First-Principles Calculation of MoO2 and MoO3 Electronic and Optical Properties Compared with Experimental Data.

MoO3 and MoO2 systems have attracted particular attention for many widespread applications thanks to their electronic and optical peculiarities; from the crystallographic point of view, MoO3 adopts a thermodynamically stable orthorhombic phase (α-MoO3) belonging to the space group Pbmn, while MoO2 assumes a monoclinic arrangement characterized by space group P21/c. In the present paper, we investigated the electronic and optical properties of both MoO3 and MoO2 by using Density Functional Theory calculations, in particular, the Meta Generalized Gradient Approximation (MGGA) SCAN functional together with the PseudoDojo pseudopotential, which were used for the first time to obtain a deeper insight into the nature of different Mo-O bonds in these materials. The calculated density of states, the band gap, and the band structure were confirmed and validated by comparison with already available experimental results, while the optical properties were validated by recording optical spectra. Furthermore, the calculated band-gap energy value for the orthorhombic MoO3 showed the best match to the experimental value reported in the literature. All these findings suggest that the newly proposed theoretical techniques reproduce the experimental evidence of both MoO2 and MoO3 systems with high accuracy.

Plasmonic hot-electron reconfigurable photodetector based on phase-change material Sb2S3.

Hot-carrier based photodetectors and enhanced by surface plasmons (SPs) hot-electron injection into semiconductors, are drawing significant attention. This photodetecting strategy yields to narrowband photoresponse while enabling photodetection at sub-bandgap energies of the semiconductor materials. In this work, we analyze the design of a reconfigurable photodetector based on a metal-semiconductor (MS) configuration with interdigitated dual-comb Au electrodes deposited on the semiconducting Sb2S3 phase-change material. The reconfigurability of the device relies on the changes of refractive index between the amorphous and crystalline phases of Sb2S3 that entail a modulation of the properties of the SPs generated at the dual-comb Au electrodes. An exhaustive numerical study has been realized on the Au grating parameters formed by the dual-comb electrodes, and on the SP order with the purpose of optimizing the absorption of the device, and thus, the responsivity of the photodetector. The optimized photodetector layout proposed here enables tunable narrowband photodetection from the O telecom band (λ = 1310 nm) to the C telecom band (λ = 1550 nm).

Interlaboratory study on Sb2S3 interplay between structure, dielectric function, and amorphous-to-crystalline phase change for photonics.

Antimony sulfide, Sb2S3, is interesting as the phase-change material for applications requiring high transmission from the visible to telecom wavelengths, with its band gap tunable from 2.2 to 1.6 eV, depending on the amorphous and crystalline phase. Here we present results from an interlaboratory study on the interplay between the structural change and resulting optical contrast during the amorphous-to-crystalline transformation triggered both thermally and optically. By statistical analysis of Raman and ellipsometric spectroscopic data, we have identified two regimes of crystallization, namely 250°C ≤ T < 300°C, resulting in Type-I spherulitic crystallization yielding an optical contrast Δn ∼ 0.4, and 300 ≤ T < 350°C, yielding Type-II crystallization bended spherulitic structure with different dielectric function and optical contrast Δn ∼ 0.2 below 1.5 eV. Based on our findings, applications of on-chip reconfigurable nanophotonic phase modulators and of a reconfigurable high-refractive-index core/phase-change shell nanoantenna are designed and proposed.

Investigation of the Effects of Rapid Thermal Annealing on the Electron Transport Mechanism in Nitrogen-Doped ZnO Thin Films Grown by RF Magnetron Sputtering.

Nitrogen-doped ZnO (ZnO:N) thin films, deposited on Si(100) substrates by RF magnetron sputtering in a gas mixture of argon, oxygen, and nitrogen at different ratios followed by Rapid Thermal Annealing (RTA) at 400 °C and 550 °C, were studied in the present work. Raman and photoluminescence spectroscopic analyses showed that introduction of N into the ZnO matrix generated defects related to oxygen and zinc vacancies and interstitials. These defects were deep levels which contributed to the electron transport properties of the ZnO:N films, studied by analyzing the current-voltage characteristics of metal-insulator-semiconductor structures with ZnO:N films, measured at 298 and 77 K. At the appliedtechnological conditions of deposition and subsequent RTA at 400 °C n-type ZnO:N films were formed, while RTA at 550 °C transformed the n-ZnO:N films to p-ZnO:N ones. The charge transport in both types of ZnO:N films was carried out via deep levels in the ZnO energy gap. The density of the deep levels was in the order of 1019 cm-3. In the temperature range of 77-298 K, the electron transport mechanism in the ZnO:N films was predominantly intertrap tunneling, but thermally activated hopping also took place.

Reconfigurable horizontal-vertical carrier transport in graphene/HfZrO field-effect transistors.

We have fabricated at wafer level field-effect-transistors (FETs) having as channel graphene monolayers transferred on a HfZrO ferroelectric, grown by atomic layer deposition on a doped Si (100) substrate. These FETs display either horizontal or vertical carrier transport behavior, depending on the applied gate polarity. In one polarity, the FETs behave as a graphene FET where the transport is horizontal between two contacts (drain and grounded source) and is modulated by a back-gate. Changing the polarity, the transport is vertical between the drain and the back-gate and, irrespective of the metallic contact type, Ti/Au or Cr/Au, the source-drain bias modulates the height of the potential barrier between HfZrO and the doped Si substrate, the carrier transport being described by a Schottky mechanism at high gate voltages and by a space-charge limited mechanism at low gate voltages. Vertical transport is required by three-dimensional integration technologies to increase the density of transistors on chip.

MoS2 radio: detecting radio waves with a two-dimensional transition metal dichalcogenide semiconductor.

In this paper, we designed, fabricated and tested a microwave circuit based on a MoS2 self-switching diode. The MoS2 thin film (10-monolayers nominal thickness) was grown on a 4 inch Al2O3/high-resistivity silicon wafer by chemical vapor deposition process. The Raman measurements confirm the high quality of the MoS2 over the whole area of the 4 inch wafer. We show experimentally that a microwave circuit based on a few-layers MoS2 self-switching diode fabricated at the wafer level is able to detect the audio spectrum from amplitude-modulated microwave signals in the band 0.9-10 GHz, i.e. in the frequency range mostly used by current wireless communications. In particular, the 900 MHz band is widely exploited for GSM applications, whereas the 3.6 GHz band has been identified as the primary pioneer band for 5G in the European Union.

Wafer-scale very large memory windows in graphene monolayer/HfZrO ferroelectric capacitors.

We have fabricated and electrically characterized at the wafer scale tens of metal-ferroelectric (HfZrO)-semiconductor capacitors and metal-graphene monolayer-ferroelectric (HfZrO)-semiconductor capacitors with the same top electrode dimensions. We have found that the memory windows of the capacitors containing graphene are 3-4 times larger than the ferroelectric capacitors without graphene, and increase even more after annealing. This physical effect can be attributed to the additional electric field exerted by the graphene monolayer on the HfZrO ferroelectric semiconductor capacitor, and to the negative thermal extension coefficient of graphene, respectively.

Electromagnetic energy harvesting based on HfZrO tunneling junctions.

HfZrO ferroelectrics with a thickness of 6 nm were grown directly on Si using atomic layer deposition, top and bottom metallic electrodes being subsequently deposited by electron-beam metallization techniques. Depending on the polarity of the ±10 V poling voltages, the current-voltage dependence of these tunneling diodes shows a rectifying behavior for different polarizations, the ON-OFF ratio being about 104. Because the currents are at mA level, the HfZrO tunneling diodes coupled to an antenna array can harvest electromagnetic energy at 26 GHz (a bandwidth designated for internet of things), with a responsivity of 63 V W-1 and a NEP of 4 nW/Hz0.5.

Exploring the optical properties of Vernier phase yttrium oxyfluoride thin films grown by pulsed liquid injection MOCVD.

In this work, we report on the first successful deposition of Vernier phase yttrium oxyfluoride (V-YOF) thin films on Si (100) wafers using pulsed liquid injection metal organic chemical vapor deposition (PLI-MOCVD). The formation of V-YOF has been confirmed by X-ray diffraction measurements and electron probe microanalysis. The infrared phonon modes of V-YOF thin films and their corresponding optical constants as inferred from spectroscopic ellipsometry are reported here for the first time. The V-YOF thin films are featured by a broad absorption band centering around 370-373 cm-1; their refractive index is located between those of YF3 and Y2O3, and which shows an intimate relationship with the oxygen content in the film. The luminescence properties of Er3+ doped V-YOF thin films are finally examined and compared with that of YF3. Our results highlight that the as-deposited V-YOF thin films by PLI-MOCVD serve as promising candidates as efficient host material for spectral conversion for photovoltaic applications.

Very large phase shift of microwave signals in a 6 nm Hf x Zr1-x O2 ferroelectric at ±3 V.

In this letter, we report for the first time very large phase shifts of microwaves in the 1-10 GHz range, in a 1 mm long gold coplanar interdigitated structure deposited over a 6 nm Hf x Zr1-x O2 ferroelectric grown directly on a high resistivity silicon substrate. The phase shift is larger than 60° at 1 GHz and 13° at 10 GHz at maximum applied DC voltages of ±3 V, which can be supplied by a simple commercial battery. In this way, we demonstrate experimentally that the new ferroelectrics based on HfO2 could play an important role in the future development of wireless communication systems for very low power applications.

Study of high order plasmonic modes on ceramic nanodisks.

Transition metal nitrides are promising alternative plasmonic materials to noble metals for data storage applications as they exhibit localized surface plasmon resonances and have high melting temperatures. Here, angle dependent spectral measurements of the plasmonic resonances of nanodisk arrays made from titanium nitride are examined. Polarized light is used to excite the quadrupole and higher order resonance plasmonic modes which are required in the state-of-the-art designs of near-field transducers used in plasmonic enhanced magnetic recording. Numerical simulations compare the energy distribution and absorption efficiencies for different sized Au and Ti nanodisks. A high electric field enhancement is calculated at the termination of a lollipop plasmonic transducer made of titanium nitride which is shifted to longer wavelengths when compared with an Au transducer of the same dimensions. This, together with its outstanding material properties makes TiN a favourable material for data storage applications.

Carboxyl functionalised MWCNT/polymethyl methacrylate bone cement for orthopaedic applications.

The incorporation of carboxyl functionalised multi-walled carbon nanotube (MWCNT-COOH) into a leading proprietary grade orthopaedic bone cement (Simplex P™) at 0.1 wt% has been investigated. Resultant static and fatigue mechanical properties, in addition to thermal and polymerisation properties, have been determined. Significant improvements (p ≤ 0.001) in bending strength (42%), bending modulus (55%) and fracture toughness (22%) were demonstrated. Fatigue properties were improved (p ≤ 0.001), with mean number of cycles to failure and fatigue performance index being increased by 64% and 52%, respectively. Thermal necrosis index values at ≥44℃ and ≥55℃ were significantly reduced (p ≤ 0.001) (28% and 27%) versus the control. Furthermore, the onset of polymerisation increased by 58% (p < 0.001), as did the duration of the polymerisation reaction (52%). Peak energy during polymerisation increased by 672% (p < 0.001). Peak area of polymerisation increased by 116% (p < 0.001) indicating that the incorporation of MWCNT-COOH reduced the rate of polymerisation significantly. A non-significant reduction (8%) in percentage monomer conversion was also recorded. Raman spectroscopy clearly showed that the addition of MWCNT-COOH increased the ratio between normalised intensities of the G-Band and D-Band (IG/ID ), and also increased the theoretical compressive strain (-1.72%) exerted on the MWCNT-COOH by the Simplex P™ cement matrix. Therefore, demonstrating a level of chemical interactivity between the MWCNT-COOH and the Simplex P™ bone cement exists and consequently a more effective mechanism for successful transfer of mechanical load. The extent of homogenous dispersion of the MWCNT-COOH throughout the bone cement was determined using Raman mapping.

Raman spectroscopic monitoring of the osteogenic differentiation of human mesenchymal stem cells.

The differentiation of stem cells into multi-lineages is essential to aid the development of tissue engineered materials that replicate the functionality of their tissue of origin. For this study, Raman spectroscopy was used to monitor the formation of a bone-like apatite mineral during the differentiation of human mesenchymal stem cells (hMSCs) towards an osteogenic lineage. Raman spectroscopy observed dramatic changes in the region dominated by the stretching of phosphate groups (950-970 cm(-1)) during the period of 7-28 days. Changes were also seen at 1030 cm(-1) and 1070 cm(-1), which are associated with the P-O symmetric stretch of PO(4)(3-) and the C-O vibration in the plane stretch of CO(3)(2-). Multivariate factor analysis revealed the presence of various mineral species throughout the 28 day culture period. Bone mineral formation was observed first at day 14 and was identified as a crystalline, non-substituted apatite. During the later stages of culture, different mineral species were observed, namely an amorphous apatite and a carbonate, substituted apatite, all of which are known to be Raman markers for a bone-like material. Band area ratios revealed that both the carbonate-to-phosphate and mineral-to-matrix ratios increased with age. When taken together, these findings suggest that the osteogenic differentiation of hMSCs at early stages resembles endochondral ossification. Due to the various mineral species observed, namely a disordered amorphous apatite, a B-type carbonate-substituted apatite and a crystalline non-substituted hydroxyapatite, it is suggested that the bone-like mineral observed here can be compared to native bone. This work demonstrates the successful application of Raman spectroscopy combined with biological and multivariate analyses for monitoring the various mineral species, degree of mineralisation and the crystallinity of hMSCs as they differentiate into osteoblasts.

Effect of annealing on the properties of indium-tin-oxynitride films as ohmic contacts for gan-based optoelectronic devices.

Indium-tin-oxynitride (ITON) films have been fabricated by rf sputtering from an indium-tin-oxide target in nitrogen plasma. The influence of postdeposition annealing up to 800 degrees C is analyzed by electrical, optical, and surface characterization of the films in comparison to indium-tin-oxide (ITO) films fabricated in argon plasma. High-temperature annealing resulted in ITO(N) films with similar carrier concentrations. However, the resistivity and optical transmittance of the ITON films were higher than those of the ITO films. Photoelectron spectroscopy revealed that nitrogen is incorporated into the ITON structure in an unbound state as well as through the formation of metal-nitrogen and oxynitride bonds that decorate oxygen vacancies. When the core level electron spectra of ITO and ITON films are compared, a correlation between carrier concentration and the incorporated nitrogen is found. Changes in ITON electrical properties are mainly induced by the release of nitrogen at temperatures above 550 degrees C. In this context, ohmic contact behavior was achieved for ITON on p-type GaN after annealing at 600 degrees C, while no ohmic contact could be realized using ITO.