Ross A. Kerner

Valence and Conduction Band Densities of States of Metal Halide Perovskites: A Combined Experimental–Theoretical Study

We report valence and conduction band densities of states measured via ultraviolet and inverse photoemission spectroscopies on three metal halide perovskites, specifically methylammonium lead iodide and bromide and cesium lead bromide (MAPbI3, MAPbBr3, CsPbBr3), grown at two different institutions on different substrates. These are compared with theoretical densities of states (DOS) calculated via density functional theory. The qualitative agreement achieved between experiment and theory leads to the identification of valence and conduction band spectral features, and allows a precise determination of the position of the band edges, ionization energy and electron affinity of the materials. The comparison reveals an unusually low DOS at the valence band maximum (VBM) of these compounds, which confirms and generalizes previous predictions of strong band dispersion and low DOS at the MAPbI3 VBM. This low DOS calls for special attention when using electron spectroscopy to determine the frontier electronic states of lead halide perovskites.

Diode-Pumped Organo-Lead Halide Perovskite Lasing in a Metal-Clad Distributed Feedback Resonator

Organic-inorganic lead halide perovskite semiconductors have recently reignited the prospect of a tunable, solution-processed diode laser, which has the potential to impact a wide range of optoelectronic applications. Here, we demonstrate a metal-clad, second-order distributed feedback methylammonium lead iodide perovskite laser that marks a significant step toward this goal. Optically pumping this device with an InGaN diode laser at low temperature, we achieve lasing above a threshold pump intensity of 5 kW/cm(2) for durations up to ∼25 ns at repetition rates exceeding 2 MHz. We show that the lasing duration is not limited by thermal runaway and propose instead that lasing ceases under continuous pumping due to a photoinduced structural change in the perovskite that reduces the gain on a submicrosecond time scale. Our results indicate that the architecture demonstrated here could provide the foundation for electrically pumped lasing with a threshold current density Jth < 5 kA/cm(2) under sub-20 ns pulsed drive.

In Situ Preparation of Metal Halide Perovskite Nanocrystal Thin Films for Improved Light-Emitting Devices

Hybrid organic-inorganic halide perovskite semiconductors are attractive candidates for optoelectronic applications, such as photovoltaics, light-emitting diodes, and lasers. Perovskite nanocrystals are of particular interest, where electrons and holes can be confined spatially, promoting radiative recombination. However, nanocrystalline films based on traditional colloidal nanocrystal synthesis strategies suffer from the use of long insulating ligands, low colloidal nanocrystal concentration, and significant aggregation during film formation. Here, we demonstrate a facile method for preparing perovskite nanocrystal films in situ and that the electroluminescence of light-emitting devices can be enhanced up to 40-fold through this nanocrystal film formation strategy. Briefly, the method involves the use of bulky organoammonium halides as additives to confine crystal growth of perovskites during film formation, achieving CH3NH3PbI3 and CH3NH3PbBr3 perovskite nanocrystals with an average crystal size of 5.4 ± 0.8 nm and 6.4 ± 1.3 nm, respectively, as confirmed through transmission electron microscopy measurements. Additive-confined perovskite nanocrystals show significantly improved photoluminescence quantum yield and decay lifetime. Finally, we demonstrate highly efficient CH3NH3PbI3 red/near-infrared LEDs and CH3NH3PbBr3 green LEDs based on this strategy, achieving an external quantum efficiency of 7.9% and 7.0%, respectively, which represent a 40-fold and 23-fold improvement over control devices fabricated without the additives.

Ultrasmooth metal halide perovskite thin films via sol–gel processing

We demonstrate that lead halide perovskite thin film formation displays the characteristics of a sol–gel process. By performing a solvent exchange at different times, the stages of the sol–gel process are elucidated and their sensitivity to processing conditions are examined. For CH3NH3PbI3, the reaction and aging kinetics are found to be extremely rapid, complete within 10 s, and a competing formation of a highly crystalline PbI2:N,N-dimethylformamide (DMF) complex introduces additional complications relative to a well-behaved sol–gel process. Perovskite formation from strongly polar solvents can be described, in most cases, by the sol–gel processing of PbI2 regarding other solution components as additives. Understanding the details of additive and environmental influences on the sol–gel properties allow us to exploit fundamental concepts of sol–gel engineering to direct solvent and surfactant choices to control particle size and demonstrate multiple widely employed lead halide perovskite films (CH3NH3PbI3, CH3NH3PbBr3, and CsPbBr3) with unprecedented surface roughness of less than 2 nm.

Linking Chemistry at the TiO2/CH3NH3PbI3 Interface to Current-Voltage Hysteresis

We demonstrate that reversible chemical reactions occur at TiO2/gas and CH3NH3PbI3/gas interfaces on a time scale of seconds to minutes. The chemisorption strongly affects their electronic properties, mainly acting to deplete TiO2 of free electrons and passivate surface traps on the perovskite. Although the chemistry is not directly probed, we infer that reversible chemistry occurs at the solid-state TiO2/CH3NH3PbI3 interface. Equilibrium or steady-state concentrations established for adsorbed species associated with each material would be voltage- and illumination-dependent due to free or photocarriers being a main reactant. Interfacial chemistry provides an additional physical mechanism to explain the origins of normal and anomalous hysteretic current-voltage characteristics of perovskite devices. Furthermore, chemical reactions help us to understand why measured perovskite ion-transport properties and the nature of hysteresis are highly dependent on interfaces.

Mixed-Halide Perovskites with Stabilized Bandgaps

One merit of organic-inorganic hybrid perovskites is their tunable bandgap by adjusting the halide stoichiometry, an aspect critical to their application in tandem solar cells, wavelength-tunable light emitting diodes (LEDs), and lasers. However, the phase separation of mixed-halide perovskites caused by light or applied bias results in undesirable recombination at iodide-rich domains, meaning open-circuit voltage (VOC) pinning in solar cells and infrared emission in LEDs. Here, we report an approach to suppress halide redistribution by self-assembled long-chain organic ammonium capping layers at nanometer-sized grain surfaces. Using the stable mixed-halide perovskite films, we are able to fabricate efficient and wavelength-tunable perovskite LEDs from infrared to green with high external quantum efficiencies of up to 5%, as well as linearly tuned VOC from 1.05 to 1.45 V in solar cells.

Ionic–Electronic Ambipolar Transport in Metal Halide Perovskites: Can Electronic Conductivity Limit Ionic Diffusion?

Ambipolar transport describes the nonequilibrium, coupled motion of positively and negatively charged particles to ensure that internal electric fields remain small. It is commonly invoked in the semiconductor community where the motion of excess electrons and holes drift and diffuse together. However, the concept of ambipolar transport is not limited to semiconductor physics. Materials scientists working on ion conducting ceramics understand ambipolar transport dictates the coupled diffusion of ions and the rate is limited by the ion with the lowest diffusion coefficient. In this Perspective, we review a third application of ambipolar transport relevant to mixed ionic-electronic conducting materials for which the motion of ions is expected to be coupled to electronic carriers. In this unique situation, the ambipolar diffusion model has been successful at explaining the photoenhanced diffusion of metal ions in chalcogenide glasses and other properties of materials. Recent examples of photoenhanced phenomena in metal halide perovskites are discussed and indicate that mixed ionic-electronic ambipolar transport is similarly important for a deep understanding of these emerging materials.

Electron-blocking NiO/crystalline n-Si heterojunction formed by ALD at 175°C

Silicon heterojunction solar cells have been the subject of growing research interest. Such cells replace the typical p+nn+ or n+pp+ structure of standard devices with selective heterojunction contacts, which block one type of carrier while allowing the other to pass freely (Fig. 1) [1-3]. Previously [4], we demonstrated a PEDOT/n-Si/TiO2 heterojunction cell fabricated below 100°C with no p-n junctions in the Si. However, the organic polymer PEDOT is known to be unstable over long periods of time; furthermore, recent data indicates that the PEDOT/n-Si interface might be a non-ideal minority carrier emitter, leading to a high J0 and low upper limit to VOC. Therefore, we are currently investigating inorganic electron-blockers on crystalline silicon. Nickel oxide (NiO), because of its large conduction band offset and small valence band offset with silicon (Fig. 2) [5], is a potential candidate for electron-blocking on n-Si. Here, we report atomic layer deposited (ALD) metal/15nm-i-NiO/Si diodes. We find that the NiO film leads to a heterojunction which blocks electrons compared to diodes with the NiO omitted. The characteristics depend on the top metal, indicating that the NiO passivates the Si surface so that the Fermi level is depinned and diodes with a higher Schottky barrier height can be fabricated. Devices with Ag have electron-blocking and hole-transmitting behavior.

Variable charge transfer state energies at nanostructured pentacene/C60 interfaces

While it has recently been recognized that organic donor-acceptor charge transfer (CT) state energies can vary substantially under different interfacial morphologies, this behavior is under-appreciated in the context of organic singlet fission solar cells where a specific alignment between the triplet state of the fission material and the CT state of the donor-acceptor interface is necessary to the function of the device. In this work, we demonstrate that the CT state energy of a prototypical pentacene-C60 singlet fission system is around 1 eV in most systems, but can vary over 300 meV depending on the composition and morphology of the interface. Moreover, we show that the inclusion of a poly(3-hexylthiophene-2,5-diyl) underlayer, which commonly serves as a triplet blocker and hole collector in pentacene/C60 solar cells, helps promote active layer morphologies with stabilized, low energy CT states. These trends in the interfacial energetics are correlated with structural characterization of the films by atomic force microscopy and x-ray diffraction.While it has recently been recognized that organic donor-acceptor charge transfer (CT) state energies can vary substantially under different interfacial morphologies, this behavior is under-appreciated in the context of organic singlet fission solar cells where a specific alignment between the triplet state of the fission material and the CT state of the donor-acceptor interface is necessary to the function of the device. In this work, we demonstrate that the CT state energy of a prototypical pentacene-C60 singlet fission system is around 1 eV in most systems, but can vary over 300 meV depending on the composition and morphology of the interface. Moreover, we show that the inclusion of a poly(3-hexylthiophene-2,5-diyl) underlayer, which commonly serves as a triplet blocker and hole collector in pentacene/C60 solar cells, helps promote active layer morphologies with stabilized, low energy CT states. These trends in the interfacial energetics are correlated with structural characterization of the films by a...