Cellulose-Based Laser-Induced Graphene Devices for Electrochemical Monitoring of Bacterial Phenazine Production and Viability.

As an easily disposable substrate with a microporous texture, paper is a well-suited, generic substrate to build analytical devices for studying bacteria. Using a multi-pass lasing process, cellulose-based laser-induced graphene (cLIG) with a sheet resistance of 43.7 ± 2.3 Ωsq-1 is developed and utilized in the fabrication of low-cost and environmentally-friendly paper sensor arrays. Two case studies with Pseudomonas aeruginosa and Escherichia coli demonstrate the practicality of the cLIG sensors for the electrochemical analysis of bacteria. The first study measures the time-dependent profile of phenazines released from both planktonic (up to 60 h) and on-chip-grown (up to 22 h) Pseudomonas aeruginosa cultures. While similarities do exist, marked differences in phenazine production are seen with cells grown directly on cLIG compared to the planktonic culture. Moreover, in planktonic cultures, pyocyanin levels increase early on and plateau around 20 h, while optical density measurements increase monotonically over the duration of testing. The second study monitors the viability and metabolic activity of Escherichia coli using a resazurin-based electrochemical assay. These results demonstrate the utility of cLIG paper sensors as an inexpensive and versatile platform for monitoring bacteria and could enable new opportunities in high-throughput antibiotic susceptibility testing, ecological studies, and biofilm studies.

Growth Kinetics and Atomistic Mechanisms of Native Oxidation of ZrSxSe2-x and MoS2 Crystals.

A thorough understanding of native oxides is essential for designing semiconductor devices. Here, we report a study of the rate and mechanisms of spontaneous oxidation of bulk single crystals of ZrSxSe2-x alloys and MoS2. ZrSxSe2-x alloys oxidize rapidly, and the oxidation rate increases with Se content. Oxidation of basal surfaces is initiated by favorable O2 adsorption and proceeds by a mechanism of Zr-O bond switching, that collapses the van der Waals gaps, and is facilitated by progressive redox transitions of the chalcogen. The rate-limiting process is the formation and out-diffusion of SO2. In contrast, MoS2 basal surfaces are stable due to unfavorable oxygen adsorption. Our results provide insight and quantitative guidance for designing and processing semiconductor devices based on ZrSxSe2-x and MoS2 and identify the atomistic-scale mechanisms of bonding and phase transformations in layered materials with competing anions.

Role of Bilayer Graphene Microstructure on the Nucleation of WSe2 Overlayers.

Over the past few years, graphene grown by chemical vapor deposition (CVD) has gained prominence as a template to grow transition metal dichalcogenide (TMD) overlayers. The resulting two-dimensional (2D) TMD/graphene vertical heterostructures are attractive for optoelectronic and energy applications. However, the effects of the microstructural heterogeneities of graphene grown by CVD on the growth of the TMD overlayers are relatively unknown. Here, we present a detailed investigation of how the stacking order and twist angle of CVD graphene influence the nucleation of WSe2 triangular crystals. Through the combination of experiments and theory, we correlate the presence of interlayer dislocations in bilayer graphene with how WSe2 nucleates, in agreement with the observation of a higher nucleation density of WSe2 on top of Bernal-stacked bilayer graphene versus twisted bilayer graphene. Scanning/transmission electron microscopy (S/TEM) data show that interlayer dislocations are present only in Bernal-stacked bilayer graphene but not in twisted bilayer graphene. Atomistic ReaxFF reactive force field molecular dynamics simulations reveal that strain relaxation promotes the formation of these interlayer dislocations with localized buckling in Bernal-stacked bilayer graphene, whereas the strain becomes distributed in twisted bilayer graphene. Furthermore, these localized buckles in graphene are predicted to serve as thermodynamically favorable sites for binding WSex molecules, leading to the higher nucleation density of WSe2 on Bernal-stacked graphene. Overall, this study explores synthesis-structure correlations in the WSe2/graphene vertical heterostructure system toward the site-selective synthesis of TMDs by controlling the structural attributes of the graphene substrate.

Epitaxial graphene transistors: enhancing performance via hydrogen intercalation.

We directly demonstrate the importance of buffer elimination at the graphene/SiC(0001) interface for high frequency applications. Upon successful buffer elimination, carrier mobility increases from an average of 800 cm(2)/(V s) to >2000 cm(2)/(V s). Additionally, graphene transistor current saturation increases from 750 to >1300 mA/mm, and transconductance improves from 175 mS/mm to >400 mS. Finally, we report a 10× improvement in the extrinsic current gain response of graphene transistors with optimal extrinsic current-gain cutoff frequencies of 24 GHz.

Enhanced transport and transistor performance with oxide seeded high-κ gate dielectrics on wafer-scale epitaxial graphene.

We explore the effect of high-κ dielectric seed layer and overlayer on carrier transport in epitaxial graphene. We introduce a novel seeding technique for depositing dielectrics by atomic layer deposition that utilizes direct deposition of high-κ seed layers and can lead to an increase in Hall mobility up to 70% from as-grown. Additionally, high-κ seeded dielectrics are shown to produce superior transistor performance relative to low-κ seeded dielectrics and the presence of heterogeneous seed/overlayer structures is found to be detrimental to transistor performance, reducing effective mobility by 30-40%. The direct deposition of high-purity oxide seed represents the first robust method for the deposition of uniform atomic layer deposited dielectrics on epitaxial graphene that improves carrier transport.

Influence of the Underlying Substrate on the Physical Vapor Deposition of Zn-Phthalocyanine on Graphene.

Graphene shows great promise not only as a highly conductive flexible and transparent electrode for fabricating novel device architectures but also as an ideal synthesis platform for studying fundamental growth mechanisms of various materials. In particular, directly depositing metal phthalocyanines (MPc's) on graphene is viewed as a compelling approach to improve the performance of organic photovoltaics and light-emitting diodes. In this work, we systematically investigate the ZnPc physical vapor deposition (PVD) on graphene either as-grown on Cu or as-transferred on various substrates including Si(100), C-plane sapphire, SiO2/Si, and h-BN. To better understand the effect of the substrate on the ZnPc structure and morphology, we also compare the ZnPc growth on highly crystalline single- and multilayer graphene. The experiments show that, for identical deposition conditions, ZnPc exhibits various morphologies such as high-aspect-ratio nanowires or a continuous film when changing the substrate supporting graphene. ZnPc morphology is also found to transition from a thin film to a nanowire structure when increasing the number of graphene layers. Our observations suggest that substrate-induced changes in graphene affect the adsorption, surface diffusion, and arrangement of ZnPc molecules. This study provides clear guidelines to control MPc crystallinity, morphology, and molecular orientations which drastically influence the (opto)electronic properties.

Thermal Conductivity of ß-Phase Ga2O3 and (AlxGa1-x)2O3 Heteroepitaxial Thin Films.

Heteroepitaxy of ß-phase gallium oxide (ß-Ga2O3) thin films on foreign substrates shows promise for the development of next-generation deep ultraviolet solar blind photodetectors and power electronic devices. In this work, the influences of the film thickness and crystallinity on the thermal conductivity of (2̅01)-oriented ß-Ga2O3 heteroepitaxial thin films were investigated. Unintentionally doped ß-Ga2O3 thin films were grown on c-plane sapphire substrates with off-axis angles of 0° and 6° toward ⟨112̅0⟩ via metal-organic vapor phase epitaxy (MOVPE) and low-pressure chemical vapor deposition. The surface morphology and crystal quality of the ß-Ga2O3 thin films were characterized using scanning electron microscopy, X-ray diffraction, and Raman spectroscopy. The thermal conductivities of the ß-Ga2O3 films were measured via time-domain thermoreflectance. The interface quality was studied using scanning transmission electron microscopy. The measured thermal conductivities of the submicron-thick ß-Ga2O3 thin films were relatively low as compared to the intrinsic bulk value. The measured thin film thermal conductivities were compared with the Debye-Callaway model incorporating phononic parameters derived from first-principles calculations. The comparison suggests that the reduction in the thin film thermal conductivity can be partially attributed to the enhanced phonon-boundary scattering when the film thickness decreases. They were found to be a strong function of not only the layer thickness but also the film quality, resulting from growth on substrates with different offcut angles. Growth of ß-Ga2O3 films on 6° offcut sapphire substrates was found to result in higher crystallinity and thermal conductivity than films grown on on-axis c-plane sapphire. However, the ß-Ga2O3 films grown on 6° offcut sapphire exhibit a lower thermal boundary conductance at the ß-Ga2O3/sapphire heterointerface. In addition, the thermal conductivity of MOVPE-grown (2̅01)-oriented ß-(AlxGa1-x)2O3 thin films with Al compositions ranging from 2% to 43% was characterized. Because of phonon-alloy disorder scattering, the ß-(AlxGa1-x)2O3 films exhibit lower thermal conductivities (2.8-4.7 W/m·K) than the ß-Ga2O3 thin films. The dominance of the alloy disorder scattering in ß-(AlxGa1-x)2O3 is further evidenced by the weak temperature dependence of the thermal conductivity. This work provides fundamental insight into the physical interactions that govern phonon transport within heteroepitaxially grown ß-phase Ga2O3 and (AlxGa1-x)2O3 thin films and lays the groundwork for the thermal modeling and design of ß-Ga2O3 electronic and optoelectronic devices.

Ga2O3-on-SiC Composite Wafer for Thermal Management of Ultrawide Bandgap Electronics.

ß-phase gallium oxide (Ga2O3) is an emerging ultrawide bandgap (UWBG) semiconductor (EG ∼ 4.8 eV), which promises generational improvements in the performance and manufacturing cost over today's commercial wide bandgap power electronics based on GaN and SiC. However, overheating has been identified as a major bottleneck to the performance and commercialization of Ga2O3 device technologies. In this work, a novel Ga2O3/4H-SiC composite wafer with high heat transfer performance and an epi-ready surface finish has been developed using a fusion-bonding method. By taking advantage of low-temperature metalorganic vapor phase epitaxy, a Ga2O3 epitaxial layer was successfully grown on the composite wafer while maintaining the structural integrity of the composite wafer without causing interface damage. An atomically smooth homoepitaxial film with a room-temperature Hall mobility of ∼94 cm2/Vs and a volume charge of ∼3 × 1017 cm-3 was achieved at a growth temperature of 600 °C. Phonon transport across the Ga2O3/4H-SiC interface has been studied using frequency-domain thermoreflectance and a differential steady-state thermoreflectance approach. Scanning transmission electron microscopy analysis suggests that phonon transport across the Ga2O3/4H-SiC interface is dominated by the thickness of the SiNx bonding layer and an unintentionally formed SiOx interlayer. Extrinsic effects that impact the thermal conductivity of the 6.5 µm thick Ga2O3 layer were studied via time-domain thermoreflectance. Thermal simulation was performed to estimate the improvement of the thermal performance of a hypothetical single-finger Ga2O3 metal-semiconductor field-effect transistor fabricated on the composite substrate. This novel power transistor topology resulted in a ∼4.3× reduction in the junction-to-package device thermal resistance. Furthermore, an even more pronounced cooling effect is demonstrated when the composite wafer is implemented into the device design of practical multifinger devices. These innovations in device-level thermal management give promise to the full exploitation of the promising benefits of the UWBG material, which will lead to significant improvements in the power density and efficiency of power electronics over current state-of-the-art commercial devices.

Thermal Conductivity of Aluminum Scandium Nitride for 5G Mobile Applications and Beyond.

Radio frequency (RF) microelectromechanical systems (MEMS) based on Al1-xScxN are replacing AlN-based devices because of their higher achievable bandwidths, suitable for the fifth-generation (5G) mobile network. However, overheating of Al1-xScxN film bulk acoustic resonators (FBARs) used in RF MEMS filters limits power handling and thus the phone's ability to operate in an increasingly congested RF environment while maintaining its maximum data transmission rate. In this work, the ramifications of tailoring of the piezoelectric response and microstructure of Al1-xScxN films on the thermal transport have been studied. The thermal conductivity of Al1-xScxN films (3-8 W m-1 K-1) grown by reactive sputter deposition was found to be orders of magnitude lower than that for c-axis-textured AlN films due to alloying effects. The film thickness dependence of the thermal conductivity suggests that higher frequency FBAR structures may suffer from limited power handling due to exacerbated overheating concerns. The reduction of the abnormally oriented grain (AOG) density was found to have a modest effect on the measured thermal conductivity. However, the use of low AOG density films resulted in lower insertion loss and thus less power dissipated within the resonator, which will lead to an overall enhancement of the device thermal performance.

Methacholine-induced pulmonary gas trapping in a mouse model of allergic asthma: effect of inhaled budesonide and ciglitazone.

Previously, we found pulmonary gas trapping to be a rapid, simple and objective measure of methacholine-induced airway obstruction in naïve mice. In this study we extended that finding by using methacholine-induced pulmonary gas trapping to differentiate airway responses of ovalbumin-sensitized, ovalbumin-exposed (Positive Control) and ovalbumin-sensitized, sodium chloride-exposed (Negative Control) mice. Additionally, pulmonary gas trapping and enhanced pause were compared following methacholine exposure in sensitized and nonsensitized mice. Finally, we examined by nose-only inhalation the ability of the glucocorticosteroid budesonide and the peroxisome proliferator-activated receptor-gamma agonist ciglitazone to modify methacholine-induced airway responses in ovalbumin-sensitized mice. Positive Controls exhibited a 7.8-fold increase in sensitivity and a 2.4-fold enhancement in the maximal airway obstruction to methacholine versus Negative Controls. Following methacholine, individual Positive and Negative Control mouse enhanced pause values overlapped in 9 of 9 studies, whereas individual Positive and Negative Control mouse excised lung gas volume values overlapped in only 1 of 9 studies, and log[excised lung gas volume] correlated (P=0.023) with in vivo log[enhanced pause] in nonsensitized mice. Finally, budesonide (100.0 or 1000.0 microg/kg) reduced methacholine-mediated airway responses and eosinophils and neutrophils, whereas ciglitazone (1000.0 microg/kg) had no effect on methacholine-induced pulmonary gas trapping, but reduced eosinophils. In conclusion, pulmonary gas trapping is a more reproducible measure of methacholine-mediated airway responses in ovalbumin-sensitized mice than enhanced pause. Also, excised lung gas volume changes can be used to monitor drug interventions like budesonide. Finally, this study highlights the importance of running a positive comparator when examining novel treatments like ciglitazone.

Thermal characterization of gallium oxide Schottky barrier diodes.

The higher critical electric field of ß-gallium oxide (Ga2O3) gives promise to the development of next generation power electronic devices with improved size, weight, power, and efficiency over current state-of-the-art wide bandgap devices based on 4H-silicon carbide (SiC) and gallium nitride (GaN). However, it is expected that Ga2O3 devices will encounter serious thermal issues due to the poor thermal conductivity of the material. In this work, self-heating in Ga2O3 Schottky barrier diodes under different regimes of the diode operation was investigated using diverse optical thermography techniques including thermoreflectance thermal imaging, micro-Raman thermography, and infrared thermal microscopy. 3D coupled electro-thermal modeling was used to validate experimental results and to understand the mechanism of heat generation for the diode structures. Measured top-side and cross-sectional temperature fields suggest that device and circuit engineers should account for the concentrated heat generation that occurs near the anode/Ga2O3 interface and/or the lightly doped drift layer under both forward and high voltage reverse bias conditions. Results of this study suggest that electro-thermal co-design techniques and top-side thermal management solutions are necessary to exploit the full potential of the Ga2O3 material system.

Cessation of dexamethasone exacerbates airway responses to methacholine in asthmatic mice.

In asthmatic mice, dexamethasone (30.0 mg/kg) was administered orally once daily on Days 24-27. One hour after dexamethasone on Day 25-27, the mice were exposed to ovalbumin aerosols. Twenty-eight days after the initial ovalbumin immunization, we found that dexamethasone reduced methacholine-induced pulmonary gas trapping and inhibited bronchoalveolar lavage eosinophils and neutrophils. However, five days after the last dose of dexamethasone and last ovalbumin aerosol exposure in other asthmatic mice, the airway obstructive response to methacholine was exacerbated in dexamethasone-treated mice compared to vehicle-treated mice on Day 32. Further, eosinophils, but not neutrophils, were still inhibited after cessation of dexamethasone. Thus, discontinuing dexamethasone worsened methacholine-induced pulmonary gas trapping of asthmatic mice in the absence of eosinophilic airway inflammation.

Investigation of the terminal P4 domain in a series of D-phenylglycinamide-based factor Xa inhibitors.

Several P4 domain derivatives of the general d-phenylglycinamide-based scaffold (2) were synthesized and evaluated for their ability to bind to the serine protease factor Xa. Some of the more potent compounds were evaluated for their anticoagulant effects in vitro. A select subset containing various P1 indole constructs was further evaluated for their pharmacokinetic properties after oral administration to rats.

Carbocyclic[g]indole inhibitors of human nonpancreatic s-PLA2.

A vinyl azide cyclization method was used to synthesize three different carbocyclic[g]indole scaffolds as inhibitors of human nonpancreatic secretory phospholipase A2. Each scaffold demonstrated potent enzyme activity in a chromogenic assay system, with select examples also demonstrating potent activity in a secondary DOC/PC assay. Compound 11, representative of the cyclopent[g]indole series, gave an IC50 of 10 nM for the inhibition of hnps-PLA2 in the chromogenic assay.

Impact of copper overpressure on the synthesis of hexagonal boron nitride atomic layers.

Hexagonal boron nitride (h-BN) atomic layers are synthesized on polycrystalline copper foils via a novel chemical vapor deposition (CVD) process that maintains a vapor-phase copper overpressure during growth. Compared to h-BN films grown without a copper overpressure, this process results in a >10× reduction of 3-dimensional BN fullerene-like surface features, a reduction of carbon and oxygen contamination of 65% and 62%, respectively, an increase in h-BN grain size of >2×, and an 89% increase in electrical breakdown strength.

Integration of hexagonal boron nitride with quasi-freestanding epitaxial graphene: toward wafer-scale, high-performance devices.

Hexagonal boron nitride (h-BN) is a promising dielectric material for graphene-based electronic devices. Here we investigate the potential of h-BN gate dielectrics, grown by chemical vapor deposition (CVD), for integration with quasi-freestanding epitaxial graphene (QFEG). We discuss the large scale growth of h-BN on copper foil via a catalytic thermal CVD process and the subsequent transfer of h-BN to a 75 mm QFEG wafer. X-ray photoelectron spectroscopy (XPS) measurements confirm the absence of h-BN/graphitic domains and indicate that the film is chemically stable throughout the transfer process, while Raman spectroscopy indicates a 42% relaxation of compressive stress following removal of the copper substrate and subsequent transfer of h-BN to QFEG. Despite stress-induced wrinkling observed in the films, Hall effect measurements show little degradation (<10%) in carrier mobility for h-BN coated QFEG. Temperature dependent Hall measurements indicate little contribution from remote surface optical phonon scattering and suggest that, compared to HfO(2) based dielectrics, h-BN can be an excellent material for preserving electrical transport properties. Graphene transistors utilizing h-BN gates exhibit peak intrinsic cutoff frequencies >30 GHz (2.4× that of HfO(2)-based devices).

Characterization of graphene films and transistors grown on sapphire by metal-free chemical vapor deposition.

We present a novel method for the direct metal-free growth of graphene on sapphire that yields high quality films comparable to that of graphene grown on SiC by sublimation. Graphene is synthesized on sapphire via the simple decomposition of methane at 1425-1600 °C. Film quality was found to be a strong function of growth temperature. The thickness, structure, interface characteristics, and electrical transport properties were characterized in order to understand the utility of this material for electronic devices. Graphene synthesized on sapphire is found to be strain relieved, with no evidence of an interfacial buffer layer. There is a strong correlation between the graphene structural quality and carrier mobility. Room temperature Hall effect mobility values were as high as 3000 cm(2)/(V s), while measurements at 2 K reached values of 10,500 cm(2)/(V s). These films also display evidence of the quantum Hall effect. Field effect transistors fabricated from this material had a typical current density of 200 mA/mm and transconductance of 40 mS/mm indicating that material performance may be comparable to graphene on SiC.

High-temperature piezoelectric single crystal ReCa(4)O(BO(3))(3) for sensor applications.

Large-size and high-quality ReCa(4)O(BO(3))(3) (ReCOB, Re = rare earth) single crystals were grown by the Czochralski pulling method. In this work, the electrical properties were investigated at room temperature and elevated temperature for YCa(4)O(BO(3))(3) (YCOB). The dielectric permittivity, piezoelectric strain coefficient, and electromechanical coupling were found to be on the order of 11, 6.5 pC/N, and 12.5%, respectively, with a high piezoelectric voltage coefficient around 0.067 Vm/N. The electrical resistivity of YCOB was found to be 2 x 10(8) Ohm.m at 800 degrees C, with Q values of 4,500 at 950 degrees C. The frequency/temperature coefficient of YCOB was found to be -75 to -85ppm/K in the temperature range of 30 to 950 degrees C, depending on the crystal orientations. Together with their temperature-independent properties, ReCOB crystals are promising candidates for sensing applications at elevated temperatures.