Direct observation of the ad- and desorption of guest atoms into a mesoporous host

Battery electrodes, storage devices for gases, and some catalyst materials have tiny functional pores that can accommodate atoms, ions, and molecules. How these guest atoms are absorbed into or released from the pores is crucial to understanding the porous materials’ functionality. However, usually these processes can only be observed indirectly. A team from the Helmholtz Zentrum Berlin (HZB) has employed two experimental approaches using the ASAXS instrument at the PTB X-ray beamline of the HZB BESSY II synchrotron to directly observe the adsorption process of atoms in a mesoporous model system. The work lays the foundations for new insights into these kinds of energy materials.

Most battery materials, novel catalysts, and storage materials for hydrogen have one thing in common: they have a structure comprised of tiny pores in the nanometer range. These pores provide space which can be occupied by guest atoms, ions, and molecules. As a consequence, the properties of the guest and the host can change dramatically. Understanding the processes inside the pores is crucial to develop innovative energy technologies.

Read more on the HZB website

Image: From the measurement data, the team was able to determine that the xenon atoms first accumulate on the inner walls of the pores (state 1), before they fill them up (state 2). The X-ray beam penetrates the sample from below.

Credit: © M. Künsting/HZB

Towards catalysts for solar hydrogen production

Thin films of molybdenum and sulfur belong to a class of materials that can be considered for use as photocatalysts. Inexpensive catalysts such as these are needed to produce hydrogen as a fuel using solar energy. However, they are still not very efficient as catalysts. A new instrument at the Helmholtz-Berlin Zentrum’s BESSY II now shows how a light pulse alters the surface properties of the thin film and activates the material as a catalyst.

MoS2 thin films of superposed alternating layers of molybdenum and sulfur atoms form a two-dimensional semiconducting surface. However, even a surprisingly low-intensity blue light pulse is enough to alter the properties of the surface and make it metallic. This has now been demonstrated by a team at BESSY II.

Read more on the HZB website

Image: A new instrument at BESSY II can be used to study molybdenum-sulfide thin films that are of interest as catalysts for solar hydrogen production. A light pulse triggers a phase transition from the semiconducting to the metallic phase and thus enhances the catalytic activity.

Credit: © Martin Künsting /HZB

Perfect recipe for efficient perovskite solar cells

A long-cherished dream of materials researchers is a solar cell that converts sunlight into electrical energy as efficiently as silicon, but that can be easily and inexpensively fabricated from abundant materials. Scientists at the Helmholtz-Zentrum Berlin have now come a step closer to achieving this. They have improved a process for vertically depositing a solution made from an inexpensive perovskite solute onto a moving substrate below. Not only have they discovered the crucial role played by one of the solvents used, but they have also taken a closer look at the aging and storage properties of the solution.

Solar cells made of crystalline silicon still account for the lion’s share of roof installations and solar farms. But other technologies have long since become established as well – such as those that convert sunlight into electrical energy through use of extremely thin layers of solar-cell material deposited upon a substrate. The perovskite solar cells that Prof. Eva Unger and her team at the Helmholtz-Zentrum Berlin (HZB) are researching belong to this group. “These are the best solar cells to date that can be made using a 2D ink”, the researcher explains. “And now their efficiencies are approaching those for cells made of crystalline silicon.”

Read more on the HZB website

Image: The liquid solution of perovskite precursor, solvent, and additive flows from a slit-shaped nozzle onto the glass substrate being conveyed below.

Credit: © Jinzhao Li / HZB

Experiment reveals new options for synchrotron light sources

An international team has shown through a sensational experiment how diverse the possibilities for employing synchrotron light sources are. Accelerator experts from the Helmholtz-Zentrum Berlin (HZB), the German federal metrology institute Physikalisch-Technische Bundesanstalt (PTB), and Tsinghua University in Beijing have used a laser to manipulate electron bunches at PTB’s Metrology Light Source so that they emitted intense light pulses having a laser-like character. Using this method, specialised synchrotron radiation sources would potentially be able to fill a gap in the arsenal of available light sources and offer a prototype for industrial applications. The work was published on 24 February 2021 in the leading scientific publication Nature.

The most modern light sources for research are based on particle accelerators. These are large facilities in which electrons are accelerated to almost the speed of light, and then emit light pulses of a special character. In storage-ring-based synchrotron radiation sources, the electron bunches travel in the ring for billions of revolutions, then generate a rapid succession of very bright light pulses in the deflecting magnets. In contrast, the electron bunches in free-electron lasers (FELs) are accelerated linearly and then emit a single super-bright flash of laser-like light. Storage ring sources as well as FEL sources have facilitated advances in many fields in recent years, from deep insights into biological and medical questions to materials research, technology development, and quantum physics.

Combining the virtues of both systems

Now a Sino-German team has shown that a pattern of pulses can be generated in a synchrotron radiation source that combines the advantages of both systems. The synchrotron source delivers short, intense microbunches of electrons that produce radiation pulses having a laser-like character (as with FELs), but which can also follow each other closely in sequence (as with synchrotron light sources).

Read more on the HZB website

Image credit: © Tsinghua University

World’s first video recording of a space-time crystal

A German-Polish research team has succeeded in creating a micrometer-sized space-time crystal consisting of magnons at room temperature. With the help of the scanning transmission X-ray microscope MAXYMUS at Bessy II at Helmholtz Zentrum Berlin, they were able to film the recurring periodic magnetization structure in a crystal. The research project was a collaboration between scientists from the Max Planck Institute for Intelligent Systems (MPI-IS) in Stuttgart, Germany, the Adam Mickiewicz University and the Polish Academy of Sciences in Poznań in Poland.

A crystal is a solid whose atoms or molecules are regularly arranged in a particular structure. If one looks at the arrangement with a microscope, one discovers an atom or a molecule always at the same intervals. It is similar with space-time crystals: however, the recurring structure exists not only in space, but also in time. The smallest components are constantly in motion until, after a certain period, they arrange again into the original pattern.

In 2012, the Nobel Prize winner in physics Frank Wilczek discovered the symmetry of matter in time. He is considered the discoverer of these so-called time crystals, although as a theorist he predicted them only hypothetically. Since then, several scientists have searched for materials in which the phenomenon is observed. The fact that space-time crystals actually exist was first confirmed in 2017. However, the structures were only a few nanometers in size and formed only at very cold temperatures below -250 degrees Celsius. The fact that the German-Polish scientists have now succeeded in imaging relatively large space-time crystals of a few micrometers in a video at room temperature is therefore considered groundbreaking. But also because they were able to show that their space-time crystal, which consists of magnons, can interact with other magnons that encounter it.

Read more on the HZB website

Image credit: © MPI-IS

An efficient tool to link X-ray experiments and ab initio theory

The electronic structure of complex molecules and their chemical reactivity can be assessed by the method of resonant inelastic X-ray scattering (RIXS) at BESSY II. However, the evaluation of RIXS data has so far required very long computing times. A team at BESSY II has now developed a new simulation method that greatly accelerates this evaluation. The results can even be calculated during the experiment. Guest users could use the procedure like a black box.

Molecules consisting of many atoms are complex structures. The outer electrons are distributed among the different orbitals, and their shape and occupation determine the chemical behaviour and reactivity of the molecule. The configuration of these orbitals can be analysed experimentally. Synchrotron sources such as BESSY II provide a method for this purpose: Resonant inelastic X-ray scattering (RIXS). However, to obtain information about the orbitals from experimental data, quantum chemical simulations are necessary. Typical computing times for larger molecules take weeks, even on high-performance computers.

Read more on the HZB website

Image: The electronic structure of complex molecules can be assessed by the method of resonant inelastic X-ray scattering (RIXS) at BESSY II

Credit: © Martin Künsting /HZB

Solar hydrogen: Photoanodes made of α-SnWO4 promise high efficiencies

Photoanodes made of metal oxides are considered to be a viable solution for the production of hydrogen with sunlight. α-SnWO4 has optimal electronic properties for photoelectrochemical water splitting with sunlight, but corrodes easily. Protective layers of nickel oxide prevent corrosion, but reduce the photovoltage and limit the efficiency. Now a team at HZB has investigated at BESSY II what happens at the interface between the photoanode and the protective layer. Combined with theoretical methods, the measurement data reveal the presence of an oxide layer that impairs the efficiency of the photoanode.

Hydrogen is an important factor in a sustainable energy system. The gas stores energy in chemical form and can be used in many ways: as a fuel, a feedstock for other fuels and chemicals or even to generate electricity in fuel cells. One solution to produce hydrogen in a climate-neutral way is the electrochemical splitting of water with the help of sunlight. This requires photoelectrodes that provide a photovoltage and photocurrent when exposed to light and at the same time do not corrode in water. Metal oxide compounds have promising prerequisites for this. For example, solar water splitting devices using bismuth vanadate (BiVO4) photoelectrodes achieve already today ~8 % solar-to-hydrogen efficiency, which is close to the material’s theoretical maximum of 9 %.

Read more on the HZB website

Image: TEM-Image of a α-SnWOfilm (pink) coated with 20 nm NiO(green). At the interface of α-SnWO4 and NiOx an additional interfacial layer can be observed.

Credit: HZB

High Frequency-Couplers for bERLinPro prove resilient

In synchrotron light sources, an electron accelerator brings electron bunches to almost the speed of light so that they can emit the special “synchrotron light”. The electron bunches get their enormous energy and their special shape from a standing electromagnetic alternating field in so-called cavities. With high electron currents, as required in the bERLinPro project, the power needed for the stable excitation of this high-frequency alternating field is enormous. The coupling of this high power is achieved with special antennas, so-called couplers, and is considered a great scientific and technical challenge. Now, a first measurement campaign with optimised couplers at bERLinPro shows that the goal can be achieved.

Read more on the HZB website

Image: For the measurement campaign, two couplers were mounted in a horizontal test position under a local clean room tent.

Credit: © A. Neumann/HZB

Towards industrial-scale manufacturing of perovskite solar cells

For the production of high-quality metal-halide perovskite thin-films for large area photovoltaic modules often optimized inks are used which contain a mixture of solvents. An HZB team at BESSY II has now analysed the crystallisation processes within such mixtures. A model has also been developed to assess the kinetics of the crystallisation processes for different solvent mixtures. The results are of high importance for the further development of perovskite inks for industrial-scale deposition processes of these semiconductors.

Hybrid organic perovskite semiconductors are a class of materials for solar cells, which promise high efficiencies at low costs. They can be processed from precursor solutions that upon evaporation on a substrate form a polycrystalline thin film. Simple manufacturing processes, such as spin coating a precursor solution, often only lead to good results on a laboratory scale, i.e. for very small samples.

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Image: Schematic illustration: the solvants (ink) are used to produce a thin film of polycrystalline perovskite. 

Credit: © HZB

Graphite electrodes for rechargeable batteries investigated

Rechargeable graphite dual ion batteries are inexpensive and powerful.

A team of the Technical University of Berlin has investigated at the EDDI Beamline of BESSY II how the morphology of the graphite electrodes changes reversibly during cycling (operando).

The 3D X-ray tomography images combined with simultaneous diffraction now allow a precise evaluation of the processes, especially of changes in the volume of the electrodes. This can help to further optimise graphite electrodes.

Read more on the HZB website

Image: The tomogram during the charging process shows the spatially resolved changes in the graphite electrode thickness of a rechargeable aluminium ion battery in a discharged and charged state.

Credit: © HZB

Germanium telluride’s hidden properties revealed

Germanium Telluride is an interesting candidate material for spintronic devices. In a comprehensive study at BESSY II, a Helmholtz-RSF Joint Research Group has now revealed how the spin texture switches by ferroelectric polarization within individual nanodomains.

Germanium telluride (GeTe) is known as a ferrolectric Rashba semiconductor with a number of interesting properties. The crystals consist of nanodomains, whose ferrolectric polarization can be switched by external electric fields. Because of the so-called Rashba effect, this ferroelectricity can also be used to switch electron spins within each domain. Germanium telluride is therefore an interesting material for spintronic devices, which allow data processing with significantly less energy input.

Russian German Cooperation

Now a team from HZB and the Lomonosov Moscow State University, which has established a Helmholtz-RSF Joint Research Group, has provided comprehensive insights into this material at the nanoscale. The group is headed by physical chemist Dr. Lada Yashina (Lomonosov State University) and HZB physicist Dr. Jaime Sánchez-Barriga. “We have examined the material using a variety of state-of-the-art methods to not only determine its atomic structure, but also the internal correlation between its atomic and electronic structure at the nanoscale,” says Lada Yashina, who produced the high-quality crystalline samples in her laboratory.

Read more on the BESSY II website

Image: The Fermi surface of multidomain GeTe (111) bulk single crystal measured with high-resolution angle-resolved photoemission at BESSY II. © HZB

Order in the disorder: density fluctuations in amorphous silicon discovered

For the first time, a team at HZB has identified the atomic substructure of amorphous silicon with a resolution of 0.8 nanometres using X-ray and neutron scattering at BESSY II and BER II. Such a-Si:H thin films have been used for decades in solar cells, TFT displays, and detectors. The results show that three different phases form within the amorphous matrix, which dramatically influences the quality and lifetime of the semiconductor layer. The study was selected for the cover of the actual issue of Physical Review Letters.

Silicon does not have to be crystalline, but can also be produced as an amorphous thin film. In such amorphous films, the atomic structure is disordered like in a liquid or glass. If additional hydrogen is incorporated during the production of these thin layers, so-called a-Si:H layers are formed. “Such a-Si:H thin films have been known for decades and are used for various applications, for example as contact layers in world record tandem solar cells made of perovskite and silicon, recently developed by HZB” explains Prof. Klaus Lips from HZB. “With this study, we show that the a-Si:H is by no means a homogeneously amorphous material. The amorphous matrix is interspersed with nanometre-sized areas of varying local density, from cavities to areas of extremely high order,” the physicist comments.

Read more on the BESSY II website

Image: Structural model of highly porous a-Si:H, which was deposited very quickly, calculated based on measurement data. Densely ordered domains (DOD) are drawn in blue and cavities in red. The grey layer represents the disordered a-Si:H matrix. The round sections show the nanostructures enlarged to atomic resolution (below, Si atoms: grey, Si atoms on the surfaces of the voids: red; H: white) © Eike Gericke/HZB

Hope for better batteries – researchers follow the charging and discharging of silicon electrodes live

Using silicon as a material for electrodes in lithium-ion batteries promises a significant increase in battery amp-hour capacity.The shortcoming of this material is that it is easily damaged by the stress caused by charging and discharging.Scientists at the Helmholtz-Zentrum Berlin für Materialien und Energie (HZB) have now succeeded for the first time in observing this process directly on crystalline silicon electrodes in detail.Operando experiments using the BESSY II synchrotronprovided new insights into how fractures occur in silicon – and also how the material can nevertheless be utilised advantageously.

Whether in smartphones or electric cars – wherever mobile electric power needs to be available, it usually comes from rechargeable lithium-ion batteries. One of the two electrodes inside these batteries consists of graphite in which lithium ions are lodged, thereby storing electrical energy. The disadvantage of this carbon material is that its energy storage capacity is quite small – which makes frequent recharging of the battery necessary. For this reason, researchers worldwide are searching for alternative electrode materials to lengthen the battery charge/discharge cycles.

Read more on the Helmholtz Zentrum Berlin website

Image: The design of the experimental set-up shows how the structure of the silicon electrode periodically changes during charging and discharging on the basis of voltage measurements. © HZB

New substance library to accelerate the search for active compounds

In order to accelerate the systematic development of drugs, the MX team at the Helmholtz-Zentrum Berlin (HZB) and the Drug Design Group at the University of Marburg have established a new substance library. It consists of 1103 organic molecules that could be used as building blocks for new drugs. The MX team has now validated this library in collaboration with the FragMAX group at MAX IV. The substance library of the HZB is available for research worldwide and also plays a role in the search for substances active against SARS-CoV-2.

For drugs to be effective, they usually have to dock to proteins in the organism. Like a key in a lock, part of the drug molecule must fit into recesses or cavities of the target protein. For several years now, the team of the Macromolecular Crystallography Department (MX) at HZB headed by Dr. Manfred Weiss together with the Drug Design Group headed by Prof. Gerhard Klebe (University of Marburg) has therefore been working on building up what are known as fragment libraries. These consist of small organic molecules (fragments) with which the functionally important cavities on the surface of proteins can be probed and mapped. Protein crystals are saturated with the fragments and then analysed using powerful X-ray light. This allows three-dimensional structural information to be obtained at levels of atomic resolution. Among other things, it is possible to find out how well a specific molecule fragment docks to the target protein. The development of these substance libraries took place as part of the joint Frag4Lead research project and was funded by the German Federal Ministry of Education and Research (BMBF).

Read more on the BESSY II website

Image : For the study, the enzyme endothiapepsin (grey) was combined with molecules from the fragment library. The analysis shows that numerous substances are able to dock to the enzyme (blue and orange molecules). Every substance found is a potential starting point for the development of larger molecules. 

Credit: Wollenhaupt/HZB

Formation of a 2D meta-stable oxide in reactive environments

The chemical behaviour of solid material surfaces is an important physical characteristic for applications of catalysis, chemical sensors, fuel cells and electrodes. A research team from the Max Planck Institute for Chemical Energy Conversion has now described an important phenomenon that can occur when metal alloys are exposed to reactive environments at the synchrotron source BESSY II.

In a recent work published in ACS Applied Materials & Interfaces, a researchers’ team led by Dr. Mark Greiner (Surface Structure Analysis, Department of Heterogeneous Reactions) demonstrates an important phenomenon that can occur when metal alloys face reactive environments. They can form meta-stable 2D oxides on their surfaces. Such oxides exhibit chemical and electronic properties that are different from their bulk counterparts. Due to their meta-stability, their existence is also difficult to predict.

Read more on the BESSY II (at HZB) website

Image : Illustration of a CuxOy structure formed on a AgCu alloy in oxidizing environments described in this work. (c) ACS Applied Materials & Interfaces.

Credit: © (2020) ACS Publishing

Experiment shows for the first time in detail how electrolytes become metallic

An international team has developed a sophisticated experimental technique at BESSY II to observe the formation of a metallic conduction band in electrolytes.

To accomplish this, the team first prepared cryogenic solutions of liquid ammonia containing different concentrations of alkali metals. The colour of the solutions changes with concentration from blue to golden as the individual atoms of metal in solution transition to a metallic compound. The team then examined these liquid jets using soft X-rays at BESSY II and subsequently has been able to analyse this process in detail from the data they acquired combined with theoretical predictions. The work has been published in Science and appears even on the cover.

What distinguishes metals from other materials is generally well understood. In a metal, some of the atoms’ outer electrons move through the crystalline lattice in what is called a conduction band. This is how metals conduct electric current. In contrast to metals, the ions in electrolytes are disordered and electrical conductivity even decreases with increasing ion concentration. So how does metallic behaviour arise from the many individual metal atoms dissolved in the electrolyte? At what concentration and exactly how does a conduction band form, and how do the electron orbitals behave during this process?

>Read more on the Bessy II (at HZB) website

Image: The theorists in the team have elaborately simulated the structure of the solvated electron in liquid ammonia.

Credit : Charles Universität Prag/O. Maršálek & T. Martinek