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.

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.

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.

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.

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.

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.

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.

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.

Solar-Blind Self-Powered Photodetector Using Solution-Processed Amorphous Core-Shell Gallium Oxide Nanoparticles.

Solution-processed deep ultraviolet (DUV) photodetectors based on wide band gap oxide semiconductors (WBGS) working in the <280 nm wavelength range are drawing increasing attention of the research community because of their cost-effective production and potential use in diverse applications. Here, we report on the synthesis of novel core-shell amorphous gallium oxide nanoparticles (NPs) (a-Ga2Ox/GaOx NPs) that have not been previously obtained. The amorphous gallium oxide NPs were synthesized from gallium nitride using the femtosecond laser ablation in liquid technique. Transmission electron microscopy and electron energy-loss spectroscopy measurements revealed the amorphous NP nature with a Ga-rich core and oxide-rich shell. Optical properties of these core-shell amorphous gallium oxide NPs were investigated by time-resolved spectroscopy and photoluminescence. As a proof of concept, the amorphous gallium oxide NPs were used as an active layer in a solar-blind DUV photodetector with high responsivity (778 mA/W) at 244 nm, which is the highest responsivity recorded to date for any solution-processed DUV photodetector. This work on a high-performance solution-processed device paves the way for large-scale industrial application of the WBGS.

Catalyst-Free Vertical ZnO-Nanotube Array Grown on p-GaN for UV-Light-Emitting Devices.

One-dimensional (1D) structures-based UV-light-emitting diode (LED) has immense potential for next-generation applications. However, several issues related to such devices must be resolved first, such as expensive material and growth methods, complicated fabrication process, efficiency droop, and unavoidable metal contamination due to metal catalyst that reduces device efficiency. To overcome these obstacles, we have developed a novel growth method for obtaining a high-quality hexagonal, well-defined, and vertical 1D Gd-doped n-ZnO nanotube (NT) array deposited on p-GaN films and other substrates by pulsed laser deposition. By adopting this approach, the desired high optical and structural quality is achieved without utilizing metal catalyst. Transmission electron microscopy measurements confirm that gadolinium dopants in the target form a transparent in situ interface layer to assist in vertical NT formation. Microphotoluminescence (PL) measurements of the NTs reveal an intense ZnO band edge emission without a defect band, indicating high quality. Carrier dynamic analysis via time-resolved PL confirms that the emission of n-ZnO NTs/p-GaN LED structure is dominated significantly by the radiative recombination process without efficiency droop when high carrier density is injected optically. We developed an electrically pumped UV Gd-doped ZnO NTs/GaN LED as a proof of concept, demonstrating its high internal quantum efficiency (>65%). The demonstrated performance of this cost-effective UV LED suggests its potential application in large-scale device production.

Self-Patterned CsPbBr3 Nanocrystals for High-Performance Optoelectronics.

All-inorganic lead halide perovskites are promising materials for many optoelectronic applications. However, two issues that arise during device fabrication hinder their practical use, namely, inadequate continuity of coated inorganic perovskite films across large areas and inability to integrate these films with traditional photolithography due to poor adhesion to wafers. Herein, for the first time, to address these issues, we show a room-temperature synthesis process employed to produce CsPbBr3 perovskite nanocrystals with two-dimensional (2D) nanosheet features. Due to the unique properties of these 2D nanocrystals, including the "self-assembly" characteristic, the "double solvent evaporation inducing self-patterning" strategy is used to generate high-quality patterned thin films in selected areas automatically after drop-casting, enabling fabrication of high-performance devices without using complex and expensive fabrication processing techniques. The films are free from microcracks. In a proof-of-concept experiment, photodetector arrays are used to demonstrate the superior properties of such films. We provide evidence of both high responsivity (9.04 A/W) and high stability across large areas. The photodetectors fabricated on a flexible substrate exhibit outstanding photoresponse stability. Advanced optical and structural studies reveal the possible mechanism. Our simple and cost-effective method paves the way for the next-generation nanotechnology based on high-performance, cost-effective optoelectronic devices.

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.

High-Performance Ultraviolet-to-Infrared Broadband Perovskite Photodetectors Achieved via Inter-/Intraband Transitions.

A high-performance vertically injected broadband UV-to-IR photodetector based on Gd-doped ZnO nanorods (NRs)/CH3NH3PbI3 perovskite heterojunction was fabricated on metal substrates. Our perovskite-based photodetector is sensitive to a broad spectral range, from ultraviolet to infrared light region (λ = 250-1357 nm). Such structure leads to a high photoresponsivity of 28 and 0.22 A/W, for white light and IR illumination, respectively, with high detectivity values of 1.1 × 1012 and 9.3 × 109 Jones. Optical characterizations demonstrate that the IR detection is due to intraband transition in the perovskite material. Metal substrate boosts carrier injection, resulting in higher responsivity compared to the conventional devices grown on glass, whereas the presence of Gd increases the ZnO NRs performance. For the first time, the perovskite-based photodetector is demonstrated to extend its detection capability to IR (>1000 nm) with high room temperature responsivity across the detected spectrum, leading to a high-performance ingenious cost-effective UV-to-IR broadband photodetector design for large-scale applications.

A Photodetector Based on p-Si/n-ZnO Nanotube Heterojunctions with High Ultraviolet Responsivity.

Enhanced ultraviolet (UV) photodetectors (PDs) with high responsivity comparable to that of visible and infrared photodetectors are needed for commercial applications. n-Type ZnO nanotubes (NTs) with high-quality optical, structural, and electrical properties on a p-type Si(100) substrate are successfully fabricated by pulsed laser deposition (PLD) to produce a UV PD with high responsivity, for the first time. We measure the current-voltage characteristics of the device under dark and illuminated conditions and demonstrated the high stability and responsivity (that reaches ∼101.2 A W-1) of the fabricated UV PD. Time-resolved spectroscopy is employed to identify exciton confinement, indicating that the high PD performance is due to optical confinement, the high surface-to-volume ratio, the high structural quality of the NTs, and the high photoinduced carrier density. The superior detectivity and responsivity of our NT-based PD clearly demonstrate that fabrication of high-performance UV detection devices for commercial applications is possible.

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.

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.

Impact of Silicon Nanocrystal Oxidation on the Nonmetallic Growth of Carbon Nanotubes.

Carbon nanotube (CNT) growth has been demonstrated recently using a number of nonmetallic semiconducting and metal oxide nanoparticles, opening up pathways for direct CNT synthesis from a number of more desirable templates without the need for metallic catalysts. However, CNT growth mechanisms using these nonconventional catalysts has been shown to largely differ and reamins a challenging synthesis route. In this contribution we show CNT growth from partially oxidized silicon nanocrystals (Si NCs) that exhibit quantum confinement effects using a microwave plasma enhanced chemical vapor deposition (PECVD) method. On the basis of solvent and a postsynthesis frgamentation process, we show that oxidation of our Si NCs can be easily controlled. We determine experimentally and explain with theoretical simulations that the Si NCs morphology together with a necessary shell oxide of ∼1 nm is vital to allow for the nonmetallic growth of CNTs. On the basis of chemical analysis post-CNT-growth, we give insight into possible mechanisms for CNT nucleation and growth from our partially oxidized Si NCs. This contribution is of significant importance to the improvement of nonmetallic catalysts for CNT growth and the development of Si NC/CNT interfaces.

Temperature-dependent photoluminescence of surface-engineered silicon nanocrystals.

In this work we report on temperature-dependent photoluminescence measurements (15-300 K), which have allowed probing radiative transitions and understanding of the appearance of various transitions. We further demonstrate that transitions associated with oxide in SiNCs show characteristic vibronic peaks that vary with surface characteristics. In particular we study differences and similarities between silicon nanocrystals (SiNCs) derived from porous silicon and SiNCs that were surface-treated using a radio-frequency (RF) microplasma system.

Varying Surface Chemistries for p-Doped and n-Doped Silicon Nanocrystals and Impact on Photovoltaic Devices.

Doping of quantum confined nanocrystals offers unique opportunities to control the bandgap and the Fermi energy level. In this contribution, boron-doped (p-doped) and phosphorus-doped (n-doped) quantum confined silicon nanocrystals (SiNCs) are surface-engineered in ethanol by an atmospheric pressure radio frequency microplasma. We reveal that surface chemistries induced on the nanocrystals strongly depend on the type of dopants and result in considerable diverse optoelectronic properties (e.g., photoluminescence quantum yield is enhanced more than 6 times for n-type SiNCs). Changes in the position of the SiNCs Fermi levels are also studied and implications for photovoltaic application are discussed.

Enhanced Dispersion of TiO2 Nanoparticles in a TiO2/PEDOT:PSS Hybrid Nanocomposite via Plasma-Liquid Interactions.

A facile method to synthesize a TiO2/PEDOT:PSS hybrid nanocomposite material in aqueous solution through direct current (DC) plasma processing at atmospheric pressure and room temperature has been demonstrated. The dispersion of the TiO2 nanoparticles is enhanced and TiO2/polymer hybrid nanoparticles with a distinct core shell structure have been obtained. Increased electrical conductivity was observed for the plasma treated TiO2/PEDOT:PSS nanocomposite. The improvement in nanocomposite properties is due to the enhanced dispersion and stability in liquid polymer of microplasma treated TiO2 nanoparticles. Both plasma induced surface charge and nanoparticle surface termination with specific plasma chemical species are proposed to provide an enhanced barrier to nanoparticle agglomeration and promote nanoparticle-polymer binding.