Atomic Layer Deposition of Molybdenum Disulfide Films Using MoF\u3csub\u3e6\u3c/sub\u3e and H\u3csub\u3e2\u3c/sub\u3eS

Molybdenum sulfide films were grown by atomic layer deposition on silicon and fused silica substrates using molybdenum hexafluoride (MoF6) and hydrogen sulfide at 200 °C. In situ quartz crystal microbalance (QCM) measurements confirmed linear growth at 0.46 Å/cycle and self-limiting chemistry for both precursors. Analysis of the QCM step shapes indicated that MoS2 is the reaction product, and this finding is supported by x-ray photoelectron spectroscopy measurements showing that Mo is predominantly in the Mo(IV) state. However, Raman spectroscopy and x-ray diffraction measurements failed to identify crystalline MoS2 in the as-deposited films, and this might result from unreacted MoFx residues in the films. Annealing the films at 350 °C in a hydrogen rich environment yielded crystalline MoS2 and reduced the F concentration in the films. Optical transmission measurements yielded a bandgap of 1.3 eV. Finally, the authors observed that the MoS2 growth per cycle was accelerated when a fraction of the MoF6 pulses were substituted with diethyl zinc

First-Principles Studies of MoF Absorption on Hydroxylated and Non-Hydroxylated Metal Oxide Surfaces and Implications for Atomic Layer Deposition of MoS\u3csub\u3e2\u3c/sub\u3e

Significant interest in two-dimensional transition metal dichalcogenides has led to numerous experimental studies of their synthesis using scalable vapor phase methods, such as chemical vapor deposition (CVD) and atomic layer deposition (ALD). ALD typically allows lower deposition temperatures, and nucleation of chemical precursors requires reactions with surface functional groups. A common first-principles method used to study ALD modeling is the calculation of activation energy for a proposed reaction pathway. In this work we calculated the partial charge densities, local density of states (LDoS), Bader charge analysis, adsorption energies, and charge density difference using density functional theory (DFT) to investigate the nucleation of MoF6 on three oxide surfaces, including Al2O3, HfO2, and MgO. Our findings indicate that hydroxyl groups (OH) help lower the reaction barrier during the first half-cycle of MoF6 and promote the chemisorption of a precursor on the oxide substrates. This discovery is supported by the formation of highly ionic MFx (M = metal, x = 1, 2, 3) bonds at the oxide surfaces. By comparing surfaces with and without hydroxyl groups, we highlight the importance of surface chemistry

Nanometrology and super-resolution imaging with DNA

Peer reviewe

Kinetics of DNA and RNA Hybridization in Serum and Serum-SDS

Cancer is recognized as a serious health challenge both in the United States and throughout the world. While early detection and diagnosis of cancer leads to decreased mortality rates, current screening methods require significant time and costly equipment. Recently, increased levels of certain micro-ribonucleic acids (miRNAs) in the blood have been linked to the presence of cancer. While blood-based biomarkers have been used for years in cancer detection, studies analyzing trace amounts of miRNAs in blood and serum samples are just the beginning. Recent developments in deoxyribonucleic acid (DNA) nanotechnology and DNA computing have shown that it is possible to construct nucleic-acid-based chemical networks that accept miRNAs as inputs, perform Boolean logic functions on those inputs, and generate as an output a large number of DNA strands that can be readily detected. Since miRNAs occur in blood in low abundance, these networks would allow for amplification without using polymerase chain reaction. In this study, we report initial progress in the development of a DNA-based cross-catalytic network engineered to amplify specific cancer-related miRNAs. Subcomponents of the DNA network were tested individually, and their operation in serum, as well as a mixture of serum with sodium dodecyl sulfate, is demonstrated. Preliminary simulations of the full cross-catalytic network indicate successful operation

Open-Source Automated Chemical Vapor Deposition System for the Production of Two-Dimensional Nanomaterials

The study of two- dimensional (2D) materials is a rapidly growing area within nanomaterials research. However, the high equipment costs, which include the processing systems necessary for creating these materials, can be a barrier to entry for some researchers interested in studying these novel materials. Such process systems include those used for chemical vapor deposition, a preferred method for making these materials. To address this challenge, this article presents the first open-source design for an automated chemical vapor deposition system that can be built for less than a third of the cost for a comparable commercial system. The materials and directions for the system are divided by subsystems, which allows the system to be easily built, customized and upgraded, depending upon the needs of the user. We include the details for the specific hardware that will be needed, instructions for completing the build, and the software needed to automate the system. With a chemical vapor deposition system built as described, a variety of 2D nanomaterials and their heterostructures can be grown. Specifically, the experimental results clearly demonstrate the capability of this open-source design in producing high quality, 2D nanomaterials such as graphene and tungsten disulfide, which are at the forefront of research in emerging semiconductor devices, sensors, and energy storage applications

Synthesis and Functionalization of Small Silver Nanoparticles

Metal nanoparticles in general exhibit interesting properties due to their small sizes. This response shows up as an intense absorption band in the visible region making metallic nanoparticles ideal probes for medical imaging as well as for countless other applications. Functionalizing metallic nanoparticles with DNA enables targeted labeling, controlled by their base sequence. Another purpose of functionalization is to attach the nanoparticle to a DNA substrate allowing controlled bottom up engineering of nanoscale devices. Gold or gold-encapsulated silver is usually used for these purposes instead of bare silver due to the ease with which silver is oxidized although silver nanoparticles show more intense plasmon resonance. The functionalization of silver with DNA is difficult because their surfaces are easily oxidized. The goal of this experiment was to attach thiolated DNA strands to bare 5-10 nm silver nanoparticles proving that it can indeed be done without extensive modification of the functionalization procedure. In order for this to be accomplished silver nanoparticles were synthesized using two different methods: a UV light directed growth method and a sodium borohydride/sodium citrate buffered reduction method. The first method resulted in nanoparticles in the 10-15 nm range while the second resulted in smaller particles (5-10 nm). DNA was then attached to purified particles using a process that has previously been applied to gold nanoparticles. The functionalization was verified using UV-Vis spectroscopy (to measure changes in the Plasmon peak and concentration) and the stability of the final product in a 0.3 M sodium chloride solution. Several samples have exhibited minimal peak shifts and minimal concentration loss indicating that little or no silver was oxidized in the functionalization process. These samples also remained stable as the sodium chloride concentration was slowly brought up to 0.3 M. Control samples precipitated out of solution almost immediately upon the addition of sodium chloride. Successful functionalization of silver nanoparticles opens up the way for the addition of functionalized silver particles and their inherent optical properties onto DNA heterostructures where they can then be used as seeds for directed growth of nanowires or nanoprisms. This will be accomplished by adding target strands to the DNA structure that are complimentary to the sequence bound to the nanoparticles which then hybridize with the strands on the nanoparticle resulting the incorporation of the nanoparticle into the DNA heterostructure

Photonic Band Tuning in 2D Photonic Crystals by Atomic Layer Deposition

Atomic layer deposition (ALD) has become a powerful tool for the fabrication of high quality 3-dimentional photonic crystals (PCs) from both inorganic (opal) and organic (holographically patterned polymer) templates [1,2]. With ALD, highly conformal films can be grown with a precision of 0.05 nm, which, when combined with the availability of a wide range of low temperature film growth protocols, enables a high degree of control over material and structural properties to precisely tune optical properties [3]. Two-dimensional photonic crystals have been developed extensively for applications in optical interconnects, beam steering, and sensor devices; and are predominantly fabricated by electron-beam lithography. The optical properties of 2D photonic crystal slab waveguides are determined by the precision of the lithography process, with limited post fabrication tunability

Advanced Scanning Probe Microscopy for Materials Research

Scanning probe microscopy (SPM) encompasses a set of advanced techniques for mapping the structure and properties of the surfaces of materials from the atomic to micro scales. The most widely used SPM technique is atomic force microscopy (AFM), in which forces exerted between the tip of a needle probe and the sample surface can be measured with extremely high precision. By recording these forces as the tip rasters across the surface, an image of the sample surface topography is obtained. Beyond the surface topography, several SPM techniques can provide quantitative information about the properties of a material’s surface. These include scanning Kelvin probe force microscopy (KPFM) for surface potential measurements, scanning capacitance microscopy (SCM) for surface capacitance mapping, conductive and tunneling AFM (C-AFM and TUNA) for imaging the electrical conductance of a surface, as well as several techniques for imaging the mechanical properties of a surface. These advanced SPM techniques provide tools for direct structure-property correlations in materials at the nanoscale and are powerful capabilities for materials research, especially when co-located with other surface analytical techniques. Each of these advanced SPM techniques is available for materials research in the Boise State University Surface Science Laboratory

Advanced Atomic Force Microscopy for BioMaterials Research

Optical microscopy uses the interactions between light and materials to provide images of the microscopic world. It is widely employed in science to study the behavior and properties of microscopic organisms and cells. Atomic force microscopy (AFM) is a technique for obtaining images of the surfaces of materials at the atomic to micrometer scales. AFM operates by rastering an ultra-sharp needle across a sample surface and recording the height of the needle at each position. While AFM can provide atomic resolution images of the contours (topography) of a surface, it can also perform extremely sensitive measurements of surface mechanical properties. By fabricating custom AFM probes, the mechanical properties of specific locations of living cells can be studied and manipulated. In addition, high-speed imaging of biological materials can provide images of changes to cellular surfaces in response to chemical or electrical signals. This poster will present examples and applications of advanced AFM capabilities for research in biomaterials available in the Boise State University Surface Science Laboratory

Toward Improving Ambient Volta Potential Measurements with SKPFM for Corrosion Studies

Scanning Kelvin probe force microscopy (SKPFM) is used in corrosion studies to quantify the relative nobility of different microstructural features present within complex metallic systems and thereby elucidate possible corrosion initiation sites. However, Volta potential differences (VPDs) measured via SKPFM in the literature for metal alloys exhibit large variability, making interpretation and application for corrosion studies difficult. We have developed an improved method for referencing SKPFM VPDs by quantifying the closely related work function of the probe relative to an inert gold standard whose modified work function is calculated via density functional theory (DFT). By measuring and tracking changes in the probe vs. gold VPD, this method compensates for some of the complex effects that cause changes in an individual probe\u27s work function. Furthermore, it provides a path toward direct, quantitative comparison of SKPFM results obtained by different researchers. Application of this method to a Cu-Ag-Ti eutectic braze of a steel sample imaged with multiple SKPFM probes of differing compositions led to enhanced repeatability both within and among probe types, as well as enabled the calculation of modified work function values for each of the microstructural constituents present