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OAK RIDGE, Tenn., July 22, 2015—Semiconductors, metals and insulators must be integrated to make the transistors that are the electronic building blocks of your smartphone, computer and other microchip-enabled devices. Today’s transistors are miniscule—a mere 10 nanometers wide—and formed from three-dimensional (3D) crystals.

But a disruptive new technology looms that uses two-dimensional (2D) crystals, just 1 nanometer thick, to enable ultrathin electronics. Scientists worldwide are investigating 2D crystals made from common layered materials to constrain electron transport within just two dimensions. Researchers had previously found ways to lithographically pattern single layers of carbon atoms called graphene into ribbon-like “wires” complete with insulation provided by a similar layer of boron nitride. But until now they have lacked synthesis and processing methods to lithographically pattern junctions between two different semiconductors within a single nanometer-thick layer to form transistors, the building blocks of ultrathin electronic devices.

Now for the first time, researchers at the Department of Energy’s Oak Ridge National Laboratory have combined a novel synthesis process with commercial electron-beam lithography techniques to produce arrays of semiconductor junctions in arbitrary patterns within a single, nanometer-thick semiconductor crystal. The process relies upon transforming patterned regions of one existing, single-layer crystal into another. The researchers first grew single, nanometer-thick layers of molybdenum diselenide crystals on substrates and then deposited protective patterns of silicon oxide using standard lithography techniques. Then they bombarded the exposed regions of the crystals with a laser-generated beam of sulfur atoms. The sulfur atoms replaced the selenium atoms in the crystals to form molybdenum disulfide, which has a nearly identical crystal structure. The two semiconductor crystals formed sharp junctions, the desired building blocks of electronics. Nature Communications reports the accomplishment.

“We can literally make any kind of pattern that we want,” said Masoud Mahjouri-Samani, who co-led the study with David Geohegan. Geohegan, head of ORNL’s Nanomaterials Synthesis and Functional Assembly Group at the Center for Nanophase Materials Sciences, is the principal investigator of a Department of Energy basic science project focusing on the growth mechanisms and controlled synthesis of nanomaterials. Millions of 2D building blocks with numerous patterns may be made concurrently, Mahjouri-Samani added. In the future, it might be possible to produce different patterns on the top and bottom of a sheet. Further complexity could be introduced by layering sheets with different patterns.

Added Geohegan, “The development of a scalable, easily implemented process to lithographically pattern and easily form lateral semiconducting heterojunctions within two-dimensional crystals fulfills a critical need for ‘building blocks’ to enable next-generation ultrathin devices for applications ranging from flexible consumer electronics to solar energy.”

Tuning the bandgap

“We chose pulsed laser deposition of sulfur because of the digital control it gives you over the flux of the material that comes to the surface,” said Mahjouri-Samani. “You can basically make any kind of intermediate alloy. You can just replace, say, 20 percent of the selenium with sulfur, or 30 percent, or 50 percent.” Added Geohegan, “Pulsed laser deposition also lets the kinetic energy of the sulfur atoms be tuned, allowing you to explore a wider range of processing conditions.”

It is important that by controlling the ratio of sulfur to selenium within the crystal, the researchers can tune the bandgap of the semiconductors, an attribute that determines electronic and optical properties. To make optoelectronic devices such as electroluminescent displays, microchip fabricators integrate semiconductors with different bandgaps. For example, molybdenum disulfide’s bandgap is greater than molybdenum diselenide’s. Applying voltage to a crystal containing both semiconductors causes electrons and “holes” (positive charges created when electrons vacate) to move from molybdenum disulfide into molybdenum diselenide and recombine to emit light at the bandgap of molybdenum diselenide. For that reason, engineering the bandgaps of monolayer systems can allow the generation of light with many different colors, as well as enable other applications such as transistors and sensors, Mahjouri-Samani said.

Next the researchers will see if their pulsed laser vaporization and conversion method will work with atoms other than sulfur and selenium. “We’re trying to make more complex systems in a 2D plane—integrate more ingredients, put in different building blocks—because at the end of the day, a complete working device needs different semiconductors and metals and insulators,” Mahjouri-Samani said.

To understand the process of converting one nanometer-thick crystal into another, the researchers used powerful electron microscopy capabilities available at ORNL, notably atomic-resolution Z-contrast scanning transmission electron microscopy, which was developed at the lab and is now available to scientists worldwide using the Center for Nanophase Materials Sciences. Employing this technique, electron microscopists Andrew Lupini and visiting scientist Leonardo Basile imaged hexagonal networks of individual columns of atoms in the nanometer-thick molybdenum diselenide and molybdenum disulfide crystals.

“We could directly distinguish between sulfur and selenium atoms by their intensities in the image,” Lupini said. “These images and electron energy loss spectroscopy allowed the team to characterize the semiconductor heterojunction with atomic precision.”

The title of the paper is “Patterned Arrays of Lateral Heterojunctions within Monolayer Two-Dimensional Semiconductors.”

The research was sponsored by the U.S. Department of Energy, Office of Science. A portion of the work was conducted at the Center for Nanophase Materials Sciences, a DOE Office of Science User Facility at ORNL. Basile received support from the National Secretariat of Higher Education, Science, Technology and Innovation of Ecuador.

UT-Battelle manages ORNL for DOE’s Office of Science. The single largest supporter of basic research in the physical sciences in the United States, the Office of Science is working to address some of the most pressing challenges of our time.

GNT Thumbnail Alt 3 2015-page-001“Imagine getting fire-hose volumes and velocities out of your garden hose. Nanotechnology could fundamentally change the economics of desalination.”

Nearly three-quarters of the Earth’s surface is covered by water, but according to the United Nations, more than 97 percent of it is saltwater unsuited for human consumption or agriculture.

The United Nations Population Fund reports that by 2025 two-thirds of the world’s projected population of 7.9 billion may live in areas where access to safe water is limited. “Every time we add a person, it’s not just the water that person consumes but also the additional water for agriculture and industry that you have to use,” says Earl Jones, director of water-scarcity solutions in General Electric Co.’s (GE) Water & Process Technologies unit.

UN World Water Crisis 070615 1386965848_png_CROP_promovar-mediumlarge

The removal of salt from seawater is an increasingly cost effective answer to the earth’s growing clean-water needs. By 2025, two-thirds of the world’s population may live in areas where access to safe water is limited, reports the U.N.

The removal of salt from water is emerging as one of the best solutions to the world’s water problem, analysts say. According to GOLDMAN SACH S Group Inc. (GS), desalination is a $5 billion global market, with growth of 10 percent to 15 percent a year. Water Desalination Report, a trade journal, reports that more than 12,000 desalination plants are operating World-wide, with 53 percent of the world’s desalination capacity in the Middle East.

“Today, the global capacity is about 40 million cubic meters of desalinated water per day,” says Antoine Frérot, CEO of Veolia Water, the water division of Veolia Environnement (VE). “By 2015, it will be around 70 million cubic meters per day.” Improvements in two technologies are making desalination more cost-efficient, say the experts:

The thermal process, which couples a thermal desalination plant with a power plant to provide the energy, involves evaporating water to remove salt.

Reverse osmosis, the other process, uses semipermeable membranes. About 84 percent of the world’s thermal desalination capacity, which requires more energy than reverse-osmosis facilities, is located in the Middle East, according to Water Desalination Report.  

Ashkelon Desal onearth_creattica_desalination-process 2

“We have one huge advantage in the Gulf,” says Phil Cox, CEO of International Power PLC (IPR), which builds, owns and operates thermal desalination plants in that region. “The price of natural gas is extremely low here compared with the rest of the world,” he adds. Outside the Middle East, reverse osmosis is the less expensive alternative, says Jean-Louis Chaussade, CEO of Suez Environment, a unit of Suez SA (SZE). “At our biggest reverse osmosis plants, we operate at roughly 60 cents per cubic meter of use,” says Chaussade.

Aside from GE, International Power, Suez and Veolia, other companies that construct, own and/or operate desalination systems worldwide include The AE S Corp. (AES), Crane Co.’s (CR) Crane Environmental, Siemens AG’s (SI) Power Generation unit and ITT Corp. (ITT). ABB Ltd . (ABB) provides electrical systems for desalination plants, and Met-Pro Corp.’s (MPR) Fybroc division manufactures pumps used in reverse-osmosis plants.

The motivation is there to solve the world’s water needs, the companies say. “According to the U.N., the No. 1 cause of death and illness in developing nations is waterborne diseases,” says GE’s Jones. “We have the technology to fix these problems. It’s very easy to get motivated because of the great opportunity to do good.”  

The Scale Effect  

The world’s largest reverse-osmosis plant in terms of production is Veolia Water’s Ashkelon Seawater Desalination Plant (see illustration) south of Tel Aviv, which has a daily capacity of 320,000 cubic meters per day, according to the company. The plant produces enough water to meet the needs of 15 percent of Israeli households, Veolia reports. “There is a scale effect,” says Veolia Water CEO Antoine Frérot. “At a small desalination plant, the price of water is around $2 per cubic meter. In Ashkelon, the price is 55 cents per cubic meter.”

Other big projects are in the works: General Electric Co.’s (GE) Infrastructure, Water & Process Technologies reports that it plans to open Africa’s largest seawater desalination project in Algiers, Algeria. An international consortium led by Siemens’ Power Generation unit says it plans to build the world’s largest independent water and power project in Riyadh, Saudi Arabia. Uwe Rokossa, Siemens projects sales director for new plants and services in the Middle East predicts: “We will see a continuation of big power and desalination projects.”

Steam Power and Hybrids

Thermal desalination requires steam to boil seawater, GE explains. According to GE’s Earl Jones, the most widely used thermal process is called multistage flash, which heats seawater in a brine tank, immediately converting it to steam. The resulting salt-free steam is captured, cooled and condensed, creating desalinated water, Jones reports. Since only some of the seawater is converted to steam, the process is repeated multiple times in different receptacles, each time using lower atmospheric pressures. The hybrid approach, which combines thermal and reverse-osmosis processes, is an emerging technology, according to Suez Environment, which provides the reverse-osmosis part of the first-ever hybrid facility in the United Arab Emirates. Having both techniques in one plant allows for flexibility, the company says. Suez Environment reports that when demand for electricity from the thermal side’s power plant is low, priority can be given to the less-energy-intensive reverse-osmosis process.

Another form of the hybrid approach involves having a mixture of different membranes inside a reverse-osmosis pressure vessel, says Lance Johnson, senior sales and marketing manager for Dow Water Solutions. “As the water moves down the vessel, the salt concentration increases. At the tail end, where the salinity is highest, you’d have a lower-pressure membrane than at the front end to boost productivity.

Emerging “Nano-Materials” and Membranes

Mixing high and low pressure membranes in a pressure vessel can lower cost.” Applying nanotechnology to membrane science is another promising avenue, according to GE’s Jones, who notes that membranes made out of nanotubes can process water faster than older methods. “Imagine getting fire-hose volumes and velocities out of your garden hose. Nanotechnology could fundamentally change the economics of desalination.”        

Graphene Nano Membrane 071615

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