Electron Paramagnetic Resonance Characterization of Sodium- and Carbonate-Containing Hydroxyapatite Cement.

Ionizing radiation-induced paramagnetic defects in calcified tissues like tooth enamel are indicators of irradiation dose. Hydroxyapatite (HA), the principal constituent in these materials, incorporates a variety of anions (CO32-, F-, Cl-, and SiO44-) and cations (Mn2+, Li+, Cu2+, Fe3+, Mg2+, and Na+) that directly or indirectly contribute to the formation of stable paramagnetic centers upon irradiation. Here, we used an underexploited synthesis method based on the ambient temperature setting reaction of a self-hardening calcium phosphate cement (CPC) to create carbonate-containing hydroxyapatite (CHA) and investigate its paramagnetic properties following γ-irradiation. Powder X-ray diffraction and IR spectroscopic characterization of the hardened CHA samples indicate the formation of pure B-type CHA cement. CHA samples exposed to γ-radiation doses ranging from 1 Gy to 150 kGy exhibited an electron paramagnetic resonance (EPR) signal from an orthorhombic CO2•- free radical. At γ-radiation doses from 30 to 150 kGy, a second signal emerged that is assigned to the CO3•- free radical. We observed that the formation of this second species is dose-dependent, which provided a means to extend the useful dynamic range of irradiated CHA to doses >30 kGy. These results indicate that CHA synthesized via a CPC cement is a promising substrate for EPR-based dosimetry. Further studies on the CHA cement are underway to determine the suitability of these materials for a range of biological and industrial dosimetry applications.

Low-Resistance, High-Yield Electrical Contacts to Atom Scale Si:P Devices Using Palladium Silicide.

Scanning tunneling microscopy (STM) enables the fabrication of two-dimensional δ-doped structures in Si with atomistic precision, with applications from tunnel field-effect transistors to qubits. The combination of a very small contact area and the restrictive thermal budget necessary to maintain the integrity of the δ layer make developing a robust electrical contact method a significant challenge to realizing the potential of atomically precise devices. We demonstrate a method for electrical contact using Pd2Si formed at the temperature of silicon overgrowth (250 °C), minimizing the diffusive impact on the δ layer. We use the transfer length method to show our Pd2Si contacts have very high yield (99.7% +0.2% -1.5%) and low resistivity (272±41Ωµm) in contacting mesa-etched Si:P δ layers. We also present three terminal measurements of low contact resistance (<1 kΩ) to devices written by STM hydrogen depassivation lithography with similarly high yield (100% +0% -3.2%).

Quantifying atom-scale dopant movement and electrical activation in Si:P monolayers.

Advanced hydrogen lithography techniques and low-temperature epitaxial overgrowth enable the patterning of highly phosphorus-doped silicon (Si:P) monolayers (ML) with atomic precision. This approach to device fabrication has made Si:P monolayer systems a testbed for multiqubit quantum computing architectures and atomically precise 2-D superlattice designs whose behaviors are directly tied to the deterministic placement of single dopants. However, dopant segregation, diffusion, surface roughening, and defect formation during the encapsulation overgrowth introduce large uncertainties to the exact dopant placement and activation ratio. In this study, we develop a unique method by combining dopant segregation/diffusion models with sputter profiling simulation to monitor and control, at the atomic scale, dopant movement using room-temperature grown locking layers (LLs). We explore the impact of LL growth rate, thickness, rapid thermal annealing, surface accumulation, and growth front roughness on dopant confinement, local crystalline quality, and electrical activation within Si:P 2-D systems. We demonstrate that dopant movement can be more efficiently suppressed by increasing the LL growth rate than by increasing the LL thickness. We find that the dopant segregation length can be suppressed below a single Si lattice constant by increasing the LL growth rates at room temperature while maintaining epitaxy. Although dopant diffusivity within the LL is found to remain high (on the order of 10-17 cm2 s-1) even below the hydrogen desorption temperature, we demonstrate that exceptionally sharp dopant confinement with high electrical quality within Si:P monolayers can be achieved by combining a high LL growth rate with low-temperature LL rapid thermal annealing. The method developed in this study provides a key tool for 2-D fabrication techniques that require precise dopant placement to suppress, quantify, and predict a single dopant's movement at the atomic scale.

Strain Engineering a 4a×√3a Charge Density Wave Phase in Transition Metal Dichalcogenide 1T-VSe2.

We report a rectangular charge density wave (CDW) phase in strained 1T-VSe2 thin films synthesized by molecular beam epitaxy on c-sapphire substrates. The observed CDW structure exhibits an unconventional rectangular 4a×√3a periodicity, as opposed to the previously reported hexagonal 4a×4a structure in bulk crystals and exfoliated thin layered samples. Tunneling spectroscopy shows a strong modulation of the local density of states of the same 4a×√3a CDW periodicity and an energy gap of 2ΔCDW = (9.1 ± 0.1) meV. The CDW energy gap evolves into a full gap at temperatures below 500 mK, indicating a transition to an insulating phase at ultra-low temperatures. First-principles calculations confirm the stability of both 4a×4a and 4a×√3a structures arising from soft modes in the phonon dispersion. The unconventional structure becomes preferred in the presence of strain, in agreement with experimental findings.

Toward Clean Suspended CVD Graphene.

The application of suspended graphene as electron transparent supporting media in electron microscopy, vacuum electronics, and micromechanical devices requires the least destructive and maximally clean transfer from their original growth substrate to the target of interest. Here, we use thermally evaporated anthracene films as the sacrificial layer for graphene transfer onto an arbitrary substrate. We show that clean suspended graphene can be achieved via desorbing the anthracene layer at temperatures in the 100 °C to 150 °C range, followed by two sequential annealing steps for the final cleaning, using Pt catalyst and activated carbon. The cleanliness of the suspended graphene membranes was analyzed employing the high surface sensitivity of low energy scanning electron microscopy and x-ray photoelectron spectroscopy. A quantitative comparison with two other commonly used transfer methods revealed the superiority of the anthracene approach to obtain larger area of clean, suspended CVD graphene. Our graphene transfer method based on anthracene paves the way for integrating cleaner graphene in various types of complex devices, including the ones that are heat and humidity sensitive.

Silicon epitaxy on H-terminated Si (100) surfaces at 250 °C.

Low temperature Si epitaxy has become increasingly important due to its critical role in the encapsulation and performance of buried nanoscale dopant devices. We demonstrate epitaxial growth up to nominally 25 nm, at 250°C, with analysis at successive growth steps using STM and cross section TEM to reveal the nature and quality of the epitaxial growth. STM images indicate that growth morphology of both Si on Si and Si on H-terminated Si (H: Si) is epitaxial in nature at temperatures as low as 250 °C. For Si on Si growth at 250 °C, we show that the Si epitaxial growth front maintains a constant morphology after reaching a specific thickness threshold. Although the in-plane mobility of silicon is affected on the H: Si surface due to the presence of H atoms during initial sub-monolayer growth, STM images reveal long range order and demonstrate that growth proceeds by epitaxial island growth albeit with noticeable surface roughening.