Rich electronic features of a kagome superconductor

The recently discovered layered kagome metals AV3Sb5 (A=K, Rb, Cs) exhibit diverse correlated phenomena, thought to be linked to so-called Van Hove singularities (VHSs) and flat bands in the material. Using a combination of polarization-dependent angle-resolved photoemission spectroscopy (ARPES) and density-functional theory, researchers led by Professor Ming Shi at the Paul Scherrer Institute directly revealed the sublattice properties of 3d-orbital VHSs and flat bands, as well as topologically non-trivial surface states in CsV3Sb5. The research reveals important insights into the material’s electronic structure and provides a basis for understanding correlation phenomena in the metals.

So-called kagome metals, named after the Japanese woven bamboo pattern their structure resembles, feature symmetrical patterns of interlaced, corner-sharing triangles. This unusual lattice geometry and its inherent features lead, in turn, to curious quantum phenomena such as unconventional, or high-temperature, superconductivity.

The potential for devices that might transport electricity without dissipation at room temperature—as well as a thirst for fundamental theoretical understanding—have led researchers to investigate this new class of quantum materials and try to figure out how electrons interact with the kagome lattice to generate such remarkable features.

A recently discovered class of AV3Sb5 kagome metals, where A can be =K, Rb or Cs, was shown, for instance, to feature bulk superconductivity in single crystals at a maximum Tc of 2.5 at ambient pressure. Researchers suspect that this is a case of unconventional superconductivity, driven by some mechanism other than the phonon exchange that characterizes bonding in the electron-phonon coupled superconducting electron-pairs of conventional superconductivity.

This, as well as other exotic properties observed in the metal, are thought to be connected to its multiple “Van Hove singularities” (VHSs) near the Fermi level. VHSs, associated with the density of states (DOS), or set of different states that electrons may occupy at a particular energy level, can enhance correlation effects when a material is close to or reaches this energy level. If the Fermi level lies in the vicinity of a Van Hove point, the singular DOS determines the physical behavior due to the large number of available low-energy states. In particular, interaction effects get amplified not only in the particle-particle, but also in the particle-hole channels, leading to the notion of competing orders.

Read more on the PSI website

Image: Yong Hu, first author, and Nicholas Clark Plumb, who made the experimental station, at the Surface/Interface Spectroscopy (SIS) beamline of the Swiss Light Source (SLS) (L to R)

Credit: Paul Scherrer Institut / Mahir Dzambegovic

The fourth signature of the superconducting transition in cuprates

The results cap 15 years of detective work aimed at understanding how these materials transition into a superconducting state where they can conduct electricity with no loss.

When an exciting and unconventional new class of superconducting materials was discovered 35 years ago, researchers cheered.

Like other superconductors, these materials, known as copper oxides or cuprates, conducted electricity with no resistance or loss when chilled below a certain point – but at much higher temperatures than scientists had thought possible. This raised hopes of getting them to work at close to room temperature for perfectly efficient power lines and other uses.

Research quickly confirmed that they showed two more classic traits of the transition to a superconducting state: As superconductivity developed, the material expelled magnetic fields, so that a magnet placed on a chunk of the material would levitate above the surface. And its heat capacity – the amount of heat needed to raise their temperature by a given amount – showed a distinctive anomaly at the transition. 

But despite decades of effort with a variety of experimental tools, the fourth signature, which can be seen only on a microscopic scale, remained elusive: the way electrons pair up and condense into a sort of electron soup as the material transitions from its normal state to a superconducting state.

Now a research team at the Department of Energy’s SLAC National Accelerator Laboratory and Stanford University has finally revealed that fourth signature with precise, high-resolution measurements made with angle-resolved photoemission spectroscopy, or ARPES, which uses light to eject electrons from the material. Measuring the energy and momentum of those ejected electrons reveals how the electrons inside the material behave.

In a paper published in Nature, the team confirmed that the cuprate material they studied, known as Bi2212, made the transition to a superconducting state in two distinct steps and at very different temperatures.

Read more on the SLAC website

Image: How can you tell if a material is a superconductor? Four classic signatures are illustrated here. Left to right: 1) It conducts electricity with no resistance when chilled below a certain temperature. 2) It expels magnetic fields, so a magnet placed on top of it will levitate. 3) Its heat capacity – the amount of heat needed to raise its temperature by a given amount – shows a distinctive anomaly as the material transitions to a superconducting state. 4) And at that same transition point, its electrons pair up and condense into a sort of electron soup that allows current to flow freely. Now experiments at SLAC and Stanford have captured this fourth signature in cuprates, which become superconducting at relatively high temperatures, and shown that it occurs in two distinct steps and at very different temperatures. Knowing how that happens in fine detail suggests a new and very practical direction for research into these enigmatic materials.

Credit: Greg Stewart, SLAC National Accelerator Laboratory

Disorder brings out quantum physical talents

Quantum effects are most noticeable at extremely low temperatures, which limits their usefulness for technical applications. Thin films of MnSb2Te4, however, show new talents due to a small excess of manganese. Apparently, the resulting disorder provides spectacular properties: The material proves to be a topological insulator and is ferromagnetic up to comparatively high temperatures of 50 Kelvin, measurements at BESSY II show.  This makes this class of material suitable for quantum bits, but also for spintronics in general or applications in high-precision metrology.

Quantum effects such as the anomalous quantum Hall effect enable sensors of highest sensitivity, are the basis for spintronic components in future information technologies and also for qubits in quantum computers of the future. However, as a rule, the quantum effects relevant for this only show up clearly enough to make use of them at very low temperatures near absolute zero and in special material systems.

Read more on the HZB website

Image: The Dirac cone is typical for topological insulators and is practically unchanged on all 6 images (ARPES measurements at BESSY II). The blue arrow additionally shows the valence electrons in the volume. The synchrotron light probes both and can thus distinguish the Dirac cone at the surface (electrically conducting) from the three-dimensional volume (insulating).

Credit: © HZB

Unusual electronic properties taking shape

In a recent study, an international team led by researchers from The Pennsylvania State University in the US investigated the one-dimensional (1D) material tantalum selenide iodide (TaSe4 )2I. Its electronic properties had been theoretically predicted but not observed experimentally before the study conducted at the Bloch beamline. Evaporating iodine atoms turn out to drive unforeseen electronic changes.

Materials with unusual electronic properties such as charge density waves or topological states push the understanding of the fundamentals of quantum matter. They are also exciting candidates for the next generations of energy-efficient electronic and spintronic devices.

In the present study, the researchers found that the electronic properties of (TaSe4 )2I were different from the theoretical prediction. The band structure of a material can loosely be compared to a map of the material’s electronic properties. (TaSe4 )2I has something called Dirac bands, which is often found in this type of materials. The prediction said that the Dirac bands would split due to Weyl physics, which is not the case. The bands split with temperature, and the driver behind it is iodine atoms evaporating from the material’s surface.

Read more on the MAX IV website

Image: Surface charge induced Dirac band splitting in 1D material (TaSe4 )2I

Synthesis of mesoscale ordered 2D π-conjugated polymers with semiconducting properties

Two-dimensional materials can exhibit intriguing electronic properties that stem from their geometry. The best-known example is graphene’s Dirac cone that gives rise to massless electrons, which originates from the all-carbon hexagonal lattice. Two-dimensional conjugated polymers (2DCPs) can be considered as analogues of graphene, yet offering greater potential to design geometry and properties by carefully selecting their building blocks. Strikingly, 2DCPs on a kagome lattice (i.e. a trihexagonal tiling) can show both Dirac cones and flat bands, with highly-massive charge carriers.

Despite experimental efforts spanning more than a decade, the poor crystallinity of the synthesized polymers made the study of the electronic properties of 2DCPs a scientific niche reserved to theorists. A collaboration between the “Istituto di Struttura della Materia” of the Italian CNR three Canadian universities (INRS, McGill and Lakehead) realized the milestone of the synthesis of a long-range ordered 2D polymeric network, enabling the measurement of their Dirac cone and flat band features by angle-resolved photoelectron spectroscopy (ARPES). This achievement paves the way to study the intriguing electronic properties of this new class of materials, which make them promising for applications in future electronic and optoelectronic technologies.

Read more on the Elettra website

Image :  a) Scanning tunneling microscope image of a highly-ordered polymeric network with the theoretical model superimposed b) second derivative of the ARPES map for the polymer on Au(111) along the ΓKM direction, where it is possible to observe the Dirac cone feature converging at a Dirac point (DP) around 0.55 eV; the theoretical calculated band structure is superimposed.

Beyond graphene: monolayer arsenene observed for the first time

An article recently published in 2D Materials shows the first experimental evidence of the successful formation of arsenene, an analogue of graphene with noteworthy semiconducting properties.

This material shows a great potential for the development of new nanoelectronics. Crucial sample preparation and electron spectroscopy experiments were performed at the Bloch beamline at MAX IV.

The discovery of graphene, the single-layer carbon honeycomb material worth the Nobel Prize in Physics in 2010, surely has had a revolutionary impact on research. It triggered a whole new field of study within two-dimensional (2D) materials. However, its application in developing new 2D electronics has been hindered by its lack on an intrinsic band gap. Researchers therefore started to turn their attention to other elements in the periodic table and set their eyes on group V, to which arsenic belongs.
“The aim of the study was to show that arsenene can be formed. Our article is the first to report this”, says Roger Uhrberg, professor at Linköping University and spokesperson for the Bloch beamline at MAX IV. Arsenene, a single-layer buckled honeycomb structure of arsenic, had been previously predicted by various theoretical studies, but this is the first experimental observation that verifies its existence.

>Read more on the MAX IV website

Image: A view of the Bloch beamline at MAX IV. The Bloch beamline consists of two branchlines, and is dedicated to high resolution photoelectron spectroscopy, encompassing angle-resolved (ARPES), spin resolved (spin-ARPES) and core-level spectroscopy.

Visualizing electrostatic gating effects in two-dimensional heterostructures

Electronic and optoelectronic devices utilise electric fields to manipulate material properties, controlling band structures and band alignments across heterostructures that combine metals, semiconductors and insulators. With two-dimensional materials, 2D heterostructures (2DHS) can be fabricated with atomic precision by simply stacking layers. In these, applied out-of-plane electric fields are a powerful tool that can be used to degenerately dope semiconductors, modify electronic structure through the Stark effect, and alter band-alignments between layers. As a result, out-of-plane electric fields have been used to engineer functional architectures such as high-efficiency light-emitting diodes and tunnelling transistors, and to probe many-body phenomena.
Despite the fundamental importance of electric-field control over band structure, direct experimental measurements are challenging and have been limited. Whilst gate electrodes are routinely applied for electrical transport investigations, and many studies have reported electric-field dependent light-emission from 2DHS, these depend upon but do not directly reveal the single-particle electronic structure. Angle resolved photoemission spectroscopy (ARPES) has proven to be a powerful tool for probing the momentum-resolved valence band structure of 2D materials such as graphene and semiconducting transition metal dichalcogenides (MX2). But it is challenging to apply conventional ARPES, which typically averages over lengthscales > 100 µm, to 2DHS which are usually only a few µm across. Using the high spatial resolution and flux of the Spectromicroscopy beamline at Elettra, we have shown that submicrometre spatially resolved ARPES (µARPES) can determine band parameters and band alignments across 2DHS of mechanically exfoliated flakes. These heterostructures are similar to those used for optical spectroscopy and transport measurements, opening the way to study operating devices.

>Read more on the Elettra website

Illustration: Direct momentum-resolved electronic structure measurements of in-operando microelectronic devices.

Progress on low energy electronics

Soft X-ray experiments used to characterise new thin film topological Dirac Semimetal

A large international collaboration including scientists from Monash University, the ARC Centre for Future Low Energy Electronics (FLEET), the Monash Centre for Anatomically Thin Materials and the Australian Synchrotron reported today in Nature on the development of an advanced material that is able to switch between an electrically conductive state to an insulating state, simply by applying an electric field.
The work represents a step towards the development of a new generation of ultra-low energy electronics at room temperature. 
Co-author Dr Anton Tadich, a beamline scientist at the Soft X-ray beamline and Partner Investigator with FLEET, collaborated with investigators from Monash University, Singapore and Lawrence Berkeley National Lab on the use of photoemission techniques at the Australian Synchrotron X-ray Photoelectron Spectroscopy (XPS) and the Advanced Light Source in the US Angle Resolved Photoelectron Spectroscopy, (ARPES).
The chemical composition and growth mechanisms of thin films of the topological Dirac semi-metal sodium bismuthide Na3Bi on a silicon substrate was investigated using XPS at the Australian Synchrotron’s Soft X-ray beamline.

>Read more on the Australian Synchrotron at ANSTO website

Doped epitaxial graphene close to the Lifshitz transition

Graphene, an spbonded sheet of carbon atoms, is still attracting lots of interest almost 15 years after its discovery. Angle-resolved photoemission spectroscopy (ARPES) is a uniquely powerful method to study the electronic structure of graphene and it has been used extensively to study the coupling of electrons to lattice vibrations (phonons) in doped graphene. This electron-phonon coupling (EPC) manifests as a so-called “kink” feature in the electronic band structure probed by ARPES. What is much less explored is the effect of EPC on the phonon structure. A very accurate probe of the phonons in graphene is Raman spectroscopy.
M.G. Hell and colleagues from Germany, Italy, Indonesia, and Japan combined ARPES (carried out at the BaDelPhbeamline – see Figure 1) with low energy electron diffraction (LEED) and Raman spectroscopy (carried out at the University of Cologne in Germany) in a clever way to fully understand the coupled electron-phonon system in alkali metal doped graphene. LEED revealed ordered (1×1), (2×2), and (sqrt3xsqrt3)R30°adsorbate patterns with increasing alkali metal deposition. The ARPES analysis yielded not only the carrier concentration but also the EPC coupling constant. Ultra-High Vacuum (UHV) Raman spectra carried out using identically prepared samples with the very same carrier concentrations provided the EPC induced changes in the phonon frequencies.

>Read more on the Elettra Sincrotrone Trieste website

Image:  Top: ARPES spectra along the Γ-K-M high symmetry direction of the hexagonal Brillouin zone for Cs doped graphene/Ir(111) with increasing Cs deposition. The Dirac energy ED and the observed LEED reconstruction are also indicated. Bottom: Corresponding Fermi surfaces at the indicated charge carrier concentration. 

Graphene on the way to superconductivity

Scientists at HZB have found evidence that double layers of graphene have a property that may let them conduct current completely without resistance. They probed the bandstructure at BESSY II with extremely high resolution ARPES and could identify a flat area at a surprising location.

Carbon atoms have diverse possibilities to form bonds. Pure carbon can therefore occur in many forms, as diamond, graphite, as nanotubes, football molecules or as a honeycomb-net with hexagonal meshes, graphene. This exotic, strictly two-dimensional material conducts electricity excellently, but is not a superconductor. But perhaps this can be changed.

A complicated option for superconductivity
In April 2018, a group at MIT, USA, showed that it is possible to generate a form of superconductivity in a system of two layers of graphene under very specific conditions: To do this, the two hexagonal nets must be twisted against each other by exactly the magic angle of 1.1°. Under this condition a flat band forms in the electronic structure. The preparation of samples from two layers of graphene with such an exactly adjusted twist is complex, and not suitable for mass production. Nevertheless, the study has attracted a lot of attention among experts.

>Read more on the BESSY II at HZB website

Image: The data show that In the case of the two-layer graphene, a flat part of bandstructure only 200 milli-electron volts below the Fermi energy. Credit: HZB

The human behind the beamline

Happy Birthday, Felix Bloch – 23rd October 1905

Felix Bloch was born on this day (23rd October) in 1905 in Zürich, Switzerland. He got a Ph.D. in 1928 studying under Werner Heisenberg. In his thesis, he established the quantum theory of solids describing how electrons moved through crystalline materials using Bloch waves. The phenomena he described are observed today using the technique ARPES which is carried out at the Bloch beamline at MAX IV.

>Read more on the MAX IV Laboratory website

Image: Detail of a Max Bloch illustration. To discover the entire illustration click here.
Credit: Emelie Hilner.

Blue phosphorus – mapped and measured for the first time

For the first time an HZB team was able to examine samples of blue phosphorus at BESSY II and confirm via mapping of their electronic band structure that this is actually this exotic phosphorus modification.

Blue phosphorus is an interesting candidate for new optoelectronic devices. The results have been published in Nano Letters.
The element phosphorus can exist in  various allotropes and changes its properties with each new form. So far, red, violet, white and black phosphorus have been known. While some phosphorus compounds are essential for life, white phosphorus is poisonous and inflammable and black phosphorus – on the contrary – particularly robust. Now, another allotrope has been identified: In 2014, a team from Michigan State University, USA, performed model calculations to predict that “blue phosphorus” should be also stable. In this form, the phosphorus atoms arrange in a honeycomb structure similar to graphene, however, not completely flat but regularly “buckled”. Model calculations showed that blue phosphorus is not a narrow gap semiconductor like black phosphorus in the bulk but possesses the properties of a semiconductor with a rather large band gap of 2 electron volts. This large gap, which is seven times larger than in bulk black phosphorus, is important for optoelectronic applications.

>Read more on the BESSY II at HZB website

Image: https://pubs.acs.org/doi/10.1021/acs.nanolett.8b01305

Lattice Coupling conspires in the correlated cuprate high-Tc superconductivity

For the cuprate high temperature superconductivity (high-Tc) research over the past three decades, the biggest challenge is to identify the relevant low energy degrees of freedom that are critical to formulating the correct theoretical model for high-Tc superconductivity. The main difficulty lies in the closeness between various relevant energy scales. For low energy processes that are comparable to the superconducting gap energy ∆sc, there are the spin exchange energy J, the lattice vibration (phonon) energy Ωph, and the van Hove singularity energy E(π,0). However, anomalous isotope effects on Tc and superfluid density in the cuprates cannot be captured by traditional phonon-mediated superconductivity theories. Historically, a purely electronic Hamiltonian – the Hubbard model – was widely regarded to encapsulate all the core physics of the high-Tc phenomena.

In a recent paper published in Science, scientists from Stanford University and from Stanford Institute for Materials and Energy Sciences (SIMES), in collaboration with material scientists from Japan and theoreticians from Japan, the Netherlands, and Berkeley, reinstated the substantial role of the lattice vibration in the cuprate high-Tc superconductivity – however, in a subtle way that is highly intertwined with the electronic correlations. They finely straddled 18 differently hole-doped high-Tc compound Bi2Sr2CaCu2O8+δ within 8% change of hole carrier concentration, a doping range where Tc evolves from 47 K to 95 K through a putative quantum critical point, around which the electronic correlation effect experiences a sudden change. Then systematic experiments were carried out using the angle-resolved photoemission spectroscopy (ARPES) facility at SSRL Beam Line 5-4. Here, the high-resolution ARPES end station provided critical information of both the superconducting gap and the electron-lattice coupling.

>Read more on the Stanford Synchrotron Radiation Lightsource website

Image: Intertwined growth of the superconductivity and the electron-phonon coupling tuned by the hole concentration. The red line is an illustration of the Tc in Bi-2212 (Tcmax = 95 K). The blue shade and line represent the single-layer Bi-2201 system, where the coupling to the B1g mode is weak and T max is only 38 K. The yellow ball represents the optimally doped tri-layer Bi-2223 where Tcmax is 108 K. The top-right inset shows the intertwined relation between the pseudogap and the EPC under strong electronic correlation. The Madelung potential and the lattice stacking along the c-axis are schematically depicted for the single- layer, bi-layer and tri-layer systems. The dark grey blocks represent the CuO2n- plane, and the light grey blocks represent the charge reservoir layers (Ca2+, SrO, BiO+). The orange dots mark the CuO2n- planes that experience to the first order a non-zero out-of-plane electric field.
Credit: Science, doi: 10.1126/science.aar3394

The electronic structure of a “Kagome” material

Functionalized graphdiyne nanowires

… on-surface synthesis and assessment of band structure, flexibility, and information storage potential

With their extraordinary mechanical and electronic properties carbon-based nanomaterials are central in 21st century research and carry high hopes for future nanotechnology applications. Established sp2-hybridized scaffolds include carbon nanotubes (CNTs), graphene sheets, and graphene nanoribbons. Recently, the interest in carbon allotropes incorporating both sp2and sp-hybridized atoms rose tremendously, especially for the most popular member, the so-called graphdiyne. According to theory, the related nanomaterials possess characteristics desirable for applications such as molecular electronics, energy storage, gas filtering and light harvesting. However, achieving the targeted materials with high quality remained challenging until now.
Here, we employed covalent on-surface synthesis on well-defined metal substrates under ultra-high vacuum (UHV) conditions to the homocoupling reaction of terminal alkyne compounds and fabricated the first functionalized graphdiyne (f-GDY) nanowires. Combining the substrate templating of the Ag(455) vicinal surface with specifically designed CN-functionalized precursors we achieved the controlled polymerization to atom-precise strands with their length reaching 40 nm. The left panel of Figure 1a depicts a scanning tunneling microscopy (STM) image of an area of the silver surface featuring two step edges where an example of such a f-GDY wire is lying at the lower side of the right step edge. The right panel displays a molecular model of the situation highlighting the structure of the nanowire adsorbed in the lower terrace (darker blue) consisting of covalently coupled monomers (red outline) with the CN moieties pointing towards the atoms of the upper terrace (brighter blue).

>Read more on the Elettra Sincrotrone website

Figure: (extract)  Synthesis and characterization of functionalized graphdiyne nanowires. a) STM topograph of a f-GDY polymer covering the left step edge. b) ARPES data: Before annealing a non-dispersing feature originates from the HOMO of the monomer. After annealing a dispersing features (blue) can be identified. c) Schematic representation of the deduced intrinsic band structure of the f-GDY nanowires. d) STM topograph of a strongly bent nanowire. e) Information storage thru conformational cis-trans switching of benzonitrile units. Full image here.

Bespoke beamline engineering: the Diamond Sample Manipulator

The Surface and Interfaces village brings together six beamlines with a range of techniques for investigating structural, magnetic and electronic properties of surfaces and interfaces. Many of those beamlines rely on a Sample Manipulator to hold samples securely in an X-ray beam less than a tenth of a millimetre across, whilst also enabling them to move and rotate around multiple axes and rotate around each axis. The differing requirements of each beamline mean that the basic design of the Sample Manipulator is customised for each one.

The I09 beamline, for example, is used for studying atomic structures and electronic properties across a wide variety of surfaces and material interfaces. The Sample Manipulator on I09 makes it possible to use X-ray techniques to study monolayer adsorption and surface reconstructions in a vacuum, crystalline and non-crystalline thin films, nano-particulates, large molecules and complex organic films and magnetism and magnetic thin-films.

>Read more on the Diamond Light Source website

Image: The Sample Manipulator in situ as seen through the vacuum window.
Credit: Diamond Light Source.