A comparison of the etch mechanisms of germanium and silicon

Time multiplexed, deep reactive ion etching (DRIE) is a standard silicon microfabrication technique for fabricating MEMS sensors, actuators, and more recently in CMOS development for 2.5D and 3D memory devices.

At CHESS, we have adopted this microfabrication technique to develop novel x-ray optics called,Collimating Channel Arrays  (CCAs) [1], for confocal x-ray fluorescence microscopy (CXRF). Because the first CCA optics were fabricated from silicon substrates, the range of x-ray fluorescence energies for which they could be used, and hence the elements they could be used to study, was limited. Unwanted x-rays above about 11 keV could penetrate through the silicon, showing up as background and interfering with the measurement.

To solve the background problem, germanium substrates were used to fabricate the CCA optics. Germanium, which is much denser and therefore x-ray opaque than silicon, is also etch compatible with the fluorine etch chemistry for silicon DRIE. However, small differences in etch behavior between germanium and silicon can cause big differences in the outcome. Here, Genova et al JVST B [2] report a systematic comparison of  the etch mechanisms of silicon and germanium, performed with the Plasma Therm Versaline deep silicon etcher at the Cornell NanoScale Science & Technology Facility (CNF). The etch rates of silicon and germanium were compared by varying critical parameters in the DRIE process, especially the applied power and voltage used for each of 3 steps in the etch process,  on custom-designed wafers with a variety of features with systematically varying dimensions.

>Read more on the CHESS website

Image: (extract, full image here) SEM of high aspect ratio (>13:1) etched features in Si at 3.7 μm/min (a) and Ge at 3.4 μm/min (b)

Magnetic trick triples the power of SLAC’s X-ray laser

The new technique will allow researchers to observe ultrafast chemical processes previously undetectable at the atomic scale.

Scientists at the Department of Energy’s SLAC National Accelerator Laboratory have discovered a way to triple the amount of power generated by the world’s most powerful X-ray laser. The new technique, developed at SLAC’s Linac Coherent Light Source (LCLS), will enable researchers to observe the atomic structure of molecules and ultrafast chemical processes that were previously undetectable at the atomic scale.

The results, published in a Jan. 3 study in Physical Review Letters (PRL), will help address long-standing mysteries about photosynthesis and other fundamental chemical processes in biology, medicine and materials science, according to the researchers.

“LCLS produces the world’s most powerful X-ray pulses, which scientists use to create movies of atoms and molecules in action,” said Marc Guetg, a research associate at SLAC and lead author of the PRL study. “Our new technique triples the power of these short pulses, enabling higher contrast.”

>Read more on the LCSL website

Picture: The research team, from left: back row, Yuantao Ding, Matt Gibbs, Nora Norvell, Alex Saad, Uwe Bergmann, Zhirong Huang; front row, Marc Guetg and Timothy Maxwell.
Credit: Dawn Harmer/SLAC

 

Molecular dynamics on the femtosecond timescale

A photochemical reaction in its becoming has been observed with unprecedented detail at the Free Electron Laser FERMI in Trieste.

The result of the experiment published in Nature Communications paves the way for investigations that can shed new light on photochemical processes.

“Shooting the movie” of a photochemical reaction, interpreting its hidden details with the help of a computer: this is what has been done, thanks to the extraordinary capabilities of the FERMI free electron laser source in Trieste, by a research team composed of the Universities of Uppsala and Gothenburg in Sweden, the Institut Ruđer Bošković of Zagreb, the Elettra-FERMI Laboratory, the University of Trieste and the Laboratory of Physical Chemistry, Matter and Radiation in Paris. The study was published in Nature Communications.

The researchers wanted to capture the details of a chemical reaction promoted by the absorption of light (photochemical process), to understand how the excitation generated by a light beam induces changes on a target molecule. The first steps in a photochemical process involve changes in the electronic and geometric structure of a molecule over extremely short times measured in femtoseconds (1 fs = 10-15 s), which had so far hindered the accurate reconstruction of the entire sequence of the reaction.

The combination of intensity, energy resolution and very short pulse duration of the FERMI seeded free-electron laser source can now for the first time provide exceptionally detailed information on photoexcitation-deexcitation and fragmentation processes of isolated molecules in pump-probe experiments on the 50-femtosecond time scale.

Photoelectron spectroscopy with high resolution in energy and time, combined with accurate electronic structure and molecular dynamics calculations, has allowed to visualize in its entirety the temporal evolution of the prototype system chosen for the experiment: acetylacetone—a stable molecule used in environmental and medical applications.

“Besides revealing the dynamics of the reaction—explains Maria Novella Piancastelli of the University of Uppsala, principal investigator—a strong point of the experiment lies in the general applicability of the method, which leads us to consider it as the best way to investigate fundamental photochemical processes such as photosynthesis, photovoltaic energy production and vision.  The stairway that goes from simple to complex molecules, and from the understanding of phenomena to practical applications is of course a long one, and we are specifically interested in its ‘first step’.

>Read more on the FERMI website

Figure: A pictorial representation of the potential energy surfaces involved in the relaxation mechanism of acetylacetone: the ground state S0 (darker blue), two singlet S2 (ππ*) (light blue) and S1 (nπ*) (orange), and two triplet T2 (nπ*) (light green) and T1 (ππ*) (green) states. This approach based on high-resolution valence spectra backed by high-level calculations is the ultimate way to shed light on fundamental, basic photo processes such as photosynthesis, photovoltaic energy production, and vision.

 

 

Prehistoric Iranian glass under synchrotron light

Scientists from University of Isfahan in Iran have analysed in the ALBA Synchrotron how were made ancient Iranian glass objects that date back to 2.500 BC. These decorative glass pieces were excavated from the ziggurat of Chogha-Zanbil, a type of stepped pyramidal monument, inscribed on the UNESCO World Heritage List.

Ziggurats, the most distinct architectural feature of the Mesopotamian, are a type of massive stone structure built thousand years ago as a temple where deities lived. Nevertheless, Chogha-Zanbil, near Susa (Iran), is one of the few existent ziggurats found outside the Mesopotamian area. During ancient times Chogha-Zanbil was known as Dur Untaš, and may had been a sacred city of the Elamite Kingdom, an ancient Pre-Iranian civilization centred in the far West and Southwest of what is now modern-day Iran.

In order to determine the chemical composition of these unique samples, including one piece of ceramics and one piece of metallurgical crucible, a team of Iranian scientists came to ALBA Synchrotron to analyse them using X-Rays Powder Diffraction at the MSPD beamline. The MSPD analyses were carried out on more than 100 points on the glass objects. Synchrotron light enabled them to obtain high resolution diffraction patterns, from whose interpretation researchers have deduced the exact composition of the clay based structure as well as glassy part of the samples.

>Read more on the ALBA website

Image: The glass objects were originally used at the walls and doors of the tempel Chogha-Zanbil.
Credit: Mohammadamin Emami

Fuel from the sun: insight into electrode performance

Soft x-ray studies of hematite electrodes—potentially key components in producing fuel from sunlight—revealed the material’s electronic band positions under realistic operating conditions.

In photosynthesis, plants use sunlight to split water into oxygen and hydrogen. The oxygen is released into the atmosphere, and the hydrogen is used to produce molecules—such as carbohydrates and sugars—that store energy in chemical bonds. Such compounds constitute the original feedstocks for subsequent forms of fuel consumed by society.

Photoelectrochemical (PEC) water splitting is a form of “artificial” photosynthesis that uses semiconductor material, rather than organic plant material, to facilitate water splitting. Electrodes made of semiconductor material are immersed in an electrolyte, with sunlight driving the water-splitting process. The performance of such PEC devices is largely determined at the interface between the photoanode (the electrode at which light gets absorbed) and the electrolyte.

>Read more on the ALS webpage

Photo: Roy Kaltschmidt

Complex tessellations, extraordinary materials

Simple organic molecules form complex materials through self-organisation

An international team of researchers lead by the Technical University of Munich (TUM) has discovered a reaction path that produces exotic layers with semiregular structures. These kinds of materials are interesting because they frequently possess extraordinary properties. In the process, simple organic molecules are converted to larger units which form the complex, semiregular patterns. With experiments at BESSY II at Helmholtz-Zentrum Berlin this could be observed in detail.

Only a few basic geometric shapes lend themselves to covering a surface without overlaps or gaps using uniformly shaped tiles: triangles, rectangles and hexagons. Considerably more and significantly more complex regular patterns are possible with two or more tile shapes. These are so-called Archimedean tessellations or tilings.

Materials can also exhibit tiling characteristics. These structures are often associated with very special properties, for example unusual electrical conductivity, special light reflectivity or extreme mechanical strength. But, producing such materials is difficult. It requires large molecular building blocks that are not compatible with traditional manufacturing processes.

 

>Read more on the Bessy II website

Image: The new building block (left, red outline) comprises two modified starting molecules connected to each other by a silver atom (blue). This leads to complex, semiregular tessellations (right, microscope image).
Credit: Klappenberger and Zhang / TUM

Structure and Catalytic Activity of Copper Nanoparticles

Research investigates the addition of ceria on the activity of catalysts for the water-gas shift reaction

Catalysts are substances that promote and accelerate chemical reactions without being consumed during the process and are widely used in industrial processes to produce various chemicals.

Catalysts based on copper nanoparticles dispersed in an oxide support benefit various reactions, such as the synthesis of methanol, the alcohol dehydrogenation, or the water gas shift (WGS) reaction which is one of the main processes for hydrogen production on an industrial scale. In this reaction, carbon monoxide reacts with water to produce carbon dioxide CO2 and hydrogen gas H2.

>Read more on the LNLS website

Figure 1: Correlation between the bond length of CuO and the catalyst turnover frequency (TOF) for the catalysts analyzed under WGS conditions with different proportions of copper and ceria.

 

Pigments in Oil Paintings Linked to Artwork Degradation

Scientists have observed how lithium moves inside individual nanoparticles that make up batteries.

The finding could help companies develop batteries that charge faster and last longer. Experts have long known that as oil paintings age, soaps can form within the paint, degrading the appearance of the artworks. The process significantly complicates the preservation of oil paintings—and cultural manifestations, which the paintings themselves help to preserve.

“These soaps may form protrusions that grow within the paint and break up through the surface, creating a bumpy texture,” said Silvia Centeno, a member of the Department of Scientific Research at the New York Metropolitan Museum of Art (The Met). “In other cases, the soaps can increase the transparency of the paint, or form a disfiguring, white crust on the painting.”

Scientists do not understand why the soaps take on different manifestations, and for many years, the underlying mechanisms of how the soaps form remained a mystery.

“The Met, alongside our colleagues from other institutions, is trying to figure out why the process takes place, what triggers it, and if there’s a way we can prevent it,” Centeno said.

 

>Read more on the NSLS-II website

Picture: Scientists from Brookhaven Lab and The Met used beamline 5-ID at NSLS-II to analyze a microscopic sample of a 15th century oil painting. Pictured from left to right are Karen Chen-Wiegart (Stony Brook University/BNL), Silvia Centeno (The Met), Juergen Thieme (BNL), and Garth Williams (BNL).

 

 

 

Scientists decipher key principle behind reaction of metalloenzymes

So-called pre-distorted states accelerate photochemical reactions too

What enables electrons to be transferred swiftly, for example during photosynthesis? An interdisciplinary team of researchers has worked out the details of how important bioinorganic electron transfer systems operate. Using a combination of very different, time-resolved measurement methods at DESY’s X-ray source PETRA III and other facilities, the scientists were able to show that so-called pre-distorted states can speed up photochemical reactions or make them possible in the first place. The group headed by Sonja Herres-Pawlis from the RWTH Aachen University  Michael Rübhausen from the University of Hamburg and Wolfgang Zinth from Munich’s Ludwig Maximilian University, is presenting its findings in the journal Nature Chemistry.

The scientists had studied the pre-distorted, “entatic” state using a model system. An entatic state is the term used by chemists to refer to the configuration of a molecule in which the normal arrangement of the atoms is modified by external binding partners such that the energy threshold for the desired reaction is lowered, resulting in a higher speed of reaction. One example of this is the metalloprotein plastocyanin, which has a copper atom at its centre and is responsible for important steps in the transfer of electrons during photosynthesis. Depending on its oxidation state, the copper atom either prefers a planar configuration, in which all the surrounding atoms are arranged in the same plane (planar geometry), or a tetrahedral arrangement of the neighbouring ligands. However the binding partner in the protein forces the copper atom to adopt a sort of intermediate arrangement. This highly distorted tetrahedron allows a very rapid shift between the two oxidation states of the copper atom.

>Read more on the PETRA III website

Image Caption: Entatic state model complexes optimize the energies of starting and final configuration to enable fast reaction rates (illustrated by the hilly ground). The work demonstrates that the entatic state principle can be used to tune the photochemistry of copper complexes.
Credit: RWTH Aachen, Sonja Herres-Pawlis

Watching nanocrystals in action

The assembly of colloidal nanocrystal building blocks into ordered superlattices presents many scientifically interesting and technologically important research challenges to create programmable matter from “crystals-of-crystals”.

The formation of superlattices is a fascinating mesoscale phenomenon governed by the interplay of a range of thermodynamic and kinetic factors. Long-time collaborators Detlef Smilgies, CHESS, and Tobias Hanrath, Chemical and Biomolecular Engineering, have recently summarized the role of time-resolved X-ray scattering techniques in combination with in-situ sample environments to gain unique insights into the relevant processes. Their EPL Focus Article was recently published in a special issue on superlattice formation, edited by Marie-Paule Pileni [1].

A variety of factors influence the assembly. First of all there are the nanoparticles themselves: their size variation, their shape, and their ligand coverage influence which superlattice symmetries are formed. A spectacular example has been the self-assembly of lead sulfide and lead selenide nanocrystals: These spheroidal nanocrystals have well defined facets formed by (100) and (111) crystallographic planes of the inorganic cores which form cuboctrahedra. Initially these nanocrystals form the expected FCC superlattice, but as solvent further evaporates and particles move closer together, the lattice symmetry changes to body-centered tetragonal and finally to BCC [2,3]. This transition is accompanied by increasing orientational ordering of particles relative to each other. The reason for this peculiar behavior seems to lie in the ligand-ligand and solvent-ligand interactions as superlattices dry. Due to the facetting of the particles the ligand density around the particle is inhomogeneous; in particular at edges and corners there is sterically not enough space to anchor ligands at the same density as on the facets.  As particles move closer to each other this anisotropy becomes more pronounced and leads to orientational ordering and superlattice symmetry change.

>Read more on the CHESS website

Image Caption: The “periodic table” of nanocrystal superlattices. Nanocrystals can be made from most elements in the periodic table. In addition, their size, shape and dimensionality is controlled by the synthesis. Finally superlattices with different symmetries can be made by exploiting shape and dimensionality as well as processing parameters. 
Credit:Tobias Hanrath, Cornell

Studying Gas Mask Filters So People Can Breathe Easier

Scientists have put the x-ray spotlight on composite materials in respirators used by the military, police, and first responders. The results provide reassuring news about the effectiveness of current filters and provide fundamental information that could lead to more advanced gas masks as well as protective gear for civilian applications.

Read more on the ALS website.

Image: credit ALS

New Catalyst Gives Artificial Photosynthesis a Big Boost

Inspired by plants: Inorganic catalyst converts electrical energy to chemical energy at 64% efficiency

Researchers have created a new catalyst that brings them one step closer to artificial photosynthesis — a system that would use renewable energy to convert carbon dioxide (CO2) into stored chemical energy.

As in plants, their system consists of two linked chemical reactions: one that splits water (H2O) into protons and oxygen gas, and another that converts CO2 into carbon monoxide (CO). The CO can then be converted into hydrocarbon fuels through an established industrial process. The system would allow both the capture of carbon emissions and the storage of energy from solar or wind power.

Yufeng Liang and David Prendergast – scientists at the Molecular Foundry, a nanoscale research facility at the U.S. Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab) – performed theoretical modeling work used to interpret X-ray spectroscopy measurements made in the study, published Nov. 20 in Nature Chemistry. This work was done in support of a project originally proposed by the University of Toronto team to the Molecular Foundry, a DOE Office of Science User Facility.

 

>Read more on the ALS website

Image: Phil De Luna of University of Toronto is one of the lead authors of a new study that reports a low-cost, highly efficient catalyst for chemical conversion of water into oxygen. The catalyst is part of an artificial photosynthesis system in development at the University of Toronto.
Credit: Tyler Irving/University of Toronto

NSRRC User, Jennifer Kung elected as a MSA Fellow

First female scientist ever awarded MSA fellowship in Asia.

NSRRC user, Jennifer Kung is among the 11 new elected fellows for 2018, announced by the Mineralogical Society of America (MSA) Council at its Fall Council Meeting in Seattle, WA, USA. She is the only recipient from Taiwan, as well as the first female scientist ever awarded MSA fellowship in Asia.

Prof. Kung is an Associate Professor in Earth Science at National Cheng-Kung University. She runs “Mineral and Rock Physics Lab” to investigate the behaviors of earth materials under high pressure and high temperature using the knowledge of crystal chemistry, mineral physics to understand the interior of the Earth. The major research methods she employs include X-ray diffraction, vibrational spectroscopy and ultrasonic measurements in conjunction with high pressure facilities, like large volume high pressure apparatus or diamond anvil.

 

A mixtape for drug discovery

New method enables automated fast investigation of enzymatic processes

Scientists at DESY have developed a new method that enables automated and fast screening of promising drug candidates. This novel technique, called mix-and-diffuse serial synchrotron crystallography, can image the interaction of potential drug targets with drug candidates or other molecules. The concept has the potential to take structure and fragment based drug design to a new level, as the researchers write in the Journal of the International Union of Crystallography (IUCrJ).

>Read More on the PETRA III website

Image: Principle of the mix-and-diffuse serial synchrotron crystallography: protein crystals are mixed with a solution of a drug candidate and X-rayed on a tape running through the X-ray beam.
Credit: Beyerlein et al., IUCrJ 

Scientists Named 2017 American Physical Society Fellows

Five Brookhaven Lab Scientists recognized for their outstanding contributions

The American Physical Society (APS), the world’s largest physics organization, has elected five scientists from the U.S. Department of Energy’s (DOE) Brookhaven National Laboratory as 2017 APS fellows. With more than 53,000 members from academia, government, and industry, APS seeks to advance and share physics knowledge through research journals, scientific meetings, and activities in education, outreach, and advocacy. Each year, a very small percentage of APS members are elevated to the status of fellow through a peer nomination process. Fellows are recognized for their exceptional contributions to physics, including in research, applications, leadership and service, and education.

The 2017 APS fellows representing Brookhaven Lab are Anatoly Frenkel, Morgan May, Rachid Nouicer, Eric Stach, and Peter Steinberg.

Anatoly Frenkel, APS Division of Materials Physics

“For seminal contributions to in situ X-ray absorption spectroscopy, transformative development of structural characterization methods for nanoparticles, and their pioneering applications to a broad range of functional nanomaterials in materials physics and catalysis science.”

Anatoly Frenkel holds a joint appointment as a senior chemist in Brookhaven Lab’s Chemistry Division—where he serves as principal investigator of the Structure and Dynamics of Applied Nanomaterials Group—and tenured professor in Stony Brook University’s Materials Science and Chemical Engineering Department. Frenkel’s research focuses on the application of synchrotron-based x-ray methods to characterize materials and study how their structures and properties relate.

 

>Read more on the NSLS II website

Image: Anatoly Frenkel

 

Bing-Joe Hwang received National Chair Professorship from Ministry of Education

Exceptional award for this NSRRC User

The Ministry of Education recently announced the recipients of the 21st National Chair Professorships and the 61st Academic Awards. Prof. Bing-Joe Hwang, a long-term user of NSRRC, was given the National Chair Professorship in the category of Engineering and Applied Sciences. Prof. Hwang is a Chair Professor in Chemical Engineering at National Taiwan University of Science and Technology. He is also an adjunct scientist of NSRRC. His research interests include electrochemistry, nanomaterials, nanoscience, fuel cells, lithium ion batteries, solar cells, sensors, and interfacial phenomena.