Bulk Semiconductors Research Articles

Charge Diffusion and Repulsion in Semiconductor Detectors

Semiconductor detectors for high-energy sensing (X/γ-rays) play a critical role in fields such as astronomy, particle physics, spectroscopy, medical imaging, and homeland security. The increasing need for precise detector characterization highlights the importance of developing advanced digital twins, which help optimize the design and performance of imaging systems. Current simulation frameworks primarily focus on modeling electron–hole pair dynamics within the semiconductor bulk after the photon absorption, leading to the current signals at the nearby electrodes. However, most simulations neglect charge diffusion and Coulomb repulsion, which spatially expand the charge cloud during propagation due to the high complexity they add to the physical models. Although these effects are relatively weak, their inclusion is essential for achieving a high-fidelity replication of real detector behavior. There are some existing methods that successfully incorporate these two phenomena with minimal computational cost, including those developed by Gatti in 1987 and by Benoit and Hamel in 2009. The present work evaluates these two approaches and proposes a novel Monte Carlo technique that offers higher accuracy in exchange for increased computational time. Our new method enables more realistic performance predictions while remaining within practical computational limits.

Reversible Redox Probes to Determine Band‐Edge Locations and Dopant Concentrations of Nano‐TiO2 Thin‐Films: Settling the Mott‐Schottky Conundrum

Knowing the exact location of the semiconductor band‐edges is key for mechanistic insights into their use for water and CO2 photo/electrocatalysis. In this regard, a reliable strategy for nano‐semiconductors did not exist yet. We demonstrate the use of reversible redox probes on nano‐semiconductor electrodes to determine their band‐edge locations in aqueous solutions. Rectifying current‐potential (i‐U) characteristics with the high work function Fe(CN)63‐/Fe(CN)64‐ redox couple yielded the exact flatband potential at various pH whereas the reversible i‐U characteristics with the low work function Ru(NH3)63+/Ru(NH3)62+ redox couple provided the conduction band‐edge location and dopant concentration for a 30nm thin‐film n‐TiO2. The methodology can be extended to other nano‐semiconductors and serves as an alternative to and goes beyond the capabilities of the Mott‐Schottky procedure for bulk semiconductor electrodes.

Reversible Redox Probes to Determine Band-Edge Locations and Dopant Concentrations of Nano-TiO2 Thin-Films: Settling the Mott-Schottky Conundrum.

Knowing the exact location of the semiconductor band-edges is key for mechanistic insights into their use for water and CO2 photo/electrocatalysis. In this regard, a reliable strategy for nano-semiconductors did not exist yet. We demonstrate the use of reversible redox probes on nano-semiconductor electrodes to determine their band-edge locations in aqueous solutions. Rectifying current-potential (i-U) characteristics with the high work function Fe(CN)63-/Fe(CN)64- redox couple yielded the exact flatband potential at various pH whereas the reversible i-U characteristics with the low work function Ru(NH3)63+/Ru(NH3)62+ redox couple provided the conduction band-edge location and dopant concentration for a 30nm thin-film n-TiO2. The methodology can be extended to other nano-semiconductors and serves as an alternative to and goes beyond the capabilities of the Mott-Schottky procedure for bulk semiconductor electrodes.

All‐Electronic Memristor Based on Charge Carrier Confinement in Bulk Semiconductor of Metal–Semiconductor–Metal Structure

AbstractMemristors have gained significant attention in recent years due to their potential applications in computing and memory technology by offering higher performance, lower power consumption, and increased storage capacity. In this paper, a new type of volatile memristor is presented by analyzing the dynamic behavior of charge carriers within a metal–semiconductor–metal (MSM) structure. It is shown that an all‐electronic memristor is achieved through the confinement of majority charge carriers within the bulk semiconductor by the favor of high barrier Schottky contacts. The findings reveal a remarkable current offset between forward and backward scans, along with exceptional current pulse consistency with a tunable current level using pulse frequency. These characteristics greatly simplify the process of designing electrical circuits incorporating this memristor variant. Furthermore, this research paves the way for the development of crystalline semiconductor‐based memristors. While various semiconductors with controllable doping densities can be considered as potential candidates for this type of memristor, the calculations using silicon demonstrate the integration of this semiconductor with the current technology holds significant promise for two terminal memristors.

Tailoring electronic structure and thermodynamic stability of (Al, In)-substituted GaAs: Ab-initio insights into bulk and (001) surfaces

Ab-initio calculations are conducted to investigate the structural properties, electronic structure, and thermodynamic stabilities of bulk and (001) surface systems of the GaAs semiconductor in its zinc-blende crystal phase. For the bulk case, we focus on the impact of substituting gallium atoms with M atoms (M = Al, In) at various concentrations (5.55 %, 11 %, and 22 %). We present the resulting structural parameters, along with the formation and substitutional energies associated with these substitutions. For surface systems, we explore indium (In) or aluminum (Al) substitutions at coverages of 0.25, 0.50, and 1.0 monolayers. This includes investigating the effects of substituting M atoms within the first atomic layer of the slabs. Ab-initio thermodynamic calculations reveal that high Al substitutions, in both bulk and surface, result in more favorable formation and surface energies. In contrast, In substitutions exhibit the opposite behavior, with increasing In content leading to less favorable energetics. Moreover, density of states analysis reveals that bulk systems maintained a semiconducting character, while all studied surface configurations exhibited a metallic electronic behavior. This study provides valuable insights into the influence of Al and In substitutions on the structural, electronic, and thermodynamic properties of GaAs, both in bulk and on the (001) surface.

Revealing Bipolar Photoresponse in Multiheterostructured WTe2-GaTe/ReSe2-WTe2 P-N Diode by Hybrid 2D Contact Engineering.

The van der Waals (vdW) heterostructures based on two-dimensional (2D) semiconducting materials have been thoroughly investigated with regard to practical applications. Recent studies on 2D materials have reignited attraction in the p-n junction, with promising potential for applications in both electronics and optoelectronics. 2D materials provide exceptional band structural diversity in p-n junction devices, which is rare in regular bulk semiconductors. In this article, we demonstrate a p-n diode based on multiheterostructure configuration, WTe2-GaTe-ReSe2-WTe2, where WTe2 acts as heterocontact with GaTe/ReSe2 junction. Our devices with heterocontacts of WTe2 showed excellent performance in electronic and optoelectronic characteristics as compared to contacts with basic metal electrodes. However, the highest rectification ratio was achieved up to ∼2.09 × 106 with the lowest ideality factor of ∼1.23. Moreover, the maximum change in photocurrent (Iph) is measured around 312 nA at Vds = 0.5 V. The device showed a high responsivity (R) of 4.7 × 104 m·AW-1, maximum external quantum efficiency (EQE) of 2.49 × 104 (%), and detectivity (D*) of 2.1 × 1011 Jones at wavelength λ = 220 nm. Further, we revealed the bipolar photoresponse mechanisms in WTe2-GaTe-ReSe2-WTe2 devices due to band alignment at the interface, which can be modified by applying different gate voltages. Hence, our promising results render heterocontact engineering of the GaTe-ReSe2 heterostructured diode as an excellent candidate for next-generation optoelectronic logic and neuromorphic computing.

Stimulated Emission and Lasing from Bulk CdSe Nanocrystals.

Nanocrystals with a size in the regime of vanishing quantum confinement, or bulk nanocrystals (BNCs), have emerged recently as viable solution processable optical gain materials in the green part of the spectrum. Here, we show that these properties can be extended to the crucial red region using CdSe BNCs. Through quantitative time-resolved spectroscopy, we can model these nanocrystals as bulk semiconductors, thereby revealing that the gain originates from an unbound electron-hole plasma state. The gain is broadband in nature and is not capped by Auger processes, but by a slower second-order recombination resulting in nanosecond gain lifetimes. Finally, optically pumped lasers under femtosecond pulsed and quasi-continuous wave operation are demonstrated using a photonic crystal surface emitting laser cavity, thereby stretching from 635 to 720 nm. Our results indicate that compositional variation can indeed provide spectral versatility to the BNC concept, while preserving the excellent gain metrics associated with it.

Orthogonal Electrochemical Stability of Bulk and Surface in Lead Halide Perovskite Thin Films and Nanocrystals.

Lead halide perovskites have attracted significant attention for their wide-ranging applications in optoelectronic devices. A ubiquitous element in these applications is that charging of the perovskite is involved, which can trigger electrochemical degradation reactions. Understanding the underlying factors governing these degradation processes is crucial for improving the stability of perovskite-based devices. For bulk semiconductors, the electrochemical decomposition potentials depend on the stabilization of atoms in the lattice-a parameter linked to the material's solubility. For perovskite nanocrystals (NCs), electrochemical surface reactions are strongly influenced by the binding equilibrium of passivating ligands. Here, we report a spectro-electrochemical study on CsPbBr3 NCs and bulk thin films in contact with various electrolytes, aimed at understanding the factors that control cathodic degradation. These measurements reveal that the cathodic decomposition of NCs is primarily determined by the solubility of surface ligands, with diminished cathodic degradation for NCs in high-polarity electrolyte solvents where ligand solubilities are lower. However, the solubility of the surface ligands and bulk lattice of NCs are orthogonal, such that no electrolyte could be identified where both the surface and bulk are stabilized against cathodic decomposition. This poses inherent challenges for electrochemical applications: (i) The electrochemical stability window of CsPbBr3 NCs is constrained by the reduction potential of dissolved Pb2+ complexes, and (ii) cathodic decomposition occurs well before the conduction band can be populated with electrons. Our findings provide insights to enhance the electrochemical stability of perovskite thin films and NCs, emphasizing the importance of a combined selection of surface passivation and electrolyte.

Three-gap superconductivity with Tc above 80 K in hydrogenated 2D monolayer LiBC

Although the metallization of semiconductor bulk LiBC has been experimentally achieved, various flaws, including the strong lattice distortion, the uncontrollability of phase transition under pressure, usually appear. In this work, based on the first-principles calculations, we propose a new way of hydrogenation to realize metallization. Using the fully anisotropic Migdal-Eliashberg theory, we investigate the superconducting behaviors in the stable monolayers LiBCH and LiCBH, in which C and B atoms are hydrogenated, respectively. Our findings indicate that the monolayers possess the high Tc of 82.0 and 82.5 K, respectively, along with the interesting three-gap superconducting natures. The Fermi sheets showing the obvious three-region distribution characteristics and the abnormally strong electron-phonon coupling are responsible for the high-Tc three-gap superconductivity. Furthermore, the Tc can be dramatically boosted up to 120.0 K under 3.5% tensile strain. To a great extent, the high Tc is beyond the liquid nitrogen temperature (77 K), which is beneficial for the applications in future experiments. This study not only explores the superconducting properties of the monolayers LiBCH and LiCBH, but also offers practical insights into the search for high-Tc superconductors. Published by the American Physical Society 2024

Occurrence of the collective Ziman limit of heat transport in cubic semiconductors Si, Ge, AlAs and AlP: scattering channels and size effects

In this work, we discuss the possibility of reaching the Ziman conditions for collective heat transport in cubic bulk semiconductors, such as Si, Ge, AlAs and AlP. In natural and enriched silicon and germanium, the collective heat transport limit is impossible to reach due to strong isotopic scattering. However, we show that in hyper-enriched silicon and germanium, as well as in materials with one single stable isotope like AlAs and AlP, at low temperatures, normal scattering plays an important role, making the observation of the collective heat transport possible. We further discuss the effects of sample sizes, and analyse our results for cubic materials by comparing them to bulk bismuth, in which second sound has been detected at cryogenic temperatures. We find that collective heat transport in cubic semiconductors studied in this work is expected to occur at temperatures between 10 and 20 K.

Facile formation of van der Waals metal contact with III-nitride semiconductors

Metal–semiconductor contacts play a pivotal role in controlling carrier transport in the fabrication of modern electronic devices. The exploration of van der Waals (vdW) metal contacts in semiconductor devices can potentially mitigate Fermi-level pinning at the metal–semiconductor interface, with particular success in two-dimensional layered semiconductors, triggering unprecedented electrical and optical characteristics. In this work, for the first time, we report the direct integration of vdW metal contacts with bulk wide bandgap gallium nitride (GaN) by employing a dry transfer technique. High-angle annular dark-field scanning transmission electron microscopy explicitly illustrates the existence of a vdW gap between the metal electrode and GaN. Strikingly, compared with devices fabricated with electron beam-evaporated metal contacts, the vdW contact device exhibits a responsivity two orders of magnitude higher with a significantly suppressed dark current in the nanoampere range. Furthermore, by leveraging the high responsivity and persistent photoconductivity obtained from vdW contact devices, we demonstrate imaging, wireless optical communication, and neuromorphic computing functionality. The integration of vdW contacts with bulk semiconductors offers a promising architecture to overcome device fabrication challenges, forming nearly ideal metal–semiconductor contacts for future integrated electronics and optoelectronics.

The effect of quantum confinement and the role of electron-phonon interaction on the band gap shrinkage of some II-VI semiconductors

The role of electron-phonon interaction in band gap shrinkage for some II-VI bulk and low-dimensional semiconductors is investigated in this work. The variation of the energy band gap is studied as a function of temperature using Varshni's, Vina's, and Passler's relations. It is observed that the change in the energy band gap is affected due to the quantum confinement as the dimensionality of these semiconductors is decreased.

Quantum Prism-Nano Source of Light with Dispersive Spectrum and Optical Upconversion.

A quantum prism, a new structure, consisting of many quantum wires with a diameter that gradually decreases from the base to the top, is the focus of our research. This distribution of quantum wires leads to a dispersive emitted spectrum. The red edge of the spectrum is determined by the band gap width of the bulk semiconductor, and the blue edge is determined by the quantum size of the excitons at the top of the prism. The PL spectrum of the silicon prismatic sample was excited by weak and strong light absorption. At weak absorption (hνex = 1.2 eV), the PL spectrum is located in the visible part of the spectrum, from 1.4 eV to 1.9 eV, with an energy higher than the band gap of the Si crystal. Such a "blue shift" of PL spectra by 0.7 eV is characteristic of the quantum confinement effect. It is a rainbow spectrum with an optical upconversion. The quantum prism is a new type of nano light source, as it replaces two elements in a conventional spectrometer: a light source and a dispersive element. These features enable to create a nano-spectrometer for measuring the absorption spectrum of individual molecules or viruses.

Measuring the Electronic Bandgap of Carbon Nanotube Networks in Non-Ideal p-n Diodes.

The measurement of the electronic bandgap and exciton binding energy in quasi-one-dimensional materials such as carbon nanotubes is challenging due to many-body effects and strong electron-electron interactions. Unlike bulk semiconductors, where the electronic bandgap is well known, the optical resonance in low-dimensional semiconductors is dominated by excitons, making their electronic bandgap more difficult to measure. In this work, we measure the electronic bandgap of networks of polymer-wrapped semiconducting single-walled carbon nanotubes (s-SWCNTs) using non-ideal p-n diodes. We show that our s-SWCNT networks have a short minority carrier lifetime due to the presence of interface trap states, making the diodes non-ideal. We use the generation and recombination leakage currents from these non-ideal diodes to measure the electronic bandgap and excitonic levels of different polymer-wrapped s-SWCNTs with varying diameters: arc discharge (~1.55 nm), (7,5) (0.83 nm), and (6,5) (0.76 nm). Our values are consistent with theoretical predictions, providing insight into the fundamental properties of networks of s-SWCNTs. The techniques outlined here demonstrate a robust strategy that can be applied to measuring the electronic bandgaps and exciton binding energies of a broad variety of nanoscale and quantum-confined semiconductors, including the most modern nanoscale transistors that rely on nanowire geometries.

Dielectric‐Doped 2D Tellurium Diodes for Zero‐Bias Radio Frequency Power Detection

AbstractThis work presents a 2D tellurium (Te)‐based diode that exploits the doping achieved by atomic layer deposited (ALD) Al2O3 to enhance its rectifying performance. The proposed device comprises a Schottky junction that is dielectric‐doped to significantly reduce the reverse bias current. A boosted current responsivity four times higher compared to that of undoped devices is achieved, maximizing the performance for radio frequency (RF) power detectors. The application measurement results demonstrate sensitivities as low as −45 dBm, and at −30 dBm RF input power outstanding tangential responsivities up to 6.5 kV W–1, 4.3 kV W–1, and 650 V W–1 at 0.5, 1, and 2.5 GHz, respectively, while reaching linear dynamic range (DR) of over 30 dB. These are the highest reported values for 2D‐based material devices by almost two orders of magnitude. Furthermore, the DR is ≈10 dB larger compared to state‐of‐the‐art power detectors based on bulk semiconductors.

Multiphoton-initiated laser writing of semiconductors using nanosecond mid-infrared pulses

The advent of more powerful mid-infrared nanosecond laser sources allows using them as attractive tools in material laser processing. For semiconductor bulk processing, laser intensities must remain modest to avoid detrimental nonlinear propagation and pre-focal plasma screening effects. Accordingly, nanosecond pulses are usually appropriate to locally initiate energy deposition by multiphoton absorption and subsequent modification, hardly achievable with ultrashort pulses. Employing a 2.8-μm 2.5-ns laser source, we explore the possibility to modify silicon and other semiconductors. With interactions initiated by three-photon absorption, we modify and determine the surface and bulk modification thresholds of Si, GaAs, and InP. For Si, compared to previous studies at telecom wavelengths, we report on a reduction of the energy threshold for volume modification with processing depth, and repeatable rear-surface modifications. Compared to Si, we find for GaAs and InP important fluctuations in the modification responses, which we attribute to an absorption mechanism initially triggered by a greater presence of defects. We also study germanium, as this narrower bandgap semiconductor very interesting for mid-infrared electro-optical applications is transparent at the newly introduced wavelength. Despite the ability to modify the surface, the bulk of Ge remains inaccessible in this two-photon regime, mainly attributed to beam aberrations and nonlinearities. Nonetheless, we demonstrate the ability to process Si chips integrating Ge layers. All these results showcase the potential of mid-infrared wavelengths to offer new degrees of flexibility for 3D laser processing technologies turned to silicon photonics and microelectronics packaging.

Slow Hot-Exciton Cooling and Enhanced Interparticle Excitonic Coupling in HgTe Quantum Dots.

Rapid hot-carrier/exciton cooling constitutes a major loss channel for photovoltaic efficiency. How to decelerate the hot-carrier/exciton relaxation remains a crux for achieving high-performance photovoltaic devices. Here, we demonstrate slow hot-exciton cooling that can be extended to hundreds of picoseconds in colloidal HgTe quantum dots (QDs). The energy loss rate is 1 order of magnitude smaller than bulk inorganic semiconductors, mediated by phonon bottleneck and interband biexciton Auger recombination (BAR) effects, which are both augmented at reduced QD sizes. The two effects are competitive with the emergence of multiple exciton generation. Intriguingly, BAR dominates even under low excitation fluences with a decrease in interparticle distance. Both experimental evidence and numerical evidence reveal that such efficient BAR derives from the tunneling-mediated interparticle excitonic coupling induced by wave function overlap between neighboring HgTe QDs in films. Thus, our study unveils the potential for realizing efficient hot-carrier/exciton solar cells based on HgTe QDs. Fundamentally, we reveal that the delocalized nature of quantum-confined wave function intensifies BAR. The interparticle excitonic coupling may cast light on the development of next-generation photoelectronic materials, which can retain the size-tunable confinement of colloidal semiconductor QDs while simultaneously maintaining high mobilities and conductivities typical for bulk semiconductor materials.

Layer-dependent topological surface states in BiSb

The emergence of topological materials has changed the understanding of their electronic and magnetic properties. This work investigated the structural and electronic properties of bulk and a few layers of BiSb material. Interestingly, only the bulk and monolayer systems present semiconductor characteristics. From two monolayers onwards, a semi-metallic character is found. This semi-metallic behavior is due to valance and conduction bands crossing the Fermi level near the Γ point. These band crossings are related to topological surface states, which are achieved without inducing strain into the system, contrary to their bulk and monolayer counterparts. Defects, like deformations, vacancies, or doping, are expected not to affect the surface states. As a probe of concept, the biaxial strain was induced in BiSb surfaces, making no changes in the surface states. These robust surface states are desirable for constructing magnetic-topological junctions for new-generation solid-state storage applications.

Observation of 2D-magnesium-intercalated gallium nitride superlattices

Since the demonstration of p-type gallium nitride (GaN) through doping with substitutional magnesium (Mg) atoms1,2, rapid and comprehensive developments, such as blue light-emitting diodes, have considerably shaped our modern lives and contributed to a more carbon-neutral society3–5. However, the details of the interplay between GaN and Mg have remained largely unknown6–11. Here we observe that Mg-intercalated GaN superlattices can form spontaneously by annealing a metallic Mg film on GaN at atmospheric pressure. To our knowledge, this marks the first instance of a two-dimensional metal intercalated into a bulk semiconductor, with each Mg monolayer being intricately inserted between several monolayers of hexagonal GaN. Characterized as an interstitial intercalation, this process induces substantial uniaxial compressive strain perpendicular to the interstitial layers. Consequently, the GaN layers in the Mg-intercalated GaN superlattices exhibit an exceptional elastic strain exceeding −10% (equivalent to a stress of more than 20 GPa), among the highest recorded for thin-film materials12. The strain alters the electronic band structure and greatly enhances hole transport along the compression direction. Furthermore, the Mg sheets induce a unique periodic transition in GaN polarity, generating polarization-field-induced net charges. These characteristics offer fresh insights into semiconductor doping and conductivity enhancement, as well as into elastic strain engineering of nanomaterials and metal–semiconductor superlattices13.

Strain and piezoelectric control of electronic and photonic properties of p − n diodes

Piezoelectricity is a well-known effect in a vast number of technologically important insulators and semiconductors and exists in 20 out of the 32 three-dimensional crystal classes. The piezoelectric effect is the driving mechanism behind several classical sensors and transmitters, and also most recently, in many nanodevices. Zhong Lin Wang coined the fields piezotronics and piezo-phototronics where the piezoelectric effect plays a dominant role. Piezoelectricity couples in a linear fashion mechanical strain to electrical fields and vice versa. In solids, there is another linear coupling between strain and the electric potential, known as the deformation potential effect. While linear in its coupling nature, this effect does not require the solid to be non-centrosymmetric in contrast to the piezoelectric effect. Moreover, the deformation potential effect is quantitatively huge and leads to changes in the conduction and valence band edges of III–V and II–VI materials of, typically, 50–100 meV in the presence of 1 % strain. Therefore, the deformation potential effect is essential to determine the electronic and photonic properties of bulk and nanostructure semiconductors in the presence of strain. In this work, we compute the relative importance of piezoelectricity and the deformation potential effect in the presence of lattice mismatch and external strain. We choose p − n junctions of ZnO/GaN structures but anticipate that the general conclusions can be carried over to other material structures. The main result of the present work is that both the inclusion of the deformation potential effect and piezoelectricity is crucial to correctly compute the effect of strain on p − n junction current–voltage curves and photonic properties. In our analysis of wurtzite heterostructures, the spontaneous polarization effect is also included but this effect appears to play a minor role for electronic and photonic properties.