Solving an organic semiconductor mystery
Organic semiconductors are prized for light emitting diodes (LEDs), field effect transistors (FETs) and photovoltaic cells. As they can be printed from solution, they provide a highly scalable, cost-effective alternative to silicon-based devices. Uneven performances, however, have been a persistent problem. Scientists have known that the performance issues originate in the domain interfaces within organic semiconductor thin films, but have not known the cause. This mystery now appears to have been solved.
Naomi Ginsberg, a faculty chemist with the U.S. Department of Energy (DOE)’s Lawrence Berkeley National Laboratory and the University of California (UC) Berkeley, led a team that used a unique form of microscopy to study the domain interfaces within an especially high-performing solution-processed organic semiconductor called TIPS-pentacene. She and her team discovered a cluttered jumble of randomly oriented nanocrystallites that become kinetically trapped in the interfaces during solution casting. Like debris on a highway, these nanocrystallites impede the flow of charge-carriers.
“If the interfaces were neat and clean, they wouldn’t have such a large impact on performance, but the presence of the nanocrystallites reduces charge-carrier mobility,” Ginsberg says. “Our nanocrystallite model for the interface, which is consistent with observations, provides critical information that can be used to correlate solution-processing methods to optimal device performances.”
Ginsberg, who holds appointments with Berkeley Lab’s Physical Biosciences Division and its Materials Sciences Division, as well as UC Berkeley’s departments of chemistry and physics, is the corresponding author of a paper describing this research in Nature Communications. The paper is titled “Exciton dynamics reveals aggregates with intermolecular order at hidden interfaces in solution-cast organic semiconducting films.” Co-authors are Cathy Wong, Benjamin Cotts and Hao Wu.
Ginsberg and her group overcame the challenges by using transient absorption (TA) microscopy, a technique in which femtosecond laser pulses excite transient energy states and detectors measure the changes in the absorption spectra. The Berkeley researchers carried out TA microscopy on an optical microscope they constructed themselves that enabled them to generate focal volumes that are a thousand times smaller than is typical for conventional TA microscopes. They also deployed multiple different light polarizations that allowed them to isolate interface signals not seen in either of the adjacent domains.
“Instrumentation, including very good detectors, the painstaking collection of data to ensure good signal-to-noise ratios, and the way we crafted the experiment and analysis were all critical to our success,” Ginsberg says. “Our spatial resolution and light polarization sensitivity were also essential to be able to unequivocally see a signature of the interface that was not swamped by the bulk, which contributes much more to the raw signal by volume.”
The methology developed by Ginsberg and her team to uncover structural motifs at hidden interfaces in organic semiconductor thin films should add a predictive factor to scalable and affordable solution-processing of these materials. This predictive capability should help minimize discontinuities and maximize charge-carrier mobility. Currently, researchers use what is essentially a trial-and-error approach, in which different solution casting conditions are tested to see how well the resulting devices perform.
“Our methodology provides an important intermediary in the feedback loop of device optimization by characterizing the microscopic details of the films that go into the devices, and by inferring how the solution casting could have created the structures at the interfaces,” Ginsberg says. “As a result, we can suggest how to alter the delicate balance of solution casting parameters to make more functional films.”
Rice-sized laser, powered one electron at a time, bodes well for quantum computing
Princeton University researchers have built a rice grain-sized laser powered by single electrons tunneling through artificial atoms known as quantum dots. The tiny microwave laser, or “maser,” is a demonstration of the fundamental interactions between light and moving electrons.
The researchers built the device — which uses about one-billionth the electric current needed to power a hair dryer — while exploring how to use quantum dots, which are bits of semiconductor material that act like single atoms, as components for quantum computers.
“It is basically as small as you can go with these single-electron devices,” said Jason Petta, an associate professor of physics at Princeton who led the study, which was published in the journal Science.
The device demonstrates a major step forward for efforts to build quantum-computing systems out of semiconductor materials, according to co-author and collaborator Jacob Taylor, an adjunct assistant professor at the Joint Quantum Institute, University of Maryland-National Institute of Standards and Technology.
“I consider this to be a really important result for our long-term goal, which is entanglement between quantum bits in semiconductor-based devices,” Taylor said.
The original aim of the project was not to build a maser, but to explore how to use double quantum dots — which are two quantum dots joined together — as quantum bits, or qubits, the basic units of information in quantum computers.
“The goal was to get the double quantum dots to communicate with each other,” said Yinyu Liu, a physics graduate student in Petta’s lab. The team also included graduate student Jiri Stehlik and associate research scholar Christopher Eichler in Princeton’s Department of Physics, as well as postdoctoral researcher Michael Gullans of the Joint Quantum Institute.
Because quantum dots can communicate through the entanglement of light particles, or photons, the researchers designed dots that emit photons when single electrons leap from a higher energy level to a lower energy level to cross the double dot.
Each double quantum dot can only transfer one electron at a time, Petta explained. “It is like a line of people crossing a wide stream by leaping onto a rock so small that it can only hold one person,” he said. “They are forced to cross the stream one at a time. These double quantum dots are zero-dimensional as far as the electrons are concerned — they are trapped in all three spatial dimensions.”
The researchers fabricated the double quantum dots from extremely thin nanowires (about 50 nanometers, or a billionth of a meter, in diameter) made of a semiconductor material called indium arsenide. They patterned the indium arsenide wires over other even smaller metal wires that act as gate electrodes, which control the energy levels in the dots.
To construct the maser, they placed the two double dots about 6 millimeters apart in a cavity made of a superconducting material, niobium, which requires a temperature near absolute zero, around minus 459 degrees Fahrenheit. “This is the first time that the team at Princeton has demonstrated that there is a connection between two double quantum dots separated by nearly a centimeter, a substantial distance,” Taylor said.
When the device was switched on, electrons flowed single-file through each double quantum dot, causing them to emit photons in the microwave region of the spectrum. These photons then bounced off mirrors at each end of the cavity to build into a coherent beam of microwave light.
One advantage of the new maser is that the energy levels inside the dots can be fine-tuned to produce light at other frequencies, which cannot be done with other semiconductor lasers in which the frequency is fixed during manufacturing, Petta said. The larger the energy difference between the two levels, the higher the frequency of light emitted.
Claire Gmachl, who was not involved in the research and is Princeton’s Eugene Higgins Professor of Electrical Engineering and a pioneer in the field of semiconductor lasers, said that because lasers, masers and other forms of coherent light sources are used in communications, sensing, medicine and many other aspects of modern life, the study is an important one.
“In this paper the researchers dig down deep into the fundamental interaction between light and the moving electron,” Gmachl said. “The double quantum dot allows them full control over the motion of even a single electron, and in return they show how the coherent microwave field is created and amplified. Learning to control these fundamental light-matter interaction processes will help in the future development of light sources.”
Carbon nanotube finding could lead to flexible electronics with longer battery life
University of Wisconsin-Madison materials engineers have made a significant leap toward creating higher-performance electronics with improved battery life — and the ability to flex and stretch.
Led by materials science Associate Professor Michael Arnold and Professor Padma Gopalan, the team has reported the highest-performing carbon nanotube transistors ever demonstrated. In addition to paving the way for improved consumer electronics, this technology could also have specific uses in industrial and military applications.
In a paper published recently in the journal ACS Nano, Arnold, Gopalan and their students reported transistors with an on-off ratio that’s 1,000 times better and a conductance that’s 100 times better than previous state-of-the-art carbon nanotube transistors.
“Carbon nanotubes are very strong and very flexible, so they could also be used to make flexible displays and electronics that can stretch and bend, allowing you to integrate electronics into new places like clothing,” says Arnold. “The advance enables new types of electronics that aren’t possible with the more brittle materials manufacturers are currently using.”
Carbon nanotubes are single atomic sheets of carbon rolled up into a tube. As some of the best electrical conductors ever discovered, carbon nanotubes have long been recognized as a promising material for next-generation transistors, which are semiconductor devices that can act like an on-off switch for current or amplify current. This forms the foundation of an electronic device.
However, researchers have struggled to isolate purely semiconducting carbon nanotubes, which are crucial, because metallic nanotube impurities act like copper wires and “short” the device. Researchers have also struggled to control the placement and alignment of nanotubes. Until now, these two challenges have limited the development of high-performance carbon nanotube transistors.
Building on more than two decades of carbon nanotube research in the field, the UW-Madison team drew on cutting-edge technologies that use polymers to selectively sort out the semiconducting nanotubes, achieving a solution of ultra-high-purity semiconducting carbon nanotubes.
Previous techniques to align the nanotubes resulted in less-than-desirable packing density, or how close the nanotubes are to one another when they are assembled in a film. However, the UW-Madison researchers pioneered a new technique, called floating evaporative self-assembly, or FESA, which they described earlier in 2014 in the ACS journal Langmuir. In that technique, researchers exploited a self-assembly phenomenon triggered by rapidly evaporating a carbon nanotube solution.
The team’s most recent advance also brings the field closer to realizing carbon nanotube transistors as a feasible replacement for silicon transistors in computer chips and in high-frequency communication devices, which are rapidly approaching their physical scaling and performance limits.
“This is not an incremental improvement in performance,” Arnold says. “With these results, we’ve really made a leap in carbon nanotube transistors. Our carbon nanotube transistors are an order of magnitude better in conductance than the best thin film transistor technologies currently being used commercially while still switching on and off like a transistor is supposed to function.”
The researchers have patented their technology through the Wisconsin Alumni Research Foundation and have begun working with companies to accelerate the technology transfer to industry.