Krzysztof Galkowski

Determination of the exciton binding energy and effective masses for methylammonium and formamidinium lead tri-halide perovskite semiconductors

The family of organic–inorganic halide perovskite materials has generated tremendous interest in the field of photovoltaics due to their high power conversion efficiencies. There has been intensive development of cells based on the archetypal methylammonium (MA) and recently introduced formamidinium (FA) materials, however, there is still considerable controversy over their fundamental electronic properties. Two of the most important parameters are the binding energy of the exciton (R*) and its reduced effective mass μ. Here we present extensive magneto optical studies of Cl assisted grown MAPbI3 as well as MAPbBr3 and the FA based materials FAPbI3 and FAPbBr3. We fit the excitonic states as a hydrogenic atom in magnetic field and the Landau levels for free carriers to give R* and μ. The values of the exciton binding energy are in the range 14–25 meV in the low temperature phase and fall considerably at higher temperatures for the tri-iodides, consistent with free carrier behaviour in all devices made from these materials. Both R* and μ increase approximately proportionally to the band gap, and the mass values, 0.09–0.117m0, are consistent with a simple k.p perturbation approach to the band structure which can be generalized to predict values for the effective mass and binding energy for other members of this perovskite family of materials.

Excitons in atomically thin black phosphorus

Raman scattering and photoluminescence spectroscopy are used to investigate the optical properties of single layer black phosphorus obtained by mechanical exfoliation of bulk crystals under an argon atmosphere. The Raman spectroscopy, performed in situ on the same flake as the photoluminescence measurements, demonstrates the single layer character of the investigated samples. The emission spectra, dominated by excitonic effects, display the expected in plane anisotropy. The emission energy depends on the type of substrate on which the flake is placed due to the different dielectric screening. Finally, the blue shift of the emission with increasing temperature is well described using a two oscillator model for the temperature dependence of the band gap.

Unraveling the Exciton Binding Energy and the Dielectric Constant in Single-Crystal Methylammonium Lead Triiodide Perovskite

We have accurately determined the exciton binding energy and reduced mass of single crystals of methylammonium lead triiodide using magneto-reflectivity at very high magnetic fields. The single crystal has excellent optical properties with a narrow line width of ∼3 meV for the excitonic transitions and a 2s transition that is clearly visible even at zero magnetic field. The exciton binding energy of 16 ± 2 meV in the low-temperature orthorhombic phase is almost identical to the value found in polycrystalline samples, crucially ruling out any possibility that the exciton binding energy depends on the grain size. In the room-temperature tetragonal phase, an upper limit for the exciton binding energy of 12 ± 4 meV is estimated from the evolution of 1s-2s splitting at high magnetic field.

The Impact of Phase Retention on the Structural and Optoelectronic Properties of Metal Halide Perovskites

The extent to which the soft structural properties of metal halide perovskites affect their optoelectronic properties is unclear. X-ray diffraction and micro-photoluminescence measurements are used to show that there is a coexistence of both tetragonal and orthorhombic phases through the low-temperature phase transition, and that cycling through this transition can lead to structural changes and enhanced optoelectronic properties.

Impact of microstructure on the electron–hole interaction in lead halide perovskites

Despite the remarkable progress in the performance of devices based on the lead halide perovskite semiconductor family, there is still a lack of consensus on their fundamental photophysical properties. Here, using magneto-optical transmission spectroscopy we elucidate the impact of the microstructure on the Coulomb interaction between photo-created electron–hole pairs in methylammonium lead triiodide (MAPbI3) and the triple-cation lead mixed-halide composition, Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3 (Cs: cesium, MA: methylammonium, FA: formamidinium) by investigating thin films with a wide range of grain sizes from tens of nanometers to microns. At low temperatures, in which thermal fluctuations of the interactions are frozen and the rotational disorder of the organic cation is negligible, the exciton binding energy and reduced effective mass of carriers remain effectively unchanged with grain size. We conclude that the microstructure plays a negligible role in the Coulomb interaction of the photo-created electron–hole pairs, in contrast to previous reports. This renewed understanding of the relationship between these fundamental electronic properties and the microstructure is critical for future fundamental studies and improving device design.

Onset of exciton-exciton annihilation in single-layer black phosphorus

The exciton dynamics in monolayer black phosphorus is investigated over a very wide range of photoexcited exciton densities using time resolved photoluminescence. At low excitation densities, the exciton dynamics is successfully described in terms of a double exponential decay. With increasing exciton population, a fast, non-exponential component develops as exciton-exciton annihilation takes over as the dominant recombination mechanism under high excitation conditions. Our results identify an upper limit for the injection density, after which exciton-exciton annihilation reduces the quantum yield, which will significantly impact the performance of light emitting devices based on single layer black phosphorus.

Single-color, in situ photolithography marking of individual CdTe/ZnTe quantum dots containing a single Mn2+ ion

A simple, single-color method for permanent marking of the position of individual self-assembled semiconductor Quantum Dots (QDs) at cryogenic temperatures is reported. The method combines in situ photolithography with standard micro-photoluminescence spectroscopy. Its utility is proven by a systematic magnetooptical study of a single CdTe/ZnTe QD containing a Mn2+ ion, where a magnetic field of up to 10 T in two orthogonal, Faraday and Voigt, configurations is applied to the same QD. The presented approach can be applied to a wide range of solid state nanoemitters.

Modification of Emission Properties of ZnO Layers due to Plasmonic Near-Field Coupling to Ag Nanoislands.

A simple fabrication method of silver (Ag) nanoislands on ZnO films is presented. Continuous wave and time-resolved photoluminescence and transmission are employed to investigate modifications of visible and UV emissions of ZnO brought about by coupling to localized surface plasmons residing on Ag nanoislands. The size of the nanoislands, determining their absorption and scattering efficiencies, is found to be an important factor governing plasmonic modification of optical response of ZnO films. The presence of the Ag nanoislands of appropriate dimensions causes a strong (threefold) increase in emission intensity and up to 1.5 times faster recombination. The experimental results are successfully described by model calculations within the Mie theory.

Impact of the Halide Cage on the Electronic Properties of Fully Inorganic Cesium Lead Halide Perovskites

Perovskite solar cells with record power conversion efficiency are fabricated by alloying both hybrid and fully inorganic compounds. While the basic electronic properties of the hybrid perovskites are now well understood, key electronic parameters for solar cell performance, such as the exciton binding energy of fully inorganic perovskites, are still unknown. By performing magneto-transmission measurements, we determine with high accuracy the exciton binding energy and reduced mass of fully inorganic CsPbX3 perovskites (X = I, Br, and an alloy of these). The well-behaved (continuous) evolution of the band gap with temperature in the range of 4–270 K suggests that fully inorganic perovskites do not undergo structural phase transitions like their hybrid counterparts. The experimentally determined dielectric constants indicate that at low temperature, when the motion of the organic cation is frozen, the dielectric screening mechanism is essentially the same for both hybrid and inorganic perovskites and is do...

Revealing Large-Scale Homogeneity and Trace Impurity Sensitivity of GaAs Nanoscale Membranes

III-V nanostructures have the potential to revolutionize optoelectronics and energy harvesting. For this to become a reality, critical issues such as reproducibility and sensitivity to defects should be resolved. By discussing the optical properties of molecular beam epitaxy (MBE) grown GaAs nanomembranes we highlight several features that bring them closer to large scale applications. Uncapped membranes exhibit a very high optical quality, expressed by extremely narrow neutral exciton emission, allowing the resolution of the more complex excitonic structure for the first time. Capping of the membranes with an AlGaAs shell results in a strong increase of emission intensity but also in a shift and broadening of the exciton peak. This is attributed to the existence of impurities in the shell, beyond MBE-grade quality, showing the high sensitivity of these structures to the presence of impurities. Finally, emission properties are identical at the submicron and submillimeter scale, demonstrating the potential of these structures for large scale applications.