Category Archives: Process Materials

Electrons can extend our view of microscopic objects well beyond what’s possible with visible light–all the way to the atomic scale. A popular method in electron microscopy for looking at tough, resilient materials in atomic detail is called STEM, or scanning transmission electron microscopy, but the highly-focused beam of electrons used in STEM can also easily destroy delicate samples.

This is why using electrons to image biological or other organic compounds, such as chemical mixes that include lithium–a light metal that is a popular element in next-generation battery research–requires a very low electron dose.

Scientists at the Department of Energy’sc Lawrence Berkeley National Laboratory (Berkeley Lab) have developed a new imaging technique, tested on samples of nanoscale gold and carbon, that greatly improves images of light elements using fewer electrons.

The newly demonstrated technique, dubbed MIDI-STEM, for matched illumination and detector interferometry STEM, combines STEM with an optical device called a phase plate that modifies the alternating peak-to-trough, wave-like properties (called the phase) of the electron beam.

This phase plate modifies the electron beam in a way that allows subtle changes in a material to be measured, even revealing materials that would be invisible in traditional STEM imaging.

Another electron-based method, which researchers use to determine the detailed structure of delicate, frozen biological samples, is called cryo-electron microscopy, or cryo-EM. While single-particle cryo-EM is a powerful tool–it was named as science journal Nature‘s 2015 Method of the Year –it typically requires taking an average over many identical samples to be effective. Cryo-EM is generally not useful for studying samples with a mixture of heavy elements (for example, most types of metals) and light elements like oxygen and carbon.

“The MIDI-STEM method provides hope for seeing structures with a mixture of heavy and light elements, even when they are bunched closely together,” said Colin Ophus, a project scientist at Berkeley Lab’s Molecular Foundry and lead author of a study, published Feb. 29 in Nature Communications, that details this method.

If you take a heavy-element nanoparticle and add molecules to give it a specific function, conventional techniques don’t provide an easy, clear way to see the areas where the nanoparticle and added molecules meet.

“How are they aligned? How are they oriented?” Ophus asked. “There are so many questions about these systems, and because there wasn’t a way to see them, we couldn’t directly answer them.”

While traditional STEM is effective for “hard” samples that can stand up to intense electron beams, and cryo-EM can image biological samples, “We can do both at once” with the MIDI-STEM technique, said Peter Ercius, a Berkeley Lab staff scientist at the Molecular Foundry and co-author of the study.

The phase plate in the MIDI-STEM technique allows a direct measure of the phase of electrons that are weakly scattered as they interact with light elements in the sample. These measurements are then used to construct so-called phase-contrast images of the elements. Without this phase information, the high-resolution images of these elements would not be possible.

In this study, the researchers combined phase plate technology with one of the world’s highest resolution STEMs, at Berkeley Lab’s Molecular Foundry, and a high-speed electron detector.

They produced images of samples of crystalline gold nanoparticles, which measured several nanometers across, and the super-thin film of amorphous carbon that the particles sat on. They also performed computer simulations that validated what they saw in the experiment.

The phase plate technology was developed as part of a Berkeley Lab Laboratory Directed Research and Development grant in collaboration with Ben McMorran at University of Oregon.

The MIDI-STEM technique could prove particularly useful for directly viewing nanoscale objects with a mixture of heavy and light materials, such as some battery and energy-harvesting materials, that are otherwise difficult to view together at atomic resolution.

It also might be useful in revealing new details about important two-dimensional proteins, called S-layer proteins, that could serve as foundations for engineered nanostructures but are challenging to study in atomic detail using other techniques.

In the future, a faster, more sensitive electron detector could allow researchers to study even more delicate samples at improved resolution by exposing them to fewer electrons per image.

“If you can lower the electron dose you can tilt beam-sensitive samples into many orientations and reconstruct the sample in 3-D, like a medical CT scan. There are also data issues that need to be addressed,” Ercius said, as faster detectors will generate huge amounts of data. Another goal is to make the technique more “plug-and-play,” so it is broadly accessible to other scientists.

 

A new one atom-thick flat material that could upstage the wonder material graphene and advance digital technology has been discovered by a physicist at the University of Kentucky working in collaboration with scientists from Daimler in Germany and the Institute for Electronic Structure and Laser (IESL) in Greece.

Reported in Physical Review B, Rapid Communication, the new material is made up of silicon, boron and nitrogen – all light, inexpensive and earth abundant elements – and is extremely stable, a property many other graphene alternatives lack.

“We used simulations to see if the bonds would break or disintegrate – it didn’t happen,” said Madhu Menon, a physicist in the UK Center for Computational Sciences. “We heated the material up to 1,000 degree Celsius and it still didn’t break.”

Using state-of-the-art theoretical computations, Menon and his collaborators Ernst Richter from Daimler and a former UK Department of Physics and Astronomy post-doctoral research associate, and Antonis Andriotis from IESL, have demonstrated that by combining the three elements, it is possible to obtain a one atom-thick, truly 2D material with properties that can be fine-tuned to suit various applications beyond what is possible with graphene.

While graphene is touted as being the world’s strongest material with many unique properties, it has one downside: it isn’t a semiconductor and therefore disappoints in the digital technology industry. Subsequent search for new 2D semiconducting materials led researchers to a new class of three-layer materials called transition-metal dichalcogenides (TMDCs). TMDCs are mostly semiconductors and can be made into digital processors with greater efficiency than anything possible with silicon. However, these are much bulkier than graphene and made of materials that are not necessarily earth abundant and inexpensive.

Searching for a better option that is light, earth abundant, inexpensive and a semiconductor, the team led by Menon studied different combinations of elements from the first and second row of the Periodic Table.

Although there are many ways to combine silicon, boron and nitrogen to form planar structures, only one specific arrangement of these elements resulted in a stable structure. The atoms in the new structure are arranged in a hexagonal pattern as in graphene, but that is where the similarity ends.

The three elements forming the new material all have different sizes; the bonds connecting the atoms are also different. As a result, the sides of the hexagons formed by these atoms are unequal, unlike in graphene. The new material is metallic, but can be made semiconducting easily by attaching other elements on top of the silicon atoms.

The presence of silicon also offers the exciting possibility of seamless integration with the current silicon-based technology, allowing the industry to slowly move away from silicon instead of eliminating it completely, all at once.

“We know that silicon-based technology is reaching its limit because we are putting more and more components together and making electronic processors more and more compact,” Menon said. “But we know that this cannot go on indefinitely; we need smarter materials.”

Furthermore, in addition to creating an electronic band gap, attachment of other elements can also be used to selectively change the band gap values – a key advantage over graphene for solar energy conversion and electronics applications.

Other graphene-like materials have been proposed but lack the strengths of the material discovered by Menon and his team. Silicene, for example, does not have a flat surface and eventually forms a 3D surface. Other materials are highly unstable, some only for a few hours at most.

The bulk of the theoretical calculations required were performed on the computers at the UK Center for Computational Sciences with collaborators Richter and Andriotis directly accessing them through fast networks. Now the team is working in close collaboration with a team led by Mahendra Sunkara of the Conn Center for Renewable Energy Research at University of Louisville to create the material in the lab. The Conn Center team has had close collaborations with Menon on a number of new materials systems where they were able to test his theory with experiments for a number of several new solar materials.

“We are very anxious for this to be made in the lab,” Menon said. “The ultimate test of any theory is experimental verification, so the sooner the better!”

Some of the properties, such as the ability to form various types of nanotubes, are discussed in the paper but Menon expects more to emerge with further study.

“This discovery opens a new chapter in material science by offering new opportunities for researchers to explore functional flexibility and new properties for new applications,” he said. “We can expect some surprises.”

Soitec (Euronext), a manufacturer of semiconductor materials and a supplier of wafers for radio-frequency silicon-on-insulator (RF-SOI) applications, has begun mass production of 300mm RF-SOI substrates for mobile communications. The 300mm version of Soitec’s RFeSI90 substrate is made possible by the company’s proprietary technologies, long-time experience with 200mm RF-SOI and 300mm high-volume manufacturing expertise. These advanced wafers open the door for new enhancements that enable more highly integrated ICs for 4G/LTE-Advanced communications and the next generation of wireless technologies, including 5G.

This announcement comes at the same time as Soitec reports cumulative sales of one million 200mm RF-SOI wafers since 2009, hitting a milestone that underscores the pivotal role of RF-SOI in the booming wireless communications market. The one million RF-SOI wafers manufactured and shipped by Soitec have yielded approximately 20 billion ICs for front-end modules (FEMs). Soitec’s RF-SOI substrates are now integral in manufacturing antenna switches, antenna tuners, some power amplifiers and WiFi circuits, meeting the demanding requirements of leading-edge smart phone ICs. They have been widely adopted by leading RF semiconductor companies to address cost, performance and integration needs for the 3G and 4G/LTE mobile wireless markets.

“The widespread use of Soitec’s materials technology in existing 3G and 4G portable communications demonstrates the important role of RF-SOI in high-volume, cost-sensitive applications such as cellular phones, tablets and other fast-growing markets involving mobile internet devices,” said Bernard Aspar, senior vice president of Soitec’s Communication & Power Business Unit. “Now the high-volume availability of our newest 300mm RF-SOI offering enables our customers and their customers to continue to deliver higher performance while giving them access to foundries’ larger global production capacities and more manufacturing flexibility.”

While Soitec has been shipping large volumes of 200mm RF-SOI wafers for many years and continuing to increase its 200mm production capacity, the company has been delivering over the past 18 months.

300mm RFeSI90 wafer samples for product qualification. Key partnerships with fabless semiconductor companies and foundries have been instrumental in achieving the production milestones and performance levels of Soitec’s new 300mm RF-SOI product. The large supply of 300mm wafers allows Soitec’s customers to expand their production capacities for RF-SOI devices and produce more highly integrated ICs.

The new wafers – based on a more advanced SOI process – offer higher levels of performance such as better uniformity, a key parameter in achieving greater control of transistor matching for analog semiconductor designs and allowing designs with thinner transistors and additional process options to improve RonCoff performance, the figure of merit that is used to rate the performance of an RF switch.

Soitec continues to work on future generations of RF-SOI substrates with a product roadmap to further enable more innovation and cost effectiveness for future mobile communication markets.

Neon shortage coming


February 18, 2016

The current Neon demand is growing in “stealth mode” – hidden from the layman’s view because of significant factors only analysts fully versed in lithography, OLED/FPD and semiconductor device trends would catch. The traditional method of using historical data to predict future Neon demand will grossly underestimate future usage.

“Those who are basing their thinking on projections of historical Neon growth are in for a big surprise,” said TECHCET’s President/CEO, Lita Shon-Roy.   “Even with the recovery of the Neon supply chain, Neon conservation actions, and new sources in China, we predict that Neon demand will grow faster than Neon supply,” she added.

The largest and most rapidly growing Neon demand drivers are Lasik, OLED/FPD (displays) and DUV lithography. However, Neon gas consumed by DUV excimer laser gases is growing at a faster pace and represents more than 90% of world’s Neon consumption.

Semiconductor lithographic use of Neon is increasing more rapidly than expected for several reasons including the delay of EUVL while demand for finer line width patterning is increasing. In addition, new consumer related markets drive increased usage of legacy device processing. Each increase in the number of lithographic steps increases the need for more DUV lithography tools, and drives up the volume demand for Neon. This is true for V-NAND process flows, as well as DRAM and Logic devices dependent on multi-patterning.

Currently, the installed base of DUV lithography tools is ~ 4,400. In contrast, there have only been a dozen or so EUVL tools shipped through the end of 2015.

“The continued growth of DUV tools will push up demand for NEON beyond which supply can support,” cautioned Shon-Roy.

More details can be found from TECHCET’s latest Critical Materials Report on NEON Supply & Demand. Information will also be presented at the CMC Conference, scheduled for May 5-6, in Hillsboro, Oregon – this is the open forum portion of the Critical Materials Council meetings. For more information go to http://techcet.com/product/neon-a-supply-alert-report/ For more information on the CMC Conference please go to www.cmcfabs.org/seminars/

CMC Fabs is a membership based group that actively works to identify issues surrounding the supply, availability, and accessibility of semiconductor process materials, current and emerging, “Critical Materials.” CMC Fabs is managed by TECHCET CA LLC, a firm focused on Process Materials Supply Chains, Electronic Materials Technology Trends, and Materials Market Analysis for the Semiconductor, Display, Solar/PV, and LED Industries. The Company has been responsible for producing the SEMATECH Critical Material Reports since 2000.

University of Colorado Boulder researchers have demonstrated the use of the world’s first ultrafast optical microscope, allowing them to probe and visualize matter at the atomic level with mind-bending speed.

The ultrafast optical microscope assembled by the research team is 1,000 times more powerful than a conventional optical microscope, said CU-Boulder physics Professor Markus Raschke, lead study author. The “image frame” rate, or speed captured by the team, is 1 trillion times faster than the blink of an eye, allowing the researchers to make real-time, slow-motion movies of light interacting with electrons in nanomaterials – in this case a thin gold film.

“This is the first time anyone has been able to probe matter on its natural time and length scale,” said Raschke. “We imaged and measured the motions of electrons in real space and time, and we were able to make it into a movie to help us better understand the fundamental physical processes.”

A paper on the subject appears in the Feb. 8 issue of Nature Nanotechnology.

Matter is sometimes described as the “stuff of the universe” – the molecules, atoms and charged particles, or ions, that make up everything around us. Matter has several states, most prominently solid, liquid and gas.

According to the CU-Boulder researchers, a number of important processes like photosynthesis, energy conversion and use, and biological functions are based on the transfer of electrons and ions from molecule to molecule. The team used a technique called “plasmonic nanofocusing” to focus extraordinarily short laser pulses into tiny bits of gold film matter using a nanometer-sized metal tip.

“Our study brings nanoscale microscopy to the next level, with the ability to capture detailed images evolving on extremely fast time scales,” said Vasily Kravtsov, a CU-Boulder graduate student in physics and first author of the paper.

Other co-authors on the Nature Nanotechnology paper include CU-Boulder postdoctoral researcher Ronald Ulbricht and former CU-Boulder postdoctoral researcher Joanna Atkin, now a faculty member at the University of North Carolina-Chapel Hill.

“This work expands the reach of optical microscopes,” said Raschke. “Using this technique, researchers can image the elementary processes in materials ranging from battery electrodes to solar cells, helping to improve their efficiency and lifetime.”

Unlike electron microscope approaches, the new technique does not require ultra-high vacuum techniques and is particularly promising for studying ultrafast processes like charge and energy transport in soft matter, including biological materials, said Kravtsov.

A team of Korean researchers, affiliated with UNIST has recently pioneered in developing a new type of multilayered (Au NPs/TiO2/Au) photoelectrode that boosts the ability of solar water-splitting to produce hydrogen. According to the research team, this special photoelectrode, inspired by the way plants convert sunlight into energy is capable of absorbing visible light from the sun, and then using it to split water molecules (H2O) into hydrogen and oxygen.

This study is a collaboration among scientists, including Prof. Jeong Min Baik (School of Materials Science and Engineering, UNIST), Prof. Jae Sung Lee (School of Energy and Chemical Engineering, UNIST), Prof. Heon Lee (School of Materials Science and Engineering, Korea University), and Prof. Jonghwa Shin (Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology).

This multilayered photoelectrode takes the form of two-dimensional hybrid metal-dielectric structure, which mainly consists of three layers of gold (Au) film, ultrathin TiO2 layer (20 nm), and gold nanoparticles (Au NPs). In a study, reported in the January 21, 2016 issue of Nano Energy, the team reported that this promising photoelectrode shows high light absorption of about 90% in the visible range 380-700nm, as well as significant enhancement in photo-catalytic applications.

Many structural designs, such as hierarchical and branched assemblies of nanoscale materials have been suggested to increase the UV-visible absorption and to enhance water-splitting efficiency. However, through incorporation of plasmonic metal nanoparticles (i.e. Au) to TiO2 structures, their photoelectrodes have shown to enhance the photoactivity in the entire UV-visible region of solar spectrum when compared to the existing ones, the team reports.

Prof. Jeong Min Baik of UNIST (School of Materials Science and Engineering) states, “Several attemps have been made to use UV-based photoelectrodes for hydrogen production, but this is the first time to use the metal-dielectric hybrid-structured film with TiO2 for oxygen production.” Moreover, according to Prof. Baik, this special type of photoelectrode uses approximately 95% of the visible spectrum of sunlight, which makes up a substantial portion (40%) of full sunlight. He adds, “The developed technology is expected to improve hydrogen production efficiency.”

Prof. Heon Lee (Korean University) states, “This metal-dielectric hybrid-structured film is expected to further reduce the overall cost of producing hydrogen, as it doesn’t require complex operation processes.” He continues by saying, “Using nanoimprint lithography, mass production of hydrogen will be soon possible.”

Prof. Baik adds, “This simple system may serve as an efficient platform for solar energy conversion, utilizing the whole UV-visible range of solar spectrum based on two-dimensional plasmonic photoelectrodes.”

This work was supported by the Pioneer Center Program through the National Research Foundation of Korea (NRF) grant, funded by the Korean government (MSIP). It has been also equivalently funded by the 2014 Research Fund of UNIST (Ulsan National Institute of Science and Technology), as well as by the KIST-UNIST partnership program.

In what may provide a potential path to processing information in a quantum computer, researchers have switched an intrinsic property of electrons from an excited state to a relaxed state on demand using a device that served as a microwave “tuning fork.”

The team’s findings could also lead to enhancements in magnetic resonance techniques, which are widely used to explore the structure of materials and biomolecules, and for medical imaging.

The international research team, which included scientists at the Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab), demonstrated how to dramatically increase the coupling of microwaves in a specially designed superconducting cavity to a fundamental electron property called spin–which, like a coin, can be flipped.

By zapping an exotic silicon material developed at Berkeley Lab with the microwaves, they found that they could rapidly change the electron spins from an excited state to a relaxed, ground state by causing the electrons to emit some of their energy in the form of microwave particles known as photons.

Left on their own, the electron spins would be extremely unlikely to flip back to a relaxed state and to also emit a photon – the natural rate for this light-emitting effect, known as the Purcell effect, is about once every 10,000 years. The experiment demonstrated an accelerated, controllable relaxation of electron spins and the release of a microwave photon in about 1 second, said Thomas Schenkel, a physicist in Berkeley Lab’s Accelerator Technology and Applied Physics Division who led the design and development of the silicon-bismuth sample used in the experiment.

“It’s like a juggler who throws the balls up, and the balls come down 1,000 times faster than normal, and they also emit a microwave flash as they drop,” he said. The results were published online Feb. 15 in the journal Nature.

“Our results are highly significant for quantum information processing,” said Patrice Bertet, a quantum electronics scientist at the French Atomic Energy Commission (CEA) who led the experiment. “Indeed, they are a first step toward the strong coupling of individual electron spins to microwave photons, which could form the basis of a new spin-based quantum computer architecture.”

John Morton, a professor at the London Center for Nanotechnology and co-author of the study, said, “Our ultimate aim is to find a link between quantum information that is fixed and quantum information that can be transported by photons.”

In today’s computers, information is stored as individual bits, and each bit can either be a one or a zero. Quantum computers, though, could conceivably be exponentially more powerful than modern computers because they would use a different kind of bit, called a qubit, that because of the weird ways of quantum mechanics can simultaneously behave as both a one and a zero.

A coupled array of qubits would allow a quantum computer to perform many, many calculations at the same time, and electron spins are candidates for qubits in a quantum computer. The latest study shows how the microwave photons could work in concert with the spins of electrons to move information in a new type of computer.

“What we need now is ways to wire up these systems–to couple these spins together,” Morton said. “We need to make coupled qubits that can perform computations.”

In the experiment, conducted at CEA in France, a small sample of a highly purified form of silicon was implanted with a matrix of bismuth atoms, and a superconducting aluminum circuit was deposited on top to create a high-quality resonant cavity that allowed precise tuning of the microwaves. The electron spins of the bismuth atoms were then flipped into the excited, “spin-up” state.

The microwave cavity was then tuned, like a musical tuning fork, to a particular resonance that coaxed the spins into emitting a photon as they flipped back to a relaxed state. The cavity boosted the number of states into which a photon can be emitted, which greatly increased the decay rate for the electron spins in a controllable way. The technique is much like buying more lottery tickets to increase your chances of winning, Morton said.

The large bismuth atoms embedded in the silicon sample provided the electrons with unique spin properties that enabled the experiment. Schenkel said that implanting the bismuth atoms into the delicate silicon framework, a process known as “doping,” was “like squeezing bowling balls into a lattice of ping-pong balls.”

“We did a new trick with silicon. People wouldn’t expect you could squeeze anything new out of silicon,” Schenkel said. “Now we’re looking into further improving bismuth-doped silicon and into tailoring the spin properties of other materials, and using this experimental technique for these materials.”

To enhance the performance of materials used in future experiments, Schenkel said it will be necessary to improve the doping process so it is less damaging to the silicon lattice. Also, the implantation process could be designed to produce regularly spaced arrays of individual electron spins that would be more useful for quantum computing than a concentrated ensemble of electron spins.

“We are now doing experiments on processing this and other materials at higher temperature and pressure with nanosecond ion pulses at NDCX-II, one of the accelerators here at Berkeley Lab,” Schenkel said. “There are indications that it will improve the overall spin quality.”

Researchers said the latest research could potentially prove useful in boosting the sensitivity of scientific techniques like nuclear magnetic resonance spectroscopy and dynamic nuclear polarization, useful for a range of experiments, and could also shorten experimental times by manipulating spin properties.

“You need a way to reset spins–the ability to cause them to relax on demand to improve the rate at which you can repeat an experiment,” Morton said.

Bertet said it may be possible to further accelerate the electron-flipping behavior to below 1 millisecond, compared to the 1-second rate in the latest results.

“This will then open the way to many new applications,” he said.

Engineering material magic


February 15, 2016

University of Utah engineers have discovered a new kind of 2D semiconducting material for electronics that opens the door for much speedier computers and smartphones that also consume a lot less power.

The semiconductor, made of the elements tin and oxygen, or tin monoxide (SnO), is a layer of 2D material only one atom thick, allowing electrical charges to move through it much faster than conventional 3D materials such as silicon. This material could be used in transistors, the lifeblood of all electronic devices such as computer processors and graphics processors in desktop computers and mobile devices. The material was discovered by a team led by University of Utah materials science and engineering associate professor Ashutosh Tiwari. A paper describing the research was published online Monday, Feb. 15, 2016 in the journal, Advanced Electronic Materials. The paper, which also will be the cover story on the printed version of the journal, was co-authored by University of Utah materials science and engineering doctoral students K. J. Saji and Kun Tian, and Michael Snure of the Wright-Patterson Air Force Research Lab near Dayton, Ohio.

University of Utah materials science and engineering associate professor Ashutosh Tiwari holds up a substrate layered with a newly discovered 2-D material made of tin and oxygen. Tiwari and his team have discovered this new material, tin monoxide, which allows electrical charges to move through it much faster than common 3-D material such as silicon. This breakthrough in semiconductor material could lead to much faster computers and mobile devices such as smartphones that also run on less power and with less heat. Credit: Dan Hixson/University of Utah College of Engineering

University of Utah materials science and engineering associate professor Ashutosh Tiwari holds up a substrate layered with a newly discovered 2-D material made of tin and oxygen. Tiwari and his team have discovered this new material, tin monoxide, which allows electrical charges to move through it much faster than common 3-D material such as silicon. This breakthrough in semiconductor material could lead to much faster computers and mobile devices such as smartphones that also run on less power and with less heat. Credit: Dan Hixson/University of Utah College of Engineering

Transistors and other components used in electronic devices are currently made of 3D materials such as silicon and consist of multiple layers on a glass substrate. But the downside to 3D materials is that electrons bounce around inside the layers in all directions.

The benefit of 2D materials, which is an exciting new research field that has opened up only about five years ago, is that the material is made of one layer the thickness of just one or two atoms. Consequently, the electrons “can only move in one layer so it’s much faster,” says Tiwari.

While researchers in this field have recently discovered new types of 2D material such as graphene, molybdenun disulfide and borophene, they have been materials that only allow the movement of N-type, or negative, electrons. In order to create an electronic device, however, you need semiconductor material that allows the movement of both negative electrons and positive charges known as “holes.” The tin monoxide material discovered by Tiwari and his team is the first stable P-type 2D semiconductor material ever in existence.

“Now we have everything — we have P-type 2D semiconductors and N-type 2D semiconductors,” he says. “Now things will move forward much more quickly.”

Now that Tiwari and his team have discovered this new 2D material, it can lead to the manufacturing of transistors that are even smaller and faster than those in use today. A computer processor is comprised of billions of transistors, and the more transistors packed into a single chip, the more powerful the processor can become.

Transistors made with Tiwari’s semiconducting material could lead to computers and smartphones that are more than 100 times faster than regular devices. And because the electrons move through one layer instead of bouncing around in a 3D material, there will be less friction, meaning the processors will not get as hot as normal computer chips. They also will require much less power to run, a boon for mobile electronics that have to run on battery power. Tiwari says this could be especially important for medical devices such as electronic implants that will run longer on a single battery charge.

“The field is very hot right now, and people are very interested in it,” Tiwari says. “So in two or three years we should see at least some prototype device.”

Ever smaller, ever faster, ever cheaper – since the start of the computer age the performance of processors has doubled on average every 18 months. 50 years ago already, Intel co-founder Gordon E. Moore prognosticated this astonishing growth in performance. And Moore’s law seems to hold true to this day.

But the miniaturization of electronics is now reaching its physical limits. “Today already, transistors are merely a few nanometers in size. Further reductions are horrendously expensive,” says Professor Jonathan Finley, Director of the Walter Schottky Institute at TUM. “Improving performance is achievable only by replacing electrons with photons, i.e. particles of light.”

Photonics – the silver bullet of miniaturization

Data transmission and processing with light has the potential of breaking the barriers of current electronics. In fact, the first silicon-based photonics chips already exist. However, the sources of light for the transmission of data must be attached to the silicon in complicated and elaborate manufacturing processes. Researchers around the world are thus searching for alternative approaches.

Scientists at the TU Munich have now succeeded in this endeavor: Dr. Gregor Koblmüller at the Department of Semiconductor Quantum-Nanosystems has, in collaboration with Jonathan Finley, developed a process to deposit nanolasers directly onto silicon chips. A patent for the technology is pending.

The candidate Benedikt Mayer and Masters student Lisa Janker in an experiment at the molecular beam epitaxy in the Walter Schottky Institute of the Technische Universitaet Muenchen am teaching Suhl for semiconductor nanostructures and quantum devices, with Prof. Dr. Jonathan Finley; persons depicted (from left): Benedikt Mayer, Lisa Janker; Location: Walter Schottky Institute, Am Coulombwall 4, 85748 Garching, Germany; Date: 02/10/2016; CREDIT: Uli Benz / TU Muenchen

The candidate Benedikt Mayer and Masters student Lisa Janker in an experiment at the molecular beam epitaxy in the Walter Schottky Institute of the Technische Universitaet Muenchen am teaching Suhl for semiconductor nanostructures and quantum devices, with Prof. Dr. Jonathan Finley; persons depicted (from left): Benedikt Mayer, Lisa Janker; Location: Walter Schottky Institute, Am Coulombwall 4, 85748 Garching, Germany; Date: 02/10/2016; CREDIT: Uli Benz / TU Muenchen

Growing a III-V semiconductor onto silicon requires tenacious experimentation. “The two materials have different lattice parameters and different coefficients of thermal expansion. This leads to strain,” explains Koblmüller. “For example, conventional planar growth of gallium arsenide onto a silicon surface results therefore in a large number of defects.”

The TUM team solved this problem in an ingenious way: By depositing nanowires that are freestanding on silicon their footprints are merely a few square nanometers. The scientists could thus preclude the emerging of defects in the GaAs material.

Atom by atom to a nanowire

But how do you turn a nanowire into a vertical-cavity laser? To generate coherent light, photons must be reflected at the top and bottom ends of the wire, thereby amplifying the light until it reaches the desired threshold for lasing.

To fulfil these conditions, the researchers had to develop a simple, yet sophisticated solution: “The interface between gallium arsenide and silicon does not reflect light sufficiently. We thus built in an additional mirror – a 200 nanometer thick silicon oxide layer that we evaporated onto the silicon,” explains Benedikt Mayer, doctoral candidate in the team led by Koblmüller and Finley. “Tiny holes can then be etched into the mirror layer. Using epitaxy, the semiconductor nanowires can then be grown atom for atom out of these holes.”

Only once the wires protrude beyond the mirror surface they may grow laterally – until the semiconductor is thick enough to allow photons to jet back and forth to allow stimulated emission and lasing. “This process is very elegant because it allows us to position the nanowire lasers directly also onto waveguides in the silicon chip,” says Koblmüller.

GaAs nanowires on a silicon surface - Picture: Thomas Stettner / Philipp Zimmermann / TUM

GaAs nanowires on a silicon surface – CREDIT: Thomas Stettner / Philipp Zimmermann / TUM

Basic research on the path to applications

Currently, the new gallium arsenide nanowire lasers produce infrared light at a predefined wavelength and under pulsed excitation. “In the future we want to modify the emission wavelength and other laser parameters to better control temperature stability and light propagation under continuous excitation within the silicon chips,” adds Finley.

The team has just published its first successes in this direction. And they have set their sights firmly on their next goal: “We want to create an electric interface so that we can operate the nanowires under electrical injection instead of relying on external lasers,” explains Koblmüller.

“The work is an important prerequisite for the development of high-performance optical components in future computers,” sums up Finley. “We were able to demonstrate that manufacturing silicon chips with integrated nanowire lasers is possible.”

The research was funded by the German Research Foundation (DFG) through the TUM Institute for Advanced Study, the Excellence Cluster Nanosystems Initiative Munich (NIM) and the International Graduate School of Science and Engineering (IGSSE) of the TUM, as well as by IBM through an international postgraduate program.

A novel SACVD PMD invention sets the benchmark for helium reduction efforts by achieving four key objectives: cost reduction, quality, process robustness and productivity.

BY JAE HEE KIM, Thin Film Dielectric Fabrication Engineering, Texas Instruments, Dallas, TX

The United States is the world’s largest helium supplier and half of its supply comes from a helium reserve regulated by the Bureau of Land Management just outside of Amarillo, Texas. As many predict, at the current rate of production the maximum expected life of this reserve is 2020. As a result of a shortage that began in 2013, the cost of bulk helium has been increasing significantly (FIGURE 1).

Helium 1

Considering semiconductor manufacturing is one of largest helium consuming industries [2], it becomes crucial to invest continuous efforts to minimize helium usage during wafer fabrication processes and to identify new opportunities for helium reduction. In this article, we’ll take a look at a new innovative process to do just that.

Sub-Atmospheric Chemical Vapor Deposition (SACVD) for pre-metal layer consumes a significant amount of helium to assist in process gas delivery during deposition and in-situ chamber clean which makes the best candidate for helium reduction effort benchmarking. Also, SACVD Pre-Metal Dielectric (PMD) consists of various processes including phosphosilicate glass (PSG) and borophospho-silicate glass (BPSG) which makes the fan-out process more applicable for a bigger impact on helium reduction. So how do we do it?

Objectives

There are four key objectives to a new SACVD PMD process development that my team has looked at: cost, quality, process robustness, and productivity. First, a new carrier gas was identified to maximize helium usage reduction. Second, solutions to both new hardware and process conditions were developed for quality improvement. A new blocker plate was qualified to improve within wafer thickness uniformity. Additionally, gas conditions were developed to improve the gap-fill capability for leakage reduction. Third, a new pressure condition was qualified for process robustness improvement. An old two-step baseline process was designed for better gap fill by depos- iting initial 4kA film at 700Torr for lower deposition rate and the rest of the film at BKM pressure, 200Torr for better cycle time. However, this baseline two-step process, which operates at near atmospheric pressure on a sub-atmospheric CVD tool platform, is marginal for pumping speed degradation which leads to inline defect. Susceptibility of defect formation was reduced by lowering process pressure from 700Torr to 600Torr during the initial PMD layer. Last, overall process conditions were evaluated to achieve a desirable deposition rate in order to ensure comparable manufacturing throughput. Furthermore, a new process condition was selected to avoid process chamber restriction for flexibility of manufacturing.

New process carrier gas identification

Initial process development was divided into two categories: BPSG and PSG. Development began with PSG since there is one less process parameter, Boron compared to BPSG process. Preliminary tests showed that a 100 percent N2 carrier drives an unstable film thickness range. Based on findings, a helium and nitrogen mix carrier gas was selected for further process evaluation. The main focus at this stage of evaluation were to identify process conditions including a helium and nitrogen mix carrier gas flow to achieve maximum helium savings, comparable cycle time, and thickness uniformity improvement.

Process condition development

Based on design of experiments (DOE) with four key process parameters (N2, He, O3, spacing), we learned that deposition rate is faster with increasing He and slower with increasing N2 and O3. Thickness uniformity degrades with total carrier gas flow. Based on DOE results, initial proposed condition was carrier 5500sccm (3:1 = N2:He), O3 3000sccm, spacing 200mils for better thickness uniformity and shorter cycle time while saving the maximum amount of helium.

Unfortunately, this condition degraded at baseline margin to form voids in 700Torr deposition film due to faster deposition rate. Focus was then shifted to identify a recipe condition that lowers the deposition rate during 700Torr deposition for a better gap fill capability which also can be used for both 200Torr PSG and two-step PSG to ensure manufacturing flexibility.

Based on deposition rate DOE with three parameters including Ozone, tetraethyl orthosilicate (TEOS) and spacing (TABLE 1), ozone flow has first-order effects on the deposition rate, and spacing has second-order effects. TEOS flow has third-order effects on deposition rates but also reduces dopant concentration of film. Temperature change was not considered since it affects other recipe conditions at a greater degree. Increasing pressure was also not considered since the process already operates at a high pressure of 700Torr.

Helium Table 1

Then it was decided to include Ozone and spacing, in addition to helium and nitrogen, into further process characterization. We ran comprehensive three factorial DOE to deposit 4kA PSG film at 700Torr at various settings of total carrier flow, spacing, and ozone. This was in order to achieve a lower deposition rate for better gap fill and good thickness uniformity. DOE conditions were determined based on JMP prediction profiler and calculators to evaluate a wide spectrum of different deposition rates at 700Torr and thickness range.

To evaluate the DOE result, two techniques were used. First, wafer samples were prepared by sputtering top down until they reached the very initial layer of PMD to open up any voids that are present in PSG film. Effectiveness of gap-fill capability was rated by quantifying a number of voids on the scanning electron microscopy (SEM) images captured at same magnification on the consistent location of the wafer sample. This is a more effective technique than collecting transmission electron microscopy (TEM) on a defined location on samples since top down SEM can capture broader areas of wafer samples. Second, wafers were also submitted for dynamic secondary ion mass spectrometry (SIMS) to ensure if the dopant profile throughout PSG film is comparable to the baseline. This critical step is to verify that there is no sign of unstable dopant distribution that could lead to any adverse effects, such as increased etch selectivity or poor gettering (FIGURE 2).

Helium 2

Based on DSIMS collected, it was found that the dopant concentration profile becomes unstable if the total carrier gas flow is less than 5500sccm. Phosphorous (P) concentration profile shows fluctuation all throughout the film at a total carrier gas flow less than 5500sccm while phosphorous percent profile was steady at total carrier gas at 5500sccm or higher (FIGURE 3).

Helium 3

Among many conditions that satisfy a total carrier gas flow of less than 5500sccm, when ozone flow is 5000sccm and total carrier gas is 5500sccm with a 3:1 ratio of nitrogen to helium, the top down SEM result shows a greatly reduced number of voids in film. This means the deposition rate during 700Torr is slow enough to improve gap-fill capability. At the same time, Ozone flow at 5000sccm was fast enough during 200Torr to maintain a comparable cycle time. Therefore, this condition can be used for both single step PSG and two-step PSG which allows flexibility for manufacturing to run both processes without equipment restriction. Dynamic SIMS also verified that this condition provided a stable dopant profile. Thickness uniformity was also comparable to the baseline on this recipe condition. Therefore, spacing 200mils, ozone 5000sccm, and a total carrier flow 5500sccm was chosen as a finalized new PSG condition.

For the BPSG process, the same technique was used for evaluation. DSIMS was used to ensure both Boron and phosphorous concentration profiles are comparable. The same carrier gas conditions with nitrogen and helium at a ratio of 3:1 of 5500sccm and Ozone 5000sccm were selected for the final condition. TEOS was increased from 600mgm to 800mgm to make sure the deposition rate is comparable to maintain manufacturing cycle time at PMD (TABLE 2).

Helium Table 2

Flash parametric legacy issue improvement

A high aspect ratio of device structure can cause voids in PMD that lead to poor isolation and yield loss. There are many contributing factors that modulate PMD voids, including a stacked gate vertical profile and a sidewall spacer profile. Among all contributing factors, however, a void-free PMD process was proven to be the most effective way to minimize leakage. The void-free PMD was achieved by qualifying a new two-step PSG process with a mix carrier gas.

The new two-step PSG process with a mix carrier greatly lowers the deposition rate during the initial PMD layer. This helps deposit film more uniformly at higher pressures to minimize voids, while depositing the rest of the PMD at a faster deposition rate at lower pressure helps to compensate cycle time loss from the initial deposition.

The new two-step PSG alleviates leakage susceptibility on the wafer edge and reduces sensitivity to the PMD void-contributing factors by adding significant margins to leakage failure due to voids. Notably, the PMD gap-fill improvement added significant integration marginality between the sidewall spacer profile and the PMD which led to lower process and tool sensitivity at the sidewall spacer etch. This increases manufacturing capacity by releasing sidewall spacer etch process chambers with historical leakage failure susceptibility to production. Most importantly, parametric outlier probability was greatly improved by 20 percent and a zero standard parametric failure rate was achieved by qualifying void-free PMD (FIGURE 4).

FIGURE 4. Void-free PMD (right) shows excellent gap fill while baseline PMD (left) shows a void filled with W [3].

FIGURE 4. Void-free PMD (right) shows excellent gap fill while baseline PMD (left) shows a void filled with W [3].

Process robustness improvement

There were technical challenges with center cluster defects on the new two-step process. Center cluster defects affected isolation contact resistance. Based on TEM (FIGURE 5), defects formed around where a low deposition rate completed and a faster deposition rate resumed. Dynamic SIMS showed a phosphorous concen- tration peak at the defect which explained why this defect had a high contact etch selectivity.

Helium 5

After exposing the test wafer for 24 hours at atmosphere, haze was formed on its substrate. Time of flight secondary ion mass spectroscopy showed that haze was caused by a reaction between excessive phosphorous and atmospheric moisture. Additionally, a repeatability test showed that the tail of cluster defects extended towards gas exhaust. Based on these findings, this baseline two-step process which operates at near-atmospheric pressure on a sub-atmospheric CVD tool platform is marginal to maintain sufficient pumping speed during pressure transition from high process pressure to low process pressure (FIGURE 6). This significantly increased the chances of forming center cluster defects with a heavier carrier gas. This is because the pumping speed is lower at a higher pressure and mean residence time is longer at a higher pressure. Additionally, conductance is lower with N2 than with He due to heavier molecular weight.

Helium 6

In order to address this issue, the new two-step process was reevaluated and a new process condition was developed. As summarized in TABLE 3, it was decided to maintain the same carrier gas flow to maintain bulk helium savings. Pressure condition for the first deposition step was modified from 700Torr to 600Torr. This new two-step process improved robustness by reducing risks of pumping speed degra- dation during the pressure transition from 600Torr to 200Torr. The new two-step process is also able to deliver a strong PMD void-fill improvement by maintaining a zero parametric failure rate for leakage.

Helium Table 3

Thickness uniformity improvement

The new SACVD PMD invention took part not only in process development but also in hardware improvement. The new process with a baseline helium blocker plate that helps uniform process gases dispersion showed higher within wafer thickness range which appeared on wafer substrate as in forms of lightly discolored spots. Based on Energy Disperse Spectroscopy (EDS) and Dynamic SIMS, defects were a part of the top 270A of PSG film. The location of spots were nicely matched to the hole pattern of the helium blocker plate. The nitrogen blocker plate was qualified as it consisted of the same material as the helium blocker plate but had a more dense hole pattern. It was not only able to eradicate the anomaly on the surface film but also to alleviate the baseline starburst pattern on the deposited film.

DSIMS confirmed that the dopant profiles on the nitrogen blocker plates are comparable to the ones on the helium blocker plate. The nitrogen blocker plate improved within wafer thickness uniformity by 35 percent on a new PSG film ranging from 12kA to 16kA compared to an old PMD baseline performance (FIGURE 7). Consequently, this improved the process capability index at post PMD Chemical Mechanical Polish (CMP) by improving process targeting based on improved thickness uniformity.

Helium 7

Manufacturing and engineering productivity increased, as well, due to reduced tool down time. New blocker plate qualification also alleviated the sensitivity of film thickness uniformity to the heater age and possibly helped to extend heater life on the PSG chambers and reduce tool down time for range failure.

Conclusion

This novel SACVD PMD invention successfully set the benchmark for helium reduction efforts by achieving four key objectives: cost reduction, quality, process robustness, and productivity. It brings a substantial impact on bulk helium gas savings with worldwide limited supplies and increasing demand. The new PMD reduces bulk helium usage by 80.4 percent and 77.1 percent for PSG and BPSG respectively during deposition and completely eliminates helium usage during in-situ chamber clean.

This new process achieved outstanding gap-fill capability by lowering the deposition rate at initial PMD layer. The process successfully eliminated leakage failure at parametric by adding significant process integration marginality for void formation. It also improves process robustness by reducing risks of pumping speed degra- dation during the pressure transition from 600Torr to 200Torr. Process conditions are carefully developed for comparable manufacturing throughput and harmonized between single step PSG and two-step PSG in order to ensure manufacturing flexibility. Lastly, new hardware qualification also helps improve quality and productivity by lowering within wafer thickness range.

References

[1] C. Kaneshige, 2013, an excerpt from GE Healthcare published in 2012
[2] Semiconductor Industry Association, August 1, 2012, Hearing on “Helium: Supply Shortages Impacting our Economy, National Defense and Manufacturing” (Hearing held on July 10, 2012). Testimony for the Record of the Semiconductor Industry Association.
[3] D. Rodriguez, 2014, unpublished