPbI3 thin films exposed to air, nitrogen, and vacuum environments, the latter being possible by using dedicated air-free transfer setups, after their fabrication into a nitrogen-filled glovebox. We observed that even less than 3 min of air exposure increases the sensitivity to electron beam deterioration and modifies the structural transformation pathway as compared to MAPbI3 thin films which are not exposed to air. Similarly, the time evolution of the optical responses and the defect formation of both air-exposed and non-air-exposed MAPbI3 thin films are measured by time-resolved photoluminescence. The formation of defects in the air-exposed MAPbI3 thin films is first observed by optical techniques at longer timescales, while structural modifications are observed by transmission electron microscopy (TEM) measurements and supported by X-ray photoelectron spectroscopy (XPS) measurements. Based on the complementarity of TEM, XPS, and time-resolved optical measurements, we propose two different degradation mechanism pathways for air-exposed and non-air-exposed MAPbI3 thin films. We find that when exposed to air, the crystalline structure of MAPbI3 shows gradual evolution from its initial tetragonal MAPbI3 structure to PbI2 through three different stages. No significant structural changes over time from the initial structure are observed for the MAPbI3 thin films which are not exposed to air.

Project description:Single crystalline perovskite solar cells (PSC) are promising for their inherent stability due to the absence of grain boundaries. While the development of single crystals of perovskite with enhanced optoelectronic properties is known, studies on the growth, device performance and understanding of the intrinsic stability of single crystalline perovskite thin film solar cell devices fabricated on electron selective contacts are scarcely explored. In this work, we examine the impact of mesoporous TiO2 (m-TiO2) and planar TiO2 (p-TiO2) on the growth of single crystalline-methyl ammonium lead iodide (SC-MAPbI3) film, PSC device performance and film stability under harsh weather conditions (T ∼ 85 °C and RH ∼ 85%). Self-grown SC-MAPbI3 films are developed on m-TiO2 and p-TiO2 by inverse temperature crystallization under ambient conditions without the need for sophisticated glove-box processing. The best device with m-TiO2 as an electron transport layer showed a promising power conversion efficiency of 3.2% on an active area of 0.3 cm2 in hole transport material free configuration, whereas, only 0.7% was achieved for the films developed on p-TiO2. Complete conversion of precursor to perovskite phase and better surface coverage of the film leading to enhanced absorption and reduced defects of single crystalline perovskite on m-TiO2 compared to its p-TiO2 leads to this large difference in efficiency. Mesoporous device retained more than 70% of its initial performance when stored at 30 °C under dark for more than 5000 h at 50% RH; while the planar device degraded after 1500 h. Thermal and moisture endurance of SC-MAPbI3 films are investigated by subjecting them to temperatures ranging from 35 °C to 85 °C at a constant relative humidity (RH) of 85%. X-ray diffraction studies show that the SC-MAPbI3 films are stable even at 85 °C and 85% RH, with only slight detection (30-35%) of PbI2 at these conditions. This study highlights the superior stability of SC-MAPbI3 films which paves way for further studies on improving the stability and performance of the ambient processed PSCs.

Dataset Information

Auger Electron Spectroscopy Analysis of the Thermally Induced Degradation of MAPbI₃ Perovskite Films.

Publications

Auger Electron Spectroscopy Analysis of the Thermally Induced Degradation of MAPbI<sub>3</sub> Perovskite Films.

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