Single-crystalline Nanosheets Research Articles

Vapor Phase Growth of Air-Stable Hybrid Perovskite FAPbBr3 Single-Crystalline Nanosheets.

Organic-inorganic hybrid perovskites have attracted tremendous attention owing to their fascinating optoelectronic properties. However, their poor air stability seriously hinders practical applications, which becomes more serious with thickness down to the nanoscale. Here we report a one-step vapor phase growth of HC(NH2)2PbBr3 (FAPbBr3) single-crystalline nanosheets of tunable size up to 50 μm and thickness down to 20 nm. The FAPbBr3 nanosheets demonstrate high stability for over months of exposure to air with no degradation in surface roughness and photoluminescence efficiency. Besides, the FAPbBr3 photodetectors exhibit superior overall performance as compared to previous devices based on nonlayered perovskite nanosheets, such as an ultralow dark current of 24 pA, an ultrahigh responsivity of 1033 A/W, an external quantum efficiency over 3000%, a rapid response time around 25 ms, and a high on/off ratio of 104. This work provides a strategy to tackle the challenges of hybrid perovskites toward integrated optoelectronics with requirements of nanoscale thickness, high stability, and excellent performance.

Controlled Growth of Submillimeter-Scale Cr5Te8 Nanosheets and the Domain Wall Nucleation Governed Magnetization Reversal Process.

Two-dimensional (2D) ferromagnets have attracted widespread attention for promising applications in compact spintronic devices. However, the controlled synthesis of high-quality, large-sized, and ultrathin 2D magnets via facile, economical method remains challenging. Herein, we develop a hydrogen-tailored chemical vapor deposition approach to fabricating 2D Cr5Te8 ferromagnetic nanosheets. Interestingly, the time period of introducing hydrogen was found to be crucial for controlling the lateral size, and a Cr5Te8 single-crystalline nanosheet of lateral size up to ∼360 μm with single-unit-cell thickness has been obtained. These samples exhibit a leading role of domain wall nucleation in governing the magnetization reversal process, providing important references for optimizing the performances of associated devices. The nanosheets also show notable magnetotransport response, including nonmonotonous magnetic-field-dependent magnetoresistance and sizable anomalous Hall resistivity, demonstrating Cr5Te8 as a promising material for constructing high-performance magnetoelectronic devices. This study presents a breakthrough of large-sized CVD-grown 2D magnetic materials, which is indispensable for constructing 2D spintronic devices.

Ultrahigh responsivity of non-van der Waals Bi2O2Se photodetector

Bismuth oxyselenide has recently gained tremendous attention as a promising 2D material for next-generation electronic and optoelectronic devices due to its ultrahigh mobility, moderate bandgap, exceptional environmental stability, and presence of high-dielectric constant native oxide. In this study, we have synthesized single-crystalline nanosheets of Bismuth oxyselenide with thicknesses measuring below ten nanometers on Fluorophlogopite mica using an atmospheric pressure chemical vapor deposition system. We transferred as-grown samples to different substrates using a non-corrosive nail polish-assisted dry transfer method. Back-gated Bi2O2Se field effect transistors showed decent field effect mobility of 100 cm2 V−1s−1. The optoelectronic property study revealed an ultrahigh responsivity of 1.16 × 106 A W−1 and a specific detectivity of 2.55 × 1013 Jones. The samples also exhibited broadband photoresponse and gate-tunable photoresponse time. These results suggest that Bi2O2Se is an excellent candidate for future high-performance optoelectronic device applications.

Spontaneous Dewetting of Au-Thin Layers on Oxide- and Fluorine-Terminated Single Crystalline Anatase and Efficient Use in Photocatalytic H2 Production.

In the present work, the spontaneous dewetting of thin Au layers on single crystalline anatase nanosheets into narrow-disperse Au nanoparticles is investigated. Patterns of the Au particles can be formed on the main facets of anatase that provide a high co-catalytic activity for photocatalytic generation of H2 . Dewetting is distinctly influenced by the respective facets (001) and (101), the deposit thickness, and secondary thermal dewetting, but most strongly by the surface termination of the nanosheets. Fluoride termination not only leads to an enhanced Au-phobic behavior but strongly affects the co-catalytic activity for photocatalytic generation of H2 . While fluoride termination with or without Au decoration is detrimental for hole transfer, the interplay of the Au co-catalyst and surface fluoride yields highly beneficial effect for electron transfer. This results in a three-times higher photocatalytic H2 production for the F-terminated surface. The findings suggest that dewetting of Au on surface fluorinated TiO2 is an effective way to modulate surface dewetting and achieve a strongly enhanced photocatalytic activity.

Ambient-condition strategy for rapid mass production of crystalline gallium oxide nanoarchitectures toward device application

Currently, the synthesis of nanostructures still encounters two grand challenges: one is the often-required high temperatures and/or high pressures, and the other is the scalable fabrication. Here, to break through such bottlenecks, we demonstrate an ambient-condition strategy for rapid mass production of fourth-generation semiconductor Ga2O3 nanoarchitectures assembled by single-crystalline nanosheets in a controlled manner based on sonochemistry. Their growth is fundamentally determined by the introduced ethanediamine in rationally designed source materials, which could not only protect the metal Ga against reacting with H2O into GaOOH, but facilitate the reaction of Ga with OH· radicals for target crystalline Ga2O3 nanostructures. As a proof of concept for applications, the as-fabricated Ga2O3 nanoarchitectures exhibit superb performances for electromagnetic wave absorption with a reflection loss value of 52.2 dB at 8.1 GHz, and ammonia sensing with high sensitivity and selectivity at room temperature, representing their bright future to be commercially applied in modern devices.

Van der Waals Epitaxy Growth of 2D Single-Element Room-Temperature Ferromagnet.

2D single-element materials, which are pure and intrinsically homogeneous on the nanometer scale, can cut the time-consuming material-optimization process and circumvent the impure phase, bringing about opportunities to explore new physics and applications. Herein, for the first time, the synthesis of ultrathin cobalt single-crystalline nanosheets with a sub-millimeter scale via van der Waals epitaxy is demonstrated. The thickness can be as low as ≈6nm. Theoretical calculations reveal their intrinsic ferromagnetic nature and epitaxial mechanism: that is, the synergistic effect between van der Waals interactions and surface energy minimization dominates the growth process. Cobalt nanosheets exhibit ultrahighblocking temperatures above 710 K and in-plane magnetic anisotropy. Electrical transport measurements further reveal that cobalt nanosheets have significant magnetoresistance (MR) effect, and can realize a unique coexistence of positive MR and negative MR under different magnetic field configurations, which can be attributed to the competition and cooperation effect among ferromagnetic interaction, orbital scattering, and electronic correlation. These results provide a valuable case for synthesizing 2D elementary metal crystals with pure phase and room-temperature ferromagnetism and pave the way for investigating new physics and related applications in spintronics.

Chelated Ion-Exchange Strategy toward BiOCl Mesoporous Single-Crystalline Nanosheets for Boosting Photocatalytic Selective Aromatic Alcohols Oxidation.

The photoresponse and photocatalytic efficiency of bismuth oxychloride (BiOCl) are greatly limited by rapid recombination of photogenerated carriers. The construction of porous single-crystal BiOCl photocatalyst can effectively alleviate this issue and provide accessible active sites. Herein, a facile chelated ion-exchange strategy is developed to synthesize BiOCl mesoporous single-crystalline nanosheets (BiOCl MSCN) using acetic acid and ammonia solution respectively as chelating agent and ionization promoter. The strong chelation between acetate ions and Bi3+ ions introduces acetate ions into the precipitated product to exchange with Cl- ions, resulting in large lattice mismatch, strain release, and formation of void-like mesopores. The prepared BiOCl MSCN photocatalyst exhibits excellent catalytic performance with 99% conversion and 98% selectivity for oxidation of benzyl alcohol to benzaldehyde and superior general adaptability for various aromatic alcohols. The theoretical calculations and characterizations confirm that the superior performance is mainly attributed to the abundant oxygen vacancies, plenty of accessible adsorption/active sites and fast charge transport path without grain boundaries.

Self-Doping Based Facet Junctions and Oxygen Vacancies in Ferroelectric Bi3TixNb2-xO9 Nanosheets for Boosting Photocatalytic Degradation and Antibacterial Activity.

Constructing facet junction in semiconductor photocatalysts has been demonstrated as an effective method to promote charge-carrier separation and suppress carrier recombination. Herein, we proposed a novel but facile self-doping strategy to regulate the crystal facet exposure ratio in ferroelectric Bi3TixNb2-xO9 single-crystalline nanosheets, thereby optimizing its facet junction effect. Through tuning the atomic ratio of Ti and Nb, the exposure ratio of {001} and {110} crystal planes in Bi3TixNb2-xO9 nanosheets can be delicately modulated, and more {110} facets were exposed with the increase of the Ti/Nb atomic ratio as evidenced by the X-ray diffraction and scanning electron microscopy results. A facet junction between {110} and {001} crystal planes was verified based on the density functional theory calculation and photodeposition experiment results. Photogenerated electrons tend to accumulate in {110}, while holes gathered in {001} crystal planes. Owing to the optimal facet junction effect, the sample of Ti1.05 shows the most efficient charge-carrier separation and transportation compared to Ti0.95 and Ti1.00 as supported by the photoluminescence, surface photovoltage, photoelectrochemistry, and electron paramagnetic resonance (EPR) results. In addition, the oxygen vacancy arising from the inequivalent substitution of Nb5+ by Ti4+ as proved by X-ray photoelectron spectroscopy and EPR results and the enhanced ferroelectricity supported by P-E loops can also assist charge-carrier separation and migration. Benefiting from these properties, Ti1.05 outperformed Ti0.95 and Ti1.00 in the photodegradation of organic dye and antibiotic molecules. Meanwhile, the excellent antibacterial activity of Ti1.05 under visible light was also demonstrated by the Escherichia coli sterilization experiment. This work not only presents a novel pathway to adjust the facet junction but also provides new deep insights into the crystal facet engineering in ferroelectrics as photocatalysts.

Regioselective Friedel-Crafts Acylation Reaction Using Single Crystalline and Ultrathin Nanosheet Assembly of Scrutinyite-SnO2.

Peculiar physicochemical properties of two-dimensional (2D) nanomaterials have attracted research interest in developing new synthetic technology and exploring their potential applications in the field of catalysis. Moreover, ultrathin metal oxide nanosheets with atomic thickness exhibit abnormal surficial properties because of the unique 2D confinement effect. In this work, we present a facile and general approach for the synthesis of single crystalline and ultrathin 2D nanosheets assembly of scrutinyite-SnO2 through a simple solvothermal method. The structural and compositional characterization using X-ray diffraction (Rietveld refinement analysis), high-resolution transmission electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, and so on reveal that the as-synthesized 2D nanosheets are ultrathin and single crystallized in the scrutinyite-SnO2 phase with high purity. The ultrathin SnO2 nanosheets show predominant growth in the [011] direction on the main surface having a thickness of ca. 1.3 nm. The SnO2 nanosheets are further employed for the regioselective Friedel–Crafts acylation to synthesize aromatic ketones that have potential significance in chemical industry as synthetic intermediates of pharmaceuticals and fine chemicals. A series of aromatic substrates acylated over the SnO2 nanosheets have afforded the corresponding aromatic ketones with up to 92% yield under solvent-free conditions. Comprehensive catalytic investigations display the SnO2 nanosheet assembly as a better catalytic material compared to the heterogeneous metal oxide catalysts used so far in the view of its activity and reusability in solvent-free reaction conditions.

A double quantum dot defined by top gates in a single crystalline InSb nanosheet* *Project supported by the National Key Research and Development Program of China (Grant Nos. 2017YFA0303304, 2016YFA0300601, 2017YFA0204901,and 2016YFA0300802), the National Natural Science Foundation of China (Grant Nos. 91221202, 91421303, 11874071, 11974030, and 61974138), the Beijing Academy of Quantum Information Sciences (Grant No. Y18G22), the Key-Area Research

We report on the transport study of a double quantum dot (DQD) device made from a freestanding, single crystalline InSb nanosheet. The freestanding nanosheet is grown by molecular beam epitaxy and the DQD is defined by the top gate technique. Through the transport measurements, we demonstrate how a single quantum dot (QD) and a DQD can be defined in an InSb nanosheet by tuning voltages applied to the top gates. We also measure the charge stability diagrams of the DQD and show that the charge states and the inter-dot coupling between the two individual QDs in the DQD can be efficiently regulated by the top gates. Numerical simulations for the potential profile and charge density distribution in the DQD have been performed and the results support the experimental findings and provide a better understanding of fabrication and transport characteristics of the DQD in the InSb nanosheet. The achieved DQD in the two-dimensional InSb nanosheet possesses pronounced benefits in lateral scaling and can thus serve as a new building block for the developments of quantum computation and quantum simulation technologies.

Single-Crystalline Ultrathin 2D Porous Nanosheets of Chiral Metal-Organic Frameworks.

Two-dimensional (2D) materials with highly ordered in-plane nanopores are crucial for numerous applications, but their rational synthesis and local structural characterization remain two grand challenges. We illustrate here that single-crystalline ultrathin 2D MOF nanosheets (MONs) with intrinsic porosity can be prepared by exfoliating layered metal-organic frameworks (MOFs), whose layers are stabilized by sterically bulky groups. As a result, three three-dimensional (3D) isostructural lanthanide MOFs possessing porous layer structures are constructed by coordinating metal ions with an angular dicarboxylate linker derived from chiral 1,1'-biphenyl phosphoric acid with pendant mesityl groups. The Eu-MOF is readily ultrasonic exfoliated into single-crystalline nanosheets with a thickness of ca. 6.0 nm (2 layers) and a lateral size of 1.5 × 3.0 μm2. The detailed structural information, i.e., the pore channels and individual organic and inorganic building units in the framework, is clearly visualized by a low-dose high-resolution transmission electron microscopy (HRTEM) technique. Benefiting from their ultrathin feature, the nanosheets are well embedded into the polymer matrix to form free-standing mixed-matrix membranes. In both the solution and membrane phase, the fluorescence of the MONs can be effectively quenched by a total of 17 chiral terpenes and terpenoids through supramolecular interactions with uncoordinated chiral phosphoric acids, leading to a chiral optical sensor for detecting vapor enantiomers, which is among the most challenging molecular recognition tasks.

Pressure Induced Assembly and Coalescence of Lead Chalcogenide Nanocrystals.

We report here pressure induced nanocrystal coalescence of ordered lead chalcogenide nanocrystal arrays into one-dimensional (1D) and 2D nanostructures. In particular, atomic crystal phase transitions and mesoscale coalescence of PbS and PbSe nanocrystals have been observed and monitored in situ respectively by wide- and small-angle synchrotron X-ray scattering techniques. At the atomic scale, both nanocrystals underwent reversible structural transformations from cubic to orthorhombic at significantly higher pressures than those for the corresponding bulk materials. At the mesoscale, PbS nanocrystal arrays displayed a superlattice transformation from face-centered cubic to lamellar structures, while no clear mesoscale lattice transformation was observed for PbSe nanocrystal arrays. Intriguingly, transmission electron microscopy showed that the applied pressure forced both spherical nanocrystals to coalesce into single crystalline 2D nanosheets and 1D nanorods. Our results confirm that pressure can be used as a straightforward approach to manipulate the interparticle spacing and engineer nanostructures with specific morphologies and, therefore, provide insights into the design and functioning of new semiconductor nanocrystal structures under high-pressure conditions.

Piezotronic effect and oxygen vacancies boosted photocatalysis C‒N coupling of benzylamine

Photocatalytic selective oxidation of benzylamine into high-value-added organic intermediates holds great promise. Herein, to achieve the goal of efficient separation of photo-generated electrons/holes and regulation of abundant active sites, we systematically investigated the synergistic impact of piezotronic effect and oxygen vacancies on selectively aerobic oxidation of benzylamine into N-benzylidenebenzylamine with Bi4NbO8Br single-crystalline nanosheets (BNO). We found that piezotronic effect and oxygen vacancies could collaboratively enhance the separation of photogenerated electrons and holes. Furthermore, theoretical calculations and experimental results demonstrated that oxygen vacancies can also optimize the adsorption and activation of O2 and benzylamine molecules to favor the efficient conversion of which. As a result, the conversion rates of benzylamine increased by about 2.1 times owing to the presence of piezotronic effect and oxygen vacancies. The present work opens an avenue for enhancing photocatalytic activity in selective oxidation of organic pollutant into value-added products, and also shed light on an understanding for the design of a highly efficient multi-field catalytic system in the future.

Wavelength-Tunable Mid-Infrared Lasing from Black Phosphorus Nanosheets.

Van der Waals layered semiconductor materials own unique physical properties and have attracted intense interest in developing high-performance electronic and photonic devices. Among them, black phosphorus (BP) is distinct for its layer number-tuned direct band gap which spans from near- to mid-infrared (MIR) waveband. In addition, the puckered honey comb crystal lattice endows the material with highly linear-polarized emission and marked anisotropy in carrier transportation. These unique material properties render BP as an intriguing and promising building block for constructing mid-infrared-ranged coherent light sources. Here, a room temperature surface-emitting MIR laser based on single crystalline BP nanosheets coupled with a distributed Bragg reflector cavity is reported. MIR stimulated emission at 3611 nm is achieved with a near-unity linear polarization, which exhibits robust thermal stability up to 360 K. Most importantly, the lasing wavelength can be tuned from 3425 to 4068 nm by varying the cavity length via thickness control of BP layer. The demonstrated highly polarized lasing output and wavelength-tunable capacity of the proposed device scheme in MIR spectral range opens up promising opportunities for a broad array of applications in polarization-resolved IR imaging, range-finding, and free space quantum communications.

Fabrication of CuCo2S4 nanosheet/carbon cloth as a flexible electrode for high-performance electro-catalysis

CuCo2S4 single crystalline nanosheets were fabricated directly on flexible carbon cloth (CC) substrate by a one-step hydrothermal process. The vertically oriented nanosheets exhibited abundant active sites and low charge transfer resistance, resulting an enhanced electro-catalytic performance to the reduction of I3−. Dye-sensitized solar cells based on CuCo2S4@CC as a counter electrode achieved a high photovoltaic conversion efficiency of 7.68% versus Pt of 7.39%. This work provides a feasible approach to designing high-quality two-dimensional ternary chalcogenides for further applications in wearable electronic devices.

Ultrathin two-dimensional conjugated metal-organic framework single-crystalline nanosheets enabled by surfactant-assisted synthesis.

Two-dimensional conjugated metal–organic frameworks (2D c-MOFs) have recently emerged for potential applications in (opto-)electronics, chemiresistive sensing, and energy storage and conversion, due to their excellent electrical conductivity, abundant active sites, and intrinsic porous structures. However, developing ultrathin 2D c-MOF nanosheets (NSs) for facile solution processing and integration into devices remains a great challenge, mostly due to unscalable synthesis, low yield, limited lateral size and low crystallinity. Here, we report a surfactant-assisted solution synthesis toward ultrathin 2D c-MOF NSs, including HHB-Cu (HHB = hexahydroxybenzene), HHB-Ni and HHTP-Cu (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene). For the first time, we achieve single-crystalline HHB-Cu(Ni) NSs featured with a thickness of 4–5 nm (∼8–10 layers) and a lateral size of 0.25–0.65 μm2, as well as single-crystalline HHTP-Cu NSs with a thickness of ∼5.1 ± 2.6 nm (∼10 layers) and a lateral size of 0.002–0.02 μm2. Benefiting from the ultrathin feature, the synthetic NSs allow fast ion diffusion and high utilization of active sites. As a proof of concept, when serving as a cathode material for Li-ion storage, HHB-Cu NSs deliver a remarkable rate capability (charge within 3 min) and long-term cycling stability (90% capacity retention after 1000 cycles), superior to the corresponding bulk materials and other reported MOF cathodes.

Solid-state template-free fabrication of uniform Mo2C microflowers with lithium storage towards Li-ion batteries

Herein, we first report one-step synthesis of uniform Mo2C microflowers (MCMFs) from low-cost precursors via industrialized solid-state strategy. With fine optimization in precursor ratio and pyrolysis temperatures, the as-fabricated MCMFs are assembled well with interconnected single-crystalline nanosheet subunits. More encouragingly, the resultant MCMFs are further highlighted as a competitive anode with robust and long-duration lithium-storage behaviors towards high-performance Li-ion batteries

Synthesis of centimeter-size free-standing perovskite nanosheets from single-crystal lead bromide for optoelectronic devices

Considerable attention has been drawn to the lead halide perovskites (LHPs) because of their outstanding optoelectronic characteristics. LHP nanosheets (NSs) grown from single crystalline lead halide possess advantages in device applications as they provide the possibility for control over morphology, composition, and crystallinity. Here, free-standing lead bromide (PbBr2) single-crystalline NSs with sizes up to one centimeter are synthesized from solution. These NSs can be converted to LHP while maintaining the NS morphology. We demonstrate that these perovskite NSs can be processed directly for fabrication of photodetector and laser arrays on a large scale. This strategy will allow high-yield synthesis of large-size perovskite NSs for functional devices in an integrated photonics platform.

Ultrathin Free-Standing Nanosheets of Bi2O2Se: Room Temperature Ferroelectricity in Self-Assembled Charged Layered Heterostructure

Ultrathin ferroelectric semiconductors with high charge carrier mobility are much coveted systems for the advancement of various electronic and optoelectronic devices. However, in traditional oxide ferroelectric insulators, the ferroelectric transition temperature decreases drastically with decreasing material thickness and ceases to exist below certain critical thickness owing to depolarizing fields. Herein, we show the emergence of an ordered ferroelectric ground state in ultrathin (∼2 nm) single crystalline nanosheets of Bi2O2Se at room temperature. Free-standing ferroelectric nanosheets, in which oppositely charged alternating layers are self-assembled together by electrostatic interactions, are synthesized by a simple, rapid, and scalable wet chemical procedure at room temperature. The existence of ferroelectricity in Bi2O2Se nanosheets is confirmed by dielectric measurements and piezoresponse force spectroscopy. The spontaneous orthorhombic distortion in the ultrathin nanosheets breaks the local inversion symmetry, thereby resulting in ferroelectricity. The local structural distortion and the formation of spontaneous dipole moment were directly probed by atomic resolution scanning transmission electron microscopy and density functional theory calculations.

Single-Crystalline Nanosheets of Hybrid Perovskite Fabricated by a Vapor-Solution Sequential Deposition Route.

Organic-inorganic hybrid perovskite single crystals have attracted much attention due to their superior optoelectronic properties. Herein, we report a facile vapor-solution sequential route to prepare single-crystalline nanosheets of hybrid lead triiodide perovskite. It is found that this two-step deposition is able to fabricate sizeable high-quality single-crystalline nanosheets with no need of delicate control of crystallization conditions such as concentration or temperature for normal single crystal growth. The resulting perovskite nanosheets show good reproducibility and single crystallinity with bright and uniform photoluminescence. Our study provides a promising strategy for scalable fabrication of perovskite single crystals with great potential in optoelectronic applications.