Michael Kulbak

Chloride Inclusion and Hole Transport Material Doping to Improve Methyl Ammonium Lead Bromide Perovskite-Based High Open-Circuit Voltage Solar Cells

Low-cost solar cells with high VOC, relatively small (EG - qVOC), and high qVOC/EG ratio, where EG is the absorber band gap, are long sought after, especially for use in tandem cells or other systems with spectral splitting. We report a significant improvement in CH3NH3PbBr3-based cells, using CH3NH3PbBr3-xClx, with EG = 2.3 eV, as the absorber in a mesoporous p-i-n device configuration. By p-doping an organic hole transport material with a deep HOMO level and wide band gap to reduce recombination, the cells VOC increased to 1.5 V, a 0.2 V increase from our earlier results with the pristine Br analogue with an identical band gap. At the same time, in the most efficient devices, the current density increased from ∼1 to ∼4 mA/cm(2).

Cesium Enhances Long-Term Stability of Lead Bromide Perovskite-Based Solar Cells

Direct comparison between perovskite-structured hybrid organic-inorganic methylammonium lead bromide (MAPbBr3) and all-inorganic cesium lead bromide (CsPbBr3), allows identifying possible fundamental differences in their structural, thermal and electronic characteristics. Both materials possess a similar direct optical band gap, but CsPbBr3 demonstrates a higher thermal stability than MAPbBr3. In order to compare device properties, we fabricated solar cells, with similarly synthesized MAPbBr3 or CsPbBr3, over mesoporous titania scaffolds. Both cell types demonstrated comparable photovoltaic performances under AM1.5 illumination, reaching power conversion efficiencies of ∼6% with a poly aryl amine-based derivative as hole transport material. Further analysis shows that Cs-based devices are as efficient as, and more stable than methylammonium-based ones, after aging (storing the cells for 2 weeks in a dry (relative humidity 15-20%) air atmosphere in the dark) for 2 weeks, under constant illumination (at maximum power), and under electron beam irradiation.

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.

Light-Induced Increase of Electron Diffusion Length in a p–n Junction Type CH3NH3PbBr3 Perovskite Solar Cell

High band gap, high open-circuit voltage solar cells with methylammonium lead tribromide (MAPbBr3) perovskite absorbers are of interest for spectral splitting and photoelectrochemical applications, because of their good performance and ease of processing. The physical origin of high performance in these and similar perovskite-based devices remains only partially understood. Using cross-sectional electron-beam-induced current (EBIC) measurements, we find an increase in carrier diffusion length in MAPbBr3(Cl)-based solar cells upon low intensity (a few percent of 1 sun intensity) blue laser illumination. Comparing dark and illuminated conditions, the minority carrier (electron) diffusion length increases about 3.5 times from Ln = 100 ± 50 nm to 360 ± 22 nm. The EBIC cross section profile indicates a p-n structure between the n-FTO/TiO2 and p-perovskite, rather than the p-i-n structure, reported for the iodide derivative. On the basis of the variation in space-charge region width with varying bias, measured by EBIC and capacitance-voltage measurements, we estimate the net-doping concentration in MAPbBr3(Cl) to be 3-6 × 10(17) cm(-3).

Electronic structure of the CsPbBr3/polytriarylamine (PTAA) system

The inorganic lead halide perovskite CsPbBr3 promises similar solar cell efficiency to its hybrid organic-inorganic counterpart CH3NH3PbBr3 but shows greater stability. Here, we exploit this stability for the study of band alignment between perovskites and carrier selective interlayers. Using ultraviolet, X-ray, and inverse photoemission spectroscopies, we measure the ionization energy and electron affinities of CsPbBr3 and the hole transport polymer polytriarylamine (PTAA). We find that undoped PTAA introduces a barrier to hole extraction of 0.2–0.5 eV, due to band bending in the PTAA and/or a dipole at the interface. p-doping the PTAA eliminates this barrier, raising PTAAs highest occupied molecular orbital to 0.2 eV above the CsPbBr3 valence band maximum and improving hole transport. However, IPES reveals the presence of states below the PTAA lowest unoccupied molecular level. If present at the CsPbBr3/PTAA interface, these states may limit the polymers efficacy at blocking electrons in solar cells w...

New insights into the nanostructure of innovative thin film solar cells gained by positron annihilation spectroscopy

Recent studies showed that positron annihilation methods can provide key insights into the nanostructure and electronic structure of thin film solar cells. In this study, positron annihilation lifetime spectroscopy (PALS) is applied to investigate CdSe quantum dot (QD) light absorbing layers, providing evidence of positron trapping at the surfaces of the QDs. This enables one to monitor their surface composition and electronic structure. Further, 2D-Angular Correlation of Annihilation Radiation (2D-ACAR) is used to investigate the nanostructure of divacancies in photovoltaic-high-quality a-Si:H films. The collected momentum distributions were converted by Fourier transformation to the direct space representation of the electron-positron autocorrelation function. The evolution of the size of the divacancies as a function of hydrogen dilution during deposition of a-Si:H thin films was examined. Finally, we present a first positron Doppler Broadening of Annihilation Radiation (DBAR) study of the emerging class of highly efficient thin film solar cells based on perovskites.