Photovoltaic & Optoelectronic Device Group

Abstract:

Monolithic all-perovskite tandem solar cells (TSCs) offer a route beyond single-junction efficiency limits through band-gap engineering. However, stability is hampered by hygroscopic degradation and phase segregation of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), the most common hole-transport material for narrow band-gap subcells. Here, we investigate the interface-mediated crystallization dynamics in mixed tin-lead (Sn-Pb) perovskites through in situ studies. We find that solvent-underlayer synergetic interactions with PEDOT:PSS induce metastable phase segregation during crystallization. Replacing PEDOT:PSS with a phenothiazine-functionalized interface facilitates direct phase transition and achieves preferential (100) orientation, yielding high-quality perovskite films. This enables a single-junction narrow band-gap subcell with 23.2% efficiency. Furthermore, we apply a hybrid interlayer integrating thiol and phosphonic acid anchoring groups on SnO2/Au, achieving a dense interconnecting layer for monolithic all-perovskite TSCs with 29.1% efficiency. The device retains 90% of the initial efficiency over 800 h of maximum power point tracking under simulated 1-sun illumination at 40°C, demonstrating robust operational stability.

Abstract:

Robust interconnecting layers are critical for all-perovskite tandems but are typically limited by acidic poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) and interdiffusive gold, compromising stability. Here, we substitute PEDOT:PSS with a conjugated polyelectrolyte-modified bithiophene-triphenylamine small molecule as the hole transport layer for tin-lead perovskite subcells, ensuring superior hole extraction and interfacial robustness. The gold recombination junction is replaced with a 5-nm-thick sputtercoated indium-doped zinc oxide to eliminate metal diffusion and minimize parasitic absorption. This design yields certified efficiencies of 29.80% and 30.19% for double-junction tandems employing methylammonium (MA)-free and MA-containing narrow-band-gap subcells, respectively. Furthermore, 1.0-cm² devices and 11.3-cm² mini-modules show efficiencies up to 28.7% and 25.0%, respectively. Encouragingly, encapsulated tandems maintain 90% of their initial efficiency after over 770, 530, and 220 h of maximum power point tracking under illumination at 45^◦C, 65^◦C, and 85^◦C, respectively. This work presents a viable route beyond PEDOT:PSS for narrow-band-gap perovskites toward reliable all-perovskite tandem photovoltaics.

Abstract:

Carrier mobility, recombination rates and diffusion length directly govern the efficiency of hybrid lead-halide perovskites. Yet, their behavior across different carrier concentrations and the effects of microstructure remain poorly understood. Using time-resolved photoluminescence and optical pump-THz probe spectroscopy, we quantify mobility, carrier recombination rates and diffusion length for polycrystalline films of methylammonium (MA)- and formamidinium (FA)-rich lead-halide perovskites, across carrier concentrations ranging from ∼10¹⁵ to ∼10¹⁹ cm^-3. For example, at a carrier concentration of ∼10¹⁸ cm^-3, FA_0.95MA_0.05Pb(I_0.95Br_0.05)₃ exhibits a mobility of 127 ± 9 cm² V^-1 s^-1 and a diffusion length of 392 ± 85 nm, compared to 69 ± 1 cm² V^-1 s^-1 and 139 ± 1 nm for MAPbI₃. These differences in mobility and diffusion length persist across different fluences, and are captured by a fluence-dependent rate model that accounts for both carrier generation and recombination at different material depths. From scanning electron microscopy and THz time-domain spectroscopy measurements, we attribute the increased mobility and diffusion length for the FA-rich perovskite mainly to a larger average grain size, after considering possible Fröhlich-type interactions between carriers and THz-active phonon modes. Our work establishes a mechanistic link between material microstructure and ultrafast carrier dynamics, informing crucial design principles for perovskite-based photovoltaic and optoelectronic applications.

Abstract:

Long-term stability of the perovskite top cell remains a hurdle to commercializing perovskite–silicon tandem (PST) solar cells. While accelerated tests provide valuable insights into degradation kinetics, they fail in predicting real-world degradation behavior. Keeping stressors constant, accelerated tests neglect dynamic conditions in actual operational environments, like diurnal and seasonal temperature and irradiance variability. We address this challenge by integrating a degradation function into our energy yield (EY) modelling software which integrates degradation in collection efficiency (and thus photocurrent) over time due to light and heat exposure, bridging the gap between accelerated testing and in real-world stability assessment. By linking the EY model to measurable material parameters like activation energy governing degradation pathways, this approach enables physically grounded degradation modelling. Based on degradation observed under accelerated tests, the model predicts PST operational lifetimes in diverse climates, highlighting the substantial discrepancy between lifetimes measured under accelerated testing and real-world locations. Applied to a PST solar cell, we show that an operational lifetime (T90,Agg) of about 1400 h under ISOS-L2 (1 Sun, 85 °C), translates to several months in-field (about 26 months in arid Phoenix and 42 months in temperate Seattle), demonstrating strong climate dependence. We also provide a practical mapping from ISOS-L2 to real-world lifetimes and estimate the minimum stability threshold needed for deployment as around 4000 h T90,Agg under ISOS-L2, translating to more than 5 years of operation across the investigated locations. After device-specific parameterization from appropriate aging tests, this device-agnostic framework allows stability-aware EY modelling to predict real-world degradation.