Tag Archives: metal nanostructures

Probing the physical limits of plasmons in organic molecules with fewer than 50 atoms

A Sept. 5, 2018  news item on ScienceDaily introduces the work,

Rice University [Texas, US] researchers are probing the physical limits of excited electronic states called plasmons by studying them in organic molecules with fewer than 50 atoms.

A Sept. 4, 2018 Rice University news release (also on EurekAlert published on Sept. 5, 2018), which originated the news item, explains what plasmons are and why this research is being undertaken,

Plasmons are oscillations in the plasma of free electrons that constantly swirl across the surface of conductive materials like metals. In some nanomaterials, a specific color of light can resonate with the plasma and cause the electrons inside it to lose their individual identities and move as one, in rhythmic waves. Rice’s Laboratory for Nanophotonics (LANP) has pioneered a growing list of plasmonic technologies for applications as diverse as color-changing glass, molecular sensing, cancer diagnosis and treatment, optoelectronics, solar energy collection and photocatalysis.

Reporting online in the Proceedings of the National Academy of Sciences, LANP scientists detailed the results of a two-year experimental and theoretical study of plasmons in three different polycyclic aromatic hydrocarbons (PAHs). Unlike the plasmons in relatively large metal nanoparticles, which can typically be described with classical electromagnetic theory like Maxwell’s [James Clerk Maxwell] equations, the paucity of atoms in the PAHs produces plasmons that can only be understood in terms of quantum mechanics, said study co-author and co-designer Naomi Halas, the director of LANP and the lead researcher on the project.

“These PAHs are essentially scraps of graphene that contain five or six fused benzene rings surrounded by a perimeter of hydrogen atoms,” Halas said. “There are so few atoms in each that adding or removing even a single electron dramatically changes their electronic behavior.”

Halas’ team had experimentally verified the existence of molecular plasmons in several previous studies. But an investigation that combined side by side theoretical and experimental perspectives was needed, said study co-author Luca Bursi, a postdoctoral research associate and theoretical physicist in the research group of study co-designer and co-author Peter Nordlander.

“Molecular excitations are a ubiquity in nature and very well studied, especially for neutral PAHs, which have been considered as the standard of non-plasmonic excitations in the past,” Bursi said. “Given how much is already known about PAHs, they were an ideal choice for further investigation of the properties of plasmonic excitations in systems as small as actual molecules, which represent a frontier of plasmonics.”

Lead co-author Kyle Chapkin, a Ph.D. student in applied physics in the Halas research group, said, “Molecular plasmonics is a new area at the interface between plasmonics and molecular chemistry, which is rapidly evolving. When plasmonics reach the molecular scale, we lose any sharp distinction of what constitutes a plasmon and what doesn’t. We need to find a new rationale to explain this regime, which was one of the main motivations for this study.”

In their native state, the PAHs that were studied — anthanthrene, benzo[ghi]perylene and perylene — are charge-neutral and cannot be excited into a plasmonic state by the visible wavelengths of light used in Chapkin’s experiments. In their anionic form, the molecules contain an additional electron, which alters their “ground state” and makes them plasmonically active in the visible spectrum. By exciting both the native and anionic forms of the molecules and comparing precisely how they behaved as they relaxed back to their ground states, Chapkin and Bursi built a solid case that the anionic forms do support molecular plasmons in the visible spectrum.

The key, Chapkin said, was identifying a number of similarities between the behavior of known plasmonic particles and the anionic PAHs. By matching both the timescales and modes for relaxation behaviors, the LANP team built up a picture of a characteristic dynamics of low-energy plasmonic excitations in the anionic PAHs.

“In molecules, all excitations are molecular excitations, but select excited states show some characteristics that allow us to draw a parallel with the well-established plasmonic excitations in metal nanostructures,” Bursi said.

“This study offers a window on the sometimes surprising behavior of collective excitations in few-atom quantum systems,” Halas said. “What we’ve learned here will aid our lab and others in developing quantum-plasmonic approaches for ultrafast color-changing glass, molecular-scale optoelectronics and nonlinear plasmon-mediated optics.”

Here’s a link to and a citation for the paper,

Lifetime dynamics of plasmons in the few-atom limit by Kyle D. Chapkin, Luca Bursi, Grant J. Stec, Adam Lauchner, Nathaniel J. Hogan, Yao Cui, Peter Nordlander, and Naomi J. Halas. PNAS September 11, 2018 115 (37) 9134-9139; published ahead of print August 27, 2018 DOI: https://doi.org/10.1073/pnas.1805357115

This paper is behind a paywall.

There’s more than one black gold

‘Black gold’ is a phrase I associate with oil, signifying its importance and desirability. These days, this analogic phrase can describe a material according to a July 24, 2015 news item on Nanowerk,

If colloidal gold [gold in solution] self-assembles into the form of larger vesicles, a three-dimensional state can be achieved that is called “black gold” because it absorbs almost the entire spectrum of visible light. How this novel intense plasmonic state can be established and what its characteristics and potential medical applications are is explored by Chinese scientists and reported in the journal Angewandte Chemie …

A July 24, 2015 Wiley (Angewandte Chemie) press release, which originated the news item, provides more details,

Metal nanostructures can self-assemble into superstructures that offer intriguing new spectroscopic and mechanical properties. Plasmonic coupling plays a particular role in this context. For example, it has been found that plasmonic metal nanoparticles help to scatter the incoming light across the surface of the Si substrate at resonance wavelengths, therefore enhancing the light absorbing potential and thus the effectivity of solar cells.

On the other hand, plasmonic vesicles are the promising theranostic platform for biomedical applications, a notion which inspired Yue Li and Cuncheng Li of the Chinese Academy of Science, Hefei, China, and the University of Jinan, China, as well as collaborators to prepare plasmonic colloidosomes composed of gold nanospheres.

As the method of choice, the scientists have designed an emulsion-templating approach based on monodispersed gold nanospheres as building blocks, which arranged themselves into large spherical vesicles in a reverse emulsion system.

The resulting plasmonic vesicles were of micrometer-size and had a shell composed of hexagonally close-packed colloidal nanosphere particles in bilayer or, for the very large superspheres, multilayer arrangement, which provided the enhanced stability.

“A key advantage of this system is that such self-assembly can avoid the introduction of complex stabilization processes to lock the nanoparticles together”, the authors explain.

The hollow spheres exhibited an intense plasmonic resonance in their three-dimensionally packed structure and had a dark black appearance compared to the brick red color of the original gold nanoparticles. The “black gold” was thus characterized by a strong broadband absorption in the visible light and a very regular vesicle superstructure. In medicine, gold vesicles are intensively discussed as vehicles for the drug delivery to tumor cells, and, therefore, it could be envisaged to exploit the specific light-matter interaction of such plasmonic vesicle structures for medical use, but many other applications are also feasible, as the authors propose: “The presented strategy will pave a way to achieve noble-metal superstructures for biosensors, drug delivery, photothermal therapy, optical microcavity, and microreaction platforms.” This will prove the flexibility and versatility of the noble-metal nanostructures.

Here’s a link to and a citation for the paper,

Black Gold: Plasmonic Colloidosomes with Broadband Absorption Self-Assembled from Monodispersed Gold Nanospheres by Using a Reverse Emulsion System by Dilong Liu, Dr. Fei Zhou, Cuncheng Li, Tao Zhang, Honghua Zhang, Prof. Weiping Cai, and Prof. Yue Li. Angewandte Chemie International Edition Article first published online: 25 JUN 2015 DOI: 10.1002/anie.201503384

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This article is behind a paywall.

There is an image illustrating the work but, sadly, the gold doesn’t look black,


© Wiley-VCH

That’s it!