Using a novel spectroscopy technique, physicists in Japan have revealed how organic materials accumulate electrical charge through long-term illumination by sunlight – leading to material degradation. Ryota Kabe and colleagues at the Okinawa Institute of Science and Technology have shown how charge separation occurs gradually via a rare multi-photon ionization process, offering new insights into how plastics and organic semiconductors degrade in sunlight.

In a typical organic solar cell, an electron-donating material is interfaced with an electron acceptor. When the donor absorbs a photon, one of its electrons may jump across the interface, creating a bound electron-hole pair which may eventually dissociate – creating two free charges from which useful electrical work can be extracted.

Although such an interface vastly boosts the efficiency of this process, it is not necessary for charge separation to occur when an electron donor is illuminated. “Even single-component materials can generate tiny amounts of charge via multiphoton ionization,” Kabe explains. “However, experimental evidence has been scarce due to the extremely low probability of this process.”

To trigger charge separation in this way, an electron needs to absorb one or more additional photons while in its excited state. Since the vast majority of electrons fall back into their ground states before this can happen, the spectroscopic signature of this charge separation is very weak. This makes it incredibly difficult to detect using conventional spectroscopy techniques, which can generally only make observations over timescales of up to a few milliseconds.

The opposite approach

“While weak multiphoton pathways are easily buried under much stronger excited-state signals, we took the opposite approach in our work,” Kabe describes. “We excited samples for long durations and searched for traces of accumulated charges in the slow emission decay.”

Key to this approach was an electron donor called NPD. This organic material has a relatively long triplet lifetime, where an excited electron is prevented from transitioning back to its ground state. As a result, these molecules emit phosphorescence over relatively long timescales.

In addition, Kabe’s team dispersed their NPD samples into different host materials with carefully selected energy levels. In one medium, the energies of both the highest-occupied and lowest-unoccupied molecular orbitals lay below NPD’s corresponding levels, so that the host material acted as an electron acceptor. As a result, charge transfer occurred in the same way as it would across a typical donor-acceptor interface.

Yet in another medium, the host’s lowest-unoccupied orbital lay above NPD’s – blocking charge transfer, and allowing triplet states to accumulate instead. In this case, the only way for charge separation to occur was through multi-photon ionization.

Slow emission decay analysis

Since NPD’s long triplet lifetime allowed its electrons to be excited gradually over an extended period of illumination, its weak charge accumulation became detectable through slow emission decay analysis. In contrast, more conventional methods involve multiple, ultra-fast laser pulses, severely restricting the timescale over which measurements can be made. Altogether, this approach enabled the team to clearly distinguish between the two charge generation pathways.

“Using this method, we confirmed that charge generation occurred via resonance-enhanced multiphoton ionization mediated by long-lived triplet states, even in single-component organic materials,” Kabe describes.

This result offers insights into how plastics and organic semiconductors are degraded by sunlight over years or decades. The conventional explanation is that sunlight generates free radicals. These are molecules that lose an electron through ionization, leaving behind an unpaired electron which readily reacts with other molecules in the surrounding environment. Since photodegradation unfolds over such a long timescale, researchers could not observe this charge generation in single-component organic materials – until now.

“The method will be useful for analysing charge behaviour in organic semiconductor devices and for understanding long-term processes such as photodegradation that occur gradually under continuous light exposure,” Kabe says.

The research is described in Science Advances.

The post Slow spectroscopy sheds light on photodegradation appeared first on Physics World.

Researchers in the US and Korea have created nanoparticles with carefully designed “patches” on their surfaces using a new atomic stencilling technique. These patches can be controlled with incredible precision, and could find use in targeted drug delivery, catalysis, microelectronics and tissue engineering.

The first step in the stencilling process is to create a mask on the surface of gold nanoparticles. This mask prevents a “paint” made from grafted-on polymers from attaching to certain areas of the nanoparticles.

“We then use iodide ions as a stencil,” explains Qian Chen, a materials scientist and engineer at the University of Illinois at Urbana-Champaign, US, who led the new research effort. “These adsorb (stick) to the surface of the nanoparticles in specific patterns that depend on the shape and atomic arrangement of the nanoparticles’ facets. That’s how we create the patches – the areas where the polymers selectively bind.” Chen adds that she and her collaborators can then tailor the surface chemistry of these tiny patchy nanoparticles in a very controlled way.

A gap in the field of microfabrication stencilling

The team decided to develop the technique after realizing there was a gap in the field of microfabrication stencilling. While techniques in this area have advanced considerably in recent years, allowing ever-smaller microdevices to be incorporated into ever-faster computer chips, most of them rely on top-down approaches for precisely controlling nanoparticles. By comparison, Chen says, bottom-up methods have been largely unexplored even though they are low-cost, solution-processable, scalable and compatible with complex, curved and three-dimensional surfaces.

Reporting their work in Nature, the researchers say they were inspired by the way proteins naturally self-assemble. “One of the holy grails in the field of nanomaterials is making complex, functional structures from nanoscale building blocks,” explains Chen. “It’s extremely difficult to control the direction and organization of each nanoparticle. Proteins have different surface domains, and thanks to their interactions with each other, they can make all the intricate machines we see in biology. We therefore adopted that strategy by creating patches or distinct domains on the surface of the nanoparticles.”

“Elegant and impressive”

Philip Moriarty, a physicist of the University of Nottingham, UK who was not involved in the project, describes it as “elegant and impressive” work. “Chen and colleagues have essentially introduced an entirely new mode of self-assembly that allows for much greater control of nanoparticle interactions,” he says, “and the ‘atomic stencil’ concept is clever and versatile.”

The team, which includes researchers at the University of Michigan, Pennsylvania State University, Cornell, Brookhaven National Laboratory and Korea’s Chonnam National University as well as Urbana-Champaign, agrees that the potential applications are vast. “Since we can now precisely control the surface properties of these nanoparticles, we can design them to interact with their environment in specific ways,” explains Chen. “That opens the door for more effective drug delivery, where nanoparticles can target specific cells. It could also lead to new types of catalysts, more efficient microelectronic components and even advanced materials with unique optical and mechanical properties.”

She and her colleagues say they now want to extend their approach to different types of nanoparticles and different substrates to find out how versatile it truly is. They will also be developing computational models that can predict the outcome of the stencilling process – something that would allow them to design and synthesize patchy nanoparticles for specific applications on demand.

The post ‘Patchy’ nanoparticles emerge from new atomic stencilling technique appeared first on Physics World.

A 3D-printed structure called a kagome tube could form the backbone of a new system for muffling damaging vibrations. The structure is part of a class of materials known as topological mechanical metamaterials, and unlike previous materials in this group, it is simple enough to be deployed in real-world situations. According to lead developer James McInerney of the Wright-Patterson Air Force Base in Ohio, US, it could be used as shock protection for sensitive systems found in civil and aerospace engineering applications.

McInerney and colleagues’ tube-like design is made from a lattice of beams arranged in such a way that low-energy vibrational modes called floppy modes become localized to one side. “This provides good properties for isolating vibrations because energy input into the system on the floppy side does not propagate to the other side,” McInerney says.

The key to this desirable behaviour, he explains, is the arrangement of the beams that form the lattice structure. Using a pattern first proposed by the 19^th century physicist James Clerk Maxwell, the beams are organized into repeating sub-units to form stable, two-dimensional structures known as topological Maxwell lattices.

Self-supporting design

Previous versions of these lattices could not support their own weight. Instead, they were attached to rigid external mounts, making it impractical to integrate them into devices. The new design, in contrast, is made by folding a flat Maxwell lattice into a cylindrical tube that is self-supporting. The tube features a connected inner and outer layer – a kagome bilayer – and its radius can be precisely engineered to give it the topological behaviour desired.

The researchers, who detail their work in Physical Review Applied, first tested their structure numerically by attaching a virtual version to a mechanically sensitive sample and a source of low-energy vibrations. As expected, the tube diverted the vibrations away from the sample and towards the other end of the tube.

Next, they developed a simple spring-and-mass model to understand the tube’s geometry by considering it as a simple monolayer. This modelling indicated that the polarization of the tube should be similar to the polarization of the monolayer. They then added rigid connectors to the tube’s ends and used a finite-element method to calculate the frequency-dependent patterns of vibrations propagating across the structure. They also determined the effective stiffness of the lattice as they applied loads parallel and perpendicular to it.

The researchers are targeting vibration-isolation applications that would benefit from a passive support structure, especially in cases where the performance of alternative passive mechanisms, such as viscoelastomers, is temperature-limited. “Our tubes do not necessarily need to replace other vibration isolation mechanisms,” McInerney explains. “Rather, they can enhance the capabilities of these by having the load-bearing structure assist with isolation.”

The team’s first and most important task, McInerney adds, will be to explore the implications of physically mounting the kagome tube on its vibration isolation structures. “The numerical study in our paper uses idealized mounting conditions so that the input and output are perfectly in phase with the tube vibrations,” he says. “Accounting for the potential impedance mismatch between the mounts and the tube will enable us to experimentally validate our work and provide realistic design scenarios.”

The post New cylindrical metamaterials could act as shock absorbers for sensitive equipment appeared first on Physics World.

By simply placing two identical elastic metasurfaces atop each other and then rotating them relative to each other, the topology of the elastic waves dispersing through the resulting stacked structure can be changed – from elliptic to hyperbolic. This new control technique, from physicists at the CUNY Advanced Science Research Center in the US, works over a broad frequency range and has been dubbed “twistelastics”. It could allow for advanced reconfigurable phononic devices with potential applications in microelectronics, ultrasound sensing and microfluidics.

The researchers, led by Andrea Alù, say they were inspired by the recent advances in “twistronics” and its “profound impact” on electronic and photonic systems. “Our goal in this work was to explore whether similar twist-induced topological phenomena could be harnessed in elastodynamics in which phonons (vibrations of the crystal lattice) play a central role,” says Alù.

In twistelastics, the rotations between layers of identical, elastic engineered surfaces are used to manipulate how mechanical waves travel through the materials. The new approach, say the CUNY researchers, allows them to reconfigure the behaviour of these waves and precisely control them. “This opens the door to new technologies for sensing, communication and signal processing,” says Alù.

From elliptic to hyperbolic

In their work, the researchers used computer simulations to design metasurfaces patterned with micron-sized pillars. When they stacked one such metasurface atop the other and rotated them at different angles, the resulting combined structure changed the way phonons spread. Indeed, their dispersion topology went from elliptic to hyperbolic.

At a specific rotation angle, known as the “magic angle” (just like in twistronics), the waves become highly focused and begin to travel in one direction. This effect could allow for more efficient signal processing, says Alù, with the signals being easier to control over a wide range of frequencies.

The new twistelastic platform offers broadband, reconfigurable, and robust control over phonon propagation,” he tells Physics World. “This may be highly useful for a wide range of application areas, including surface acoustic wave (SAW) technologies, ultrasound imaging and sensing, microfluidic particle manipulation and on-chip phononic signal processing.

New frontiers

Since the twist-induced transitions are topologically protected, again like in twistronics, the system is resilient to fabrication imperfections, meaning it can be miniaturized and integrated into real-world devices, he adds. “We are part of an exciting science and technology centre called ‘New Frontiers of Sound’, of which I am one of the leaders. The goal of this ambitious centre is to develop new acoustic platforms for the above applications enabling disruptive advances for these technologies.”

Looking ahead, the researchers say they are looking into miniaturizing their metasurface design for integration into microelectromechanical systems (MEMS). They will also be studying multi-layer twistelastic architectures to improve how they can control wave propagation and investigating active tuning mechanisms, such as electromechanical actuation, to dynamically control twist angles. “Adding piezoelectric phenomena for further control and coupling to the electromagnetic waves,” is also on the agenda says Alù.

The present work is detailed in PNAS.

The post Twistelastics controls how mechanical waves move in metamaterials appeared first on Physics World.

This episode explores the scientific and technological significance of 2D materials such as graphene. My guest is Antonio Rossi, who is a researcher in 2D materials engineering at the Italian Institute of Technology in Genoa.

Rossi explains why 2D materials are fundamentally different than their 3D counterparts – and how these differences are driving scientific progress and the development of new and exciting technologies.

Graphene is the most famous 2D material and Rossi talks about today’s real-world applications of graphene in coatings. We also chat about the challenges facing scientists and engineers who are trying to exploit graphene’s unique electronic properties.

Rossi’s current research focuses on two other promising 2D materials – tungsten disulphide and hexagonal boron nitride. He explains why tungsten disulphide shows great technological promise because of its favourable electronic and optical properties; and why hexagonal boron nitride is emerging as an ideal substrate for creating 2D devices.

Artificial intelligence (AI) is becoming an important tool in developing new 2D materials. Rossi explains how his team is developing feedback loops that connect AI with the fabrication and characterization of new materials. Our conversation also touches on the use of 2D materials in quantum science and technology.

The post Unlocking the potential of 2D materials: graphene and much more appeared first on Physics World.