Photovoltaic & Optoelectronic Device Group

Abstract:

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%.

Abstract:

Silver‐bismuth‐based perovskite‐inspired materials (PIMs) are increasingly being explored as non‐toxic materials in photovoltaic applications. However, many of these materials exhibit an ultrafast localization of photogenerated charge carriers that is detrimental for charge‐carrier extraction. In this work, such localization processes are explored for thermally evaporated thin films of compositions lying along the (AgI)x(BiI3)y series, namely BiI3, AgBi2I7, AgBiI4, Ag2BiI5, Ag3BiI6, and AgI, to investigate the impact of changing Ag+/Bi3+ content. A persistent presence of ultrafast charge‐carrier localization in all mixed compositions and BiI3, together with unusually broad photoluminescence spectra, reveal that eliminating silver will not suppress the emergence of a localized state. A weak change in electronic bandgap and charge‐carrier mobility reveals the resilience of the electronic band structure upon modifications in the Ag+/Bi3+ composition of the mixed‐metal rudorffites. Instead, chemical composition impacts the charge‐carrier dynamics indirectly via structural alterations: Ag‐deficient compositions demonstrate stronger charge‐carrier localization most likely because a higher density of vacant sites in the cationic sublattice imparts enhanced lattice softness. Unraveling such delicate interplay between chemical composition, crystal structure, and charge‐carrier dynamics in (AgI)x(BiI3)y rudorffites provides crucial insights for developing a material‐by‐design approach in the quest for highly efficient Bi‐based PIMs.

Abstract:

Light-emitting diodes (LEDs) based on perovskite quantum dots (QDs) have produced external quantum efficiencies (EQEs) of more than 25% with narrowband emission1,2, but these LEDs have limited operating lifetimes. We posit that poor long-range ordering in perovskite QD films—variations in dot size, surface ligand density and dot-to-dot stacking—inhibits carrier injection, resulting in inferior operating stability because of the large bias required to produce emission in these LEDs. Here we report a chemical treatment to improve the long-range order of perovskite QD films: the diffraction intensity from the repeating QD units increases three-fold compared with that of controls. We achieve this using a synergistic dual-ligand approach: an iodide-rich agent (aniline hydroiodide) for anion exchange and a chemically reactive agent (bromotrimethylsilane) that produces a strong acid that in situ dissolves smaller QDs to regulate size and more effectively removes less conductive ligands to enable compact, uniform and defect-free films. These films exhibit high conductivity (4 × 10−4 S m−1), which is 2.5-fold higher than that of the control, and represents the highest conductivity recorded so far among perovskite QDs. The high conductivity ensures efficient charge transportation, enabling red perovskite QD-LEDs that generate a luminance of 1,000 cd m−2 at a record-low voltage of 2.8 V. The EQE at this luminance is more than 20%. Furthermore, the stability of the operating device is 100 times better than previous red perovskite LEDs at EQEs of more than 20%.

Abstract:

Inverted (pin) perovskite solar cells (PSCs) afford improved operating stability in comparison to their nip counterparts but have lagged in power conversion efficiency (PCE). The energetic losses responsible for this PCE deficit in pin PSCs occur primarily at the interfaces between the perovskite and the charge-transport layers. Additive and surface treatments that use passivating ligands usually bind to a single active binding site: This dense packing of electrically resistive passivants perpendicular to the surface may limit the fill factor in pin PSCs. We identified ligands that bind two neighboring lead(II) ion (Pb2+) defect sites in a planar ligand orientation on the perovskite. We fabricated pin PSCs and report a certified quasi–steady state PCE of 26.15 and 24.74% for 0.05– and 1.04–square centimeter illuminated areas, respectively. The devices retain 95% of their initial PCE after 1200 hours of continuous 1 sun maximum power point operation at 65°C.

Abstract:

Metal halide perovskites are promising light absorbers for multijunction photovoltaic applications because of their remarkable bandgap tunability, achieved through compositional mixing on the halide site. However, poor energy-level alignment at the interface between wide-bandgap mixed-halide perovskites and charge-extraction layers still causes significant losses in solar-cell performance. Here, the origin of such losses is investigated, focusing on the energy-level misalignment between the valence band maximum and the highest occupied molecular orbital (HOMO) for a commonly employed combination, FA_0.83Cs_0.17Pb(I_1-xBr_x)₃ with bromide content x ranging from 0 to 1, and poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA). A combination of time-resolved photoluminescence spectroscopy and numerical modeling of charge-carrier dynamics reveals that open-circuit voltage (V_OC) losses associated with a rising energy-level misalignment derive from increasing accumulation of holes in the HOMO of PTAA, which then subsequently recombine non-radiatively across the interface via interfacial defects. Simulations assuming an ideal choice of hole-transport material to pair with FA_0.83Cs_0.17Pb(I_1-xBr_x)₃ show that such V_OC losses originating from energy-level misalignment can be reduced by up to 70 mV. These findings highlight the urgent need for tailored charge-extraction materials exhibiting improved energy-level alignment with wide-bandgap mixed-halide perovskites to enable solar cells with improved power conversion efficiencies.