Progress and applications of (Cu–)Ag–Bi–I semiconductors, and their derivatives, as next-generation lead-free materials for photovoltaics, detectors and memristors

The search for efficient but inexpensive photovoltaics over the past decade has been disrupted by the advent of lead-halide perovskite solar cells. Despite impressive rises in performance, the toxicity and stability concerns of these materials have prompted a broad, interdisciplinary community across the world to search for lead-free and stable alternatives. A set of such materials that have recently gained attention are semiconductors in the CuI–AgI–BiI3 phase space and their derivatives. These materials include ternary silver bismuth iodide compounds (AgaBibIa+3b), ternary copper bismuth iodide Cu–Bi–I compounds and quaternary Cu–Ag–Bi–I materials, as well as analogues with Sb substituted into the Bi site and Br into the I site. These compounds are comprised of a cubic close-packed sub-lattice of I, with Ag and Bi occupying octahedral holes, while Cu occupies tetrahedral holes. The octahedral motifs adopted by these compounds are either spinel, CdCl2-type, or NaVO2-type. NaVO2-type AgaBibIa+3b compounds are also known as rudorffites. Many of these compounds have thus far demonstrated improved stability and reduced toxicity compared to halide perovskites, along with stable bandgaps in the 1.6–1.9 eV range, making them highly promising for energy harvesting and detection applications. This review begins by discussing the progress in the development of these semiconductors over the past few years, focusing on their optoelectronic properties and process–property–structure relationships. Next, we discuss the progress in developing Ag–Bi–I and Cu–Bi–I compounds for solar cells, indoor photovoltaics, photodetectors, radiation detectors and memristors. We conclude with a discussion of the critical fundamental questions that need to be addressed to push this area forward, and how the learnings from the wider metal-halide semiconductor field can inform future directions

Air-stable bismuth sulfobromide (BiSBr) visible-light absorbers : optoelectronic properties and potential for energy harvesting

ns2 compounds have recently attracted considerable interest due to their potential to replicate the defect tolerance of lead-halide perovskites and overcome their toxicity and stability limitations. However, only a handful of compounds beyond the perovskite family have been explored thus far. Herein, we investigate bismuth sulfobromide (BiSBr), which is a quasi-one-dimensional semiconductor, but very little is known about its optoelectronic properties or how it can be processed as thin films. We develop a solution processing route to achieve phase-pure, stoichiometric BiSBr films (ca. 240 nm thick), which we show to be stable in ambient air for over two weeks without encapsulation. The bandgap (1.91 ± 0.06 eV) is ideal for harvesting visible light from common indoor light sources, and we calculate the optical limit in efficiency (i.e., spectroscopic limited maximum efficiency, SLME) to be 43.6% under 1000 lux white light emitting diode illumination. The photoluminescence lifetime is also found to exceed the 1 ns threshold for photovoltaic absorber materials worth further development. Through X-ray photoemission spectroscopy and Kelvin probe measurements, we find the BiSBr films grown to be n-type, with an electron affinity of 4.1 ± 0.1 eV and ionization potential of 6.0 ± 0.1 eV, which are compatible with a wide range of established charge transport layer materials. This work shows BiSBr to hold promise for indoor photovoltaics, as well as other visible-light harvesting applications, such as photoelectrochemical cells, or top-cells for tandem photovoltaics

Comparative roles of upwelling and glacial iron sources in Ryder Bay, coastal western Antarctic Peninsula

Iron (Fe) is an essential micronutrient for phytoplankton, and is scarce in many regions including the open Southern Ocean. The western Antarctic Peninsula (WAP), an important source region of Fe to the wider Southern Ocean, is also the fastest warming region of the southern hemisphere. The relative importance of glacial versus marine Fe sources is currently poorly constrained, hindering projections of how changing oceanic circulation, productivity, and glacial dynamics may affect the balance of Fe sources in this region.Dissolved and total dissolvable Fe concentrations were measured throughout the summer bloom period at a coastal site on the WAP. Iron inputs to the surface mixed layer in early summer were strongly correlated with meteoric meltwater from glaciers and precipitation. A significant source of Fe from underlying waters was also identified, with dissolved Fe concentrations of up to 9.5 nM at 200 m depth. These two primary Fe sources act on different timescales, with glacial sources supplying Fe during the warm summer growing period, and deep water replenishing Fe over annual periods via deep winter mixing.Iron supply from deep water is sufficient to meet biological demand relative to macronutrient supply, making Fe limitation unlikely in this area even without additional summer Fe inputs from glacial sources. Both glacial and deep-water Fe sources may increase with continued climate warming, potentially enhancing the role of the WAP as an Fe source to offshore waters

Air-stable bismuth sulfobromide (BiSBr) visible-light absorbers: optoelectronic properties and potential for energy harvesting †

ns2 compounds have recently attracted considerable interest due to their potential to replicate the defect tolerance of lead-halide perovskites and overcome their toxicity and stability limitations. However, only a handful of compounds beyond the perovskite family have been explored thus far. Herein, we investigate bismuth sulfobromide (BiSBr), which is a quasi-one-dimensional semiconductor, but very little is known about its optoelectronic properties or how it can be processed as thin films. We develop a solution processing route to achieve phase-pure, stoichiometric BiSBr films (ca. 240 nm thick), which we show to be stable in ambient air for over two weeks without encapsulation. The bandgap (1.91 ± 0.06 eV) is ideal for harvesting visible light from common indoor light sources, and we calculate the optical limit in efficiency (i.e., spectroscopic limited maximum efficiency, SLME) to be 43.6% under 1000 lux white light emitting diode illumination. The photoluminescence lifetime is also found to exceed the 1 ns threshold for photovoltaic absorber materials worth further development. Through X-ray photoemission spectroscopy and Kelvin probe measurements, we find the BiSBr films grown to be n-type, with an electron affinity of 4.1 ± 0.1 eV and ionization potential of 6.0 ± 0.1 eV, which are compatible with a wide range of established charge transport layer materials. This work shows BiSBr to hold promise for indoor photovoltaics, as well as other visible-light harvesting applications, such as photoelectrochemical cells, or top-cells for tandem photovoltaics