Higher Open Circuit Voltage and Reduced UV-Induced Reverse Current in ZnO-Based Solar Cells by a Chemically Modified Blocking Layer

Solid-state semiconductor-sensitized solar cells require a thin, dense hole-blocking layer at the conducting glass substrate (F-doped tin oxide (FTO)) to prevent shorting beween the FTO and hole conductor. We found that by adding a small amount of Sb ions to a ZnO chemical deposition bath a thin (few tens of nanometers thick) dense and uniform layer of Sb-incorporated ZnO forms. Here we investigate the electronic properties of this layer in comparison to the continuous ZnO layer at the base of the ZnO rods formed in the standard preparation. Devices incorporating the Sb-incorporated dense layer followed by a standard ZnO nanorod growth, onto which CdS or CdSe was grown followed by a CuSCN hole conductor, showed 100–200 mV higher photovoltage together with occasional improvement in the short-circuit current. Electrochemical and electrical measurements indicated complete coverage of the FTO substrate by both preparations; however, the shunt resistance (resistance to a reverse leakage current) in the cells (and films) made using the Sb-incorporated ZnO layer is dramatically increased. Using bias-dependent incident photon-to-electron conversion efficiency studies, we found that an increased dark or leakage current develops in the cell on illumination with UV light together with application of a forward bias. This can be explained by the presence of a “Schottky junction” at the FTO\ZnO interface. This increased leakage current is significantly larger in cells without the Sb-incorporated ZnO compact layer

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

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

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

Low-Temperature Solution-Grown CsPbBr₃ Single Crystals and Their Characterization

Cesium lead bromide (CsPbBr₃) was recently introduced as a potentially high performance thin-film halide perovskite (HaP) material for optoelectronics, including photovoltaics, significantly more stable than MAPbBr₃ (MA = CH₃NH₃⁺). Because of the importance of single crystals to study relevant material properties per se, crystals grown under conditions comparable to those used for preparing thin films, i.e., low-temperature solution-based growth, are needed. We show here two simple ways, antisolvent-vapor saturation or heating a solution containing retrograde soluble CsPbBr₃, to grow single crystals of CsPbBr₃ from a precursor solution, treated with acetonitrile (MeCN) or methanol (MeOH). The precursor solutions are stable for at least several months. Millimeter-sized crystals are grown without crystal-seeding and can provide a 100% yield of CsPbBr₃ perovskite crystals, avoiding a CsBr-rich (or PbBr₂-rich) composition, which is often present alongside the perovskite phase. Further growth is demonstrated to be possible with crystal seeding. The crystals are characterized in several ways, including first results of charge carrier lifetime (30 ns) and an upper-limit of the Urbach energy (19 meV). As the crystals are grown from a polar aprotic solvent (DMSO), which is similar to those used to grow hybrid organic–inorganic HaP crystals, this may allow growing mixed (organic and inorganic) monovalent cation HaP crystals

Effect of Internal Heteroatoms on Level Alignment at Metal/Molecular Monolayer/Si Interfaces

Molecular monolayers at metal/semiconductor heterointerfaces affect electronic energy level alignment at the interface by modifying the interface’s electrical dipole. On a free surface, the molecular dipole is usually manipulated by means of substitution at its external end. However, at an interface such outer substituents are in close proximity to the top contact, making the distinction between molecular and interfacial effects difficult. To examine how the interface dipole would be influenced by a single atom, internal to the molecule, we used a series of three molecules of identical binding and tail groups, differing only in the inner atom: aryl vinyl ether (<b>PhO</b>), aryl vinyl sulfide (<b>PhS</b>), and the corresponding molecule with a CH₂ groupallyl benzene (<b>PhC</b>). Molecular monolayers based on all three molecules have been adsorbed on a flat, oxide-free Si surface. Extensive surface characterization, supported by density functional theory calculations, revealed high-quality, well-aligned monolayers exhibiting excellent chemical and electrical passivation of the silicon substrate, in all three cases. Current–voltage and capacitance–voltage analysis of Hg/PhX (X = C, O, S)/Si interfaces established that the type of internal atom has a significant effect on the Schottky barrier height at the interface, i.e., on the energy level alignment. Surprisingly, despite the formal chemical separation of the internal atom and the metallic electrode, Schottky barrier heights were not correlated to changes in the semiconductor’s effective work function, deduced from Kelvin probe and ultraviolet photoemission spectroscopy on the monolayer-adsorbed Si surface. Rather, these changes correlated well with the ionization potential of the surface-adsorbed molecules. This is interpreted in terms of additional polarization at the molecule/metal interface, driven by potential equilibration considerations even in the absence of a formal chemical bond to the top Hg contact