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. reports the accomplishment ("Patterned Arrays of Lateral Heterojunctions within Monolayer Two-Dimensional Semiconductors"). 
Complex, scalable arrays of semiconductor heterojunctions -- promising building blocks for future electronics -- were formed within a two-dimensional crystalline monolayer of molybdenum deselenide by converting lithographically exposed regions to molybdenum disulfide using pulsed laser deposition of sulfur atoms. Sulfur atoms (green) replaced selenium atoms (red) in lithographically exposed regions (top) as shown by Raman spectroscopic mapping (bottom). (Illustration: Oak Ridge National Laboratory, U.S. Dept. of Energy) "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."
read more "Researchers make scalable arrays of building blocks for ultrathin electronics"
Complex, scalable arrays of semiconductor heterojunctions -- promising building blocks for future electronics -- were formed within a two-dimensional crystalline monolayer of molybdenum deselenide by converting lithographically exposed regions to molybdenum disulfide using pulsed laser deposition of sulfur atoms. Sulfur atoms (green) replaced selenium atoms (red) in lithographically exposed regions (top) as shown by Raman spectroscopic mapping (bottom). (Illustration: Oak Ridge National Laboratory, U.S. Dept. of Energy) "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."
In this schematic of the superlubricity system, the gold represents nanodiamond particles; the blue is a graphene nanoscroll; green shows underlying graphene on silicon dioxide; and the black structures are the diamond-like carbon interface. (Image: Sanket Deshmukh, Joseph Insley, and Subramanian Sankaranarayanan, Argonne National Laboratory) While reviewing the simulation results of a promising new lubricant material, Argonne researcher Sanket Deshmukh stumbled upon a phenomenon that had never been observed before. "I remember Sanket calling me and saying 'you have got to come over here and see this. I want to show you something really cool,'" said Subramanian Sankaranarayanan, Argonne computational nanoscientist, who led the simulation work at the Argonne Leadership Computing Facility (ALCF), a DOE Office of Science User Facility. They were amazed by what the computer simulations revealed. When the lubricant materials--graphene and diamond-like carbon (DLC)--slid against each other, the graphene began rolling up to form hollow cylindrical "scrolls" that helped to practically eliminate friction. These so-called nanoscrolls represented a completely new mechanism for superlubricity, a state in which friction essentially disappears. "The nanoscrolls combat friction in very much the same way that ball bearings do by creating separation between surfaces," said Deshmukh, who finished his postdoctoral appointment at Argonne in January. Superlubricity is a highly desirable property. Considering that nearly one-third of every fuel tank is spent overcoming friction in automobiles, a material that can achieve superlubricity would greatly benefit industry and consumers alike. Such materials could also help increase the lifetime of countless mechanical components that wear down due to incessant friction. Experimental origins Prior to the computational work, Argonne scientists Ali Erdemir, Anirudha Sumant, and Diana Berman were studying the hybrid material in laboratory experiments at Argonne's Tribology Laboratory and the Center for Nanoscale Materials, a DOE Office of Science User Facility. The experimental setup consisted of small patches of graphene (a two-dimensional single-sheet form of pure carbon) sliding against a DLC-coated steel ball. The graphene-DLC combination was registering a very low friction coefficient (a ratio that measures the force of friction between two surfaces), but the friction levels were fluctuating up and down for no apparent reason. The experimentalists were also puzzled to find that humid environments were causing the friction coefficient to shoot up to levels that were nearly 100 times greater than measured in dry environments. To shed light on these mysterious behaviors, they turned to Sankaranarayanan and Deshmukh for computational help. Using Mira, the ALCF's 10-petaflops IBM Blue Gene/Q supercomputer, the researchers replicated the experimental conditions with large-scale molecular dynamics simulations aimed at understanding the underlying mechanisms of superlubricity at an atomistic level. This led to their discovery of the graphene nanoscrolls, which helped to fill in the blanks. The material's fluctuating friction levels were explained by the fact that the nanoscrolls themselves were not stable. The researchers observed a repeating pattern in which the hollow nanoscrolls would form, and then cave in and collapse under the pressure of the load. "The friction was dipping to very low values at the moment the scroll formation took place and then it would jump back up to higher values when the graphene patches were in an unscrolled state," Deshmukh said. The computational scientists had an idea to overcome this issue. They tried incorporating nanodiamond particles into their simulations to see if the hard material could help stabilize the nanoscrolls and make them more permanent. Sure enough, the simulations proved successful. The graphene patches spontaneously rolled around the nanodiamonds, which held the scrolls in place and resulted in sustained superlubricity. The simulation results fed into a new set of experiments with nanodiamonds that confirmed the same. "The beauty of this particular discovery is that we were able to see sustained superlubricity at the macroscale for the first time, proving this mechanism can be used at engineering scales for real-world applications," Sankaranarayanan said. "This collaborative effort is a perfect example of how computation can help in the design and discovery of new materials." Not slippery when wet Unfortunately, the addition of nanodiamonds did not address the material's aversion to water. The simulations showed that water suppresses the formation of scrolls by increasing the adhesion of graphene to the surface. While this greatly limits the hybrid material's potential applications, its ability to maintain superlubricity in dry environments is a significant breakthrough in itself. The research team is in the process of seeking a patent for the hybrid material, which could potentially be used for applications in dry environments, such as computer hard drives, wind turbine gears, and mechanical rotating seals for microelectromechanical and nanoelectromechanical systems. Adding to the material's appeal is a relatively simple and cost-effective deposition method called drop casting. This technique involves spraying solutions of the materials on moving mechanical parts. When the solutions evaporate, it would leave the graphene and nanodiamonds on one side of a moving part, and diamond-like carbon on the other side. However, the knowledge gained from their study is perhaps even more valuable, said Deshmukh. He expects the nanoscroll mechanism to spur future efforts to develop materials capable of superlubricity for a wide range of mechanical applications. For their part, the Argonne team will continue its computational studies to look for ways to overcome the barrier presented by water. "We are exploring different surface functionalizations to see if we can incorporate something hydrophobic that would keep water out," Sankaranarayanan said. "As long as you can repel water, the graphene nanoscrolls could potentially work in humid environments as well." Simulating millions of atoms The team's groundbreaking nanoscroll discovery would not have been possible without a supercomputer like Mira. Replicating the experimental setup required simulating up to 1.2 million atoms for dry environments and up to 10 million atoms for humid environments. The researchers used the LAMMPS (Large-scale Atomic/Molecular Massively Parallel Simulator) code to carry out the computationally demanding reactive molecular dynamics simulations. With the help of ALCF catalysts, a team of computational scientists who work directly with ALCF users, they were able to overcome a performance bottleneck with the code's ReaxFF module, an add-on package that was needed to model the chemical reactions occurring in the system. The ALCF catalysts, in collaboration with researchers from IBM, Lawrence Berkeley National Laboratory, and Sandia National Laboratories, optimized LAMMPS and its implementation of ReaxFF by adding OpenMP threading, replacing MPI point-to-point communication with MPI collectives in key algorithms, and leveraging MPI I/O. Altogether, these enhancements allowed the code to perform twice as fast as before. "With the code optimizations in place, we were able to model the phenomena in real experimental systems more accurately," Deshmukh said. "The simulations on Mira showed us some amazing things that could not be seen in laboratory tests." And with the recent announcement of Aurora, the ALCF's next-generation supercomputer, Sankaranarayanan is excited about where this line of research could go in the future. "Given the advent of computing resources like Aurora and the wide gamut of the available two-dimensional materials and nanoparticle types, we envision the creation of a lubricant genome at some point in the future," he said. "Having a materials database like this would allow us to pick and choose lubricant materials for specific operational conditions."
Nanoparticles that lose their stability upon irradiation with light have been designed to extract endocrine disruptors, pesticides, and other contaminants from water and soils. The system exploits the large surface-to-volume ratio of nanoparticles, while the photoinduced precipitation ensures nanomaterials are not released in the environment. Ferdinand Brandl and Nicolas Bertrand, the two lead authors, are former postdocs in the laboratory of Robert Langer, the David H. Koch Institute Professor at MIT’s Koch Institute for Integrative Cancer Research. (Eliana Martins Lima, of the Federal University of Goiás, is the other co-author.) Both Brandl and Bertrand are trained as pharmacists, and describe their discovery as a happy accident: They initially sought to develop nanoparticles that could be used to deliver drugs to cancer cells. Brandl had previously synthesized polymers that could be cleaved apart by exposure to UV light. But he and Bertrand came to question their suitability for drug delivery, since UV light can be damaging to tissue and cells, and doesn’t penetrate through the skin. When they learned that UV light was used to disinfect water in certain treatment plants, they began to ask a different question. “We thought if they are already using UV light, maybe they could use our particles as well,” Brandl says. “Then we came up with the idea to use our particles to remove toxic chemicals, pollutants, or hormones from water, because we saw that the particles aggregate once you irradiate them with UV light.” A trap for ‘water-fearing’ pollution The researchers synthesized polymers from polyethylene glycol, a widely used compound found in laxatives, toothpaste, and eye drops and approved by the Food and Drug Administration as a food additive, and polylactic acid, a biodegradable plastic used in compostable cups and glassware. Nanoparticles made from these polymers have a hydrophobic core and a hydrophilic shell. Due to molecular-scale forces, in a solution hydrophobic pollutant molecules move toward the hydrophobic nanoparticles, and adsorb onto their surface, where they effectively become “trapped.” This same phenomenon is at work when spaghetti sauce stains the surface of plastic containers, turning them red: In that case, both the plastic and the oil-based sauce are hydrophobic and interact together. If left alone, these nanomaterials would remain suspended and dispersed evenly in water. But when exposed to UV light, the stabilizing outer shell of the particles is shed, and — now “enriched” by the pollutants — they form larger aggregates that can then be removed through filtration, sedimentation, or other methods. The researchers used the method to extract phthalates, hormone-disrupting chemicals used to soften plastics, from wastewater; BPA, another endocrine-disrupting synthetic compound widely used in plastic bottles and other resinous consumer goods, from thermal printing paper samples; and polycyclic aromatic hydrocarbons, carcinogenic compounds formed from incomplete combustion of fuels, from contaminated soil. The process is irreversible and the polymers are biodegradable, minimizing the risks of leaving toxic secondary products to persist in, say, a body of water. “Once they switch to this macro situation where they’re big clumps,” Bertrand says, “you won’t be able to bring them back to the nano state again.” The fundamental breakthrough, according to the researchers, was confirming that small molecules do indeed adsorb passively onto the surface of nanoparticles. “To the best of our knowledge, it is the first time that the interactions of small molecules with pre-formed nanoparticles can be directly measured,” they write in Nature Communications. Nano cleansing Even more exciting, they say, is the wide range of potential uses, from environmental remediation to medical analysis. The polymers are synthesized at room temperature, and don’t need to be specially prepared to target specific compounds; they are broadly applicable to all kinds of hydrophobic chemicals and molecules. “The interactions we exploit to remove the pollutants are non-specific,” Brandl says. “We can remove hormones, BPA, and pesticides that are all present in the same sample, and we can do this in one step.” And the nanoparticles’ high surface-area-to-volume ratio means that only a small amount is needed to remove a relatively large quantity of pollutants. The technique could thus offer potential for the cost-effective cleanup of contaminated water and soil on a wider scale. “From the applied perspective, we showed in a system that the adsorption of small molecules on the surface of the nanoparticles can be used for extraction of any kind,” Bertrand says. “It opens the door for many other applications down the line.” This approach could possibly be further developed, he speculates, to replace the widespread use of organic solvents for everything from decaffeinating coffee to making paint thinners. Bertrand cites DDT, banned for use as a pesticide in the U.S. since 1972 but still widely used in other parts of the world, as another example of a persistent pollutant that could potentially be remediated using these nanomaterials. “And for analytical applications where you don’t need as much volume to purify or concentrate, this might be interesting,” Bertrand says, offering the example of a cheap testing kit for urine analysis of medical patients. The study also suggests the broader potential for adapting nanoscale drug-delivery techniques developed for use in environmental remediation. “That we can apply some of the highly sophisticated, high-precision tools developed for the pharmaceutical industry, and now look at the use of these technologies in broader terms, is phenomenal,” says Frank Gu, an assistant professor of chemical engineering at the University of Waterloo in Canada, and an expert in nanoengineering for health care and medical applications. “When you think about field deployment, that’s far down the road, but this paper offers a really exciting opportunity to crack a problem that is persistently present,” says Gu, who was not involved in the research. “If you take the normal conventional civil engineering or chemical engineering approach to treating it, it just won’t touch it. That’s where the most exciting part is.”