Quasi-2D Halide Perovskite Memory Device Formed by Acid-Base Binary Ligand Solution Composed of Oleylamine and Oleic Acid.

Organometal halide perovskite materials are receiving significant attention for the fabrication of resistive-switching memory devices based on their high stability, low power consumption, rapid switching, and high ON/OFF ratios. In this study, we synthesized 3D FAPbBr3 and quasi-2D (RNH3)2(FA)1Pb2Br7 films using an acid-base binary ligand solution composed of oleylamine (OlAm) and oleic acid in toluene. The quasi-2D (RNH3)2(FA)1Pb2Br7 films were synthesized by controlling the protonated OlAm (RNH3+) solution concentration to replace FA+ cations with large organic RNH3+ cations from 3D FAPbBr3 perovskites. The quasi-2D (RNH3)2(FA)1Pb2Br7 devices exhibited nonvolatile write-once read-many (WORM) memory characteristics, whereas the 3D FAPbBr3 only exhibited hysteresis behavior. Analysis of the 3D FAPbBr3 device indicated operation in the trap-limited space-charge-limited current region. In contrast, quasi-2D (RNH3)2(FA)1Pb2Br7 devices provide low trap density that is completely filled by injected charge carriers and then subsequently form conductive filaments (CFs) to operate as WORM devices. Nanoscale morphology analysis and an associated current mapping study based on conductive atomic force microscopy measurements revealed that perovskite grain boundaries serve as major channels for high current, which may be correlated with the conductive low-resistive-switching behavior and formation of CFs in WORM devices.

Fabrication of pyramidal (111) MAPbBr3 film with low surface defect density using homogeneous quantum-dot seeds.

Nucleation and seeding of organometal halide perovskite (OHP) films have been extensively investigated for forming high-density, large-crystalline, and low-defect films. In this study, CH3NH3PbBr3 (MAPbBr3) films with a low defect density are synthesized via a molecular exchange mechanism using MAPbBr3 quantum dots as seeds. The synthesized films exhibit a pyramidal morphology with a (111) crystal plane. The distribution of the (111) plane is controlled by adjusting the seed concentration. The pyramidal MAPbBr3 films exhibit improved photoluminescence intensity and uniformity compared with films produced using seedless toluene. When the seeds are employed, the surface trap density is reduced by a factor of 3.5, suppressing the photocurrent hysteresis and nonsaturated response of photodetectors. Additionally, the films formed using the seeds have improved stability owing to the chain decomposition reaction induced by electron beam heating.

Unveiling the irreversible performance degradation of organo-inorganic halide perovskite films and solar cells during heating and cooling processes.

While organo-inorganic halide perovskite solar cells show great potential to meet future energy needs, their thermal instability raises serious questions about their commercialization viability. At present, the stability of perovskite solar cells has been studied under various environmental conditions including humidity and temperature. Nonetheless, understanding of the performance of CH3NH3PbI3-xClx perovskite solar cells is limited. This study reports the irreversible performance degradation of CH3NH3PbI3-xClx perovskite solar cells during the heating and cooling processes under AM 1.5 and unveils what triggers the irreversible performance degradation of solar cells. Particularly, the primary cause of the irreversible performance degradation of CH3NH3PbI3-xClx is quantitatively analyzed by monitoring in real time the development of deteriorated crystallinity, charge trapping/detrapping, trap depth, and the PbI2 phase, namely a critical signal of perovskite degradation while varying the temperature of the perovskite films and solar cells. Most surprisingly, it is revealed that the degradation of both perovskite films and solar cells was triggered at ∼70 °C. Remarkably, even after the device temperature cooled down to room temperature, the degraded performance of the solar cells persisted with increasing charge trapping and further development of the PbI2 phase. Identification of the irreversible performance degradation of perovskite solar cells provides guidance for future development of more stable perovskite solar cells.

A deconvoluted PL approach to probe the charge carrier dynamics of the grain interior and grain boundary of a perovskite film for perovskite solar cell applications.

We explore a new characterization approach capable of probing the grain interior (GI) and grain boundary (GB) of a CH3NH3PbI3-xClx perovskite thin film. In particular, we have found that the photoluminescence (PL) spectrum observed for a CH3NH3PbI3-xClx perovskite thin film is asymmetric, and can be deconvoluted using a bi-Gaussian function, representing the ordered and disordered phases of the perovskite film. In order to understand the origin of the ordered and disordered phases of the perovskite film, two-dimensional (2D) PL mapping was performed to resolve the PL spectra at the nanoscale level. Quantitative analysis of the local PL spectra revealed that the ordered phase originated from the GIs while the disordered phase mainly came from the GBs. In particular, power-dependent PL measurements of the deconvoluted PL spectra revealed that smaller grained perovskites showed defect-mediated recombination at GBs but exciton-like transitions at GIs. In contrast, perovskite films with large grains followed an excellent power law, showing exciton-like recombination at both GIs and GBs. As expected, perovskite solar cells fabricated with large grains showed an increased efficiency with higher light absorption and higher charge extraction efficiency.

Metal-Insulator-Semiconductor Diode Consisting of Two-Dimensional Nanomaterials.

We present a novel metal-insulator-semiconductor (MIS) diode consisting of graphene, hexagonal BN, and monolayer MoS2 for application in ultrathin nanoelectronics. The MIS heterojunction structure was fabricated by vertically stacking layered materials using a simple wet chemical transfer method. The stacking of each layer was confirmed by confocal scanning Raman spectroscopy and device performance was evaluated using current versus voltage (I-V) and photocurrent measurements. We clearly observed better current rectification and much higher current flow in the MIS diode than in the p-n junction and the metal-semiconductor diodes made of layered materials. The I-V characteristic curve of the MIS diode indicates that current flows mainly across interfaces as a result of carrier tunneling. Moreover, we observed considerably high photocurrent from the MIS diode under visible light illumination.

Semiconductor-Insulator-Semiconductor Diode Consisting of Monolayer MoS2, h-BN, and GaN Heterostructure.

We propose a semiconductor-insulator-semiconductor (SIS) heterojunction diode consisting of monolayer (1-L) MoS2, hexagonal boron nitride (h-BN), and epitaxial p-GaN that can be applied to high-performance nanoscale optoelectronics. The layered materials of 1-L MoS2 and h-BN, grown by chemical vapor deposition, were vertically stacked by a wet-transfer method on a p-GaN layer. The final structure was verified by confocal photoluminescence and Raman spectroscopy. Current-voltage (I-V) measurements were conducted to compare the device performance with that of a more classical p-n structure. In both structures (the p-n and SIS heterojunction diode), clear current-rectifying characteristics were observed. In particular, a current and threshold voltage were obtained for the SIS structure that was higher compared to that of the p-n structure. This indicated that tunneling is the predominant carrier transport mechanism. In addition, the photoresponse of the SIS structure induced by the illumination of visible light was observed by photocurrent measurements.

Silver Nanowire Transparent Conductive Electrodes for High-Efficiency III-Nitride Light-Emitting Diodes.

Silver nanowires (AgNWs) have been successfully demonstrated to function as next-generation transparent conductive electrodes (TCEs) in organic semiconductor devices owing to their figures of merit, including high optical transmittance, low sheet resistance, flexibility, and low-cost processing. In this article, high-quality, solution-processed AgNWs with an excellent optical transmittance of 96.5% at 450 nm and a low sheet resistance of 11.7 Ω/sq were demonstrated as TCEs in inorganic III-nitride LEDs. The transmission line model applied to the AgNW contact to p-GaN showed that near ohmic contact with a specific contact resistance of ~10(-3) Ωcm(2) was obtained. The contact resistance had a strong bias-voltage (or current-density) dependence: namely, field-enhanced ohmic contact. LEDs fabricated with AgNW electrodes exhibited a 56% reduction in series resistance, 56.5% brighter output power, a 67.5% reduction in efficiency droop, and a approximately 30% longer current spreading length compared to LEDs fabricated with reference TCEs. In addition to the cost reduction, the observed improvements in device performance suggest that the AgNWs are promising for application as next-generation TCEs, to realise brighter, larger-area, cost-competitive inorganic III-nitride light emitters.

Carrier localization in In-rich InGaN/GaN multiple quantum wells for green light-emitting diodes.

Carrier localization phenomena in indium-rich InGaN/GaN multiple quantum wells (MQWs) grown on sapphire and GaN substrates were investigated. Temperature-dependent photoluminescence (PL) spectroscopy, ultraviolet near-field scanning optical microscopy (NSOM), and confocal time-resolved PL (TRPL) spectroscopy were employed to verify the correlation between carrier localization and crystal quality. From the spatially resolved PL measurements, we observed that the distribution and shape of luminescent clusters, which were known as an outcome of the carrier localization, are strongly affected by the crystalline quality. Spectroscopic analysis of the NSOM signal shows that carrier localization of MQWs with low crystalline quality is different from that of MQWs with high crystalline quality. This interrelation between carrier localization and crystal quality is well supported by confocal TRPL results.

Suppressing spontaneous polarization of p-GaN by graphene oxide passivation: augmented light output of GaN UV-LED.

GaN-based ultraviolet (UV) LEDs are widely used in numerous applications, including white light pump sources and high-density optical data storage. However, one notorious issue is low hole injection rate in p-type transport layer due to poorly activated holes and spontaneous polarization, giving rise to insufficient light emission efficiency. Therefore, improving hole injection rate is a key step towards high performance UV-LEDs. Here, we report a new method of suppressing spontaneous polarization in p-type region to augment light output of UV-LEDs. This was achieved by simply passivating graphene oxide (GO) on top of the fully fabricated LED. The dipole layer formed by the passivated GO enhanced hole injection rate by suppressing spontaneous polarization in p-type region. The homogeneity of electroluminescence intensity in active layers was improved due to band filling effect. As a consequence, the light output was enhanced by 60% in linear current region. Our simple approach of suppressing spontaneous polarization of p-GaN using GO passivation disrupts the current state of the art technology and will be useful for high-efficiency UV-LED technology.

Hierarchically structured ZnO/petal hybrid composites with tuned optoelectronic and mechanical properties.

Impressive biophotonic functions of flora in Mother Nature are often attributed to the optical diffraction occurring on hierarchically structured surfaces. The petals, displaying vivid colors, have diverse surface structures. The shapes of those structures alter significantly depending on the part of the petal, and they adjust the intensity of the reflected color and the light absorbance. Here, we added semiconducting properties to those intriguing optical functions arising from the unique surface structures. By means of atomic layer deposition (ALD), we conformally deposited a ZnO layer on the yellow rose petal, which has hierarchical surface structures and exhibits peculiar light absorbance behaviors. The resulting ZnO/petal composites revealed unique optoelectronic characteristics by synergetic effects between the biophotonic structures and inherent semiconducting properties. From several control experiments, we identified that the biophotonic hierarchical structures give rise to strong modulation of the light absorbance. We found that ZnO/petal exhibits superior mechanical stability to the raw petal likely due to the Zn infiltration into the petal. The design inspired by floral creatures with photonic structures and manufactured in the form of composite with mechanical stability and distinctive optoelectronic properties is believed to offer a new paradigm for the preparation of bioinspired photonic devices.