Intrinsic 1[Formula: see text] phase induced in atomically thin 2H-MoTe2 by a single terahertz pulse.

The polymorphic transition from 2H to 1[Formula: see text]-MoTe2, which was thought to be induced by high-energy photon irradiation among many other means, has been intensely studied for its technological relevance in nanoscale transistors due to the remarkable improvement in electrical performance. However, it remains controversial whether a crystalline 1[Formula: see text] phase is produced because optical signatures of this putative transition are found to be associated with the formation of tellurium clusters instead. Here we demonstrate the creation of an intrinsic 1[Formula: see text] lattice after irradiating a mono- or few-layer 2H-MoTe2 with a single field-enhanced terahertz pulse. Unlike optical pulses, the low terahertz photon energy limits possible structural damages. We further develop a single-shot terahertz-pump-second-harmonic-probe technique and reveal a transition out of the 2H-phase within 10 ns after photoexcitation. Our results not only provide important insights to resolve the long-standing debate over the light-induced polymorphic transition in MoTe2 but also highlight the unique capability of strong-field terahertz pulses in manipulating quantum materials.

Rational Design of a Chemical Bath Deposition Based Tin Oxide Electron-Transport Layer for Perovskite Photovoltaics.

Chemical bath deposition (CBD) is widely used to deposit tin oxide (SnOx ) as an electron-transport layer in perovskite solar cells (PSCs). The conventional recipe uses thioglycolic acid (TGA) to facilitate attachments of SnOx particles onto the substrate. However, nonvolatile TGA is reported to harm the operational stability of PSCs. In this work, a volatile oxalic acid (OA) is introduced as an alternative to TGA. OA, a dicarboxylic acid, functions as a chemical linker for the nucleation and attachment of particles to the substrate in the chemical bath. Moreover, OA can be readily removed through thermal annealing followed by a mild H2 O2 treatment, as shown by FTIR measurements. Synergistically, the mild H2 O2 treatment selectively oxidizes the surface of the SnOx layer, minimizing nonradiative interface carrier recombination. EELS (electron-energy-loss spectroscopy) confirms that the SnOx surface is dominated by Sn4+ , while the bulk is a mixture of Sn2+ and Sn4+ . This rational design of a CBD SnOx layer leads to devices with T85 ≈1500 h, a significant improvement over the TGA-based device with T80 ≈250 h. The champion device reached a power conversion efficiency of 24.6%. This work offers a rationale for optimizing the complex parameter space of CBD SnOx to achieve efficient and stable PSCs.

Uncovering temperature-dependent exciton-polariton relaxation mechanisms in hybrid organic-inorganic perovskites.

Hybrid perovskites have emerged as a promising material candidate for exciton-polariton (polariton) optoelectronics. Thermodynamically, low-threshold Bose-Einstein condensation requires efficient scattering to the polariton energy dispersion minimum, and many applications demand precise control of polariton interactions. Thus far, the primary mechanisms by which polaritons relax in perovskites remains unclear. In this work, we perform temperature-dependent measurements of polaritons in low-dimensional perovskite wedged microcavities achieving a Rabi splitting of [Formula: see text] = 260 ± 5 meV. We change the Hopfield coefficients by moving the optical excitation along the cavity wedge and thus tune the strength of the primary polariton relaxation mechanisms in this material. We observe the polariton bottleneck regime and show that it can be overcome by harnessing the interplay between the different excitonic species whose corresponding dynamics are modified by strong coupling. This work provides an understanding of polariton relaxation in perovskites benefiting from efficient, material-specific relaxation pathways and intracavity pumping schemes from thermally brightened excitonic species.

Vertical full-colour micro-LEDs via 2D materials-based layer transfer.

Micro-LEDs (µLEDs) have been explored for augmented and virtual reality display applications that require extremely high pixels per inch and luminance1,2. However, conventional manufacturing processes based on the lateral assembly of red, green and blue (RGB) µLEDs have limitations in enhancing pixel density3-6. Recent demonstrations of vertical µLED displays have attempted to address this issue by stacking freestanding RGB LED membranes and fabricating top-down7-14, but minimization of the lateral dimensions of stacked µLEDs has been difficult. Here we report full-colour, vertically stacked µLEDs that achieve, to our knowledge, the highest array density (5,100 pixels per inch) and the smallest size (4 µm) reported to date. This is enabled by a two-dimensional materials-based layer transfer technique15-18 that allows the growth of RGB LEDs of near-submicron thickness on two-dimensional material-coated substrates via remote or van der Waals epitaxy, mechanical release and stacking of LEDs, followed by top-down fabrication. The smallest-ever stack height of around 9 µm is the key enabler for record high µLED array density. We also demonstrate vertical integration of blue µLEDs with silicon membrane transistors for active matrix operation. These results establish routes to creating full-colour µLED displays for augmented and virtual reality, while also offering a generalizable platform for broader classes of three-dimensional integrated devices.

Printed Organic Photovoltaic Modules on Transferable Ultra-thin Substrates as Additive Power Sources.

Thin-film photovoltaics with functional components on the order of a few microns, present an avenue toward realizing additive power onto any surface of interest without excessive addition in weight and topography. To date, demonstrations of such ultra-thin photovoltaics have been limited to small-scale devices, often prepared on glass carrier substrates with only a few layers solution-processed. We demonstrate large-area, ultra-thin organic photovoltaic (PV) modules produced with scalable solution-based printing processes for all layers. We further demonstrate their transfer onto light-weight and high-strength composite fabrics, resulting in durable fabric-PV systems ∼50 microns thin, weighing under 1 gram over the module area (corresponding to an area density of 105 g m-2 ), and having a specific power of 370 W kg-1 . Integration of the ultra-thin modules onto composite fabrics lends mechanical resilience to allow these fabric-PV systems to maintain their performance even after 500 roll-up cycles. This approach to decouple the manufacturing and integration of photovoltaics enables new opportunities in ubiquitous energy generation.

A room-temperature polarization-sensitive CMOS terahertz camera based on quantum-dot-enhanced terahertz-to-visible photon upconversion.

Detection of terahertz (THz) radiation has many potential applications, but presently available detectors are limited in many aspects of their performance, including sensitivity, speed, bandwidth and operating temperature. Most do not allow the characterization of THz polarization states. Recent observation of THz-driven luminescence in quantum dots offers a possible detection mechanism via field-driven interdot charge transfer. We demonstrate a room-temperature complementary metal-oxide-semiconductor THz camera and polarimeter based on quantum-dot-enhanced THz-to-visible upconversion mechanism with optimized luminophore geometries and fabrication designs. Besides broadband and fast responses, the nanoslit-based sensor can detect THz pulses with peak fields as low as 10 kV cm-1. A related coaxial nanoaperture-type device shows a to-date-unexplored capability to simultaneously record the THz polarization state and field strength with similar sensitivity.

Scalable Self-Limiting Dielectrophoretic Trapping for Site-Selective Assembly of Nanoparticles.

The absence of a versatile, scalable, and defect-free bottom-up assembly of nanoparticles with high precision has been a longstanding roadblock facing the large-scale integration of diverse nanoparticle-based devices. To circumvent this roadblock, we present a self-limiting dielectrophoretic approach to precisely align nanoparticles onto an array of electrodes over a large area, assisted by lithographically defined capacitors in series with the electrodes. We have experimentally verified that the on-chip capacitor can reduce the probability of trapping multiple particles at a given site, as the electric field is greatly weakened after the first nanoparticle bridges the electrodes. A 70% yield of single-nanowire assembly has been achieved, and key factors limiting the current yield are discussed. The yield is expected to further increase by improving the nanoparticle-electrode contact and reducing the capillary force during the drying process. We also demonstrate the versatility of this approach for scalable and site-selective alignment of various nanoparticles.

A versatile acoustically active surface based on piezoelectric microstructures.

We demonstrate a versatile acoustically active surface consisting of an ensemble of piezoelectric microstructures that are capable of radiating and sensing acoustic waves. A freestanding microstructure array embossed in a single step on a flexible piezoelectric sheet of polyvinylidene fluoride (PVDF) leads to high-quality acoustic performance, which can be tuned by the design of the embossed microstructures. The high sensitivity and large bandwidth for sound generation demonstrated by this acoustically active surface outperform previously reported thin-film loudspeakers using PVDF, PVDF copolymers, or voided charged polymers without microstructures. We further explore the directivity of this device and its use on a curved surface. In addition, high-fidelity sound perception is demonstrated by the surface, enabling its microphonic application for voice recording and speaker recognition. The versatility, high-quality acoustic performance, minimal form factor, and scalability of future production of this acoustically active surface can lead to broad industrial and commercial adoption for this technology.

Terahertz Field-Induced Reemergence of Quenched Photoluminescence in Quantum Dots.

The continuous and concerted development of colloidal quantum dot light-emitting diodes over the past two decades has established them as a bedrock technology for the next generation of displays. However, a fundamental issue that limits the performance of these devices is the quenching of photoluminescence due to excess charges from conductive charge transport layers. Although device designs have leveraged various workarounds, doing so often comes at the cost of limiting efficient charge injection. Here we demonstrate that high-field terahertz (THz) pulses can dramatically brighten quenched QDs on metallic surfaces, an effect that persists for minutes after THz irradiation. This phenomenon is attributed to the ability of the THz field to remove excess charges, thereby reducing trion and nonradiative Auger recombination. Our findings show that THz technologies can be used to suppress and control such undesired nonradiative decay, potentially in a variety of luminescent materials for future device applications.

Molecular Platform for Fast Low-Voltage Nanoelectromechanical Switching.

The use of molecules as active components to build nanometer-scale devices inspires emerging device concepts that employ the intrinsic functionality of molecules to address longstanding challenges facing nanoelectronics. Using molecules as controllable-length nanosprings, here we report the design and operation of a nanoelectromechanical (NEM) switch which overcomes the typical challenges of high actuation voltages and slow switching speeds for previous NEM technologies. Our NEM switches are hierarchically assembled using a molecular spacer layer sandwiched between atomically smooth electrodes, which defines a nanometer-scale electrode gap and can be electrostatically compressed to repeatedly modulate the tunneling current. The molecular layer and the top electrode structure serve as two degrees of design freedom with which to independently tailor static and dynamic device characteristics, enabling simultaneous low turn-on voltages (sub-3 V) and short switching delays (2 ns). This molecular platform with inherent nanoscale modularity provides a versatile strategy for engineering diverse high-performance and energy-efficient electromechanical devices.

Hybrid Approach to Fabricate Uniform and Active Molecular Junctions.

Molecules can serve as ultimate building blocks for extreme nanoscale devices. This requires their precise integration into functional heterojunctions, most commonly in the form of metal-molecule-metal architectures. Structural damage and nonuniformities caused by current fabrication techniques, however, limit their effective incorporation. Here, we present a hybrid fabrication approach enabling uniform and active molecular junctions. A template-stripping technique is developed to form electrodes with sub-nanometer smooth surfaces. Combined with dielectrophoretic trapping of colloidal nanorods, uniform sub-5 nm junctions are achieved. Uniquely, in our design, the top contact is mechanically free to move under an applied stimulus. Using this, we investigate the electromechanical tuning of the junction and its tunneling conduction. Here, the molecules help control sub-nanometer mechanical modulation, which is conventionally challenging due to instabilities caused by surface adhesive forces. Our versatile approach provides a platform to develop and study active molecular junctions for emerging applications in electronics, plasmonics, and electromechanical devices.

Efficient perovskite solar cells via improved carrier management.

Metal halide perovskite solar cells (PSCs) are an emerging photovoltaic technology with the potential to disrupt the mature silicon solar cell market. Great improvements in device performance over the past few years, thanks to the development of fabrication protocols1-3, chemical compositions4,5 and phase stabilization methods6-10, have made PSCs one of the most efficient and low-cost solution-processable photovoltaic technologies. However, the light-harvesting performance of these devices is still limited by excessive charge carrier recombination. Despite much effort, the performance of the best-performing PSCs is capped by relatively low fill factors and high open-circuit voltage deficits (the radiative open-circuit voltage limit minus the high open-circuit voltage)11. Improvements in charge carrier management, which is closely tied to the fill factor and the open-circuit voltage, thus provide a path towards increasing the device performance of PSCs, and reaching their theoretical efficiency limit12. Here we report a holistic approach to improving the performance of PSCs through enhanced charge carrier management. First, we develop an electron transport layer with an ideal film coverage, thickness and composition by tuning the chemical bath deposition of tin dioxide (SnO2). Second, we decouple the passivation strategy between the bulk and the interface, leading to improved properties, while minimizing the bandgap penalty. In forward bias, our devices exhibit an electroluminescence external quantum efficiency of up to 17.2 per cent and an electroluminescence energy conversion efficiency of up to 21.6 per cent. As solar cells, they achieve a certified power conversion efficiency of 25.2 per cent, corresponding to 80.5 per cent of the thermodynamic limit of its bandgap.

Nanocrystal-Sensitized Infrared-to-Visible Upconversion in a Microcavity under Subsolar Flux.

Infrared-to-visible photon upconversion could benefit applications such as photovoltaics, infrared sensing, and bioimaging. Solid-state upconversion based on triplet exciton annihilation sensitized by nanocrystals is one of the most promising approaches, albeit limited by relatively weak optical absorption. Here, we integrate the upconverting layers into a Fabry-Pérot microcavity with quality factor Q = 75. At the resonant wavelength λ = 980 nm, absorption increases 74-fold and we observe a 227-fold increase in the intensity of upconverted emission. The threshold excitation intensity is reduced by 2 orders of magnitude to a subsolar flux of 13 mW/cm2. We measure an external quantum efficiency of 0.06 ± 0.01% and a 2.2-fold increase in the generation yield of upconverted photons. Our work highlights the potential of triplet-triplet annihilation-based upconversion in low-intensity sensing applications and demonstrates the importance of photonic designs in addition to materials engineering to improve the efficiency of solid-state upconversion.

Terahertz-Driven Stark Spectroscopy of CdSe and CdSe-CdS Core-Shell Quantum Dots.

The effects of large external fields on semiconductor nanostructures could reveal much about field-induced shifting of electronic states and their dynamical responses and could enable electro-optic device applications that require large and rapid changes in optical properties. Studies of quasi-dc electric field modulation of quantum dot (QD) properties have been limited by electrostatic breakdown processes observed under high externally applied field levels. To circumvent this, here we apply ultrafast terahertz (THz) electric fields with switching times on the order of 1 ps. We show that a pulsed THz electric field, enhanced by a microslit field enhancement structure (FES), can strongly manipulate the optical absorption properties of a thin film of CdSe and CdSe-CdS core-shell QDs on the subpicosecond time scale with spectral shifts that span the visible to near-IR range. Numerical simulations using a semiempirical tight binding model show that the band gap of the QD film can be shifted by as much a 79 meV during these time scales. The results allow a basic understanding of the field-induced shifting of electronic levels and suggest electro-optic device applications.

Charge-Carrier Recombination in Halide Perovskites.

The success of halide perovskites in a host of optoelectronic applications is often attributed to their long photoexcited carrier lifetimes, which has led to charge-carrier recombination processes being described as unique compared to other semiconductors. Here, we integrate recent literature findings to provide a critical assessment of the factors we believe are most likely controlling recombination in the most widely studied halide perovskite systems. We focus on four mechanisms that have been proposed to affect measured charge carrier recombination lifetimes, namely: (1) recombination via trap states, (2) polaron formation, (3) the indirect nature of the bandgap (e.g., Rashba effect), and (4) photon recycling. We scrutinize the evidence for each case and the implications of each process on carrier recombination dynamics. Although they have attracted considerable speculation, we conclude that multiple trapping or hopping in shallow trap states, and the possible indirect nature of the bandgap (e.g., Rashba effect), seem to be less likely given the combined evidence, at least in high-quality samples most relevant to solar cells and light-emitting diodes. On the other hand, photon recycling appears to play a clear role in increasing apparent lifetime for samples with high photoluminescence quantum yields. We conclude that polaron dynamics are intriguing and deserving of further study. We highlight potential interdependencies of these processes and suggest future experiments to better decouple their relative contributions. A more complete understanding of the recombination processes could allow us to rationally tailor the properties of these fascinating semiconductors and will aid the discovery of other materials exhibiting similarly exceptional optoelectronic properties.

High-Speed Vapor Transport Deposition of Perovskite Thin Films.

Intensive research of hybrid metal-halide perovskite materials for use as photoactive materials has resulted in an unmatched increase in the power conversion efficiency of perovskite photovoltaics (PVs) over the last couple of years. Now that lab-fabricated perovskite devices rival the efficiency of silicon PVs, the next challenge of scalable mass manufacturing of large perovskite PV panels remains to be solved. For that purpose, it is still unclear which manufacturing method will provide the lowest processing cost and highest quality solar cells. Vapor deposition has been proven to work well for perovskites as a controllable and repeatable thin-film deposition technique but with processing speeds currently too slow to adequately lower the production costs. Addressing this challenge, in the present work, we demonstrate a high-speed vapor transport processing technique in a custom-built reactor that produces high-quality perovskite films with unprecedented deposition speed exceeding 1 nm/s, over 10× faster than previous vapor deposition demonstrations. We show that the semiconducting perovskite films produced with this method have excellent crystallinity and optoelectronic properties with 10 ns charge carrier lifetime, enabling us to fabricate the first photovoltaic devices made by perovskite vapor transport deposition. Our experiments are guided by computational fluid dynamics simulations that also predict that this technique could lead to deposition rates on the order of micrometers per second. This, in turn, could enable cost-effective scalable manufacturing of the perovskite-based solar technologies.

A Heterogeneous Kinetics Model for Triplet Exciton Transfer in Solid-State Upconversion.

High internal quantum efficiency semiconductor nanocrystal (NC)-based photon upconversion devices are currently based on a single monolayer of active NCs. Devices are therefore limited in their external quantum efficiency based on the low number of photons absorbed. Increasing the number of photons absorbed is expected to increase the upconversion efficiency, yet experimentally increasing the number of layers does not appreciably increase the upconverted light output. We unravel this mystery by combining kinetic modeling and transient photoluminescence spectroscopy. The inherent energetic disorder stemming from the polydispersity of the NCs means that the kinetics are governed by a stochastic transfer matrix. By drawing the rates from a probabilistic distribution and constructing a reaction network with realistic connectivity, we are able to fit complex photoluminescence traces with a very simple model. We use this model to explain the thickness-dependent performance of the upconversion devices and can attribute the reduced efficiencies to the low excitonic diffusivity of the exciton within the NC layers and increased back transfer of the created singlets from the organic annihilator rubrene. We suggest some avenues for overcoming these limitations in future devices.

M13 Virus-Based Framework for High Fluorescence Enhancement.

Fluorescence imaging is a powerful tool for studying biologically relevant macromolecules, but its applicability is often limited by the fluorescent probe, which must demonstrate both high site-specificity and emission efficiency. In this regard, M13 virus, a versatile biological scaffold, has previously been used to both assemble fluorophores on its viral capsid with molecular precision and to also target a variety of cells. Although M13-fluorophore systems are highly selective, these complexes typically suffer from poor molecular detection limits due to low absorption cross-sections and moderate quantum yields. To overcome these challenges, a coassembly of the M13 virus, cyanine 3 dye, and silver nanoparticles is developed to create a fluorescent tag capable of binding with molecular precision with high emissivity. Enhanced emission of cyanine 3 of up to 24-fold is achieved by varying nanoparticle size and particle-fluorophore separation. In addition, it is found that the fluorescence enhancement increases with increasing dye surface density on the viral capsid. Finally, this highly fluorescent probe is applied for in vitro staining of E. coli. These results demonstrate an inexpensive framework for achieving tuned fluorescence enhancements. The methodology developed in this work is potentially amendable to fluorescent detection of a wide range of M13/cell combinations.

Acetonitrile based single step slot-die compatible perovskite ink for flexible photovoltaics.

The demonstration of photovoltaic devices with high power conversion efficiencies using low cost perovskite materials hints at the possibility of dramatically lowering the cost of solar energy. Key to further exploiting the potential of these materials is developing rapid processing techniques that can be used to deliver lower cost high throughput manufacture. This work details the development of low viscosity rapid drying perovskite formulations designed to give high quality solar films when slot-die coated on flexible roll-to-roll compatible substrates. A single step slot-die compatible perovskite ink based on an acetonitrile/methylamine solvent system utilizing a chloride additive is developed, resulting in large area perovskite films from slot-die coating under ambient conditions. The drying conditions for the perovskite film are optimized and fast (<10 min), low temperature (<120 °C) drying of slot-die coated films on flexible substrates are demonstrated and result in high performance devices.

An ingestible bacterial-electronic system to monitor gastrointestinal health.

Biomolecular monitoring in the gastrointestinal tract could offer rapid, precise disease detection and management but is impeded by access to the remote and complex environment. Here, we present an ingestible micro-bio-electronic device (IMBED) for in situ biomolecular detection based on environmentally resilient biosensor bacteria and miniaturized luminescence readout electronics that wirelessly communicate with an external device. As a proof of concept, we engineer heme-sensitive probiotic biosensors and demonstrate accurate diagnosis of gastrointestinal bleeding in swine. Additionally, we integrate alternative biosensors to demonstrate modularity and extensibility of the detection platform. IMBEDs enable new opportunities for gastrointestinal biomarker discovery and could transform the management and diagnosis of gastrointestinal disease.