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1. Rectification in Molecular Tunneling Junctions Based on Alkanethiolates with Bipyridine–Metal Complexes

   https://doi.org/doi.org/10.1021/jacs.0c12641  

   J. Park, L. Belding (January 2021, Journal of the American Chemical Society)

   null (Ed.)

   This paper addresses the mechanism for rectification in molecular tunneling junctions based on alkanethiolates terminated by a bipyridine group complexed with a metal ion, that is, having the structure AuTS-S(CH2)11BIPY-MCl2 (where M = Co or Cu) with a eutectic indium–gallium alloy top contact (EGaIn, 75.5% Ga 24.5% In). Here, AuTS-S(CH2)11BIPY is a self-assembled monolayer (SAM) of an alkanethiolate with 4-methyl-2,2′-bipyridine (BIPY) head groups, on template-stripped gold (AuTS). When the SAM is exposed to cobalt(II) chloride, SAMs of the form AuTS-S(CH2)11BIPY-CoCl2 rectify current with a rectification ratio of r+ = 82.0 at ±1.0 V. The rectification, however, disappears (r+ = 1.0) when the SAM is exposed to copper(II) chloride instead of cobalt. We draw the following conclusions from our experimental results: (i) AuTS-S(CH2)11BIPY-CoCl2 junctions rectify current because only at positive bias (+1.0 V) is there an accessible molecular orbital (the LUMO) on the BIPY-CoCl2 moiety, while at negative bias (−1.0 V), neither the energy level of the HOMO or the LUMO lies between the Fermi levels of the electrodes. (ii) AuTS-S(CH2)11BIPY-CuCl2 junctions do not rectify current because there is an accessible molecular orbital on the BIPY-CuCl2 moiety at both negative and positive bias (the HOMO is accessible at negative bias, and the LUMO is accessible at positive bias). The difference in accessibility of the HOMO levels at −1.0 V causes charge transfer—at negative bias—to take place via Fowler–Nordheim tunneling in BIPY-CoCl2 junctions, and via direct tunneling in BIPY-CuCl2 junctions. This difference in tunneling mechanism at negative bias is the origin of the difference in rectification ratio between BIPY-CoCl2 and BIPY-CuCl2 junctions. 

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2. Quantitative analysis of weak current rectification in molecular tunnel junctions subject to mechanical deformation reveals two different rectification mechanisms for oligophenylene thiols versus alkane thiols

   https://doi.org/10.1039/d1nr04410a  

   Xie, Zuoti; Bâldea, Ioan; Nguyen, Quyen Van; Frisbie, C. Daniel (October 2021, Nanoscale)

   Metal-molecule-metal junctions based on alkane thiol (C n T) and oligophenylene thiol (OPT n ) self-assembled monolayers (SAMs) and Au electrodes are expected to exhibit similar electrical asymmetry, as both junctions have one chemisorbed Au–S contact and one physisorbed, van der Waals contact. Asymmetry is quantified by the current rectification ratio RR apparent in the current–voltage ( I – V ) characteristics. Here we show that RR < 1 for C n T and RR > 1 for OPT n junctions, in contrast to expectation, and further, that RR behaves very differently for C n T and OPT n junctions under mechanical extension using the conducting probe atomic force microscopy (CP-AFM) testbed. The analysis presented in this paper, which leverages results from the previously validated single level model and ab initio quantum chemical calculations, allows us to explain the puzzling experimental findings for C n T and OPT n in terms of different current rectification mechanisms. Specifically, in C n T-based junctions the Stark effect creates the HOMO level shifting necessary for rectification, while for OPT n junctions the level shift arises from position-dependent coupling of the HOMO wavefunction with the junction electrostatic potential profile. On the basis of these mechanisms, our quantum chemical calculations allow quantitative description of the impact of mechanical deformation on the measured current rectification. Additionally, our analysis, matched to experiment, facilitates direct estimation of the impact of intramolecular electrostatic screening on the junction potential profile. Overall, our examination of current rectification in benchmark molecular tunnel junctions illuminates key physical mechanisms at play in single step tunneling through molecules, and demonstrates the quantitative agreement that can be obtained between experiment and theory in these systems. 

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3. Whistler-regulated Magnetohydrodynamics: Transport Equations for Electron Thermal Conduction in the High-β Intracluster Medium of Galaxy Clusters

   https://doi.org/10.3847/1538-4357/ac1ff1  

   Drake, J. F.; Pfrommer, C.; Reynolds, C. S.; Ruszkowski, M.; Swisdak, M.; Einarsson, A.; Thomas, T.; Hassam, A. B.; Roberg-Clark, G. T. (December 2021, The Astrophysical Journal)

   Abstract Transport equations for electron thermal energy in the high- β e intracluster medium (ICM) are developed that include scattering from both classical collisions and self-generated whistler waves. The calculation employs an expansion of the kinetic electron equation along the ambient magnetic field in the limit of strong scattering and assumes whistler waves with low phase speeds V w ∼ v te / β e ≪ v te dominate the turbulent spectrum, with v te the electron thermal speed and β e ≫ 1 the ratio of electron thermal to magnetic pressure. We find: (1) temperature-gradient-driven whistlers dominate classical scattering when L c > L / β e , with L c the classical electron mean free path and L the electron temperature scale length, and (2) in the whistler-dominated regime the electron thermal flux is controlled by both advection at V w and a comparable diffusive term. The findings suggest whistlers limit electron heat flux over large regions of the ICM, including locations unstable to isobaric condensation. Consequences include: (1) the Field length decreases, extending the domain of thermal instability to smaller length scales, (2) the heat flux temperature dependence changes from T e 7 / 2 / L to V w nT e ∼ T e 1 / 2 , (3) the magneto-thermal- and heat-flux-driven buoyancy instabilities are impaired or completely inhibited, and (4) sound waves in the ICM propagate greater distances, as inferred from observations. This description of thermal transport can be used in macroscale ICM models. 

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4. Energy Harvesting Performance of a Flapping Foil with Leading Edge Motion

   Prier, M. (April 2019, Dissertation)

   F or c e d at a f or a fl a p pi n g f oil e n er g y h ar v e st er wit h a cti v e l e a di n g e d g e m oti o n o p er ati n g i n t h e l o w r e d u c e d fr e q u e n c y r a n g e i s c oll e ct e d t o d et er mi n e h o w l e a di n g e d g e m oti o n aff e ct s e n er g y h ar v e sti n g p erf or m a n c e. T h e f oil pi v ot s a b o ut t h e mi dc h or d a n d o p er at e s i n t h e l o w r e d u c e d fr e q u e n c y r a n g e of 𝑓𝑓 𝑓𝑓 / 𝑈𝑈 ∞ = 0. 0 6 , 0. 0 8, a n d 0. 1 0 wit h 𝑅𝑅 𝑅𝑅 = 2 0 ,0 0 0 − 3 0 ,0 0 0 , wit h a pit c hi n g a m plit u d e of 𝜃𝜃 0 = 7 0 ∘ , a n d a h e a vi n g a m plit u d e of ℎ 0 = 0. 5 𝑓𝑓 . It i s f o u n d t h at l e a di n g e d g e m oti o n s t h at r e d u c e t h e eff e cti v e a n gl e of att a c k e arl y t h e str o k e w or k t o b ot h i n cr e a s e t h e lift f or c e s a s w ell a s s hift t h e p e a k lift f or c e l at er i n t h e fl a p pi n g str o k e. L e a di n g e d g e m oti o n s i n w hi c h t h e eff e cti v e a n gl e of att a c k i s i n cr e a s e d e arl y i n t h e str o k e s h o w d e cr e a s e d p erf or m a n c e. I n a d diti o n a di s cr et e v ort e x m o d el wit h v ort e x s h e d di n g at t h e l e a di n g e d g e i s i m pl e m e nt f or t h e m oti o n s st u di e d; it i s f o u n d t h at t h e m e c h a ni s m f or s h e d di n g at t h e l e a di n g e d g e i s n ot a d e q u at e f or t hi s p ar a m et er r a n g e a n d t h e m o d el c o n si st e ntl y o v er pr e di ct s t h e a er o d y n a mi c f or c e s. 

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5. Improvements in 2D p-type WSe2 transistors towards ultimate CMOS scaling

   https://doi.org/10.1038/s41598-023-30317-4  

   Patoary, Naim Hossain; Xie, Jing; Zhou, Guantong; Al Mamun, Fahad; Sayyad, Mohammed; Tongay, Sefaattin; Esqueda, Ivan Sanchez (February 2023, Scientific Reports)

   Abstract This paper provides comprehensive experimental analysis relating to improvements in the two-dimensional (2D) p-type metal–oxide–semiconductor (PMOS) field effect transistors (FETs) by pure van der Waals (vdW) contacts on few-layer tungsten diselenide (WSe₂) with high-k metal gate (HKMG) stacks. Our analysis shows that standard metallization techniques (e.g., e-beam evaporation at moderate pressure ~ 10^–5 torr) results in significant Fermi-level pinning, but Schottky barrier heights (SBH) remain small (< 100 meV) when using high work function metals (e.g., Pt or Pd). Temperature-dependent analysis uncovers a more dominant contribution to contact resistance from the channel access region and confirms significant improvement through less damaging metallization techniques (i.e., reduced scattering) combined with strongly scaled HKMG stacks (enhanced carrier density). A clean contact/channel interface is achieved through high-vacuum evaporation and temperature-controlled stepped deposition providing large improvements in contact resistance. Our study reports low contact resistance of 5.7 kΩ-µm, with on-state currents of ~ 97 µA/µm and subthreshold swing of ~ 140 mV/dec in FETs with channel lengths of 400 nm. Furthermore, theoretical analysis using a Landauer transport ballistic model for WSe₂SB-FETs elucidates the prospects of nanoscale 2D PMOS FETs indicating high-performance (excellent on-state current vs subthreshold swing benchmarks) towards the ultimate CMOS scaling limit. 

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