Author: Iñigo Careaga, strategy & communication manager, CIC energiGUNE

Lithium and sodium are neighbours in the periodic table. Both are alkali metals, both have a single electron in their outer shell, and both can be used to shuttle ions between two electrodes to store and release electrical energy. At first sight, replacing lithium with sodium in a rechargeable battery might therefore seem straightforward.

There are good reasons to try. Sodium is widely available and sodium-ion batteries can rely on electrode materials containing abundant elements such as iron and manganese. But chemical similarity does not mean electrochemical equivalence. A sodium ion is larger and heavier than a lithium ion, and its interaction with the materials surrounding it is different. As a consequence, replacing Li⁺ with Na⁺ changes much more than the identity of the charge carrier.

The electrodes have to accommodate a different ion. Their structures may respond differently as sodium is inserted and removed. The electrolyte has to transport and solvate it. New interfaces form between the electrolyte and the electrodes. Even graphite, the standard anode material of most commercial lithium-ion batteries, does not store sodium under conventional conditions nearly as effectively as it stores lithium ¹.

A sodium-ion battery is therefore not simply a lithium-ion battery containing a different element. Understanding why requires looking at what happens to sodium once it enters the battery.

Graphite does not play by the same rules

Charging a conventional lithium-ion battery involves moving lithium ions from the positive electrode through the electrolyte and storing them in the negative electrode. Graphite is particularly good at this job. Its carbon atoms are arranged in sheets, and lithium can reversibly occupy the spaces between them, a process known as intercalation. It would be convenient if sodium behaved in the same way. It largely does not.

The poor ability of conventional graphite to accommodate sodium has long been one of the reasons why lithium-ion concepts cannot simply be transferred to sodium-ion batteries. Instead, one of the most widely studied negative-electrode materials is hard carbon ².

Hard carbon is still carbon, but structurally it is very different from graphite. Rather than a regular stack of extended carbon sheets, it contains disordered graphitic domains, defects and pores. This disordered architecture provides environments in which sodium can be stored, but it also makes the underlying mechanism considerably harder to describe.

Where exactly does the sodium go? Researchers have proposed contributions from adsorption at defects and surfaces, insertion between graphitic layers and storage associated with nanopores. The relative importance of these mechanisms depends on the structure and microstructure of the carbon. This is more than a microscopic detail: where and how sodium is stored determines the voltage profile, reversible capacity, first-cycle losses and, ultimately, the energy that a complete cell can deliver.

Researchers at CIC energiGUNE and collaborators have studied this connection between charge-storage mechanisms, carbon structure and electrochemical performance ³. Their analysis highlights an important point: maximizing the amount of sodium that an anode can store is not enough. The potential at which that storage occurs and the irreversible losses during the first cycle are equally important when the material is incorporated into a full battery.

The problem is therefore not simply to find a carbon that accommodates more sodium. It is to understand how its structure stores sodium and then engineer that structure so that capacity, voltage and efficiency improve together. This has led researchers to explore different ways of controlling hard-carbon structure, including the use of lignocellulosic biomass as a precursor. Work has shown that even apparently simple processing decisions, such as acid treatment of the biomass precursor, can affect the resulting carbon and its behaviour as a sodium-ion anode ⁴.

And the negative electrode is only half of the problem. At the positive electrode, sodium ions have to repeatedly leave and re-enter a solid structure. Layered transition-metal oxides are attractive candidates because sodium can be reversibly extracted from and inserted into spaces between layers of metal and oxygen atoms. Compositions based on relatively abundant elements such as iron and manganese are particularly interesting ⁵.

Again, however, accommodating sodium is not enough. The host structure has to survive the process. A useful example is the layered oxide P2-Na₂/₃[Fe₁/₂Mn₁/₂]O₂, investigated by researchers from CIC energiGUNE and collaborators ⁶. The material can provide high capacity, but its long-term stability strongly depends on the voltage range over which it is operated.

This produces a familiar battery dilemma. Increasing the operating voltage can increase the amount of energy extracted from a material. But pushing the electrode further can also trigger structural transformations that make subsequent cycles less reversible.

The researchers compared cells operating in different voltage windows and combined electrochemical measurements with structural characterization and theoretical calculations. Above approximately 4.0 V versus Na+/Na, the cathode undergoes a high-voltage phase transition. Avoiding this transition improves capacity retention, revealing a direct connection between the structural state of the electrode and its long-term electrochemical behaviour.

Changing the chemical composition can also alter this structural response. In another study, researchers investigated the effect of introducing titanium into sodium manganese-rich layered oxides ⁷. A certain degree of Ti substitution helped the crystal structure accommodate electrochemically induced strain. Too little was insufficient to stabilize it, while further substitution introduced other destabilizing effects.

Other studies have approached the same problem from a different angle, examining how the precise stoichiometry of P2 layered oxides affects their performance ⁸, or following their structural evolution under different current rates and dopants using operando techniques ⁹. The lesson is that there is no single property called “a good sodium cathode”. Composition, atomic arrangement, voltage and cycling conditions are interconnected. Even an element that does not directly provide the stored charge can determine how well the electrode survives sodium repeatedly moving through its structure.

A different chemistry

Layered oxides are not the only possible positive electrodes. Sodium chemistry allows other structural families to be explored.

One particularly instructive example is NaFePO₄, the sodium analogue of the well-known lithium iron phosphate chemistry. Researchers involving CIC energiGUNE have used in situ X-ray diffraction to follow how NaFePO₄ changes during sodium insertion and extraction ¹⁰. They have also shown that the reaction mechanism itself depends on how rapidly the electrode is charged or discharged ¹¹.

This is a subtle but important point. We often describe an electrode material as if it had a fixed reaction mechanism. In practice, what happens inside it can depend on how the battery is operated. Computational work has gone further by investigating sodium diffusion in NaₓFePO₄ ¹². Combining experiments and modelling in this way makes it possible to connect what is observed at the battery level with the motion of ions through an atomic structure.

But even understanding both electrodes is not enough. Between them lies the electrolyte, and the sodium ion spends much of its journey there. It becomes surrounded by solvent molecules, travels across the cell and eventually reaches an electrode surface. At that interface the electrolyte can decompose, producing a solid-electrolyte interphase, or SEI.

This apparently thin layer can have a disproportionate influence on battery behaviour. Researchers at CIC energiGUNE have investigated both the composition and evolution of the SEI in sodium-ion electrodes ¹³ and, more broadly, the relationship between electrode-electrolyte interphases, transport properties and electrochemical performance in non-aqueous sodium-ion batteries ¹⁴.

The interface illustrates particularly well why changing lithium for sodium is not a simple substitution. The chemistry of the ion influences its solvation, its transport and the decomposition reactions that occur when it reaches an electrode. A material that can reversibly store sodium may still perform poorly if the interface around it continuously consumes electrolyte or sodium during cycling.

This is why sodium-ion research has to consider the cell as a system. Graphite may have to give way to hard carbon. Positive electrodes require structures able to tolerate repeated sodium insertion and extraction. Electrolytes and additives have to create suitable transport conditions and stable interfaces.

And every attempt to solve one of these problems can affect the others.

Sodium is not the new lithium

Lithium has a fundamental advantage that materials engineering cannot simply remove: it is the lightest metal and has a very low electrochemical potential. Sodium is heavier and its electrochemical potential is less favourable, placing intrinsic constraints on the gravimetric energy density that sodium-ion batteries can reach.

That does not necessarily make sodium a worse battery chemistry. Energy density is only one parameter of an electrochemical storage system. Cost, raw-material availability, lifetime, power, safety and operating temperature can become equally important depending on the application. A battery designed for a mobile phone, an electric vehicle or stationary storage does not necessarily have to optimize the same variables. And sodium chemistry itself offers several possible ways of balancing them.

CIC energiGUNE researchers have explored, for example, low-cost phosphate-based cathodes for aqueous sodium-ion batteries ¹⁵, Prussian Blue compounds as positive electrodes in aqueous systems ¹⁶, alternative sodium layered oxides [5,8,9], hard-carbon anodes [2,3,4] and even materials such as NaTiOPO₄ designed to modify or potentially avoid some of the interfacial problems normally associated with sodium-ion anodes ¹⁷.

These are not different routes towards exactly the same battery. They represent different ways of deciding which compromises are acceptable.

This changes the original question. The relevant challenge may not be how to make sodium behave as much like lithium as possible. Research on hard carbons shows that sodium may require a different type of host structure. Work on layered oxides shows that extracting more energy from an electrode can alter its structure and compromise its stability. Studies of NaFePO₄ show that the reaction pathway itself can depend on cycling conditions. And research on interfaces shows that storing sodium reversibly is only part of the problem: the chemistry taking place around the active material matters as well.

Sodium-ion batteries are therefore not lithium-ion batteries in which one element has simply been exchanged for another. Changing the ion changes the materials that host it, the structures they adopt, the reactions they undergo and the interfaces they form.

Sodium may not need to beat lithium at its own game. The more interesting question is whether understanding its different chemistry will allow us to play a different one.

 

The BRTA is a consortium that remains a step ahead of future socio-economic challenges worldwide and in the Basque Autonomous Community; it addresses them through research and technological development, thus projecting itself internationally. The BRTA centres collaborate to generate knowledge and transfer it to Basque society and industry so as to make them more innovative and competitive. The BRTA is an alliance of 17 R&D centres and cooperative research centres with the support of the Basque Government, the SPRI and the Chartered Provincial Councils of Araba, Bizkaia and Gipuzkoa.

 

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The membrane uses hydrogen and palladium to dismantle troublesome PFAS.

Scientists have discovered a class of metal that can unexpectedly resist extreme cold using an unusual mechanism. Normally such temperatures would make similar materials brittle and vulnerable to breaking. The findings point to new principles for designing materials for cryogenic environments.

An international team led by University of California, Berkeley, Lawrence Berkeley National Laboratory and the University of Oxford has uncovered ¹ a novel microscopic mechanism that allows two metal alloys to remain remarkably damage-tolerant at just 20 kelvin, or -253°C.

Most metals become stronger when they are cooled, but some pay a price. The class of metals called body-centred cubic metals (such as iron, tungsten and chromium) have a particular atomic structure which can make them increasingly brittle as temperatures fall. At extremely low temperatures, a crack that might normally be absorbed by the metal bending or deforming can instead cause it to fracture.

The new study discovered that two experimental niobium-titanium-based alloys can avoid this problem even at just 20 kelvin, or -253°C. The metals remained remarkably resistant to cracking, with no measurable transition to brittle behaviour at the lowest temperature tested. The researchers found that this is due to the alloys effectively switching how they deform as they enter the deep freeze.

Normally, bending and deformation of body-centred cubic metals relies heavily on the movement of line-like defects in their crystal structure known as dislocations. At low temperatures, these become increasingly difficult to move, restricting the material’s ability to deform around a crack and making a fracture more likely.

In the alloys studied, however, a different process takes over. The researchers observed nanoscale ‘twinning’, in which small regions of the crystal reorganise into mirror-image orientations, coupled with a local transformation of the crystal structure. When these newly formed structures reach the boundaries between neighbouring crystals, they create concentrated points of stress that trigger new defects in the metal. These defects then allow the material to keep deforming rather than cracking.

The process is a little like a road network responding to frozen, blocked roads by opening new routes. As the conventional routes for deformation become increasingly difficult to use, the formation of twins creates new sites from which the defects needed for deformation can emerge. This helps the metal to absorb the forces building up around a crack, rather than breaking.

The discovery could provide scientists with a new strategy for designing metals capable of operating in exceptionally cold environments, including for energy, transport and aerospace sectors.

To find out how the alloys behaved in such extreme cold, the researchers used the Engin-X instrument at the ISIS Neutron and Muon Source in Oxfordshire. They cooled samples to around -253°C using gaseous helium. They then exposed the samples to a beam of neutrons while a testing machine pulled them from either end, precisely measuring how much force they could withstand and how far they stretched before breaking.

The team then used powerful electron microscopes to examine the tested metal at extremely small scales, allowing them to see the tiny structural changes that had taken place around cracks and inside the material. They also used atom-probe analysis to map the distribution of individual elements, alongside computer modelling to understand how the different mechanisms worked together to prevent brittle failure.

The study involved researchers from the University of California, Berkeley; Lawrence Berkeley National Laboratory; the University of Oxford; the University of Bristol; the ISIS Neutron and Muon Source, Science and Technology Facilities Council; the University of California, Irvine; Pacific Northwest National Laboratory; Texas A&M University; and Nanyang Technological University in Singapore.

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In 2004, physicists isolated graphene, a sheet of carbon just one atom thick. It launched the study of two-dimensional (2D) materials: crystals a few atoms thick in which electrons are confined to a plane and can behave quite differently from those in ordinary solids. The family of known and predicted 2D crystals has since grown to thousands of members. Two recent studies show how computation can search that family for the most promising ones, the first for unusual electronic “topology”, the second for crystals well suited to twisting.

A hidden property of electrons

Electrons in a crystal can only have energies within allowed ranges called bands, separated by forbidden gaps. If a gap separates the filled electrons from the empty states, the material is an insulator. In a semimetal, filled and empty bands just touch, so a few electrons can move freely.

Two insulators can still differ at a deeper level, described by topology: a property of the whole set of electron states that cannot change smoothly, only by closing the gap or breaking a protecting symmetry. A doughnut and a coffee mug are topologically alike because each has one hole, and neither can become a sphere without tearing.

The idea took off with the quantum spin Hall effect. Proposed for graphene in 2005, it proved unobservable there because the effect is far too weak. A 2006 proposal for thin layers of mercury telluride was confirmed in 2007. In such a topological insulator the interior blocks current, yet the edges conduct, with electrons of opposite spin travelling in opposite directions, which protects them against many kinds of imperfection.

Symmetry-based methods known as topological quantum chemistry in 2017 made it possible to decide whether a computed electronic structure is topological. Applied to three-dimensional crystals, they pointed to thousands of candidates. Flat crystals lagged behind, with only about 400 known topological or related monolayers.

The first study, “Two-dimensional Topological Quantum Chemistry and Catalog of Topological Materials” ¹, adapts these methods to 2D crystals and applies them to 8,872 entries in two computational databases. It finds 4,073 with nontrivial topology or a related property called obstruction, including 905 topological insulators, 2,129 topological semimetals and 1,003 obstructed atomic insulators, plus 36 close variants. In an obstructed insulator the electrons are centred on empty positions between the atoms rather than on the atoms themselves. The bulk looks ordinary, but cutting the crystal along certain lines produces edge states, and small flakes can carry fractions of an electron’s charge at their corners. The study also calculates edge states for selected materials. Its catalogue includes over 100 monolayers already made in laboratories, but most entries are computer predictions whose properties remain to be tested.

Twisting layers

Stack two atomic sheets and rotate one slightly, and the mismatch creates a large interference pattern, called a moiré pattern, much like two overlapping window screens. Electrons feel this longer repeating pattern, and under the right conditions their bands become nearly flat. Electrons in a flat band have little energy of motion, so their mutual repulsion dominates and strongly correlated behaviour can emerge.

In 2011, calculations predicted that two graphene sheets twisted by about 1.1 degrees, a “magic angle”, would have such flat bands. In 2018, experiments at that angle revealed insulating states caused by electron repulsion, and superconductivity. Twisted layers of other materials, such as MoTe₂ and WSe₂, have since shown many correlated phases, though the mechanisms are still debated.

Most work has focused on these few materials, because most crystals have electronic structures too complicated to predict once twisted. The second study, “2D theoretically twistable material database” ², therefore defines a material as theoretically twistable if its low-energy electrons admit a simple description. In a metal, the relevant electrons must sit at isolated points, as in graphene. In an insulator, the top of the filled band or the bottom of the empty band must stand clear of other bands. Insulators must also have gaps between 0.2 and 3 electronvolts, because larger gaps make electrical contacts difficult. The search was limited to crystals with at most 12 atoms in the repeating cell and four chemical elements.

Starting from the first study’s database, it identifies 61 semimetals and 1,568 insulators. It ranks them with a score and sorts them by lattice shape (about half are hexagonal), by where in momentum space the relevant electrons sit, and by the strength of spin-orbit coupling, the link between an electron’s spin and its motion. These choices shape the moiré pattern, which can resemble honeycomb, kagome or square lattices. Square-lattice moiré systems have been proposed but not yet realized, and could help simulate models relevant to cuprate superconductors.

Calculations on twisted bilayers of SnSe₂, SnS₂, ZrS₂, HfS₂ and Sc₂CCl₂ at a twist of about 7 degrees show isolated flat bands, as the database predicts. Experiments connect the theory to the laboratory. Bulk crystals of SnSe₂, SnS₂, HfS₂, GaTe and ZrNCl were grown. Single layers of several candidates, including SnSe₂, HfSe₂, ZrS₂ and WS₂, were peeled off with a gold-assisted technique that yields larger, cleaner flakes. A dual-gated two-layer SnSe₂ device was built for electrical measurements, and a twisted two-layer HfS₂ device was used for scanning tunnelling measurements near absolute zero.

The direction is clear. Instead of discovering materials by trial and error, it is becoming possible to search systematically for crystals with chosen properties, then test them layer by layer.

 

Author: César Tomé López is a science writer and the editor of Mapping Ignorance

Disclaimer: Parts of this article may have been copied verbatim or almost verbatim from the referenced research paper/s.

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Scientists have developed remarkably long, precisely patterned molecular threads that could open new possibilities for designing advanced materials. The scientists also discovered these threads — called supramolecular polymers — can dramatically enhance brain cell activity. ¹

Built from self-assembling molecules, the longest threads reach dimensions greater than the diameter of a cell. By molecular standards, they are giant — roughly 100 times more massive than even very large conventional polymers and the largest known proteins in biology. Yet despite their enormous size, scientists can precisely control their lengths and organize them into chemically distinct segments with defined dimensions carrying opposite electrical charges.

That precision also produced an unexpected biological effect. In cell culture studies, the structures enhanced the growth and organization of neurons and increased synapse formation.

The findings introduce a new way to use self-assembly to build highly controlled supramolecular materials with precise physical arrangement of chemical structures. Ultimately, the work could inform materials’ design for a range of applications, including biomaterials for regenerative medicine.

“These structures represent a breakthrough in materials design, and we already discovered one useful application: their superbioactivity toward neurons, which will bring new opportunities in regenerative medicine,” said Northwestern’s Samuel I. Stupp, who led the study. “Typically, when we design a regenerative material, we add biological signals, designed to activate cell receptors. Here, the material itself becomes highly bioactive simply through the precise organization of electrical charges and its dynamic behavior. That introduces a very different way of thinking about how materials can communicate with cells.”

Bringing precision to self-assembly

The new study builds on Stupp’s long history working with supramolecular materials, dynamic structures that form when molecules spontaneously organize through weak, reversible interactions. While conventional polymers, like plastics, hold together using strong, permanent chemical bonds, supramolecular polymers are dynamic, allowing their components to move and reconfigure, which generates life-like properties in synthetic systems. Supramolecular polymers exist in all living organisms, where they perform essential functions and hold promise for future soft matter technologies.

That flexible, dynamic nature can be useful for interacting with living cells in biomedical applications, but it also makes the structures difficult to control. Scientists can design the individual molecular building blocks but then struggle to control how long the resulting structures grow and how they organize their chemical components.

Stupp’s team overcame that limitation by using novel designs of molecules and carefully controlling their assembly process. With this strategy, the researchers could dictate the threads’ lengths and keep them uniform. Once the growth stopped, the structures maintained their precise lengths rather than fusing together or rearranging.

“We let these filaments sit in a test tube for months, and they surprisingly didn’t change,” Stupp said. “They remained the same length and retained their segmented structures.”

Grow, stop, grow again

Stupp and his team traced that unusual ability to a previously unknown process his laboratory calls “self-capping supramolecular polymerization.” As a thread grows, flexible portions at the ends remain highly dynamic and, at proper temperatures, allow new molecules to join in a synchronized manner. Once the available building blocks are consumed, those flexible portions fold over and protect the ends. This effectively shuts down further growth by preventing threads from fusing together or undergoing “Ostwald Ripening,” a process in which smaller structures disappear while larger ones grow.

“To make them longer and longer, we just kept adding new molecules,” Stupp said. “The new molecules stick with strong noncovalent bonds to the growing thread and elongate the assembly, which led to a breakthrough in terms of size control.

“The collective molar mass of their noncovalently bonded monomers reaches billions of daltons, and thus they are ‘giga-assemblies.’ These are the largest supramolecular polymers ever made with this degree of precision. Once the monomer is fully consumed, they finish growing and their dimensions remain stable.”

Approximately the size of one proton or neutron, a dalton is a tiny unit that scientists use to measure the mass of molecules and atoms. More than a billion daltons is enormous by molecular standards. For comparison, the largest common polymers of plastics have molar masses in the range of 10 million daltons, and the largest proteins in nature reach approximately 3 to 5 million daltons.

Researchers can later restart growth by supplying more building blocks. By adding different types of molecules in sequence, the researchers can create precisely defined segments with different chemical properties. In the study, Stupp and his team created threads with positively and negatively charged segments. Because opposites attract, the researchers expected the threads to clump together. Instead, they remained stable in water because the “capping” mechanism prevented the assemblies from fusing together.

Small anchor, big difference

To explore how the pattern of electrical charges might interact with living cells, Stupp and his team turned to neurons, which carry a strong negative charge. The team exposed several threads with different designs to cellular cultures containing cortical neurons.

“The first thing we did was make a structure with only positively charged segments, and it basically killed the neurons,” Stupp said. “Then, we tried a structure with only negatively charged segments, and nothing happened because the neurons repelled the materials.”

When Stupp’s team used supramolecular assemblies with randomly mixed positive and negative charges, the neurons didn’t respond in a notable way. But then the team designed a thread with the breakthrough polymerization strategy comprising a small positively charged segment sandwiched between two negatively charged segments of different lengths. Something interesting and unexpected occurred.

The small positive region anchored the thread to the negatively charged surface of a neuron. Repelled by the neuron’s negative charge, the thread’s negative segments remained highly mobile and in constant motion since they could not escape.

“When we used only positively charged segments, they suffocated the neuron and killed it,” Stupp said. “But with only one positively charged segment surrounded by negative ones, it couldn’t do that anymore. And the negative segments, which ordinarily couldn’t get near the neuron, were forced to stay near it because they were anchored.”

Neurons grow and spring to life

Neurons treated with the precisely segmented threads grew longer neurites — the long projections neurons use to communicate with other cells. The treated neurons also formed more elaborate branches, gaining the ability to connect with neighboring cells.

“The neurons matured to an amazing level,” Stupp said. “They grew long and highly branched neurites, which is how they can start making synaptic connections in the brain and in the spinal cord.”

After just seven days, treated neurons were much more active than untreated neurons. When stimulated, treated neurons produced a calcium response — a sign of neuronal activity. Their overall calcium activity was four times greater. And, after 14 days, treated neurons formed more synapses than untreated neurons.

Stupp and his team saw another striking effect in cultures of human neural progenitor cells, which are immature cells that can develop into neurons. Although these cultures typically grow in flat layers, the cells instead organized into raised, three-dimensional clusters connected by axons. This organization resembled aspects of the brain’s white and gray matter, where somas are separated from axons.

No signals required

Perhaps most surprisingly, the molecular threads produced these effects without carrying biological signals specifically designed to encourage neurons to grow. Stupp posits the negatively charged segments recruit specific proteins already present around the cells that help neurons survive, grow and communicate. These proteins, called neurotrophic factors, have positively charged domains. Stupp’s team also found laminin — an important protein that holds tissues together and has positively charged domains — accumulating along the supramolecular threads near neurons.

Stupp hypothesizes that the interplay between attraction and repulsion causes the threads’ negative segments to rapidly move toward and away from the neurons in a “tapping” motion. Proteins recruited by the negative segments may be drawn toward receptors on the neurons, while electrostatic forces push the segments away. This repeated tapping, occurring on millisecond timescales, could help enhance biological signaling. A live cell movie included in the Science paper has captured this phenomenon.

Beyond neurons, Stupp says the new polymerization strategy could eventually enable scientists to build long molecular structures containing many carefully positioned chemical segments. That could open opportunities to create new materials and devices with features that extend over very long distances.

“We discovered something we had never seen before in chemistry or in biology,” Stupp said. “This work gives us a new level of control over supramolecular materials. In the future, we can imagine creating many segments with different properties. The unknown functions of these structures are likely to be as surprising as the superbioactivity observed on neurons. We’re just beginning to imagine the possibilities.”

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In 1911, Heike Kamerlingh Onnes cooled mercury to a few degrees above absolute zero and watched its electrical resistance vanish. Lead soon joined the list of superconductors, losing its resistance below about 7.2 kelvin. A full explanation arrived in 1957: electrons bind into Cooper pairs that move together as one collective state below a critical temperature. Breaking a pair costs a minimum amount of energy, called the energy gap, so inside the gap a superconductor offers no states for single electrons.

Yu–Shiba–Rusinov states

Magnetism is an old enemy of this order. Magnetic impurities were known to suppress superconductivity, and in the 1960s Yu, Shiba and Rusinov showed theoretically that a magnetic atom disturbs the pairs around it and traps a localized state with an energy inside the gap. These Yu–Shiba–Rusinov (YSR) states were first seen atom by atom in 1997, using a scanning tunneling microscope (STM): a needle-sharp metal tip that measures the tiny current of electrons tunneling across a vacuum gap to a surface.

A different story concerns two superconductors joined by a very weak link. In 1962, Brian Josephson predicted that Cooper pairs can tunnel through such a link with no voltage at all, an effect confirmed in 1963. When a voltage is applied, another process takes over: multiple Andreev reflection. An electron whose energy lies inside the gap cannot enter a superconductor alone. Instead it is sent back as a hole, the absence of an electron, while a Cooper pair slips in, as Andreev described in 1964. Between two superconductors under a voltage V, a particle can bounce back and forth, gaining energy eV with each crossing, until it can finally escape above the gap. When n crossings are needed, the conductance shows a peak at a voltage equal to the sum of the two gaps divided by n. This pattern, explained in the early 1980s, is called subharmonic gap structure. For lead on lead the sum is 2.7 millivolts, so peaks are expected near 2.7, 1.35 and 0.9 millivolts.

Impurity states and Andreev reflections have usually been treated as separate subjects. A recent experiment ¹ places them in the same device. A nickelocene molecule, a nickel atom sandwiched between two five-carbon rings, sits on a lead surface above a single iron atom trapped between the molecule and the lead. On its own, the molecule carries a spin that appears as characteristic steps in the measured spectra. Above the iron, those steps vanish and YSR states appear instead. Density-functional calculations explain why: the magnetic moments of molecule and iron point in opposite directions and almost cancel, leaving a leftover spin of one half on the iron. That spin couples to the lead and produces a single pair of YSR states.

The second superconductor is a lead-coated STM tip, lowered toward the molecule at 2.4 kelvin. Far away, electrons tunnel through a wide vacuum barrier and the tip merely reads out the YSR states, which appear as lopsided peaks near the edge of the gap. As the tip approaches, the junction becomes more transparent, meaning electrons cross it more easily, and the setup becomes a weak link between two superconductors. At moderate conductance, new peaks appear at half the sum of the gaps, the signature of second-order Andreev reflection. At the highest conductances, a sharp peak develops at zero voltage: the Josephson contribution. Thermal fluctuations of the superconducting phase broaden this peak, as is typical of STM junctions.

These stages do not simply stack. As the tip approaches, the YSR peak moves to lower energy and mingles with the Andreev peaks. The interpretation is that the bound state becomes a stopping point along the Andreev path. Peaks then appear at the tip’s gap plus the bound-state energy, divided by n, rather than at the ordinary positions. This is called YSR-assisted multiple Andreev reflection.

Odd and even orders

A simple argument explains why odd and even orders differ. Each reflection carries the particle to the opposite electrode, and only the lead surface contains the magnetic atom; the tip has none. After an odd number of crossings the particle ends on the surface, where it can land in the bound state. The peak shifts and acquires the lopsided shape typical of tunneling into a single level. After an even number it ends in the tip, among ordinary states, and those peaks stay closer to their usual positions, although the second-order peak still turns lopsided at higher conductance as a YSR-assisted component splits off. Simulations reproduce this pattern. In the measurements, thermal broadening blurs finer details such as the third-order peak, and small features near zero voltage seem to reflect a mixture of both processes.

Reproducing the evolution of the spectra required two changes together: higher transparency and a stronger exchange coupling between the iron spin and the lead. Raising transparency alone gives a growth of the key peak that the measurements do not show. A likely reason is that the approaching tip slightly squeezes the molecule and strengthens the coupling, though this is an inference. The model treats the spin as classical and its two parameters as effective ones, so it is a phenomenological decomposition rather than a unique microscopic extraction. It also cannot capture the zero-voltage peak.

Even so, the result shows that YSR states and Andreev reflections are two limits of one problem, tuned continuously within a single molecular junction. Under suitable conditions, such spin-active links might also host a Josephson diode, in which supercurrent flows more easily in one direction, or a π-junction, in which the two superconductors prefer opposite phases. These remain possibilities, not demonstrated effects.

Author: César Tomé López is a science writer and the editor of Mapping Ignorance

Disclaimer: Parts of this article may have been copied verbatim or almost verbatim from the referenced research paper/s.

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In the 1980s, scientists measured quantized jumps in the energy of ions for the first time. In the 2000s, it was photons’ turn. Now, thanks to a tour de force of device engineering and nanofabrication, researchers at Stanford University in the US are reporting that phonons – mechanical vibrations like those that carry sound – also display this quantum behaviour.

“We could see it by eye [in the data], which was very satisfying,” team leader Amir Safavi-Naeini tells Physics World. “I’ve been fascinated with the interface between the quantum world and the classical world and trying to move that interface closer to daily experience…and now we have mechanical objects.”

Laying the groundwork

The Stanford team’s recipe for observing quantum jumps in phonons begins with thin films of lithium niobate (LiNbO₃). Although bulk samples of this material had been available since the 1950s, the commercialization of thin-film LiNbO₃ a decade ago was a game changer for Safavi-Naeini and his colleagues once they worked out how to process the material.

Because LiNbO₃ is piezoelectric, placing it under stress – from a vibration, say – produces a voltage. This voltage allows vibrational quanta to couple to superconducting qubits, after which the qubit states can be “read out” to determine whether a phonon was present or not.

The problem was that initially, the phonons had lifetimes of only 800 nanoseconds – well short of the millisecond the team needed to observe them falling from an excited state to the ground state. Extending these phonon coherence times “took a lot of work by a number of graduate students in my group,” Safavi-Naeini says.

After probing various sources of dissipation, including material properties that cause quantum excitations to lose coherence, the researchers realized that surface defects were key offenders. They therefore switched from polymer processing, which left a residue, to shadow masks that superimpose one chip over the other and evaporate metal through it. “There were probably three generations of students that worked on getting that four to five orders of magnitude increase in the performance of the devices,” Safavi-Naeini says.

Once they’d extended their phonon lifetimes, the researchers had to find a way of combining their “very clean, long-lived” mechanical and superconducting systems without destroying either. For this, Safavi-Naeini credits past and present students Takuma Makihara and Erik Szakiel, who spent most of their PhDs tackling issues with the mechanical oscillators before finding a way to couple them to the superconducting systems. “That was the last piece,” Safavi-Naeini recalls. “Once we had that, we could do these experiments.”

Spot the missing phonon

Because the superconducting qubits detect whether an even or odd number of phonons is present in the LiNbO₃ (which at very low energies amounts to determining whether a phonon is there at all), they are effectively performing a parity measurement. That could make the Stanford team’s system useful for quantum error correction, where the goal is to find out whether an error has crept in without actually measuring the quantum states, since doing so would destroy their useful quantum characteristics.

One of the most common sources of error in superconducting qubits is the loss of an excitation, such as when a phonon decays. However, if data is encoded into phonons in pairs and the system detects an odd number of them, this loss becomes apparent without measuring all the states. This so-called “binomial” code has already been implemented for microwave photons, and Safavi-Naeini explains that it works best for long-lived particles – a further benefit of the team’s long-lived phonons.

Protein and gravity measurements

The Stanford researchers are now collaborating with Michael Roukes and colleagues at the California Institute of Technology (Caltech) to explore possible applications in high-precision measurements of single protein masses. They are also interested in fundamental science questions such as whether it’s possible to generate entanglement between mechanical systems through gravitational fields.

However, Safavi-Naeini cautions that their phonon lifetimes would need to be much longer – a factor of 10 for error correction and mass spectrometry, and for gravity perhaps as much as six orders of magnitude, with further modifications to the experimental set-up also required – before they can achieve these goals. “The hope is that by figuring out the fundamental sources of loss in these materials we can build our way up to those experiments in the coming decade,” he says. “Every time you improve, you hit some new source of noise, you understand it, then you can deal with it, and then you go to the next one. It’s a fun physics problem.”

The research is published in Science.

The post Sound waves come in quantum jumps appeared first on Physics World.

I have been involved in tribology for most of my working life, but even today it can feel like a well-kept secret. A highly interdisciplinary field with close ties to materials science, tribology is essentially the science and technology of friction, lubrication and wear between any moving surfaces. But tribology encompasses in part one age-old challenge.

I’m talking about the use of bearings, which dates back to at least 4600 BCE, when ancient Egyptians used wood log rollers to move large stone blocks during the construction of their pyramids. In 1500 Leonardo da Vinci used ball bearings in his conceptual helicopter design, while in 1740 the clock maker John Harrison invented caged roller bearings for his marine chronometer.

It was not until the mid-1960s that the word tribology was coined by the British engineer and entrepreneur Peter Jost after discussions with the then editor of the Oxford English Dictionary

The first patent on a ball bearing was granted to Philip Vaughan, an ironmaker from Carmarthen, Wales, bringing tribology firmly into the industrial world. But despite all the history, it was not until the mid-1960s that the word was coined by the British engineer and entrepreneur Peter Jost. After discussions with the then editor of the Oxford English Dictionary, the Greek word “tribos” – meaning rubbing – was suggested as a basis for describing the discipline.

This resonated with Jost, because the terms “tribo-chemistry” and “tribo-physics” were already in use. In an interview with the magazine Machinery Lubrication in 2005, Jost explained how “tribo science and tribo technology” then simply became shortened to tribology. “I felt that because it had a Greek basis, it could easily be adopted into a number of languages by most Western countries,” Jost recalled.

Wear’s the rub?

For the most part, the aim of tribology is to minimize friction and wear between components, which involves a knowledge of both materials and lubrication. Initially, the focus of the field was on moving parts in industrial or mechanical machines, such as bearings, gears, brakes and clutches. Indeed, one reason that the term came about was a conference in Cardiff in 1964 organized by the Iron and Steel Institute and the Institution of Mechanical Engineers (IMechE).

At the conference it became apparent that significant failures in plant machinery, which were being attributed to poor lubrication, were in fact due to a lack of fundamental design knowledge. These findings led to Jost chairing a UK government committee into lubrication education and research and the needs of industry. The resulting study – generally known as the “Jost report” – came out in 1964.

Now all this may seem like ancient history, which I suppose it is, but I was intrigued to discover that delegates to that 1964 conference visited the Llanwern steelworks at nearby Newport. As some of you may recall me describing, I also visited this site during my own student days, where I saw the steel rolling line in action. It was a truly impressive sight.

The total failure was remarkable, underlining just what can happen when moving parts fail without warning

From the viewing platform, I could see a massive volume of red-hot steel thunder along the rollers when, suddenly, there was a bang. Something failed and the steel landed in a crumpled mess all over the plant floor. We were safe but the total failure was remarkable to witness, underlining just what can happen when moving parts fail without warning.

The knock-on effect of this failure would have been costly and sustained. As well as a steel rolling line being out of action, new parts would have had to be sourced and old ones repaired. There’d have been quality concerns to address, safety reviews to be undertaken and the root cause of the problems to be worked out. Quite possibly all those jobs would have needed to be completed before production could restart.

What’s more, the failure of the machine’s moving parts, which depends on tribology, would have damaged the company’s reputation and led to customers annoyed with delays and late deliveries. It is this kind of event that those involved in tribology are trying to prevent, or at least minimize. By understanding tribology, in other words, engineers can design better machines and components.

What it says on the tin

This was made clear in the 1964 Jost report, which said that adopting good tribological practices could save the UK between 1% and 1.4% of its gross domestic product (GDP). In today’s money, that would amount to some £30bn, given that country’s GDP is a shade over £3 trillion. Put simply, designing and maintaining industrial equipment, based on a solid understanding of tribology, yields significant economic benefit.

More recently, a 2017 study by Kenneth Holmberg from the VTT Technical Research Centre of Finland and Ali Erdemir of the Argonne National Laboratory in the US (Friction (5 263) suggests that 20% of the world’s energy consumption originates in tribological contacts. And by the application of best practice, as much as 40% of this could be saved.

More than 60 years after the publication of the Jost report, the influence of tribology continues to grow. Alongside its impact on transportation and manufacturing, tribology is also relevant to extreme environments from aerospace, nuclear power, marine and subsea to space technology, high-voltage electrical systems and even the human body. There are also applications in nano-tribology, cosmetics, food, computational, digital, tribotronics, geotribology, hydrogen and green tribology.

Tribology will help to reduce our carbon footprint and counter climate change

As chair of the IMechE’s tribology group committee and a member of the tribology group committee of the Institute of Physics, naturally I am biased. Still, I feel privileged to be part of the tribology community and the amazing things it achieves. Whether it’s making products more energy efficient, creating green lubricants, or making plant-based protein more palatable to meat eaters, tribology will help to reduce our carbon footprint and counter climate change.

So next time you brush your teeth, comb your hair, switch on a light or ride on a bus, spare a thought for tribologists and their dedication to making the world run smoothly. It’s hard to think of anything that doesn’t involve tribology at all.

• The Institute of Physics is hosting the 5th Tribology and Net Zero seminar on 6 November in London co-organized with the Institution of Mechanical Engineers, the Royal Society of Chemistry, and the UK student chapter of the Society of Tribologists and Lubrication Engineers.

The post The secret world of tribology appeared first on Physics World.

Each year, approximately 5000 tonnes of dyes (about 50 times the weight of a blue whale) are discharged into industrial wastewater. These dyes block light from reaching aquatic plants and animals, cause unpleasant odours and pose risks to human health. Congo red, for instance, is notably persistent in the environment. Another dye, methyl orange, is difficult to remove using standard biological or chemical treatments and has been linked to cancer and DNA damage. Researchers in Egypt and the US are devising a new method to clean up such contamination.

One of the well-established routes for cleaning wastewater from dyes is using nanoparticles (of similar size to a small virus) with high surface area, which gives the dye molecules plenty of places to adsorb onto the nanoparticle surface. It’s especially useful if the nanoparticle has magnetic properties – then it’s possible to remove nanoparticles with adsorbed dyes from water using a magnet. The nanoparticles can then be washed and reused, for up to four cycles, enabling the same material to be used again and again instead of being thrown away.

Ideas for breakfast

Lead researcher Hebatullah Hassan Farghal from The American University in Cairo and her team have synthesized magnetite nanoparticles (particles made from a naturally magnetic form of iron oxide) directly in dye-polluted water. As the particles form, they pull the dye molecules out of the water and onto their own surfaces – meaning that the water is left with less dye in it. The researchers then used those same “dirty” nanoparticles to capture two entirely different dyes afterwards. This route, described in RSC Advances, skips the usual “make-wash-dry-treat” sequence. Instead, it offers a more efficient, simpler and greener way to create a working wastewater adsorbent.

Farghal’s previous research work had been on magnetic adsorbents. “The idea for this paper came exactly one or two days after my PhD defence,” she explains. “While I was having breakfast, I realized adsorbent synthesis requires time and cost…I then went to the lab and started my experiments to find that it was successful.”

Catch and catch again

First, Farghal loaded the nanoparticles with two dyes – congo red (CR) and bromocresol green (BCG) – as they formed in the wastewater. More than 90% of both dyes stuck to the particles and the loaded particles grew slightly larger (about 34 nm, compared with 26 nm for plain magnetite). Later, the same “dirty” particles went on to adsorb almost 80% of methylene blue (MB) from a single-dye system after about 3 h, dropping to just over 50% when a second dye, methyl orange (MO), was mixed in.

To reuse the particles after adsorption of MB, the researchers rinsed them in alcohol, which pulled the trapped blue dye molecules back off. They repeated this four times without any drop in performance, and none of the originally loaded dyes leaking out in the process. They note that MB removal worked best at high pH, where the nanoparticles become negatively charged (while MB molecules are positively charged). This electrostatic attraction gave the main mechanism an extra boost.

Simulations second the results

There are several different mechanisms that can happen when a dye molecule attaches to the surface of a nanoparticle. The two most common types are chemisorption, where the molecule forms new chemical bonds with the surface, and physisorption, a weaker attraction more like static cling – no permanent bond is formed, and the molecule can be pulled off relatively easily.

Several lab measurements, including infrared spectroscopy of the particle surface, already hinted that physisorption is the main mechanism responsible for binding CR, BCG and MB molecules to nanoparticles. This weak binding is also why the ethanol wash could strip the dye back off without damaging the particle.

To confirm this idea, the team also ran a computational method called density functional theory (DFT) on a single dye molecule sitting on a magnetite surface. All dyes bound with similar strength. The simulations also showed electrons flowing in opposite directions depending on the dye’s charge – from the negatively charged CR and BCG toward the surface, and from the surface toward the positively charged MB – the same charge attraction seen in the lab.

The researchers point out that DFT and experimental outcomes cannot be compared quantitatively, only qualitatively, since the first one examines a perfect molecule on an ideal surface and the second one concerns real-world conditions. They note that the DFT analysis was carried out by Ahmed A Abokifa and Mohamed S Mohamed from the University of Illinois Chicago, with Mayyada El-Sayed supervising the wider study.

Outside of the lab

In standard tap water or saline (3% NaCl), the story gets more complicated. The researchers increased the adsorbent dose by roughly 15 times – from 0.67 to 10 g/l – to try to compensate for real-world conditions. This worked in saline, but removal in tap water was only about half of what it was in distilled water, likely because calcium, magnesium and other substances naturally present in tap water compete with the dyes for space on the particle’s surface.

“Though the dose significantly increased in tap water and saline, this dose is still applied in the literature,” Farghal says, adding that her future investigation will try to close that gap and reduce costs.

Still, one thing works in the material’s favour: making the particles is cheap. Producing 1 kg costs around $3730 – roughly eight times cheaper than other nanomaterials sometimes used for the same purpose, such as cobalt ferrite (which costs roughly $30,100 per kilogram).

Farghal says her next research will involve “circular economy approaches that will be outside the box.” Circular economy is an approach in which waste from one process becomes a resource for the next – that waste doesn’t have to be wasted. This study is itself an example of that thinking: dye-polluted water became the raw material for a new, useful adsorbent.

The post Dirty magnetite nanoparticles keep cleaning up dyes appeared first on Physics World.

The performance of optoelectronic materials and devices relies on carrier transport, recombination, ion migration and phase segregation. They unfold on length scales from nanometers to micrometers and timescales from picoseconds to hours. Conventional characterization averages over this heterogeneity and rarely captures these events in operational devices.

Optical microscopy and spectroscopy can recover this hidden picture. They convert local material function directly into optical contrast, and that contrast can be resolved across the length and time scales where the function happens.

In this webinar, Dr Sudipta Seth will talk about advanced optical microscopy and spectroscopy that interrogate halide perovskite materials and corresponding optoelectronic devices under relevant in situ and operando conditions. This approach uncovers the local fields, transport bottlenecks, and defect chemistry that set solar cell performance. He will show how these local optical signatures translate into a mechanistic understanding of device operation, and how that understanding feeds back into the design of better probes, interfaces, defects and devices.

The talk is aimed equally at materials scientists curious about what happens inside their samples and at microscopists and spectroscopists looking for new problems suited to their tools.

Certificate of attendance will be awarded upon completion of the webinar.

Sudipta Seth is a research associate at KU Leuven, Belgium, where he conducts advanced research at the intersection of materials chemistry, optoelectronic devices and spectroscopy through the development of innovative microscopy methodologies. He leads the nanoscale device spectroscopy research line at Hofkens Laboratory. He completed his PhD at the University of Hyderabad and subsequently worked as a postdoctoral fellow at Lund University and as a visiting junior fellow at the Tokyo Institute of Technology. His work integrates single-particle spectroscopy, super-resolution and nanoscale microscopy and ultrafast spectroscopy to investigate fundamental photophysics in semiconductor materials and optoelectronic devices. He has received several academic fellowships, including INSPIRE-SHE (India), Wenner-Gren Postdoctoral Fellowship (Sweden), FWO Research Stay Abroad (Belgium), and Marie Sklodowska-Curie Postdoctoral Fellowship (European Commission).

The post In situ and operando optical microscopy and spectroscopy: investigating perovskite optoelectronic devices at work appeared first on Physics World.

By combining a band-structure engineered multi-quantum-well heterostructure with a nanostructure known as a metasurface, physicists in Austria and the US have created a device that can efficiently transform light into different frequencies – including those at technologically important near-infrared wavelengths. Their technique, which boosts nonlinear frequency conversion, could help in the development of smaller and more efficient components for telecommunications, quantum information transfer and other photonics technologies.

Nonlinear frequency conversion is an optical process in which a material is used to generate light of a different frequency to that incident on the material. It is now routinely employed in a wide range of photonics devices that rely on frequency mixing, ultrafast signal processing, broadband and pulsed light sources, and high-speed light modulation. It is also used to generate entangled photon pairs for quantum communication. One common type of frequency conversion, and the one used in this new study, is second-harmonic generation. Here, two input photons are combined to produce one photon with twice the energy.

Efficient nonlinear devices require light with high electric field strengths and materials that respond to these intense electromagnetic fields by producing a light polarization that is not directly proportional to the applied field. “Only a handful of such nonlinear crystals exist and these have complicated structures with weak nonlinearities, which means they require high optical powers to make photons interact with each other,” says Marcus Ossiander from the Institute of Experimental Physics at TU Graz in Austria, one of the authors of the new study published in Nature Nanotechnology. “While, new such crystals emerge from time to time, their structure is fixed, which dictates which light wavelengths they work at and how efficiently.”

Asymmetrically coupled multi-quantum wells

Recently, a group of researchers at the University of Texas at Austin in the US, led by Seth Bank, also an author of this latest study, succeeded in creating an optical nonlinearity not via a new crystal structure but by growing a semiconductor metamaterial made from nanoscale layers of gallium arsenide and aluminium gallium arsenide. These layers contain multiple quantum wells that are asymmetrically coupled to each other.

The quantum wells confine electrons in one dimension while allowing them to move freely in the other two dimensions, something that has the effect of restricting their energy levels into discrete, quantum states. Since they are asymmetrically coupled, the electrons end up mainly moving in one direction when exposed to light. This so-called “one-way street leads to increased nonlinear electron oscillations, allowing light waves to interact with each other extremely efficiently and exceed naturally occurring nonlinearities.

Ossiander and his colleagues, including Federico Capasso at the Harvard John A. Paulson School of Engineering and Applied Sciences (SEAS), have now added a second, two-dimensional metamaterial atop the first one. This metasurface, which consists of titanium dioxide pillars, each several hundred nanometres in size, precisely creates the particular light polarization required to deflect incoming light so that it scatters along the one-way street. This enhances the interactions between light waves even further and so increases the intensity of light in the structure.

An extra lap

Researchers have known for a while now that metasurfaces are extremely good at resonantly trapping light and increasing the interaction of light with matter. Usually, the process is straightforward, explains first author Pernille Undrum Fathi, who works in Capasso’s group: you implement a resonant metasurface, and it enhances, for example, the nonlinear effects that you are aiming for.

“The new material sent us for an extra lap, however, because, during our experiments, we discovered that the designable second-order nonlinear susceptibility tensor element (the required incident polarization) is different to that of conventional materials,” she says. “Therefore, when we shone light at exactly normal incidence, the metasurface–material combination generated light waves whose polarizations cancelled each other out completely, so annihilating any enhanced optical nonlinearity.”

However, the researchers found that tilting the sample by just 0.3° broke this symmetry and solved this challenge. Indeed, they were able to increase the effective nonlinear conversion of the light to three orders of magnitude higher than that for a non-patterned heterostructure. The effect is also higher than previously reported values for comparable devices at near‑infrared wavelengths.

“Nonlinear optics are ubiquitous in modern science and technology, with examples including the generation of light at new frequencies (where lasers might be unavailable), all-optical signal processing and the generation of entangled photon pairs for quantum communication,” Ossiander tells Physics World. “Enhancing the fundamental processes enabling this technology will allow for much more efficient, compact devices and enable new measurements that would previously be impossible.”

Metasurfaces offer an excellent route to control and enhance the interaction of light with matter, and the team was intrigued to find out what could be made possible when combining these materials with nanostructures, adds Fathi.

“Working with new materials of course comes with additional uncertainty, and we spent a lot of time learning about and understanding the mechanisms of these new structures and how the particular nonlinear tensor elements of this material interact with the resonant modes introduced by the metasurface,” she says.

“The material we studied is very interesting but also complex,” adds Ossiander, noting that the reseachers believe they can learn how to make even better use of the designer nonlinearity in it by further investigating its fundamental properties. “Indeed, there is a new publication in Optica by Bank’s group on how to improve the multi-quantum-well material even more.”

The post Metasurface optical device boosts nonlinear frequency conversion appeared first on Physics World.

For a few years in the early 1990s, a lot of New York streets sparkled. Picture a Manhattan avenue at dusk, wet from a passing shower, the streetlights and headlights catching something in the road surface itself. Not the usual dull black, but a faint, restless glitter, as if the asphalt had been dusted with something. That shimmer was crushed bottles. The city had figured out how to grind its glass waste into the road.

The material had a name that told you exactly what it was: glassphalt. It went from a curiosity nobody trusted, to something people demanded outside their own buildings, and then it quietly disappeared. And it’s a small case study in why good recycling ideas so often don’t stick.

The glittering street, and why the city made it

Asphalt is mostly sand and gravel held together by a black binder. Glassphalt is what you get when crushed glass replaces part of that sand and gravel.

The Federal Highway Administration, in its guidelines on waste glass in pavement, says road-surface mixes with roughly 10 to 15 percent crushed glass perform fine. From 1989, the city’s transportation department started putting the glass content of its mix at about 10 percent.

The FHWA called the New York program the “most aggressive” glass-recycling paving effort in the country. From 1990 through 1995 the city used roughly 225,000 metric tons, about 250,000 tons, of glass in resurfacing. By 1991, crews had already laid glassphalt on nearly 900 lane-miles of Manhattan and Brooklyn streets.

What made the idea clever, as far as we can tell, is the kind of glass it used. Bottle recyclers want clean glass sorted by color. They won’t buy the mixed-color material that piles up at the bottom of a recycling stream. Glassphalt didn’t care about color. It could swallow exactly the low-value waste glass that nobody else wanted and turn it into road. The city reported saving about $500,000 a year by using crushed glass in place of some sand and gravel, and keeping 38,000 tons of glass out of landfills in the process.

From public suspicion to actual demand

People did not warm to it right away. A road that shimmers looks, at first glance, like something is wrong with it. But the turnaround, if the accounts from the time are right, was fairly complete.

Harold Watson, the transportation department’s assistant commissioner for asphalt operations, had become something of an in-house champion for the material. Watson said in 1991: “Now, when we do a road, if we don’t have glass on it, people come in and start complaining.”

That’s a nice story about public mood, not a measured fact, and it comes from a fan of the material, so we’d hold it loosely. Watson was clearly frustrated by a quieter resistance too. In his telling, “There’s a lot of people who can’t find anything wrong with glassphalt but won’t say anything good about it.” Read that as one supporter’s view rather than a neutral account, but it captures the odd spot the material was in: hard to fault, hard to fully endorse.

The Plaza, and a request for more sparkle

The clearest sign that the public had come around involved one very visible stretch of Fifth Avenue. After the city resurfaced the section in front of the Plaza Hotel with glassphalt, the hotel’s owner, Donald Trump, wanted the surrounding streets given the same treatment. A recycled-glass road surface had become something worth lobbying for outside a luxury hotel.

There’s something funny in that. The exact same crushed bottles a bottle plant would reject as worthless were, when spread across Fifth Avenue and lit up after rain, a selling point. The sparkle did real marketing work that the engineering never asked for.

Why the biggest glass-paving program in the country faded

None of the appeal saved it. The program’s central weakness was that its raw material came from curbside recycling collection, and collection is expensive.

During a budget crisis, Mayor David Dinkins floated suspending the recycling operation to save about $65 million a year, which would have cut off the glass supply. Commissioner Lucius Riccio said at the time: “That would be a shame. We’re doing a record amount of paving and we could use all the glass they could give us.” That tension is the whole story in miniature. The paving side wanted all the glass it could get, and the collection side that fed it was the first thing on the chopping block when money got tight.

What we take from a road paved with bottles

New York didn’t invent glassphalt. Baltimore had paved at least 17 streets with it from the mid-1970s through the mid-1980s, chasing the same sparkle.

What New York proved was that the idea could run at real scale, absorb hundreds of thousands of tons of the exact glass nobody else wanted, and win over a skeptical public along the way.

The sparkle was arguably the least interesting thing about it. It got the headlines, it got Trump lobbying, it made a wet avenue look faintly enchanted. But the real achievement was much plainer: a workable use for low-value mixed glass that would otherwise cost money to bury.

The reason it faded had nothing to do with whether the roads glittered, and everything to do with the fragile system behind it, the collection network and the raw cost of glass against dirt-cheap gravel. A recycling idea can be sound as engineering and still lose to logistics. That, more than the shine, is what a road made of bottles has to teach.

The post Beginning in 1990, New York City repaved streets with asphalt containing crushed recycled glass. By 1995, crews had used 250,000 tons of glass in resurfacing applications across the city, including a section of Fifth Avenue in front of the Plaza Hotel. appeared first on Space Daily.

On Tuesday, two survivors of child sex abuse accused the Justice Department of failing to notify dozens of victims found in Jeffrey Epstein’s massive collection of child sex images.

In a proposed class action, survivors explained that Epstein apparently started collecting child sex images in the 1990s, many of which the DOJ recovered after his arrest. In 2025, the FBI started reviewing “tens of thousands of videos” containing illegal child sexual abuse material (CSAM) and issued a memo confirming that “a large volume of images” seized depicted likely minors.

Some of these victims may have had contact with Epstein, as the disgraced financier kept a "modelbook" of nude photos of young girls roped into his ring. However, the FBI also identified hundreds of CSAM images in cache, which include approximately 15–20 images of known CSAM dating back to the 1990s. And so far, the DOJ has largely ignored those victims, who likely never met Epstein and have no way of knowing if he possessed, transported, or traded their images, survivors alleged.

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My dentist, Dr Albora, told me I needed a new tooth. He made me bite down on a U-shaped tray filled with polyether, an elastomeric material that’s been used in dentistry for decades. I tried not to gag while the gooey stuff set. Albora then waggled it off and sent the imprint to a company on Long Island that makes false teeth. But as my tooth’s colouring was unusual, Dr Albora said I had to go there myself.

A week later I drove to Marotta Dental Studio, where Igor Binshteyn sat me in a chair, lifted my lip and inspected a tooth to the side of my upper jaw. He was helping to fabricate its replacement and needed to get the exact colour.

As Binshteyn finished, I remarked teasingly on the company’s car park, which was chock full. Do you need that many people to make false teeth? What could possibly be involved to make things smaller than the nail on my little finger?

Binshteyn laughed. “Follow me”.

He opened a door to a huge undivided warehouse-like space about 1200 square metres in size. Some 50 people were working at lines of tables where the steady hum of conversation was punctuated by the noise of ovens, lathes and grinding machines; imagine the sounds of a metalworking shop in a busy train station.

“Do you want a tour?” Binshteyn said.

Of course I did.

Open wide

My tour guide was Marotta’s vice-president, Steven Pigliacelli, who teaches prosthodontics at New York University. A prosthodontist is a dental specialist who has completed dental school and, in the US, has had at least three additional years of advanced training to focus on restoring and replacing missing or damaged teeth. As I learned, prosthodontists must practice materials science.

The lab has two paths for making teeth, Pigliacelli explained, each with different materials and methods. The first is known as “porcelain-fused-to-metal”, or PFM. It begins with technicians applying gypsum – hydrated calcium sulphate – to create stone replicas of the jaw and teeth from the impressions given to them by dentists such as Albora.

Gypsum has different coefficients of expansion for different dental purposes, and textbook formulas give the amounts of liquid for each kind. But Marotta employees found that tiny amounts of water must be added or subtracted to the gypsum to compensate for things like humidity and temperature before the gypsum is used. “It took us months,” Pigliacelli explained, “to realize that how it’s shipped, how it’s stored, what season it is – all these affect the material.”

I watched as a technician sectioned a stone jaw replica to cut out a tooth, turn it into a master model called a die, and test it in an articulator that mimics jaw movements. I saw another wax that die, use a lost wax technique to create a solid gypsum frame, and cast a silver-palladium alloy. That creates the metal inner core for the tooth, called a coping, which is shaped and finished before porcelain is applied. Porcelain is baked onto the coping in another area of the lab.

“The metal and porcelain need closely matched coefficients of thermal expansion or the porcelain can separate from the metal,” Pagliacelli told me. “Every once in a while a company tells us ‘We’ve got this really cool new alloy!’, but we need to match the coefficients of expansion in the ceramic material. We’re working with sensitive materials for sensitive applications, and we have to experiment with and adapt them. This stuff about materials you don’t learn in school but work out in the lab.”

Smile for the camera

The second path to making a tooth involves scanning the teeth rather than waxing a die. The electronic files are worked on in the computer, printed out, reworked and rescanned, and milled by a CAD machine using materials such as zirconia – nicknamed “ceramic steel” – and EMAX, a lithium disilicate glass-ceramic. Zirconia is extremely hard and used for teeth that endure heavy grinding forces, while EMAX is more aesthetically pleasing and often used for front teeth.

“So we have two parallel paths, PFM and digital scans”, Pigliacelli said. “It’s usually a personal choice of the dentist”. But external pressures are driving a move away from PFM, he said. Five years ago the price of palladium – a key component of the PFM alloy – soared as it was increasingly used in devices to reduce auto and other emissions. “That’s cut down on the PSM market.”

In another corner of the lab I ran into Binshteyn again, who was using different porcelains and ceramic stains to create colours. “Teeth are not a solid colour,” he said, “but vary in shade from reddish near the gum line to lighter colours toward the biting edge. They also vary in translucency.” (Check this out yourself.) Furthermore, the colour of a tooth must match not its neighbours but the corresponding tooth on the other side of the mouth. To make a natural-looking tooth, Igor picks out a base colour and then layers in shades of porcelain.

As my lab tour went on, Pigliacelli showed me different materials for different applications. One challenge is making teeth for a person with bulimia, whose acidic oral environment can corrode dental materials. Other challenges arise with people who have had failed implants, or temporomandibular joint – or TMJ – a disorder involving jaw joints and muscles.

On the way out I met Lenny Marotta, Pigliacelli’s brother-in-law, who had founded Marotta Studio in 1981. Marotta is fascinated by the history of dental materials, which include bone, ivory, wood, gold and silver. He showed me his collection of early prosthodontic instruments, including milling machines, furnaces, hammers and air compressors.

Later, Marotta also pointed out a strange-looking oven. “That’s for processing vulcanite, a hardened rubber material widely used for dentures before modern plastics.” But he’s been unable to find a museum interested in old prosthodontic stuff. “Nobody knows we exist,” he complained.

The critical point

I’d assumed that materials science was required to make prosthetic teeth biocompatible, corrosion resistant, and able to withstand mechanical motions such as crushing, biting and grinding. I also knew that teeth have to be made economically enough to be widely available, aesthetic enough to be desirable, and versatile enough to withstand a variety of oral environments.

But I had no idea how much materials science was required to bring all these properties together.

Back in his office, Dr Albora installed the tooth and handed me a mirror. I had to pull up my lip to see it way on the side of my mouth. “I’d have to smile before somebody notices it,” I complained. “Well,” he said, “that’s for just in case you do.”

The post Get your teeth into the cutting edge of materials science appeared first on Physics World.

A wind turbine blade is basically glass fibre set in hardened resin. The fibres give it strength, the resin holds them in place, and the two are bonded so tightly that a blade can survive wind, rain and stress.

That same toughness is the problem once the blade comes down. Thermoset epoxy does not melt back into a workable liquid, and its stable chemical bonds are difficult to break. So retired blades are typically cut into sections and sent to landfill.

That is the waste a group of researchers decided to work with. In a 2026 study published in ACS Applied Engineering Materials, a team at Xi’an Shiyou University, with collaborators at the Beijing Institute of Technology and Monash University, ground old blade material into powder and turned it into a lightweight, sponge-like insulation.

Here is what came out of the lab, and how it stacks up against the size of the problem.

It squashes to a fifth of its thickness and springs back

The most surprising thing about the material is how far you can crush it without wrecking it. The team reports it took a squeeze of over 80 percent and recovered, meaning you can press it down to roughly a fifth of its height and it bounces back. That matters because conventional silica aerogels are famously fragile. They insulate well but can be brittle. A material that can take a squeeze and spring back is far easier to handle and install.

The trick is in the structure. Instead of a solid block, the composite is a network full of tiny connected pores, with the blade powder stiffening a soft, springy scaffold. 

It combined low density with unusually high compressibility

Weight is where the main result sits. The material reached a density of 0.184 grams per cubic centimetre while sustaining more than 80 percent compressive strain. The authors say the composite showed “a superior combination of low bulk density (0.184 g cm–3) and high compressive strain (>80%), outperforming a wide range of reported silica-based or organic aerogels and composites.”

A caution is warranted: that line is the researchers describing their own work, not an outside verdict. “Outperforming” is their framing, and the comparison is against numbers from other published papers rather than a head-to-head test by a neutral lab. The figures themselves are measurable; whether the material performs as well in practice is the kind of thing other labs and larger-scale testing would need to settle.

It holds heat in about as well as ordinary insulation

Being light and squishy would not count for much if heat poured straight through it. It doesn’t. The composite measured a thermal conductivity of 0.068 watts per metre-kelvin, and lower is better here because it means less heat gets across. For comparison, ordinary glass wool building insulation sits around 0.04. So the blade composite is not a record-setting insulator, but it is in a sensible range for the job while remaining highly compressible.

It self-extinguishes instead of feeding a flame

Insulation lives inside walls and roofs, so how it behaves near fire matters. The team reports enhanced flame self-extinguishing capability, meaning it tended to stop burning once the flame source was removed rather than carrying the fire along. Again, this is one lab result on lab samples, though, and real fire-safety ratings require standardised testing. Read it as promising, not certified.

It turns a landfill problem into the raw material

The reason any of this is interesting is the sheer number of blades headed for the ground. Worldwide, the mass of blades expected to be discarded by 2050 may reach about 43 million tonnes. Right now, around 12,000 blades are retired across Europe and the US each year, and they are typically cut up and sent to landfill. A process that takes that same material and makes something useful flips the equation.

As the authors put it, reusing the blade waste “not only helps to reduce environmental burdens and resource waste but also opens up avenues for generating high-performing, useful materials.”

Where this actually sits

This is one study and one set of lab measurements. The chemistry is clever and the numbers look good, but the gap between a lab composite and a pallet of insulation shipped to a building site is wide. The paper doesn’t answer the questions that fill that gap: cost, batch-to-batch consistency, how the material holds up over years inside a wall, and whether grinding and processing old blades at scale actually makes economic sense.

That last question is the real hinge. Something has to make the recycled route cheaper or required before a lab result becomes a real supply chain.

None of that takes away from what the team built. This is a good answer to a narrow question, which is whether hard-to-recycle blade waste can be turned into a useful, light, tough insulating material at all. The evidence here says yes. The bigger question, whether it can be done by the tonne cheaply enough to matter, is still open.

The post In 2025, researchers ground retired wind turbine blades into powder, stirred it into a gel and set it into an insulation composite. The composite combined low density with much greater compressibility than many of the insulating aerogels and composites it was compared with, squashing to a fifth of its thickness without breaking apart. appeared first on Space Daily.

When evaluating new materials for optoelectronic applications – perhaps promising solar panel materials like halide perovskites or semiconductor compounds for microLED displays – optical characterization is almost always the materials scientists’ first port of call. And up to now steady-state photoluminescence (PL) has been the de facto workhorse for this task.

This non-destructive and highly sensitive technique involves optically exciting a sample and recording the integrated intensity and wavelength of re-emitted photons. Through this, researchers gain a quick understanding into a material’s electronic structure, optical transitions and emission characteristics.

However, these spectra alone can be misleading. Materials with substantially different microscopic properties can generate similar steady-state PL results, masking the fundamental physical dynamics that govern the material’s performance in the real world. To gain deeper understanding of a given material, a more comprehensive and correlated approach is needed.

Blinding average

The core issue lies in the fact that steady-state PL provides a time-integrated view of the emission and depending on the measurement geometry, may also average over spatial variations. Steady-state PL records a static equilibrium in which charge carrier generation balances recombination. This means that, on its own, it does not directly reveal how these excited charge-carriers evolve and ultimately dictate how a device manipulates energy and light.

For example, although two semiconductor thin films may show identical steady-state emission, they can perform very differently in a real device. One film might have long carrier lifetimes consistent with low non-radiative losses – useful in solar cells, for example – while the other could suffer from high defect densities that are masked by strong light absorption or intense excitation light.

Conversely, weak emission does not necessarily mean poor material quality. Again using a layered solar cell as an example, dim luminescence often signals fast, beneficial charge extraction across an interface rather than harmful defect recombination (where structural imperfections convert charge-carrier energy into wasted heat). Because steady-state measurements only show an overall average, they cannot separate these competing mechanisms.

Resolving in time, space and spectrum

Time-resolved PL (TRPL) is a key technique in illuminating these hidden dynamics. Unlike steady-state PL, which continuously bathes a sample with light, TRPL uses a short laser pulse and measures how the photoluminescence intensity evolves afterwards. This can reveal carrier dynamics over timescales ranging from picoseconds to microseconds.

TRPL is particularly important in materials where local variations strongly influence device behaviour. For instance, it can expose the difference between regions that exhibit long-lived emission consistent with efficient radiative recombination, and those that exhibit fast decay caused by, for example, defect recombination.

Of course, steady-state PL averages over time and space, and therefore TRPL only solves part of the problem. Spatially resolved TRPL addresses the missing spatial dimension. Combining a high-precision, motorized XY stage with TRPL’s precise timing, spatially resolved TRPL forms a 2D map that directly correlates localized structural features – such as grain boundaries and defects – with variations in carrier kinetics across the surface.

Complementary to these techniques is time-resolved emission spectroscopy (TRES), which combines spectral selection with time-resolved detection to measure how emission dynamics vary across the spectrum. By recording wavelength-dependent decay behaviour, TRES reveals how different spectral contributions evolve following excitation.

In short, where TRPL reveals kinetics over time and spatially resolved TRPL locates variations in space, TRES adds a spectral dimension, showing how the emission spectrum evolves after excitation. This allows researchers to track changes in the distribution of photon energies over time to understand carrier evolution and gain insight into the mechanisms underlying material behaviour.

A correlative approach

Though powerful in isolation, reconciling insights across these different instruments is slow and prone to errors. There can be microscopic differences between samples or even within positions in a single sample that dramatically alter emission spectra. Moreover, moving a sample between separate instruments is fraught with difficulty, potentially damaging the sample or causing delays that lead to sample degradation.

More comprehensive and reliable physical insight comes when temporal, spatial and spectral factors are recorded correlatively on the exact same sample region. This need for correlation is the motivation behind PicoQuant’s Solira, an integrated workflow platform for steady-state PL, TRPL, spatially resolved TRPL and TRES (the latter when combined with the complementary FlexLambda Kit), as well as additional imaging techniques, such as hyperspectral imaging, required for different scientific questions.

Bringing these techniques together within one configurable microscope system means a materials scientist can gain a more informed interpretation of material behaviour. For instance, they can identify the relevant emission bands at selected points of interest with steady-state PL. They can then wield TRPL to measure the associated decay kinetics, before perhaps applying TRES to resolve how those kinetics vary across the emission spectrum.

Bright demonstration

The power of this correlated approach was demonstrated recently by Professor Eva Unger’s group at Helmholtz-Zentrum Berlin, Germany, with measurements carried out by Maxim Simmonds. Investigating perovskite solar mini-modules, the team worked with PicoQuant and used Solira to locate precise laser-patterned lines – microscopic scribes used to interconnect individual cells in a solar module – before verifying emission from the active layer. Localized TRPL measurements then revealed significantly faster decay dynamics next to these laser cuts compared to the pristine bulk material, indicating altered carrier recombination or diffusion near structured features.

However, point measurements alone were not enough to discern whether the laser had fully removed the perovskite or merely modified it. Switching to spatially resolved TRPL imaging on Solira revealed that measurable photoluminescence persisted along the laser-patterned lines. This showed that laser structuring had altered local photophysical properties rather than eliminating the active layer – a conclusion only made possible by consistently mapping charge-carrier dynamics across temporal, spatial and spectral dimensions together on one setup.

As semiconductor materials and optoelectronic devices become more complex, optical characterization tools must keep pace. By unifying these tools within an integrated workflow platform such as Solira, materials scientists now have the means to paint a more complete picture of material characteristics and thereby unlock the next generation of innovative functional materials.

 

The post Above-average correlative materials characterization appeared first on Physics World.

Researchers used a specially designed cavity to strengthen quantum vacuum fluctuations and enhance superconductivity in a thin material. Empty space is not truly empty. Even a vacuum contains restless quantum fluctuations, and researchers have now shown for the first time that these normally subtle effects can be engineered to strengthen superconductivity. The work, led by [...]

A material once thought to be nonmagnetic may reveal a hidden magnetic side when made just a few atomic layers thick. A newly proposed class of magnetism known as altermagnetism could open new possibilities for making computer memory smaller and more efficient. Now, researchers have found evidence that ruthenium dioxide, a quantum material long debated [...]

Billions of people still suffer from hunger and food insecurity worldwide. Meanwhile, microbial contamination causes a third of global food waste annually, resulting in major economic losses and illnesses. Although antibiotics and pesticides help control contamination, their excessive use can promote bacterial resistance or leave toxic residues. 

One alternative uses materials that generate highly reactive forms of oxygen when exposed to light, called photocatalysts, to prolong food freshness. These molecules kill bacteria by damaging their cell components in a process called photodynamic inactivation or PDI. However, current PDI systems rely on energy-intensive lasers and long exposure times because the bacteria’s protective cell membranes block reactive oxygen molecules. As a result, the systems don’t kill bacteria effectively and risk overheating food, affecting its freshness and nutritional value.

Scientists at Zhejiang University in China thought that it would be possible to achieve a PDI system using accessible, free sunlight with the right photocatalyst. Moreover, they also wanted to integrate this photocatalyst into food packaging to combat microbes during storage. 

To make the photocatalyst, the researchers mixed water with a glue-like plant fiber that provides structural support, called pectin, and a chemical from plant seeds that supplies phosphorus, called phytic acid. Then they heated the mixture in a sealed reactor at 220ºC (428ºF) for 5 hours to form tiny structures composed of a carbon core surrounded by a phosphorus-rich shell called phosphorus-modified carbonized polymer dots or PCDs.

To incorporate the PCDs into film packaging, the researchers dissolved equal amounts of a plant fiber from konjac, called glucomannan, and another plant-derived molecule, called carboxymethylcellulose, in warm water to form a network of entangled molecular chains. Then, they added 1.5 milligrams of PCD per milliliter to this mixture, which linked the chains together like molecular fasteners. Finally, they added a moisture-binding chemical called glycerin to prevent brittleness. The researchers cast this mixture onto separate Petri dishes and dried them, forming thin, plastic-like PCD films.

To test the films, the researchers placed Escherichia coli bacteria between 2 sterilized film sheets and exposed the samples to either darkness or simulated sunlight for 20 minutes. They then transferred the microbes onto agar plates and incubated them for 15 hours, allowing surviving bacteria to form visible colonies. They compared the number of bacterial colonies with those of untreated samples to calculate the percentage of bacteria the films eliminated in each environment. 

Tests under darkness showed that the films eliminated about 60% of the bacteria. The researchers attributed this result to the positive electrical charge of PCDs, which attracts the bacteria’s negatively charged cell surfaces. The electrical attraction stresses their cell membranes, interfering with essential life processes. This result suggested that the films use a separate charge-based antibacterial mechanism apart from PDI, which requires light to work.

Under simulated sunlight, the films eliminated nearly 100% of the bacteria. The researchers identified 2 principal mechanisms causing this. First, the PCDs acted as tiny heaters that generated localized heat, which stretched holes in the bacterial membranes, allowing contents to leak out of their cells through a process called photoporation. Second, the PCDs generated reactive oxygen molecules that could then penetrate the bacteria. Once inside the cells, these molecules irreversibly damage the bacteria’s internal components and genetic material through PDI. 

The researchers also investigated whether PCD films could serve as food packaging by using them to wrap fresh strawberries. Compared with conventional nonbiodegradable polyethylene packaging where visible rotting occurred, the PCD films kept the strawberries fresh for more than 4 days by suppressing bacterial growth and regulating moisture levels. When the team tested whether the films were toxic, they found that the films are safe for humans and compatible for food applications. They also buried the films in soil for 24 days and found that they degraded by 78%, demonstrating biodegradability suitable for packaging fresh foods.

The team concluded that PCD films could be a biodegradable food packaging that combines plant-based materials with multiple antibacterial strategies. The films retained antibacterial activity in darkness and became more effective under sunlight through the combined effects of photoporation and PDI. These findings demonstrated that by combining multiple mechanisms into a single material, researchers can create multifunctional food packaging that remains effective across different storage conditions.

The post Harnessing sunlight to fight bacteria appeared first on Sciworthy.

Scientists have unveiled a computational design for a terahertz metasurface biosensor that combines five distinct materials—graphene, MXene, tungsten disulfide, gold, and copper—into a single multilayer architecture capable of detecting refractive-index changes associated with chikungunya virus infection. The study, published in Results in Optics by G. Arunachalam, A.R. Kalaiarasi, Giri.G. Hallur, and V. Parthasarathy, reports a numerically predicted sensitivity of 907 GHz per refractive-index unit, among the highest values reported for hybrid-material terahertz biosensors, and couples the electromagnetic design to an XGBoost machine-learning surrogate model that predicts sensor behavior with accuracies exceeding 99.8 percent.

Chikungunya virus is an enveloped, positive-sense single-stranded RNA alphavirus transmitted primarily by Aedes aegypti and Aedes albopictus mosquitoes. While mortality remains low, generally below 0.1 percent, the broader public health burden arises from severe polyarthralgia that can persist for months or even years in a substantial fraction of patients across tropical and subtropical regions. With no approved antiviral therapy or licensed vaccine currently available, diagnostic accuracy sits at the center of clinical management and transmission control. Yet existing diagnostic tools face significant practical constraints, particularly in point-of-care and field settings.

Serological methods such as enzyme-linked immunosorbent assay suffer from cross-reactivity with related alphaviruses, including Ross River and O’nyong-nyong viruses, reducing diagnostic specificity. Real-time reverse transcription polymerase chain reaction offers high sensitivity during the acute phase but depends on laboratory infrastructure, trained personnel, and controlled sample handling. Virus isolation in cell culture provides confirmatory results but requires biosafety level-3 facilities and extended processing time. These limitations have motivated the search for rapid, label-free sensing approaches capable of operating at clinically relevant concentrations in decentralized environments.

The new work turns to the terahertz band, spanning roughly 0.1 to 10 THz, which lies between microwave and infrared regions of the electromagnetic spectrum. Terahertz radiation is non-ionising, with photon energies in the millielectronvolt range, allowing interaction with biological samples without causing ionising damage. Crucially, terahertz waves couple to low-frequency vibrational and rotational modes of biomolecules such as proteins, nucleic acids, and polysaccharides, producing measurable spectral features that support label-free detection. Because biological media including blood plasma and viral suspensions exhibit refractive-index variations in this domain, differences on the order of 0.01 to 0.02 refractive-index units can shift resonance frequency and field distribution when coupled to resonant sensing structures.

The proposed sensor is built around a periodically repeated square unit cell containing two identical square resonators, 2000 nanometers on a side, coated with tungsten disulfide—a two-dimensional transition metal dichalcogenide with strong light–matter interaction, high carrier mobility, and excellent dielectric confinement. This layer localizes the electric field in the sensing region and increases the interaction volume between the resonant field and the surrounding analyte. A pair of concentric circular rings, 3200 and 3800 nanometers in diameter and functionalized with MXene, surrounds the resonators, enhancing electromagnetic coupling, promoting efficient charge transport, and strengthening plasmonic interactions between resonator elements. An outer gold ring, 6000 nanometers in diameter, serves as the main plasmonic resonator supporting strong localized surface plasmon resonances with low optical loss. The entire multi-resonant assembly is embedded within a monolayer graphene sheet measuring 14,000 by 14,000 nanometers, which acts as a broadband absorber and a high-mobility charge transport medium whose electrically tunable chemical potential allows dynamic, active control of the resonance characteristics. Copper elements woven into the architecture provide supplementary conductive pathways that reinforce current distribution and coupling among the hybrid resonators. The structure rests on a silicon dioxide substrate, chosen for its low dielectric loss and mechanical robustness, which preserves the resonance quality factor.

The authors stress that the multilayer design is compatible with established microfabrication techniques. Fabrication would begin with a cleaned silicon dioxide substrate, followed by polymer-assisted transfer of monolayer graphene and thermal annealing. Gold and copper resonators can be deposited through electron-beam evaporation or magnetron sputtering with lift-off patterning, MXene rings through solution-based deposition, and the tungsten disulfide layer through chemical vapor deposition or thin-film transfer. With a unit-cell dimension of approximately 14 micrometers, the required feature sizes fall comfortably within conventional photolithography capabilities, and because fabrication imperfections remain far smaller than the operating terahertz wavelength, moderate tolerances are expected to have only limited influence on the electromagnetic response. For biosensing, the graphene surface could subsequently be functionalized with chikungunya-specific antibodies or aptamers using EDC/NHS or pyrene-based linker chemistries.

The electromagnetic modeling, performed in COMSOL Multiphysics, reveals a pronounced resonance at 0.355 THz, where electric-field simulations show the strongest and most spatially extensive enhancement. Varying the graphene chemical potential from 0.1 to 0.9 electronvolts produced dramatic modulation of the transmission contrast, which increased roughly 36-fold at the highest bias, from less than one percentage point to more than 27 percentage points, while peak transmission remained essentially unchanged above 98.6 percent. This asymmetric response—stable maxima paired with strongly modulated minima—arises because increasing chemical potential enhances graphene’s intraband conductivity, deepening resonant absorption through stronger light–matter interaction. The sensor also demonstrated remarkable angular robustness, maintaining peak transmittance above 97.8 percent across incident angles from 0 to 80 degrees, an important tolerance for realistic deployment where normal incidence cannot always be guaranteed.

Geometric optimization identified an outer circular resonator radius of 2500 nanometers and a square resonator side length of 2500 nanometers as the dimensions that maximize resonance strength, driving minimum transmittance down to approximately 65 to 67 percent and signifying optimal electromagnetic confinement within the active sensing region. When evaluated across refractive indices from 1.33 to 1.39, a range encompassing reported values for healthy plasma (approximately 1.35 RIU), healthy platelets (1.39 RIU), chikungunya-infected plasma (1.33 RIU), and infected platelets (1.38 RIU), the optimized configuration achieved a maximum sensitivity of 907 GHz/RIU, a figure of merit of 18.519 RIU⁻¹, a minimum detection limit of 0.061 RIU, a sensor resolution of 55.178, and a refractive-index resolution of 0.001 RIU. In comparative benchmarks against recently reported graphene- and hybrid-material-based terahertz biosensors—including graphene/copper/aluminum, graphene/silicon dioxide, MXene–graphene–black phosphorus, and graphene-integrated copper–silver designs—the proposed architecture’s sensitivity exceeded most published values, reflecting the synergistic field confinement produced by the five-material stack.

The machine-learning component addresses one of the central bottlenecks in metasurface development: the computational cost of repeated full-wave finite-element simulations during structural optimization. The team trained an XGBoost regressor, an ensemble method based on gradient-boosted decision trees, on simulation data covering incidence-angle variation and circular-ring dimension variation, using stratified sampling with 80 percent of data for training and 20 percent held out for independent testing, alongside five-fold cross-validation and grid-search hyperparameter optimization. The model captured more than 99.7 percent of response variance on unseen data, with mean absolute percentage errors below 0.162 percent and prediction accuracies from 99.838 to 99.959 percent. Acting as a computational surrogate, the trained model enables rapid interpolation across the design space without sacrificing the fidelity of the underlying electromagnetic model.

The authors are careful to frame the work as a computational proof-of-concept rather than an experimentally validated diagnostic. The sensor detects changes in the local dielectric environment surrounding the resonators, not viral particles or nucleic acids directly, and refractive-index sensing alone cannot intrinsically distinguish chikungunya from other viruses with similar dielectric properties. Analytical specificity in practice will depend on surface biofunctionalization with chikungunya-specific recognition molecules immobilized on the graphene or gold sensing surface. Future work will focus on device fabrication, biofunctionalization, calibration with reference refractive-index standards, experimental validation with clinically relevant plasma and platelet samples, and systematic evaluation of selectivity against related arboviruses—steps that would transform this numerically validated platform into a practical tool for rapid, label-free infectious disease diagnostics in the field.