Topological quantum materials combine unusual electronic states with properties such as magnetism or superconductivity, offering possibilities for future electronics and quantum technologies. Researchers at Tohoku University have now shown that changing the number of layers in a crystal can provide a systematic way to design topological magnets. The work is published in the Journal of the American Chemical Society.

Topological quantum materials combine unusual electronic states with properties such as magnetism or superconductivity, offering possibilities for future electronics and quantum technologies. Researchers at Tohoku University have now shown that changing the number of layers in a crystal can provide a systematic way to design topological magnets. The work is published in the Journal of the American Chemical Society.

Material properties such as sound insulation, resistance to extreme heat and thermal expansion originate from how the zillions of microscopic building blocks (nuclei and electrons) interact at equilibrium and respond to perturbations. Atoms are typically about one ten-billionth of a meter across, so there can be a lot of parts to keep track of—a task that is complicated at the quantum-mechanical level, where particles are neither here nor there until observed.

Material properties such as sound insulation, resistance to extreme heat and thermal expansion originate from how the zillions of microscopic building blocks (nuclei and electrons) interact at equilibrium and respond to perturbations. Atoms are typically about one ten-billionth of a meter across, so there can be a lot of parts to keep track of—a task that is complicated at the quantum-mechanical level, where particles are neither here nor there until observed.

Researchers at Nagoya University have built a graphene nanoribbon that can switch which way it twists using a natural solvent. Graphene nanoribbons are thin ribbon-shaped structures made of fused carbon rings. Twisted or helical versions of these ribbons show promise for advanced light and electronic devices. However, no graphene nanoribbon could switch that twist on demand, until now.

Scientists have worked out how to switch between a right-handed and left-handed twist (chirality) by changing the solvent around it. The discovery ¹ opens opportunities for new optical switches, chemical sensors, and spintronic components that adapt to changing environments.

Tomoyuki Ikai, lead author and professor at Nagoya University’s Graduate School of Engineering, is a polymer chemist inspired by natural helical structures such as DNA and proteins. Polymers are large molecules built from many small, repeating units linked together in a chain. Ikai had been working on ladder polymers, where each repeating unit is locked into place and cannot freely rotate around the bond connecting to its neighbor (unlike a typical flexible linear polymer).

In 2019, Ikai and his collaborators built the first rigid, helix-shaped polymer. In 2021, they perfected a chemical method to fuse these building blocks together without flaws. This method is what let them build the new graphene nanoribbon.

“We used the same fusion approach already used to make predictable helical ladder polymers. But instead of a stable building block, such as [6]helicene, we used [4]helicene, a 4-ring unit written off as too unstable to be useful,” Ikai said.

Soak, twist, repeat

These units are difficult to control on their own because they switch their chirality too fast to hold one handedness. The team’s method fuses these small, restless units into one long chain. Once joined, they found that a neighbor effect took hold: each unit’s twist began to match its neighbors, and long stretches of the ribbon settled into a single, shared spiral.

To lock it in one overall direction, the researchers dissolved the ribbon in a natural chiral liquid, a liquid made of molecules that come in two mirror-image versions. They tested six candidates before they found the right one: beta-pinene, a compound found in pine trees and citrus peel.

Because beta-pinene molecules can be arranged in left- and right-hand mirror-images, these two versions each push the ribbon toward the opposite spiral. This also changed the twist direction of light the ribbon gave off, a property called circularly polarized luminescence, and is the first graphene nanoribbon shown to switch its light this way.

The switching induced a remarkably high degree of helical bias, with almost all of the helicene units aligning in the same direction. The switching effect is strongest at –90°C and grows weaker as the temperature rises toward room temperature.

“For a long time, people saw [4]helicene as unsuitable for chiral materials, because it could not be controlled,” Ikai said. “In this paper, we show that once you link enough of these units together, the instability itself becomes the useful part.”

A chiral solvent’s nudge toward one handedness is usually very weak on its own. Here, the ribbon’s own structure, with each unit mechanically linked to its neighbors, amplifies that weak nudge into a strong, nearly one-handed result.

An adaptive material

The researchers point to several possible future uses: The switchable light could serve optical devices. The ribbon’s chemical sensitivity to beta-pinene suggests it may work as a chiral sensor, and a similar design could one day help detect hazardous or unstable chemicals. Because graphene conducts electricity well, the ribbon may also suit electronic sensors.

The molecule’s twisted shape connects to spintronics, a field that uses the spin of electrons rather than just their charge. Ikai noted that a right-handed or left-handed structure can, in principle, let electrons of one spin pass through more easily than the other, a property helical structures are known for in physics literature.

The current design only holds its twist while it stays in the chiral liquid. If the solvent is removed, the ribbon drifts back to a mixed, unstable state. Ikai’s next goal is a form of “chiral memory,” a way for the ribbon to lock in its twist even after the solvent is gone. This next step builds on memory techniques the researchers have explored in other helical systems and is now applied to graphene for the first time.

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Water droplets sliding across solid surfaces can acquire electric potentials of thousands of volts and thereby corrode non-conductive surfaces on metals when they discharge. That is the conclusion of researchers in Germany who say that the poorly-understood phenomenon warrants further investigation to help prevent corrosion of vulnerable outdoor equipment and cultural heritage sites.

Metal corrosion by water droplets is a serious economic and safety issue, and prevention begins with the proper understanding of the relevant processes. Conventional wisdom is that most corrosion is caused by a combination of physical abrasion by the motion of the droplets and chemical degradation from natural acids and anthropogenic pollutants in the water. The notion that electrochemistry might play a significant role in corrosion had not been seriously considered, says physical chemist Hans-Jürgen Butt of the Max Planck Institute for Polymer Research in Mainz.

Part of the reason, he believes, is that, until relatively recently, it was thought that the triboelectric effect (electrically charging objects by rubbing them together) did not work in liquids. “If you have a solid and you rub another insulating solid against it you get electron transfer – I think this has been known for more than 2500 years” he says. However, this relies on atomic-scale roughness of the surface to concentrate charge at specific points where bonds can be broken – and fluids cannot, by definition, be rough.

“If you take a water droplet and let it slide there is some mechanical force from surface tension, but that’s much too low,” says Butt. “There is no way you could generate enough energy locally to pick up an electron or to put an electron or an ion from the water onto the surface.” In the past 10 years, however, it has become increasingly clear that sliding droplets do become highly charged.

Sloping surfaces

In their present work Butt and colleagues deposited water droplets onto copper surfaces covered with 60 nm of Teflon.  When they dropped droplets straight onto the surface, they observed no corrosion. They then deposited droplets first onto a variety of other sloped insulating surfaces such as plant leaves, PVC construction boards and the perfluorooctadecyltrichlorosilane (PFOTS) hydrophobic coating often used on window glass. The droplets ran down these surfaces and then fell onto the Teflon-coated copper. After around 3000 droplet impacts, atomic force microscopy and confocal microscopy revealed evidence that the droplets had corroded both the coating and the underlying copper.

The researchers believe that the droplets become positively charged as they slide down the sloping surface. As they fall onto the coating, the potential difference between the copper and the underlying copper can exceed 1 kV. This is greater than the dielectric breakdown strength of the coating, causing the droplet to discharge. This damages the coating and leaves the underlying metal vulnerable to further oxidation.

To test their hypothesis, the researchers measured charge movement within the copper surface, showing that negative charge flowed towards droplets dripping off insulating surfaces. They also used high-speed cameras to show that, whereas a drop deposited directly retained its spherical shape before impact, a dripping drop was drawn into a cone shape, producing a tip of positive charge that would increase its corrosive capacity.

Uncertain consequences

The practical implications of this are unclear. “Technical coatings on cars, ships etc. are typically 100 microns and thicker, so the process we describe is probably not of direct relevance,”says Butt. However, the phenomenon could be involved in the degradation of monuments and other outdoor historical objects. “We have evidence that surfaces change their properties when you slide charges over them, but the real consequences are not yet known,” explains Butt.

He says his own group is most clearly focused on understanding the fundamental physics involved. “We still don’t know why the heck there is such a charge separation: it’s energetically unfavourable, it should not happen, but it happens.” he says. “The one effect we describe here is, in a way, pretty trivial – everyone knows that if you have a high potential and it’s somehow grounded there is a breakthrough – but what happens at the surface with this deposited charge is not clear.”

Materials scientist Zhong Lin Wang of Georgia Institute of Technology in Atlanta was one of the first researchers to discover the triboelectric effect in liquids, and helped to develop the triboelectric nanogenerator used to quantify it. “The transferred electrons can be kicked back to the water solution, resulting in chemical reaction at the vicinity surface. This process, called contact-electro-catalysis, was first proposed in 2022, and is now an active field of research in chemistry, materials and environmental science.” He says. “[Butt and colleagues] show that the electrons transferred from the water droplet can ‘break’ the surface coating layer and lead to local oxidation. This is an interesting discovery.”

The research is described in Nature.

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