Two-dimensional halide perovskite lateral epitaxial heterostructures.

Epitaxial heterostructures based on oxide perovskites and III-V, II-VI and transition metal dichalcogenide semiconductors form the foundation of modern electronics and optoelectronics1-7. Halide perovskites-an emerging family of tunable semiconductors with desirable properties-are attractive for applications such as solution-processed solar cells, light-emitting diodes, detectors and lasers8-15. Their inherently soft crystal lattice allows greater tolerance to lattice mismatch, making them promising for heterostructure formation and semiconductor integration16,17. Atomically sharp epitaxial interfaces are necessary to improve performance and for device miniaturization. However, epitaxial growth of atomically sharp heterostructures of halide perovskites has not yet been achieved, owing to their high intrinsic ion mobility, which leads to interdiffusion and large junction widths18-21, and owing to their poor chemical stability, which leads to decomposition of prior layers during the fabrication of subsequent layers. Therefore, understanding the origins of this instability and identifying effective approaches to suppress ion diffusion are of great importance22-26. Here we report an effective strategy to substantially inhibit in-plane ion diffusion in two-dimensional halide perovskites by incorporating rigid π-conjugated organic ligands. We demonstrate highly stable and tunable lateral epitaxial heterostructures, multiheterostructures and superlattices. Near-atomically sharp interfaces and epitaxial growth are revealed by low-dose aberration-corrected high-resolution transmission electron microscopy. Molecular dynamics simulations confirm the reduced heterostructure disorder and larger vacancy formation energies of the two-dimensional perovskites in the presence of conjugated ligands. These findings provide insights into the immobilization and stabilization of halide perovskite semiconductors and demonstrate a materials platform for complex and molecularly thin superlattices, devices and integrated circuits.

Organic Ligand Engineering for Tailoring Electron-Phonon Coupling in 2D Hybrid Perovskites.

In the emerging two-dimensional organic-inorganic hybrid perovskites, the electronic structures and carrier behaviors are strongly impacted by intrinsic electron-phonon interactions, which have received inadequate attention. In this study, we report an intriguing phenomenon of negative carrier diffusion induced by electron-phonon coupling in (2T)2PbI4. Theoretical calculations reveal that the electron-phonon coupling drives the band alignment in (2T)2PbI4 to alternate between type I and type II heterostructures. As a consequence, photoexcited holes undergo transitions between the organic ligands and inorganic layers, resulting in abnormal carrier transport behavior compared to other two-dimensional hybrid perovskites. These findings provide valuable insights into the role of electron-phonon coupling in shaping the band alignments and carrier behaviors in two-dimensional hybrid perovskites. They also open up exciting avenues for designing and fabricating functional semiconductor heterostructures with tailored properties.

Designing artificial two-dimensional landscapes via atomic-layer substitution.

Technology advancements in history have often been propelled by material innovations. In recent years, two-dimensional (2D) materials have attracted substantial interest as an ideal platform to construct atomic-level material architectures. In this work, we design a reaction pathway steered in a very different energy landscape, in contrast to typical thermal chemical vapor deposition method in high temperature, to enable room-temperature atomic-layer substitution (RT-ALS). First-principle calculations elucidate how the RT-ALS process is overall exothermic in energy and only has a small reaction barrier, facilitating the reaction to occur at room temperature. As a result, a variety of Janus monolayer transition metal dichalcogenides with vertical dipole could be universally realized. In particular, the RT-ALS strategy can be combined with lithography and flip-transfer to enable programmable in-plane multiheterostructures with different out-of-plane crystal symmetry and electric polarization. Various characterizations have confirmed the fidelity of the precise single atomic layer conversion. Our approach for designing an artificial 2D landscape at selective locations of a single layer of atoms can lead to unique electronic, photonic, and mechanical properties previously not found in nature. This opens a new paradigm for future material design, enabling structures and properties for unexplored territories.

Synthesis of Ultralong Carbon Nanotubes with Ultrahigh Yields.

Ultralong carbon nanotubes (CNTs) are in huge demand in many cutting-edge fields due to their macroscale lengths, perfect structures, and extraordinary properties, while their practical application is limited by the difficulties in their mass production. Herein, we report the synthesis of ultralong CNTs with a dramatically increased yield by a simple but efficient substrate interception and direction strategy (SIDS), which couples the advantages of floating-catalyst chemical vapor deposition with the flying-kite-like growth mechanism of ultralong CNTs. The SIDS-assisted approach prominently improves the catalyst utilization and significantly increases the yield. The areal density of the ultralong CNT arrays with length of over 1 cm reached a record-breaking value of ∼6700 CNTs mm-1, which is 2-3 orders of magnitude higher than the previously reported values obtained by traditional methods. The SIDS provides a solution for synthesizing high-quality ultralong CNTs with high yields, laying the foundation for their mass production.

Additive manufacturing of patterned 2D semiconductor through recyclable masked growth.

The 2D van der Waals crystals have shown great promise as potential future electronic materials due to their atomically thin and smooth nature, highly tailorable electronic structure, and mass production compatibility through chemical synthesis. Electronic devices, such as field effect transistors (FETs), from these materials require patterning and fabrication into desired structures. Specifically, the scale up and future development of "2D"-based electronics will inevitably require large numbers of fabrication steps in the patterning of 2D semiconductors, such as transition metal dichalcogenides (TMDs). This is currently carried out via multiple steps of lithography, etching, and transfer. As 2D devices become more complex (e.g., numerous 2D materials, more layers, specific shapes, etc.), the patterning steps can become economically costly and time consuming. Here, we developed a method to directly synthesize a 2D semiconductor, monolayer molybdenum disulfide (MoS2), in arbitrary patterns on insulating SiO2/Si via seed-promoted chemical vapor deposition (CVD) and substrate engineering. This method shows the potential of using the prepatterned substrates as a master template for the repeated growth of monolayer MoS2 patterns. Our technique currently produces arbitrary monolayer MoS2 patterns at a spatial resolution of 2 µm with excellent homogeneity and transistor performance (room temperature electron mobility of 30 cm2 V-1 s-1 and on-off current ratio of 107). Extending this patterning method to other 2D materials can provide a facile method for the repeatable direct synthesis of 2D materials for future electronics and optoelectronics.

Large-Scale Plasmonic Hybrid Framework with Built-In Nanohole Array as Multifunctional Optical Sensing Platforms.

Light coupling with patterned subwavelength hole arrays induces enhanced transmission supported by the strong surface plasmon mode. In this work, a nanostructured plasmonic framework with vertically built-in nanohole arrays at deep-subwavelength scale (6 nm) is demonstrated using a two-step fabrication method. The nanohole arrays are formed first by the growth of a high-quality two-phase (i.e., Au-TiN) vertically aligned nanocomposite template, followed by selective wet-etching of the metal (Au). Such a plasmonic nanohole film owns high epitaxial quality with large surface coverage and the structure can be tailored as either fully etched or half-way etched nanoholes via careful control of the etching process. The chemically inert and plasmonic TiN plays a role in maintaining sharp hole boundary and preventing lattice distortion. Optical properties such as enhanced transmittance and anisotropic dielectric function in the visible regime are demonstrated. Numerical simulation suggests an extended surface plasmon mode and strong field enhancement at the hole edges. Two demonstrations, including the enhanced and modulated photoluminescence by surface coupling with 2D perovskite nanoplates and the refractive index sensing by infiltrating immersion liquids, suggest the great potential of such plasmonic nanohole array for reusable surface plasmon-enhanced sensing applications.

Long-lived charge separation in two-dimensional ligand-perovskite heterostructures.

Rational design of heterojunctions using nanostructured materials is a useful strategy for achieving efficient interfacial charge separation in photovoltaics. Heterojunctions can be constructed between the organic ligands and the inorganic layers in two-dimensional perovskites, taking advantage of their highly programmable structures. Here, we investigate charge transfer and recombination at the interface between the thiophene-based semiconducting ligands and the lead halide inorganic sublattices using time-resolved photoluminescence and transient reflection spectroscopy in single two-dimensional perovskite crystals. These measurements demonstrate the charge transfer time around 10 ps and long-lived charge-separated state over the nanosecond time scale in two-dimensional ligand-perovskite heterostructures. The efficient charge transfer processes coupled with slow charge recombination suggest the potential for improving exciton dissociation and charge transport in two-dimensional perovskite solar cells.

Highly Stable Lead-Free Perovskite Field-Effect Transistors Incorporating Linear π-Conjugated Organic Ligands.

Sn(II)-based halide perovskite semiconductor materials are promising for a variety of electronics and optoelectronics applications but suffer from poor intrinsic materials stability. Here, we report the synthesis and characterization of a stable Sn (II)-based two-dimensional perovskite featuring a π-conjugated oligothiophene ligand, namely (4Tm)2SnI4, where 4Tm is 2-(3″',4'-dimethyl-[2,2':5',2″:5″,2″'-quaterthiophen]-5-yl)ethan-1-ammonium. The conjugated ligands facilitate formation of micrometer-size large grains, improve charge injections, and stabilize the inorganic perovskite layers. Thin film field-effect transistors based on (4Tm)2SnI4 exhibit enhanced hole mobility up to 2.32 cm2 V-1 s-1 and dramatically improved stability over the previous benchmark material (PEA)2SnI4. Stabilization mechanisms were investigated via single-crystal structure analysis as well as density functional theory calculations. It was found that the large conjugated organic layers not only serve as thick and dense barriers for moisture and oxygen but also increase the crystal formation energy via strong intermolecular interactions. This work demonstrates the great potential of molecular engineering for organic-inorganic hybrid perovskite materials toward applications in high-performance electronics and optoelectronics.

Two-dimensional halide perovskite nanomaterials and heterostructures.

Over the last several years, there has been tremendous progress in the development of nanoscale halide perovskite materials and devices that possess a wide range of band gaps and tunable optical and electronic properties. Particularly, the emerging two-dimensional (2D) forms of halide perovskites are attracting more interest due to the long charge carrier lifetime, high photoluminescence quantum efficiency, and great defect tolerance. Interfacing 2D halide perovskites with other 2D materials including graphene and transition metal dichalcogenides (TMDs) significantly broadens the application range of the 2D materials and enhances the performance of the functional devices. The synthesis and characterization of 2D halide perovskite nanostructures, the interface of the 2D halide perovskites with other 2D materials, and the integration of them into high-performance optoelectronic devices including solar cells, photodetectors, transistors, and memory devices are currently under investigation. In this article, we review the progress of the above-mentioned topics in a timely manner and discuss the current challenges and future promising directions in this field.

Highly Crumpled All-Carbon Transistors for Brain Activity Recording.

Neural probes based on graphene field-effect transistors have been demonstrated. Yet, the minimum detectable signal of graphene transistor-based probes is inversely proportional to the square root of the active graphene area. This fundamentally limits the scaling of graphene transistor-based neural probes for improved spatial resolution in brain activity recording. Here, we address this challenge using highly crumpled all-carbon transistors formed by compressing down to 16% of its initial area. All-carbon transistors, chemically synthesized by seamless integration of graphene channels and hybrid graphene/carbon nanotube electrodes, maintained structural integrity and stable electronic properties under large mechanical deformation, whereas stress-induced cracking and junction failure occurred in conventional graphene/metal transistors. Flexible, highly crumpled all-carbon transistors were further verified for in vivo recording of brain activity in rats. These results highlight the importance of advanced material and device design concepts to make improvements in neuroelectronics.

Hierarchically designed three-dimensional macro/mesoporous carbon frameworks for advanced electrochemical capacitance storage.

Mesoporous carbon (m-C) has potential applications as porous electrodes for electrochemical energy storage, but its applications have been severely limited by the inherent fragility and low electrical conductivity. A rational strategy is presented to construct m-C into hierarchical porous structures with high flexibility by using a carbon nanotube (CNT) sponge as a three-dimensional template, and grafting Pt nanoparticles at the m-C surface. This method involves several controllable steps including solution deposition of a mesoporous silica (m-SiO2 ) layer onto CNTs, chemical vapor deposition of acetylene, and etching of m-SiO2 , resulting in a CNT@m-C core-shell or a CNT@m-C@Pt core-shell hybrid structure after Pt adsorption. The underlying CNT network provides a robust yet flexible support and a high electrical conductivity, whereas the m-C provides large surface area, and the Pt nanoparticles improves interfacial electron and ion diffusion. Consequently, specific capacitances of 203 and 311 F g(-1) have been achieved in these CNT@m-C and CNT@m-C@Pt sponges as supercapacitor electrodes, respectively, which can retain 96 % of original capacitance under large degree compression.

Colloidal antireflection coating improves graphene-silicon solar cells.

Carbon nanotube-Si and graphene-Si solar cells have attracted much interest recently owing to their potential in simplifying manufacturing process and lowering cost compared to Si cells. Until now, the power conversion efficiency of graphene-Si cells remains under 10% and well below that of the nanotube-Si counterpart. Here, we involved a colloidal antireflection coating onto a monolayer graphene-Si solar cell and enhanced the cell efficiency to 14.5% under standard illumination (air mass 1.5, 100 mW/cm(2)) with a stable antireflection effect over long time. The antireflection treatment was realized by a simple spin-coating process, which significantly increased the short-circuit current density and the incident photon-to-electron conversion efficiency to about 90% across the visible range. Our results demonstrate a great promise in developing high-efficiency graphene-Si solar cells in parallel to the more extensively studied carbon nanotube-Si structures.

Patterned growth of two-dimensional atomic layer semiconductors.

Transition metal dichalcogenides (TMDCs), which are representative of two-dimensional (2D) semiconductors, have attracted tremendous attention over the last two decades. TMDCs are regarded as potential candidates in modern nano- and optoelectronic applications due to their unique crystal structures and outstanding electronic and optoelectronic properties. For practical use, 2D semiconductors need to be fabricated with diverse morphologies for integration into electronic devices and to perform different functionalities. Controlled patterning synthesis with programmable geometries is therefore highly desired. We review state-of-the-art strategies for the patterned growth of atomic layer TMDCs and their heterostructures, including additive manufacturing and subtractive manufacturing for patterning single TMDC materials and the introduction of other low-dimensional nanomaterials as growth templates or hetero-atoms for element conversion in patterning TMDC heterostructures. The optoelectronic and electronic applications of the as-grown monolayer TMDC patterns are introduced. Future challenges and the prospects for the patterned growth of 2D semiconductors are discussed based on present achievements.

Robust and Efficient Out-of-Plane Exciton Transport in Two-Dimensional Perovskites via Ultrafast Förster Energy Transfer.

Two-dimensional (2D) perovskites, comprising inorganic semiconductor layers separated by organic spacers, hold promise for light harvesting and optoelectronic applications. Exciton transport in these materials is pivotal for device performance, often necessitating deliberate alignment of the inorganic layers with respect to the contacting layers to facilitate exciton transport. While much attention has focused on in-plane exciton transport, little has been paid to out-of-plane interlayer transport, which presumably is sluggish and unfavorable. Herein, by time-resolved photoluminescence, we unveil surprisingly efficient out-of-plane exciton transport in 2D perovskites, with diffusion coefficients (up to ∼0.1 cm2 s-1) and lengths (∼100 nm) merely a few times smaller or comparable to their in-plane counterparts. We unambiguously confirm that the out-of-plane exciton diffusion coefficient corresponds to a subpicosecond interlayer exciton transfer, governed by the Förster resonance energy transfer (FRET) mechanism. Intriguingly, in contrast to temperature-sensitive intralayer band-like transport, the interlayer exciton transport exhibits negligible temperature dependence, implying a lowest-lying bright exciton state in 2D perovskites, irrespective of spacer molecules. The robust and ultrafast interlayer exciton transport alleviates the constraints on crystal orientation that are crucial for the design of 2D perovskite-based light harvesting and optoelectronic devices.

Adaptive nanotube networks enabling omnidirectionally deformable electro-driven liquid crystal elastomers towards artificial muscles.

Artificial muscles that can convert electrical energy into mechanical energy promise broad scientific and technological applications. However, existing electro-driven artificial muscles have been plagued with problems that hinder their practical applications: large electro-mechanical attenuation during deformation, high-driving voltages, small actuation strain, and low power density. Here, we design and create novel electro-thermal-driven artificial muscles rationally composited by hierarchically structured carbon nanotube (HS-CNT) networks and liquid crystal elastomers (LCEs), which possess adaptive sandwiched nanotube networks with angulated-scissor-like microstructures, thus effectively addressing above problems. These HS-CNT/LCE artificial muscles demonstrate not only large strain (>40%), but also remarkable conductive robustness (R/R0 < 1.03 under actuation), excellent Joule heating efficiency (≈ 233 °C at 4 V), and high load-bearing capacity (R/R0 < 1.15 at 4000 times its weight loaded). In addition, our artificial muscles exhibit real-muscle-like morphing intelligence that enables preventing mechanical damage in response to excessively heavyweight loading. These high-performance artificial muscles uniquely combining omnidirectional stretchability, robust electrothermal actuation, low driving voltage, and powerful mechanical output would exert significant technological impacts on engineering applications such as soft robotics and wearable flexible electronics.

Strain regulates the photovoltaic performance of thick-film perovskites.

Perovskite photovoltaics, typically based on a solution-processed perovskite layer with a film thickness of a few hundred nanometres, have emerged as a leading thin-film photovoltaic technology. Nevertheless, many critical issues pose challenges to its commercialization progress, including industrial compatibility, stability, scalability and reliability. A thicker perovskite film on a scale of micrometres could mitigate these issues. However, the efficiencies of thick-film perovskite cells lag behind those with nanometre film thickness. With the mechanism remaining elusive, the community has long been under the impression that the limiting factor lies in the short carrier lifetime as a result of defects. Here, by constructing a perovskite system with extraordinarily long carrier lifetime, we rule out the restrictions of carrier lifetime on the device performance. Through this, we unveil the critical role of the ignored lattice strain in thick films. Our results provide insights into the factors limiting the performance of thick-film perovskite devices.

Phase-pure 2D tin halide perovskite thin flakes for stable lasing.

Ruddlesden-Popper tin halide perovskites are a class of two-dimensional (2D) semiconductors with exceptional optoelectronic properties, high carrier mobility, and low toxicity. However, the synthesis of phase-pure 2D tin perovskites is still challenging, and the fundamental understanding of their optoelectronic properties is deficient compared to their lead counterparts. Here, we report the synthesis of a series of 2D tin perovskite bulk crystals with high phase purity via a mixed-solvent strategy. By engineering the quantum-well thickness (related to n value) and organic ligands, the optoelectronic properties, including photoluminescence emission, exciton-phonon coupling strength, and exciton binding energy, exhibit a wide tunability. In addition, these 2D tin perovskites exhibited excellent lasing performance. Both high-n value tin perovskite (n > 1) and n = 1 tin perovskite thin flakes were successfully optically pumped to lase. Furthermore, the lasing from 2D tin perovskites could be maintained up to room temperature. Our findings highlight the tremendous potential of 2D tin perovskites as promising candidates for high-performance lasers.

Thickness control of organic semiconductor-incorporated perovskites.

Two-dimensional organic semiconductor-incorporated perovskites are a promising family of hybrid materials for optoelectronic applications, owing in part to their inherent quantum well architecture. Tuning their structures and properties for specific properties, however, has remained challenging. Here we report a general method to tune the dimensionality of phase-pure organic semiconductor-incorporated perovskite single crystals during their synthesis, by judicious choice of solvent. The length of the conjugated semiconducting organic cations and the dimensionality (n value) of the inorganic layers can be manipulated at the same time. The energy band offsets and exciton dynamics at the organic-inorganic interfaces can therefore be precisely controlled. Furthermore, we show that longer and more planar π-conjugated organic cations induce a more rigid inorganic crystal lattice, which leads to suppressed exciton-phonon interactions and better optoelectronic properties as compared to conventional two-dimensional perovskites. As a demonstration, optically driven lasing behaviour with substantially lower lasing thresholds was realized.

Giant room-temperature nonlinearities in a monolayer Janus topological semiconductor.

Nonlinear optical materials possess wide applications, ranging from terahertz and mid-infrared detection to energy harvesting. Recently, the correlations between nonlinear optical responses and certain topological properties, such as the Berry curvature and the quantum metric tensor, have attracted considerable interest. Here, we report giant room-temperature nonlinearities in non-centrosymmetric two-dimensional topological materials-the Janus transition metal dichalcogenides in the 1 T' phase, synthesized by an advanced atomic-layer substitution method. High harmonic generation, terahertz emission spectroscopy, and second harmonic generation measurements consistently show orders-of-the-magnitude enhancement in terahertz-frequency nonlinearities in 1 T' MoSSe (e.g., > 50 times higher than 2H MoS2 for 18th order harmonic generation; > 20 times higher than 2H MoS2 for terahertz emission). We link this giant nonlinear optical response to topological band mixing and strong inversion symmetry breaking due to the Janus structure. Our work defines general protocols for designing materials with large nonlinearities and heralds the applications of topological materials in optoelectronics down to the monolayer limit.

Wire-supported CdSe nanowire array photoelectrochemical solar cells.

Previous fiber-shaped solar cells are based on polymeric materials or dye-sensitized wide band-gap oxides. Here, we show that efficient fiber solar cells can be made from semiconducting nanostructures (e.g. CdSe) with smaller band-gap as the light absorption material. We directly grow a vertical array of CdSe nanowires uniformly around a core metal wire and make the device by covering the top of nanowires with a carbon nanotube (CNT) film as the porous transparent electrode. The CdSe-CNT fiber solar cells show power conversion efficiencies of 1-2% under AM 1.5 illumination after the nanowires are infiltrated with redox electrolyte. We do not use a secondary metal wire (e.g. Pt) as in conventional fiber-shaped devices, instead, the end part of the CNT film is condensed into a conductive yarn to serve as the secondary electrode. In addition, our CdSe nanowire-based photoelectrochemical fiber solar cells maintain good flexibility and stable performance upon rotation and bending to large angles.