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Small Tweaks to Its Recipe and "White Graphene" Could Change Electronics

Strictly speaking, hexagonal boron nitride is a semiconductor, but its band gap is so big that, for all practical purposes, it behaves like an insulator.

It’s because of this pseudo-insulator characteristic that researchers have been interested in combining boron nitride with other two-dimensional materials such as graphene to create hybrid materials capable of doing what each constituent can’t do on its own.

Now researchers at the Department of Energy’s Oak Ridge National Laboratory (ORNL) have developed a process for producing a nearly perfect single layer of hexagonal boron nitride—dubbed “white graphene”—that the researchers believe could be a game changer for the use of the material in electronic applications.

In research published in the journal Chemistry of Materials, the ORNL researchers followed traditional chemical vapor deposition (CVD) steps, in which gaseous reactants are introduced into a furnace to form a film on a metal substrate that’s usually made of copper. However, they added a little something to the recipe that provided a more gentle and controllable way to introduce the reactants into the furnace and took better advantage of the conditions inside the furnace.

“I just thought carefully beforehand and was curious. For example, I remind myself that there are many conditions in this experiment that can be adjusted and could make a difference,” said ORNL’s Yijing Stehle, postdoctoral associate and lead author of a paper, in a press release. “Whenever I see non-perfect results, I do not count them as another failure but, instead, another condition adjustment to be made. This ‘failure’ may become valuable.”

The result of finding value in failure was a “white graphene” that has lived up to the material’s previously unachieved theoretical performance potential. What this means is that if white graphene were used as a substrate material for its carbon analogue, the electron mobility of the combined materials would be a thousand times higher than that of graphene on other substrate materials.

“Imagine batteries, capacitors, solar cells, video screens and fuel cells as thin as a piece of paper,” said Stehle in the press release. “Imagine your message being sent thousands of times faster.”

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Laser-Induced Graphene Looks to Displace Batteries With Supercapacitors

Almost exactly a year ago, we first got word that researchers at Rice University had developed a method for producing graphene that features a computer-controlled laser. They dubbed the result laser-induced graphene (LIG).

Since then, LIG has been proposed for flexible supercapacitors that could power wearable electronics.

The researchers at Rice have continued to pursue supercapacitors for this new form of graphene and have continued to refine the LIG process to the point where they now believe it may be capable of moving energy storage away from batteries and towards supercapacitors.

The key attribute of LIG is how comparatively easy it is to produce as opposed to graphene made via chemical vapor deposition. For LIG, all that is needed is a commercial polyimide plastic sheet and a computer-controlled laser. The Rice researchers discovered that the laser would burn everything on the polyimide except the carbon from the top layer. What remains is a form of graphene.

You can see a description and demonstration of the process in the video below.

The researchers think that this process will ultimately lend itself to roll-to-roll production. That will eliminate complex manufacturing conditions that have thus far limited the widespread application of microsupercapacitors.

“It’s a pain in the neck to build microsupercapacitors now,” said James Tour, who has been leading this line of research at Rice since the beginning, in a press release. “They require a lot of lithographic steps. But these we can make in minutes: We burn the patterns, add electrolyte and cover them.”

The researchers claim that the microsupercapacitors they have fabricated using LIG have demonstrated an energy density that is on par with thin-film lithium-ion batteries. The microsupercapitors’ capacitance was measured at 934 microfarads per square centimeter; they boast an energy density of 3.2 milliwatt-hours per cubic centimeter. As these are supercapacitors, their power density far exceeds that of batteries. Perhaps most importantly, the devices did not exhibit any degradation over time, maintaining mechanical stability even after being bent 10,000 times.

Encouraging as these numbers are, there yet remains some work to be done before supercapacitors displace batteries.

We’re not quite there yet, but we’re getting closer all the time,” said Tour in the press release. “In the interim, they’re able to supplement batteries with high power. What we have now is as good as some commercial supercapacitors. And they’re just plastic.”

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Light-scattering Nanoparticles Could Lead to Invisbility Cloaks and Smaller Optical Antennas

A research team from A*STAR Data Storage Institute in Singapore and St. Petersburg University in Russia has discovered certain light-scattering properties of nanoparticles that could lead to smaller and more effective optical nanoantennas and even invisibility cloaks.

The research, which was published in the journal ACS Photonics, took the form of numerical calculations of the light-scattering properties of dielectric nanoparticles, which are nanoparticles that are electrical insulators and can be polarized by an applied electric field.

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Nanopillars Hide Solar Wiring

Photovoltaics convert the photons from light into a voltage—thus the name. And anything that reduces the number of photons that strike the electric field of the semiconducting P-N junction inside the solar cell will reduce the voltage it generates.

One of things that curtail the amount of photons interacting with the solar cell is the design of the device’s outer layer. In many silicon solar cell designs, a grid of metal wires is employed in order to get the electricity to and from the device. The problem: the wires reflect light away from the surface, reducing the amount of photons that are absorbed. (It should be noted that in some photovoltaics, indium tin oxide is used to create transparent conducting films that stand in for the metal wire grids.)

Researchers at Stanford University have taken a novel approach to addressing this problem by creating a nanostructure comprising so-called nanopillars that rise above the metal surfaces. The nanopillars direct the light into the solar cell in a way that avoids reflection by the metal, effectively making the metal invisible to the incoming light.

In research published in the journal ACS Nano, the researchers were able to fabricate the nanopillars in a one-step chemical process. They started with a 16-nanometer-thick film of gold that had been layered onto a flat sheet of silicon. The gold film was covered with an array of nanoscale holes.

“We immersed the silicon and the perforated gold film together in a solution of hydrofluoric acid and hydrogen peroxide,” said Thomas Hymel, a Stanford graduate student who co-authored the ACS Nano article, in a press release. “The gold film immediately began sinking into the silicon substrate, and silicon nanopillars began popping up through the holes in the film.”

Once the gold-coated silicon is dipped in the chemicals, the metal is transformed from a shiny gold to a dark red, which indicates that the material will no longer reflect light. You can watch a demonstration of this process in the video below:

The results of this change are dramatic. The Stanford researchers estimate that this could increase the efficiency of some silicon solar cells by as much as 22 percent.

“Solar cells are typically shaded by metal wires that cover 5 to 10 percent of the top surface,” said lead author Vijay Narasimhan in a press release. “In our best design, nearly two-thirds of the surface can be covered with metal, yet the reflection loss is only 3 percent. Having that much metal could increase conductivity and make the cell far more efficient at converting light to electricity.”

This nanopillar architecture is not limited to use with gold; it can also function with contacts made of silver, platinum, nickel and other metals. Using the technique with other semiconductor materials could make it useful in applications such as photosensors, light-emitting diodes and displays, and transparent batteries.

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New Method for Producing Nanowires Could Offer a Commercial Avenue

Nanowires are developing quite the reputation in photonics. But even that growing status is dwarfed by the amount of research that has gone into developing semiconductor nanowires since the late 1990s. Research teams like those run by Charles Lieber at Harvard University, Zhong Lin Wang at Georgia Tech, and Lars Samuelson at Lund University are a few of the leading groups that have been spearheading this research over the last decade.

Now a research group at the University of Wollongong in Australia claims to have made a breakthrough in the production of semiconductor nanowires that could have an enormous impact on photonics applications such as telecommunications.

In a paper published in the journal Nanoscale, the researchers say that the key to the breakthrough was the addition of the element bismuth to the elements arsenic and gallium. The heavier element bismuth resists joining the arsenic-gallium crystal, and as a result, forms a coating on the surface of the crystal that is an array of small droplets.

“These droplets act as a catalyst for the growth of nanostructures, which in this case turned out to self-assemble in the form of tracks,” said Julian Steele, a coauthor of the research, in a press release. The nanotracks themselves were grown by the Australian team’s UK and U.S. collaborators; they were actually trying to grow solid thin-film materials.

“We were able to add to the work in understanding what we were seeing and why the tracks formed,” says Steele. “The problem with trying to understand how the nanotrack shape is formed is the fact that only a handful of theoretical models exist to describe how they grow, and none that explains our unusual shapes.”

The Australian researchers demonstrated in simulations a new self-assembly new growth model for the nanowires that could overcome the prohibitive costs associated with using nanowires in a range of electronic applications.

“Because of the price tag currently attached with their fabrication, the science of nanowires still remains in the world of laboratories,” said Steele in the press release. He added:

In the same way that the development of new materials late in the 20th century helped to realize our current tech-age—from smartphones to driverless cars—the next frontier is how to assemble these materials at the nanoscale in order to exploit small-scale physics (quantum mechanics) for enhanced efficiency and function.

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Perovskite Nanoplatelets Yield Bright LEDs

Perovskites have become the hottest material for solar cells because they are cheap and very easy to process. They’ve also been tapped for use in light-emitting diodes and lasers, but LEDs incorporating materials with the perovskite crystal structure have not been very bright.

But researchers at Florida State University (FSU) now report that they have made perovskite LEDs that are more than four times as bright as earlier versions. They have a brightness of over 10,000 candelas per square meter, comparable to that of organic LEDs and quantum dot LEDs.

Instead of the perovskite thin films that others have used to make LEDs, the FSU team used flat perovskite nanoparticles, or nanoplatelets. Nanoparticles deliver a big efficiency advantage, says Hanwei Gao, a professor of physics at FSU. The small, single-crystal pieces have very few defects at which electrons and positively charged holes can recombine without producing a photon.

The researchers used common precursor materials and a simple chemical solution process to produce the highly crystalline nanoplatelets of the perovskite methyl ammonium lead bromide. They used the nanoparticles as the light emitting material in a conventional stacked architecture to make a bright green LED. Gao, professor of chemical engineering Biwu Ma, and their colleagues outlined the details in a paper in the journal Advanced Materials.

The new device also overcomes a common problem with perovskites: their penchant to quickly degrade when exposed to moisture. Because of this sensitivity to water, perovskite devices have to be made in glove boxes and also require expensive packaging. But the process that the FSU team uses to make the nanoplatelets leaves a layer of a water-repelling organic compound on their surfaces. Gao says that he and his colleagues made the new LEDs without a glove box and that the devices retained their brightness for more than a week when when exposed to humid Florida air.

But these LEDs are still a pretty early prototype. Right now, they need several volts to glow bright because the efficiency with which they convert electricity to light is low. In a practical LED, Gao says, “you need to inject charges, make sure they are confined in a small space so they can meet and recombine.” But the principal limiting factor for an efficient, bright LED is the emitter itself.

So, says Ma, “we’re making sure we have good emitters first. Now we need to do device engineering to make a practical device. It took a long time for other kinds of LEDs to reach a high efficiency level.”

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New Production Method Could Make Graphene 100 Times Cheaper to Manufacture

Whether or not the costs associated with the production of graphene remain one of the most significant obstacles to its wider commercial adoption is debatable. Most graphene producers will tell you that they could ramp up production of graphene overnight to the point where, as one producer said two years ago, the price for the material could drop from $550 per square centimeter to between $100 and $200/cm2 in short order. But—and it’s a really big but—that’s if the demand were there.

Nonetheless, there is a regular stream of research aimed at improving production techniques in order to lower costs of graphene in the hope that it will stimulate demand. The most popular production method for getting good quality graphene at a reasonable cost is chemical vapor deposition (CVD), in which gaseous reactants form a film on a metal substrate that’s usually made of copper.

In a new twist on CVD production of graphene, researchers at the University of Glasgow in Scotland have used the smooth surface of copper foils commonly used as the negative electrodes in lithium-ion batteries. The result: large-area graphene 100 times cheaper than previous methods.

“The commercially-available copper we used in our process retails for around one dollar per square meter, compared to around $115 for a similar amount of the copper currently used in graphene production,” said Ravinder Dahiyam who led the research, in a press release. He explained that the more expensive form of copper required additional processing before it could be used, which tacked on even more cost.

“Our process produces high-quality graphene at low cost,” says Dahiyam. This breakthrough, he adds, takes us, “one step closer to creating affordable new electronic devices with a wide range of applications, from the smart cities of the future to mobile healthcare.”

In research published in the journal Scientific Reports, the researchers demonstrated that the graphene produced with copper foil substrates could help to realize electronics over large and flexible substrates such as soft plastics and paper.

Dahiyam has just such an application in mind for this graphene.

“Much of my own research is in the field of synthetic skin,” said Dahiyam. “Graphene could help provide an ultraflexible, conductive surface which could provide people with prosthetics capable of providing sensation in a way that is impossible for even the most advanced prosthetics today.”

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Nanosubmarines Promise a Fast Drug Delivery Device

Let’s just get this out of the way from the outset: this technology has absolutely nothing to do with the miniature submarine from the sixties sci-fi classic “Fantastic Voyage”.

Now that that’s clear, research out of Rice University led by James Tour has accomplished something perhaps even more impressive because it’s real. Tour and his team have designed and fabricated a molecule consisting of 244 atoms that can move within a liquid environment using a tail-like propeller powered by ultraviolet light.

What is really impressive about the nanoscale submarines is their speed. One wag of its tail can move it 18 nanometers. Not impressed? Consider that the tail can wag a million revolutions per minute (RPM), which translates to propelling the molecule about 2.5 centimeters per second. In nano-scale terms that’s really fast.

In research published in the journal ACS Nano, the speed of the 10-nanometer scale submersibles are fast enough that they can work their way through a solution containing molecules of the same size without being slowed down.

"This is akin to a person walking across a basketball court with 1,000 people throwing basketballs at him," Tour said in a press release.

The operation of the motor resembles the movement of a bacterium’s flagellum. The process involves four steps. In the first, when light hits the double bond that holds the rotor to the main body, it becomes a single bond. This removal of a single bond allows the rotor to turn a quarter rotation. This motor is seeking to get to a lower energy state, which leads it to jump to the next adjacent atom. This causes the rotor to turn another quarter step, and so goes the process while the light shines on it.

The longer-term aim of such a submarine would be to serve as a cargo delivery device with drug delivery being the most likely possibility.

Victor García-López, lead author and Rice graduate student, added: "This is the first step, and we've proven the concept. Now we need to explore opportunities and potential applications."

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Quantum Dots Made From Fool's Gold Could Lead to a New Generation of Batteries

Quantum dots have developed quite a reputation for themselves, in next-generation displays and photovoltaics. However, in the field of battery technology, they’re less heralded. 

Nonetheless, research has shown that if you add quantum dots, which are semiconducting metal nanoparticles, to a lithium-ion (Li-ion) battery, it’s then possible to charge the battery completely in 30 seconds. While that sounds great, it turns out that this fast-charging trick can be executed for only a couple of cycles before the quantum dots start to interact with the electrolyte and it stops working.

Now researchers at Vanderbilt University have discovered a way to forestall that interaction by making the quantum dots out of iron pyrite, otherwise known as “fool’s gold”.

In research published in the journal ACS Nano, the Vanderbilt researchers added iron pyrite quantum dots of varying sizes to standard Li-ion button batteries like those used in watches. The results showed that they could achieve those fast recharging times with no negative effect on performance after dozens of cycles.

It turns out that fool’s gold is a material with a few tricks up it sleeve. Unlike other materials, iron pyrite changes its form, becoming an iron and a lithium-sulfur (or sodium sulfur) compound when it’s time to store energy.

“This is a different mechanism from how commercial lithium-ion batteries store charge,” said Anna Douglas, graduate student and co-author of the ACS Nano paper, in a press release. “Lithium inserts into a material during charging and is extracted while discharging—all the while leaving the material that stores the lithium mostly unchanged,” she explained.

Cary Pint, a professor of mechanical engineering, describes this unique mechanism using a pastry-based metaphor: “You can think of it like vanilla cake. Storing lithium or sodium in conventional battery materials is like pushing chocolate chips into the cake and then pulling the intact chips back out. With the interesting materials we’re studying, you put chocolate chips into vanilla cake and it changes into a chocolate cake with vanilla chips.”

Iron pyrite does not behave this way in its bulk form; it’s only possible on the nanoscale—ideally in nanoparticles 4.5 nanometers in size. The reason for this is that in the bulk form, the iron diffuses too slowly. However, if you shrink the size of the iron pyrite down to the nanoscale, the iron is closer to the surface and diffuses more quickly. With the iron rapidly diffused, the sulfur in the iron pyrite can more easily interact with the lithium or the sodium as the case may be.

“The batteries of tomorrow that can charge in seconds and discharge in days will not just use nanotechnology,” said Pint. “They will benefit from the development of new tools that will allow us to design nanostructures that can stand up to tens of thousands of cycles and possess energy storage capacities rivaling that of gasoline.” Pint and his colleagues feel that their breakthrough is a significant step in that direction.

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Molybdenum Disulfide Outperforms Graphene in Water Desalination

When the World Economic Forum published its Global Risks Report this year, it identified the number one greatest risk facing the world as the looming water shortage. While there are both new and old technology solutions for desalinating water that could address this water shortfall,  they have remained highly energy intensive, rendering many of them out of reach for most regions outside of the oil-rich Persian Gulf.

Scientists have been looking to graphene in the search for ways of easing the energy demands of water desalination. Here the material acts a porous membrane that allows water through but blocks the flow of salt ions—a pressure-driven process called reverse osmosis. Researchers at the University of Illinois recently took a look at that material’s two-dimensional cousin molybdenum disulfide (MoS2) in that role and believe that it may remove salt much better.

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Nanoclast

IEEE Spectrum’s nanotechnology blog, featuring news and analysis about the development, applications, and future of science and technology at the nanoscale.

 
Editor
Dexter Johnson
Madrid, Spain
 
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Rachel Courtland
Associate Editor, IEEE Spectrum
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