Tunable Direct Bandgap Research Articles

Achieving Tunable Band Structure and Photocarrier Dynamics by Regulating 2D Atomic Layer Stacking Toward High‐Performance Self‐Powered Broadband and Deep‐UV Photodetection

Abstract2D materials with unique layer‐dependent electronic structure can bring precise control to their photocarrier dynamics for optimizing and expanding optoelectronic applications, while the challenge of controlling layer stacking makes the layer dependency law still underexplored in emerging 2D ternary metal chalcogenides. Herein, 2D rhombohedral‐phase ZnIn2S4 (R‐ZIS) with controllable layer thickness is achieved by confined‐growth strategy in high yield, exhibiting continuously tunable direct bandgap (2.39–2.77 eV) with evident upshift of conduction band minimum (CBM) and Fermi level (EF), demonstrated arising from the synergistic effect of reduced interlayer interaction with inevitably increasing Zn defects. Remarkably, the carrier dynamics of R‐ZIS in photoelectrochemical (PEC) device is successfully regulated by adjusted CBM and EF, resulting in continuously tunable optical absorption band, photocarrier separation efficiency, self‐powered capability, and dark current noise. Beneficial from tailored band structure and carrier dynamics, self‐powered PEC‐type photodetector with broadband photoresponse (254–765 nm), is achieved fast response speed (12.3/5.3 ms) and high responsivity (90.29 mA W−1) in multilayer R‐ZIS, while deep‐UV photodetector with ultra‐high specific detectivity (1.62 × 1012 Jones) at 254 nm in monolayer R‐ZIS, exhibiting the record performance in both fields. This work motivates the development of tailored band structure for 2D‐materials‐based optoelectronic devices in strategy and mechanism.

A comprehensive review on the usability of black phosphorus in energy and wastewater treatment

Increasing population and industrial development brings with it many problems that need to be solved, such as energy production, storage, saving, protection of limited reserves, and environmental pollution. Nanomaterials, which emerged with the introduction of nanotechnology into our lives, play an important role in many areas. The novel two-dimensional nanomaterial black phosphorus (BP) exhibits great potential in photocatalytic applications, energy technologies, and purification with properties such as broad light absorption spectrum, tunable direct band gap, and exceptionally high charge carrier mobility. This review gives a outline of the manufacturing techniques, structural, chemical, electrical and thermal properties of BP. Then, the success of BP derivatives with different dimensions and morphologies in environmental and energy applications is presented by comparing them with previous studies in these fields. The results show that heterojunction structures produced by combining BP with MoS2 and MOFs improve the electrochemical properties of BP, while carbonization processes increase its efficiency in battery and supercapacitor applications. Finally, in this review, a summary of BP’s potential future uses, awareness of easy production methods, and its activities in environmental and energy applications are discussed in a broad context.

Tunable band gaps and high carrier mobilities in germanene by Si doping in the presence of an external electric field: Field effect transistors

We have systematically investigated the electronic properties of Si doping germanene under external electric fields by the first-principle calculations. The results show that a wide range of linearly tunable and sizable direct band gaps for the Ge31Si1 and Ge28Si4 systems (3–1048 meV and 6–716 meV) are merely determined by the strength of the electric field. More importantly, the high carrier mobilities of the stable Ge31Si1 and Ge28Si4 systems are largely retained under external electric field. The mechanism of charge transfer confirms the p-type semiconductor properties in the Si doping germanene systems. These results indicate that the electronic properties of Si doping germanene can be effectively modulated under the external electric field, providing a potential application in novel electronic devices, such as Field effect transistors.

A critical review of solution-process engineering for kesterite thin-film solar cells: current strategies and prospects

The Cu2ZnSn(S,Se)4 (CZTSSe) material is considered a promising semiconductor material for commercial photovoltaic applications due to its high theoretical efficiency, high absorption coefficient, tunable direct bandgap, high element abundance, and low production cost.

SCAPS-FDTD simulation of 20.1 % efficient Perovskite-SnS tandem solar cell based on alternative charge transport layers and Au-nanoparticles

Perovskite-based tandem solar cells emerged as potential candidates for efficient photovoltaic applications. These devices exhibit high optical absorption properties and tunable direct band-gap. In this work, a novel lead-free Perovskite-SnS Tandem solar cell based on alternative charge transport layers combined with plasmonic-based light management approach is proposed. Accurate numerical investigation is carried out to assess the influence of the charge transport layers of top sub-cell on the optoelectronic properties of the tandem cell. The obtained results reveal the potential of SnO2 and CuO materials as electron and hole transport layers, respectively, demonstrating a good conduction band offset (CBO) and thereby enhanced recombination losses. Furthermore, the role of Gold-nanoparticles in enhancing absorption and light-trapping mechanisms in the bottom SnS-based sub-cell is investigated using FDTD computations. It is found that the optimized tandem cell with Au-NPs exhibits a high power conversion efficiency of 20.1%. Therefore, this work can open up new paths to boost the power conversion of Sn-based Perovskite/SnS Tandem cells for high-performance and eco-friendly photovoltaic applications.

Recent Advances in Black Phosphorous-Based Photocatalysts for Degradation of Emerging Contaminants.

The recalcitrant nature of emerging contaminants (ECs) in aquatic environments necessitates the development of effective strategies for their remediation, given the considerable impacts they pose on both human health and the delicate balance of the ecosystem. Semiconductor-based photocatalytic technology is recognized for its dual benefits in effectively addressing both ECs and energy-related challenges simultaneously. Among the plethora of photocatalysts, black phosphorus (BP) stands as a promising nonmetallic candidate, offering a host of advantages including its tunable direct band gap, broad-spectrum light absorption capabilities, and exceptional charge mobility. Nevertheless, pristine BP frequently underperforms, primarily due to issues related to its limited ambient stability and the rapid recombination of photogenerated electron-hole pairs. To overcome these challenges, substantial research efforts have been devoted to the creation of BP-based photocatalysts in recent years. However, there is a noticeable absence of reviews regarding the advancement of BP-based materials for the degradation of ECs in aqueous solutions. Therefore, to fill this gap, a comprehensive review is undertaken. In this review, we first present an in-depth examination of the fabrication processes for bulk BP and BP nanosheets (BPNS). The review conducts a thorough analysis and comparison of the merits and limitations inherent in each method, thereby delineating the most auspicious avenues for future research. Then, in line with the pathways followed by photogenerated electron-hole pairs at the interface, BP-based photocatalysts are systematically categorized into heterojunctions (Type I, Type II, Z-scheme, and S-scheme) and hybrids, and their photocatalytic performances against various ECs and the corresponding degradation mechanisms are comprehensively summarized. Finally, this review presents personal insights into the prospective avenues for advancing the field of BP-based photocatalysts for ECs remediation.

Optical Signatures of Phosphorene Chemical Evolvement in Liquid Environment

Phosphorene possesses a unique combination of physical and chemical properties, including tunable direct bandgap, anisotropic electronic and optical properties. However, application of phosphorene is hampered by its fast degradation under ambient conditions. It is believed that H2O and O2 play key roles in the instability of phosphorene, but their exact contributions have not yet been completely understood in experiment. Herein, a technique of probing the mechanism of phosphorene oxidation through the evolvement of its photoluminescence spectra in a liquid suspension is introduced. With the addition of H2O2, the photoluminescence intensity of the suspension surprisingly increases, indicating a passivation effect due to the formation of phosphorene oxide, which is also verified by Raman spectroscopy. In contrast, direct addition of H2O leads to irreversible and rapid degradation as shown by the quenching of photoluminescence. Furthermore, monolayer phosphorene suspension photoluminescence at 2.17 eV is obtained by completely eliminating effects from contaminations, substrate strain, dielectric substrate, and oxidation of samples. Solvent protection in combination with the optical probing method provides an effective approach in investigating the chemistry of active materials like phosphorene. Phosphorene has great potential in the range of sensing applications including high‐resolution H2O2 and humidity sensors.

Surface treatment of GaN nanowires for enhanced photoelectrochemical water-splitting

High-efficiency hydrogen production through photoelectrochemical (PEC) water splitting has emerged as a promising solution to address current global energy challenges. III-nitride semiconductor photoelectrodes with nanostructures have demonstrated great potential in the near future due to their high light absorption, tunable direct band gap, and strong physicochemical stability. However, several issues, including surface trapping centers, surface Fermi level pinning, and surface band bending, need to be addressed. In this work, enhanced photovoltaic properties have been achieved using gallium nitride (GaN) nanowires (NWs) photoelectrodes by adopting an alkaline solution surface treatment method to reduce the surface states. It was found that surface oxides on NWs can be removed by an alkaline solution treatment without changing the surface morphology through X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and other characterization methods. These findings provide new insights to the development of high-efficiency photoelectrodes for new energy source applications.

Large Phase-Transition Temperature Enhancement Achieved in a Layered Lead Iodide Hybrid Crystal by H/F Substitution.

Organic-inorganic hybrid metal halides with structural flexibility and solution processability have been widely investigated for different application scenarios. However, the effective construction of phase-transition materials with a high phase-transition temperature (Ttr) for potential practical applications remains a great challenge, and reports on the regulation of Ttr with significant enhancement have been rare. In this manuscript, we have realized a large Ttr increase of 148 K in a layered hybrid lead iodide crystal (4-FTMBA)4Pb3I10 (4-FTMBA = 4-fluoro-N,N,N-trimethylbenzenaminium) by the H/F substitution strategy. Compared to the parent (TMBA)4Pb3I10 (TMBA = N,N,N-trimethylbenzenaminium), H/F substitution preserves the structural framework and crystal symmetry in (4-FTMBA)4Pb3I10. The introduction of heavier fluorine will significantly increase the motion barrier for the order-disorder transition, resulting in the remarkably improved Ttr. Temperature-dependent crystal structures, Raman spectra, and dielectric analyses well support the phase-transition behavior. In addition, evident thermochromism with a tunable direct band gap in (4-FTMBA)4Pb3I10 has been observed using UV-vis spectra. To the best of our knowledge, the achieved Ttr enhancement of 148 K by H/F substitution is the highest among the organic-inorganic hybrid lead halide phase-transition materials. This finding would greatly inspire the rational design of functional materials with high performance.

Growth of single-crystal black phosphorus and its alloy films through sustained feedstock release

Black phosphorus (BP), a fascinating semiconductor with high mobility and a tunable direct bandgap, has emerged as a candidate beyond traditional silicon-based devices for next-generation electronics and optoelectronics. The ability to grow large-scale, high-quality BP films is a prerequisite for scalable integrated applications but has thus far remained a challenge due to unmanageable nucleation events. Here we develop a sustained feedstock release strategy to achieve subcentimetre-size single-crystal BP films by facilitating the lateral growth mode under a low nucleation rate. The as-grown single-crystal BP films exhibit high crystal quality, which brings excellent field-effect electrical properties and observation of pronounced Shubnikov-de Haas oscillations, with high mobilities up to ~6,500 cm2 V-1 s-1 at low temperatures. We further extend this approach to the growth of single-crystal BP alloy films, which broaden the infrared emission regime of BP from 3.7 μm to 6.9 μm at room temperature. This work will greatly facilitate the development of high-performance electronics and optoelectronics based on BP family materials.

External field regulation strategies for exciton dynamics in 2D TMDs

Two-dimensional (2D) transition metal chalcogenides (TMDs) are regarded as promising materials for micro-optoelectronic devices and next-generation logic devices due to their novel optoelectronic properties, such as strong excitonic effects, tunable direct bandgap from visible to near-infrared regions, valley pseudospin degree of freedom, and so on. Recently, triggered by the growing demand to optimize the performance of TMDs devices, external field regulation engineering has attracted great attention. The goal of this operation is to exploit the external fields to control exciton dynamics in 2D TMDs, including exciton formation and relaxation, and to finally achieve high-performance 2D TMDs devices. Although the regulation strategies of exciton dynamics in 2D TMDs have been well explored, the underlying mechanisms of different regulation strategies need to be further understood due to the complex many-body interactions in exciton dynamics. Here, we first give a brief summary of the fundamental processes of exciton dynamics in 2D TMDs and then summarize the main field-regulation strategies. Particular emphasis is placed on discussing the underlying mechanisms of how different field-regulation strategies control varied fundamental processes. A deep understanding of field regulation provides direct guidelines for the integrated design of 2D TMDs devices in the future.

Layer-dependent optically induced spin polarization in InSe

Optical control of spin in semiconductors has been pioneered using nanostructures of III-V and II-VI semiconductors, but the emergence of two-dimensional van der Waals materials offers an alternative low-dimensional platform for spintronic phenomena. Indium selenide (InSe), a group-III monochalcogenide van der Waals material, has shown promise for opto-electronics due to its high electron mobility, tunable direct bandgap, and quantum transport. There are predictions of spin-dependent optical selection rules suggesting potential for all-optical excitation and control of spin in a two-dimensional layered material. Despite these predictions, layer-dependent optical spin phenomena in InSe have yet to be explored. Here, we present measurements of layer-dependent optical spin dynamics in few-layer and bulk InSe. Polarized photoluminescence reveals layer-dependent optical orientation of spin, thereby demonstrating the optical selection rules in few-layer InSe. Spin dynamics are also studied in many-layer InSe using time-resolved Kerr rotation spectroscopy. By applying out-of-plane and in-plane static magnetic fields for polarized emission measurements and Kerr measurements, respectively, the $g$-factor for InSe was extracted. Further investigations are done by calculating precession values using a $\textbf{k} \cdot \textbf{p}$ model, which is supported by \textit{ab-initio} density functional theory. Comparison of predicted precession rates with experimental measurements highlights the importance of excitonic effects in InSe for understanding spin dynamics. Optical orientation of spin is an important prerequisite for opto-spintronic phenomena and devices, and these first demonstrations of layer-dependent optical excitation of spins in InSe lay the foundation for combining layer-dependent spin properties with advantageous electronic properties found in this material.

Plasmonic Metasurface Integrated Black Phosphorus‐Based Mid‐Infrared Photodetector with High Responsivity and Speed

AbstractBlack Phosphorus (BP), a van der Waals (vdW) semiconducting material, is studied intensively due to its unique structural and anisotropic optical properties. BP exhibits optical anisotropy with thickness tunable direct bandgap from 0.3–2.0 eV. Many BP‐based photodetectors operating in the mid‐infrared (MIR) band are proposed, but their performance is still limited due to the small optical absorption cross section at room temperature. In this work, a plasmonic metasurface that has localized surface plasmon resonance (LSPR) at 3.7 µm is designed, matching well with the band edge of a BP flake and field confinement around the edge of Au‐disk as confirmed by finite difference time domain simulation and Fourier‐transform infrared spectroscopy measurement results. In addition, a BP flake is integrated on the plasmonic metasurface and a significant quenching (twelve‐fold) is observed in the photoluminescence owing to the Förster resonance energy transfer effect induced by dipole–dipole coupling. Following that, a BP‐based MIR photodetector is fabricated on the plasmonic metasurface. Here, the demonstrated BP/plasmonic metasurface‐based photodetector achieves the peak responsivity of 495.85 mAW−1 and ultrahigh operation speed (>10 MHz) at the power of 8.55 µW under 3.7 µm incident wavelength. This demonstrated photodetector opens a new opportunity for optoelectronic applications in the MIR region.

Atomically thin two-dimensional hybrid perovskites using hydrophobic superalkali cations with tunable electron transition type.

The direct band gaps of two-dimensional (2D) metal halide perovskites can be tuned via component engineering, but their electron transition type hardly changes. Herein, atomically thin (C5NH6)2MX4 (M = Ge, Sn, Pb; X = Cl, Br, I) hybrid perovskites with hydrophobic superalkali cations were systematically explored using high-throughput hybrid density functional calculations and ab initio molecular dynamics simulations. We found that the electron transition between the M and X atoms was converted into that between the C5NH6 parts and X atoms via X change in the 2D (C5NH6)2MX4 perovskites. Negative formation energy, stable thermodynamic and kinetic properties, sharp valence bands, and tunable direct band gaps were obtained for the 2D perovskites. A power conversion efficiency (PCE) of 32.54% was obtained in theory for the passivated cubic NH2CHNH2PbI3 (FAPbI3) perovskite containing the 2D (C5NH6)2PbI4 perovskite. The hybrid Pb-free (C5NH6)2SnI4 perovskite with a direct bandgap of 1.56 eV may be viewed as a potential passivation material for perovskite devices. Moreover, the C5NH6 cations and X atoms show different hydrogen bonding interactions, which can be extended to other atomically thin organic-inorganic hybrid perovskites.

Electronic Structures of Monolayer Binary and Ternary 2D Materials: MoS2, WS2, Mo1−xCrxS2, and W1−xCrxS2 Using Density Functional Theory Calculations

Two-dimensional (2D) materials with binary compounds, such as transition-metal chalcogenides, have emerged as complementary materials due to their tunable band gap and modulated electrical properties via the layer number. Ternary 2D materials are promising in nanoelectronics and optoelectronics. According to the calculation of density functional theory, in this work, we study the electronic structures of ternary 2D materials: monolayer Mo1-xCrxS2 and W1-xCrxS2. They are mainly based on monolayer molybdenum disulfide and tungsten disulfide and have tunable direct band gaps and work functions via the different mole fractions of chromium (Cr). Meanwhile, the Cr atoms deform the monolayer structures and increase their thicknesses. Induced by different mole fractions of Cr material, energy band diagrams, the projected density of states, and charge transfers are further discussed.

Emerging low-dimensional black phosphorus: from physical-optical properties to biomedical applications

Low-dimensional black phosphorus (BP) is a class of nanomaterial derived from layered semiconductor BP which has gained tremendous attention in a variety of fields, owing to its uncommon structural features and appealing physical properties. More surprisingly, it has addressed current biomedical obstacles due to its orthorhombic puckered honeycomb crystal structure and unique properties such as tunable direct-bandgap, high carrier mobility, and exceptional photo-responsiveness. However, few reviews have focused on the interactions of low-dimensional BP’s physical properties with its biomedical performances. Herein, we discuss the physical properties of low-dimensional BP and potential biomedical applications associated with these physical properties. Moreover, different preparation methods, surface modification techniques, and future challenges, as well as future outlooks, are presented. This comprehensive review will provide a clear understanding of the relationship between low-dimensional BP’s physical properties and biomedical performances, with the ultimate goal of better knowledge of utilizing BP.

2D Layers of Group VA Semiconductors: Fundamental Properties and Potential Applications.

Members of the 2D group VA semiconductors (phosphorene, arsenene, antimonene, and bismuthine) present a new class of 2D materials, which are recently gaining a lot of research interest. These materials possess layered morphology, tunable direct bandgap, high charge carrier mobility, high stability, unique in-plane anisotropy, and negative Poisson's ratio. They prepare the ground for novel and multifunctional applications in electronics, optoelectronics, and batteries. The most recent analytical and empirical developments in the fundamental characteristics, fabrication techniques, and potential implementation of 2D group VA materials in this review, along with presenting insights and concerns for the field's future are analyzed.

3D Nanoscale Mapping of Short-Range Order in GeSn Alloys.

GeSn on Si has attracted much research interest due to its tunable direct bandgap for mid-infrared applications. Recently, short-range order (SRO) in GeSn alloys has been theoretically predicted, which profoundly impacts the band structure. However, characterizing SRO in GeSn is challenging. Guided by physics-informed Poisson statistical analyses of k-nearest neighbors (KNN) in atom probe tomography (APT), a new approach is demonstrated here for 3D nanoscale SRO mapping and semi-quantitative strain mapping in GeSn. For GeSn with ≈14 at. % Sn, the SRO parameters of Sn-Sn 1NN in 10 × 10 × 10 nm3 nanocubes can deviate from that of the random alloys by ±15 %. The relatively large fluctuation of the SRO parameters contributes to band-edge softening observed optically. Sn-Sn 1NN also tends to be more favored toward the surface, less favored under strain relaxation or tensile strain, while almost independent of local Sn composition. An algorithm based on least square fit of atomic positions further verifies this Poisson-KNN statistical method. Compared to existing macroscopic spectroscopy or electron microscopy techniques, this new APT statistical analysis uniquely offers 3D SRO mapping at nanoscale resolution in a relatively large volume with millions of atoms. It can also be extended to investigate SRO in other alloysystems.

Room‐Temperature Non‐Local Spin Transport in Few‐Layer Black Phosphorus Passivated with MgO

AbstractBlack phosphorus (BP), a new member of 2D materials, is an ideal selection to construct spin‐based devices due to its tunable direct bandgap and high carrier mobility. Assembling van der Waals heterostructures is the most popular method to create spintronic devices for 2D materials, especially for the easily oxidized BP. However, it is too complicated to be realized for fabricating large‐scale integrated circuits in practical applications. To overcome this flaw, an oxide layer on BP simultaneously serving as the protection layer and barrier to fabricate a Co/MgO/BP‐based non‐local spin valve is employed. The non‐local spin signals demonstrate the diffusion of pure spin current in the BP channel, which is the direct evidence of the spin injection from Co into BP. Combining the Hanle precession measurements with the Bloch equation fitting, the spin transport parameters of the few‐layer BP can be extracted. The spin diffusion length λs and spin relaxation time τs are 6.15 µm and 241.7 ps, respectively. Therefore, the MgO layer in the non‐local spin valve can simplify the fabrication of 2D material‐based spintronic devices and accelerate their applications.

Localized surface plasmon resonance-enhanced solar-blind Al0.4Ga0.6N MSM photodetectors exhibiting high-temperature robustness

The appealing properties of tunable direct wide bandgap, high-temperature robustness and chemical hardness, make Al x Ga1−x N a promising candidate for fabricating robust solar-blind photodetectors (PDs). In this work, we have utilized the optical phenomenon of localized surface plasmon resonance (LSPR) in metal nanoparticles (NPs) to significantly enhance the performance of solar-blind Al0.4Ga0.6N metal–semiconductor–metal PDs that exhibit high-temperature robustness. We demonstrate that the presence of palladium (Pd) NPs leads to a remarkable enhancement by nearly 600, 300, and 462%, respectively, in the photo-to-dark current ratio (PDCR), responsivity, and specific detectivity of the Al0.4Ga0.6N PD at the wavelength of 280 nm. Using the optical power density of only 32 μW cm−2 at −10 V, maximum values of ∼3 × 103, 2.7 AW−1, and 2.4 × 1013 Jones are found for the PDCR, responsivity and specific detectivity, respectively. The experimental observations are supported by finite difference time domain simulations, which clearly indicate the presence of LSPR in Pd NPs decorated on the surface of Al0.4Ga0.6N. The mechanism behind the enhancement is investigated in detail, and is ascribed to the LSPR induced effects, namely, improved optical absorption, enhanced local electric field and LSPR sensitization effect. Moreover, the PD exhibits a stable operation up to 400 K, thereby exhibiting the high-temperature robustness desirable for commercial applications.