Regulating surface potential maximizes voltage in all-perovskite tandems.

The open-circuit voltage (VOC) deficit in perovskite solar cells is greater in wide-bandgap (over 1.7 eV) cells than in perovskites of roughly 1.5 eV (refs. 1,2). Quasi-Fermi-level-splitting measurements show VOC-limiting recombination at the electron-transport-layer contact3-5. This, we find, stems from inhomogeneous surface potential and poor perovskite-electron transport layer energetic alignment. Common monoammonium surface treatments fail to address this; as an alternative, we introduce diammonium molecules to modify perovskite surface states and achieve a more uniform spatial distribution of surface potential. Using 1,3-propane diammonium, quasi-Fermi-level splitting increases by 90 meV, enabling 1.79 eV perovskite solar cells with a certified 1.33 V VOC and over 19% power conversion efficiency (PCE). Incorporating this layer into a monolithic all-perovskite tandem, we report a record VOC of 2.19 V (89% of the detailed balance VOC limit) and over 27% PCE (26.3% certified quasi-steady state). These tandems retained more than 86% of their initial PCE after 500 h of operation.

Suppressed phase segregation for triple-junction perovskite solar cells.

The tunable bandgaps and facile fabrication of perovskites make them attractive for multi-junction photovoltaics1,2. However, light-induced phase segregation limits their efficiency and stability3-5: this occurs in wide-bandgap (>1.65 electron volts) iodide/bromide mixed perovskite absorbers, and becomes even more acute in the top cells of triple-junction solar photovoltaics that require a fully 2.0-electron-volt bandgap absorber2,6. Here we report that lattice distortion in iodide/bromide mixed perovskites is correlated with the suppression of phase segregation, generating an increased ion-migration energy barrier arising from the decreased average interatomic distance between the A-site cation and iodide. Using an approximately 2.0-electron-volt rubidium/caesium mixed-cation inorganic perovskite with large lattice distortion in the top subcell, we fabricated all-perovskite triple-junction solar cells and achieved an efficiency of 24.3 per cent (23.3 per cent certified quasi-steady-state efficiency) with an open-circuit voltage of 3.21 volts. This is, to our knowledge, the first reported certified efficiency for perovskite-based triple-junction solar cells. The triple-junction devices retain 80 per cent of their initial efficiency following 420 hours of operation at the maximum power point.

Dicarboxylic Acid-Assisted Surface Oxide Removal and Passivation of Indium Antimonide Colloidal Quantum Dots for Short-Wave Infrared Photodetectors.

Heavy-metal-free III-V colloidal quantum dots (CQDs) are promising materials for solution-processed short-wave infrared (SWIR) photodetectors. Recent progress in the synthesis of indium antimonide (InSb) CQDs with sizes smaller than the Bohr exciton radius enables quantum-size effect tuning of the band gap. However, it has been challenging to achieve uniform InSb CQDs with band gaps below 0.9 eV, as well as to control the surface chemistry of these large-diameter CQDs. This has, to date, limited the development of InSb CQD photodetectors that are sensitive to ≥ ${\ge }$ 1400 nm light. Here we adopt solvent engineering to facilitate a diffusion-limited growth regime, leading to uniform CQDs with a band gap of 0.89 eV. We then develop a CQD surface reconstruction strategy that employs a dicarboxylic acid to selectively remove the native In/Sb oxides, and enables a carboxylate-halide co-passivation with the subsequent halide ligand exchange. We find that this strategy reduces trap density by half compared to controls, and enables electronic coupling among CQDs. Photodetectors made using the tailored CQDs achieve an external quantum efficiency of 25 % at 1400 nm, the highest among III-V CQD photodetectors in this spectral region.

Effects of intrinsic and atmospherically induced defects in narrow bandgap (FASnI3)x(MAPbI3)1-x perovskite films and solar cells.

Narrow bandgap mixed tin (Sn) + lead (Pb) perovskites are necessary for the bottom sub-cell absorber in high efficiency all-perovskite polycrystalline tandem solar cells. We report on the impact of mixed cation composition and atmospheric exposure of perovskite films on sub-gap absorption in films and performance of solar cells based on narrow bandgap mixed formamidinium (FA) + methylammonium (MA) and Sn + Pb halide perovskites, (FASnI3)x(MAPbI3)1-x. Structural and optical properties of 0.3 ≤ x ≤ 0.8 (FASnI3)x(MAPbI3)1-x perovskite thin film absorbers with bandgaps ranging from 1.25 eV (x = 0.6) to 1.34 eV (x = 0.3) are probed with and without atmospheric exposure. Urbach energy, which quantifies the amount of sub-gap absorption, is tracked for pristine perovskite films as a function of composition, with x = 0.6 and 0.3 demonstrating the lowest and highest Urbach energies of 23 meV and 36 meV, respectively. Films with x = 0.5 and 0.6 compositions show less degradation upon atmospheric exposure than higher or lower Sn-content films having greater sub-gap absorption. The corresponding solar cells based on the x = 0.6 absorber show the highest device performance. Despite having a low Urbach energy, higher Sn-content solar cells show reduced device performances as the amount of degradation via oxidation is the most substantial.

Methylammonium-Mediated Evolution of Mixed-Organic-Cation Perovskite Thin Films: A Dynamic Composition-Tuning Process.

Methylammonium-mediated phase-evolution behavior of FA1-x MAx PbI3 mixed-organic-cation perovskite (MOCP) is studied. It is found that by simply enriching the MOCP precursor solutions with excess methylammonium cations, the MOCPs form via a dynamic composition-tuning process that is key to obtaining MOCP thin films with superior properties. This simple chemical approach addresses several key challenges, such as control over phase purity, uniformity, grain size, composition, etc., associated with the solution-growth of MOCP thin films with targeted compositions.

Hot-Carrier Cooling Regulation for Mixed Sn-Pb Perovskite Solar Cells.

The rapid relaxation of hot carriers leads to energy loss in the form of heat and consequently restricts the theoretical efficiency of single-junction solar cells; However, this issue has not received much attention in tin-lead perovskites solar cells. Herein, tin(II) oxalate (SnC2O4) is introduced into tin-lead perovskite precursor solution to regulate hot-carrier cooling dynamics. The addition of SnC2O4 increases the length of carrier diffusion, extends the lifetime of carriers, and simultaneously slows down the cooling rate of carriers. Furthermore, SnC2O4 can bond with uncoordinated Sn2+ and Pb2+ ions to regulate the crystallization of perovskite and enable large grains. The strongly reducing properties of the C2O4 2- can inhibit the oxidation of Sn2+ to Sn4+ and minimize the formation of Sn vacancies in the resulting perovskite films. Additionally, as a substitute for tin(II) fluoride, the introduction of SnC2O4 avoids the carrier transport issues caused by the aggregation of F- ions at the interface. As a result, the SnC2O4-treated Sn-Pb cells show a champion efficiency of 23.36%, as well as 27.56% for the all-perovskite tandem solar cells. Moreover, the SnC2O4-treated devices show excellent long-term stability. This finding is expected to pave the way toward stable and highly efficient all-perovskite tandem solar cells.

Analysis of the relationship between drug susceptibility of Cryptococcus neoformans isolates and mortality in HIV-negative cryptococcal meningitis.

OBJECTIVES: The relationship between antifungal susceptibility and mortality of cryptococcal meningitis (CM) in HIV-negative patients is poorly understood. METHODS: We conducted a retrospective analysis of 1-year follow-up of 200 HIV-negative CM patients with an initial cerebrospinal fluid (CSF) culture for Cryptococcus neoformans. According to the cut-off values of minimum inhibitory concentration (MIC), two groups of five antifungal agents were classified: amphotericin B (AmB), ≤0.5 µg/mL, >0.5 µg/mL; 5-flucytosine (5-FC), ≤4 µg/mL, >4 µg/mL; fluconazole (FLU), ≤4 µg/mL, >4 µg/mL; itraconazole (ITR), ≤0.125 µg/mL, >0.125 µg/mL; and voriconazole (VOR), <0.25 µg/mL, ≥0.25 µg/mL. Comparisons were performed to analyse clinical features, laboratory, modified Rankin Scale (mRS) scores, and CSF findings under different prognosis outcomes in 1-year. RESULTS: All of Cryptococcus neoformans isolates were sensitive to AmB and VOR, most of them were sensitive to 5-FC and FLU (95.5% and 90.5%, respectively) while only 55.0% of them were susceptible to ITR. Minimum inhibitory concentrations of ITR and VOR were significantly related to baseline mRS scores. All-cause mortality was not significantly related to MICs in Cryptococcus neoformans strains. The combination of actual antifungal agents and two groups of the MICs values for antifungal agents had no significant effects on all-cause mortality. CONCLUSION: Most Cryptococcus neoformans isolates were sensitive to AmB, VOR, 5-FC, and FLU. Because of the small number of deaths, we are not able to comment on whether MIC is associated with mortality of CM in HIV-negative patients.

Sustainable thermal regulation improves stability and efficiency in all-perovskite tandem solar cells.

Mixed Sn-Pb perovskites have emerged as promising photovoltaic materials for both single- and multi-junction solar cells. However, achieving their scale-up and practical application requires further enhancement in stability. We identify that their poor thermal conductivity results in insufficient thermal transfer, leading to heat accumulation within the absorber layer that accelerates thermal degradation. A thermal regulation strategy by incorporating carboranes into perovskites is developed; these are electron-delocalized carbon-boron molecules known for their efficient heat transfer capability. We specifically select ortho-carborane due to its low thermal hysteresis. We observe its existence through the perovskite layer showing a decreasing trend from the buried interface to the top surface, effectively transferring heat and lowering the surface temperature by around 5 °C under illumination. o-CB also facilitates hole extraction at the perovskite/PEDOT:PSS interface and reduces charge recombination. These enable mixed Sn-Pb cells to exhibit improved thermal stability, retaining 80% of their initial efficiencies after aging at 85 °C for 1080 hours. When integrated into monolithic all-perovskite tandems, we achieve efficiencies of over 27%. A tandem cell maintains 87% of its initial PCE after 704 h of continuous operation under illumination.

The dynamic adsorption affinity of ligands is a surrogate for the passivation of surface defects.

Surface defects in semiconducting materials, though they have been widely studied, remain a prominent source of loss in optoelectronic devices; here we sought a new angle of approach, looking into the dynamic roles played by surface defects under atmospheric stressors and their chemical passivants in the lifetime of optoelectronic materials. We find that surface defects possess properties distinct from those of bulk defects. ab initio molecular dynamics simulations reveal a previously overlooked reversible degradation mechanism mediated by hydrogen vacancies. We find that dynamic surface adsorption affinity (DAA) relative to surface treatment ligands is a surrogate for passivation efficacy, a more strongly-correlated feature than is the static binding strength emphasized in prior reports. This guides us to design targeted passivator ligands with high molecular polarity: for example, 4-aminobutylphosphonic acid exhibits strong DAA and provides defect passivation applicable to a range of perovskite compositions, including suppressed hydrogen vacancy formation, enhanced photovoltaic performances and operational stability in perovskite solar cells.

Arresting Ion Migration from the ETL Increases Stability in Infrared Light Detectors Based on III-V Colloidal Quantum Dots.

III-V colloidal quantum dots (CQDs) are of interest in infrared photodetection, and recent developments in CQDs synthesis and surface engineering have improved performance. Here this work investigates photodetector stability, finding that the diffusion of zinc ions from charge transport layers (CTLs) into the CQDs active layer increases trap density therein, leading to rapid and irreversible performance loss during operation. In an effort to prevent this, this work introduces organic blocking layers between the CQDs and ZnO layers; but these negatively impact device performance. The device is then, allowing to use a C60:BCP as top electron-transport layer (ETL) for good morphology and process compatibility, and selecting NiOX as the bottom hole-transport layer (HTL). The first round of NiOX -based devices show efficient light response but suffer from high leakage current and a low open-circuit voltage (Voc) due to pinholes. This work introduces poly[bis(4-phenyl) (2,4,6-trimethylphenyl)amine] (PTAA) with NiOX NC to form a hybrid HTL, an addition that reduces pinhole formation, interfacial trap density, and bimolecular recombination, enhancing carrier harvesting. The photodetectors achieve 53% external quantum efficiency (EQE) at 970 nm at 1 V applied bias, and they maintain 95% of initial performance after 19 h of continuous illuminated operation. The photodetectors retain over 80% of performance after 80 days of shelf storage.

Rational design of Lewis base molecules for stable and efficient inverted perovskite solar cells.

Lewis base molecules that bind undercoordinated lead atoms at interfaces and grain boundaries (GBs) are known to enhance the durability of metal halide perovskite solar cells (PSCs). Using density functional theory calculations, we found that phosphine-containing molecules have the strongest binding energy among members of a library of Lewis base molecules studied herein. Experimentally, we found that the best inverted PSC treated with 1,3-bis(diphenylphosphino)propane (DPPP), a diphosphine Lewis base that passivates, binds, and bridges interfaces and GBs, retained a power conversion efficiency (PCE) slightly higher than its initial PCE of ~23% after continuous operation under simulated AM1.5 illumination at the maximum power point and at ~40°C for >3500 hours. DPPP-treated devices showed a similar increase in PCE after being kept under open-circuit conditions at 85°C for >1500 hours.

Perovskite Solar Cells Go Bifacial-Mutual Benefits for Efficiency and Durability.

Bifacial solar cells hold the potential to achieve a higher power output per unit area than conventional monofacial devices without significantly increasing manufacturing costs. However, efficient bifacial designs are challenging to implement in inorganic thin-film solar cells because of their short carrier lifetimes and high rear surface recombination. The emergence of perovskite photovoltaic (PV) technology creates a golden opportunity to realize efficient bifacial thin-film solar cells, owing to their outstanding optoelectronic properties and unique features of device physics. More importantly, transparent conducting oxide electrodes can prevent electrode corrosion by halide ions, mitigating one major instability issue of the perovskite devices. Here, the theory of bifacial PV devices is summarized and the advantages of bifacial perovskite solar cells, such as high power output, enhanced device durability, and low economic and environmental costs, are reviewed. The limitations and challenges for bifacial perovskite solar cells are also discussed. Finally, the awareness of bifacial solar cells as a feasible commercialization pathway of perovskite PV for mainstream solar power generation and building-integrated PV is advocated and future research directions are suggested.

Urbach Energy and Open-Circuit Voltage Deficit for Mixed Anion-Cation Perovskite Solar Cells.

The Urbach energy indicating the width of the exponentially decaying sub-bandgap absorption tail is commonly used as the indicator of electronic quality of thin-film materials used as absorbers in solar cells. Urbach energies of hybrid inorganic-organic metal halide perovskites with various anion-cation compositions are measured by photothermal deflection spectroscopy. The variation in anion-cation composition has a substantial effect on the measured Urbach energy and hence the electronic quality of the perovskite. Depending upon the compositions, the Urbach energy varies from 18 to 65 meV for perovskite films with similar bandgap energies. For most of the perovskite compositions studied here including methylammonium (MA) + formamidinium (FA)-based Pb iodides, mixed Sn + Pb narrow-bandgap perovskites with low or intermediate Sn contents, and wide-bandgap FA + Cs- and I + Br-based perovskites, the correlation between the Urbach energy of the perovskite thin film and open-circuit voltage (VOC) deficit for corresponding solar cells shows a direct relationship with reduction of the Urbach energy occurring with a beneficial decrease in the VOC deficit. However, due to issues related to material quality, impurity phases and stability in laboratory ambient air, and unoptimized film processing techniques, the solar cells incorporating Cs-based inorganic and mixed Sn + Pb perovskites with a higher than optimum Sn content show a higher VOC deficit even though the corresponding films show a lower Urbach energy.

Optical and Electronic Losses Arising from Physically Mixed Interfacial Layers in Perovskite Solar Cells.

Perovskite solar cell device performance is affected by optical and electronic losses. To minimize these losses in solar cells, it is important to identify their sources. Here, we report the optical and electronic losses arising from physically mixed interfacial layers between the adjacent component materials in highly efficient two terminal (2T) all-perovskite tandem, single-junction wide-bandgap, and single-junction narrow-bandgap perovskite-based solar cells. Physically mixed interfacial layers as the sources of optical and electronic losses are identified from spectroscopic ellipsometry measurements and data analysis followed by comparisons of simulated and measured external quantum efficiency spectra. Parasitic absorbance in the physically mixed regions between silver metal electrical contacts and electron transport layers (ETLs) near the back contact and a physical mixture of commercial indium tin oxide and hole transport layers (HTL) near the front electrical contact lead to substantial optical loss. A lower-density void + perovskite nucleation layer formed during perovskite deposition at the interface between the perovskite absorber layer and the HTL causes electronic losses because of incomplete collection of photogenerated carriers likely originating from poor coverage and passivation of the initially nucleating grains.

Correlating Hysteresis and Stability with Organic Cation Composition in the Two-Step Solution-Processed Perovskite Solar Cells.

The two-step solution-based process has demonstrated substantial success in fabricating high-efficiency perovskite solar cells in recent years. Despite the high performance, the underlying mechanisms that govern the formation of perovskite films and corresponding device performance are yet to be fully understood. Particularly, organic cation composition used in the two-step solution processing of mixed-cation lead halide perovskite solar cells plays a critical role in the perovskite film formation and the resultant device performance. However, little is understood about the impacts of organic cation composition on the current density-voltage (J-V) hysteretic behavior and stability of perovskite solar cells. To address this need, here, we study the effect of mixed organic cations, that is, the fraction of formamidinium (FA) and methylammonium (MA) contents, used for the two-step solution-processed perovskite thin films on solar cell performance, including efficiency, J-V hysteresis, and stability. In addition to the efficiency variations, we find that perovskite solar cells based on FA-rich and MA-rich stoichiometries show distinct characteristics in J-V hysteresis and stability. The origins of such a discrepancy are attributed to the thermodynamically driven conversion from lead iodide to perovskites, which is determined by the combination of organic cations. The perovskite solar cells based on the mixed cation FA0.6MA0.4PbI3 composition show a champion power conversion efficiency of over 21% and robust stability (retaining more than 90% of initial efficiency) under maximum power-point tracking in dry nitrogen for more than 500 h. Our work provides insights on understanding the formation of perovskite films in the two-step process, which may benefit further investigation on perovskite solar cells.