Perovskites, the rising star for energy harvesting

Perovskites are promising candidates for photovoltaic cells, having reached an energy harvesting of more than 20% while it took silicon three decades to reach an equivalent. Scientists from all over the world are exploring these materials at the ESRF.

Photovoltaic (PV) panels exist in our society since several years now. The photovoltaic market is currently dominated by wafer-based photovoltaics or first generation PVs, namely the traditional crystalline silicon cells, which take a 90% of the market share.

Although silicon (Si) is an abundant material and the price of Si-PV has dropped in the past years, their manufacturing require costly facilities. In addition, their fabrication typically takes place in countries that rely on carbon-intensive forms of electricity generation (high carbon footprint).

But there is room for hope. There is a third generation of PV: those based on thin-film cells. These absorb light more efficiently and they currently take 10% of the market share.

>Read more on the European Synchrotron website

Image: The CEA-CNRS team on ID01. From left to right: Peter Reiss, from CEA-Grenoble/INAC, Tobias Schulli from ID01, Tao Zhou from ID01, Asma Aicha Medjahed, Stephanie Pouget (both from CEA-Grenoble/INAC) and David Djurado, from the CNRS. 
Credits: C. Argoud.

Spin and charge frozen by strain

In the development of next-generation microelectronics, a great deal of attention has been given to the use of epitaxy (the deposition of a crystalline overlayer on a crystalline substrate) to tailor the properties of materials to suit particular applications. Correlated electron systems provide an excellent platform for the development of new microelectronic devices due to the presence of multiple competing ground states of similar energy. In some cases, strain can drive these systems between two or more such states, resulting in phase transitions and dramatic changes in the properties of the material. Often, the specific mechanism by which strain accomplishes such a feat is unknown. This was precisely the case in lanthanum cobaltite, LaCoO3, which undergoes a strain-induced transition from paramagnet to ferromagnet, until a recent study carried out at the U.S. Department of Energy’s Advanced Photon Source (APS) revealed the intriguing microscopic phenomena at work in this system. These phenomena may play a role in spin-state and magnetic-phase transitions, regardless of stimulus, in many other correlated systems.

Lanthanum cobaltite is a perovskite, which means the structure can be thought of as made up of distorted cubes with cobalt at the cube centers, oxygen at the cube faces, and lanthanum at the cube corners. The cobalt ions have a nominal 3+ valence, meaning they lose three electrons to the neighboring oxygen ions. Bulk LaCoO3 is paramagnetic (that is, having a net magnetization only in the presence of an externally applied magnetic field) above 110 Kelvin, and non-magnetic below that temperature. In its ground state, all the electrons on a given cobalt ion are paired, meaning their magnetic spins cancel each other out. These are so-called low-spin (LS) Co3+ ions, and when all of the cobalt ions are in this form, LaCoO3 is non-magnetic.

>Read more on the Advanced Photon Source website

Image: Upper left: Resonant x-ray scattering at the cobalt K-edge. Inversion of the spectra at the reflections shown indicates the presence of charge order. Upper right: X-ray diffraction reciprocal space maps at the (002) and (003) reflection indicating the high epitaxial quality of the films. The satellite peaks result from lattice modulations associated with the reduced symmetry in the film. Lower left: Schematic crystal structure of epitaxial LaCoO3 showing the arrangement of cobalt sites with different charge and spin. The circulated charge transfer from oxygen to the different cobalt sites is also shown. Lower right: Calculated total energy as a function of the difference between the in-plane Co-O bond lengths of HS and LS cobalt ions (∆rCo-O).

Precise layer growth in a superlattice controls electron coupling and magnetism

Two-dimensional (2-D) crystalline films often exhibit interesting physical characteristics, such as unusual magnetic or electric properties. By layering together distinct crystalline thin films, a so-called “superlattice” is formed. Due to their close proximity, the distinct layers of a superlattice may significantly affect the properties of other layers. In this research, single 2-D layers of strontium iridium oxide were sandwiched between either one, two, or three layers of strontium titanium oxide to form three distinct superlattices. Researchers then used x-ray scattering at the U.S. Department of Energy’s Advanced Photon Source (APS) to probe the magnetic structure of each superlattice. The x-ray data revealed that the number of layers of the titanium-based material produced a dramatic difference in the magnetic behavior of the iridium-based layer. These findings are especially significant because the iridium compound is one of the perovskites, a class of materials known for their unique electric, magnetic, optical, and other properties that have proven useful in sensor and energy-related devices, and which are being intensively investigated for their application towards improved electronics and other technologies.

>Read more on the Advance Photon Source website
Image: Fig. 1. Illustration of superlattices. Panel (a) shows the Sr2IrO4 crystalline superlattice, with alternating layers of SrIrO3 and SrO. The SrIrO3 layers are perovskites, depicted as diamond-like shapes formed by six oxygen atoms; inside each diamond is a gold-colored iridium ion (cation), while pink strontium ions lay near the diamond’s ends. The SrIrO3 layers are separated by non-perovskite (inert) SrO layers, depicted as pink bars. Panel (b) shows the more-recently developed SrIrO3/SrTiO3 superlattice used for this research. Three distinct SrIrO3/SrTiO3 superlattices were created, having 1, 2, or 3 layers of inert SrTiO3 layers (colored green) separating the active SrIrO3 layers. Bold green boxes highlight the number of inert SrTiO3 layers in the three distinct lattices. While both SrIrO3 (gold diamonds) and SrTiO3 (green diamonds) are perovskites, the green-colored SrTiO3 layers buffer the active SrIrO3 layers. (The entire image is visible here)

An energy-resolution record for resonant inelastic x-ray scattering

Resonant inelastic x-ray scattering (RIXS) is a powerful technique for studying electronic excitations in a wide variety of new and complex materials, offering momentum- and energy-resolution and potentially even analysis of scattered polarization. Since its inception in the 1990s, the development of RIXS instrumentation and scientific subjects have benefited from a closely intertwined evolution; improvements in energy resolution and throughput, spurred by specific scientific cases, have in turn made new subjects of study feasible. In the continued quest for substantially improved energy resolution, a novel prototype RIXS flat-crystal spectrometer was recently tested at X-ray Science Division beamline 27-ID-B at the U.S. Department of Energy’s Advanced Photon Source (APS). The spectrometer established a new record resolution for RIXS below 10 meV, together with a promise to do even better soon.

Early RIXS work was aimed at the study of charge transfer excitations in transition metal oxides (TMO), including the high-Tc superconducting Cuprates, where electronic excitations could be observed at a few eV. As the understanding of strongly correlated electron systems progressed, orbital degrees of freedom came into focus: in many Mott insulators, transitions between the active d-orbitals, the “dd excitations”, were hot topics and could reliably be observed with the then state-of-the-art resolution of 100-200 meV. Magnetism and magnetic ordering are central questions in the study of correlated electron systems. For example, the layered perovskite Iridates showing strikingly similar magnetic exchange interactions as the Cuprates, implying that unconventional superconductivity might be found here, to the intriguing assertion that magnetic properties of honeycomb Iridates might point to a quantum spin liquid as ground state of this material, the spectrum of novel, exotic properties uncovered or anticipated promise a treasure trove of scientific discoveries. In the late 2000s, RIXS was established as a probe of magnetic excitations. However, spectral features associated with magnetic excitations (“magnons”) lie at a fraction of an eV or even in the sub-10meV regime. A significant advance in energy resolution is needed to attack such subjects with RIXS.

>Read more on the Advanced Photon Source website

Figure: Schematic rendering of the new flat-crystal RIXS spectrometer.

Scientists discover material ideal for smart photovoltaic windows

Berkeley Lab researchers make thermochromic windows with perovskite solar cell

Smart windows that are transparent when it’s dark or cool but automatically darken when the sun is too bright are increasingly popular energy-saving devices. But imagine that when the window is darkened, it simultaneously produces electricity. Such a material – a photovoltaic glass that is also reversibly thermochromic – is a green technology researchers have long worked toward, and now, scientists at Lawrence Berkeley National Laboratory (Berkeley Lab) have demonstrated a way to make it work.

Researchers at Berkeley Lab, a Department of Energy (DOE) national lab, discovered that a form of perovskite, one of the hottest materials in solar research currently due to its high conversion efficiency, works surprisingly well as a stable and photoactive semiconductor material that can be reversibly switched between a transparent state and a non-transparent state, without degrading its electronic properties.

>Read more on the Advanced Light Source website

Image Credit: iStock


Perovskite solar cells: perfection not required!

Experiments at BESSY II reveal why even inhomogeneous perovskite films are highly functional

Metal-organic perovskite layers for solar cells are frequently fabricated using the spin coating technique. If you follow the simplest synthesis pathway and use industry-relevant compact substrates, the perovskite layers laid down by spin coating generally exhibit numerous holes, yet attain astonishingly high levels of efficiency. The reason that these holes do not lead to significant short circuits between the front and back contact and thus high-rate charge carrier recombination has now been discovered by a HZB team headed by Dr.-Ing. Marcus Bär in cooperation with the group headed by Prof. Henry Snaith (Oxford Univ.) at BESSY II.

>Read more on the HZB website.