Tetracoordinate Co(II) complexes with semi-coordination as stable single-ion magnets for deposition on graphene.

We present a theoretical and experimental study of two tetracoordinate Co(II)-based complexes with semi-coordination interactions, i.e., non-covalent interactions involving the central atom. We argue that such interactions enhance the thermal and structural stability of the compounds, making them appropriate for deposition on substrates, as demonstrated by their successful deposition on graphene. DC magnetometry and high-frequency electron spin resonance (HF-ESR) experiments revealed an axial magnetic anisotropy and weak intermolecular antiferromagnetic coupling in both compounds, supported by theoretical predictions from complete active space self-consistent field calculations complemented by N-electron valence state second-order perturbation theory (CASSCF-NEVPT2), and broken-symmetry density functional theory (BS-DFT). AC magnetometry demonstrated that the compounds are field-induced single-ion magnets (SIMs) at applied static magnetic fields, with slow relaxation of magnetization governed by a combination of quantum tunneling, Orbach, and direct relaxation mechanisms. The structural stability under ambient conditions and after deposition was confirmed by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Theoretical modeling by DFT of different configurations of these systems on graphene revealed n-type doping of graphene originating from electron transfer from the deposited molecules, confirmed by electrical transport measurements and Raman spectroscopy.

Ambient effects on photogating in MoS2 photodetectors.

Atomically thin transition metal dichalcogenides (TMDs) are ideal candidates for ultrathin optoelectronics that are flexible and semitransparent. Photodetectors based on TMDs show remarkable performance, with responsivity and detectivity higher than 103 AW-1 and 1012 Jones, respectively, but they are plagued by response times as slow as several tens of seconds. Although it is well established that gas adsorbates such as water and oxygen create charge traps and significantly increase both the responsivity and the response time, the underlying mechanism is still unclear. Here we study the influence of adsorbates on MoS2 photodetectors under ambient conditions, vacuum and illumination at different wavelengths. We show that, for wavelengths sufficiently short to excite electron-hole pairs in the MoS2, light illumination causes desorption of water and oxygen molecules. The change in the molecular gating provided by the physisorbed molecules is the dominant contribution to the device photoresponse in ambient conditions.

Highly sensitive MoS2 photodetectors with graphene contacts.

Two-dimensional materials such as graphene and transition metal dichalcogenides (TMDs) are ideal candidates to create ultra-thin electronics suitable for flexible substrates. Although optoelectronic devices based on TMDs have demonstrated remarkable performance, scalability is still a significant issue. Most devices are created using techniques that are not suitable for mass production, such as mechanical exfoliation of monolayer flakes and patterning by electron-beam lithography. Here we show that large-area MoS2 grown by chemical vapor deposition and patterned by photolithography yields highly sensitive photodetectors, with record shot-noise-limited detectivities of 8.7 × 1014 Jones in ambient condition and even higher when sealed with a protective layer. These detectivity values are higher than the highest values reported for photodetectors based on exfoliated MoS2. We study MoS2 devices with gold electrodes and graphene electrodes. The devices with graphene electrodes have a tunable band alignment and are especially attractive for scalable ultra-thin flexible optoelectronics.

Low carrier density epitaxial graphene devices on SiC.

The transport characteristics of graphene devices with low n- or p-type carrier density (∼10(10) -10(11) cm(-2) ), fabricated using a new process that results in minimal organic surface residues, are reported. The p-type molecular doping responsible for the low carrier densities is initiated by aqua regia. The resulting devices exhibit highly developed ν = 2 quantized Hall resistance plateaus at magnetic field strengths of less than 4 T.

Observation of Multi-Phonon Emission in Monolayer WS2 on Various Substrates.

Transition metal dichalcogenides (TMDs) have unique absorption and emission properties that stem from their large excitonic binding energies, reduced-dielectric screening, and strong spin-orbit coupling. However, the role of substrates, phonons, and material defects in the excitonic scattering processes remains elusive. In tungsten-based TMDs, it is known that the excitons formed from electrons in the lower-energy conduction bands are dark in nature, whereas low-energy emissions in the photoluminescence spectrum have been linked to the brightening of these transitions, either via defect scattering or via phonon scattering with first-order phonon replicas. Through temperature and incident-power-dependent studies of WS2 grown by CVD or exfoliated from high-purity bulk crystal on different substrates, we demonstrate that the strong exciton-phonon coupling yields brightening of dark transitions up to sixth-order phonon replicas. We discuss the critical role of defects in the brightening pathways of dark excitons and their phonon replicas, and we elucidate that these emissions are intrinsic to the material and independent of substrate, encapsulation, growth method, and transfer approach.

Sex bias in celiac disease: XWAS and monocyte eQTLs in women identify TMEM187 as a functional candidate gene.

BACKGROUND: Celiac disease (CeD) is an immune-mediated disorder that develops in genetically predisposed individuals upon gluten consumption. HLA risk alleles explain 40% of the genetic component of CeD, so there have been continuing efforts to uncover non-HLA loci that can explain the remaining heritability. As in most autoimmune disorders, the prevalence of CeD is significantly higher in women. Here, we investigated the possible involvement of the X chromosome on the sex bias of CeD. METHODS: We performed a X chromosome-wide association study (XWAS) and a gene-based association study in women from the CeD Immunochip (7062 cases, 5446 controls). We also constructed a database of X chromosome cis-expression quantitative trait loci (eQTLs) in monocytes from unstimulated (n = 226) and lipopolysaccharide (LPS)-stimulated (n = 130) female donors and performed a Summary-data-based MR (SMR) analysis to integrate XWAS and eQTL information. We interrogated the expression of the potentially causal gene (TMEM187) in peripheral blood mononuclear cells (PBMCs) from celiac patients at onset, on a gluten-free diet, potential celiac patients and non-celiac controls. RESULTS: The XWAS and gene-based analyses identified 13 SNPs and 25 genes, respectively, 22 of which had not been previously associated with CeD. The X chromosome cis-eQTL analysis found 18 genes with at least one cis-eQTL in naïve female monocytes and 8 genes in LPS-stimulated female monocytes, 2 of which were common to both situations and 6 were unique to LPS stimulation. SMR identified a potentially causal association of TMEM187 expression in naïve monocytes with CeD in women, regulated by CeD-associated, eQTL-SNPs rs7350355 and rs5945386. The CeD-risk alleles were correlated with lower TMEM187 expression. These results were replicated using eQTLs from LPS-stimulated monocytes. We observed higher levels of TMEM187 expression in PBMCs from female CeD patients at onset compared to female non-celiac controls, but not in male CeD individuals. CONCLUSION: Using X chromosome genotypes and gene expression data from female monocytes, SMR has identified TMEM187 as a potentially causal candidate in CeD. Further studies are needed to understand the implication of the X chromosome in the higher prevalence of CeD in women.

Celiac disease (CeD) is an immune-related condition triggered by gluten consumption in genetically susceptible individuals. Women present higher prevalence of CeD than men, but the biological explanation of such difference has not been elucidated. In this study, we investigated whether specific genetic variations on the X chromosome were associated with CeD in each sex. Surprisingly, we found 13 genetic variants and 25 genes significantly linked to CeD in women, but not in men. Additionally, we identified genetic variants on the X chromosome associated with gene expression of monocytes, a type of immune cells that is activated in CeD after gluten intake. Integrating these data with our previous findings, we found that lower expression of a gene termed TMEM187 might be associated with a potential increase in CeD risk in women. Finally, validation experiments confirmed higher TMEM187 levels in blood cells from female CeD patients compared to non-celiac women, while no such difference was seen in males. In summary, our study suggests that the X-chromosome gene TMEM187 may play a key role in CeD development, providing insights into the higher prevalence of CeD in females.

Endoscopic Lipofilling for the Treatment of Bronchopleural Fistulas After Anatomic Lung Resection.

A bronchopleural fistula is a potentially fatal complication of anatomic lung resection surgery. Bronchoscopy has been described in the treatment of small-caliber fistulas. An endoscopic procedure based on instillation of mesenchymal stem cells for the treatment of bronchopleural fistula has recently been successful. Fat tissue is rich in mesenchymal stem cells, and we describe a technique based on the instillation of autologous fat (lipofilling) for the treatment of bronchopleural fistulas. The procedure was applied to 8 subjects affected by bronchopleural fistulas that were greater than 8 mm in diameter, and saw resolution in all cases.

Abrikosov vortex corrections to effective magnetic field enhancement in epitaxial graphene.

Here, we report the effects of enhanced magnetic fields resulting from type-II superconducting NbTiN slabs adjacent to narrow Hall bar devices fabricated from epitaxial graphene. Observed changes in the magnetoresistances were found to have minimal contributions from device inhomogeneities, magnet hysteresis, electron density variations along the devices, and transient phenomena. We hypothesize that Abrikosov vortices, present in type-II superconductors, contribute to these observations. By determining the London penetration depth, coupled with elements of Ginzburg-Landau theory, one can approximate an upper bound on the effect that vortex densities at low fields (< 1T) have on the reported observations. These analyses offer insights into device fabrication and how to utilize the Meissner effect for any low-field and low-temperature applications using superconductors.

Electrical properties and memory effects of field-effect transistors from networks of single- and double-walled carbon nanotubes.

We study field-effect transistors made of single- and double-walled carbon nanotube networks for applications as memory devices. The transfer characteristics of the transistors exhibit a reproducible hysteresis which enables their use as nano-sized memory cells with operations faster than 10 ms, endurance longer than 10(+4) cycles and charge retention of a few hours in air. We propose water enhanced charge trapping at the SiO(2)/air interface close to the nanotubes as the dominant mechanism for charge storage. We show that charge storage can be improved by limiting exposure of the device to air.

Novel in-situ decoration of single-walled carbon nanotube transistors with metal nanoparticles.

The carbon nanotube-metal nanoparticle complex has attracted a lot of research interest because of their potential applications in catalysis and gas sensing. Here we introduce a novel electrochemical method to realize in-situ decoration of single-walled carbon nanotube field effect transistors (CNT-FET) with metal nanoparticles using a sacrificial electrode. In this process, metal atoms are first ionized into an electrolyte solution by applying a potential difference between the sacrificial electrode and the grounded source/drain electrodes connecting the nanotube of the CNT-FET. The positive metal ions migrate under the influence of the electric field, and deposit on the grounded nanotube as metal nanoparticles. This method provides for better control over the quantity and size of the deposited nanoparticles compared to other decoration methods. We demonstrate successful deposition of Au and Ag nanoparticles on carbon nanotube field effect devices, with the quantity and size of the nanoparticles varying as a function of the applied potential. We show that the metal nanoparticle size can vary from 10 nm to over 300 nm, and the spatial distribution can change from very scarce decoration to a near continuous coating. Such metal nanoparticles have potential applications in chemical sensors, as they interact with gas molecules and generate an electrical signal in the nanotube, which can be detected. They can also be explored as biological anchoring sites for bio-functionalization of the nanotube, which is critical to developing highly sensitive and selective bio-sensors.

Epitaxial graphene quantum dots for high-performance terahertz bolometers.

Light absorption in graphene causes a large change in electron temperature due to the low electronic heat capacity and weak electron-phonon coupling. This property makes graphene a very attractive material for hot-electron bolometers in the terahertz frequency range. Unfortunately, the weak variation of electrical resistance with temperature results in limited responsivity for absorbed power. Here, we show that, due to quantum confinement, quantum dots of epitaxial graphene on SiC exhibit an extraordinarily high variation of resistance with temperature (higher than 430 MΩ K(-1) below 6 K), leading to responsivities of 1 × 10(10) V W(-1), a figure that is five orders of magnitude higher than other types of graphene hot-electron bolometer. The high responsivity, combined with an extremely low electrical noise-equivalent power (∼2 × 10(-16) W Hz(-1/2) at 2.5 K), already places our bolometers well above commercial cooled bolometers. Additionally, we show that these quantum dot bolometers demonstrate good performance at temperature as high as 77 K.

Indium Tin Oxide Nanowire Networks as Effective UV/Vis Photodetection Platforms.

We demonstrate that indium tin oxide nanowires (ITO NWs) and cationic polymer-modified ITO NWs configured in a network format can be used as high performing UV/vis photodetectors. The photovoltage response of ITO NWs is much higher than similarly constructed devices made from tin oxide, zinc tin oxide, and zinc oxide nanostructures. The ITO NW mesh-based devices exhibit a substantial photovoltage (31-100 mV under illumination with a 1.14 mW 543 nm laser) and photocurrent (225-325 µA at 3 V). The response time of the devices is fast with a rise time of 20-30 µs and a decay time of 1.5-3.7 ms when probed with a 355 nm pulsed laser. The photoresponsivity of the ITO NW devices ranges from 0.07 to 0.2 A/W at a 3 V bias, whose values are in the performance range of most commercial UV/vis photodetectors. Such useful photodetector characteristics from our ITO NW mesh devices are attained straightforwardly without the need for complicated fabrication procedures involving highly specialized lithographic tools. Therefore, our approach of ITO NW network-based photodetectors can serve as a convenient alternative to commercial or single NW-based devices.

Electron-hole transport and photovoltaic effect in gated MoS2 Schottky junctions.

Semiconducting molybdenum disulfphide has emerged as an attractive material for novel nanoscale optoelectronic devices due to its reduced dimensionality and large direct bandgap. Since optoelectronic devices require electron-hole generation/recombination, it is important to be able to fabricate ambipolar transistors to investigate charge transport both in the conduction band and in the valence band. Although n-type transistor operation for single-layer and few-layer MoS2 with gold source and drain contacts was recently demonstrated, transport in the valence band has been elusive for solid-state devices. Here we show that a multi-layer MoS2 channel can be hole-doped by palladium contacts, yielding MoS2 p-type transistors. When two different materials are used for the source and drain contacts, for example hole-doping Pd and electron-doping Au, the Schottky junctions formed at the MoS2 contacts produce a clear photovoltaic effect.

Magnetically induced field effect in carbon nanotube devices.

Three-terminal devices with conduction channels formed by quasi-metallic carbon nanotubes (CNTs) are shown to operate as nanotube-based field-effect transistors under strong magnetic fields. The off-state conductance of the devices varies exponentially with the magnetic flux intensity. We extract the quasi-metallic CNT chirality as well as the characteristics of the Schottky barriers formed at the metal-nanotube contacts from the temperature-dependent magnetoconductance measurements.