Approaching the resolution limit of nanometer-scale electron beam-induced deposition

We report the writing of very high resolution tungsten containing dots in regular arrays by electron beam-induced deposition (EBID). The size averaged over 100 dots was 1.0 nm at fwhm. Because of the statistical spread in the dot size, large and small dots are present in the arrays, with the smallest having a diameter of only 0.7 nm at fwhm. To date these are the smallest features fabricated by EBID. We have also fabricated lines with the smallest having a width at fwhm of 1.9 nm and a spacing of 3.2 nm.     

Holographic control of motive shape in plasmonic nanogap arrays

Here we demonstrate that 4-beam holographic lithography can be utilized to create plasmonic nanogaps that are 70 times smaller than the laser wavelength (488 nm). This was achieved by controlling phase, polarization, and laser beam intensity in order to tune the relative spacing of the two sublattices in the interference pattern of a compound-lattice in combination with the nonlinear resist response. Exemplarily, twin and triplet motive features were designed and patterned into polymer in a single exposure step and then transferred into gold nanogap arrays resulting in an average gap size of 22 nm and smallest features down to 7 nm. These results extend the utility of high-throughput, wafer-scale holographic lithography into the realm of nanoplasmonics.     

Regular arrays of monodisperse platinum/erbium disilicide core-shell nanowires and nanoparticles on Si(001) via a self-assembled template

We have developed a process for fabricating monodisperse noble metal/rare earth disilicide core-shell nanoparticles and nanowires in regular arrays on Si(001) with a density of 5 x 10(10) / cm2, and over areas > 1 mm2. Pt deposited via physical vapor deposition on a self-assembled rare earth disilicide nanowire template combined with reactive ion etching produces arrays of nanostructures. SEM images demonstrate the ability to select nanowires or nanoparticles as a function of Pt coverage. Statistical analysis of images of Pt nanoparticle arrays yield a mean feature size of 8 nm with a size variation of +/- 0.9 nm and interparticle spacing of approximately 15 nm.     

Self-organized inorganic nanoparticle arrays on protein lattices

Cavities formed by proteins have been utilized as the reaction chamber for the fabrication of a range of inorganic nanoparticles, providing control of the size of particles by limiting growth and preventing agglomeration. In crystal form, proteins construct molecular arrays that can provide regularly arranged sites for nanoparticles. Here we report the fabrication of nanometric iron and indium particles using ferritin, an iron-storage protein. The indium nanoparticles thus formed have uniform spherical shape with diameter of 6.6 +/- 0.5 nm, while the iron nanoparticles are somewhat irregular in shape (5.8 +/- 1.0 nm). Regular two-dimensional arrays of these nanoparticles are successfully produced by crystallizing ferritin molecules on a water-air interface using the denatured protein film method. The lattice constant of these nanoparticle arrays is 13 nm with hexagonal packing, and arrays of more than 1 microm in area can be obtained by transfer onto silicon wafer.     

One-dimensional nanorod arrays: independent control of composition, length, and interparticle spacing with nanometer precision

We report the synthesis of solution dispersible, one-dimensional metal nanostructure arrays as small as 35 nm in diameter using on-wire lithography, wherein feature thickness and spacing in the arrays is tailorable down to approximately 6 and 1 nm, respectively. Using this unique level of control, we present solution-averaged extinction spectra of 35 nm diameter Au nanorod dimers with varying gap sizes to illustrate the effect of gap size on plasmon coupling between nanorods. Additionally, we demonstrate control over the composition of the arrays with Au, Ni, and Pt segments, representing important advances in controlling the ordering of sub-100 nm nanostructures that are not available with current synthesis or assembly methods.     

Electronic excited states in bilayer graphene double quantum dots

We report tunneling spectroscopy experiments on a bilayer graphene double quantum dot device that can be tuned by all-graphene lateral gates. The diameter of the two quantum dots are around 50 nm and the constrictions acting as tunneling barriers are 30 nm in width. The double quantum dot features additional energies on the order of 20 meV. Charge stability diagrams allow us to study the tunable interdot coupling energy as well as the spectrum of the electronic excited states on a number of individual triple points over a large energy range. The obtained constant level spacing of 1.75 meV over a wide energy range is in good agreement with the expected single-particle energy spacing in bilayer graphene quantum dots. Finally, we investigate the evolution of the electronic excited states in a parallel magnetic field.     

Nondestructive evaluation of large-area PZN-8%PT single crystal wafers for medical ultrasound imaging probe applications

A nondestructive quality evaluation and control procedure for large-area, (001)-cut PZN-8%PT wafers is described. The crystals were grown by the flux technique engineered to promote (001) layer growth of the crystals. The wafers were sliced parallel to the (001) layer growth plane. Curie temperature (Tc) variations, measured with matching arrays of dot electrodes (of 5.0 mm in center-to-center spacing), were found to be better than +/- 4.0 degrees C both within wafers and from wafer to wafer. After selective dicing to give final wafers of narrower Tc distributions (e.g., +/- 3.0 degrees C or better), the wafers were coated with complete electrodes and poled at room temperature at 0.7-0.9 kV/mm. Typical overall properties of the poled wafers were: K3T = 5,200 (+/- 10% from wafer to wafer), tan delta < 0.01 (all wafers), and kt = 0.55 (+/- 5%) (all percentage variations are in relative percentages). Then, the distributions of K3S, tan delta, and kt were measured by the array dot electrode technique. The variations in K3S (hence K3T) and kt within individual wafers were found to be within +/- 10% and +/- 5%, respectively. The dielectric loss values, measured at 1 kHz, were consistently low, being < 0.01 throughout the wafers. The kt values determined by the dot electrodes were found to be about 5% smaller than those obtained with the complete electrodes, which can be attributed to an increase in capacitance ratio due to the partial electroding. The k33 values, deduced using the relation K3S approximately (1 - k33(2))K3T, from the mean K3S and overall K3T values, average 0.94 (+/- 2%). The present work shows that the distribution of Tc within wafers can be used as a convenient check for the uniformity in composition and electromechanical properties of PZN-8%PT single crystal wafers. Our results show that, to control deltaK3T and deltakt within individual wafer to < or = 10% and 5%, respectively, the variation in Tc within the wafer should be kept within +/- 3.0 degrees C or better.     

Lateral patterning of multilayer InAs/GaAs(001) quantum dot structures by in vacuo focused ion beam

We report on the effects of patterning and layering on multilayer InAs/GaAs(001) quantum dot structures laterally ordered using an in vacuo focused ion beam. The patterned hole size and lateral pattern spacing affected the quantum dot size and the fidelity of the quantum dots with respect to the lateral patterns. 100% pattern fidelity was retained after six layers of dots for a 9.0 ms focused ion beam dwell time and 2.0 μm lateral pattern spacing. Analysis of the change in quantum dot size as a function of pattern spacing provided a means of estimating the maximum average adatom surface diffusion length to be approximately 500 nm, and demonstrated the ability to alter the wetting layer thickness via pattern spacing. Increasing the number of layers from six to 26 resulted in mound formation, which destroyed the pattern fidelity at close pattern spacings and led to a bimodal quantum dot size distribution as measured by atomic force microscopy. The bimodal size distribution also affected the optical properties of the dots, causing a split quantum dot photoluminescence peak where the separation between the split peaks increased with increasing pattern spacing.     

Thermal conductivity of Si-Ge quantum dot superlattices

Quantum dot superlattices (QDSLs) have been proposed for thermoelectric applications as a means of increasing thermal conductivity, σ, and reducing the lattice thermal conductivity, κ(l), to increase the dimensionless thermoelectric figure of merit, ZT. To fully exploit the thermoelectric potential of Si-Ge quantum dot superlattices (QDSLs), we performed a thorough study of the structural interplay of QDSLs with κ(l) using Green-Kubo theory and molecular dynamics. It was found that the resulting κ(l) has less dependence on the arrangement of the dots than to dot size and spacing. In fact, regardless of arrangement or concentration, QDSLs show a minimum κ(l) at a dot diameter of 1.4-1.6 nm and can reach values as low as 0.8-1.0 W mK?1, increasing ZT by orders of magnitude over bulk Si and Ge. The drastic reduction of thermal conductivity in such a crystalline system is shown to be the result of both the stress caused by the dots as well as the quality of the Si-Ge interface.     

Single-molecule DNA patterning and detection by padlock probing and rolling circle amplification in microchannels for analysis of small sample volumes

The rolling circle amplification (RCA) is a versatile DNA amplification method in which a DNA molecule is amplified using a single DNA primer, allowing the product to be counted as a single dot. Circular templates for RCA can arise from padlock probes in highly specific DNA target-mediated ligation reactions. However, improvement of detection efficiency represents an important challenge. In homogeneous assays, the detection efficiency is generally only under 0.1%, mainly because the sample volume is too large compared with the detection volume. Here, we used microchannel surfaces in a glass microchip for DNA detection in small volume samples. First, DNA patterning on glass surfaces in microchannels was demonstrated using chemical surface patterning by UV light. By using a photochemical reaction, we realized DNA patterning in a closed space. Second, RCA was demonstrated using dilutions of target molecules, and a calibration curve was obtained. The highest detection efficiency was 22.5% by virtue of the reduced sample volumes from several hundred microliters to 5.0 nL. Accordingly, a countable number of DNA molecules was successfully detected. This method is suitable for analysis of very small volume samples such as single cells, especially by using extended-nanochannels with dimensions of 10-1000 nm.     

A Nanofilter Array Chip for Fast Gel-Free Biomolecule Separation

We report here a microfabricated nanofilter array chip that can size-fractionate SDS-protein complexes and small DNA molecules based on the Ogston sieving mechanism. Nanofilter arrays with a gap size of 40-180nm were fabricated and characterized. Complete separation of SDS-protein complexes and small DNA molecules were achieved in several minutes with a separation length of 5mm. The fabrication strategy for the nanofilter array chip allows further increasing of the nanofilter density and decreasing of the nanofilter gap size, leading, in principle, to even faster separation.     

Formation of dot arrays with a pitch of 20 nm × 20 nm for patterned media using 30 keV EB drawing on thin calixarene resist

We studied the possibility of achieving very fine-pitch dot arrays with a pitch of 20?nm × 20?nm using 30?keV electron beam (EB) drawing on negative calixarene resist. In order to form such patterns, we studied the dependence on resist thickness of the dot size and the packing. We propose EB drawing on an extremely thin film for very highly packed dot-array formation. Our experimental results demonstrate the possibility of forming highly packed dot-array patterns with a pitch of 20?nm × 20?nm and a resist thickness of about 13?nm, which corresponds to about 1.6?Tbits?in(-2).     

Crystallization of cobalt amorphous alloys under field annealing

Crystallization of Co-rich amorphous ribbons annealed under a 10 Oe external magnetic field at the early 30 minutes from their glassy status to supercooled liquid status is investigated by high-resolution transmission microscope (HR-TEM), Selected Area Fourier Transform (SA-FT), X-ray diffraction (XRD) and differential scanning calorimetry (DSC). Results indicate that the short-rang ordering feature can be refined very well in specimen annealed under temperatures about 87.4 degrees C below their glass transition (Tg), showing refined salt-pepper morphologies with a mean length changing from 1.2 +/- 0.8 nm to 0.8 +/- 0.2 nm and a mean width shifting from 0.5 +/- 0.2 nm to 0.3 +/- 0.1 nm. When the amorphous ribbons are field-annealed at temperature near to Tg (i.e., 450 degrees C), ultra-fine nanocrystalline structures can be formed on the top surface of ribbons with size of 3.5 +/- 0.5 nm and inter-grain spacing of about 0.4 +/- 0.2 nm even though the inner parts of the ribbons are still in amorphous phases. The nanocrystalline areas are featured by the formation of doped hcp cobalt phase orientated along the c-axis, with the inter-plane spacing ranging from 4 A to 6 A. When the annealing temperature is above Tg, the grain sizes are increased dramatically with multi-phased nanocrystals precipitating from the amorphous substrate, and finally reaching almost complete crystallization at 600 degrees C, causing greatly coarsening of the nanocrystal structures.     

Substrates for direct imaging of chemically functionalized SiO2 surfaces by transmission electron microscopy

A significant challenge in materials characterization is the determination of the structure of nanoparticle assemblies that have been deposited on solid substrates, such as SiO2. The best method for obtaining quantitative information about structure, size, and spacing on the nanometer-length scale is TEM; however, commercially available TEM grids offer a limited range of substrate materials. In addition, the compositions of these grids do not permit much chemical processing. Here we describe silicon-based grids with electron-transparent SiO2 windows suitable for use as substrates for high-resolution TEM that can be easily fabricated using standard silicon microfabrication techniques. These grids are physically and chemically robust and exhibit the same surface chemistry and chemical stability as an oxide grown on a silicon wafer. Thus, the grids make possible the concurrent investigation of chemical and structural information on the same sample. Convenient modification of the surfaces of the grids provides access to a wide range of new substrates for the direct imaging of chemically modified surfaces by TEM. We demonstrate the utility of these grids by aligning DNA on the chemically modified SiO2 surface in order to direct the assembly of linear arrays of nanoparticles. Using these grids, we are able to quantify the effects of assembly conditions on nanoparticle size, spacing, and dispersity in the arrays.     

Graphoepitaxy of cylinder-forming block copolymers for use as templates to pattern magnetic metal dot arrays

We report a method to fabricate high-quality patterned magnetic dot arrays using block copolymer lithography, metal deposition, and a dry lift-off technique. Long-range order of cylindrical domains oriented perpendicular to the substrate and in hexagonal arrays was induced in the block copolymer films by prepatterning the substrate with topographic features and chemically modifying the surface to exhibit neutral wetting behaviour towards the blocks of the copolymer. The uniformity of the domain size and row spacing of block copolymer templates created in this way was improved compared to those reported in previous studies that used graphoepitaxy of sphere-forming block copolymers. The pattern of block copolymer domains was transferred to a pattern of magnetic metal dots, demonstrating the potential of this technology for the fabrication of patterned magnetic recording media.     

Investigation of the growth of focal adhesions using protein nanoarrays fabricated by nanocontact printing using size tunable polymeric nanopillars

Here we describe a simple approach to create various sizes of protein nanoarrays for the investigation of cell adhesion. Using a combination of nanosphere lithography, oxygen plasma treatment, deep etching and nanomolding processes, well-ordered polymeric nanopillar arrays have been fabricated with diameters in the range of 50-600 nm. These nanopillar arrays were used as stamps for nanocontact printing to create fibronectin nanoarrays, which were used to study the size dependent formation of focal adhesion. It was found that cells can adhere and spread on fibronectin nanoarrays with a fibronectin pattern as small as 50 nm. It was also found that the average size of focal adhesion decreased as the size of the fibronectin pattern was reduced.     

Interplay of confinement, strain, and piezoelectric effects in the optical spectrum of GaN quantum dots

We theoretically investigated excitonic states, energy and oscillator strength of optical transitions in GaN quantum dots characterized by different size, shape, interface, and substrate. On the basis of our multi-band model we determined that the piezoelectric field-induced red shift of the ground state transition, observed in recent experiments, can manifest itself only in strained GaN/AIN dots with the dot height larger than 3 nm. It was also established that the oscillator strength of the red-shifted transitions is small (< 0.05) and decreases fast with increasing the dot size, while the strength of ground state transitions in c-GaN/c-AIN and GaN/dielectric dots is large (approximately 0.4-0.7) and almost independent of the dot size.     

Self-assembly routes towards creating superconducting and magnetic arrays

Using self-assembly from colloidal suspensions of polystyrene latex spheres we prepared well-ordered templates. By electrochemical deposition of magnetic and superconducting metals in the pores of such templates highly ordered magnetic and superconducting anti-dot nano-structures with 3D architectures were created. Further developments of this template preparation method allow us to obtain dot arrays and even more complicated structures. In magnetic anti-dot arrays we observe a large increase in coercive field produced by nanoscale (50–1000nm) holes. We also find the coercive field to demonstrate an oscillatory dependence on film thickness. In magnetic dot arrays we have explored the genesis of 3D magnetic vortices and determined the critical dot size. Superconducting Pb anti-dot arrays show pronounced Little-Parks oscillations in T_c and matching effects in magnetization and magnetic susceptibility. The spherical shape of the holes results in significantly reduced pinning strength as compared to standard lithographic samples. Our results demonstrate that self-assembly template methods are emerging as a viable, low cost route to prepare sub-micron structures.     

Self-assembly Routes towards Creating Superconducting and Magnetic Arrays

No Heading Using self-assembly from colloidal suspensions of polystyrene latex spheres we prepared well-ordered templates. By electrochemical deposition of magnetic and superconducting metals in the pores of such templates highly ordered magnetic and superconducting anti-dot nano-structures with 3D architectures were created. Further developments of this template preparation method allow us to obtain dot arrays and even more complicated structures. In magnetic anti-dot arrays we observe a large increase in coercive field produced by nanoscale (50–1000nm) holes. We also find the coercive field to demonstrate an oscillatory dependence on film thickness. In magnetic dot arrays we have explored the genesis of 3D magnetic vortices and determined the critical dot size. Superconducting Pb anti-dot arrays show pronounced Little-Parks oscillations in Tc and matching effects in magnetization and magnetic susceptibility. The spherical shape of the holes results in significantly reduced pinning strength as compared to standard lithographic samples. Our results demonstrate that self-assembly template methods are emerging as a viable, low cost route to prepare sub-micron structures.PACS numbers: 74.25Ha, 75.75+a.     

Drop-on-demand printing of carbon black ink by electrohydrodynamic jet printing

Electrohydrodynamic (EHD) jet printing is a technique using electric fields to eject inks through nozzle apertures. EHD jet printing is very attractive due to its non-contacting nature and compatibility with diverse materials and substrates. In this research, we have fabricated micron-sized dot arrays and line patterns with carbon black ink on Si wafer substrates using EHD jet printing. The effect of operating conditions such as applied voltage, working distance and stage speed on the size and shape of the jetted patterns and jetting cycles is investigated by using optical microscope, high speed camera and atomic force microscopy (AFM). We have also demonstrated the drop-on-demand feature of the EHD jet printing system by patterning carbon black ink lines with various widths and dot arrays with desired diameters and spacing by controlling the operating conditions.