What Limits the Open-Circuit Voltage of Bromide Perovskite-Based Solar Cells?

High band gap Pb bromide perovskite (APbBr3)-based solar cells, where A is a mixture of formamidinium, methylammonium, and Cs, show significantly higher, relative, VOC losses than their iodide analogs. Using photoluminescence-, quantum efficiency-, and surface photovoltage-spectroscopy measurements, we show the absence of any significant electronically active tail states within the bulk of the (FA0.85MA0.1Cs0.05)­PbBr3 absorber. All methods confirm that EG = 2.28 eV for this halide perovskite, HaP. Contact potential difference measurements for this HaP, on different substrates, reveal a Z-shape dependence between the substrate work functions and that of the HaP, deposited on it, indicating that the HaP is relatively low doped and that its Fermi level is affected by the substrate onto which it is deposited. We confirm results from electron beam-induced current (EBIC) and other measurements that most voltage loss of cells, made with these HaP films, is at the HaP/selective-contact interface, specifically the TiO2/HaP one, and provide a complete account of these cells’ VOC losses. Capacitance measurements indicate that 350 mV VOC could be gained by eliminating (fast) interfacial states, emphasizing the importance of interface passivation. Still, even passivating the TiO2/HaP interface cannot eliminate the band misalignment with Br-based HaPs

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

Molecular Length, Monolayer Density, and Charge Transport: Lessons from Al–AlOx/Alkyl–Phosphonate/Hg Junctions

A combined electronic transport–structure characterization of self-assembled monolayers (MLs) of alkyl–phosphonate (AP) chains on Al–AlOx substrates indicates a strong molecular structural effect on charge transport. On the basis of X-ray reflectivity, XPS, and FTIR data, we conclude that “long” APs (C14 and C16) form much denser MLs than do “short” APs (C8, C10, C12). While current through all junctions showed a tunneling-like exponential length-attenuation, junctions with sparsely packed “short” AP MLs attenuate the current relatively more efficiently than those with densely packed, “long” ones. Furthermore, “long” AP ML junctions showed strong bias variation of the length decay coefficient, β, while for “short” AP ML junctions β is nearly independent of bias. Therefore, even for these simple molecular systems made up of what are considered to be inert molecules, the tunneling distance cannot be varied independently of other electrical properties, as is commonly assumed

Impedance Spectroscopic Indication for Solid State Electrochemical Reaction in (CH₃NH₃)PbI₃ Films

Halide perovskite-based solar cells still have limited reproducibility, stability, and incomplete understanding of how they work. We track electronic processes in [CH₃NH₃]­PbI₃(Cl) (“perovskite”) films <i>in vacuo</i>, and in N₂, air, and O₂, using impedance spectroscopy (IS), contact potential difference, and surface photovoltage measurements, providing direct evidence for perovskite sensitivity to the ambient environment. Two major characteristics of the perovskite IS response change with ambient environment, viz. -1- appearance of negative capacitance <i>in vacuo</i> or post<i>-vacuo</i> N₂ exposure, indicating for the first time an electrochemical process in the perovskite, and -2- orders of magnitude decrease in the film resistance upon transferring the film from O₂-rich ambient atmosphere to vacuum. The same change in ambient conditions also results in a 0.5 V decrease in the material work function. We suggest that facile adsorption of oxygen onto the film dedopes it from n-type toward intrinsic. These effects influence any material characterization, i.e., results may be ambient-dependent due to changes in the material’s electrical properties and electrochemical reactivity, which can also affect material stability

Enhancing the Photon Absorption and Charge Carrier Dynamics of BaSnO₃ Photoanodes via Intrinsic and Extrinsic Defects

Barium stannate (BaSnO3) crystallizes in the cubic perovskite-type structure and typically exhibits a wide band gap of >3.0 eV; thus, it is often considered unsuitable as a photo-absorber material for solar energy conversion. We present a spray-pyrolysis method for the fabrication of BaSnO3 photoanodes, with a smaller optical gap of ∼2.2 eV. By annealing the photoanodes in 5% hydrogen sulfide (H2S) gas, the optical gap is further reduced to ∼1.7 eV, with an ∼20-fold increase in photocurrent density and an improved onset potential of ∼0 VRHE. To understand the reasons behind this performance enhancement, we utilize a combination of spectroscopy techniques, including photoluminescence, wavelength-dependent time-resolved surface photovoltage analysis, and photoconductivity measurements. We find that H2S annealing of BaSnO3 generates a set of filled defect states associated with oxygen vacancies (VO••), Sn2+ centers (SnSn″), and sulfur substitutions (SO×), which are situated ∼1.4 to 1.9 eV below the conduction band minimum and exhibit a degree of orbital overlap with the valence band maximum. Increasing the density of these defects shifts the optical onset of photocurrent generation to ∼1.7 eV and enables holes to transport via a hopping mechanism. Resultantly, the charge carrier mobility is shown to increase by 20-fold, reaching ∼0.04 cm2 V–1 s–1

Mobility–Lifetime Products in MAPbI₃ Films

Photovoltaic solar cells operate under steady-state conditions that are established during the charge carrier excitation and recombination. However, to date no model of the steady-state recombination scenario in halide perovskites has been proposed. In this Letter we present such a model that is based on a single type of recombination center, which is deduced from our measurements of the illumination intensity dependence of the photoconductivity and the ambipolar diffusion length in those materials. The relation between the present results and those from time-resolved measurements, such as photoluminescence that are commonly reported in the literature, is discussed

Revisiting the Determination of the Valence Band Maximum and Defect Formation in Halide Perovskites for Solar Cells: Insights from Highly Sensitive Near–UV Photoemission Spectroscopy

Using advanced near–UV photoemission spectroscopy (PES) in constant final state mode (CFSYS) with a very high dynamic range, we investigate the triple-cation lead halide perovskite Cs0.05(MA0.17FA0.83)0.95Pb­(I0.83Br0.17)3 and gain detailed insights into the density of occupied states (DOS) in the valence band and band gap. A valence band model is established which includes the parabolic valence band edge and an exponentially decaying band tail in a single equation. This allows us to precisely determine two valence band maxima (VBM) at different k-vectors in the angle-integrated spectra, where the highest one, resulting from the VBM at the R-point in the Brillouin zone, is found between −1.50 to −1.37 eV relative to the Fermi energy EF. We investigate quantitatively the formation of defect states in the band gap up to EF upon decomposition of the perovskites during sample transfer, storage, and measurements: during near–UV-based PES, the density of defect states saturates at a value that is around 4 orders of magnitude below the density of states at the valence band edge. However, even short air exposure, or 3 h of X-ray illumination, increased their density by almost a factor of six and ∼40, respectively. Upon prolonged storage in vacuum, the formation of a distinct defect peak is observed. Thus, near–UV CFSYS with modeling as shown here is demonstrated as a powerful tool to characterize the valence band and quantify defect states in 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 <i>L</i>_n = 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 × 10¹⁷ cm^–3

High-Work-Function Molybdenum Oxide Hole Extraction Contacts in Hybrid Organic–Inorganic Perovskite Solar Cells

We investigate the effect of high work function contacts in halide perovskite absorber-based photovoltaic devices. Photoemission spectroscopy measurements reveal that band bending is induced in the absorber by the deposition of the high work function molybdenum trioxide (MoO₃). We find that direct contact between MoO₃ and the perovskite leads to a chemical reaction, which diminishes device functionality. Introducing an ultrathin spiro-MeOTAD buffer layer prevents the reaction, yet the altered evolution of the energy levels in the methylammonium lead iodide (MAPbI₃) layer at the interface still negatively impacts device performance