Monolithic Perovskite-Silicon Dual-Band Photodetector for Efficient Spectral Light Discrimination.

Selective spectral discrimination of visible and near-infrared light, which accurately distinguishes different light wavelengths, holds considerable promise in various fields, such as automobiles, defense, and environmental monitoring. However, conventional imaging technologies suffer from various issues, including insufficient spatial optimization, low definition, and optical loss. Herein, a groundbreaking advancement is demonstrated in the form of a dual-band photodiode with distinct near-infrared- and visible-light discrimination obtained via simple voltage control. The approach involves the monolithic stacking integration of methylammonium lead iodide (MAPbI3) and Si semiconductors, resulting in a p-Si/n-phenyl-C61-butyric acid methyl ester/i-MAPbI3/p-spiro-MeOTAD (PNIP) device. Remarkably, the PNIP configuration can independently detect the visible and near-infrared regions without traditional optical filters under a voltage range of 3 to -3 V. In addition, an imaging system for a prototype autonomous vehicle confirms the capability of the device to separate visible and near-infrared light via an electrical bias and practicality of this mechanism. Therefore, this study pushes the boundaries of image sensor development and sets the stage for fabricating compact and power-efficient photonic devices with superior performance and diverse functionality.

Perovskite multifunctional logic gates via bipolar photoresponse of single photodetector.

The explosive demand for a wide range of data processing has sparked interest towards a new logic gate platform as the existing electronic logic gates face limitations in accurate and fast computing. Accordingly, optoelectronic logic gates (OELGs) using photodiodes are of significant interest due to their broad bandwidth and fast data transmission, but complex configuration, power consumption, and low reliability issues are still inherent in these systems. Herein, we present a novel all-in-one OELG based on the bipolar spectral photoresponse characteristics of a self-powered perovskite photodetector (SPPD) having a back-to-back p+-i-n-p-p+ diode structure. Five representative logic gates ("AND", "OR", "NAND", "NOR", and "NOT") are demonstrated with only a single SPPD via the photocurrent polarity control. For practical applications, we propose a universal OELG platform of integrated 8 × 8 SPPD pixels, demonstrating the 100% accuracy in five logic gate operations irrelevant to current variation between pixels.

High-Performance Oxide-Based p-n Heterojunctions Integrating p-SnOx and n-InGaZnO.

The fabrication of oxide-based p-n heterojunctions that exhibit high rectification performance has been difficult to realize using standard manufacturing techniques that feature mild vacuum requirements, low thermal budget processing, and scalability. Critical bottlenecks in the fabrication of these heterojunctions include the narrow processing window of p-type oxides and the charge-blocking performance across the metallurgical junction required for achieving low reverse current and hence high rectification behavior. The overarching goal of the present study is to demonstrate a simple processing route to fabricate oxide-based p-n heterojunctions that demonstrate high on/off rectification behavior, a low saturation current, and a small turn-on voltage. For this study, room-temperature sputter-deposited p-SnOx and n-InGaZnO (IGZO) films were chosen. SnOx is a promising p-type oxide material due to its monocationic system that limits complexities related to processing and properties, compared to other multicationic oxide materials. For the n-type oxide, IGZO is selected due to the knowledge that postprocessing annealing critically reduces the defect and trap densities in IGZO to ensure minimal interfacial recombination and high charge-blocking performance in the heterojunctions. The resulting oxide p-n heterojunction exhibits a high rectification ratio greater than 103 at ±3 V, a low saturation current of ∼2 × 10-10 A, and a small turn-on voltage of ∼0.5 V. In addition, the demonstrated oxide p-n heterojunctions exhibit excellent stability over time in air due to the p-SnOx with completed reaction annealing in air and the reduced trap density in n-IGZO.

Binder-free printed PEDOT wearable sensors on everyday fabrics using oxidative chemical vapor deposition.

Polymeric sensors on fabrics have vast potential toward the development of versatile applications, particularly when the ready-made wearable or fabric can be directly coated. However, traditional coating approaches, such as solution-based methods, have limitations in achieving uniform and thin films because of the poor surface wettability of fabrics. Herein, to realize a uniform poly(3,4-ethylenedioxythiophene) (PEDOT) layer on various everyday fabrics, we use oxidative chemical vapor deposition (oCVD). The oCVD technique is a unique method capable of forming patterned polymer films with controllable thicknesses while maintaining the inherent advantages of fabrics, such as exceptional mechanical stability and breathability. Utilizing the superior characteristics of oCVD PEDOT, we succeed in fabricating blood pressure­ and respiratory rate­monitoring sensors by directly depositing and patterning PEDOT on commercially available disposable gloves and masks, respectively. Those results are expected to pave efficient and facile ways for skin-compatible and affordable sensors for personal health care monitoring.

Enhanced NO2 Sensing Performance of Graphene with Thermally Induced Defects.

This paper demonstrates the enhanced NO2 sensing performance of graphene with defects generated by rapid thermal annealing (RTA). A high temperature of RTA (300-700 °C) was applied to graphene under an argon atmosphere to form defects on sp2 carbon lattices. The density of defects proportionally increased with increasing the RTA temperature. Raman scattering results confirmed significant changes in sp2 bonding. After 700 °C RTA, ID/IG, I2D/IG, and FWHM (full width at half maximum)(G) values, which are used to indirectly investigate carbon-carbon bonds' chemical and physical properties, were markedly changed compared to the pristine graphene. Further evidence of the thermally-induced defects on graphene was found via electrical resistance measurements. The electrical resistance of the RTA-treated graphene linearly increased with increasing RTA temperature. Meanwhile, the NO2 response of graphene sensors increased from 0 to 500 °C and reached maximum (R = ~24%) at 500 °C. Then, the response rather decreased at 700 °C (R = ~14%). The results imply that rich defects formed at above a critical temperature (~500 °C) may damage electrical paths of sp2 chains and thus deteriorate NO2 response. Compared to the existing functionalization process, the RTA treatment is very facile and allows precise control of the NO2 sensing characteristics, contributing to manufacturing commercial low-cost, high-performance, integrated sensors.

Reactant/polymer hybrid films on p-n junction photodetectors for self-powered, non-invasive glucose biosensors.

The portability of electronic-based biosensors is limited because of the use of batteries and/or solutions containing reactants such as enzymes for assay, which limits the utility of such biosensors in point-of-care (POC) testing. In this study, we report on the development of a self-powered biosensor composed of only portable components: a reactant-containing poly (ethylene glycol) (PEG) film for the colorimetric assay, and a self-powered n-InGaZnO/p-Si photodetector. The PEG film containing enzymes and color-developing agents was formed on a glass slide by spin coating. The self-powered biosensor was fabricated by placing the hybrid film on the p-n junction photodetector, and applied in non-invasive glucose detection (salivary glucose). Injection of the target-containing solution dissolved the PEG that led to the release of enzymes and color-developing agents, resulting in a colorimetric assay. The colorimetric assay could attenuate the light reaching the photodetector, thus facilitating target concentration verification by measuring the photocurrent. Our self-powered biosensor has two main advantages: (i) all components of the biosensor are portable and (ii) dilution of target concentration is avoided as the reagents are in the PEG film. Therefore, the self-powered biosensor, without solution-phase components, could be highly beneficial for creating portable, sensitive biosensors for POC testing.

Molecular Sieve Based on a PMMA/ZIF-8 Bilayer for a CO-Tolerable H2 Sensor with Superior Sensing Performance.

Semiconductor sensors equipped with Pd catalysts are promising candidates as low-powered and miniaturized surveillance devices that are used to detect flammable hydrogen (H2) gas. However, the following issues remain unresolved: (i) a sluggish sensing speed at room temperature and (ii) deterioration of sensing performance caused by interfering gases, particularly, carbon monoxide (CO). Herein, a bilayer comprising poly(methyl methacrylate) (PMMA) and zeolitic imidazolate framework-8 (ZIF-8) is utilized as a molecular sieve for diode-type H2 sensors based on a Pd-decorated indium-gallium-zinc oxide film on a p-type silicon substrate. While the PMMA effectively blocks the penetration of CO gas molecules into the sensing entity, the ZIF-8 improves sensing performances by modifying the catalytic activity of Pd, which is preferable for splitting H2 and O2 molecules. Consequently, the bilayer-covered sensor achieves outstanding CO tolerance with superior sensing figures of merit (response/recovery times of <10 s and sensing response of >5000% at 1% H2).

High-Performance Photovoltaic Hydrogen Sensing Platform with a Light-Intensity Calibration Module.

Although battery-free gas sensors (e.g., photovoltaic or triboelectric sensors) have recently appeared to resolve the power consumption issue of conventional chemiresistors, severe technical barriers still remain. Especially, their signals varying under ambient conditions such as light intensity restrict the utilization of these sensors. Insufficient sensing performances (low response and slow sensing rate) of previous battery-free sensors are also an obstacle for practical use. Herein, a photovoltaic hydrogen (H2)-sensing platform having constant sensing responses regardless of light conditions is demonstrated. The platform consists of two photovoltaic units: (1) a palladium (Pd)-decorated n-IGZO/p-Si photodiode covered with a microporous zeolitic imidazolate framework-8 (ZIF-8) film and (2) a device with the same configuration, but without the Pd catalyst as a reference to calibrate the base current of sensor (1). The platform after calibration yields accurate response values in real time regardless of unknown irradiance. Besides, the sensing performances (e.g., sensing response of 1.57 × 104% at 1% H2 with a response time <15 s) of our platform are comparable with those of the conventional resistive H2 sensors, which yield unprecedented results in photovoltaic H2 sensors.

Plasmon enhanced up-conversion nanoparticles in perovskite solar cells for effective utilization of near infrared light.

As an alternative to silicon-based solar cells, organic-inorganic hybrid perovskite solar cells (PSCs) have attracted much attention and achieved a comparable power conversion efficiency (PCE) to silicon-based ones, although the perovskite materials can absorb only visible light. Hence, the challenge remains to enhance the PCE utilizing near infrared (NIR) light in the solar light spectrum. One of the easiest ways to utilize the NIR is to incorporate NIR active materials in PSCs such as up-conversion nanoparticles (UCNPs); however, such a stratergy is not simple to adopt in PSCs due to the inherent vurnerability of perovskite materials towards moisture. In this work, we present NIR-utilizing PSCs by locating UCNPs within the PSC structure by a simple dry transfer method. A maximum PCE of 15.56% was obtained in the case of PSC having the UCNPs located between the hole transport layer (HTL) and gold (Au) top electrode, which is an 8.4% enhancement compared to the cell without the UCNPs. This enhancement came from the combined effects of NIR light utilization and the surface plasmon resonance (SPR) phenomenon originating from the Au top electrode, which was interfacing the UCNPs.

Improvement of perovskite crystallinity by omnidirectional heat transfer via radiative thermal annealing.

As promising photo-absorbing materials for photovoltaics, organic-inorganic hybrid perovskite materials such as methylammonium lead iodide and formamidinium lead iodide, have attracted lots of attention from many researchers. Among the various factors to be considered for high power conversion efficiency (PCE) in perovskite solar cells (PSCs), increasing the grain size of perovskite is most important. However, it is difficult to obtain a highly crystalline perovskite film with large grain size by using the conventional hot-plate annealing method because heat is transferred unidirectionally from the bottom to the top. In this work, we presented radiative thermal annealing (RTA) to improve the structural and electrical properties of perovskite films. Owing to the omnidirectional heat transfer, swift and uniform nuclei formation was possible within the perovskite film. An average grain size of 500 nm was obtained, which is 5 times larger than that of the perovskite film annealed on a hot-plate. This perovskite film led to an enhancement of photovoltaic performance of PSCs. Both short-circuit current density and PCE of the PSCs prepared by RTA were improved by 10%, compared to those of PSCs prepared by hot-plate annealing.

Surface conversion of ZnO nanorods to ZIF-8 to suppress surface defects for a visible-blind UV photodetector.

ZnO nanomaterials are promising building blocks for an efficient UV photodetector; however, their slow sensing behavior and undesired response to visible light, which are attributed to surface defects, such as oxygen or zinc vacancies, are challenges that remain to be addressed. Here, we transformed the ZnO nanorod surface into a zeolitic imidazolate framework-8 (ZIF-8) to eliminate ZnO surface defects. Vertical-type photodetectors were fabricated incorporating a Schottky junction at the ZIF-8/gold (Au) top electrode and could respond to UV light with a rapid response and recovery (1-2 s) and demonstrated a UV-to-visible rejection ratio in the order of 103, qualifying them as efficient visible-blind UV photodetectors. It is noteworthy that the ZIF-8 layer effectively separated the photogenerated electron-hole pairs, and thus reduced their recombination probability. The enhanced photodetector displayed excellent figures-of-merit: a responsivity of 291 A W-1 and a detectivity of 5.9 × 1013 cm Hz1/2 W-1 under illumination at 295 nm.

Self-Powered Biosensors Using Various Light Sources in Daily Life Environments: Integration of p-n Heterojunction Photodetectors and Colorimetric Reactions for Biomolecule Detection.

Electronic biosensors operating without power supply are high in demand owing to increasing interest in point-of-care (POC) coupled with portable and wearable electronic devices for smart healthcare services. Although self-powered electronic sensors have emerged with the promise of resolving the energy supply problems, achieving sufficient sensitivity to targets in real samples is highly challenging because of the matrix effect caused by electroactive species. In this study, we developed a self-powered biosensor platform by combining n-indium gallium zinc oxide (IGZO)/p-Si heterojunction photodetectors and physically separated colorimetric reactions. The self-powered biosensors were applied to glucose detection in real human samples using light sources from daily life environments such as fluorescent light and sunlight. The sensors showed high sensitivity and stability from 0.01 to 10 mg mL-1 of glucose in human saliva and urine without matrix effect from the electroactive species in real samples. In addition, a small change in glucose concentration in human serum was distinguishable with a resolution of 0.01 mg mL-1. Notably, these results were obtained using well-developed and widely used materials like Si and IGZO with simple deposition techniques. Moreover, this self-powered biosensing platform can be universally applied for the detection of all biomolecules being detected by colorimetric assays. To the best of our knowledge, this is the first report on such self-powered biosensors, which could be a promising candidate for future POC biosensors integrated with portable and wearable electronic devices.

Tunable graphene doping by modulating the nanopore geometry on a SiO2/Si substrate.

A tunable graphene doping method utilizing a SiO2/Si substrate with nanopores (NP) was introduced. Laser interference lithography (LIL) using a He-Cd laser (λ = 325 nm) was used to prepare pore size- and pitch-controllable NP SiO2/Si substrates. Then, bottom-contact graphene field effect transistors (G-FETs) were fabricated on the NP SiO2/Si substrate to measure the transfer curves. The graphene transferred onto the NP SiO2/Si substrate showed relatively n-doped behavior compared to the graphene transferred onto a flat SiO2/Si substrate, as evidenced by the blue-shift of the 2D peak position (∼2700 cm-1) in the Raman spectra due to contact doping. As the porosity increased within the substrate, the Dirac voltage shifted to a more positive or negative value, depending on the initial doping type (p- or n-type, respectively) of the contact doping. The Dirac voltage shifts with porosity were ascribed mainly to the compensation for the reduced capacitance owing to the SiO2-air hetero-structured dielectric layer within the periodically aligned nanopores capped by the suspended graphene (electrostatic doping). The hysteresis (Dirac voltage difference during the forward and backward scans) was reduced when utilizing an NP SiO2/Si substrate with smaller pores and/or a low porosity because fewer H2O or O2 molecules could be trapped inside the smaller pores.

Ultrathin amorphous α-Co(OH)2 nanosheets grown on Ag nanowire surfaces as a highly active and durable electrocatalyst for oxygen evolution reaction.

Ultrathin α-Co(OH)2 nanosheets, prepared via simple hydrolysis at room temperature, were directly grown on Ag nanowires. The catalyst exhibited improved activity for the oxygen evolution reaction, with a reduced onset overpotential (220 mV) and superior durability because of the enhanced electron conductivity and stability of Ag nanowires in alkaline media.