Graphene, an atom-thick material with extraordinary properties, is a promising candidate for the next generation of dramatically faster, more energy-efficient electronics. However, scientists have struggled to fabricate the material into ultra-narrow strips, called nanoribbons, that could enable the use of graphene in high-performance semiconductor electronics.

Now, University of Wisconsin-Madison engineers have discovered a way to grow graphene nanoribbons with desirable semiconducting properties directly on a conventional germanium semiconductor wafer. This advance could allow manufacturers to easily use graphene nanoribbons in hybrid integrated circuits, which promise to significantly boost the performance of next-generation electronic devices. The technology could also have specific uses in industrial and military applications, such as sensors that detect specific chemical and biological species and photonic devices that manipulate light.

In a paper published Aug. 10 in the journal Nature Communications, Michael Arnold, an associate professor of materials science and engineering at UW-Madison, Ph.D. student Robert Jacobberger, and their collaborators describe their new approach to producing graphene nanoribbons. Importantly, their technique can easily be scaled for mass production and is compatible with the prevailing infrastructure used in semiconductor processing.

“Graphene nanoribbons that can be grown directly on the surface of a semiconductor like germanium are more compatible with planar processing that’s used in the semiconductor industry, and so there would be less of a barrier to integrating these really excellent materials into electronics in the future,” Arnold says.

Graphene, a sheet of carbon atoms that is only one atom in thickness, conducts electricity and dissipates heat much more efficiently than silicon, the material most commonly found in today’s computer chips. But to exploit graphene’s remarkable electronic properties in semiconductor applications where current must be switched on and off, graphene nanoribbons need to be less than 10 nanometers wide, which is phenomenally narrow. In addition, the nanoribbons must have smooth, well-defined “armchair” edges in which the carbon-carbon bonds are parallel to the length of the ribbon.

Researchers have typically fabricated nanoribbons by using lithographic techniques to cut larger sheets of graphene into ribbons. However, this “top-down” fabrication approach lacks precision and produces nanoribbons with very rough edges.

Another strategy for making nanoribbons is to use a “bottom-up” approach such as surface-assisted organic synthesis, where molecular precursors react on a surface to polymerize nanoribbons. Arnold says surface-assisted synthesis can produce beautiful nanoribbons with precise, smooth edges, but this method only works on metal substrates and the resulting nanoribbons are thus far too short for use in electronics.

To overcome these hurdles, the UW-Madison researchers pioneered a bottom-up technique in which they grow ultra-narrow nanoribbons with smooth, straight edges directly on germanium wafers using a process called chemical vapor deposition. In this process, the researchers start with methane, which adsorbs to the germanium surface and decomposes to form various hydrocarbons. These hydrocarbons react with each other on the surface, where they form graphene.

Arnold’s team made its discovery when it explored dramatically slowing the growth rate of the graphene crystals by decreasing the amount of methane in the chemical vapor deposition chamber. They found that at a very slow growth rate, the graphene crystals naturally grow into long nanoribbons on a specific crystal facet of germanium. By simply controlling the growth rate and growth time, the researchers can easily tune the nanoribbon width be to less than 10 nanometers.

“What we’ve discovered is that when graphene grows on germanium, it naturally forms nanoribbons with these very smooth, armchair edges,” Arnold says. “The widths can be very, very narrow and the lengths of the ribbons can be very long, so all the desirable features we want in graphene nanoribbons are happening automatically with this technique.”

The nanoribbons produced with this technique start nucleating, or growing, at seemingly random spots on the germanium and are oriented in two different directions on the surface. Arnold says the team’s future work will include controlling where the ribbons start growing and aligning them all in the same direction.

The researchers are patenting their technology through the Wisconsin Alumni Research Foundation. The research was primarily supported by the Department of Energy’s Basic Energy Sciences program.

A Korean team of scientists tune BP’s band gap to form a superior conductor, allowing for the application to be mass produced for electronic and optoelectronics devices

The research team operating out of Pohang University of Science and Technology (POSTECH), affiliated with the Institute for Basic Science’s (IBS) Center for Artificial Low Dimensional Electronic Systems (CALDES), reported a tunable band gap in BP, effectively modifying the semiconducting material into a unique state of matter with anisotropic dispersion. This research outcome potentially allows for great flexibility in the design and optimization of electronic and optoelectronic devices like solar panels and telecommunication lasers.

The research team operating out of Pohang University of Science and Technology, affiliated with the Institute for Basic Science’s Center for Artificial Low Dimensional Electronic Systems, reported a tunable band gap in BP, effectively modifying the semiconducting material into a unique state of matter with anisotropic dispersion. This research outcome potentially allows for great flexibility in the design and optimization of electronic and optoelectronic devices like solar panels and telecommunication lasers. Credit: Institute for Basic Science

To truly understand the significance of the team’s findings, it’s instrumental to understand the nature of two-dimensional (2-D) materials, and for that one must go back to 2010 when the world of 2-D materials was dominated by a simple thin sheet of carbon, a layered form of carbon atoms constructed to resemble honeycomb, called graphene. Graphene was globally heralded as a wonder-material thanks to the work of two British scientists who won the Nobel Prize for Physics for their research on it.

Graphene is extremely thin and has remarkable attributes. It is stronger than steel yet many times lighter, more conductive than copper and more flexible than rubber. All these properties combined make it a tremendous conductor of heat and electricity. A defect-free layer is also impermeable to all atoms and molecules. This amalgamation makes it a terrifically attractive material to apply to scientific developments in a wide variety of fields, such as electronics, aerospace and sports. For all its dazzling promise there is however a disadvantage; graphene has no band gap.

Stepping stones to a unique state

A material’s band gap is fundamental to determining its electrical conductivity. Imagine two river crossings, one with tightly-packed stepping-stones, and the other with large gaps between stones. The former is far easier to traverse because a jump between two tightly-packed stones requires less energy. A band gap is much the same; the smaller the gap the more efficiently the current can move across the material and the stronger the current.

Graphene has a band gap of zero in its natural state, however, and so acts like a conductor; the semiconductor potential can’t be realized because the conductivity can’t be shut off, even at low temperatures. This obviously dilutes its appeal as a semiconductor, as shutting off conductivity is a vital part of a semiconductor’s function.

Birth of a revolution

Phosphorus is the fifteenth element in the periodic table and lends its name to an entire class of compounds. Indeed it could be considered an archetype of chemistry itself. Black phosphorus is the stable form of white phosphorus and gets its name from its distinctive color. Like graphene, BP is a semiconductor and also cheap to mass produce. The one big difference between the two is BP’s natural band gap, allowing the material to switch its electrical current on and off. The research team tested on few layers of BP called phosphorene which is an allotrope of phosphorus.

Keun Su Kim, an amiable professor stationed at POSTECH speaks in rapid bursts when detailing the experiment, “We transferred electrons from the dopant – potassium – to the surface of the black phosphorus, which confined the electrons and allowed us to manipulate this state. Potassium produces a strong electrical field which is what we required to tune the size of the band gap.”

This process of transferring electrons is known as doping and induced a giant Stark effect, which tuned the band gap allowing the valence and conductive bands to move closer together, effectively lowering the band gap and drastically altering it to a value between 0.0 ~ 0.6 electron Volt (eV) from its original intrinsic value of 0.35 eV. Professor Kim explained, “Graphene is a Dirac semimetal. It’s more efficient in its natural state than black phosphorus but it’s difficult to open its band gap; therefore we tuned BP’s band gap to resemble the natural state of graphene, a unique state of matter that is different from conventional semiconductors.”

The potential for this new improved form of black phosphorus is beyond anything the Korean team hoped for, and very soon it could potentially be applied to several sectors including engineering where electrical engineers can adjust the band gap and create devises with the exact behavior desired. The 2-D revolution, it seems, has arrived and is here for the long run.

Using a hybrid silica sol-gel material and self-assembled monolayers of a common fatty acid, researchers have developed a new capacitor dielectric material that provides an electrical energy storage capacity rivaling certain batteries, with both a high energy density and high power density.

Members of the research group of Joe Perry pose in their laboratory, where samples of their new hybrid sol-gel dielectric material are fabricated. (Credit: John Toon, Georgia Tech)

If the material can be scaled up from laboratory samples, devices made from it could surpass traditional electrolytic capacitors for applications in electromagnetic propulsion, electric vehicles and defibrillators. Capacitors often complement batteries in these applications because they can provide large amounts of current quickly.

The new material is composed of a silica sol-gel thin film containing polar groups linked to the silicon atoms and a nanoscale self-assembled monolayer of an octylphosphonic acid, which provides insulating properties. The bilayer structure blocks the injection of electrons into the sol-gel material, providing low leakage current, high breakdown strength and high energy extraction efficiency.

Samples of the new hybrid sol-gel material are shown placed on a clear plastic substrate for testing. (Credit: John Toon, Georgia Tech)

“Sol-gels with organic groups are well known and fatty acids such as phosphonic acids are well known,” noted Joseph Perry, a professor in the School of Chemistry and Biochemistry at the Georgia Institute of Technology. “But to the best of our knowledge, this is the first time these two types of materials have been combined into high-density energy storage devices.”

The research, supported by the Office of Naval Research and the Air Force Office of Scientific Research, was reported July 14 in the journal Advanced Energy Materials.

The need for efficient, high-performance materials for electrical energy storage has been growing along with the ever-increasing demand for electrical energy in mobile applications. Dielectric materials can provide fast charge and discharge response, high energy storage, and power conditioning for defense, medical and commercial applications. But it has been challenging to find a single dielectric material able to maximize permittivity, breakdown strength, energy density and energy extraction efficiency.

Perry and colleagues in Georgia Tech’s Center for Organic Photonics and Electronics (COPE) had been working on other capacitor materials to meet these demands, but were not satisfied with the progress. The hybrid sol-gel materials had shown potential for efficient dielectric energy storage because of their high orientational polarization under an electric field, so the group decided to pursue these materials for the new capacitor applications.

Georgia Tech professor Joseph Perry and researcher Yunsang Kim examine a sample of sol-gel solution, which is used for spin processing in the fabrication of hybrid sol-gel dielectric materials. (Credit: John Toon, Georgia Tech)

Using an aluminized mylar film coated with the hybrid sol-gel capacitor material, they showed that the capacitor could be rolled and re-rolled several times while maintaining high energy density, demonstrating its flexibility. But they were still seeing high current leakage. To address that, they deposited a nanoscale self-assembled monolayer of n-octylphosphonic acid on top of the hybrid sol-gel. Less than a nanometer thick, the monolayer serves as an insulating layer.

“Our silica sol-gel is a hybrid material because it has polar organic groups attached to the silica framework that gives the sol-gel a high dielectric constant, and in our bilayer dielectric, the n-octylphosphonic acid groups are inserted between the sol-gel layer and the top aluminum layer to block charge injection into the sol-gel,” Perry explained. “It’s really a bilayer hybrid material that takes the best of both reorientation polarization and approaches for reducing injection and improving energy extraction.”

In their structures, the researchers demonstrated maximum extractable energy densities up to 40 joules per cubic centimeter, an energy extraction efficiency of 72 percent at a field strength of 830 volts per micron, and a power density of 520 watts per cubic centimeter. The performance exceeds that of conventional electrolytic capacitors and thin-film lithium ion batteries, though it doesn’t match the lithium ion battery formats commonly used in electronic devices and vehicles.

“This is the first time I’ve seen a capacitor beat a battery on energy density,” said Perry. “The combination of high energy density and high power density is uncommon in the capacitor world.”

Researchers in Perry’s lab have been making arrays of small sol-gel capacitors in the lab to gather information about the material’s performance. The devices are made on small substrates about an inch square.

“What we see when we apply an electric field is that the polarization response – which measures how much the polar groups line up in a stable way with the field – behaves in a linear way,” said Perry. “This is what you want to see in a capacitor dielectric material.”

The next step will be to scale up the materials to see if the attractive properties transfer to larger devices. If that is successful, Perry expects to commercialize the material through a startup company or SBIR project.

“The simplicity of fully solution-based processes for our dielectric material system provides potential for facile scale-up and fabrication on flexible platforms,” the authors wrote in their paper. “This work emphasizes the importance of controlling the electrode-dielectric interface to maximize the performance of dielectric materials for energy storage application.”

In addition to Perry, the research team included Yunsang Kim, Mohanalingam Kathaperumal and Vincent Chen from the Georgia Tech School of Chemistry and Biochemistry; Yohan Park from the Georgia Tech School of Materials Science and Engineering; Canek Fuentes-Hernandez and Bernard Kippelen from the Georgia Tech School of Electrical and Computer Engineering, and Ming-Hen Pan from the Naval Research Laboratory.

This research was supported by the Office of Naval Research Dielectric Films Program (Grant N000141110462) and U.S. Air Force Office of Scientific Research, BioPAINTS MURI Program (Grant FA9550-09-0669).  The content of this article is solely the responsibility of the authors and does not necessarily represent the official views of the sponsoring agencies.

CITATION: Yunsang Kim, et al., “Bilayer Structure with Ultra-high Energy/Power Density Using Hybrid Sol-Gel Dielectric and Charge Blocking Monolayer, (Advanced Energy Materials, 2015). http://www.dx.doi.org/10.1002/aenm.201500767

When it comes to installing solar cells, labor cost and the cost of the land to house them constitute the bulk of the expense. The solar cells — made often of silicon or cadmium telluride — rarely cost more than 20 percent of the total cost. Solar energy could be made cheaper if less land had to be purchased to accommodate solar panels, best achieved if each solar cell could be coaxed to generate more power.

A huge gain in this direction has now been made by a team of chemists at the University of California, Riverside that has found an ingenious way to make solar energy conversion more efficient.  The researchers report in Nano Letters that by combining inorganic semiconductor nanocrystals with organic molecules, they have succeeded in “upconverting” photons in the visible and near-infrared regions of the solar spectrum.

“The infrared region of the solar spectrum passes right through the photovoltaic materials that make up today’s solar cells,” explained Christopher Bardeen, a professor of chemistry. The research was a collaborative effort between him and Ming Lee Tang, an assistant professor of chemistry. “This is energy lost, no matter how good your solar cell. The hybrid material we have come up with first captures two infrared photons that would normally pass right through a solar cell without being converted to electricity, then adds their energies together to make one higher energy photon. This upconverted photon is readily absorbed by photovoltaic cells, generating electricity from light that normally would be wasted.”

Bardeen added that these materials are essentially “reshaping the solar spectrum” so that it better matches the photovoltaic materials used today in solar cells. The ability to utilize the infrared portion of the solar spectrum could boost solar photovoltaic efficiencies by 30 percent or more.

In their experiments, Bardeen and Tang worked with cadmium selenide and lead selenide semiconductor nanocrystals. The organic compounds they used to prepare the hybrids were diphenylanthracene and rubrene. The cadmium selenide nanocrystals could convert visible wavelengths to ultraviolet photons, while the lead selenide nanocrystals could convert near-infrared photons to visible photons.

In lab experiments, the researchers directed 980-nanometer infrared light at the hybrid material, which then generated upconverted orange/yellow fluorescent 550-nanometer light, almost doubling the energy of the incoming photons. The researchers were able to boost the upconversion process by up to three orders of magnitude by coating the cadmium selenide nanocrystals with organic ligands, providing a route to higher efficiencies.

“This 550 — nanometer light can be absorbed by any solar cell material,” Bardeen said. “The key to this research is the hybrid composite material — combining inorganic semiconductor nanoparticles with organic compounds. Organic compounds cannot absorb in the infrared but are good at combining two lower energy photons to a higher energy photon. By using a hybrid material, the inorganic component absorbs two photons and passes their energy on to the organic component for combination. The organic compounds then produce one high-energy photon. Put simply, the inorganics in the composite material take light in; the organics get light out.”

Besides solar energy, the ability to upconvert two low energy photons into one high energy photon has potential applications in biological imaging, data storage and organic light-emitting diodes. Bardeen emphasized that the research could have wide-ranging implications.

“The ability to move light energy from one wavelength to another, more useful region, for example, from red to blue, can impact any technology that involves photons as inputs or outputs,” he said.