Experimental Determination of the Chiral and Achiral Shape Diagrams of Tellurium Nanocrystals.

The interface between chirality and crystallization and mechanisms by which chirality propagates from crystal structure to overall shapes of crystals are a key topic in crystallography and stereochemistry. Recently, nanocrystals attracted attention as useful model systems for this kind of studies. Specifically, tellurium nanocrystals have been used to address questions on relations between chirality of the crystal structure and that of the overall shape. Previous studies of this system did not offer a comprehensive shape diagram and did not survey all the factors that determine whether shapes that form are chiral or not. In the current report, the distribution of chiral and achiral shapes in this system as a function of different physical and chemical parameters is determined experimentally. It is shown that there is a common logic for formation of chiral shapes, that is, growth at conditions that favor the growth of more reactive nuclei. The experiments also reveal more morphologies than previously encountered, suggesting that a systematic change of conditions in nanocrystal growth is key for identifying morphologies that exist only in a narrow range of conditions.

FTO Darkening Rate as a Qualitative, High-Throughput Mapping Method for Screening Li-Ionic Conduction in Thin Solid Electrolytes.

We present a high-throughput (combinatorial) method to screen thin ceramic films as Li-ion conductors by mapping an optical effect of Li-ion conduction. The method, while qualitative, is fast and simple to implement, provides a planar (XY) map of Li-ion conductivity through different parts of the film. The effect, FTO darkening, is an optoelectrochemical one that relies on darkening of the FTO (F-doped tin oxide) substrate, onto which the investigated film is deposited. The rate of color change of the FTO reflects the rate of Li-ion migration through the film. The method is validated by testing two model systems, a Li-La-S-O film with uniform composition and varying thickness, and a Li-La-P-O film with varying thickness and lateral composition. The darkening rate, obtained from optical transmission, correlates linearly with inverse film thickness. The darkening rate map can be compared with a resistance map obtained by impedance measurements, showing that only Li conduction is measured. We discuss the conditions required to distinguish between areas with pure ion conductivity and those with mixed conductivity, the reversibility of the darkening effect and artifacts.

How Transparent Oxides Gain Some Color: Discovery of a CeNiO3 Reduced Bandgap Phase As an Absorber for Photovoltaics.

In this work, we describe the formation of a reduced bandgap CeNiO3 phase, which, to our knowledge, has not been previously reported, and we show how it is utilized as an absorber layer in a photovoltaic cell. The CeNiO3 phase is prepared by a combinatorial materials science approach, where a library containing a continuous compositional spread of Ce xNi1- xO y is formed by pulsed laser deposition (PLD); a method that has not been used in the past to form Ce-Ni-O materials. The library displays a reduced bandgap throughout, calculated to be 1.48-1.77 eV, compared to the starting materials, CeO2 and NiO, which each have a bandgap of ∼3.3 eV. The materials library is further analyzed by X-ray diffraction to determine a new crystalline phase. By searching and comparing to the Materials Project database, the reduced bandgap CeNiO3 phase is realized. The CeNiO3 reduced bandgap phase is implemented as the absorber layer in a solar cell and photovoltages up to 550 mV are achieved. The solar cells are also measured by surface photovoltage spectroscopy, which shows that the source of the photovoltaic activity is the reduced bandgap CeNiO3 phase, making it a viable material for solar energy.

Influence of ordering in porous TiO2 layers on electron diffusion.

Layers of porous TiO(2) fabricated by electrophoretic deposition at different temperatures with subsequent sintering in air were investigated by transient photocurrent measurements in aqueous electrolyte. The effective diffusion coefficient of excess electrons changed between 1.6 x 10(-5) and 1.4 x 10(-4) cm(2)/s depending strongly on the solution temperature during the TiO(2) layer deposition. Characterization, in terms of average degree of preferred orientation, shows that low deposition temperature results in orientation of the nanocrystals forming the porous film. Consequently, the increase of effective diffusion coefficient is attributed to a higher degree of ordering in the nanoporous TiO(2) layer.

Vapor and healing treatment for CH3NH3PbI(3-x)Cl(x) films toward large-area perovskite solar cells.

Hybrid methyl-ammonium lead trihalide perovskites are promising low-cost materials for use in solar cells and other optoelectronic applications. With a certified photovoltaic conversion efficiency record of 20.1%, scale-up for commercial purposes is already underway. However, preparation of large-area perovskite films remains a challenge, and films of perovskites on large electrodes suffer from non-uniform performance. Thus, production and characterization of the lateral uniformity of large-area films is a crucial step towards scale-up of devices. In this paper, we present a reproducible method for improving the lateral uniformity and performance of large-area perovskite solar cells (32 cm(2)). The method is based on methyl-ammonium iodide (MAI) vapor treatment as a new step in the sequential deposition of perovskite films. Following the MAI vapor treatment, we used high throughput techniques to map the photovoltaic performance throughout the large-area device. The lateral uniformity and performance of all photovoltaic parameters (V(oc), J(sc), Fill Factor, Photo-conversion efficiency) increased, with an overall improved photo-conversion efficiency of ∼100% following a vapor treatment at 140 °C. Based on XRD and photoluminescence measurements, We propose that the MAI treatment promotes a "healing effect" to the perovskite film which increases the lateral uniformity across the large-area solar cell. Thus, the straightforward MAI vapor treatment is highly beneficial for large scale commercialization of perovskite solar cells, regardless of the specific deposition method.

Open circuit potential build-up in perovskite solar cells from dark conditions to 1 sun.

The high open-circuit potential (Voc) achieved by perovskite solar cells (PSCs) is one of the keys to their success. The Voc analysis is essential to understand their working mechanisms. A large number of CH3NH3PbI3-xClx PSCs were fabricated on single large-area substrates and their Voc dependencies on illumination intensity, I0, were measured showing three distinctive regions. Similar results obtained in Al2O3 based PSCs relate the effect to the compact TiO2 rather than the mesoporous oxide. We propose that two working mechanisms control the Voc in PSCs. The rise of Voc at low I0 is determined by the employed semiconductor n-type contact (TiO2 or MgO coated TiO2). In contrast, at I0 close to AM1.5G, the employed oxide does not affect the achieved voltage. Thus, a change of regime from an oxide-dominated EFn (as in the dye sensitized solar cells) to an EFn, directly determined by the CH3NH3PbI3-xClx absorber is suggested.

Photoinduced Reversible Structural Transformations in Free-Standing CH3NH3PbI3 Perovskite Films.

In the pursuit to better understand the mechanisms of perovskite solar cells we performed Raman and photoluminescence measurements of free-standing CH3NH3PbI3 films, comparing dark with working conditions. The films, grown on a glass substrate and sealed by a thin glass coverslip, were measured subsequent to dark and white-light pretreatments. The extremely slow changes we observe in both the Raman and photoluminescence cannot be regarded as electronic processes, which are much faster. Thus, the most probable explanation is of slow photoinduced structural changes. The CH3NH3PbI3 transformation between the dark and the light structures is reversible, with faster rates for the changes under illumination. The results seem to clarify several common observations associated with solar cell mechanisms, like performance improvement under light soaking. More important is the call for solar-cell-related investigation of CH3NH3PbI3 to take the photoinduced structural changes into consideration when measuring and interpreting the results.

Extremely Slow Photoconductivity Response of CH3NH3PbI3 Perovskites Suggesting Structural Changes under Working Conditions.

Photoconductivity measurements of CH3NH3PbI3 deposited between two dielectric-protected Au electrodes show extremely slow response. The CH3NH3PbI3, bridging a gap of ∼2000 nm, was subjected to a DC bias and cycles of 5 min illumination and varying dark duration. The approach to steady -state photocurrent lasted tens of seconds with a strong dependence on the dark duration preceding the illumination. On the basis of DFT calculations, we propose that under light + bias the methylammonium ions are freed to rotate and align along the electric field, thus modifying the structure of the inorganic scaffold. While ions alignment is expected to be fast, the adjustment of the inorganic scaffold seems to last seconds as reflected in the extremely slow photoconductivity response. We propose that under working conditions a modified, photostable, perovskite structure is formed, depending on the bias and illumination parameters. Our findings seem to clarify the origin of the well-known hysteresis in perovskite solar cells.

Direct Imaging of the Recombination/Reduction Sites in Porous TiO2 Electrodes.

In photoelectrochemical cells, one major recombination pathway involves a reaction between the photogenerated electrons that diffuse inside the semiconductor electrode and holes, in the form of oxidized ions, which travel in the electrolyte to the counter electrode. Here we present direct imaging of the recombination/reduction sites in two types of porous TiO2 electrodes, P25 and submicrometer particles, chosen for studying the influence of the TiO2 particles' sizes and shapes on the recombination sites. The sites were labeled with 2-5 nm silver particles, electrodeposited on the TiO2 surface using chronoamperometry. The model assumes that reduction and recombination are similar with respect to the electron transfer from the TiO2 surface to an ionic electron acceptor in the electrolyte redox mediator/Ag(+) ion. Consequently the metal deposit marks the reaction locations. This first high-resolution view clearly identifies the connecting points between TiO2 particles and then the {101} facets as the sites of recombination.

Design Rules for High-Efficiency Quantum-Dot-Sensitized Solar Cells: A Multilayer Approach.

The effect of multilayer sensitization in quantum-dot (QD)-sensitized solar cells is reported. A series of electrodes, consisting of multilayer CdSe QDs were assembled on a compact TiO2 layer. Photocurrent measurements along with internal quantum efficiency calculation reveal similar electron collection efficiency up to a 100 nm thickness of the QD layers. Moreover, the optical density and the internal quantum efficiency measurements reveal that the desired surface area of the TiO2 electrode should be increased only by a factor of 17 compared with a compact electrode. We show that the sensitization of low-surface-area TiO2 electrode with QD layers increases the performance of the solar cell, resulting in 3.86% efficiency. These results demonstrate a conceptual difference between the QD-sensitized solar cell and the dye-based system in which dye multilayer decreases the cell performance. The utilization of multilayer QDs opens new opportunities for a significant improvement of quantum-dot-sensitized solar cells via innovative cell design.

Growing ZnO crystals on magnetite nanoparticles.

We report herein on the oriented growth of ZnO crystals on magnetite nanoparticles. The ZnO crystals were grown by hydrolyzing a supersaturated aqueous solution of zinc nitrate. The seeds for the growth were magnetite nanoparticles with a diameter of 5.7 nm and a narrow size distribution. Hollowed ZnO hexagons of 0.15 microm width and 0.5 microm length filled with Fe(3)O(4) particles were obtained. HR-TEM (high-resolution transmission electron microscopy) and selected-area EDS (energy-dispersive spectroscopy) show that the nanoparticles are homogenously spread in the ZnO tubes. Zeta potential measurements were employed to understand the relationship between the nanoparticles and the oriented growth of the ZnO crystals. The results show that the surfactants induced the directional growth of the ZnO crystals.