Tag Archives: Jeffrey B. Neaton

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. …

Good enough for the real world? A new device consisting of a singular molecule

While molecular diodes (a diode consisting of a single molecule) have been developed before, Columbia University’s Latha Venkataraman and her team have developed a new technique which may take these devices from the lab to real life. From a May 25, 2015 news item on Nanotechnology Now,

Under the direction of Latha Venkataraman, associate professor of applied physics at Columbia Engineering, researchers have designed a new technique to create a single-molecule diode, and, in doing so, they have developed molecular diodes that perform 50 times better than all prior designs. Venkataraman’s group is the first to develop a single-molecule diode that may have real-world technological applications for nanoscale devices.

A May 25, 2015 Columbia University news release on EurekAlert, which originated the news item, describes the new technique in greater detail,

“Our new approach created a single-molecule diode that has a high (>250) rectification and a high “on” current (~ 0.1 micro Amps),” says Venkataraman. “Constructing a device where the active elements are only a single molecule has long been a tantalizing dream in nanoscience. This goal, which has been the ‘holy grail’ of molecular electronics ever since its inception with Aviram and Ratner’s 1974 seminal paper, represents the ultimate in functional miniaturization that can be achieved for an electronic device.”

With electronic devices becoming smaller every day, the field of molecular electronics has become ever more critical in solving the problem of further miniaturization, and single molecules represent the limit of miniaturization. The idea of creating a single-molecule diode was suggested by Arieh Aviram and Mark Ratner who theorized in 1974 that a molecule could act as a rectifier, a one-way conductor of electric current. Researchers have since been exploring the charge-transport properties of molecules. They have shown that single-molecules attached to metal electrodes (single-molecule junctions) can be made to act as a variety of circuit elements, including resistors, switches, transistors, and, indeed, diodes. They have learned that it is possible to see quantum mechanical effects, such as interference, manifest in the conductance properties of molecular junctions.

Since a diode acts as an electricity valve, its structure needs to be asymmetric so that electricity flowing in one direction experiences a different environment than electricity flowing in the other direction. In order to develop a single-molecule diode, researchers have simply designed molecules that have asymmetric structures.

“While such asymmetric molecules do indeed display some diode-like properties, they are not effective,” explains Brian Capozzi, a PhD student working with Venkataraman and lead author of the paper. “A well-designed diode should only allow current to flow in one direction–the ‘on’ direction–and it should allow a lot of current to flow in that direction. Asymmetric molecular designs have typically suffered from very low current flow in both ‘on’ and ‘off’ directions, and the ratio of current flow in the two has typically been low. Ideally, the ratio of ‘on’ current to ‘off’ current, the rectification ratio, should be very high.”

In order to overcome the issues associated with asymmetric molecular design, Venkataraman and her colleagues–Chemistry Assistant Professor Luis Campos’ group at Columbia and Jeffrey Neaton’s group at the Molecular Foundry at UC Berkeley–focused on developing an asymmetry in the environment around the molecular junction. They created an environmental asymmetry through a rather simple method–they surrounded the active molecule with an ionic solution and used gold metal electrodes of different sizes to contact the molecule.

Their results achieved rectification ratios as high as 250: 50 times higher than earlier designs. The “on” current flow in their devices can be more than 0.1 microamps, which, Venkataraman notes, is a lot of current to be passing through a single-molecule. And, because this new technique is so easily implemented, it can be applied to all nanoscale devices of all types, including those that are made with graphene electrodes.

“It’s amazing to be able to design a molecular circuit, using concepts from chemistry and physics, and have it do something functional,” Venkataraman says. “The length scale is so small that quantum mechanical effects are absolutely a crucial aspect of the device. So it is truly a triumph to be able to create something that you will never be able to physically see and that behaves as intended.”

She and her team are now working on understanding the fundamental physics behind their discovery, and trying to increase the rectification ratios they observed, using new molecular systems.

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

Single-molecule diodes with high rectification ratios through environmental control by Brian Capozzi, Jianlong Xia, Olgun Adak, Emma J. Dell, Zhen-Fei Liu, Jeffrey C. Taylor, Jeffrey B. Neaton, Luis M. Campos, & Latha Venkataraman. Nature Nanotechnology (2015) doi:10.1038/nnano.2015.97 Published online 25 May 2015

This paper is behind a paywall but a free preview is available via ReadCube Access.