Atomically Resolved Quantum-Confined Electronic Structures at Organic-Inorganic Interfaces of Two-Dimensional Ruddlesden-Popper Halide Perovskites.

This work demonstrates the direct visualization of atomically resolved quantum-confined electronic structures at organic-inorganic heterointerfaces of two-dimensional (2D) organic-inorganic hybrid Ruddlesden-Popper perovskites (RPPs); this is accomplished with scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) by using solvent engineering to prepare perpendicularly oriented 2D RPPs. Atomically resolved band mapping images across the organic-inorganic interfaces of 2D RPPs yield typical quantum-well-like type-I heterojunction band alignment with band gaps depending on the thicknesses or n values of the inorganic perovskite slabs. The presence of edge states within the band gap due to organic cation vacancies is also observed. In addition, real-space visualization of atomic-scale structural phase transition behavior and changes in local electronic band structures are obtained simultaneously. Our results provide an unequivocal observation and explanation of the quantum-confined electronic structures formed at organic-inorganic interfaces of 2D RPPs.

Low-Threshold Lasing from 2D Homologous Organic-Inorganic Hybrid Ruddlesden-Popper Perovskite Single Crystals.

Organic-inorganic hybrid two-dimensional (2D) perovskites have recently attracted great attention in optical and optoelectronic applications due to their inherent natural quantum-well structure. We report the growth of high-quality millimeter-sized single crystals belonging to homologous two-dimensional (2D) hybrid organic-inorganic Ruddelsden-Popper perovskites (RPPs) of (BA)2(MA) n-1Pb nI3 n+1 ( n = 1, 2, and 3) by a slow evaporation at a constant-temperature (SECT) solution-growth strategy. The as-grown 2D hybrid perovskite single crystals exhibit excellent crystallinity, phase purity, and spectral uniformity. Low-threshold lasing behaviors with different emission wavelengths at room temperature have been observed from the homologous 2D hybrid RPP single crystals. Our result demonstrates that solution-growth homologous organic-inorganic hybrid 2D perovskite single crystals open up a new window as a promising candidate for optical gain media.

Intrinsic Carrier Transport of Phase-Pure Homologous 2D Organolead Halide Hybrid Perovskite Single Crystals.

This work reveals the intrinsic carrier transport behavior of 2D organolead halide perovskites based on phase-pure homologous (n = 1, 2, and 3) Ruddelsden-Popper perovskite (RPP) (BA)2 (MA)n -1 Pbn I3n+1 single crystals. The 2D perovskite field effect transistors with high-quality exfoliated 2D perovskite bulk crystals are fabricated, and characteristic output and transfer curves are measured from individual single-crystal flakes with various n values under different temperatures. Unipolar n-type transport dominated the electrical properties of all these 2D RPP single crystals. The transport behavior of the 2D organolead halide hybrid perovskites exhibits a strong dependence on the n value and the mobility substantially increases as the ratio of the number of inorganic perovskite slabs per organic spacer increases. By extracting the effect of contact resistances, the corrected mobility values for n = 1, 2, and 3 are 2 × 10-3 , 8.3 × 10-2 , and 1.25 cm2 V-1 s-1 at 77 K, respectively. Furthermore, by combining temperature-dependent electrical transport and optical measurements, it is found that the origin of the carrier mobility dependence on the phase transition for 2D organolead halide perovskites is very different from that of their 3D counterparts. Our findings offer insight into fundamental carrier transport behavior of 2D organic-inorganic hybrid perovskites based on phase-pure homologous single crystals.

Color-conversion efficiency enhancement of quantum dots via selective area nano-rods light-emitting diodes.

A large enhancement of color-conversion efficiency of colloidal quantum dots in light-emitting diodes (LEDs) with novel structures of nanorods embedded in microholes has been demonstrated. Via the integration of nano-imprint and photolithography technologies, nanorods structures can be fabricated at specific locations, generating functional nanostructured LEDs for high-efficiency performance. With the novel structured LED, the color-conversion efficiency of the existing quantum dots can be enhanced by up to 32.4%. The underlying mechanisms can be attributed to the enhanced light extraction and non-radiative energy transfer, characterized by conducting a series of electroluminescence and time-resolved photoluminescence measurements. This hybrid nanostructured device therefore exhibits a great potential for the application of multi-color lighting sources.

Internal Built-In Electric Fields at Organic-Inorganic Interfaces of Two-Dimensional Ruddlesden-Popper Perovskite Single Crystals.

Two-dimensional (2D) organic-inorganic hybrid Ruddlesden-Popper perovskites (OIRPPs), which consist of naturally formed "multiple quantum well (MQW)-like" structure, have received considerable interest in optoelectronic applications, owing to their outstanding optical properties and tailorable functionalities. While the quantum-confined electrons and holes at an MQW structure are under an applied electric field, the tilt of the energy bands may cause a significant influence on their optical properties. This work demonstrates the presence of internal built-in electric fields (BIEFs) at the as-synthesized 2D OIRPP single crystals. Spontaneous Franz-Keldysh oscillations, which usually act as the fingerprint to account for the presence of BIEFs in the MQW-like structures, are observed at 2D OIRPPs by the highly sensitive differential technique of modulated thermoreflectance spectroscopy. The strength of BIEFs at 2D OIRPP single crystals reduces with increased n values due to the increased width of the quantum well. The origin of the presence of BIEFs at 2D OIRPPs is further unveiled by atomically resolved scanning tunneling microscopy on their electronic band structures at organic-inorganic interfaces. Unlike the conventional III-V MQW semiconductors with the BIEFs, which are dominated by the spatial concentration gradients at heterointerfaces, the presence of BIEFs at the 2D OIRPP single crystals is attributed to the molecular dipoles within organic spacers pointing to the organic-inorganic interfaces. The discovery of internal BIEFs at the 2D OIRPPs may provide deep insight into understanding the fundamental optical properties for the future design of large-area and low-cost perovskite optoelectronic devices.

Direct investigation of the reorientational dynamics of A-site cations in 2D organic-inorganic hybrid perovskite by solid-state NMR.

Limited methods are available for investigating the reorientational dynamics of A-site cations in two-dimensional organic-inorganic hybrid perovskites (2D OIHPs), which play a pivotal role in determining their physical properties. Here, we describe an approach to study the dynamics of A-site cations using solid-state NMR and stable isotope labelling. 2H NMR of 2D OIHPs incorporating methyl-d3-ammonium cations (d3-MA) reveals the existence of multiple modes of reorientational motions of MA. Rotational-echo double resonance (REDOR) NMR of 2D OIHPs incorporating 15N- and ¹³C-labeled methylammonium cations (13C,15N-MA) reflects the averaged dipolar coupling between the C and N nuclei undergoing different modes of motions. Our study reveals the interplay between the A-site cation dynamics and the structural rigidity of the organic spacers, so providing a molecular-level insight into the design of 2D OIHPs.

Strong Excitonic Magneto-Optic Effects in Two-Dimensional Organic-Inorganic Hybrid Perovskites.

This work demonstrates the strong excitonic magneto-optic (MO) effects of magnetic circular dichroism (MCD) and Faraday rotation (FR) in nonmagnetic two-dimensional (2D) organic-inorganic hybrid Ruddlesden-Popper perovskites (RPPs) at room temperature. Due to their strong and sharp excitonic absorption as a result of unique quantum well structures of 2D RPPs, sizeable linear excitonic MO effects of MCD and FR can be observed at room temperature under a low magnetic field (<1 T) compared with their three-dimensional counterpart. In addition, since the band gaps of 2D organic-inorganic hybrid perovskites can be manipulated either by changing the number n of inorganic octahedral slabs per unit cell or through halide engineering, linear excitonic MO effects of 2D-RPPs can be observed through the broadband spectral ranges of visible light. Our result may pave the way for the promising research field of MO and magneto-optoelectronic applications based on 2D organic-inorganic hybrid perovskites with facile solution processes.

Coherent Förster resonance energy transfer: A new paradigm for electrically driven quantum dot random lasers.

The many distinct advantages of random lasers focused efforts on developing a breakthrough from optical pumping to electrical pumping. However, progress in these is limited due to high optical loss and low gain. In this work, we demonstrate an electrically pumped quantum dot (QD) random laser with visible emission based on a previously unexplored paradigm named coherent Förster resonance energy transfer (CFRET). In the CFRET process, when a coherent photonic mode is formed because of multiple scattering of the emitted light traveling in mixed donor and acceptor QDs, the donor QDs not only serve as scattering centers but are also enable coherent energy transfer to acceptor QDs. Therefore, the laser action can be easily achieved, and the lasing threshold is greatly reduced. Our approach of electrically pumped QD-based random lasers represents a substantial step toward a full-spectrum random laser for practical applications.

Origin of Extended UV Stability of 2D Atomic Layer Titania-Based Perovskite Solar Cells Unveiled by Ultrafast Spectroscopy.

The inherent instability of UV-induced degradation in TiO2-based perovskite solar cells was largely improved by replacing the anatase-phase compact TiO2 layer with an atomic sheet transport layer (ASTL) of two-dimensional (2D) Ti1-δO2. The vital role of microscopic carrier dynamics that govern the UV stability of perovskite solar cells was comprehensively examined in this work by performing time-resolved pump-probe spectroscopy. In conventional perovskite solar cells, the presence of a UV-active oxygen vacancy in compact TiO2 prohibits current generation by heavily trapping electrons after UV degradation. Conversely, the dominant vacancy type in the 2D Ti1-δO2 ASTL is a titanium vacancy, which is a shallow acceptor and is not UV-sensitive. Therefore, it significantly suppresses carrier recombination and extends UV stability in perovskite solar cells with a 2D Ti1-δO2 ASTL. Other carrier dynamics, such as electron diffusion, electron injection, and hot hole transfer processes, were found to be less affected by UV irradiation. Quantitative pump-probe data clearly show a correlation between the carrier dynamics and UV aging of perovskite solar cells, thus providing a profound insight into the factors driving UV-induced degradation in perovskite solar cells and the origin of its performance.

Spatially and Precisely Controlled Large-Scale and Persistent Optical Gating in a TiO x-MoS2 Heterostructure.

Optical gating derived from persistent photodoping is a promising technique that can control the transport behavior of two-dimensional (2D) materials through light modulation. The advantage of photoinduced doping is that the doping can be controlled precisely and spatially by tuning the light intensity and position. As most photoinduced doping methods suffer from a low doping level, persistent, strong photodoping was conducted in this study in TiO x-MoS2 heterostructures under ultraviolet (UV) illumination, which precisely controlled the doping to a high level (1.5 × 1013 cm-2) with a trap-mediated mechanism. This mechanism was confirmed by controlling the doping level with various UV pretreatment doses. After photodoping, devices displayed superior mobility, which is a characteristic of the modulation doping used in high-electron-mobility transistors. The modulation doping sites in the inner TiO x layer were far from the channel surface (MoS2); thus, the channel was able to preserve its high-mobility property even after doping. This dose-dependent, strong, and persistent photodoping phenomenon can render the TiO x-MoS2 heterostructure suitable for use in UV detectors and in nonvolatile light-driven memory products. Moreover, by using spatially controlled light scans, selective photodoping at the contact edges can dramatically reduce the contact resistance without destroying the on-off ratio of the device by forming an n+-n-n+ channel. Because TiO x-MoS2 heterostructures are versatile, they provide a compelling platform for high-performance 2D optoelectronic devices.

Ultra-high performance flexible piezopotential gated In1-xSnxSe phototransistor.

Flexible optoelectronic devices facilitated by the piezotronic effect have important applications in the near future in many different fields ranging from solid-state lighting to biomedicine. Two-dimensional materials possessing extraordinary mechanical strength and semiconducting properties are essential for realizing nanopiezotronics and piezo-phototronics. Here, we report the first demonstration of piezo-phototronic properties in In1-xSnxSe flexible devices by applying systematic mechanical strain under photoexcitation. Interestingly, we discover that the dark current and photocurrent are increased by five times under a bending strain of 2.7% with a maximum photoresponsivity of 1037 AW-1. In addition, the device can act as a strain sensor with a strain sensitivity up to 206. Based on these values, the device outperforms the same class of devices in two-dimensional materials. The underlying mechanism responsible for the discovered behavior can be interpreted in terms of piezoelectric potential gating, allowing the device to perform like a phototransistor. The strain-induced gate voltage assists in the efficient separation of photogenerated charge carriers and enhances the mobility of In1-xSnxSe, resulting in good performance on a freeform surface. Thus, our multifunctional device is useful for the development of a variety of advanced applications and will help meet the demand of emerging technologies.

Dirac point induced ultralow-threshold laser and giant optoelectronic quantum oscillations in graphene-based heterojunctions.

The occurrence of zero effective mass of electrons at the vicinity of the Dirac point is expected to create new paradigms for scientific research and technological applications, but the related discoveries are rather limited. Here, we demonstrate that a simple architecture composed of graphene quantum dots sandwiched by graphene layers can exhibit several intriguing features, including the Dirac point induced ultralow-threshold laser, giant peak-to-valley ratio (PVR) with ultra-narrow spectra of negative differential resistance and quantum oscillations of current as well as light emission intensity. In particular, the threshold of only 12.4 nA cm-2 is the lowest value ever reported on electrically driven lasers, and the PVR value of more than 100 also sets the highest record compared with all available reports on graphene-based devices. We show that all these intriguing phenomena can be interpreted based on the unique band structures of graphene quantum dots and graphene as well as resonant quantum tunneling.In graphene, electrons possess zero effective mass in proximity to the Dirac point, an unusual feature that could trigger the development of novel photonic devices. Here, the authors combine graphene quantum dots with two graphene layers and observe laser action with ultralow threshold.

Electrically Driven White Light Emission from Intrinsic Metal-Organic Framework.

Light-emitting diodes (LEDs) have drawn tremendous potential as a replacement of traditional lighting due to its low-power consumption and longer lifetime. Nowadays, the practical white LEDs (WLED) are contingent on the photon down-conversion of phosphors containing rare-earth elements, which limits its utility, energy, and cost efficiency. In order to resolve the energy crisis and to address the environmental concerns, designing a direct WLED is highly desirable and remains a challenging issue. To circumvent the existing difficulties, in this report, we have designed and demonstrated a direct WLED consisting of a strontium-based metal-organic framework (MOF), {[Sr(ntca)(H2O)2]·H2O}n (1), graphene, and inorganic semiconductors, which can generate a bright white light emission. In addition to the suitable design of a MOF structure, the demonstration of electrically driven white light emission based on a MOF is made possible by the combination of several factors including the unique properties of graphene and the appropriate band alignment between the MOF and semiconductor layer. Because electroluminescence using a MOF as an active material is very rare and intriguing and a direct WLED is also not commonly seen, our work here therefore represents a major discovery which should be very useful and timely for the development of solid-state lighting.

Bridging the "green gap" of LEDs: giant light output enhancement and directional control of LEDs via embedded nano-void photonic crystals.

Green LEDs do not show the same level of performance as their blue and red cousins, greatly hindering the solid-state lighting development, which is the so-called "green gap". In this work, nano-void photonic crystals (NVPCs) were fabricated to embed within the GaN/InGaN green LEDs by using epitaxial lateral overgrowth (ELO) and nano-sphere lithography techniques. The NVPCs act as an efficient scattering back-reflector to outcouple the guided and downward photons, which not only boost the light extraction efficiency of LEDs with an enhancement of 78% but also collimate the view angle of LEDs from 131.5° to 114.0°. This could be because of the highly scattering nature of NVPCs which reduce the interference giving rise to Fabry-Perot resonance. Moreover, due to the threading dislocation suppression and strain relief by the NVPCs, the internal quantum efficiency was increased by 25% and droop behavior was reduced from 37.4% to 25.9%. The enhancement of light output power can be achieved as high as 151% at a driving current of 350 mA. Giant light output enhancement and directional control via NVPCs point the way towards a promising avenue of solid-state lighting.