Bandgap-universal passivation enables stable perovskite solar cells with low photovoltage loss.

The efficiency and longevity of metal-halide perovskite solar cells are typically dictated by nonradiative defect-mediated charge recombination. In this work, we demonstrate a vapor-based amino-silane passivation that reduces photovoltage deficits to around 100 millivolts (>90% of the thermodynamic limit) in perovskite solar cells of bandgaps between 1.6 and 1.8 electron volts, which is crucial for tandem applications. A primary-, secondary-, or tertiary-amino-silane alone negatively or barely affected perovskite crystallinity and charge transport, but amino-silanes that incorporate primary and secondary amines yield up to a 60-fold increase in photoluminescence quantum yield and preserve long-range conduction. Amino-silane-treated devices retained 95% power conversion efficiency for more than 1500 hours under full-spectrum sunlight at 85°C and open-circuit conditions in ambient air with a relative humidity of 50 to 60%.

Bandlike Transport and Charge-Carrier Dynamics in BiOI Films.

Following the emergence of lead halide perovskites (LHPs) as materials for efficient solar cells, research has progressed to explore stable, abundant, and nontoxic alternatives. However, the performance of such lead-free perovskite-inspired materials (PIMs) still lags significantly behind that of their LHP counterparts. For bismuth-based PIMs, one significant reason is a frequently observed ultrafast charge-carrier localization (or self-trapping), which imposes a fundamental limit on long-range mobility. Here we report the terahertz (THz) photoconductivity dynamics in thin films of BiOI and demonstrate a lack of such self-trapping, with good charge-carrier mobility, reaching ∼3 cm2 V-1 s-1 at 295 K and increasing gradually to ∼13 cm2 V-1 s-1 at 5 K, indicative of prevailing bandlike transport. Using a combination of transient photoluminescence and THz- and microwave-conductivity spectroscopy, we further investigate charge-carrier recombination processes, revealing charge-specific trapping of electrons at defects in BiOI over nanoseconds and low bimolecular band-to-band recombination. Subject to the development of passivation protocols, BiOI thus emerges as a superior light-harvesting semiconductor among the family of bismuth-based semiconductors.

Revealing Ultrafast Charge-Carrier Thermalization in Tin-Iodide Perovskites through Novel Pump-Push-Probe Terahertz Spectroscopy.

Tin-iodide perovskites are an important group of semiconductors for photovoltaic applications, promising higher intrinsic charge-carrier mobilities and lower toxicity than their lead-based counterparts. Controllable tin vacancy formation and the ensuing hole doping provide interesting opportunities to investigate dynamic intraband transitions of charge carriers in these materials. Here, we present for the first time an experimental implementation of a novel Optical-Pump-IR-Push-THz-Probe spectroscopic technique and demonstrate its suitability to investigate the intraband relaxation dynamics of charge carriers brought into nonequilibrium by an infrared "push" pulse. We observe a push-induced decrease of terahertz conductivity for both chemically- and photodoped FA0.83Cs0.17SnI3 thin films and show that these effects derive from stimulated THz emission. We use this technique to reveal that newly photogenerated charge carriers relax within the bands of FA0.83Cs0.17SnI3 on a subpicosecond time scale when a large, already fully thermalized (cold) population of charge-carriers is present. Such rapid dissipation of the initial charge-carrier energy suggests that the propensity of tin halide perovskites toward unintentional self-doping resulting from tin vacancy formation makes these materials less suited to implementation in hot-carrier solar cells than their lead-based counterparts.

Optoelectronic Properties of Tin-Lead Halide Perovskites.

Mixed tin-lead halide perovskites have recently emerged as highly promising materials for efficient single- and multi-junction photovoltaic devices. This Focus Review discusses the optoelectronic properties that underpin this performance, clearly differentiating between intrinsic and defect-mediated mechanisms. We show that from a fundamental perspective, increasing tin fraction may cause increases in attainable charge-carrier mobilities, decreases in exciton binding energies, and potentially a slowing of charge-carrier cooling, all beneficial for photovoltaic applications. We discuss the mechanisms leading to significant bandgap bowing along the tin-lead series, which enables attractive near-infrared bandgaps at intermediate tin content. However, tin-rich stoichiometries still suffer from tin oxidation and vacancy formation which often obscures the fundamentally achievable performance, causing high background hole densities, accelerating charge-carrier recombination, lowering charge-carrier mobilities, and blue-shifting absorption onsets through the Burstein-Moss effect. We evaluate impacts on photovoltaic device performance, and conclude with an outlook on remaining challenges and promising future directions in this area.

Charge-Carrier Trapping Dynamics in Bismuth-Doped Thin Films of MAPbBr3 Perovskite.

Successful chemical doping of metal halide perovskites with small amounts of heterovalent metals has attracted recent research attention because of its potential to improve long-term material stability and tune absorption spectra. However, some additives have been observed to impact negatively on optoelectronic properties, highlighting the importance of understanding charge-carrier behavior in doped metal halide perovskites. Here, we present an investigation of charge-carrier trapping and conduction in films of MAPbBr3 perovskite chemically doped with bismuth. We find that the addition of bismuth has no effect on either the band gap or exciton binding energy of the MAPbBr3 host. However, we observe a substantial enhancement of electron-trapping defects upon bismuth doping, which results in an ultrafast charge-carrier decay component, enhanced infrared emission, and a notable decrease of charge-carrier mobility. We propose that such defects arise from the current approach to Bi-doping through addition of BiBr3, which may enhance the presence of bromide interstitials.