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1. RTD Light Emission around 1550 nm with IQE up to 6% at 300 K

   https://doi.org/10.1109/DRC50226.2020.9135175  

   Brown, E. R. ; Zhang, W-D. ; Fakhimi, P. ; Growden, T. A. ; Berger, P.R. ( June 2020 , IEEE Device Research Conference (DRC), Columbus, OH (June 22-24, 2020))

   Resonant tunneling diodes (RTDs) have come full-circle in the past 10 years after their demonstration in the early 1990s as the fastest room-temperature semiconductor oscillator, displaying experimental results up to 712 GHz and fmax values exceeding 1.0 THz [1]. Now the RTD is once again the preeminent electronic oscillator above 1.0 THz and is being implemented as a coherent source [2] and a self-oscillating mixer [3], amongst other applications. This paper concerns RTD electroluminescence – an effect that has been studied very little in the past 30+ years of RTD development, and not at room temperature. We present experiments and modeling of an n-type In0.53Ga0.47As/AlAs double-barrier RTD operating as a cross-gap light emitter at ~300K. The MBE-growth stack is shown in Fig. 1(a). A 15-μm-diam-mesa device was defined by standard planar processing including a top annular ohmic contact with a 5-μm-diam pinhole in the center to couple out enough of the internal emission for accurate free-space power measurements [4]. The emission spectra have the behavior displayed in Fig. 1(b), parameterized by bias voltage (VB). The long wavelength emission edge is at  = 1684 nm - close to the In0.53Ga0.47As bandgap energy of Ug ≈ 0.75 eV at 300 K. The spectral peaks for VB = 2.8 and 3.0 V both occur around  = 1550 nm (h = 0.75 eV), so blue-shifted relative to the peak of the “ideal”, bulk InGaAs emission spectrum shown in Fig. 1(b) [5]. These results are consistent with the model displayed in Fig. 1(c), whereby the broad emission peak is attributed to the radiative recombination between electrons accumulated on the emitter side, and holes generated on the emitter side by interband tunneling with current density Jinter. The blue-shifted main peak is attributed to the quantum-size effect on the emitter side, which creates a radiative recombination rate RN,2 comparable to the band-edge cross-gap rate RN,1. Further support for this model is provided by the shorter wavelength and weaker emission peak shown in Fig. 1(b) around = 1148 nm. Our quantum mechanical calculations attribute this to radiative recombination RR,3 in the RTD quantum well between the electron ground-state level E1,e, and the hole level E1,h. To further test the model and estimate quantum efficiencies, we conducted optical power measurements using a large-area Ge photodiode located ≈3 mm away from the RTD pinhole, and having spectral response between 800 and 1800 nm with a peak responsivity of ≈0.85 A/W at  =1550 nm. Simultaneous I-V and L-V plots were obtained and are plotted in Fig. 2(a) with positive bias on the top contact (emitter on the bottom). The I-V curve displays a pronounced NDR region having a current peak-to-valley current ratio of 10.7 (typical for In0.53Ga0.47As RTDs). The external quantum efficiency (EQE) was calculated from EQE = e∙IP/(∙IE∙h) where IP is the photodiode dc current and IE the RTD current. The plot of EQE is shown in Fig. 2(b) where we see a very rapid rise with VB, but a maximum value (at VB= 3.0 V) of only ≈2×10-5. To extract the internal quantum efficiency (IQE), we use the expression EQE= c ∙i ∙r ≡ c∙IQE where ci, and r are the optical-coupling, electrical-injection, and radiative recombination efficiencies, respectively [6]. Our separate optical calculations yield c≈3.4×10-4 (limited primarily by the small pinhole) from which we obtain the curve of IQE plotted in Fig. 2(b) (right-hand scale). The maximum value of IQE (again at VB = 3.0 V) is 6.0%. From the implicit definition of IQE in terms of i and r given above, and the fact that the recombination efficiency in In0.53Ga0.47As is likely limited by Auger scattering, this result for IQE suggests that i might be significantly high. To estimate i, we have used the experimental total current of Fig. 2(a), the Kane two-band model of interband tunneling [7] computed in conjunction with a solution to Poisson’s equation across the entire structure, and a rate-equation model of Auger recombination on the emitter side [6] assuming a free-electron density of 2×1018 cm3. We focus on the high-bias regime above VB = 2.5 V of Fig. 2(a) where most of the interband tunneling should occur in the depletion region on the collector side [Jinter,2 in Fig. 1(c)]. And because of the high-quality of the InGaAs/AlAs heterostructure (very few traps or deep levels), most of the holes should reach the emitter side by some combination of drift, diffusion, and tunneling through the valence-band double barriers (Type-I offset) between InGaAs and AlAs. The computed interband current density Jinter is shown in Fig. 3(a) along with the total current density Jtot. At the maximum Jinter (at VB=3.0 V) of 7.4×102 A/cm2, we get i = Jinter/Jtot = 0.18, which is surprisingly high considering there is no p-type doping in the device. When combined with the Auger-limited r of 0.41 and c ≈ 3.4×10-4, we find a model value of IQE = 7.4% in good agreement with experiment. This leads to the model values for EQE plotted in Fig. 2(b) - also in good agreement with experiment. Finally, we address the high Jinter and consider a possible universal nature of the light-emission mechanism. Fig. 3(b) shows the tunneling probability T according to the Kane two-band model in the three materials, In0.53Ga0.47As, GaAs, and GaN, following our observation of a similar electroluminescence mechanism in GaN/AlN RTDs (due to strong polarization field of wurtzite structures) [8]. The expression is Tinter = (2/9)∙exp[(-2 ∙Ug 2 ∙me)/(2h∙P∙E)], where Ug is the bandgap energy, P is the valence-to-conduction-band momentum matrix element, and E is the electric field. Values for the highest calculated internal E fields for the InGaAs and GaN are also shown, indicating that Tinter in those structures approaches values of ~10-5. As shown, a GaAs RTD would require an internal field of ~6×105 V/cm, which is rarely realized in standard GaAs RTDs, perhaps explaining why there have been few if any reports of room-temperature electroluminescence in the GaAs devices. [1] E.R. Brown,et al., Appl. Phys. Lett., vol. 58, 2291, 1991. [5] S. Sze, Physics of Semiconductor Devices, 2nd Ed. 12.2.1 (Wiley, 1981). [2] M. Feiginov et al., Appl. Phys. Lett., 99, 233506, 2011. [6] L. Coldren, Diode Lasers and Photonic Integrated Circuits, (Wiley, 1995). [3] Y. Nishida et al., Nature Sci. Reports, 9, 18125, 2019. [7] E.O. Kane, J. of Appl. Phy 32, 83 (1961). [4] P. Fakhimi, et al., 2019 DRC Conference Digest. [8] T. Growden, et al., Nature Light: Science & Applications 7, 17150 (2018). [5] S. Sze, Physics of Semiconductor Devices, 2nd Ed. 12.2.1 (Wiley, 1981). [6] L. Coldren, Diode Lasers and Photonic Integrated Circuits, (Wiley, 1995). [7] E.O. Kane, J. of Appl. Phy 32, 83 (1961). [8] T. Growden, et al., Nature Light: Science & Applications 7, 17150 (2018). 

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2. Assessing environmental change associated with early Eocene hyperthermals in the Atlantic Coastal Plain, USA

   https://doi.org/10.5194/cp-19-1677-2023  

   Rush, William ; Self-Trail, Jean ; Zhang, Yang ; Sluijs, Appy ; Brinkhuis, Henk ; Zachos, James ; Ogg, James G. ; Robinson, Marci ( January 2023 , Climate of the Past)

   Abstract. Eocene transient global warming events (hyperthermals) can provide insight into a future warmer world. While much research has focused on the Paleocene–Eocene Thermal Maximum (PETM), hyperthermals of a smaller magnitude can be used to characterize climatic responses over different magnitudes of forcing. This study identifies two events, namely the Eocene Thermal Maximum 2 (ETM2 and H2), in shallow marine sediments of the Eocene-aged Salisbury Embayment of Maryland, based on magnetostratigraphy, calcareous nannofossil, and dinocyst biostratigraphy, as well as the recognition of negative stable carbon isotope excursions (CIEs) in biogenic calcite. We assess local environmental change in the Salisbury Embayment, utilizing clay mineralogy, marine palynology, δ18O of biogenic calcite, and biomarker paleothermometry (TEX86). Paleotemperature proxies show broad agreement between surface water and bottom water temperature changes. However, the timing of the warming does not correspond to the CIE of the ETM2 as expected from other records, and the highest values are observed during H2, suggesting factors in addition to pCO2 forcing have influenced temperature changes in the region. The ETM2 interval exhibits a shift in clay mineralogy from smectite-dominated facies to illite-rich facies, suggesting hydroclimatic changes but with a rather dampened weathering response relative to that of the PETM in the same region. Organic walled dinoflagellate cyst assemblages show large fluctuations throughout the studied section, none of which seem systematically related to CIE warming. These observations are contrary to the typical tight correspondence between climate change and assemblages across the PETM, regionally and globally, and ETM2 in the Arctic Ocean. The data do indicate very warm and (seasonally) stratified conditions, likely salinity-driven, across H2. The absence of evidence for strong perturbations in local hydrology and nutrient supply during ETM2 and H2, compared to the PETM, is consistent with the less extreme forcing and the warmer pre-event baseline, as well as the non-linear response in hydroclimates to greenhouse forcing. 

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3. Laser-induced atmospheric Cu x O formation on copper surface with enhanced electrochemical performance for non-enzymatic glucose sensing

   https://doi.org/10.1039/d1tc01289d  

   Sedaghat, Sotoudeh ; Nejati, Sina ; Bermejo, Luis Helena ; He, Zihao ; Alcaraz, Alejandro M. ; Roth, Alexander ; Li, Zheng ; Pol, Vilas G. ; Wang, Haiyan ; Rahimi, Rahim ( November 2021 , Journal of Materials Chemistry C)

   Copper oxide nanostructures are widely used for various applications due to their unique optical and electrical properties. In this work, we demonstrate an atmospheric laser-induced oxidation technique for the fabrication of highly electrochemically active copper oxide hierarchical micro/nano structures on copper surfaces to achieve highly sensitive non-enzymatic glucose sensing performance. The effect of laser processing power on the composition, crystallinity, microstructure, wettability, and color of the laser-induced oxide on copper (LIO-Cu) surface was systematically studied using scanning electron microscopy (SEM), grazing incidence X-ray diffraction (GI-XRD), Raman spectroscopy, energy dispersive X-ray spectroscopy (EDX), EDX-mapping, water contact angle measurements, and optical microscopy. Results of these investigations showed a remarkable increase in copper oxide composition by increasing the laser processing power. The pore size distribution and surface area of the pristine and LIO-Cu sample estimated by N 2 adsorption–desorption data showed a developed mesoporous LIO-Cu structure. The size of the generated nano-oxides, crystallinity, and electroactivity of the LIO-Cu were observed to be adjustable by the laser processing power. The electrocatalytic activity of LIO-Cu surfaces was studied by means of cyclic voltammetry (CV) within a potential window of −0.8 to +0.8 V and chronoamperometry in an applied optimized potential of +0.6 V, in 0.1 M NaOH solution and phosphate buffer solution (PBS), respectively. LIO-Cu surfaces with optimized laser processing powers exhibited a sensitivity of 6950 μA mM −1 cm −2 within a wide linear range from 0.01 to 5 mM, with exceptional specificity and response time (<3 seconds). The sensors also showed excellent response stability over a course of 50 days that was originated from the binder-free robust electroactive film fabricated directly onto the copper surface. The demonstrated one-step LIO processing onto commercial metal films, can potentially be applied for tuneable and scalable roll-to-roll fabrication of a wide range of high surface area metal oxide micro/nano structures for non-enzymatic biosensing and electrochemical applications. 

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4. Nanostructure and Fracture Behavior of Carbon Nanofiber-Reinforced Cement Using Nanoscale Depth-Sensing Methods

   https://doi.org/10.3390/ma13173837  

   Akono, Ange-Therese ( September 2020 , Materials)

   In recent years, carbon nanofibers have been investigated as a suitable reinforcement for cementitious composites to yield novel multifunctional materials with improved mechanical, electrical, magnetic, and self-sensing behavior. Despite several studies, the interactions between carbon nanofibers and Portland cement hydration products are not fully understood, with significant implications for the mechanical response and the durability at the macroscopic lengthscale. Thus, the research objective is to investigate the influence of carbon nanofibers on the nanostructure and on the distribution of hydration products within Portland cement paste. Portland cement w/c = 0.44 specimens reinforced with 0.0 wt%, 0.1 wt%, and 0.5 wt% CNF by mass fraction of cement are cast using a novel synthesis procedure. A uniform dispersion of carbon nanofibers (CNF) via a multi-step approach: after pre-dispersing carbon nanofibers using ultrasonic energy, the carbon nanofibers are further dispersed using un-hydrated cement particles in high shear mixing and mechanical stirring steps. High-resolution scanning electron microscopy analysis shows that carbon nanofibers fill nanopores and connect calcium–silicate hydrates (C–S–H) grains. Grid nano-indentation testing shows that Carbon nanofibers influence the probability distribution function of the local packing density by inducing a shift towards higher values, η = 0.76–0.93. Statistical deconvolution analysis shows that carbon nanofibers result in an increase in the fraction of high-density C–S–H by 6.7% from plain cement to cement + 0.1 wt% CNF and by 10.7% from plain cement to cement + 0.5 wt% CNF. Moreover, CNF lead to an increase in the C–S–H gel porosity and a decrease in both the capillary porosity and the total porosity. Based on scratch testing, adding 0.1 wt% CNF yields a 4.5% increase in fracture toughness and adding 0.5 wt% CNF yields a 7.6% increase in fracture toughness. Finally, micromechanical modelling predicts an increase of respectively 5.97% and 21.78% in the average Young’s modulus following CNF modification at 0.1 wt% CNF and 0.5 wt% CNF levels. 

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5. Staying Grounded: Establishing Baseline Critical Zone Conditions in Mississippi Prior to the Onset of Paleocene-Eocene Hyperthermals

   Rathbun, S. ; Platt, B.F. ( January 2021 , AGU Fall Meeting)

   Paleocene-Eocene hyperthermals are viewed as some of the best ancient analogs for projected future anthropogenic climate change. In order to fully evaluate the magnitude of these climactic perturbations, however, a more complete understanding of prevailing background conditions is necessary. The Mississippi Embayment, a major southwest-dipping sedimentary basin in the Gulf of Mexico coastal region of North America, contains an extensive record of Paleocene strata deposited prior to the onset of the Paleocene Carbon Isotope Maximum (PCIM), a gradual warming trend upon which the Paleocene-Eocene Thermal Maximum (PETM) was superimposed. In order to evaluate pre-PCIM paleoclimate, we focus on paleosols in the Upper Paleocene Naheola Formation. A continuous section of the Naheola is available in archival core collected by Mississippi Minerals Resources Institute from Tippah County, Mississippi, USA. We performed a suite of initial core description methods, including logging of visual observations (e.g., grain size and Munsell colors), gamma density, magnetic susceptibility, smear slide analysis, and scanning electron microscopy with energy dispersive x-ray spectroscopy (SEM-EDS). Results indicate a > 8-m-thick interval of 5 stacked paleosols associated with 4 lignite seams. The paleosols range in thickness from 0.6 m to 1.9 m, while the lignite seams range in thickness from 0.3 m to 1.3 m. Paleosols are characterized by low chroma matrix colors, mottling, and abundant carbonized roots. The thickest paleosols each exhibit an interval that coarsens and then fines upward; these are likely composite paleosols. Applying SEM-EDS results from all paleosols to the chemical index of alteration minus potash (CIA-K) yields preliminary mean annual precipitation estimates between 1200 and 1300 mm. The oldest paleosol contains abundant kaolinite and future stable isotope analysis will be used to reconstruct paleotemperature. Ongoing work will evaluate the relative influence of each of the five soil-forming factors on Naheola paleosol development and reexamine Paleocene- Eocene hyperthermals within the context of our results. Future work will include pollen analysis to improve chronostratigraphic control and evaluate paleoecological response to the Paleocene- Eocene climate change. 

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