Tag Archives: nanoplasmonics

Colo(u)r-changing building surfaces thanks to gold nanoparticles

Gold, at the nanoscale, has different properties than it has at the macroscale and research at the University of Cambridge has found a new way to exploit gold’s unique properties at the nanoscale according to a May 13, 2019 news item item on ScienceDaily,

The smallest pixels yet created — a million times smaller than those in smartphones, made by trapping particles of light under tiny rocks of gold — could be used for new types of large-scale flexible displays, big enough to cover entire buildings.

The colour pixels, developed by a team of scientists led by the University of Cambridge, are compatible with roll-to-roll fabrication on flexible plastic films, dramatically reducing their production cost. The results are reported in the journal Science Advances [May 10, 2019].

A May 10,2019 University of Cambridge press release (also on EurekAlert), which originated the news item, delves further into the research,

It has been a long-held dream to mimic the colour-changing skin of octopus or squid, allowing people or objects to disappear into the natural background, but making large-area flexible display screens is still prohibitively expensive because they are constructed from highly precise multiple layers.

At the centre of the pixels developed by the Cambridge scientists is a tiny particle of gold a few billionths of a metre across. The grain sits on top of a reflective surface, trapping light in the gap in between. Surrounding each grain is a thin sticky coating which changes chemically when electrically switched, causing the pixel to change colour across the spectrum.

The team of scientists, from different disciplines including physics, chemistry and manufacturing, made the pixels by coating vats of golden grains with an active polymer called polyaniline and then spraying them onto flexible mirror-coated plastic, to dramatically drive down production cost.

The pixels are the smallest yet created, a million times smaller than typical smartphone pixels. They can be seen in bright sunlight and because they do not need constant power to keep their set colour, have an energy performance that makes large areas feasible and sustainable. “We started by washing them over aluminized food packets, but then found aerosol spraying is faster,” said co-lead author Hyeon-Ho Jeong from Cambridge’s Cavendish Laboratory.

“These are not the normal tools of nanotechnology, but this sort of radical approach is needed to make sustainable technologies feasible,” said Professor Jeremy J Baumberg of the NanoPhotonics Centre at Cambridge’s Cavendish Laboratory, who led the research. “The strange physics of light on the nanoscale allows it to be switched, even if less than a tenth of the film is coated with our active pixels. That’s because the apparent size of each pixel for light is many times larger than their physical area when using these resonant gold architectures.”

The pixels could enable a host of new application possibilities such as building-sized display screens, architecture which can switch off solar heat load, active camouflage clothing and coatings, as well as tiny indicators for coming internet-of-things devices.
The team are currently working at improving the colour range and are looking for partners to develop the technology further.

The research is funded as part of a UK Engineering and Physical Sciences Research Council (EPSRC) investment in the Cambridge NanoPhotonics Centre, as well as the European Research Council (ERC) and the China Scholarship Council.

This image accompanies the press release,

Caption: eNPoMs formed from gold nanoparticles (Au NPs) encapsulated in a conductive polymer shell. Credit: NanoPhotonics Cambridge/Hyeon-Ho Jeong, Jialong Peng Credit: NanoPhotonics Cambridge/Hyeon-Ho Jeong, Jialong Peng

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

Scalable electrochromic nanopixels using plasmonics by Jialong Peng, Hyeon-Ho Jeong, Qianqi Lin, Sean Cormier, Hsin-Ling Liang, Michael F. L. De Volder, Silvia Vignolini, and Jeremy J. Baumberg. Science Advances Vol. 5, no. 5, eaaw2205 DOI: 10.1126/sciadv.aaw2205 Published: 01 May 2019

This paper appears to be open access.

Opals, Diana Ross, and nanophotonic hybridization

It was a bit of a stretch to include Diana Ross in a Jan. 12, 2015 news item on Nanowerk about nanophotonic research at the University of Twente’s MESA+ Institute for Nano­technology  but I’m glad they did,

Ever since the early 1900s work of Niels Bohr and Hendrik Lorentz, it is known that atoms display characteristic resonant behavior to light. The hallmark of a resonance is its characteristic peak-trough behavior of the refractive index with optical frequency. Scientists from the Dutch MESA+ Institute for Nano­technology at the University of Twente have recently infiltrated cesium atoms in a self-assembled opal to create a hybrid nanophotonic system. By tuning the opal’s forbidden gap relative to the atomic resonance, dra­matic changes are observed in reflectivity. In the most extreme case, the atomic reflection spectrum is turned upside down[1] compared to the traditional case. Since dispersion is crucial in the control of optical signal pulses, the new results offer opportunities for optical information manipulation. As atoms are exquisite storage de­vices for light quanta, the results open vistas on quantum information processing, as well as on new nanoplasmonics.

A Jan. 12, 2015 MESA+ Institute for Nano­technology at the University of Twente press release, which originated the news item, provides an illustrative diagram and a wealth of technical detail about the research,

Courtesy of the University of Twente

Courtesy of the University of Twente

While the speed of light c is proverbial, it can readily be modified by sending light through a medium with a certain refractive index n. In the medium, the speed will be decreased by the index to c/n. In any material, the refractive index depends on the frequency of the light. Usually the refractive index increases with frequency, called normal dispersion as it prevails at most frequencies in most materials such as a glass of water, a telecom fiber, or an atomic vapor. Close to the resonance frequency of the material, the index strongly decreases, called anomalous dispersion.

Dispersion is essential to control how optical bits of information – encoded as short pulses – is manipulated optical circuits. In modern optics at the nanoscale, called nanophotonics, dispersion is controlled with classes of complex nanostruc­tures that cause novel behavior to emerge. An example is a photonic crystal fiber, which does not consist of only glass like a traditional fiber, but of an intricate arrange­ment of holes and glass nanostructures.

The Twente team led by Harding devised a hybrid system consisting of an atomic vapor infiltrated in an opal photonic crystal. Photonic crystals have attracted considerable attention for their ability to radically control propagation and emission of light. These nanostructures are well-known for their ability to control the emission and propagation of light. The opals have a periodic variation of the refractive index (see Figure 1) that ensures that a certain color of light is forbidden to exist inside the opal. The light cannot enter the opal as it is reflected, which is called a gap (see Figure 1). In an analogy to semiconductors, such an effect is called a “photonic band gap”. Photonic gaps are at the basis of tiny on-chip light sources and lasers, efficient solar cells, invisibility cloaks, and devices to process optical information.

The Twente team changed the index of refraction of the voids in a photonic crystal by substituting the air by a vapor of atoms with a strong resonance, as shown in Figure 1. The contrast of the refractive index between the vapor and the opal’s silica nano­spheres was effectively used as a probe. The density of the cesium vapor was greatly varied by changing the temperature in the cell up to 420 K. At the same time, the photonic gap of the opal shifted relative to the atomic resonance due to a slow chemical reaction between the opal’s backbone material (silica) and the cesium.

On resonance, light excites an atom to a higher state and subsequently the atom reemits the light. Hence, an atom behaves like a little cavity that stores light. Simultaneously the index of refraction changes strongly for colors near resonance. For slightly longer wavelengths the index of refraction is high, on resonance it is close to one, and slightly shorter wavelengths it can even decrease below one. This effect of the cesium atoms is clearly visible in the reflectivity spectra, shown in Figure 2 [not included here], as a sharp increase and decrease of the reflectivity near the atomic resonance. Intriguingly, the characteristic peak-and-trough behavior of atoms (seen at 370 K) was turned upside down at the highest temperature (420 K), where the ce­sium reso­nance was on the red side of the opal’s stopgap.

In nanophotonics, many efforts are currently being devoted to create arrays of nanoresonators in photonic crystals, for exquisite optical signal control on a chip. Unfortunately, however, there is a major challenge in engineering high-quality pho­tonic resonators: they are all different due to inevitable fabrication variations. Hence, it is difficult to tune every resonator in sync. “Our atoms in the opal may be consid­ered as the equivalent of an carefully engineered array of nano-resonators” explains Willem Vos, “Nature takes care that all resonators are all exactly the same. Our hy­brid system solves the variability problem and could perhaps be used to make pho­tonic memories, sensors or switches that are naturally tuned.” And leading Spanish theorist Javier Garcia de Abajo (ICFO) enthuses: “This is a fine and exciting piece of work, initiating the study of atomic resonances with photonic modes in a genuinely new fashion, and suggesting many exciting possibilities, for example through the extension of this study towards combinations with metal nanoplasmonics.”

Here’s a link to and a citation for the paper published in Physical Review B,

Nanophotonic hybridization of narrow atomic cesium resonances and photonic stop gaps of opaline nanostructures by Philip J. Harding, Pepijn W. H. Pinkse, Allard P. Mosk, and Willem L. Vos. Phys. Rev. B 91, 045123 – Published 20 January 2015 DOI: http://dx.doi.org/10.1103/PhysRevB.91.045123

This paper is behind a paywall but there is an earlier iteration of the paper available on the open access arXiv.org website operated by Cornell University,

Nanophotonic hybridization of narrow atomic cesium resonances and photonic stop gaps of opaline nanostructures by Philip J. Harding, Pepijn W.H. Pinkse, Allard P. Mosk, Willem L. Vos. (Submitted on 11 Sep 2014) arXiv:1409.3417

As I understand it, the arXiv.org website is intended to open up access to research and to offer an informal peer review process.

Finally, for anyone who’s nostalgic or perhaps has never heard Diana Ross sing ‘Upside Down’,

Fishnet of gold atoms improves solar cell performance

Apparently they’re calling the University of Western Ontario by a new name, Western University. Given the university’s location in what is generally acknowledged as central Canada or, sometimes, as eastern Canada, this seems like a geographically confusing approach not only in Canada but elsewhere too. After all, more than one country boasts a ‘west’.

A Sept. 26, 2014 news item on Nanowerk highlights new work on improving solar cell performance (Note: A link has been removed),

Scientists at Western University [Ontario, Canada] have discovered that a small molecule created with just 144 atoms of gold can increase solar cell performance by more than 10 per cent. These findings, published recently by the high-impact journal Nanoscale (“Tessellated gold nanostructures from Au144(SCH2CH2Ph)60 molecular precursors and their use in organic solar cell enhancement”), represent a game-changing innovation that holds the potential to take solar power mainstream and dramatically decrease the world’s dependence on traditional, resource-based sources of energy, says Giovanni Fanchini from Western’s Faculty of Science.

For those of us who remember ‘times tables’, the number 144 can have a special meaning as it is the last number (’12’ times ’12’ equals ‘144’) one was obliged to memorize. At least, that was true at my school in Vancouver, Canada but perhaps not elsewhere, eh?

Getting back to the ‘fishnet’, a Sept. 25, 2014 Western University news release, which originated the news item, expands the business possibilities for this work,

Fanchini, the Canada Research Chair in Carbon-based Nanomaterials and Nano-optoelectronics, says the new technology could easily be fast-tracked and integrated into prototypes of solar panels in one to two years and solar-powered phones in as little as five years.

“Every time you recharge your cell phone, you have to plug it in,” says Fanchini, an assistant professor in Western’s Department of Physics and Astronomy. “What if you could charge mobile devices like phones, tablets or laptops on the go? Not only would it be convenient, but the potential energy savings would be significant.”

The Western researchers have already started working with manufacturers of solar components to integrate their findings into existing solar cell technology and are excited about the potential.

“The Canadian business industry already has tremendous know-how in solar manufacturing,” says Fanchini. “Our invention is modular, an add-on to the existing production process, so we anticipate a working prototype very quickly.”

The news release then gives a few technical details,

Making nanoplasmonic enhancements, Fanchini and his team use “gold nanoclusters” as building blocks to create a flexible network of antennae on more traditional solar panels to attract an increase of light. While nanotechnology is the science of creating functional systems at the molecular level, nanoplasmonics investigates the interaction of light with and within these systems.

“Picture an extremely delicate fishnet of gold,” explains Fanchini explains, noting that the antennae are so miniscule they are unseen even with a conventional optical microscope. “The fishnet catches the light emitted by the sun and draws it into the active region of the solar cell.”

According to Fanchini, the spectrum of light reflected by gold is centered on the yellow colour and matches the light spectrum of the sun making it superior for such antennae as it greatly amplifies the amount of sunlight going directly into the device.

“Gold is very robust, resilient to oxidization and not easily damaged, making it the perfect material for long-term use,” says Fanchini. “And gold can also be recycled.”

It has been known for some time that larger gold nanoparticles enhance solar cell performance, but the Western team is getting results with “a ridiculously small amount” – approximately 10,000 times less than previous studies, which is 10,000 times less expensive too.

I hope to hear about a working prototype soon. Meanwhile, here’s a link to and a citation for the paper,

Tessellated gold nanostructures from Au144(SCH2CH2Ph)60 molecular precursors and their use in organic solar cell enhancement by Reg Bauld, Mahdi Hesari, Mark S. Workentin, and Giovanni Fanchini. Nanoscale, 2014,6, 7570-7575 DOI: 10.1039/C4NR01821D
First published online 06 May 2014

This paper is behind a paywall.

One final comment, it seems like a long lead time between publication of the paper and publicity. I wonder if the paper failed to get notice in May 2014, assuming there was a campaign at the time, or if this is considered a more optimal time period for getting noticed.

Light: harvesting with transformation *optics and sensing with a photovoltaic bracelet

There’s a good general description (although it’s still quite technical and challenging) of nanoplasmonics in a Jan. 6, 2014 news release on EurekAlert (later in this posting I have an item about a practical application for photovoltaics),

The control of light is vital to many applications, including imaging, communications, sensing, cancer treatment, and even welding processes for automobile parts. Transformation optics is an emerging field that has revolutionized our understanding of how to control light by constituting an effectively curved electromagnetic space. This revolutionary strategy not only revisits the fundamental physics of light-matter interactions, but also renders trivial the design of optical functions that may otherwise be difficult or virtually impossible, such as an “invisibility cloak,” which could only previously be found in science fiction. When compared with ray optics, the new transformation optics technique provides a picture that is equally intuitive, but that is much more accurate in its description of the wave nature of light by using the electric and magnetic field lines as its basis. Therefore, the validity of this method is not restricted to the macroscopic regime, but can also be extended to the subwavelength scale. In a recent review paper published by SCIENCE CHINA Information Sciences, Yu Luo and colleagues from Imperial College London illustrate how the general capabilities of the transformation optics technique can be used to treat the subwavelength fields that occur in plasmonic systems and review the latest developments in transformation optics as applied to nanophotonics.

Here’s a more detailed description of the difficulties and the solution (transformation optics) from the news release,

In plasmonics, metallic structures with sharp corners can trap light into nanometric volumes, thus giving rise to strong near-field enhancements. This effect can be used to detect single molecules, generate high harmonic signals, and even improve absorption in photovoltaic devices. Further developments using these techniques need to be guided by accurate and versatile theoretical modeling. However, modeling of this type can be difficult, because various aspects associated with the sharp plasmonic structures can hinder provision of accurate and convenient solutions to the problem at hand. First, the size of the sharp metallic point structure is normally much smaller than that of the device overall, which makes it difficult to create meshes for numerical simulations. Second, the strong contrast in the dielectric functions at the metal-dielectric interfaces leads to slow convergence of the field expansions. Yu Luo and colleagues deploy the theory of transformation optics to circumvent these problems. Their idea is to transform a complex plasmonic system with little intrinsic geometrical symmetry into a canonical structure with translational or rotational symmetry, which is then relatively easy to study using conventional theory. For example, two touching nanowires can be transformed into two flat metal surfaces that are separated by a gap, and a sharp metal edge can be related to a periodic array of metal slabs. Other structures that can be studied using transformation optics include pairs of metallic nanospheres, asymmetric core-shell structures and rough metal surfaces. In fact, using transformation optics techniques, we could reverse engineer the optical properties of complex plasmonic nanostructures and redesign these structures based on the requirements of the desired applications.

And then, there’s what seems to be a plea for more researchers in the field,

Practical issues with the realization of plasmonic devices, such as the effects of edge rounding at sharp boundaries on the local field enhancement and resonance properties, can also be considered theoretically using transformation optics and provide useful guidance for the fabrication of these devices. In particular, the necessary conditions are highlighted for both broadband light absorption effects and large field enhancements. Experimental evidence for phenomena that have been predicted by transformation optics has also been reviewed, indicating potential applications in biosensing and broadband solar photovoltaics. These studies demonstrate the accuracy and versatility of transformation optics methods and are expected to encourage more researchers to enter this field. [emphasis mine]

Honestly, I don’t understand nanoplasmonics very well even after reading the description but there’s enough accessible information in the news release to help me achieve a better understanding. For those who want to further explore this latest work in trransformative optics and nanoplasmonics, here’s a link to and a citation for the paper,

Harvesting light with transformation optics by LUO Yu, ZHAO RongKuo, FERNANDEZ-DOMINGUEZ Antonio I., MAIER Stefan A., & PENDRY John B… Sci China Inf Sci, 2013, 56(12): 120401(13).

This paper is open access as of Jan. 8, 2014.

Photovoltaic bracelet/brooch

On to the other ‘light’ topic mentioned earlier. John Brownlee has written about June, a photovoltaic bracelet, which tells you how much sun exposure you’ve had, in a Jan. 7, 2014 article for Fast Company (aka Co-Design; Note: Links have been removed),

… Meet the June, a bedazzling, Bluetooth-connected bracelet that tells you how much sun you’re getting. But don’t dismiss the June just because you’re not worried about the SPF. This is the future of wearables. [emphasis mine]

… fashionably designed wearable that measures exposure to the sun. Made by Netatmo and designed by Louis Vuitton and Harry Winston collaborator Camille Toupet, the June syncs over Bluetooth to a paired iPhone, where an app tells you how much sun you’re getting based upon readings from the bracelet’s photovoltaic gem, and then recommends sunglasses, a hat or a specific sunscreen based upon the measurements. It costs $100,

Lily Hay Newman in a Jan. 8, 2014 posting on Slate’s future tense blog challenges the notion that June is the “future of wearables,”

… it really only does one thing: It measures sun exposure. It’s a single-use device that syncs to a single-use app. Perhaps it foreshadows a world where we each customize our array of wearable sensors by picking and choosing among single-focus gadgets from day to day. Which sensors we want and how we want to look would both play a part in dictating how we dressed and accessorized. Wearables certainly would be a lot more attractive if they weren’t crammed with maximal functionality. But this is also wildly inefficient, and previous technologies haven’t evolved this way. Cameras, MP3 players, calculators, notebooks, calendars, phones, and everything else eventually collapsed into smartphones: one device. No matter how attractive a sensor-turned-bracelet is, there’s a limit to how many wearables one person can actually, you know, wear.

She also notes that June is being marketed to women primarily and suggests that wearables offer an opportunity to change how technology is marketed (Note:Llinks have been removed),

Since the aesthetic direction of wearables is still undetermined, and is currently dictated by the tech inside, the devices present a good opportunity to move away from traditional, often reductive, male and female marketing, which can be particularly blatant in tech. Example: the EPad Femme tablet for women. Alternate example: The Honda Fit She’s. It’s a tall order, but balancing form and function is the crux of the uncertainty in wearables right now.

I recommend reading both articles (Brownlee’s contains a June promotional video). For the curious here’s what the bracelet looks like (from the June webpage),

[downloaded from http://www.netatmo.com/en-US/product/june]

[downloaded from http://www.netatmo.com/en-US/product/june]

June  can also be worn as a brooch; the Netatmo website’s June webpage states,

Versatile, JUNE can be worn as a bracelet or as a brooch.

I haven’t been able to find a product launch date other than it will be ‘sometime in 2014’.

* Removed an extra preposition ‘with’ that preceded the word optics.

Sensitive plasmon resonance and the Lycurgus Cup

It’s been a while since I’ve written about the Lycurgus Cup (my Sept. 21, 2010 posting). Dated from the 4th Century AD or CE, the cup is often cited as ancient nanotechnology due to certain optical properties made possible by the inclusion of nanoparticles so it glows green or red depending on the direction of the light.

A Feb. 14, 2013 news item on ScienceDaily features some work in the area of nanoplasmonics that was inspired by the cup,

Utilizing optical characteristics first demonstrated by the ancient Romans, researchers at the University of Illinois at Urbana-Champaign have created a novel, ultra-sensitive tool for chemical, DNA, and protein analysis.

“With this device, the nanoplasmonic spectroscopy sensing, for the first time, becomes colorimetric sensing, requiring only naked eyes or ordinary visible color photography,” explained Logan Liu, an assistant professor of electrical and computer engineering and of bioengineering at Illinois. “It can be used for chemical imaging, biomolecular imaging, and integration to portable microfluidics devices for lab-on-chip-applications. His research team’s results were featured in the cover article of the inaugural edition of Advanced Optical Materials (AOM, optical section of Advanced Materials).

The Lycurgus cup was created by the Romans in 400 A.D. Made of a dichroic glass, the famous cup exhibits different colors depending on whether or not light is passing through it; red when lit from behind and green when lit from in front. It is also the origin of inspiration for all contemporary nanoplasmonics research — the study of optical phenomena in the nanoscale vicinity of metal surfaces.

The University of Illinois College of Engineering Feb. 14, 2013 news release, which originated the news item,

“This dichroic effect was achieved by including tiny proportions of minutely ground gold and silver dust in the glass,” Liu added. “In our research, we have created a large-area high density array of a nanoscale Lycurgus cup using a transparent plastic substrate to achieve colorimetric sensing. The sensor consists of about one billion nano cups in an array with sub-wavelength opening and decorated with metal nanoparticles on side walls, having similar shape and properties as the Lycurgus cups displayed in a British museum. Liu and his team were particularly excited by the extraordinary characteristics of the material, yielding  100 times better sensitivity than any other reported nanoplasmonic device.

This image shows a model of nano cup arrays. (Credit: University of Illinois at Urbana-Champaign)

This image shows a model of nano cup arrays. (Credit: University of Illinois at Urbana-Champaign)

Here’s a little more about colorimetrics and what the researchers are trying to accomplish (from the news release; Note: A link has been removed),

Colorimetric techniques are mainly attractive because of their low cost, use of inexpensive equipment, requirement of fewer signal transduction hardware, and above all, providing simple-to-understand results. … The current design will also enable new technology development in the field of DNA/protein microarray.

“Our label-free colorimetric sensor eliminates the need of problematic fluorescence tagging of DNA/ protein molecules, and the hybridization of probe and target molecule is detected from the color change of the sensor,” stated Manas Gartia, first author of the article, “Colorimetrics: Colorimetric Plasmon Resonance Imaging Using Nano Lycurgus Cup Arrays.” “Our current sensor requires just a light source and a camera to complete the DNA sensing process. This opens the possibility for developing affordable, simple and sensitive mobile phone-based DNA microarray detector in near future. Due to its low cost, simplicity in design, and high sensitivity, we envisage the extensive use of the device for DNA microarrays, therapeutic antibody screening for drug discovery, and pathogen detection in resource poor setting.”

In addition to Gartia and Liu, the paper’s co-authors included Austin Hsiao, Anusha Pokhriyal, Sujin Seo, Gulsim Kulsharova, and Brian T. Cunningham at Illinois, and  Tiziana C. Bond, at the Meso, Micro and Nano Technologies Center at Lawrence Livermore National Laboratory, California.

The team’s article is behind a paywall and you can find a complete citation by clicking on the link to ScienceDaily news item.