Atomic fluctuations lifting the energy degeneracy in Si/SiGe quantum dots.

Electron spins in Si/SiGe quantum wells suffer from nearly degenerate conduction band valleys, which compete with the spin degree of freedom in the formation of qubits. Despite attempts to enhance the valley energy splitting deterministically, by engineering a sharp interface, valley splitting fluctuations remain a serious problem for qubit uniformity, needed to scale up to large quantum processors. Here, we elucidate and statistically predict the valley splitting by the holistic integration of 3D atomic-level properties, theory and transport. We find that the concentration fluctuations of Si and Ge atoms within the 3D landscape of Si/SiGe interfaces can explain the observed large spread of valley splitting from measurements on many quantum dot devices. Against the prevailing belief, we propose to boost these random alloy composition fluctuations by incorporating Ge atoms in the Si quantum well to statistically enhance valley splitting.

Quantum stochastic resonance of individual Fe atoms.

Stochastic resonance, where noise synchronizes a system's response to an external drive, is a wide-reaching phenomenon found in noisy systems spanning from the dynamics of neurons to the periodicity of ice ages. Quantum tunneling can extend stochastic resonance to the quantum realm. We demonstrate quantum stochastic resonance for magnetic transitions in atoms by inelastic electron tunneling with a scanning tunneling microscope. Stochastic resonance is shown deep in the quantum regime, where spin-state fluctuations are driven by tunneling of the magnetization, and in a semiclassical crossover region, where thermally excited electrons drive transitions between ground and excited states. Inducing synchronization by periodically modulating transition rates provides a general mechanism to determine real-time spin dynamics ranging from milliseconds to picoseconds.

Effect of Quantum Hall Edge Strips on Valley Splitting in Silicon Quantum Wells.

We determine the energy splitting of the conduction-band valleys in two-dimensional electrons confined to low-disorder Si quantum wells. We probe the valley splitting dependence on both perpendicular magnetic field B and Hall density by performing activation energy measurements in the quantum Hall regime over a large range of filling factors. The mobility gap of the valley-split levels increases linearly with B and is strikingly independent of Hall density. The data are consistent with a transport model in which valley splitting depends on the incremental changes in density eB/h across quantum Hall edge strips, rather than the bulk density. Based on these results, we estimate that the valley splitting increases with density at a rate of 116 µeV/10^{11} cm^{-2}, which is consistent with theoretical predictions for near-perfect quantum well top interfaces.

Gate fidelity and coherence of an electron spin in an Si/SiGe quantum dot with micromagnet.

The gate fidelity and the coherence time of a quantum bit (qubit) are important benchmarks for quantum computation. We construct a qubit using a single electron spin in an Si/SiGe quantum dot and control it electrically via an artificial spin-orbit field from a micromagnet. We measure an average single-qubit gate fidelity of ∼99% using randomized benchmarking, which is consistent with dephasing from the slowly evolving nuclear spins in the substrate. The coherence time measured using dynamical decoupling extends up to ∼400 µs for 128 decoupling pulses, with no sign of saturation. We find evidence that the coherence time is limited by noise in the 10-kHz to 1-MHz range, possibly because charge noise affects the spin via the micromagnet gradient. This work shows that an electron spin in an Si/SiGe quantum dot is a good candidate for quantum information processing as well as for a quantum memory, even without isotopic purification.

Nanoscale Transforming Mineral Phases in Fresh Nacre.

Nacre, or mother-of-pearl, the iridescent inner layer of many mollusk shells, is a biomineral lamellar composite of aragonite (CaCO3) and organic sheets. Biomineralization frequently occurs via transient amorphous precursor phases, crystallizing into the final stable biomineral. In nacre, despite extensive attempts, amorphous calcium carbonate (ACC) precursors have remained elusive. They were inferred from non-nacre-forming larval shells, or from a residue of amorphous material surrounding mature gastropod nacre tablets, and have only once been observed in bivalve nacre. Here we present the first direct observation of ACC precursors to nacre formation, obtained from the growth front of nacre in gastropod shells from red abalone (Haliotis rufescens), using synchrotron spectromicroscopy. Surprisingly, the abalone nacre data show the same ACC phases that are precursors to calcite (CaCO3) formation in sea urchin spicules, and not proto-aragonite or poorly crystalline aragonite (pAra), as expected for aragonitic nacre. In contrast, we find pAra in coral.

Electronic Transport Properties of Epitaxial Si/SiGe Heterostructures Grown on Single-Crystal SiGe Nanomembranes.

To assess possible improvements in the electronic performance of two-dimensional electron gases (2DEGs) in silicon, SiGe/Si/SiGe heterostructures are grown on fully elastically relaxed single-crystal SiGe nanomembranes produced through a strain engineering approach. This procedure eliminates the formation of dislocations in the heterostructure. Top-gated Hall bar devices are fabricated to enable magnetoresistivity and Hall effect measurements. Both Shubnikov-de Haas oscillations and the quantum Hall effect are observed at low temperatures, demonstrating the formation of high-quality 2DEGs. Values of charge carrier mobility as a function of carrier density extracted from these measurements are at least as high or higher than those obtained from companion measurements made on heterostructures grown on conventional strain graded substrates. In all samples, impurity scattering appears to limit the mobility.

Incommensurate phases of a supported nanoparticle film subjected to uniaxial compression.

We investigate experimentally and theoretically the sequence of phases that occurs when a self-assembled monolayer of gold nanoparticles supported on a fluid is compressed uniaxially in a Langmuir trough. Uniaxial compression of the monolayer results in the appearance of lines that have been shown to be regions of trilayer. These lines exhibit complex patterns that depend on the extent of compression. We show that these patterns can be understood in terms of an equilibrium statistical mechanical theory, originally developed in the context of commensurate-incommensurate transitions in krypton monolayers adsorbed on graphite, in which there is an energy cost to line deformations and to line intersections. Even though line intersections are energetically costly, they lower the free energy because they cause the entropy of the system to increase when the density of lines is low enough. Our analytic and Monte Carlo analyses of the model demonstrate that the model exhibits two-phase coexistence. Our experimental observations are qualitatively consistent with the predictions of the model.

Measurement of c-axis angular orientation in calcite (CaCO3) nanocrystals using X-ray absorption spectroscopy.

We demonstrate that the ability to manipulate the polarization of synchrotron radiation can be exploited to enhance the capabilities of X-ray absorption near-edge structure (XANES) spectroscopy, to include linear dichroism effects. By acquiring spectra at the same photon energies but different polarizations, and using a photoelectron emission spectromicroscope (PEEM), one can quantitatively determine the angular orientation of micro- and nanocrystals with a spatial resolution down to 10 nm. XANES-PEEM instruments are already present at most synchrotrons, hence these methods are readily available. The methods are demonstrated here on geologic calcite (CaCO(3)) and used to investigate the prismatic layer of a mollusk shell, Pinctada fucata. These XANES-PEEM data reveal multiply oriented nanocrystals within calcite prisms, previously thought to be monocrystalline. The subdivision into multiply oriented nanocrystals, spread by more than 50°, may explain the excellent mechanical properties of the prismatic layer, known for decades but never explained.

Distance dependence of neuronal growth on nanopatterned gold surfaces.

Understanding network development in the brain is of tremendous fundamental importance, but it is immensely challenging because of the complexity of both its architecture and function. The mechanisms of axonal navigation to target regions and the specific interactions with guidance factors such as membrane-bound proteins, chemical gradients, mechanical guidance cues, etc., are largely unknown. A current limitation for the study of neural network formation is the ability to control precisely the connectivity of small groups of neurons. A first step in designing such networks is to understand the "rules" central nervous system (CNS) neurons use to form functional connections with one another. Here we begin to delineate novel rules for growth and connectivity of small numbers of neurons patterned on Au substrates in simplified geometries. These studies yield new insights into the mechanisms determining the organizational features present in intact systems. We use a previously reported atomic force microscopy (AFM) nanolithography method to control precisely the location and growth of neurons on these surfaces. By examining a series of systems with different geometrical parameters, we quantitatively and systematically analyze how neuronal growth depends on these parameters.

Nacre protein fragment templates lamellar aragonite growth.

Proteins play a major role in the formation of all biominerals. In mollusk shell nacre, complex mixtures and assemblies of proteins and polysaccharides were shown to induce aragonite formation, rather than the thermodynamically favored calcite (both aragonite and calcite are CaCO(3) polymorphs). Here we used N16N, a single 30 amino acid-protein fragment originally inspired by the mineral binding site of N16, a protein in the nacre layer of the Japanese pearl oysters (Pinctada fucata). In a calcite growth solution this short peptide induces in vitro biomineralization. This model biomineral was analyzed using X-ray PhotoElectron Emission spectroMicroscopy (X-PEEM) and found to be strikingly similar to natural nacre: lamellar aragonite with interspersed N16N layers. This and other findings combined suggest a hypothetical scenario in which in vivo three proteins (N16, Pif80, and Pif97) and a polysaccharide (chitin) work in concert to form lamellar nacre.

Mechanism of calcite co-orientation in the sea urchin tooth.

Sea urchin teeth are remarkable and complex calcite structures, continuously growing at the forming end and self-sharpening at the mature grinding tip. The calcite (CaCO(3)) crystals of tooth components, plates, fibers, and a high-Mg polycrystalline matrix, have highly co-oriented crystallographic axes. This ability to co-orient calcite in a mineralized structure is shared by all echinoderms. However, the physico-chemical mechanism by which calcite crystals become co-oriented in echinoderms remains enigmatic. Here, we show differences in calcite c-axis orientations in the tooth of the purple sea urchin ( Strongylocentrotus purpuratus ), using high-resolution X-ray photoelectron emission spectromicroscopy (X-PEEM) and microbeam X-ray diffraction (muXRD). All plates share one crystal orientation, propagated through pillar bridges, while fibers and polycrystalline matrix share another orientation. Furthermore, in the forming end of the tooth, we observe that CaCO(3) is present as amorphous calcium carbonate (ACC). We demonstrate that co-orientation of the nanoparticles in the polycrystalline matrix occurs via solid-state secondary nucleation, propagating out from the previously formed fibers and plates, into the amorphous precursor nanoparticles. Because amorphous precursors were observed in diverse biominerals, solid-state secondary nucleation is likely to be a general mechanism for the co-orientation of biomineral components in organisms from different phyla.

Positioning and guidance of neurons on gold surfaces by directed assembly of proteins using Atomic Force Microscopy.

We demonstrate that Atomic Force Microscopy nanolithography can be used to control effectively the adhesion, growth and interconnectivity of cortical neurons on Au surfaces. We demonstrate immobilization of neurons at well-defined locations on Au surfaces using two different types of patterned proteins: 1) poly-d-lysine (PDL), a positively charged polypeptide used extensively in tissue culture and 2) laminin, a component of the extracellular matrix. Our results show that both PDL and laminin patterns can be used to confine neuronal cells and to control their growth and interconnectivity on Au surfaces, a significant step towards the engineering of artificial neuronal assemblies with well-controlled neuron position and connections.

Gradual ordering in red abalone nacre.

Red abalone (Haliotis rufescens) nacre is a layered composite biomineral that contains crystalline aragonite tablets confined by organic layers. Nacre is intensely studied because its biologically controlled microarchitecture gives rise to remarkable strength and toughness, but the mechanisms leading to its formation are not well understood. Here we present synchrotron spectromicroscopy experiments revealing that stacks of aragonite tablet crystals in nacre are misoriented with respect to each other. Quantitative measurements of crystal orientation, tablet size, and tablet stacking direction show that orientational ordering occurs not abruptly but gradually over a distance of 50 microm. Several lines of evidence indicate that different crystal orientations imply different tablet growth rates during nacre formation. A theoretical model based on kinetic and gradual selection of the fastest growth rates produces results in qualitative and quantitative agreement with the experimental data and therefore demonstrates that ordering in nacre is a result of crystal growth kinetics and competition either in addition or to the exclusion of templation by acidic proteins as previously assumed. As in other natural evolving kinetic systems, selection of the fastest-growing stacks of tablets occurs gradually in space and time. These results suggest that the self-ordering of the mineral phase, which may occur completely independently of biological or organic-molecule control, is fundamental in nacre formation.

Assignment of polarization-dependent peaks in carbon K-edge spectra from biogenic and geologic aragonite.

Many biominerals, including mollusk and echinoderm shells, avian eggshells, modern and fossil bacterial sediments, planktonic coccolithophores, and foraminifera, contain carbonates in the form of biogenic aragonite or calcite. Here we analyze biogenic and geologic aragonite using different kinds of surface- and bulk-sensitive X-ray absorption near-edge structure (XANES) spectroscopy at the carbon K-edge, as well as high-resolution scanning transmission X-ray microscopy (STXM). Besides the well-known main pi* and sigma* carbonate peaks, we observed and fully characterized four minor peaks, at energies between the main pi* and sigma* peaks. As expected, the main peaks are similar in geologic and biogenic aragonite, while the minor peaks differ in relative intensity. In this and previous work, the minor peaks appear to be the ones most affected in biomineralization processes, hence the interest in characterizing them. Peak assignment was achieved by correlation of polarization-dependent behavior of the minor peaks with that of the main pi* and sigma* peaks. The present characterization provides the background for future studies of aragonitic biominerals.

Probing the organic-mineral interface at the molecular level in model biominerals.

It is widely known that macromolecules, such as proteins, can control the nucleation and growth of inorganic solids in biomineralizing organisms. However, what is not known are the complementary molecular interactions, organization, and rearrangements that occur when proteins interact with inorganic solids during the formation of biominerals. The organic-mineral interface (OMI) is expected to be the site for these phenomena, and is therefore extraordinarily interesting to investigate. In this report, we employ X-ray absorption near edge (XANES) spectromicroscopy to investigate the electronic structure of both calcium carbonate mineral crystals and polypeptides, and detect changing bonds at the OMI during crystal growth in the presence of polypeptides. We acquired XANES spectra from calcium carbonate crystals grown in the presence of three mollusk nacre-associated polypeptides (AP7N, AP24N, n16N) and in the presence of a sea urchin spicule matrix protein, LSM34. All these model biominerals gave similar results, including the disruption of CO bonds in calcite and enhancement of the peaks associated with C-H bonds and C-O bonds in peptides, indicating ordering of the amino acid side chains in the mineral-associated polypeptides and carboxylate binding. This is the first evidence of the mutual effect of calcite on peptide chain and peptide chain on calcite during biomineralization. We also show that these changes do not occur when Asp and Glu are replaced in the n16N sequence with Asn and Gln, respectively, demonstrating that carboxyl groups in Asp and Glu do participate in polypeptide-mineral molecular associations.

Architecture of columnar nacre, and implications for its formation mechanism.

We analyze the structure of Haliotis rufescens nacre, or mother-of-pearl, using synchrotron spectromicroscopy and x-ray absorption near-edge structure spectroscopy. We observe imaging contrast between adjacent individual nacre tablets, arising because different tablets have different crystal orientations with respect to the radiation's polarization vector. Comparing previous data and our new data with models for columnar nacre growth, we find the data are most consistent with a model in which nacre tablets are nucleated by randomly distributed sites in the organic matrix layers.

A microfluidic system for large DNA molecule arrays.

Single molecule approaches offer the promise of large, exquisitely miniature ensembles for the generation of equally large data sets. Although microfluidic devices have previously been designed to manipulate single DNA molecules, many of the functionalities they embody are not applicable to very large DNA molecules, normally extracted from cells. Importantly, such microfluidic devices must work within an integrated system to enable high-throughput biological or biochemical analysis-a key measure of any device aimed at the chemical/biological interface and required if large data sets are to be created for subsequent analysis. The challenge here was to design an integrated microfluidic device to control the deposition or elongation of large DNA molecules (up to millimeters in length), which would serve as a general platform for biological/biochemical analysis to function within an integrated system that included massively parallel data collection and analysis. The approach we took was to use replica molding to construct silastic devices to consistently deposit oriented, elongated DNA molecules onto charged surfaces, creating massive single molecule arrays, which we analyzed for both physical and biochemical insights within an integrated environment that created large data sets. The overall efficacy of this approach was demonstrated by the restriction enzyme mapping and identification of single human genomic DNA molecules.

Spectroscopically determined collagen Pyr/deH-DHLNL cross-link ratio and crystallinity indices differ markedly in recombinant congenic mice with divergent calculated bone tissue strength.

Whole bone strength can be partitioned into structural and material components. In three-point bending tests of 6-month-old female humeri from the HcB/Dem recombinant congenic series, strains HcB/8 and HcB/23 differed markedly in calculated failure stress but not ash percentage. Fourier transform infrared spectroscopic imaging was used to determine whether differences in the ratio of pyridinoline (pyr; nonreducible) to dehydrodihydroxynorleucine (de-DHLNL; reducible) collagen cross-links (XLR), mineral crystallinity, or spatial ordering could account for the strains' differing biomechanical performance. HcB/8 had significantly higher XLR and significantly higher crystallinity than HcB/23. XLR and crystallinity were highly and similarly correlated in both strains. There were no significant differences between the strains' one-dimensional spatial correlation functions, suggesting no difference in short-range order between them. The strong correlation between XLR and crystallinity reflects the interdependence of the protein and mineral elements of bone. The data illustrate the importance of material properties in addition to mineral quantity to bone tissue strength.