It is the Philosopher’s Stone of Nanotechnology: using a technological trick, scientists at TU Wien (Vienna) have succeeded in creating nanostructures made of pure gold.
This work is a giant leap forward for 3D nano-printing of gold structures which will be the core part of nanoplasmonics and bioelectronics devices
The idea is reminiscent of the ancient alchemists’ attempts to create gold from worthless substances: Researchers from TU Wien (Vienna) have discovered a novel way to fabricate pure gold nanostructures using an additive direct-write lithography technique. An electron beam is used to turn an auriferous organic compound into pure gold. This new technique can now be used to create nanostructures, which are needed for many applications in electronics and sensor technology. Just like with a 3D-printer on the nanoscale, almost arbitrary shapes can be created.
The long search for the right production process
“Gold is not only a noble metal of exceptional beauty, but also a highly desired material for functional nanostructures”, says Professor Heinz Wanzenböck from TU Wien. Especially patterned gold nanostructures are key enabling structures in plasmonic devices, for biosensors with immobilized antibodies and as electrical contacts. For decades the fabrication of pure gold nanostructures on non-planar surfaces as well as of 3-dimensional gold nanostructures has been the bottleneck. Up to now, only 2-dimensional gold nanostructures on planar surfaces were achievable by resist based lithography.
The new technology, developed at TU Wien, can now solve this problem. The principle is the local decomposition of a metalorganic precursor by the focused electron beam of an electron microscope. With extremely high precision, the electron beam can decompose the organic compound at exactly the right position, leaving behind a 3D-trail of solid gold.
The final obstacle was getting the material purity right, as the electron-induced decomposition of metalorganic precursors has typically yielded metals with high carbon contaminations. This last bottleneck on the road to custom-designed, pure gold nanostructures has now been overcome as described in the work on “Highly conductive and pure gold nanostructures grown by electron beam induced deposition” published in Scientific Reports.
While conventional gold deposition usually contains about 70 atomic % carbon and only 30 atomic % gold, the new approach developed by a research group lead by Dr. Heinz Wanzenboeck at TU Wien has allowed to fabricate pure gold structures by in-situ addition of an oxidizing agent during the gold deposition. “The whole community has been working hard for the last 10 years to directly deposit pure gold nanostructures”, says Heinz Wanzenböck. At last, the group’s expertise in engineering and chemical reactions paid off and direct deposition of pure gold was successful. “It’s a bit like discovering the legendary philosopher’s stone that turns common, ignoble material into gold” joked Wanzenboeck.
This deposited pure gold structure exhibits extremely low resistivity near that of bulk gold. Generally, a FEBID gold structure has a resistivity around 1-Ohm-cm which is about 1 million times worse than the resistivity of purest bulk gold. However, this specially enhanced FEBID process produces a resistivity of 8.8 micro-Ohm-cm which is only a factor 4 away from the bulk resistivity of purest gold (2.4 micro-Ohm-cm).
The authors of the paper Dr. Mostafa Moonir Shawrav and Dipl.Ing. Philipp Taus stated, “This highly conductive and pure gold structure will open a new door for novel nanoelectronic devices. For example, it will be easier to produce pure gold structures for nanoantennas and biomolecule immobilization which will change our everyday life”. Dr. Shawrav added “it is remarkable how a regular SEM (Scanning Electron Microscope) nowadays can deposit nanostructures compared to 20 years back when it was only a characterization device”. And with pure gold direct deposition available now, he expects nanodevices to be deposited directly and utilized in many different applications for technological revolution. Concluding, this work is a giant leap forward for 3D nano-printing of gold structures which will be the core part of nanoplasmonics and bioelectronics devices.
Learn more: Nanostructures Made of Pure Gold
Scientists at the Department of Energy’s Oak Ridge National Laboratory are the first to harness a scanning transmission electron microscope (STEM) to directly write tiny patterns in metallic “ink,” forming features in liquid that are finer than half the width of a human hair.
The automated process is controlled by weaving a STEM instrument’s electron beam through a liquid-filled cell to spur deposition of metal onto a silicon microchip. The patterns created are “nanoscale,” or on the size scale of atoms or molecules.
Usually fabrication of nanoscale patterns requires lithography, which employs masks to prevent material from accumulating on protected areas. ORNL’s new direct-write technology is like lithography without the mask.
Details of this unique capability are published online in Nanoscale, a journal of the Royal Society of Chemistry, and researchers are applying for a patent. The technique may provide a new way to tailor devices for electronics and other applications.
“We can now deposit high-purity metals at specific sites to build structures, with tailored material properties for a specific application,” said lead author Raymond Unocic of the Center for Nanophase Materials Sciences (CNMS), a DOE Office of Science User Facility at ORNL. “We can customize architectures and chemistries. We’re only limited by systems that are dissolvable in the liquid and can undergo chemical reactions.”
The experimenters used grayscale images to create nanoscale templates. Then they beamed electrons into a cell filled with a solution containing palladium chloride. Pure palladium separated out and deposited wherever the electron beam passed.
Liquid environments are a must for chemistry. Researchers first needed a way to encapsulate the liquid so the extreme dryness of the vacuum inside the microscope would not evaporate the liquid. The researchers started with a cell made of microchips with a silicon nitride membrane to serve as a window through which the electron beam could pass.
Then they needed to elicit a new capability from a STEM instrument. “It’s one thing to utilize a microscope for imaging and spectroscopy. It’s another to take control of that microscope to perform controlled and site-specific nanoscale chemical reactions,” Unocic said. “With other techniques for electron-beam lithography, there are ways to interface that microscope where you can control the beam. But this isn’t the way that aberration-corrected scanning transmission electron microscopes are set up.”
Enter Stephen Jesse, leader of CNMS’s Directed Nanoscale Transformations theme. This group looks at tools that scientists use to see and understand matter and its nanoscale properties in a new light, and explores whether those tools can also transform matter one atom at a time and build structures with specified functions. “Think of what we are doing as working in nanoscale laboratories,” Jesse said. “This means being able to induce and stop reactions at will, as well as monitor them while they are happening.”
Jesse had recently developed a system that serves as an interface between a nanolithography pattern and a STEM’s scan coils, and ORNL researchers had already used it to selectively transform solids. The microscope focuses the electron beam to a fine point, which microscopists could move just by taking control of the scan coils. Unocic with Andrew Lupini, Albina Borisevich and Sergei Kalinin integrated Jesse’s scan control/nanolithography system within the microscope so that they could control the beam entering the liquid cell. David Cullen performed subsequent chemical analysis.
“This beam-induced nanolithography relies critically on controlling chemical reactions in nanoscale volumes with a beam of energetic electrons,” said Jesse. The system controls electron-beam position, speed and dose. The dose—how many electrons are being pumped into the system—governs how fast chemicals are transformed.
This nanoscale technology is similar to larger-scale activities, such as using electron beams to transform materials for 3D printing at ORNL’s Manufacturing Demonstration Facility. In that case, an electron beam melts powder so that it solidifies, layer by layer, to create an object.
“We’re essentially doing the same thing, but within a liquid,” Unocic said. “Now we can create structures from a liquid-phase precursor solution in the shape that we want and the chemistry that we want, tuning the physiochemical properties for a given application.”
Precise control of the beam position and the electron dose produces tailored architectures. Encapsulating different liquids and sequentially flowing them during patterning customizes the chemistry too.
The current resolution of metallic “pixels” the liquid ink can direct-write is 40 nanometers, or twice the width of an influenza virus. In future work, Unocic and colleagues would like to push the resolution down to approach the state of the art of conventional nanolithography, 10 nanometers. They would also like to fabricate multi-component structures.