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The role of the alkali metal cations in halide perovskite solar cells is not well understood. Using synchrotron-based nano-x-ray fluorescence and complementary measurements, we found that the halide distribution becomes homogenized upon addition of cesium iodide, either alone or with rubidium iodide, for substoichiometric, stoichiometric, and overstoichiometric preparations, where the lead halide is varied with respect to organic halide precursors. Halide homogenization coincides with long-lived charge carrier decays, spatially homogeneous carrier dynamics (as visualized by ultrafast microscopy), and improved photovoltaic device performance. We found that rubidium and potassium phase-segregate in highly concentrated clusters. Alkali metals are beneficial at low concentrations, where they homogenize the halide distribution, but at higher concentrations, they form recombination-active second-phase clusters.

Silicon dominates contemporary solar cell technologies.sup.1. But when absorbing photons, silicon (like other semiconductors) wastes energy in excess of its bandgap.sup.2. Reducing these thermalization losses and enabling better sensitivity to light is possible by sensitizing the silicon solar cell using singlet exciton fission, in which two excited states with triplet spin character (triplet excitons) are generated from a photoexcited state of higher energy with singlet spin character (a singlet exciton).sup.3-5. Singlet exciton fission in the molecular semiconductor tetracene is known to generate triplet excitons that are energetically matched to the silicon bandgap.sup.6-8. When the triplet excitons are transferred to silicon they create additional electron-hole pairs, promising to increase cell efficiencies from the single-junction limit of 29 per cent to as high as 35 per cent.sup.9. Here we reduce the thickness of the protective hafnium oxynitride layer at the surface of a silicon solar cell to just eight angstroms, using electric-field-effect passivation to enable the efficient energy transfer of the triplet excitons formed in the tetracene. The maximum combined yield of the fission in tetracene and the energy transfer to silicon is around 133 per cent, establishing the potential of singlet exciton fission to increase the efficiencies of silicon solar cells and reduce the cost of the energy that they generate. A silicon and tetracene solar cell employing singlet fission uses an eight-angstrom-thick hafnium oxynitride interlayer to promote efficient triplet transfer, increasing the efficiency of the cell., Author(s): Markus Einzinger [sup.1] , Tony Wu [sup.1] , Julia F. Kompalla [sup.1] , Hannah L. Smith [sup.2] , Collin F. Perkinson [sup.1] , Lea Nienhaus [sup.1] , Sarah Wieghold [...]

Photon upconversion, particularly via triplet–triplet annihilation (TTA), could prove beneficial in expanding the efficiencies and overall impacts of optoelectronic devices across a multitude of technologies. The recent development of bulk metal halide perovskites as triplet sensitizers is one potential step toward the industrialization of upconversion-enabled devices. Here, we investigate the impact of varying additions of bromide into a lead iodide perovskite thin film on the TTA upconversion process in the annihilator molecule rubrene. We find an interplay between the bromide content and the overall device efficiency. In particular, a higher bromide content results in higher internal upconversion efficiencies enabled by more efficient charge extraction at the interface likely due to a more favorable band alignment. However, the external upconversion efficiency decreases as the absorption cross section in the near infrared is reduced. The highest upconversion performance is found in our study for a bromide content of 5%. This result can be traced back to a high absorption cross section in the near infrared and higher photoluminescence quantum yield in comparison to the iodide-only perovskite and an increased driving force for charge transfer. [ABSTRACT FROM AUTHOR]

Lead halide perovskites have emerged as promising absorber materials over the last decade to increase the efficiency of photovoltaics beyond its current limits. However, to further optimize the performance of perovskites more detailed studies need to be performed, which allow for the correlation of film morphology and local electronic properties at the nanoscale. Here, we present a scanning tunneling microscopy (STM) approach to probe the effect of an applied electric field of a methylammonium formamidinium lead triiodide perovskite thin film on the film response by current–voltage spectroscopy, current imaging tunneling spectroscopy, differential conductance mapping, and x-ray absorption spectroscopy by means of synchrotron x-ray STM. We find a strong correlation between the measurement conditions and the obtained current–voltage characteristics when imaging under opposite bias polarities. In particular, we find similarities to already observed poling effects for lead halide perovskites, which result in either a positively or negatively charged interface due to ion and vacancy migration. Our results provide insight into the influence of measurement conditions such as bias polarity on the performance assessment of perovskite thin films by STM. [ABSTRACT FROM AUTHOR]

Triplet–triplet annihilation-based photon upconversion (UC) using bulk perovskite sensitizers has been previously shown to facilitate efficient UC at low fluences. However, the fabrication of the UC devices has not been fully optimized; thus, there is room for improvement. Here, we apply techniques that have been successful in enhancing the performance of perovskite solar cells in order to also improve perovskite-sensitized UC devices. In particular, we investigate the use of a post-fabrication thermal annealing step, overstoichiometric vs stoichiometric addition of PbI2 to the perovskite precursors, methylammonium vs formamidinium cation-rich lead halide perovskite compositions, and the use of different solvents for the annihilator molecules on the perovskite/annihilator interface. We find that excess PbI2 does not significantly affect the UC process, while the perovskite composition is crucial for the yield of extracted carriers across the interface. Comparing toluene and chlorobenzene, we find that the solvent used to deposit the annihilator is also a key factor in the overall device performance. Moreover, we find that thermal annealing of the whole device architecture significantly improves the UC performance by a factor of three. [ABSTRACT FROM AUTHOR]

Ferroelectric nanomaterials are of interest in catalysis, nonvolatile memory, and neuromorphic computing among other applications because of their switchable structure that can alter the electronic and interface properties of a single material. The investigation of the role of polarization on the surface structure and chemistry of ferroelectric nanomaterials is a longstanding challenge, as it ideally requires a combination of both nanoscale imaging and chemical spectroscopy. In this work, we study a model ferroelectric BaTiO3 thin film by synchrotron X-ray scanning tunneling microscopy (SX-STM), a unique method that integrates nanoscale surface imaging and chemically sensitive spectroscopy. We find that polarization switching from downward to upward in (001) single-crystalline BaTiO3 thin films increases the intensity of X-ray absorption across Ba M, Ti L, and O K edges. Chemical mapping of nanometer-sized domains further demonstrates the modulation of surface structures upon polarization switching, as well as confirming the trends observed in single-point experiments across the surface. We complement these measurements with ab initio computational absorption spectroscopy to elucidate the effect of polarization switching on the core–hole excitations using the Bethe–Salpeter equation approach. Our experimental and theoretical results thus confirm a stronger binding strength for the upward-polarized surface with molecular O2 as a model reactant, offering mechanistic evidence that supports previous reports. This work advances the understanding of the surface chemistry and electronic structure of ferroelectrics, which can ultimately aid strategies to design interfaces with tailored properties. [ABSTRACT FROM AUTHOR]

Triplet–triplet annihilation‐based photon upconversion (TTA‐UC) can efficiently generate higher energy photons at low relative fluences. Bulk metal halide perovskites have offered promise in efficiently sensitizing molecular triplet states in the solid state, necessary for the integration of TTA‐UC into device‐based applications. Recent work focused on TTA‐UC from a rubrene triplet annihilator sensitized by perovskite thin films has established relatively efficient charge extraction from the perovskite, forming the triplet exciton in rubrene. Yet, the specifics underpinning charge transfer at the perovskite/rubrene interface are not fully elucidated. To improve device performance and study the properties governing charge transfer at the interface, various organic solvents are explored to treat the perovskite surface. Scanning tunneling microscopy and spectroscopy show a difference in the electronic band structure, where both n‐ and p‐type terminated perovskite surfaces are observed depending on the solvent used. Supported by optical spectroscopy, the impact of the perovskite electronic structure is monitored, indicating that n‐type perovskite sensitizers feature higher TTA‐UC efficiencies due to favorable band bending resulting in efficient hole‐mediated triplet formation. Overall, the tuning of the electronic structure of the perovskite sensitizer through solvent treatment is shown to be a key force in tuning the mechanism of efficient triplet generation. [ABSTRACT FROM AUTHOR]