The electronic and optical properties of 2D transition metal dichalcogenides are dominated by strong excitonic resonances. Exciton dynamics plays a critical role in the functionality and performance of many miniaturized 2D optoelectronic devices; however, the measurement of nanoscale excitonic behaviors remains challenging. Here, a near-field transient nanoscopy is reported to probe exciton dynamics beyond the diffraction limit. Exciton recombination and exciton-exciton annihilation processes in monolayer and bilayer MoS2 are studied as the proof-of-concept demonstration. Moreover, with the capability to access local sites, intriguing exciton dynamics near the monolayer-bilayer interface and at the MoS2 nano-wrinkles are resolved. Such nanoscale resolution highlights the potential of this transient nanoscopy for fundamental investigation of exciton physics and further optimization of functional devices.
Black phosphorus (BP) is a narrow bandgap (â¼0.3 eV) semiconductor with a great potential for optoelectronic devices in the mid-infrared wavelength. However, it has been challenging to achieve a high-quality scalable BP thin film. Here we present the successful synthesis of optically active BP films on a centimeter scale. We utilize the pulsed laser deposition of amorphous red phosphorus, another allotrope of phosphorus, followed by a high-pressure treatment at â¼8 GPa to induce a phase conversion into BP crystals. The crystalline quality was improved through thermal annealing, resulting in the observation of photoluminescence emission at mid-infrared wavelengths. We demonstrate high-pressure conversion on a centimeter scale with a continuous film with a thickness of â¼18 nm using a flat-belt-type high-pressure apparatus. This synthesis procedure presents a promising route to obtain optical-quality BP films, enabling the exploration of integrated optoelectronic device applications such as light-emitting devices and mid-infrared cameras on a chip scale.
Black phosphorus (bP) is a promising material for mid-infrared (mid-IR) optoelectronic applications, exhibiting high performance light emission and detection. Alloying bP with arsenic extends its operation toward longer wavelengths from 3.7 µm (bP) to 5 µm (bP3As7), which is of great practical interest. Quantitative optical characterizations are performed to establish black phosphorus-arsenic (bPAs) alloys optoelectronic quality. Anisotropic optical constants (refractive index, extinction coefficient, and absorption coefficient) of bPAs alloys from near-infrared to mid-IR (0.2-0.9 eV) are extracted with reflection measurements, which helps optical device design. Quantitative photoluminescence (PL) of bPAs alloys with different As concentrations are measured from room temperature to 77 K. PL quantum yield measurements reveal a 2 orders of magnitude decrease in radiative efficiency with increasing As concentration. An optical cavity is designed for bP3As7, which allows for up to an order of magnitude enhancement in the quantum yield due to the Purcell effect. Our comprehensive optical characterization provides the foundation for high performance mid-IR optical device design using bPAs alloys.
The potential of monitoring biomarkers in sweat for health-related applications has spurred rapid growth in the field of wearable sweat sensors over the past decade. Some of the key challenges have been addressed, including measuring sweat-secretion rate and collecting sufficient sample volumes for real-time, continuous molecular analysis without intense exercise. However, except for assessment of cystic fibrosis and regional nerve function, the ability to accurately measure analytes of interest and their physiological relevance to health metrics remain to be determined. Although sweat is not a crystal ball into every aspect of human health, we expect sweat measurements to continue making inroads into niche applications involving active sweating, such as hydration monitoring for athletes and physical laborers and later for medical and casual health monitoring of relevant drugs and hormones.
The mid-wave infrared (MWIR), ranging from 2 to 5 micrometers, is of substantial interest for chemical sensing, imaging, and spectroscopy. Black phosphorus (bP)-based MWIR light emitters and detectors have been shown to outperform the state-of-the-art for commercial devices due to the low Auger recombination coefficient of bP. However, the scalability of these devices remains a challenge. Here, we report a bP ink formula that preserves the exceptional MWIR optoelectronic properties of bP to deposit centimeter-scale, uniform, and pinhole free films with a photoluminescence quantum yield higher than competing III-V and II-VI semiconductors with similar bandgaps at high excitation regime. As a proof of concept, we use bP ink as a "phosphor" on a red commercial light-emitting diode to demonstrate bright MWIR light emission. We also show that these films can be integrated into heterostructure device architectures with electron and hole selective contacts for direct-injected light emission and detection in MWIR.
In recent years, there has been an increasing focus on 2D nongraphene materials that range from insulators to semiconductors to metals. As a single-elemental van der Waals semiconductor, tellurium (Te) has captivating anisotropic physical properties. Recent work demonstrated growth of ultrathin Te on WSe2 with the atomic chains of Te aligned with the armchair directions of the substrate using physical vapor deposition (PVD). In this system, a moiré superlattice is formed where micrometer-scale Te flakes sit on top of the continuous WSe2 film. Here, we determined the precise orientation of the Te flakes with respect to the substrate and detailed structure of the resulting moiré lattice by combining electron microscopy with image simulations. We directly visualized the moiré lattice using center of mass-differential phase contrast (CoM-DPC). We also investigated the local strain within the Te/WSe2 layered materials using scanning nanodiffraction techniques. There is a significant tensile strain at the edges of flakes along the direction perpendicular to the Te chain direction, which is an indication of the preferred orientation for the growth of Te on WSe2. In addition, we observed local strain relaxation regions within the Te film, specifically attributed to misfit dislocations, which we characterize as having a screw-like nature. The detailed structural analysis gives insight into the growth mechanisms and strain relaxation in this moiré heterostructure.
Formation of charged trions is detrimental to the luminescence quantum efficiency of colloidal quantum dot (QD) thin films as they predominantly undergo nonradiative recombination. In this regard, control of charged trion formation is of interest for both fundamental characterization of the quasi-particles and performance optimization. Using CdSe/CdS QDs as a prototypical material system, here we demonstrate a metal-oxide-semiconductor capacitor based on QD thin films for studying the background charge effect on the luminescence efficiency and lifetime. The concentration ratio of the charged and neutral quasiparticles in the QDs is reversibly controlled by applying a gate voltage, while simultaneous steady-state and time-resolved photoluminescence measurements are performed. Notably, the photoluminescence intensity is modulated by up to 2 orders of magnitude with a corresponding change in the effective lifetime. In addition, chip-scale modulation of brightness is demonstrated, where the photoluminescence is effectively turned on and off by the gate, highlighting potential applications in voltage-controlled electrochromics.
Black phosphorus (BP) is a narrow bandgap layered semiconductor promising for mid-infrared optoelectronic applications. BP-based devices have been shown to surpass state-of-the-art mid-infrared detectors and light-emitting diodes (LEDs) in terms of performance. Despite their device advantages, the material's inherent instability in the air could hinder its use in practical optoelectronic applications. Here, we investigated the impact of passivation on the device lifetime of BP LEDs, which deteriorate in a matter of seconds without using passivation. The lifetime is significantly extended with an Al2O3 passivation layer and nitrogen packaging via atomic layer deposition and ultra-violet curable resin sealing. The operational lifetime (half-life) at room temperature is extrapolated to be ~15,000 h with an initial power density of 340 mW/cm2 based on accelerated life testing. The present results indicate that efficient BP optoelectronics can be highly robust through simple and scalable packaging technologies, with important practical implications for mid-infrared applications.
Large-area epitaxial growth of III-V nanowires and thin films on van der Waals substrates is key to developing flexible optoelectronic devices. In our study, large-area InAs nanowires and planar structures are grown on hexagonal boron nitride templates using metal organic chemical vapor deposition method without any catalyst or pre-treatments. The effect of basic growth parameters on nanowire yield and thin film morphology is investigated. Under optimised growth conditions, a high nanowire density of 2.1×109cm-2is achieved. A novel growth strategy to achieve uniform InAs thin film on h-BN/SiO2/Si substrate is introduced. The approach involves controlling the growth process to suppress the nucleation and growth of InAs nanowires, while promoting the radial growth of nano-islands formed on the h-BN surface. A uniform polycrystalline InAs thin film is thus obtained over a large area with a dominant zinc-blende phase. The film exhibits near-band-edge emission at room temperature and a relatively high Hall mobility of 399 cm-2/(Vs). This work suggests a promising path for the direct growth of large-area, low-temperature III-V thin films on van der Waals substrates.
We demonstrate an alternating current (AC) driven light emitting capacitor in which the color of the emission spectra can be changed via an applied AC frequency. The device has a simple metal-oxide-semiconductor (MOS) capacitor structure with an organic emissive layer, enabling facile fabrication processing. The organic emissive layer comprises a thin, submonolayer low energy dye layer underneath a thick host matrix (â¼30 nm) with higher energy emitting dyes. The emission of the lower energy dyes dominates at low frequency, while the higher energy emission of the host matrix dominates at high frequency. This simple color tunable device could be used for full-color displays and lighting in the future.
Miniaturized spectrometers in the mid-infrared (MIR) are critical in developing next-generation portable electronics for advanced sensing and analysis. The bulky gratings or detector/filter arrays in conventional micro-spectrometers set a physical limitation to their miniaturization. In this work, we demonstrate a single-pixel MIR micro-spectrometer that reconstructs the sample transmission spectrum by a spectrally dispersed light source instead of spatially grated light beams. The spectrally tunable MIR light source is realized based on the thermal emissivity engineered via the metal-insulator phase transition of vanadium dioxide (VO2). We validate the performance by showing that the transmission spectrum of a magnesium fluoride (MgF2) sample can be computationally reconstructed from sensor responses at varied light source temperatures. With potentially minimum footprint due to the array-free design, our work opens the possibility where compact MIR spectrometers are integrated into portable electronic systems for versatile applications.
Miniaturized, multicolored light-emitting device arrays are promising for applications in sensing, imaging, computing, and more, but the range of emission colors achievable by a conventional light-emitting diode is limited by material or device constraints. In this work, we demonstrate a highly multicolored light-emitting array with 49 different, individually addressable colors on a single chip. The array consists of pulsed-driven metal-oxide-semiconductor capacitors, which generate electroluminescence from microdispensed materials spanning a diverse range of colors and spectral shapes, enabling facile generation of arbitrary light spectra across a broad wavelength range (400 to 1400 nm). When combined with compressive reconstruction algorithms, these arrays can be used to perform spectroscopic measurements in a compact manner without diffractive optics. As an example, we demonstrate microscale spectral imaging of samples using a multiplexed electroluminescent array in conjunction with a monochrome camera.
Black phosphorus has emerged as a unique optoelectronic material, exhibiting tunable and high device performance from mid-infrared to visible wavelengths. Understanding the photophysics of this system is of interest to further advance device technologies based on it. Here we report the thickness dependence of the photoluminescence quantum yield at room temperature in black phosphorus while measuring the various radiative and non-radiative recombination rates. As the thickness decreases from bulk to ~4 nm, a drop in the photoluminescence quantum yield is initially observed due to enhanced surface carrier recombination, followed by an unexpectedly sharp increase in photoluminescence quantum yield with further thickness scaling, with an average value of ~30% for monolayers. This trend arises from the free-carrier to excitonic transition in black phosphorus thin films, and differs from the behaviour of conventional semiconductors, where photoluminescence quantum yield monotonically deteriorates with decreasing thickness. Furthermore, we find that the surface carrier recombination velocity of black phosphorus is two orders of magnitude lower than the lowest value reported in the literature for any semiconductor with or without passivation; this is due to the presence of self-terminated surface bonds in black phosphorus.
Humans rely increasingly on sensors to address grand challenges and to improve quality of life in the era of digitalization and big data. For ubiquitous sensing, flexible sensors are developed to overcome the limitations of conventional rigid counterparts. Despite rapid advancement in bench-side research over the last decade, the market adoption of flexible sensors remains limited. To ease and to expedite their deployment, here, we identify bottlenecks hindering the maturation of flexible sensors and propose promising solutions. We first analyze challenges in achieving satisfactory sensing performance for real-world applications and then summarize issues in compatible sensor-biology interfaces, followed by brief discussions on powering and connecting sensor networks. Issues en route to commercialization and for sustainable growth of the sector are also analyzed, highlighting environmental concerns and emphasizing nontechnical issues such as business, regulatory, and ethical considerations. Additionally, we look at future intelligent flexible sensors. In proposing a comprehensive roadmap, we hope to steer research efforts towards common goals and to guide coordinated development strategies from disparate communities. Through such collaborative efforts, scientific breakthroughs can be made sooner and capitalized for the betterment of humanity.
Wearable Electronic Devices , Humans , Quality of Life
Exciton-exciton annihilation (EEA) is a nonradiative process commonly observed in excitonic materials at high exciton densities. Like Auger recombination, EEA degrades luminescence efficiency at high exciton densities and causes efficiency roll-off in light-emitting devices. Near-unity photoluminescence quantum yield has been demonstrated in transition metal dichalcogenides (TMDCs) at all exciton densities with optimal band structure modification mediated by strain. Although the recombination pathways in TMDCs are well understood, the practical application of light-emitting devices has been challenging. Here, we demonstrate a roll-off free electroluminescence (EL) device composed of TMDC monolayers tunable by strain. We show a 2 orders of magnitude EL enhancement from the WSe2 monolayer by applying a small strain of 0.5%. We attain an internal quantum efficiency of 8% at all injection rates. Finally, we demonstrate transient EL turn-on voltages as small as the band gap. Our approach will contribute to practical applications of roll-off free optoelectronic devices based on excitonic materials.
Dominant recombination pathways in monolayer transition metal dichalcogenides (TMDCs) depend primarily on background carrier concentration, generation rate, and applied strain. Charged excitons formed in the presence of background carriers mainly recombine nonradiatively. Neutral excitons recombine completely radiatively at low generation rates, but experience nonradiative exciton-exciton annihilation (EEA) at high generation rates. Strain can suppress EEA, resulting in near-unity photoluminescence quantum yield (PL QY) at all exciton densities. Although exciton diffusion is the primary channel of energy transport in excitonic materials and a critical optoelectronic design consideration, the combined effects of these factors on exciton diffusion are not clearly understood. In this work, we decouple the diffusion of neutral and charged excitons with chemical counterdoping and explore the effect of strain and generation rate on exciton diffusion. According to the standard semiconductor paradigm, a shorter carrier recombination lifetime should lead to a smaller diffusion length. Surprisingly, we find that increasing generation rate shortens the exciton lifetime but increases the diffusion length in unstrained monolayers of TMDCs. When we suppress EEA by strain, both lifetime and diffusion length become independent of generation rate. During EEA one exciton nonradiatively recombines and kinetically energizes another exciton, which then diffuses fast. Our results probe concentration-dependent diffusion of pure neutral excitons by counterdoping and elucidate how strain controls exciton transport and many-body interactions in TMDC monolayers.
Wearable sweat sensors are emerging as promising platforms for personalized and real-time tracking of evolving health and fitness parameters. While most wearable sweat sensors focus on tracking biomarker concentration profiles, sweat secretion rate is a key metric with broad implications for assessing hydration, cardiac, and neural conditions. Here we present a wearable microfluidic sensor for continuous sweat rate measurement. A discrete impedimetric sensing scheme relying on interdigitated electrodes within a microfluidic sweat collector allows for precise and selective sweat rate measurement across a broad physiological range. Integration of a manually activated pressure pump to expel sweat from the device prevents sensor saturation and enables continuous sweat rate tracking over hours. By enabling broad range and prolonged sweat rate measurement, this platform tackles a key obstacle to realizing meaningful and actionable sweat sensing for applications in exercise physiology and medicine.
Sweat , Wearable Electronic Devices , Electrodes , Microfluidics
The mid-wave infrared (MWIR) wavelength range plays a central role in a variety of applications, including optical gas sensing, industrial process control, spectroscopy, and infrared (IR) countermeasures. Among the MWIR light sources, light-emitting diodes (LEDs) have the advantages of simple design, room-temperature operation, and low cost. Owing to the low Auger recombination at high carrier densities and direct bandgap of black phosphorus (bP), it can serve as a high quantum efficiency emitting layer in LEDs. In this work, we demonstrate bP-LEDs exhibiting high external quantum efficiencies and wall-plug efficiencies of up to 4.43 and 1.78%, respectively. This is achieved by integrating the device with an Al2O3/Au optical cavity, which enhances the emission efficiency, and a thin transparent conducing oxide [indium tin oxide (ITO)] layer, which reduces the parasitic resistance, both resulting in order of magnitude improvements to performance.
