Tag Archives: D. Frank Ogletree

Pushing efficiency of perovskite-based solar cells to 31%

This atomic force microscopy image of the grainy surface of a perovskite solar cell reveals a new path to much greater efficiency. Individual grains are outlined in black, low-performing facets are red, and high-performing facets are green. A big jump in efficiency could possibly be obtained if the material can be grown so that more high-performing facets develop. (Credit: Berkeley Lab)

This atomic force microscopy image of the grainy surface of a perovskite solar cell reveals a new path to much greater efficiency. Individual grains are outlined in black, low-performing facets are red, and high-performing facets are green. A big jump in efficiency could possibly be obtained if the material can be grown so that more high-performing facets develop. (Credit: Berkeley Lab)

It’s always fascinating to observe a trend (or a craze) in science, an endeavour that outsiders (like me) tend to think of as impervious to such vagaries. Perovskite seems to be making its way past the trend/craze phase and moving into a more meaningful phase. From a July 4, 2016 news item on Nanowerk,

Scientists from the Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab) have discovered a possible secret to dramatically boosting the efficiency of perovskite solar cells hidden in the nanoscale peaks and valleys of the crystalline material.

Solar cells made from compounds that have the crystal structure of the mineral perovskite have captured scientists’ imaginations. They’re inexpensive and easy to fabricate, like organic solar cells. Even more intriguing, the efficiency at which perovskite solar cells convert photons to electricity has increased more rapidly than any other material to date, starting at three percent in 2009 — when researchers first began exploring the material’s photovoltaic capabilities — to 22 percent today. This is in the ballpark of the efficiency of silicon solar cells.

Now, as reported online July 4, 2016 in the journal Nature Energy (“Facet-dependent photovoltaic efficiency variations in single grains of hybrid halide perovskite”), a team of scientists from the Molecular Foundry and the Joint Center for Artificial Photosynthesis, both at Berkeley Lab, found a surprising characteristic of a perovskite solar cell that could be exploited for even higher efficiencies, possibly up to 31 percent.

A July 4, 2016 Berkeley Lab news release (also on EurekAlert), which originated the news item, details the research,

Using photoconductive atomic force microscopy, the scientists mapped two properties on the active layer of the solar cell that relate to its photovoltaic efficiency. The maps revealed a bumpy surface composed of grains about 200 nanometers in length, and each grain has multi-angled facets like the faces of a gemstone.

Unexpectedly, the scientists discovered a huge difference in energy conversion efficiency between facets on individual grains. They found poorly performing facets adjacent to highly efficient facets, with some facets approaching the material’s theoretical energy conversion limit of 31 percent.

The scientists say these top-performing facets could hold the secret to highly efficient solar cells, although more research is needed.

“If the material can be synthesized so that only very efficient facets develop, then we could see a big jump in the efficiency of perovskite solar cells, possibly approaching 31 percent,” says Sibel Leblebici, a postdoctoral researcher at the Molecular Foundry.

Leblebici works in the lab of Alexander Weber-Bargioni, who is a corresponding author of the paper that describes this research. Ian Sharp, also a corresponding author, is a Berkeley Lab scientist at the Joint Center for Artificial Photosynthesis. Other Berkeley Lab scientists who contributed include Linn Leppert, Francesca Toma, and Jeff Neaton, the director of the Molecular Foundry.

A team effort

The research started when Leblebici was searching for a new project. “I thought perovskites are the most exciting thing in solar right now, and I really wanted to see how they work at the nanoscale, which has not been widely studied,” she says.

She didn’t have to go far to find the material. For the past two years, scientists at the nearby Joint Center for Artificial Photosynthesis have been making thin films of perovskite-based compounds, and studying their ability to convert sunlight and CO2 into useful chemicals such as fuel. Switching gears, they created pervoskite solar cells composed of methylammonium lead iodide. They also analyzed the cells’ performance at the macroscale.

The scientists also made a second set of half cells that didn’t have an electrode layer. They packed eight of these cells on a thin film measuring one square centimeter. These films were analyzed at the Molecular Foundry, where researchers mapped the cells’ surface topography at a resolution of ten nanometers. They also mapped two properties that relate to the cells’ photovoltaic efficiency: photocurrent generation and open circuit voltage.

This was performed using a state-of-the-art atomic force microscopy technique, developed in collaboration with Park Systems, which utilizes a conductive tip to scan the material’s surface. The method also eliminates friction between the tip and the sample. This is important because the material is so rough and soft that friction can damage the tip and sample, and cause artifacts in the photocurrent.

Surprise discovery could lead to better solar cells

The resulting maps revealed an order of magnitude difference in photocurrent generation, and a 0.6-volt difference in open circuit voltage, between facets on the same grain. In addition, facets with high photocurrent generation had high open circuit voltage, and facets with low photocurrent generation had low open circuit voltage.

“This was a big surprise. It shows, for the first time, that perovskite solar cells exhibit facet-dependent photovoltaic efficiency,” says Weber-Bargioni.

Adds Toma, “These results open the door to exploring new ways to control the development of the material’s facets to dramatically increase efficiency.”

In practice, the facets behave like billions of tiny solar cells, all connected in parallel. As the scientists discovered, some cells operate extremely well and others very poorly. In this scenario, the current flows towards the bad cells, lowering the overall performance of the material. But if the material can be optimized so that only highly efficient facets interface with the electrode, the losses incurred by the poor facets would be eliminated.

“This means, at the macroscale, the material could possibly approach its theoretical energy conversion limit of 31 percent,” says Sharp.

A theoretical model that describes the experimental results predicts these facets should also impact the emission of light when used as an LED. …

The Molecular Foundry is a DOE Office of Science User Facility located at Berkeley Lab. The Joint Center for Artificial Photosynthesis is a DOE Energy Innovation Hub led by the California Institute of Technology in partnership with Berkeley Lab.

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

Facet-dependent photovoltaic efficiency variations in single grains of hybrid halide perovskite by Sibel Y. Leblebici, Linn Leppert, Yanbo Li, Sebastian E. Reyes-Lillo, Sebastian Wickenburg, Ed Wong, Jiye Lee, Mauro Melli, Dominik Ziegler, Daniel K. Angell, D. Frank Ogletree, Paul D. Ashby, Francesca M. Toma, Jeffrey B. Neaton, Ian D. Sharp, & Alexander Weber-Bargioni. Nature Energy 1, Article number: 16093 (2016  doi:10.1038/nenergy.2016.93 Published online: 04 July 2016

This paper is behind a paywall.

Dexter Johnson’s July 6, 2016 posting on his Nanoclast blog (on the IEEE [Institute of Electrical and Electronics Engineers] website} presents his take on the impact that this new finding may have,

The rise of the crystal perovskite as a potential replacement for silicon in photovoltaics has been impressive over the last decade, with its conversion efficiency improving from 3.8 to 22.1 percent over that time period. Nonetheless, there has been a vague sense that this rise is beginning to peter out of late, largely because when a solar cell made from perovskite gets larger than 1 square centimeter the best conversion efficiency had been around 15.6 percent. …

Cooling it—an application using carbon nanotubes and a theory that hotter leads to cooler

The only thing these two news items have in common is their focus on cooling down electronic devices. Well, there’s also the fact that the work is being done at the nanoscale.

First, there’s a Jan. 23, 2014 news item on Azonano about a technique using carbon nanotubes to cool down microprocessors,

“Cool it!” That’s a prime directive for microprocessor chips and a promising new solution to meeting this imperative is in the offing. Researchers with the U.S. Department of Energy (DOE)’s Lawrence Berkeley National Laboratory (Berkeley Lab) have developed a “process friendly” technique that would enable the cooling of microprocessor chips through carbon nanotubes.

Frank Ogletree, a physicist with Berkeley Lab’s Materials Sciences Division, led a study in which organic molecules were used to form strong covalent bonds between carbon nanotubes and metal surfaces. This improved by six-fold the flow of heat from the metal to the carbon nanotubes, paving the way for faster, more efficient cooling of computer chips. The technique is done through gas vapor or liquid chemistry at low temperatures, making it suitable for the manufacturing of computer chips.

The Jan. 22, 2014 Berkeley Lab news release (also on EurekAlert), which originated the news item, describes the nature  of the problem in more detail,

Overheating is the bane of microprocessors. As transistors heat up, their performance can deteriorate to the point where they no longer function as transistors. With microprocessor chips becoming more densely packed and processing speeds continuing to increase, the overheating problem looms ever larger. The first challenge is to conduct heat out of the chip and onto the circuit board where fans and other techniques can be used for cooling. Carbon nanotubes have demonstrated exceptionally high thermal conductivity but their use for cooling microprocessor chips and other devices has been hampered by high thermal interface resistances in nanostructured systems.

“The thermal conductivity of carbon nanotubes exceeds that of diamond or any other natural material but because carbon nanotubes are so chemically stable, their chemical interactions with most other materials are relatively weak, which makes for  high thermal interface resistance,” Ogletree says. “Intel came to the Molecular Foundry wanting to improve the performance of carbon nanotubes in devices. Working with Nachiket Raravikar and Ravi Prasher, who were both Intel engineers when the project was initiated, we were able to increase and strengthen the contact between carbon nanotubes and the surfaces of other materials. This reduces thermal resistance and substantially improves heat transport efficiency.”

The news release then describes the proposed solution,

Sumanjeet Kaur, lead author of the Nature Communications paper and an expert on carbon nanotubes, with assistance from co-author and Molecular Foundry chemist Brett Helms, used reactive molecules to bridge the carbon nanotube/metal interface – aminopropyl-trialkoxy-silane (APS) for oxide-forming metals, and cysteamine for noble metals. First vertically aligned carbon nanotube arrays were grown on silicon wafers, and thin films of aluminum or gold were evaporated on glass microscope cover slips. The metal films were then “functionalized” and allowed to bond with the carbon nanotube arrays. Enhanced heat flow was confirmed using a characterization technique developed by Ogletree that allows for interface-specific measurements of heat transport.

“You can think of interface resistance in steady-state heat flow as being an extra amount of distance the heat has to flow through the material,” Kaur says. “With carbon nanotubes, thermal interface resistance adds something like 40 microns of distance on each side of the actual carbon nanotube layer. With our technique, we’re able to decrease the interface resistance so that the extra distance is around seven microns at each interface.”

Although the approach used by Ogletree, Kaur and their colleagues substantially strengthened the contact between a metal and individual carbon nanotubes within an array, a majority of the nanotubes within the array may still fail to connect with the metal. The Berkeley team is now developing a way to improve the density of carbon nanotube/metal contacts. Their technique should also be applicable to single and multi-layer graphene devices, which face the same cooling issues.

For anyone who’s never heard of the Molecular Foundry before (from the news release),

The Molecular Foundry is one of five DOE [Department of Energy] Nanoscale Science Research Centers (NSRCs), national user facilities for interdisciplinary research at the nanoscale, supported by the DOE Office of Science. Together the NSRCs comprise a suite of complementary facilities that provide researchers with state-of-the-art capabilities to fabricate, process, characterize, and model nanoscale materials, and constitute the largest infrastructure investment of the National Nanotechnology Initiative. The NSRCs are located at DOE’s Argonne, Brookhaven, Lawrence Berkeley, Oak Ridge and Sandia and Los Alamos national laboratories.

My second item comes from the University of Buffalo (UB), located in the US. From a Jan. 21, 2014 University of Buffalo news release by Cory Nealon (also on EurekAlert),

Heat in electronic devices is generated by the movement of electrons through transistors, resistors and other elements of an electrical network. Depending on the network, there are a variety of ways, such as cooling fans and heat sinks, to prevent the circuits from overheating.

But as more integrated circuits and transistors are added to devices to boost their computing power, it’s becoming more difficult to keep those elements cool. Most nanoelectrics research centers are working to develop advanced materials that are capable of withstanding the extreme environment inside smartphones, laptops and other devices.

While advanced materials show tremendous potential, the UB research suggests there may still be room within the existing paradigm of electronic devices to continue developing more powerful computers.

To support their findings, the researchers fabricated nanoscale semiconductor devices in a state-of-the-art gallium arsenide crystal provided to UB by Sandia’s Reno [John L. Reno, Center for Integrated Nanotechnologies at Sandia National Laboratories]. The researchers then subjected the chip to a large voltage, squeezing an electrical current through the nanoconductors. This, in turn, increased the amount of heat circulating through the chip’s nanotransistor.

But instead of degrading the device, the nanotransistor spontaneously transformed itself into a quantum state that was protected from the effect of heating and provided a robust channel of electric current. To help explain, Bird [Jonathan Bird, UB professor of electrical engineering] offered an analogy to Niagara Falls.

“The water, or energy, comes from a source; in this case, the Great Lakes. It’s channeled into a narrow point (the Niagara River) and ultimately flows over Niagara Falls. At the bottom of waterfall is dissipated energy. But unlike the waterfall, this dissipated energy recirculates throughout the chip and changes how heat affects, or in this case doesn’t affect, the network’s operation.”

While this behavior may seem unusual, especially conceptualizing it in terms of water flowing over a waterfall, it is the direct result of the quantum mechanical nature of electronics when viewed on the nanoscale. The current is made up of electrons which spontaneously organize to form a narrow conducting filament through the nanoconductor. It is this filament that is so robust against the effects of heating.

“We’re not actually eliminating the heat, but we’ve managed to stop it from affecting the electrical network. In a way, this is an optimization of the current paradigm,” said Han [J. E. Han, UB Dept. of Physics], who developed the theoretical models which explain the findings.

What an interesting and counter-intuitive approach to managing the heat in our devices.

For those who want more, here’s a link to and citation for the carbon nanotube paper,

Enhanced thermal transport at covalently functionalized carbon nanotube array interfaces by Sumanjeet Kaur, Nachiket Raravikar, Brett A. Helms, Ravi Prasher, & D. Frank Ogletree. Nature Communications 5, Article number: 3082 doi:10.1038/ncomms4082 Published 22 January 2014

This paper is behind a paywall.

Now here’s a link to and a citation for the ‘making it hotter to make it cooler’ paper,

Formation of a protected sub-band for conduction in quantum point contacts under extreme biasing by J. Lee, J. E. Han, S. Xiao, J. Song, J. L. Reno, & J. P. Bird. Nature Nanotechnology (2014) doi:10.1038/nnano.2013.297 Published online 19 January 2014

This paper is behind a paywall although there is an option to preview it for free via ReadCube Access.