Quantitative Evaluation of Nanosecond Pulsed Laser-Induced Photomodification of Plasmonic Gold Nanoparticles

Biophotonic application of plasmonic gold nanoparticles has become a highly active field of research in recent years due to their unique chemical and physical properties, such as high absorption cross sections and spectral tunability1. Many of the unique properties of gold nanoparticles are governed by the surface plasmon resonance (SPR) effect, a collective oscillation of electrons on the nanoparticle surface that occurs when excited with light at an appropriate wavelength. The SPR results in a strongly enhanced electromagnetic field near the particle surface, which causes unique, shape- and material-dependent spectral variations in light absorption and scattering. These properties allow nanoparticles to be used not only as therapeutic agents2,3,4, but also for diagnostic imaging5,6. The therapeutic effects produced by laser-nanoparticle interaction can occur through a variety of mechanisms. Photothermal transduction causes rapid heating in a localized area around the irradiated nanoparticles and has been used for the treatment of solid tumors in vivo, with both continuous-wave and nanosecond-pulsed lasers7,8,9. Photomechanical effects, such as cavitation, can occur when exposing plasmonic nanoparticles to pulsed laser light (nanosecond-to-femtosecond), and the resultant bubbles are capable of disrupting cancer cell membranes10,11,12. Photochemical effects, like the production of reactive oxygen species, have also been observed from laser irradiation of gold nanoparticles, with pulsed lasers having a greater effect than continuous-wave lasers13,14. The properties that make gold nanoparticles so effective for laser-based therapeutics can also lead to unintended side-effects in diagnostic procedures.

One of the most promising diagnostic techniques that may employ gold nanoparticle contrast agents is photoacoustic imaging (PAI), a rapidly maturing biomedical modality capable of macro- and micro-scale imaging5. In PAI, tissue is illuminated with a nanosecond pulsed laser, typically a Q-switched Nd:YAG with pulse duration in the range of 5–10 ns, at exposures below standard safety limits15. This exposure causes rapid optical absorption and thermal expansion that produces acoustic waves, which can be detected using an ultrasonic transducer. The use of gold nanoparticles as contrast agents for PAI has the potential to generate photothermal, photomechanical, or photochemical effects that result in tissue injury. Furthermore, the spectral changes brought about by nanoparticle photomodification can cause spectral shifts in absorption that degrade PAI-nanoparticle product performance16.

While there are well-established laser safety standards for the skin and eye, these standards are insufficient when exogenous chromophores such as nanoparticles are present. Additionally, no standards exist for evaluating the performance of laser-nanoparticle combination products for medicine. In recent years, a number of studies have contributed knowledge on the laser-nanoparticle interaction processes and resultant bioeffects, as well as test methods that could form the basis of new standards. One key step in elucidating laser-nanoparticle interactions is to understand the photostability of nanoparticles and characterize laser induced photomodification processes, including photothermally-induced melting/reshaping effects that have been documented for different types of metallic nanoparticles16,17,18,19,20,21,22. they chose to study spherical gold nanoparticles as their surface plasmon resonance is close to the wavelength (532 nm) of the second-harmonic Q-switched Nd:YAG laser, which is broadly employed in biophotonics and photomedicine23,24,25, and because these nanoparticles possess well-defined morphological properties and their spherical shape is well-suited for theoretical investigation.

Several prior studies have evaluated the effect of pulsed laser irradiation on gold nanospheres – more accurately gold “pseudospheres” since most of the particles studied, as well as commercially available versions, have faceted rather than smooth edges. One such study by Takami et al. looked at the size reduction of approximately 50 nm gold nanospheres at different pulse energies18. Werner et al. investigated the effect of irradiation wavelength on 55 nm gold nanospheres and was mostly concerned with modeling the difference between interband and intraband excitation22. Another study used dynamic light scattering (DLS), electron microscopy and UV-Vis spectroscopy to examine the impact of a single laser pulse on particles of different sizes26. While results were presented for a range of energy levels, specific damage thresholds were not determined and comparison with theoretical results was not presented. These prior studies have provided significant insights, yet are deficient in terms of generating a standardized test methodology as they either only used a single nanoparticle size or provided a qualitative description of the damage with no well-defined threshold.

Our overall objective was to facilitate the optimization of safety and effectiveness in emerging biophotonic products incorporating nanoparticles. Previous works have not established a common approach for assessing laser damage thresholds in nanoparticles, and information on the role of particle size in nanosphere damage is typically spread across multiple reports with inconsistent experimental conditions. Therefore, the goals of this proof-of-concept study were to implement and assess methodologies to quantitatively determine nanoparticle photomodification thresholds, and to generate data on the melting process and damage thresholds that can be used to improve understanding of this process. Specifically, we have conducted quantitative experimental and analytical investigation of the interaction between nanosecond laser pulses at 532 nm and plasmonic gold nanoparticles with diameters from 20 to 100 nm over a wide range of laser radiant exposures.

More information: Andrew M. Fales et al. Quantitative evalution of nanosecond pulsed laser-induced photomodification of plasmonic gold nanoparticles, Scientific Reports(2017). 10.1038/s41598-017-16052-7.




Optoelectronics without glass

Microscopic image of a chip. Top left: functional modulator with electrical contacts; right: test modulator without electrical contact; below: test components.

Researchers at ETH Zurich have developed the first opto-electronic circuit component that works without glass and is instead made of metal. The component, referred to as a modulator, converts electrical data signals into optical signals. It is smaller and faster than current modulators, and much easier and cheaper to make.

Optical components for microelectronics must be made of glass. Metals are not suitable for this purpose, since optical data can propagate only across roughly a distance of 100 micrometres. This was the general view of scientists until recently. A team of researchers headed by Juerg Leuthold, professor in the Department of Information Technology and Electrical Engineering, has now succeeded in doing what was thought to be impossible and developed a light-processing component made of metal. The researchers have presented their findings in the latest issue of the journal Science.

They accomplished this feat by building a small enough component: at just 3 x 36 micrometres, it is within a size range in which both optical and electrical information can propagate in metals.

Component for fibre optic networks

The component is a : modulators convert electrical data signals into . They are installed in modern internet routers used for fibre optic networks and enable fibre optic data connections between computer units in data centres. However, the standard components used today function differently than the new modulators.

The new component works by aiming the light from a fibre optic source at the modulator, causing the electrons on its surface to oscillate. Experts refer to this as a surface plasmon oscillation. This oscillation can be changed indirectly by electrical data pulses. When the oscillation of the electrons is converted back into light, the electrical information is now encoded onto the optical signal. This means that the information is converted from an electrical into an optical data pulse that can be transmitted via fibre optics.

Schematic representation of the metallic modulator: Left: a continuous beam of light strikes a metallic lattice that deflects the light onto the chip. Right: an optical data pulse exits the component.

Faster and smaller

Two years ago, Leuthold and his colleagues developed one of these plasmonic modulators. At the time, it was the smallest and fastest modulator ever built, but the semiconductor chip still had various glass components.

By replacing all the glass components with metallic ones, the scientists have succeeded in building an even smaller modulator that works up to highest speed. “In metals, electrons can move at practically any speed, whereas the speed in glass is limited due to its physical properties,” says Masafumi Ayata, a doctoral student in Leuthold’s group and lead author of the study. In the experiment, the researchers succeeded in transmitting data at 116 gigabits per second. They are convinced that with further improvements, even higher data transfer rates will be possible.

Etched from a gold layer

The modulator prototype tested by the ETH researchers is made of a gold layer that lies on a glass surface. The scientists emphasised that the glass has no function. “Instead of the layer, we could also use other suitable smooth surfaces,” says Leuthold. It might also be possible to use less expensive copper instead of gold for industrial applications. The important point is that only one metallic coating is required for the new modulators. “This makes them much easier and cheaper to fabricate,” says Leuthold.

The researchers are already working with an industrial partner in order to put the new modulator into practice, and talks with other partners are in progress. However, Leuthold believes that further development may be required before the technology is ready for the market; for example, he expects that the current loss of signal strength during modulation can be reduced further.

For computers and autonomous vehicles

The new modulator could one day be used not only for telecommunications applications, but for computers as well. “The computer industry is considering using fibre optics to transfer data between the individual chips inside computers,” says Leuthold. However, this would require tiny modulators – such as Leuthold and his team have developed.

Ultimately, it is also conceivable that the modulators could be used in displays – including bendable ones – and optical sensors, such as those in the Lidar system for distance measurement that are used in (semi-) autonomous cars.

More information: Masafumi Ayata et al. High-speed plasmonic modulator in a single metal layer, Science (2017). DOI: 10.1126/science.aan5953




Switching light with a silver atom

The switch is based on the voltage-induced displacement of one or more silver atoms in the narrow gap between a silver and a platinum plate.

Researchers working under Juerg Leuthold, Professor of Photonics and Communications, have created the world’s smallest integrated optical switch. Applying a small voltage causes an atom to relocate, turning the switch on or off.

The quantity of data exchanged via  around the globe is growing at a breathtaking rate. The volume of data for wired and  is currently increasing by 23% and 57% respectively every year. It is impossible to predict when this growth will end. This also means that all network components must constantly be made more efficient.

These components include so-called modulators, which convert the information that is originally available in electrical form into optical signals. Modulators are therefore nothing more than fast electrical switches that turn a laser signal on or off at the frequency of the incoming electrical signals. Modulators are installed in  centres in their thousands. However, they all have the disadvantage of being quite large. Measuring a few centimetres across, they take up a great deal of space when used in large numbers.

From micromodulators to nanomodulators

Six months ago, a working group led by Jürg Leuthold, Professor of Photonics and Communications already succeeded in proving that the technology could be made smaller and more energy-efficient. As part of that work, the researchers presented a micromodulator measuring just 10 micrometres across – or 10,000 times smaller than modulators in commercial use.

Tiny plates made of silver (light grey) and platinum (mint) are placed on an optical waveguide (blue)

Leuthold and his colleagues have now taken this to the next level by developing the world’s smallest optical modulator. And this is probably as small as it can get: the component operates at the level of individual atoms. The footprint has therefore been further reduced by a factor of 1,000 if you include the switch together with the light guides. However, the switch itself is even smaller, with a size measured on the atomic scale. The team’s latest development was recently presented in the journal Nano Letters.

In fact, the modulator is significantly smaller than the wavelength of light used in the system. In telecommunications, optical signals are transmitted using laser light with a wavelength of 1.55 micrometres. Normally, an optical device can not be smaller than the wavelength it should process. “Until recently, even I thought it was impossible for us to undercut this limit,” stresses Leuthold.

New structure

But his senior scientist Alexandros Emboras proved the laws of optics wrong by successfully reconfiguring the construction of a modulator. This construction made it possible to penetrate the order of magnitude of individual atoms, even though the researchers were using light with a “standard wavelength”.

Emboras’s modulator consists of two tiny pads, one made of silver and the other of platinum, on top of an optical waveguide made of silicon. The two pads are arranged alongside each other at a distance of just a few nanometres, with a small bulge on the silver pad protruding into the gap and almost touching the platinum pad.

Set-up used in the lab to test the new type of switches.

Short circuit thanks to a silver atom

And here’s how the modulator works: light entering from an optical fibre is guided to the entrance of the gap by the optical waveguide. Above the metallic surface, the light turns into a surface plasmon. A plasmon occurs when light transfers energy to electrons in the outermost atomic layer of the metal surface, causing the electrons to oscillate at the frequency of the incident light. These electron oscillations have a far smaller diameter than the ray of light itself. This allows them to enter the gap and pass through the bottleneck. On the other side of the gap, the electron oscillations can be converted back into optical signals.

If a voltage is now applied to the silver pad, a single silver atom or, at most, a few silver  move towards the tip of the point and position themselves at the end of it. This creates a short circuit between the silver and platinum pads, so that electrical current flows between them. This closes the loophole for the plasmon; the switch flips and the state changes from “on” to “off” or vice versa. As soon as the voltage falls below a certain threshold again, a silver atom moves back. The gap opens, the plasmon flows, and the switch is “on” again. This process can be repeated millions of times.

ETH Professor Mathieu Luisier, who participated in this study, simulated the system using a high-performance computer at the CSCS in Lugano. This allowed him to confirm that the short circuit at the tip of the silver point is brought about by a single atom.

A truly digital signal

As the plasmon has no other options than to pass through the bottleneck either completely or not at all, this produces a truly digital signal – a one or a zero. “This allows us to create a digital switch, as with a transistor. We have been looking for a solution like this for a long time,” summarises Leuthold.

As yet, the modulator is not ready for series production. Although it has the advantage of operating at room temperature, unlike other devices that work using quantum effects at this order of magnitude, it still remains very slow for a modulator: so far, it only works for switching frequencies in the megahertz range or below. The ETH researchers want to fine-tune it for frequencies in the gigahertz to terahertz range.

Improving the lithography process

The researchers also want to further improve the lithography method, which was redeveloped by Emboras from scratch to build the parts, so that components like this can be produced reliably in future. At present, fabrication is only successful in one out of every six attempts. Nevertheless, the researchers consider this a success, as lithography processes on the atomic scale remain uncharted territory.

In order to continue his research into the nanomodulator, Leuthold has strengthened his team. However, he points out that greater resources would be required to develop a commercially available solution. Despite this, the ETH professor is confident that he and his team will be able to present a practicable solution within the next few years.

More information: Alexandros Emboras et al. Atomic Scale Plasmonic Switch, Nano Letters (2016). DOI: 10.1021/acs.nanolett.5b04537




Our New paper in Photonics and Nanostructures: Fundamentals and applications

Congratulations for the publication of paper”All-optical photonic crystal logic gates using nonlinear directional coupler” in Journal of Photonics and Nanostructures – Fundamentals and Applications, by H. Sharifi,  S. M. Hamidi and K. Navi.




Assembly of nanoparticles proceeds like a zipper

Assembly of nanoparticles proceeds like a zipper

It has always been the Holy Grail of materials science to describe and control the material’s structure-function relationship. Nanoparticles are an attractive class of components to be used in functional materials because they exhibit size-dependent properties, such as superparamagnetism and plasmonic absorption of light. Furthermore, controlling the arrangement of nanoparticles can result in unforeseen properties, but such studies are hard to carry out due to limited efficient approaches to produce well-defined three-dimensional nanostructures.

According to scientists from the Biohybrid Materials Group, led by Prof. Mauri Kostiainen, nature’s own charged nanoparticles – protein cages and viruses – can be utilized to determine the structure of composite nanomaterials.

Viruses and proteins are ideal model particles to be used in , as they are genetically encoded and have an atomically precise structure. These well-defined biological particles can be used to guide the arrangement of other nanoparticles in an aqueous solution. In the present study, the researchers show that combining native Tobacco Mosaic Virus with  in a controlled manner leads to metal-protein superlattice wires.

“They initially studied geometrical aspects of nanoparticle superlattice engineering. We hypothesized that the size-ratio of oppositely charged nanorods (TMV viruses) and nanospheres (gold nanoparticles) could efficiently be used to control the two-dimensional superlattice geometry. They were actually able to demonstrate this. Even more interestingly, our structural characterization revealed details about the cooperative assembly mechanisms that proceeds in a zipper-like manner, leading to high-aspect-ratio superlattice wires,” Kostiainen says. “Controlling the macroscopic habit of self-assembled nanomaterials is far from trivial,” he adds.

Superlattice wires potential to form new materials

The results showed that nanoscale interactions really controls the macroscopic habit of the formed superlattice wires. The researchers observed that the formed macroscopic wires undergo a right-handed helical twist that was explained by the electrostatic attraction between the asymmetrically patterned TMV  and the oppositely charged spherical nanoparticles. As plasmonic nanostructures efficiently affect the propagation of light, the helical twisting resulted in asymmetric optical properties (plasmonic circular dichroism) of the material.

“This result is ground breaking in the sense that it demonstrates that macroscopic structures and physical properties can be determined by the detailed nanostructure, i.e. the amino acid sequence of the virus particles. Genetical engineering routinely deals with designing the  of proteins, and it is a matter of time when similar or even more sophisticated macroscopic habit and structure-function properties are demonstrated for ab-initio designed protein cages,” explains Dr. Ville Liljeström who worked on the project during three years of his doctoral studies.

The research group demonstrated a proof-of-concept showing that the superlattice wires can be used to form materials with physical properties controlled by external fields. By functionalizing the  wires with magnetic nanoparticles, the wires could be aligned by a magnetic field. In this manner they produced plasmonic polarizing films. The purpose of the demonstration was to show that electrostatic self-assembly of  can potentially be used to form processable  for future applications.

 Explore further: Self-assembled nanostructures can be selectively controlled

More information: Ville Liljeström et al. Cooperative colloidal self-assembly of metal-protein superlattice wires, Nature Communications (2017). DOI: 10.1038/s41467-017-00697-z

Read more at: https://phys.org/news/2017-09-nanoparticles-proceeds-zipper.html#jCp




our new paper in IEEE Transaction on magnetism

Congratulations for the publication of paper” characterization of Au/Co/Au Magneto-plasmonic multilayer as an ethanol vapor sensor” in Journal of IEEE transaction on magnetism by M.Afsharia and S. M. Hamidi.

 




Our New paper in Journal of Superconductivity and Novel Magnetism

Congratulations for the publication of paper “Transverse Tunable Magneto-Plasmonic Kerr Effect in Large Area Micro-Patterned Au/Co/Au Structures” in the “Journal of Superconductivity and Novel Magnetism” by S. M. Hamidi, S. Behjati, F. Sohrabi.




Our New Paper in Journal of optics and laser technology

Congratulations for the publication of paper “Large area multi-channel plasmonic absorber based on the touching triangular dimers fabricated by angle controlled colloidal nanolithography” in the “Journal of optics and Laser Technology” by S. M. Hamidi, S. Behjati.




Fano resonances in photonics


Rapid progress in photonics and nanotechnology brings many examples of resonant optical phenomena associated with the physics of Fano resonances, with applications in optical switching and sensing. For successful design of photonic devices, it is important to gain deep insight into different resonant phenomena and understand their connection. Here, they review a broad range of resonant electromagnetic effects by using two effective coupled oscillators, including the Fano resonance, electromagnetically induced transparency, Kerker and Borrmann effects, and parity–time symmetry breaking. they discuss how to introduce the Fano parameter for describing a transition between two seemingly different spectroscopic signatures associated with asymmetric Fano and symmetric Lorentzian shapes. they also review the recent results on Fano resonances in dielectric nanostructures and metasurfaces.

Source: www.nature.com/nphoton/journal/v11/n9/full/nphoton.2017.142.html?foxtrotcallback=true

Related paper:Mikhail F. Limonov et al., Fano resonances in photonics, Nature Photonics.11,(2017).

 




Congratulations for the publication of paper “Plasmon- exciton induced circular dichroism in Gold/PMMA (RB) complex”

Congratulations for the publication of paper “Plasmon- exciton induced circular dichroism in Gold/PMMA (RB) complex” by Dr Hamidi, Ms Jafari, Mr Behjati and Ms Sohrabi.

In this paper, we have investigated the strong coupling between exciton-plasmon by the aid of reflectance spectroscopy under different dye molecules weight in the samples. For this purpose, we have prepared five different samples as Glass/Cr/Au/PMMA (RBx); in which the weight of RB has been changed from 0 to 4 mg. The spectroscopy of the samples has been done under angular modulation and also the dispersion relation of the samples has been extracted from this measurement. These measurements revealed the formation of two split polaritonic extreme in reflectance spectra as a function of wavelength. Then we have shown exciton–plasmon coupling in dispersiondiagram which presented an extra allowed mode between the polaritonic branches. After that, the circular dichroism spectra of samples have been measured to see the strong coupling circular dichroism. Our results show that, we have significant change in the dichroism of gold thin film due to strong coupling in all of visible region.