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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