Improving the long-term stability of perovskite solar cells is critical to the deployment of this technology. Despite the great emphasis laid on stability-related investigations, publications lack consistency in experimental procedures and parameters reported. It is therefore challenging to reproduce and compare results and thereby develop a deep understanding of degradation mechanisms. Here, we report a consensus between researchers in the field on procedures for testing perovskite solar cell stability, which are based on the International Summit on Organic Photovoltaic Stability (ISOS) protocols. We propose additional procedures to account for properties specific to PSCs such as ion redistribution under electric fields, reversible degradation and to distinguish ambient-induced degradation from other stress factors. These protocols are not intended as a replacement of the existing qualification standards, but rather they aim to unify the stability assessment and to understand failure modes. Finally, we identify key procedural information which we suggest reporting in publications to improve reproducibility and enable large data set analysis. Reliability of stability data for perovskite solar cells is undermined by a lack of consistency in the test conditions and reporting. This Consensus Statement outlines practices for testing and reporting stability tailoring ISOS protocols for perovskite devices.

/pdf/consensus-statement-for-stability-assessment-and-reporting-37ng2o1dmx.pdf

Consensus statement for stability assessment and reporting for perovskite photovoltaics based on ISOS procedures

The electronic structure of the perovskite LaCoO$_3$ for different spin states of Co ions was calculated in the LDA+U approach. The ground state was found to be a nonmagnetic insulator with Co ions in a low-spin state. Somewhat higher in energy we found two intermediate-spin states followed by a high-spin state at significantly higher energy. The calculation results show that Co 3$d$ states of $t_{2g}$ symmetry form narrow bands which could easily localize whilst $e_g$ orbitals, due to their strong hybridization with the oxygen 2$p$ states, form a broad $\sigma^*$ band. With the increase of temperature which is simulated by the corresponding increase of the lattice parameter, the transition from the low- to intermediate-spin states occurs. This intermediate-spin (occupation $t_{2g}^5e_g^1$) can develop an orbital ordering which can account for the nonmetallic nature of LaCoO$_3$ at 90 K$<$T$<$500 K. Possible explanations of the magnetic behavior and gradual insulating-metal transition are suggested.

https://arxiv.org/pdf/cond-mat/9709060.pdf

Intermediate-spin state and properties of LaCoO_3

Recent progress of half-Heusler for moderate temperature thermoelectric applications

Organic–inorganic halide perovskite materials (e.g., MAPbI3, FAPbI3, etc.; where MA = CH3NH3+, FA = CH(NH2)2+) have been studied intensively for photovoltaic applications. Major concerns for the commercialization of perovskite photovoltaic technology to take off include lead toxicity, long-term stability, hysteresis, and optimal bandgap. Therefore, there is still need for further exploration of alternative candidates. Elemental composition engineering of MAPbI3 and FAPbI3 has been proposed to address the above concerns. Among the best six certified power conversion efficiencies reported by National Renewable Energy Laboratory on perovskite-based solar cells, five are based on mixed perovskites (e.g., MAPbI1–xBrx, FA0.85MA0.15PbI2.55Br0.45, Cs0.1FA0.75MA0.15PbI2.49Br0.51). In this paper, we review the recent progress on the synthesis and fundamental aspects of mixed cation and halide perovskites correlating with device performance, long-term stability, and hysteresis. In the outlook, we outline the future ...

Progress on Perovskite Materials and Solar Cells with Mixed Cations and Halide Anions

Hybrid lead halide perovskites have emerged as promising active materials for photovoltaic cells. Although superb efficiencies have been achieved, it is widely recognized that long-term stability is a key challenge intimately determining the future development of perovskite-based photovoltaic technology. Herein, we present reversible and irreversible photodecomposition reactions of methylammonium lead iodide (MAPbI3). Simulated sunlight irradiation and temperature (40–80 °C) corresponding to solar cell working conditions lead to three degradation pathways: (1) CH3NH2 + HI (identified as the reversible path), (2) NH3 + CH3I (the irreversible or detrimental path), and (3) a reversible Pb(0) + I2(g) photodecomposition reaction. If only the reversible reactions (1) and (3) take place and reaction (2) can be avoided, encapsulated MAPbI3 can be regenerated during the off-illumination timeframe. Therefore, to further improve operational stability in hybrid perovskite solar cells, detailed understanding of how to mitigate photodegradation and thermal degradation processes is necessary. First, encapsulation of the device is necessary not only to avoid contact of the perovskite with ambient air, but also to prevent leakage of volatile products released from the perovskite. Second, careful selection of the organic cations in the compositional formula of the perovskite is necessary to avoid irreversible reactions. Third, selective contacts must be as chemically inert as possible toward the volatile released products. Finally, hybrid halide perovskite materials are speculated to undergo a dynamic formation and decomposition process; this can gradually decrease the crystalline grain size of the perovskite with time; therefore, efforts to deposit highly crystalline perovskites with large crystal sizes may fail to increase the long-term stability of photovoltaic devices.

/pdf/photodecomposition-and-thermal-decomposition-in-32h9ked3lr.pdf

Photodecomposition and thermal decomposition in methylammonium halide lead perovskites and inferred design principles to increase photovoltaic device stability

Magnetic properties of compacted La0.8Ca0.2MnO3 manganite nanoparticles with average particle size of 18 and 70 nm and Curie temperatures TC 231 K and TC 261 K, respectively, have been investigated. The relative volume of the ferromagnetic phase has been estimated to be 52% for ensembles of 18 nm particles and 92% for 70 nm particles. It was found that applied hydrostatic pressure enhances TC of La0.8Ca0.2MnO3 nanoparticles at a rate dTC /dP 1.8– 1.9 K / kbar, independently on the average particle size. Pronounced irreversibility of magnetization below Tirr 208 K and strong frequency dependent ac susceptibility below TC for smaller 18 nm particles have been observed. 18 nm particles have also shown aging and memory effects in zero-field-cooled ZFC and field-cooled magnetization. These features indicate the appearance of spin-glasslike state, partially reminiscent the behavior of La1�xCaxMnO3 crystals, doped below the percolation threshold xxC = 0.225. In contrast, ensembles of larger 70 nm particles have shown insignificant irreversibility of magnetization only and no frequency dependence of ac susceptibility, similarly to the behavior of La1�xCaxMnO3 crystals with xxC. The temperature of the ZFC magnetization maximum for 18 nm particles decreases with increasing magnetic field and forms a critical line with an exponent 1.89 0.56. The results suggest that superspin-glass features in ensembles of interacting 18 nm particles appear along with superferromagnetic-like features.

Spin-glass-like properties ofLa0.8Ca0.2MnO3nanoparticles ensembles

In an attempt to reduce our reliance on fossil fuels, associated with severe environmental effects, the current research is focused on the identification of the thermoelectric potential of p-type (GeTe)1−x(Bi2Te3)x alloys, with x values of up to 20%. Higher solubility limit of Bi2Te3 in GeTe, than previously reported, was identified around ∼9%, extending the doping potential of GeTe by the Bi2Te3 donor dopant, for an effective compensation of the high inherent hole concentration of GeTe toward thermoelectrically optimal values. Around the solubility limit of 9%, an electronic optimization resulted in an impressive maximal thermoelectric figure of merit, ZT, of ∼1.55 at ∼410 °C, which is one of the highest ever reported for any p-type GeTe-rich alloys. Beyond the solubility limit, a Fermi Level Pinning effect of stabilizing the Seebeck coefficient was observed in the x = 12%–17% range, leading to stabilization of the maximal ZTs over an extended temperature range; an effect that was associated with the pot...

High thermoelectric potential of Bi2Te3 alloyed GeTe-rich phases

Texture anisotropy of higher manganese silicide following arc-melting and hot-pressing

The MNiSn (M = Ti, Zr, Hf) half-Heusler semiconducting compounds are widely investigated due to their good potential for thermoelectric (TE) power generation applications. In the current work, the evolution of the transport and structural properties of the Ti0.3Zr0.35Hf0.35NiSn compound upon various thermal treatments was studied. The nominal composition was arc melted, ball milled, and spark plasma sintered (SPS). Following SPS, large Hf-rich domains were found by scanning electron microscopy (SEM) and energy-dispersive x-ray spectroscopy (EDS). Subsequently, the samples were subjected to homogenization treatments at 1163 K for 480 h and 610 h under argon atmosphere. Following these thermal treatments, the relative amount of the Hf-rich domains was reduced and they became smaller in size, with increasing thermal treatment duration. Nevertheless, no uniphased structure was reached. The dissolution of the Hf-rich domains in the half-Heusler matrix resulted in increase of both the Seebeck coefficient and electrical resistivity values and a decrease of the carrier concentration, attributed to elimination of these metallic domains. Resulting from the high atomic disorder caused by substitution at the M site, low thermal conductivity values of ~3.8 W m−1 K−1 were obtained leading to high ZT values of up to 0.82 following SPS.

Effects of Microstructural Evolution on the Thermoelectric Properties of Spark-Plasma-Sintered Ti 0.3 Zr 0.35 Hf 0.35 NiSn Half-Heusler Compound

Magnetic properties of compacted $50\phantom{\rule{0.3em}{0ex}}\mathrm{nm}$ ${\mathrm{CaMnO}}_{3\ensuremath{-}\ensuremath{\delta}}$ (CMO) nanoparticles have been investigated. Measurements of ac-susceptibility exhibit upon cooling two magnetic transitions at $T\ensuremath{\sim}270\phantom{\rule{0.3em}{0ex}}\mathrm{K}$ accompanied by a small spontaneous magnetic moment and a para-antiferromagnetic (AFM) transition at ${T}_{\text{N}}\ensuremath{\sim}120\phantom{\rule{0.3em}{0ex}}\mathrm{K}$, observed previously in bulk CMO. Asymmetric magnetization hysteresis loops observed in applied magnetic fields $H\ensuremath{\le}90\phantom{\rule{0.3em}{0ex}}\mathrm{kOe}$ are attributed to an exchange coupling between the antiferromagnetic core and the ferromagnetic (FM) shell of the CMO nanoparticles. This work provides the observation of exchange bias effect in manganite nanoparticles with inverted AFM-core--FM-shell structure, as compared to the typical FM-core--AFM-shell. Effects of surface and exchange anisotropy are also discussed.

D. Mogilyansky

Papers

Spin-glass-like properties ofLa0.8Ca0.2MnO3nanoparticles ensembles

High thermoelectric potential of Bi2Te3 alloyed GeTe-rich phases

Texture anisotropy of higher manganese silicide following arc-melting and hot-pressing

Effects of Microstructural Evolution on the Thermoelectric Properties of Spark-Plasma-Sintered Ti 0.3 Zr 0.35 Hf 0.35 NiSn Half-Heusler Compound

Surface and exchange-bias effects in compacted CaMnO 3 − δ nanoparticles