Effects of MgF2anti-reflection coating on optical losses in metal halide perovskite solar cells.

The importance of light management for perovskite solar cells (PSCs) has recently been emphasized because their power conversion efficiency approaches their theoretical thermodynamic limits. Among optical strategies, anti-reflection (AR) coating is the most widely used method to reduce reflectance loss and thus increase light-harvesting efficiency. Monolayer MgF2is a well-known AR material because of its optimal refractive index, simple fabrication process, and physical and chemical durabilities. Nevertheless, quantitative estimates of the improvement achieved by the MgF2AR layer are lacking. In this study, we conducted theoretical and experimental evaluations to assess the AR effect of MgF2on the performance of formamidinium lead-triiodide PSCs. A sinusoidal tendency to enhance the short-circuit current density (JSC) was observed depending on the thickness, which was attributed to the interference of the incident light. A transfer matrix method-based simulation was conducted to calculate the optical losses, demonstrating the critical impact of reflectance loss on theJSCimprovement. The predictedJSCs values, depending on the perovskite thickness and the incident angle, are also presented. The combined use of experimental and theoretical approaches offers notable advantages, including accurate interpretation of photocurrent generation, detailed optical analysis of the experimental results, and device performance predictions under unexplored conditions.

Atmospheric Humidity Underlies Irreproducibility of Formamidinium Lead Iodide Perovskites.

Metal halide perovskite solar cells (PSCs) are infamous for their batch-to-batch and lab-to-lab irreproducibility in terms of stability and performance. Reproducible fabrication of PSCs is a critical requirement for market viability and practical commercialization. PSC irreproducibility plagues all levels of the community; from institutional research laboratories, start-up companies, to large established corporations. In this work, the critical function of atmospheric humidity to regulate the crystallization and stabilization of formamidinium lead triiodide (FAPbI3) perovskites is unraveled. It is demonstrated that the humidity content during processing induces profound variations in perovskite stoichiometry, thermodynamic stability, and optoelectronic quality. Almost counterintuitively, it is shown that the presence of humidity is perhaps indispensable to reproduce phase-stable and efficient FAPbI3-based PSCs.

Stability-limiting heterointerfaces of perovskite photovoltaics.

Optoelectronic devices consist of heterointerfaces formed between dissimilar semiconducting materials. The relative energy-level alignment between contacting semiconductors determinately affects the heterointerface charge injection and extraction dynamics. For perovskite solar cells (PSCs), the heterointerface between the top perovskite surface and a charge-transporting material is often treated for defect passivation1-4 to improve the PSC stability and performance. However, such surface treatments can also affect the heterointerface energetics1. Here we show that surface treatments may induce a negative work function shift (that is, more n-type), which activates halide migration to aggravate PSC instability. Therefore, despite the beneficial effects of surface passivation, this detrimental side effect limits the maximum stability improvement attainable for PSCs treated in this way. This trade-off between the beneficial and detrimental effects should guide further work on improving PSC stability via surface treatments.

Effect of alkaline earth metal chloride additives BCl2 (B = Mg, Ca, Sr and Ba) on the photovoltaic performance of FAPbI3 based perovskite solar cells.

Additive engineering is known to be an effective method for inducing a simultaneous effect of enlarging the grain size and surface passivation. As compared to the monovalent halides frequently used as additives, divalent halides are relatively less investigated in the role of additives. In this work, we report effects of alkaline earth metal halides BCl2 (B = Mg, Ca, Sr, Ba) as additives on the opto-electronic properties and photovoltaic performance of FAPbI3 based perovskite solar cells (PSCs). A significant improvement in power conversion efficiency (PCE) from 17.27% to 21.11% is observed by MgCl2 addition in the FAPbI3 precursor solution, while a marginal increment for CaCl2 or BaCl2 and a negative effect for SrCl2 is observed. The lattice constant of cubic FAPbI3 is hardly changed by additives, while the crystallinity is improved by MgCl2. The carrier lifetime increases from 40 ns to 287 ns and the trap density is reduced from 1.08 × 1016 cm-3 to 3.19 × 1015 cm-3 by addition of 5 mol% MgCl2, which is responsible for the enhancement in photovoltaic parameters. The steady-state PCE of the PSC with the MgCl2-additive-treated FAPbI3 measured under continuous illumination at the maximum power point remains unchanged for 1500 s.

Simulated Biomass Sorghum GHG Reduction Potential is Similar to Maize.

Policy support for cellulosic biofuels is contingent on their achieving much greater reductions in life-cycle greenhouse gas emissions than corn starch ethanol. Biomass sorghum has been suggested as a genetically and agronomically tractable feedstock species to augment near-term cellulosic feedstock production. This study used DayCent modeling to investigate biomass sorghum production emissions relative to corn with and without stover utilization at 3,265 across the rainfed United States. Sorghum produced greater average feedstock dry matter (15.6 ± 1.4 vs 14.8 ± 2.2 Mg ha-1 yr-1) and slightly lower estimated ethanol energy yields (10.6 ± 1.0 vs 11.8 ± 2.9 MJ m-2 yr-1) as corn grain with 75% stover collection. The high biomass removals in both the sorghum and corn stover scenarios led to soil organic carbon losses on 90 and 100% of sites, respectively. Average feedstock production emissions intensities were similar between sorghum and corn with 75% stover removal (17.6 ± 2.8 vs 18.8 ± 3.0 g CO2e MJ-1), but were notably lower under sorghum for sites in the southwestern study region (13.6 ± 3.0 vs 22.5 ± 3.1 g CO2e MJ-1). These results suggest that biomass sorghum produces cellulosic feedstock with similar emissions to corn grain and at current yield levels is unlikely to meet the Renewable Fuel Standard emissions reduction threshold for cellulosic biofuels.

Light Emission Enhancement by Tuning the Structural Phase of APbBr3 (A = CH3NH3, Cs) Perovskites.

Lead halide perovskite (APbX3) has recently emerged as a promising active layer in light-emitting diodes (LEDs) as well as an absorber for photovoltaic devices. For better LED properties, it is important to understand the fundamental mechanism of the optoelectronic behaviors, e.g., how the nanostructure of the APbX3 thin film correlates with its emitting properties. We investigated the effect of APbBr3 (A = CH3NH3, Cs) crystallite size on the photophysical properties regarding its crystallographic changes and spin-orbit coupling. Photoluminescence lifetime measurements, X-ray and electron diffraction analyses, and density functional theory calculations were performed. We demonstrate that the emitting properties of mesoscale APbBr3 crystallites are improved due to the formation of a pure cubic phase that leads to the spin- and momentum-allowed carrier recombination. Our findings provide fundamental insights into the emitting behavior of APbBr3, which suggests a control of its optoelectronic properties by means of modulating the crystal morphology and resultant electronic band structures.

CH3 NH3 PbI3 and HC(NH2 )2 PbI3 Powders Synthesized from Low-Grade PbI2 : Single Precursor for High-Efficiency Perovskite Solar Cells.

High-efficiency perovskite solar cells are generally fabricated by using highly pure (>99.99 %) PbI2 mixed with an organic iodide in polar aprotic solvents. However, the use of such an expensive chemical may impede progress toward large-scale industrial applications. Here, we report on the synthesis of perovskite powders by using inexpensive low-grade (99 %) PbI2 and on the photovoltaic performance of perovskite solar cells prepared from a powder-based single precursor. Pure APbI3 [A=methylammonium (MA) or formamidinium (FA)] perovskite powders were synthesized by treating low-grade PbI2 with MAI or FAI in acetonitrile at ambient temperature. The structural phase purity was confirmed by X-ray diffraction. The solar cell with a MAPbI3 film prepared from the synthesized perovskite powder demonstrated a power conversion efficiency (PCE) of 17.14 %, which is higher than the PCE of MAPbI3 films prepared by using both MAI and PbI2 as precursors (PCE=13.09 % for 99 % pure PbI2 and PCE=16.39 % for 99.9985 % pure PbI2 ). The synthesized powder showed better absorption and photoluminescence, which were responsible for the better photovoltaic performance. For the FAPbI3 powder, a solution with a yellow non-perovskite δ-FAPbI3 powder synthesized at room temperature was found to lead to a black perovskite film, whereas a solution with the black perovskite α-FAPbI3 powder synthesized at 150 °C was not transformed into a black perovskite film. The α↔δ transition between the powder and film was assumed to correlate with the difference in the iodoplumbates in the powder-dissolved solution. An average PCE of 17.21 % along with a smaller hysteresis [ΔPCE=PCEreverse -PCEforward )=1.53 %] was demonstrated from the perovskite solar cell prepared by using δ-FAPbI3 powder; this PCE is higher than the average PCE of 17.05 % with a larger hysteresis (ΔPCE=2.71 %) for a device based on a conventional precursor solution dissolving MAI with high-purity PbI2 . The smaller hysteresis was indicative of fewer defects in the resulting FAPbI3 film prepared by using the δ-FAPbI3 powder.

The Interplay between Trap Density and Hysteresis in Planar Heterojunction Perovskite Solar Cells.

Anomalous current-voltage (J-V) hysteresis in perovskite (PSK) solar cell is open to dispute, where hysteresis is argued to be due to electrode polarization, dipolar polarization, and/or native defects. However, a correlation between those factors and J-V hysteresis is hard to be directly evaluated because they usually coexist and are significantly varied depending on morphology and crystallinity of the PSK layer, selective contacts, and device architecture. In this study, without changing morphology and crystallinity of PSK layer in a planar heterojunction structure employing FA0.9Cs0.1PbI3, a correlation between J-V hysteresis and trap density is directly evaluated by means of thermally induced PbI2 regulating trap density. Increase in thermal annealing time at a given temperature of 150 °C induces growth of PbI2 on the PSK grain surface, which results in significant reduction of nonradiative recombination. Hysteresis index is reduced from 0.384 to 0.146 as the annealing time is increased from 5 to 100 min due to decrease in the amplitude of trap-mediated recombination. Reduction of hysteresis by minimizing trap density via controlling thermal annealing time leads to the stabilized PCE of 18.84% from the normal planar structured FA0.9Cs0.1PbI3 PSK solar cell.

Comparison of phosphate materials for immobilizing cadmium in soil.

A study was conducted to compare the effects of phosphate (P) materials in reducing cadmium extractability. Seven P materials (commercial P fertilizers--fused phosphate (FP), 'fused and superphosphate' [FSP], and rock phosphate [RP]; P chemicals--Ca[H(2)PO(4)](2).H(2)O, [NH(4)](2)HPO(4), KH(2)PO(4), and K(2)HPO(4)) were selected for the test. The selected P source was mixed with Cd-contaminated soil at the rate of 0, 200, 400, 800, and 1,600 mg P kg(-1) under controlled moisture conditions at 70% of water holding capacity, then incubated for 8 weeks. FP, Ca(H(2)PO(4))(2) H(2)O, KH(2)PO(4), and K(2)HPO(4) significantly decreased NH(4)OAc-extractable Cd (plant-available form) concentrations with increasing application rates. Compared to other phosphate materials used, K(2)HPO(4) was found to be the most effective in reducing the plant-available Cd concentration in soil, mainly due to the negative charge increase caused by soil pH and phosphate adsorption. Contrary to the general information, FSP and (NH(4))(2)HPO(4) increased Cd extractability at low levels of P application (<400 mg kg(-1)), and thereafter Cd extractability decreased significantly with increasing application rate. RP scarcely had an effect on reducing Cd extractability. Ion activity products of CdHPO(4), Cd(OH)(2), and CdCO(3) analyzed by the MINTEQ program were significantly increased by K(2)HPO(4) addition, but the effect of Cd-P compound formation on reducing Cd extractability was negligible. Conclusively, the P-induced alleviation of Cd extractability can be attributed primarily to Cd immobilization due to the increase in soil pH and negative charge rather than Cd-P precipitation, and therefore, alkaline P materials such as K(2)HPO(4) are effective for immobilizing soil Cd.

Effects of oyster shell on soil chemical and biological properties and cabbage productivity as a liming materials.

Oyster shell, a byproduct of shellfish-farming in Korea and containing a high amount of CaCO(3), has a high potential to be used as a liming material in agriculture. However, the agricultural utilization of oyster shell is limited due to its high concentration NaCl. The oyster-shell meal collected had a low concentration of water soluble NaCl (mean 2.7 g kg(-1)), which might be a result of stacking the material for 6 months in the open field. It has a very similar liming potential with calcium carbonate, with 3.4 and 3.8 Mg ha(-1) for silt loam (SiL, pH 6.2) and sandy loam (SL, pH 5.8) to bring the soil pH to 6.5, respectively. To determine the effect of crushed oyster-shell meal on improving soil chemical and biological properties and crop plant productivity, oyster-shell meal was applied at rates of 0, 4, 8, 12, and 16 Mg ha(-1) before transplanting Chinese cabbage (Brassica campestris L.) in the two soils mentioned above. Soil pH was significantly increased to 6.9 and 7.4 by 16 Mg ha(-1) shell meal application (4 times higher level than the recommendation) in SiL and SL, respectively, at harvesting stage. The effect of liming was found higher in SL compared to SiL soil, probably due to the different buffering capacity of the two soils. The concentration of NaCl and EC value of soils were found slightly increased with shell meal applications, but no salt damage was observed. Oyster-shell meal application increased soil organic matter, available P, and exchangeable cations concentrations. The improved soil pH and nutrient status significantly increased the microbial biomass C and N concentrations and stimulated soil enzyme activities. With the exception of acid phosphomonoesterase (PMEase) activity, which decreased with increasing soil pH in SL but slightly increased in SiL, the activities of urease and alkali PMEase increased markedly with increasing soil pH by shell meal application. The improved soil chemical and biological properties resulted in increased crop productivity. The highest yield in Chinese cabbage was achieved following the application of 8 Mg ha(-1) oyster-shell meal. Conclusively, crushed oyster shell could be used as an alternative liming material to restore the soil chemical and microbial properties in upland soil and to increase crop productivity.

Feasibility of phosphate fertilizer to immobilize cadmium in a field.

To reduce effectively cadmium (Cd) phytoextractability by phosphate fertilizer in Cd contaminated soil, fused and superphosphate (FSP) was applied at the rate of 0, 33.5 (recommendation level), 167.5, and 335 kg P ha(-1) for radish (Raphanus sativa L.). Unlike from what we expected, soil Cd extractability and Cd concentration in radish increased with increasing FSP application in the field. To determine the effect of FSP on Cd immobilization, FSP was mixed with the selected soil at the rate of 0, 200, 400, 800, and 1600 mg P kg(-1) and then incubated for 8 weeks. As observed in the field study, NH(4)OAc extractable Cd concentration increased slightly with FSP addition up to 400 mg P kg(-1) and thereafter dramatically decreased upon increasing its application rate. Soil pH and negative charge were decreased at low level of FSP application up to 400 mg P kg(-1), but thereafter continually increased with increasing application level. This could be indirect evidence that net soil negative charge was increased by the specific adsorption of phosphate at the high rate of FSP application over 400 mg P kg(-1). The labile Cd fraction (water soluble and exchangeable+acidic fraction) increased with increasing FSP application by 400 mg P kg(-1) and thereafter gradually decreased with corresponding increase in unlabile fraction (oxidizable and residual fraction). Based on these results, FSP might be applied with a very high rate over 800 mg P kg(-1) to decrease Cd extractability in the selected field. However, this level is equivalent to 1440 kg P ha(-1), which is about 43 times higher than the recommendation levels for radish production and resulted in a significant increase in water soluble P concentration creating a new environmental problem. Therefore, the feasibility of FSP to reduce Cd extractability in the field is very low.

Liming effects on cadmium stabilization in upland soil affected by gold mining activity.

To reduce cadmium (Cd) uptake of plants cultivated in heavy metal-contaminated soil, the best liming material was selected in the incubation test. The effect of the selected material was evaluated in the field. In the incubation experimentation, CaCO(3), Ca(OH)(2), CaSO(4).2H(2)O, and oyster shell meal were mixed with soil at rates corresponding to 0, 400, 800, 1600, 3200 mg Ca kg(-1). The limed soil was moistened to 70% of field moisture capacity, and incubated at 25 degrees C for 4 weeks. Ca(OH)(2) was found to be more efficient on reducing soil NH(4)OAc extractable Cd concentration, due to pH increase induced net negative charge. The selected Ca(OH)(2) was applied at rates 0, 2, 4, 8 Mg ha(-1) and then cultivated radish (Raphanus sativa L.) in the field. NH(4)OAc extractable Cd concentration of soil and plant Cd concentration decreased significantly with increasing Ca(OH)(2) rate, since alkaline-liming material markedly increased net negative charge of soil induced by pH increase, and decreased bioavailable Cd fractions (exchangeable + acidic and reducible Cd fraction) during radish cultivation. Cadmium uptake of radish could be reduced by about 50% by amending with about 5 Mg ha(-1) Ca(OH)(2) without adverse effect on radish yield and growth. The increase of net negative charge of soil by Ca(OH)(2) application may suppress Cd uptake and the competition between Ca(2+) and Cd(2+) may additionally affect the suppression of Cd uptake.