Identifying Carrier Behavior in Ultrathin Indirect-Bandgap CsPbX3 Nanocrystal Films for Use in UV/Visible-Blind High-Energy Detectors.

High-energy radiation detectors such as X-ray detectors with low light photoresponse characteristics are used for several applications including, space, medical, and military devices. Here, an indirect bandgap inorganic perovskite-based X-ray detector is reported. The indirect bandgap nature of perovskite materials is revealed through optical characterizations, time-resolved photoluminescence (TRPL), and theoretical simulations, demonstrating that the differences in temperature-dependent carrier lifetime related to CsPbX3 (X = Br, I) perovskite composition are due to the changes in the bandgap structure. TRPL, theoretical analyses, and X-ray radiation measurements reveal that the high response of the UV/visible-blind yellow-phase CsPbI3 under high-energy X-ray exposure is attributed to the nature of the indirect bandgap structure of CsPbX3 . The yellow-phase CsPbI3 -based X-ray detector achieves a relatively high sensitivity of 83.6 µCGyair-1 cm-2 (under 1.7 mGyair s-1 at an electron field of 0.17 V µm-1 used for medical diagnostics) although the active layer is based solely on an ultrathin (≈6.6 µm) CsPbI3 nanocrystal film, exceeding the values obtained for commercial X-ray detectors, and further confirming good material quality. This CsPbX3 X-ray detector is sufficient for cost-effective device miniaturization based on a simple design.

Ultraviolet-to-blue color-converting scintillating-fibers photoreceiver for 375-nm laser-based underwater wireless optical communication.

Underwater wireless optical communication (UWOC) can offer reliable and secure connectivity for enabling future internet-of-underwater-things (IoUT), owing to its unlicensed spectrum and high transmission speed. However, a critical bottleneck lies in the strict requirement of pointing, acquisition, and tracking (PAT), for effective recovery of modulated optical signals at the receiver end. A large-area, high bandwidth, and wide-angle-of-view photoreceiver is therefore crucial for establishing a high-speed yet reliable communication link under non-directional pointing in a turbulent underwater environment. In this work, we demonstrated a large-area, of up to a few tens of cm2, photoreceiver design based on ultraviolet(UV)-to-blue color-converting plastic scintillating fibers, and yet offering high 3-dB bandwidth of up to 86.13 MHz. Tapping on the large modulation bandwidth, we demonstrated a high data rate of 250 Mbps at bit-error ratio (BER) of 2.2 × 10-3 using non-return-to-zero on-off keying (NRZ-OOK) pseudorandom binary sequence (PRBS) 210-1 data stream, a 375-nm laser-based communication link over the 1.15-m water channel. This proof-of-concept demonstration opens the pathway for revolutionizing the photodetection scheme in UWOC, and for non-line-of-sight (NLOS) free-space optical communication.

Enhanced Performance of MoS2 Photodetectors by Inserting an ALD-Processed TiO2 Interlayer.

2D molybdenum disulfide (MoS2 ) possesses excellent optoelectronic properties that make it a promising candidate for use in high-performance photodetectors. Yet, to meet the growing demand for practical and reliable MoS2 photodetectors, the critical issue of defect introduction to the interface between the exfoliated MoS2 and the electrode metal during fabrication must be addressed, because defects deteriorate the device performance. To achieve this objective, the use of an atomic layer-deposited TiO2 interlayer (between exfoliated MoS2 and electrode) is reported in this work, for the first time, to enhance the performance of MoS2 photodetectors. The TiO2 interlayer is inserted through 20 atomic layer deposition cycles before depositing the electrode metal on MoS2 /SiO2 substrate, leading to significantly enhanced photoresponsivity and response speed. These results pave the way for practical applications and provide a novel direction for optimizing the interlayer material.

Carrier dynamics of InxGa1-xN/GaN multiple quantum wells grown on (-201) ß-Ga2O3 for bright vertical light emitting diodes.

High-quality InxGa1-xN/GaN multi-quantum well (MQW) structures (0.05≤x≤0.13), are successfully grown on transparent and conductive (-201)-oriented ß-Ga2O3 substrate. Scanning-transmission electron microscopy and secondary ion mass spectrometry (SIMS) show well-defined high quality MQWs, while the In and Ga compositions in the wells and the barriers are estimated by SIMS. Temperature-dependant Photoluminescence (PL) confirms high optical quality with a strong bandedge emission and negligble yellow band. time-resolved PL measurements (via above/below-GaN bandgap excitations) explain carrier dynamics, showing that the radiative recombination is predominant. Our results demonstrate that (-201)-oriented ß-Ga2O3 is a strong candidate as a substrate for III-nitride-based vertical- emitting devices.

Surface Passivation of GaN Nanowires for Enhanced Photoelectrochemical Water-Splitting.

Hydrogen production via photoelectrochemical water-splitting is a key source of clean and sustainable energy. The use of one-dimensional nanostructures as photoelectrodes is desirable for photoelectrochemical water-splitting applications due to the ultralarge surface areas, lateral carrier extraction schemes, and superior light-harvesting capabilities. However, the unavoidable surface states of nanostructured materials create additional charge carrier trapping centers and energy barriers at the semiconductor-electrolyte interface, which severely reduce the solar-to-hydrogen conversion efficiency. In this work, we address the issue of surface states in GaN nanowire photoelectrodes by employing a simple and low-cost surface treatment method, which utilizes an organic thiol compound (i.e., 1,2-ethanedithiol). The surface-treated photocathode showed an enhanced photocurrent density of -31 mA/cm2 at -0.2 V versus RHE with an incident photon-to-current conversion efficiency of 18.3%, whereas untreated nanowires yielded only 8.1% efficiency. Furthermore, the surface passivation provides enhanced photoelectrochemical stability as surface-treated nanowires retained ∼80% of their initial photocurrent value and produced 8000 µmol of gas molecules over 55 h at acidic conditions (pH ∼ 0), whereas the untreated nanowires demonstrated only <4 h of photoelectrochemical stability. These findings shed new light on the importance of surface passivation of nanostructured photoelectrodes for photoelectrochemical applications.

Double Charged Surface Layers in Lead Halide Perovskite Crystals.

Understanding defect chemistry, particularly ion migration, and its significant effect on the surface's optical and electronic properties is one of the major challenges impeding the development of hybrid perovskite-based devices. Here, using both experimental and theoretical approaches, we demonstrated that the surface layers of the perovskite crystals may acquire a high concentration of positively charged vacancies with the complementary negatively charged halide ions pushed to the surface. This charge separation near the surface generates an electric field that can induce an increase of optical band gap in the surface layers relative to the bulk. We found that the charge separation, electric field, and the amplitude of shift in the bandgap strongly depend on the halides and organic moieties of perovskite crystals. Our findings reveal the peculiarity of surface effects that are currently limiting the applications of perovskite crystals and more importantly explain their origins, thus enabling viable surface passivation strategies to remediate them.

Droop-Free, Reliable, and High-Power InGaN/GaN Nanowire Light-Emitting Diodes for Monolithic Metal-Optoelectronics.

A droop-free nitride light-emitting diode (LED) with the capacity to operate beyond the "green gap" has been a subject of intense scientific and engineering interest. While several properties of nanowires on silicon make them promising for use in LED development, the high aspect ratio of individual nanowires and their laterally discontinuous features limit phonon transport and device performance. Here, we report on the monolithic integration of metal heat-sink and droop-free InGaN/GaN quantum-disks-in-nanowire LEDs emitting at ∼710 nm. The reliable operation of our uncooled nanowire-LEDs (NW-LEDs) epitaxially grown on molybdenum was evident in the constant-current soft burn-in performed on a 380 µm × 380 µm LED. The square LED sustained 600 mA electrical stress over an 8 h period, providing stable light output at maturity without catastrophic failure. The absence of carrier and phonon transport barriers in NW-LEDs was further inferred from current-dependent Raman measurements (up to 700 mA), which revealed the low self-heating. The radiative recombination rates of NW-LEDs between room temperature and 40 °C was not limited by Shockley-Read-Hall recombination, Auger recombination, or carrier leakage mechanisms, thus realizing droop-free operation. The discovery of reliable, droop-free devices constitutes significant progress toward the development of nanowires for practical applications. Our monolithic approach realized a high-performance device that will revolutionize the way high power, low-junction-temperature LED lamps are manufactured for solid-state lighting and for applications in high-temperature harsh environment.

Defect induced d(0) ferromagnetism in a ZnO grain boundary.

Several experimental studies have referred to the grain boundary (GB) defect as the origin of ferromagnetism in zinc oxide (ZnO). However, the mechanism of this hypothesis has never been confirmed. Present study investigates the atomic structure and the effect of point defects in a ZnO GB using the generalized gradient approximation+U approximation. The relaxed GB possesses large periodicity and channels with 8 and 10 numbered atoms having 4 and 3 fold coordination. The Zn vacancy (V(Zn)) shows a tendency to be attracted to the GB, relative to the bulk-like region. Although no magnetization is obtained from point defect-free GB, V(Zn) induces spin polarization as large as 0.68 µ(B)/atom to the O sites at the GB. Ferromagnetic exchange energy >150 eV is obtained by increasing the concentration of V(Zn) and by the injection of holes into the system. Electronic structure analysis indicates that the spin polarization without external dopants originates from the O 2p orbitals, a common feature of d(0) semiconductors.

In situ analysis of corrosion inhibitors using a portable mass spectrometer with paper spray ionization.

Paper spray (PS) ambient ionization is implemented using a portable mass spectrometer and applied to the detection of alkyl quaternary ammonium salts in a complex oil matrix. These salts are commonly used as active components in the formulation of corrosion inhibitors. They were identified in oil and confirmed by their fragmentation patterns recorded using tandem mass spectrometry (MS/MS). The cations of alkyl and benzyl-substituted quaternary ammonium salts showed characteristic neutral losses of CnH2n (n carbon number of the longest chain) and C7H8, respectively. Individual quaternary ammonium compounds were detected at low concentrations (<1 ng µL(-1)) and over a dynamic range of ∼5 pg µL(-1) to 500 pg µL(-1) (ppb). Direct detection of these compounds in complex oil samples without prior sample preparation or pre-concentration was also demonstrated using a home-built miniature mass spectrometer at levels below 1 ng µL(-1).

Enhanced Photoresponsivity UV-C Photodetectors Using a p-n Junction Based on Ultra-Wide-Band Gap Sn-Doped ß-Ga2O3 Microflake/MnO Quantum Dots.

Solar-blind self-powered UV-C photodetectors suffer from low performance, while heterostructure-based devices require complex fabrication and lack p-type wide band gap semiconductors (WBGSs) operating in the UV-C region (<290 nm). In this work, we mitigate the aforementioned issues by demonstrating a facile fabrication process for a high-responsivity solar-blind self-powered UV-C photodetector based on a p-n WBGS heterojunction structure, operating under ambient conditions. Here, heterojunction structures based on p-type and n-type ultra-wide band gap WBGSs (i.e. both are characterized by energy gap ≥4.5 eV) are demonstrated for the first time; mainly p-type solution-processed manganese oxide quantum dots (MnO QDs) and n-type Sn-doped ß-Ga2O3 microflakes. Highly crystalline p-type MnO QDs are synthesized using cost-effective and facile pulsed femtosecond laser ablation in ethanol (FLAL), while the n-type Ga2O3 microflakes are prepared by exfoliation. The solution-processed QDs are uniformly dropcasted on the exfoliated Sn-doped ß-Ga2O3 microflakes to fabricate a p-n heterojunction photodetector, resulting in excellent solar-blind UV-C photoresponse characteristics (with a cutoff at ∼265 nm) being demonstrated. Further analyses using XPS demonstrate the good band alignment between p-type MnO QDs and n-type ß-Ga2O3 microflakes with a type-II heterojunction. Superior photoresponsivity (922 A/W) is obtained under bias, while the self-powered responsivity is ∼86.9 mA/W. The fabrication strategy adopted in this study will provide a cost-effective means for the development of flexible and highly efficient UV-C devices suitable for energy-saving large-scale fixable applications.

Simultaneous Growth Strategy of High-Optical-Efficiency GaN NWs on a Wide Range of Substrates by Pulsed Laser Deposition.

Here, we explore a catalyst-free single-step growth strategy that results in high-quality self-assembled single-crystal vertical GaN nanowires (NWs) grown on a wide range of common and novel substrates (including GaN, Ga2O3, and monolayer two-dimensional (2D) transition-metal dichalcogenide (TMD)) within the same chamber and thus under identical conditions by pulsed laser deposition. High-resolution transmission electron microscopy and scanning transmission electron microscopy (HR-STEM) and grazing incidence X-ray diffraction measurements confirm the single-crystalline nature of the obtained NWs, whereas advanced optical and cathodoluminescence measurements provide evidence of their high optical quality. Further analyses reveal that the growth is initiated by an in situ polycrystalline layer formed between the NWs and substrates during growth, while as its thickness increases, the growth mode transforms into single-crystalline NW nucleation. HR-STEM and corresponding energy-dispersive X-ray compositional analyses indicate possible growth mechanisms. All samples exhibit strong band edge UV emission (with a negligible defect band) dominated by radiative recombination with a high optical efficiency (∼65%). As all NWs have similar structural and optical qualities irrespective of the substrate used, this strategy will open new horizons for developing III-nitride-based devices.

Enhanced-Performance Self-Powered Solar-Blind UV-C Photodetector Based on n-ZnO Quantum Dots Functionalized by p-CuO Micro-pyramids.

Smart solar-blind UV-C band photodetectors suffer from low responsivity in a self-powered mode. Here, we address this issue by fabricating a novel enhanced solar-blind UV-C photodetector array based on solution-processed n-ZnO quantum dots (QDs) functionalized by p-CuO micro-pyramids. Self-assembled catalyst-free p-CuO micro-pyramid arrays are fabricated on a pre-ablated Si substrate by pulsed laser deposition without a need for a catalyst layer or seeding, while the solution-processed n-ZnO QDs are synthesized by the femtosecond-laser ablation in liquid technique. The photodetector is fabricated by spray-coating ZnO QDs on a CuO micro-pyramid array. The photodetector performance is optimized via a p-n junction structure as both p-ZnO QDs and p-CuO micro-pyramid layers are characterized by wide band gap energies. Two photodetectors (with and without CuO micro-pyramids) are fabricated to show the role of p-CuO in enhancing the device performance. The n-ZnO QD/p-CuO micro-pyramid/Si photodetector is characterized by a superior photo-responsivity of ∼956 mA/W at 244 nm with a faster photoresponse (<80 ms) and 260 nm cut-off compared to ZnO QDs/Si photodetectors, confirming that the p-CuO micro-pyramids enhance the device performance. The self-powered photoresponse with a high photo-responsivity of ∼29 mA/W is demonstrated. These high-responsivity solar-bind UV-C photodetector arrays can be used for a wide range of applications.

Manipulation of hot carrier cooling dynamics in two-dimensional Dion-Jacobson hybrid perovskites via Rashba band splitting.

Hot-carrier cooling processes of perovskite materials are typically described by a single parabolic band model that includes the effects of carrier-phonon scattering, hot phonon bottleneck, and Auger heating. However, little is known (if anything) about the cooling processes in which the spin-degenerate parabolic band splits into two spin-polarized bands, i.e., the Rashba band splitting effect. Here, we investigated the hot-carrier cooling processes for two slightly different compositions of two-dimensional Dion-Jacobson hybrid perovskites, namely, (3AMP)PbI4 and (4AMP)PbI4 (3AMP = 3-(aminomethyl)piperidinium; 4AMP = 4-(aminomethyl)piperidinium), using a combination of ultrafast transient absorption spectroscopy and first-principles calculations. In (4AMP)PbI4, upon Rashba band splitting, the spin-dependent scattering of hot electrons is responsible for accelerating hot-carrier cooling at longer delays. Importantly, the hot-carrier cooling of (4AMP)PbI4 can be extended by manipulating the spin state of the hot carriers. Our findings suggest a new approach for prolonging hot-carrier cooling in hybrid perovskites, which is conducive to further improving the performance of hot-carrier-based optoelectronic and spintronic devices.

Modulating Electronic Structures of Armchair GaN Nanoribbons by Chemical Functionalization under an Electric Field Effect.

The electronic and magnetic properties of oxygen- and sulfur-passivated one-dimensional armchair GaN nanoribbons (A-GaNNRs) are revealed using both first-principles density-functional theory and ab initio molecular dynamics simulations. We explore that an applied external electric field can further modulate the electronic properties of both pristine and passivated A-GaNNRs, thus changing their properties (semiconducting-metallic-half-metallic). A-GaNNRs of 0.9-3.1 nm width are subjected to further investigations, which reveal that sulfur termination transforms pristine A-GaNNRs from direct into indirect band gap semiconductors, without affecting their nonmagnetic nature. On the other hand, oxygen passivation introduces spin-polarized behavior with a finite magnetic moment. Magnetism characteristics in both bare and sulfur-passivated A-GaNNRs are induced by applying a critical electric field along the direction of NR width. The passivated A-GaNNRs are more stable compared to bare ones, while sulfur-passivated A-GaNNRs exhibit higher stability at higher temperatures (>500 °C). Thus, our results suggest that A-GaNNRs can be used in a broad range of electronic, optoelectronic, and spintronic applications.

Optimized performance III-nitride-perovskite-based heterojunction photodetector via asymmetric electrode configuration.

Organometal halide perovskite photodetectors have recently drawn significant attention due to their excellent potential to perform as broadband photodetectors. However, the photoresponse in the ultraviolet (UV) spectrum can be improved by introducing wide bandgap semiconductors. In this work, we report on a methylammonium lead iodide/p-type gallium nitride (MAPI/p-GaN) heterojunction photodetector. We demonstrate that the device is capable of detecting in the UV region by p-GaN being hybridized with MAPI. We further investigate different symmetric and asymmetric metal-electrode contacts to enhance the device performance including the response time. The asymmetric electrode configuration is found to be the most optimal configuration which results in high photoresponse (photo-responsivity is 55 mA W-1 and fall time < 80 ms). As the light illumination occurs through the GaN side, its presence ultimately reduces MAPI degradation due to efficient absorption of the UV photons by GaN film.

Enhanced UV Emission of GaN Nanowires Functionalized by Wider Band Gap Solution-Processed p-MnO Quantum Dots.

GaN-based UV light-emitting devices suffer from low efficiency. To mitigate this issue, we hybridized GaN nanowires (NWs) grown on Si substrates by plasma-assisted molecular beam epitaxy with solution-processed p-type MnO quantum dots (QDs) characterized by a wider band gap (∼5 eV) than that of GaN. Further investigations reveal that the photoluminescence intensity of the GaN NWs increases up to ∼3.9-fold (∼290%) after functionalizing them with p-MnO QDs, while the internal quantum efficiency is improved by ∼1.7-fold. Electron energy loss spectroscopy (EELS) incorporated into transmission electron microscopy reveals an increase in the density of states in QD-decorated NWs compared to the bare ones. The advanced optical and EELS analyses indicate that the energy transfer from the wider band gap p-MnO QDs to n-GaN NW can lead to substantial emission enhancement and greater radiative recombination contribution because of the good band alignment between MnO QDs and GaN NWs. This work provides valuable insights into an environmentally friendly strategy for improving UV device performance.

Quantifying the Transverse-Electric-Dominant 260 nm Emission from Molecular Beam Epitaxy-Grown GaN-Quantum-Disks Embedded in AlN Nanowires: A Comprehensive Optical and Morphological Characterization.

There has been a relentless pursuit of transverse electric (TE)-dominant deep ultraviolet (UV) optoelectronic devices for efficient surface emitters to replace the environmentally unfriendly mercury lamps. To date, the use of the ternary AlGaN alloy inevitably has led to transverse magnetic (TM)-dominant emission, an approach that is facing a roadblock. Here, we take an entirely different approach of utilizing a binary GaN compound semiconductor in conjunction with ultrathin quantum disks (QDisks) embedded in AlN nanowires (NWs). The growth of GaN QDisks is realized on a scalable and low-cost Si substrate using plasma-assisted molecular beam epitaxy as a highly controllable monolayer growth platform. We estimated an internal quantum efficiency of ∼81% in a wavelength regime of ∼260 nm for these nanostructures. Additionally, strain mapping obtained by high-angle annular dark-field scanning transmission electron microscopy is studied in conjunction with the TE and TM modes of the carrier recombination. Moreover, for the first time, we quantify the TE and TM modes of the PL emitted by GaN QDisks for deep-UV emitters. We observed nearly pure TE-polarized photoluminescence emission at a polarization angle of ∼5°. This work proposes highly quantum-confined ultrathin GaN QDisks as a promising candidate for deep-UV vertical emitters.

Titanium Carbide MXene Nucleation Layer for Epitaxial Growth of High-Quality GaN Nanowires on Amorphous Substrates.

Growing III-nitride nanowires on 2D materials is advantageous, as it effectively decouples the underlying growth substrate from the properties of the nanowires. As a relatively new family of 2D materials, MXenes are promising candidates as III-nitride nanowire nucleation layers capable of providing simultaneous transparency and conductivity. In this work, we demonstrate the direct epitaxial growth of GaN nanowires on Ti3C2 MXene films. The MXene films consist of nanoflakes spray coated onto an amorphous silica substrate. We observed an epitaxial relationship between the GaN nanowires and the MXene nanoflakes due to the compatibility between the triangular lattice of Ti3C2 MXene and the hexagonal structure of wurtzite GaN. The GaN nanowires on MXene show good material quality and partial transparency at visible wavelengths. Nanoscale electrical characterization using conductive atomic force microscopy reveals a Schottky barrier height of ∼330 meV between the GaN nanowire and the Ti3C2 MXene film. Our work highlights the potential of using MXene as a transparent and conductive preorienting nucleation layer for high-quality GaN growth on amorphous substrates.

Structural, magnetic and electronic properties of two dimensional NdN: an ab initio study.

The peculiar magnetic properties of rare earth nitrides (RENs) make them suitable for a wide range of applications. Here, we report on a density functional theory (DFT) study of an interesting member of the family, two-dimensional (2D) NdN film, using the generalized gradient approximation (GGA), including the Hubbard (U) parameter. We consider different film thicknesses, taking into account the effects of N vacancies (V N) and dopants (C and O). Formation energy values show that, even though N vacancy is the predominant defect, C and O dopants are also probable impurities in these films. Individual Nd and N magnetic moments oscillate in the presence of V N and dopants owing to the induced lattice distortions. The density of states calculations show that the 2D NdN film has a semi-metallic nature, while the f orbitals are separated into fully filled and empty bands. A magnetic anisotropy energy of ∼50 µeV is obtained, and the easy axis aligns along the film orientation as the film thickness increases, revealing that such films are ideal candidates for spintronic applications.

Correction: Analysis on the energetics, magnetism and electronic properties in a 45° ZnO grain boundary doped with Gd.

[This corrects the article DOI: 10.1039/C8RA00985F.].