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We reveal an iodine vapor-induced degradation mechanism in formamidinium–lead-iodide-based perovskite solar cells stressed under combined heat and light illumination.

Postdeposition treatments (PDTs) with sodium fluoride (NaF) and potassium fluoride (KF) were introduced as a way to improve the efficiency of Cu­(In,Ga)­Se2 (CIGS) based solar cells. Here, we apply postdeposition treatments with rubidium fluoride (RbF) to low-temperature coevaporated CIGS absorbers after a first PDT with NaF and compare the effects of the addition of Rb and K on the solar cell performance and material properties of the CIGS films. KF and RbF PDTs lead to similar improvements in the open-circuit voltage (V oc) and fill factor (FF), while allowing a reduction of the thickness of the cadmium sulfide (CdS) buffer layer without loss in electronic performance. KF and RbF PDTs lead to comparable modifications of the morphology and composition of the CIGS films. After the PDT, K and Rb accumulate in a nanopatterned copper-poor secondary phase at the CIGS surface, while also diffusing within the CIGS layer and strongly reducing the concentration of lighter alkali element sodium. These findings corroborate theoretical calculations published by another group, which predicted the segregation of potassium indium selenide (KInSe2) and rubidium indium selenide (RbInSe2) at CIGS surfaces under the used PDT conditions.

kesterite material with its optimal bandgap and absorption coefficient. [2] Alkali treatment of kesterite solar cells is one of the measures to reduce the high V OC -deficit and most of today's >10% efficiency kesterite devices utilize the beneficial effects of alkali elements on absorber layer morphology and optoelectronic properties. So far the most research attention has been paid to sodium, resulting in many thorough investigations which revealed grain size enhancement, passivation of grain boundaries, and an increase in net hole concentration as the major beneficial effects of sodium treatments. [3][4][5][6] Also lithium addition has shown to improve device performance by boosting the electronic quality of the CZTSSe absorber material and grain boundaries. [7] First studies on the effect of potassium addition confirmed advantageous effects on kesterite absorber growth and optoelectronic properties similar to Na. [8,9] Several studies comparing different alkali elements and their effect on solar cell properties and device performance have recently been published. [10][11][12][13] Table 1 compares the effects on device performance by extracting a ranking of the various alkali elements in each publication in the order of their capability to improve device performance. It is apparent from these rankings that no consistent experimental results have been obtained, which triggers two questions: (i) Why do the published results differ so much? (ii) Which alkali element possesses the highest potential for efficiency improvements?This paper aims to unveil the discrepancy between the recently published results comparing the effects of alkali treatments on device performance. Our hypothesis is that each alkali element requires a different absorber composition to achieve the highest PV performance and we therefore prepared a comprehensive set of samples with different alkali elements and alkali concentrations as well as various metal ratios. All samples were thoroughly characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray fluorescence (XRF), inductively coupled plasma-mass spectrometry (ICP-MS), as well as current-voltage (J-V), capacitance-voltage (C-V), time-resolved photoluminescence (TRPL), and external quantum efficiency (EQE) measurements.The methodology used for absorber synthesis is based on the solution process described elsewhere, [14] allowing for accurate alkali incorporation by simply adding alkali chlorides to the solution. [15] Figure 1a illustrates the matrix of sample compositions prepared with five different alkali elements: lithium (Li), Sodium treatment of kesterite layers is a widely used and efficient method to boost solar cell efficiency. However, first experiments employing other alkali elements cause confusion as reported results contradict each other. In this comprehensive investigation, the effects of absorber composition, alkali element, and concentration on optoelectronic properties and device performance are investigated. Experimental results show that in the r...

The performance‐boosting effect of alkali treatments is well known for chalcogenide thin‐film solar cells based on Cu(In,Ga)Se2 (CIGS) and Cu2ZnSn(S,Se)4 (CZTSSe–kesterite) absorbers. In contrast to heavier alkali elements, lithium is expected to alloy with the kesterite phase leading to the solid solution (LixCu1−x)2ZnSn(S,Se)4 (LCZTSSe), which offers a way of tuning the semiconductor bandgap by changing the ratio Li/(Li+Cu). Here is presented an experimental series of solution‐processed LCZTSSe with lithium fraction Li/(Li+Cu) ranging from x = 0 to 0.12 in the selenized absorber as measured by means of inductively coupled plasma mass spectrometry. The proportional increase in lattice parameter a and bandgap from 1.05 to 1.18 eV confirms the lithium alloying in the kesterite phase. Increase in grain size is observed for x up to 0.07, whereas a higher lithium fraction leads to a porous absorber morphology due to an inhomogeneous distribution of Li‐containing compounds in the kesterite layer. An increase of the photoluminescence quantum yield is observed as the Li fraction increases in the absorber layer. A champion device exhibits a remarkable efficiency of 11.6% (12.2% active area) for x = 0.06, close to the world record value of 12.6% demonstrating the effectiveness of lithium alloying.

Research in global change ecology relies heavily on global climatic grids derived from estimates of air temperature in open areas at around 2 m above the ground. These climatic grids thus fail to reflect conditions below vegetation canopies and near the ground surface, where critical ecosystem functions are controlled and most terrestrial species reside. Here we provide global maps of soil temperature and bioclimatic variables at a 1-km² resolution for 0-5 and 5-15 cm depth. These maps were created by calculating the difference (i.e., offset) between in-situ soil temperature measurements, based on time series from over 1200 1-km² pixels (summarized from 8500 unique temperature sensors) across all of the world's major terrestrial biomes, and coarse-grained air temperature estimates from ERA5-Land (an atmospheric reanalysis by the European Centre for Medium-Range Weather Forecasts). We show that mean annual soil temperature differs markedly from the corresponding 2 m gridded air temperature, by up to 10°C (mean = 3.0 ± 2.1°C), with substantial variation across biomes and seasons. Over the year, soils in cold and/or dry biomes are substantially warmer (3.6 ± 2.3°C warmer than gridded air temperature), whereas soils in warm and humid environments are on average slightly cooler (0.7 ± 2.3°C cooler). The observed substantial and biome-specific offsets underpin that the projected impacts of climate and climate change on biodiversity and ecosystem functioning are inaccurately assessed when air rather than soil temperature is used, especially in cold environments. The global soil-related bioclimatic variables provided here are an important step forward for any application in ecology and related disciplines. Nevertheless, we highlight the need to fill remaining global gaps by collecting more in-situ measurements of microclimate conditions to further enhance the spatiotemporal resolution of global soil temperature products for ecological applications.

The debate on the relative benefits of conventional and organic farming systems has in recent time gained significant interest. So far, global agricultural development has focused on increased productivity rather than on a holistic natural resource management for food security. Thus, developing more sustainable farming practices on a large scale is of utmost importance. However, information concerning the performance of farming systems under organic and conventional management in tropical and subtropical regions is scarce. This study presents agronomic and economic data from the conversion phase (2007–2010) of a farming systems comparison trial on a Vertisol soil in Madhya Pradesh, central India. A cotton-soybean-wheat crop rotation under biodynamic, organic and conventional (with and without Bt cotton) management was investigated. We observed a significant yield gap between organic and conventional farming systems in the 1st crop cycle (cycle 1: 2007–2008) for cotton (−29%) and wheat (−27%), whereas in the 2nd crop cycle (cycle 2: 2009–2010) cotton and wheat yields were similar in all farming systems due to lower yields in the conventional systems. In contrast, organic soybean (a nitrogen fixing leguminous plant) yields were marginally lower than conventional yields (−1% in cycle 1, −11% in cycle 2). Averaged across all crops, conventional farming systems achieved significantly higher gross margins in cycle 1 (+29%), whereas in cycle 2 gross margins in organic farming systems were significantly higher (+25%) due to lower variable production costs but similar yields. Soybean gross margin was significantly higher in the organic system (+11%) across the four harvest years compared to the conventional systems. Our results suggest that organic soybean production is a viable option for smallholder farmers under the prevailing semi-arid conditions in India. Future research needs to elucidate the long-term productivity and profitability, particularly of cotton and wheat, and the ecological impact of the different farming systems.

& Key message Shade trees in agroforestry systems protect the understory cocoa from climate extremes. Shade tree pruning manages microclimatic conditions in favor of cocoa production while tree diversity is maintained. Adaptation of pruning has to consider seasonal changes in temperature and precipitation to protect the understory cocoa. & Context Structural characteristics of tree stands such as species diversity, tree density, and stratification can affect throughfall and microclimate. Pruning changes the canopy and may therefore modulate internal conditions. & Aims The aim of this study is to assess the environmental growing conditions of cocoa trees. & Methods We monitored canopy openness and the impact of stand structure on throughfall and microclimate in three cocoa production systems (monoculture, agroforestry, and successional agroforestry) and a natural regrowth in a long-term trial in Bolivia from 2013 to 2015. We further focused on the effect of annual shade tree and cocoa pruning on these variables to evaluate the potential impact of this activity. & Results Agroforestry systems buffered extreme climate events like temperature fluctuations compared to monocultures but reduced light and throughfall drastically. Spatial variability of throughfall and transmitted light were low under a high and closed shade tree canopy. Shade tree pruning resulted in higher canopy openness, light transmittance, and throughfall, while the buffer function of the agroforestry systems concerning temperature and humidity fluctuations was reduced. & Conclusion Differences between cocoa production systems regarding throughfall and microclimate were overlain by pruning activities. Cocoa agroforestry systems are temporal dynamic systems. Pruning timing and intensity is pivotal for balancing light and water availability under seasonally varying environmental conditions to conserve micro-environments for cocoa production with less exposure to unfavorable climate.