Anti-Electrostatic Pi-Hole Bonding: How Covalency Conquers Coulombics

Intermolecular bonding attraction at π-bonded centers is often described as “electrostatically driven” and given quasi-classical rationalization in terms of a “pi hole” depletion region in the electrostatic potential. However, we demonstrate here that such bonding attraction also occurs between closed-shell ions of like charge, thereby yielding locally stable complexes that sharply violate classical electrostatic expectations. Standard DFT and MP2 computational methods are employed to investigate complexation of simple pi-bonded diatomic anions (BO−, CN−) with simple atomic anions (H−, F−) or with one another. Such “anti-electrostatic” anion–anion attractions are shown to lead to robust metastable binding wells (ranging up to 20–30 kcal/mol at DFT level, or still deeper at dynamically correlated MP2 level) that are shielded by broad predissociation barriers (ranging up to 1.5 Å width) from long-range ionic dissociation. Like-charge attraction at pi-centers thereby provides additional evidence for the dominance of 3-center/4-electron (3c/4e) nD-π*AX interactions that are fully analogous to the nD-σ*AH interactions of H-bonding. Using standard keyword options of natural bond orbital (NBO) analysis, we demonstrate that both n-σ* (sigma hole) and n-π* (pi hole) interactions represent simple variants of the essential resonance-type donor-acceptor (Bürgi–Dunitz-type) attraction that apparently underlies all intermolecular association phenomena of chemical interest. We further demonstrate that “deletion” of such π*-based donor-acceptor interaction obliterates the characteristic Bürgi–Dunitz signatures of pi-hole interactions, thereby establishing the unique cause/effect relationship to short-range covalency (“charge transfer”) rather than envisioned Coulombic properties of unperturbed monomers.

Dark current and 1/f noise in forward biased InAs photodiodes

Dark current and low-frequency noise have been studied in forward biased InAs photodiodes within the temperature range 77…290 K. Photodiodes were fabricated by diffusion of Cd into n-InAs single crystal substrates. It has been shown that, at the temperatures >130 K, the forward current is defined by recombination of charge carriers with participation of deep states in the middle of band gap. At these temperatures, a correlation is found between forward current and 1/f noise. At lower temperatures, the forward current and noise have been analyzed within the model of inhomogeneous p-n junction caused by dislocations in the depletion region. The experimental evidence has been obtained that multiple carrier tunneling is the main transport mechanism at low temperatures, which leads to an increase in low-frequency noise.

Characterization of Predictable Quantum Efficient Detector over a wide range of incident optical power and wavelength.

We investigate the Predictable Quantum Efficient Detector (PQED) in the visible and near-infrared wavelength range. The PQED consists of two n-type induced junction photodiodes with Al2O3 entrance window. Measurements are performed at the wavelengths of 488 nm and 785 nm with incident power levels ranging from 100 µW to 1000 µW. A new way of presenting the normalized photocurrents on a logarithmic scale as a function of bias voltage reveals two distinct negative slope regions and allows direct comparison of charge carrier losses at different wavelengths. The comparison indicates mechanisms that can be understood on the basis of different penetration depths at different wavelengths (0.77 μm at 488 nm and 10.2 μm at 785 nm). The difference in the penetration depths leads also to larger difference in the charge-carrier losses at low bias voltages than at high voltages due to the voltage dependence of the depletion region.

Electrical Characterization of Germanium Nanowires Using a Symmetric Hall Bar Configuration: Size and Shape Dependence

The fabrication of individual nanowire-based devices and their comprehensive electrical characterization remains a major challenge. Here, we present a symmetric Hall bar configuration for highly p-type germanium nanowires (GeNWs), fabricated by a top-down approach using electron beam lithography and inductively coupled plasma reactive ion etching. The configuration allows two equivalent measurement sets to check the homogeneity of GeNWs in terms of resistivity and the Hall coefficient. The highest Hall mobility and carrier concentration of GeNWs at 5 K were in the order of 100 cm2/(Vs) and 4×1019cm−3, respectively. With a decreasing nanowire width, the resistivity increases and the carrier concentration decreases, which is attributed to carrier scattering in the region near the surface. By comparing the measured data with simulations, one can conclude the existence of a depletion region, which decreases the effective cross-section of GeNWs. Moreover, the resistivity of thin GeNWs is strongly influenced by the cross-sectional shape.

Electrical and dielectric parameters in TiO2-NW/Ge-NW heterostructure MOS device synthesized by glancing angle deposition technique

This paper reports the catalyst-free coaxial TiO2/Ge-nanowire (NW) heterostructure synthesis using the glancing angle deposition (GLAD) technique integrated into an electron beam evaporator. The frequency and voltage dependence of the capacitance–voltage (C–V) and conductance–voltage (G/ω–V) characteristics of an Ag/TiO2-NW/Ge-NW/Si device over a wide range of frequency (10 kHz–5 MHz) and voltage (− 5 V to + 5 V) at room temperature were investigated. The study established strong dependence on the applied frequency and voltage bias. Both C–V and G/ω–V values showed wide dispersion in depletion region due to interface defect states (Dit) and series resistance (Rs). The C and G/ω value decreases with an increase in applied frequency. The voltage and frequency-dependent Dit and Rs were calculated from the Hill-Coleman and Nicollian–Brews methods, respectively. It is observed that the overall Dit and Rs for the device decrease with an increase in the frequency at different voltages. The dielectric properties such as dielectric constant ($$\upepsilon$$ ϵ ′), loss ($$\upepsilon$$ ϵ ″) and loss tangent (tan δ) were determined from the C–V and G/ω–V measurements. It is observed that $$\upepsilon$$ ϵ ′, $$\upepsilon$$ ϵ ″ decreases with the increase in frequency. Therefore, the proposed MOS structure provides a promising alternative approach to enhance the device capability in the opto-electronics industry.

Simulation Study of Silicon-Based Single-Photon Avalanche Diodes with Double Buried Layers and Deep Trench Electrodes

In this paper we present a study of a silicon-based Single-Photon Avalanche Diode (SPAD) in the near-infrared band with double buried layers and deep trench electrodes fabricated by the complimentary metal–oxide semiconductor (CMOS) technology. The deep trench electrodes aim to promote the movement of carriers in the device and reduce the transit time of the photo-generated carrier. The double buried layers are introduced to increase the electric field in the avalanche area and withstand a larger excess bias voltage as its larger depletion region. The semiconductor device simulation software TCAD is used to simulate the performance of this SPAD model, such as the I-V characteristic, the electric field and the Photon Detection Efficiency (PDE). Further optimization of the structure are studied with influence factors such as the doping concentration and depletion region thickness. Based on the results in this study, the designed a structure that can provide a high detecting efficiency in the near-infrared band.