I-2 vapor-induced degradation of formamidinium lead iodide based perovskite solar cells under heat-light soaking conditions

Over the last years, the operational stability of perovskite solar cells has been significantly improved by compositional engineering, interface modification, and improved encapsulation techniques. However, irreversible degradation is still ubiquitously observed during the first 1000 hours of operation, particularly at elevated temperatures. In this work, we elucidate a major mechanism controlling this degradation. For that, formamidinium lead iodide-based perovskite solar cells were stressed under continuous 1 sun illumination at 80 degrees C in N-2, before extensive characterization of their microstructure and composition. The cell active area and hence the photocurrent are found to decrease with time due to the growth of porous PbI2-rich regions. This degradation was observed to originate from a few seed points in the perovskite bulk rather than from the interfaces with the charge-selective layers or from the cell edges. I-2 vapor, first released at these defective points and then further released from the decomposition of the perovskite exposed to this vapor, controls the degradation process. Furthermore, this autocatalytic degradation process is shown to locally rupture the top electrode due to vapor pressure build-up. In addition to highlighting the detrimental influence of residual PbI2, we show that such a degradation pathway can be alleviated by reducing the methylammonium and/or iodine content, providing a path to more stable perovskite solar cells.

A chain is as strong as its weakest link - Stability study of MAPbI(3) under light and temperature

Michael Graetzel, Ulf Anders Hagfeldt, Philippe Jürgen Holzhey, Michael Saliba, Silver Hamill Turren Cruz, Amita Ummadisingu, Pankaj Kumar Yadav

The stability of perovskite solar cells is a key issue for industrial development. One reason for this is the volatile organic methylammonium (MA) cation, which is prone to degas under elevated temperatures from the perovskite. At the same time, small amounts of MA are used for practically all highest performing solar cells. These compositions have also shown relatively promising stabilities. This raises the question of MA stability with respect to different, application-dependent stability requirements. Interestingly, MA stability was mainly studied on thin films that differ from full devices or with architectures which are also prone to degrade. Therefore, the degradation behavior on complete MA containing devices with a relatively stable architecture is required to quantify the long-term stability of MA. This enables to determine at which timescales MA is unstable and which role it can play in future compositions. If MA is indeed unstable at much longer timescales than previously recorded, it also indicates that more severe degradation pathways are currently underappreciated. Here, "weakest link" MAPbI(3) solar cells show stability where devices retained 100% of their initial efficiency over 1000 h of aging under constant illumination and maximum power point tracking at 20 degrees C. At elevated temperatures of 50 and 65 degrees C, the devices retained 100% and 90% of their initial efficiency after 500 h of illumination, respectively. Impressively, at 95 degrees C the MAPbI(3) device retained 85% of its initial efficiency after 500 h under constant illumination, which is some of the best stability data reported to date for MA. Thus, MA-containing devices require further studying. Nevertheless to achieve the necessary industrial lifetimes of more than 25 years, the complete removal of MA is a sensible precaution to systematically avoid any long-term risk factors.

2019

Window Layers for Silicon Heterojunction Solar Cells

Johannes Peter Seif

Currently, crystalline silicon (c-Si) wafer-based solar cells dominate the photovoltaic market (80-90%). In this thesis we concentrate on silicon heterojunction (SHJ) solar cells that--in contrast to diffused homojunction cells--rely on the application of amorphous silicon (a-Si:H) thin films. Unlike standard homojunction devices, which are typically limited by their highly recombination-active semiconductor-to-metal contacts, SHJ devices exhibit excellent surface passivation enabled by intrinsic and doped a-Si:H films. These a-Si:H layers, however, entail drawbacks for optical performance and carrier transport, two topics that will be addressed in this work. To this end we investigate non-traditional materials for SHJ devices, with the goal of replacing the a-Si:H or the transparent electrodes. These materials include microcrystalline silicon (uc-Si:H) and organic semiconductors for contact formation; amorphous silicon suboxides (a-SiOx:H) for surface passivation; and transparent electrodes applied by atomic layer deposition (ALD) as protective layers against subsequent processing steps. Along with the optical and electrical properties of these materials, we study the impact on device performance associated with their deposition. For this we test the devices under standard testing conditions (25 °C) and at elevated temperatures closer to those encountered in the field. For the investigations on uc-Si:H layers, we vary process parameters (including temperature, pressure, power, excitation frequency and hydrogen dilution) as well as pre-treatments, gas variations and nucleation layers. We assess the suitability of these approaches for SHJ solar cells and apply selected measures in devices. Thereby we demonstrate a gain in short-circuit current density in the range of 0.5-1 mA.cm-2 and good fill factor values of up to 79.2% using either n- and p-type uc-Si:H layers. Furthermore, with the goal of reducing optical losses, we test wide-bandgap a-SiOx:H layers for passivation. In terms of current gain without negative side effects on transport, we argue that these layers are best applied to the electron-collecting contact--put at the front of the device--as their application to the hole-collecting contact introduces a transport barrier for holes. This barrier deteriorates the device performance at 25 °C, but shows a beneficial effect on the temperature coefficient of the device, yielding coefficients as low as -0.1%/°C. In some cases--compared to standard devices--devices with a-SiOx:H layers exhibit superior performance at elevated temperatures, which can be of interest in warmer climates. In parallel to these main topic we also study aluminium-doped zinc oxide (ZnO:Al) layers deposited by ALD as a protective layer against sputter-induced damage and organic semiconductors as transparent electrodes for the hole-collecting contact. In both cases we observe a gain in terms of surface passivation, which indicates that these materials may be beneficial for the contact formation in future device structures. In addition to these material-related investigations, we unravel the temperature-dependence of each individual cell parameter and present a brief comparison of state-of-the-art technologies and their respective temperature dependence.

EPFL2015

Room Temperature as a Goldilocks Environment for CH3NH3PbI3 Perovskite Solar Cells: The Importance of Temperature on Device Performance

Juan-Pablo Correa-Baena, Ulf Anders Hagfeldt, Tor Jesper Jacobsson, Wolfgang Richard Tress

Terrestrial applications of solar cells during day-night cycling as well as operation in winter and summer involve substantial temperature variations, which influence the photophysics as well as the charge separation and transport properties in the various materials employed in a device. In this study, the optical absorption of methylammonium lead iodide (MAPbI(3)) and the device performance of MAPbI(3) solar cells have been investigated in an extended temperature range between -190 and 80 degrees C. The optical properties were found to change by only a small amount in that temperature range. The device performance did, however, show more dramatic changes and decreased in a reversible manner for temperatures both higher and lower than room temperature. For temperatures up to 80 degrees C and down to -80 degrees C, the drop in performance was up to 25% compared to the room temperature value. Given thermal stability and reversible device performance, this is probably not a showstopper for terrestrial applications of perovskite solar cells but should be considered when evaluating the total energy yield under outdoor operations. At temperatures of 100 degrees C and below, which are relevant for outer atmosphere and space applications, the performance decreases rather dramatically and approaches zero at even lower temperature. Irreversible changes set in for temperatures above 50 degrees C. In addition, the hysteresis decreases at reduced temperatures. As the effects for the absorption properties are minor, the decrease in performance can be attributed to a temperature induced limitation in the transport and extraction of the photogenerated charge carriers which is seen as a strong increase of the series resistance at reduced temperature. The drop of the photovoltage for temperatures below -100 degrees C might be related to reduced charge carrier separation in the perovskite due to excitonic effects and a lower dielectric constant.

American Chemical Society2016