Fabrication of a Spherical Superstructure of Carbon Nanorods.

Hierarchical superstructures in nano/microsize have attracted great attention owing to their wide potential applications. Herein, a self-templated strategy is presented for the synthesis of a spherical superstructure of carbon nanorods (SS-CNR) in micrometers through the morphology-preserved thermal transformation of a spherical superstructure of metal-organic framework nanorods (SS-MOFNR). The self-ordered SS-MOFNR with a chestnut-shell-like superstructure composed of 1D MOF nanorods on the shell is synthesized by a hydrothermal transformation process from crystalline MOF nanoparticles. After carbonization in argon, the hierarchical SS-MOFNR transforms into SS-CNR, which preserves the original chestnut-shell-like superstructure with 1D porous carbon nanorods on the shell. Taking the advantage of this functional superstructure, SS-CNR immobilized with ultrafine palladium (Pd) nanoparticles (Pd@SS-CNR) exhibits excellent catalytic activity for formic acid dehydrogenation. This synthetic strategy provides a facile method to synthesize uniform spherical superstructures constructed from 1D MOF nanorods or carbon nanorods for applications in catalysis and energy storage.

Efficient carrier multiplication in CsPbI3 perovskite nanocrystals.

The all-inorganic perovskite nanocrystals are currently in the research spotlight owing to their physical stability and superior optical properties-these features make them interesting for optoelectronic and photovoltaic applications. Here, we report on the observation of highly efficient carrier multiplication in colloidal CsPbI3 nanocrystals prepared by a hot-injection method. The carrier multiplication process counteracts thermalization of hot carriers and as such provides the potential to increase the conversion efficiency of solar cells. We demonstrate that carrier multiplication commences at the threshold excitation energy near the energy conservation limit of twice the band gap, and has step-like characteristics with an extremely high quantum yield of up to 98%. Using ultrahigh temporal resolution, we show that carrier multiplication induces a longer build-up of the free carrier concentration, thus providing important insights into the physical mechanism responsible for this phenomenon. The evidence is obtained using three independent experimental approaches, and is conclusive.

Chemical Growth of 1T-TaS2 Monolayer and Thin Films: Robust Charge Density Wave Transitions and High Bolometric Responsivity.

Ultrathin two-dimensional (2D) charge density wave (CDW) materials, with sharp resistance change at the phase-transition temperature, yet with ultrathin thickness, hold great potential for electrical device applications. However, chemical synthesis of high-quality samples and observation of the CDW states down to the monolayer limit is still of great challenge. Chemical vapor deposition of 1T-TaS2 sheets on hexagonal boron nitride (h-BN) with robust CDW states even down to the monolayer extreme is reported here. Further, based on the near commensurate CDW to incommensurate CDW phase transition with a high temperature coefficient of resistance (TCR), highly responsive room-temperature bolometers are fabricated by suspending the as-grown 1T-TaS2 sheets.

Auto-optimizing Hydrogen Evolution Catalytic Activity of ReS2 through Intrinsic Charge Engineering.

Optimizing active electronic states responding to catalysis is of paramount importance for developing high-activity catalysts because thermodynamics itself may not favor forming an optimal electronic state. Setting the monolayer transition metal dichalcogenide (TMD) ReS2 as a model for the hydrogen evolution reaction (HER), we uncover that intrinsic charge engineering has an auto-optimizing effect on enhancing catalytic activity through regulating active electronic states. The experimental and theoretical results show that intrinsic charge compensation from S to Re-Re bonds could manipulate the active electronic states, allowing hydrogen to absorb the active sites neither strongly nor weakly. Two types of S sites exhibit the optimal hydrogen adsorption free energies (Δ GH*) of 0.016 and 0.061 eV, which are the closest to zero corresponding to the highest HER activity. This auto-optimization via charge engineering is further demonstrated by higher turnover frequency per sulfur atom of 1-10 s-1 and lower overpotential of -147 mV at 10 mA cm-2 than those of other TMDs through multiscale activation and optimization. This work opens an avenue in designing extensive active catalysts through intrinsic charge engineering strategy.

Extraordinary Interfacial Stitching between Single All-Inorganic Perovskite Nanocrystals.

All-inorganic cesium lead halide perovskite nanocrystals are extensively studied because of their outstanding optoelectronic properties. Being of a cubic shape and typically featuring a narrow size distribution, CsPbX3 (X = Cl, Br, and I) nanocrystals are the ideal starting material for the development of homogeneous thin films as required for photovoltaic and optoelectronic applications. Recent experiments reveal spontaneous merging of drop-casted CsPbBr3 nanocrystals, which is promoted by humidity and mild-temperature treatments and arrested by electron beam irradiation. Here, we make use of atom-resolved annular dark-field imaging microscopy and valence electron energy loss spectroscopy in a state-of-the-art low-voltage monochromatic scanning transmission electron microscope to investigate the aggregation between individual nanocrystals at the atomic level. We show that the merging process preserves the elemental composition and electronic structure of CsPbBr3 and takes place between nanocrystals of different sizes and orientations. In particular, we reveal seamless stitching for aligned nanocrystals, similar to that reported in the past for graphene flakes. Because the crystallographic alignment occurs naturally in drop-casted layers of CsPbX3 nanocrystals, our findings constitute the essential first step toward the development of large-area nanosheets with band gap energies predesigned by the nanocrystal choice-the gateway to large-scale photovoltaic applications of inorganic perovskites.

Correction to "Hybridization of Single Nanocrystals of Cs4PbBr6 and CsPbBr3".

[This corrects the article DOI: 10.1021/acs.jpcc.7b05752.].

Chemical vapor deposition of trigonal prismatic NbS2 monolayers and 3R-polytype few-layers.

Group VB transition-metal dichalcogenides (TMDs) have an intriguing structure-dependent charge density wave and superconductivity. Here, we report the direct chemical vapor deposition of large-size NbS2 monolayers and few-layers with trigonal prismatic coordination and 3R polytype layer-layer stacking on hexagonal boron nitride (h-BN). The structure has been confirmed by micro-Raman spectroscopy and atomic-resolution scanning transmission electron microscopy (STEM).

Scalable van der Waals Heterojunctions for High-Performance Photodetectors.

Atomically thin two-dimensional (2D) materials have attracted increasing attention for optoelectronic applications in view of their compact, ultrathin, flexible, and superior photosensing characteristics. Yet, scalable growth of 2D heterostructures and the fabrication of integrable optoelectronic devices remain unaddressed. Here, we show a scalable formation of 2D stacks and the fabrication of phototransistor arrays, with each photosensing element made of a graphene-WS2 vertical heterojunction and individually addressable by a local top gate. The constituent layers in the heterojunction are grown using chemical vapor deposition in combination with sulfurization, providing a clean junction interface and processing scalability. The aluminum top gate possesses a self-limiting oxide around the gate structure, allowing for a self-aligned deposition of drain/source contacts to reduce the access (ungated) channel regions and to boost the device performance. The generated photocurrent, inherently restricted by the limited optical absorption cross section of 2D materials, can be enhanced by 2 orders of magnitude by top gating. The resulting photoresponsivity can reach 4.0 A/W under an illumination power density of 0.5 mW/cm2, and the dark current can be minimized to few picoamperes, yielding a low noise-equivalent power of 2.5 × 10-16 W/Hz1/2. Tailoring 2D heterostacks as well as the device architecture moves the applications of 2D-based optoelectronic devices one big step forward.

Hybridization of Single Nanocrystals of Cs4PbBr6 and CsPbBr3.

Nanocrystals of all-inorganic cesium lead halide perovskites (CsPbX3, X = Cl, Br, I) feature high absorption and efficient narrow-band emission which renders them promising for future generation of photovoltaic and optoelectronic devices. Colloidal ensembles of these nanocrystals can be conveniently prepared by chemical synthesis. However, in the case of CsPbBr3, its synthesis can also yield nanocrystals of Cs4PbBr6 and the properties of the two are easily confused. Here, we investigate in detail the optical characteristics of simultaneously synthesized green-emitting CsPbBr3 and insulating Cs4PbBr6 nanocrystals. We demonstrate that, in this case, the two materials inevitably hybridize, forming nanoparticles with a spherical shape. The actual amount of these Cs4PbBr6 nanocrystals and nanohybrids increases for synthesis at lower temperatures, i.e., the condition typically used for the development of perovskite CsPbBr3 nanocrystals with smaller sizes. We use state-of-the-art electron energy loss spectroscopy to characterize nanoparticles at the single object level. This method allows distinguishing between optical characteristics of a pure Cs4PbBr6 and CsPbBr3 nanocrystal and their nanohybrid. In this way, we resolve some of the recent misconceptions concerning possible visible absorption and emission of Cs4PbBr6. Our method provides detailed structural characterization, and combined with modeling, we conclusively identify the nanospheres as CsPbBr3/Cs4PbBr6 hybrids. We show that the two phases are independent of each other's presence and merge symbiotically. Herein, the optical characteristics of the parent materials are preserved, allowing for an increased absorption in the UV due to Cs4PbBr6, accompanied by the distinctive efficient green emission resulting from CsPbBr3.

Structural Distortions and Charge Density Waves in Iodine Chains Encapsulated inside Carbon Nanotubes.

Atomic chains are perfect systems for getting fundamental insights into the electron dynamics and coupling between the electronic and ionic degrees of freedom in one-dimensional metals. Depending on the band filling, they can exhibit Peierls instabilities (or charge density waves), where equally spaced chain of atoms with partially filled band is inherently unstable, exhibiting spontaneous distortion of the lattice that further leads to metal-insulator transition in the system. Here, using high-resolution scanning transmission electron microscopy, we directly image the atomic structures of a chain of iodine atoms confined inside carbon nanotubes. In addition to long equidistant chains, the ones consisting of iodine dimers and trimers were also observed, as well as transitions between them. First-principles calculations reproduce the experimentally observed bond lengths and lattice constants, showing that the ionic movement is largely unconstrained in the longitudinal direction, while naturally confined by the nanotube in the lateral directions. Moreover, the trimerized chain bears the hallmarks of a charge density wave. The transition is driven by changes in the charge transfer between the chain and the nanotube and is enabled by the charge compensation and additional screening provided by the nanotube.

Synthesis of Highly Active Sub-Nanometer Pt@Rh Core-Shell Nanocatalyst via a Photochemical Route: Porous Titania Nanoplates as a Superior Photoactive Support.

Sub-nanometer Pt@Rh nanoparticles highly dispersed on MIL-125-derived porous TiO2 nanoplates are successfully prepared for the first time by a photochemical route, where the porous TiO2 nanoplates with a relatively high specific surface area play a dual role as both effective photoreductant and catalyst support. The resulting Pt@Rh/p-TiO2 can be utilized as a highly active catalyst.

Unexpected Huge Dimerization Ratio in One-Dimensional Carbon Atomic Chains.

Peierls theory predicted atomic distortion in one-dimensional (1D) crystal due to its intrinsic instability in 1930. Free-standing carbon atomic chains created in situ in transmission electron microscope (TEM)1-3 are an ideal example to experimentally observe the dimerization behavior of carbon atomic chain within a finite length. We report here a surprisingly huge distortion found in the free-standing carbon atomic chains at 773 K, which is 10 times larger than the value expected in the system. Such an abnormally distorted phase only dominates at the elevated temperatures, while two distinct phases, distorted and undistorted, coexist at lower or ambient temperatures. Atom-by-atom spectroscopy indeed shows considerable variations in the carbon 1s spectra at each atomic site but commonly observes a slightly downshifted π* peak, which proves its sp1 bonding feature. These results suggest that the simple model, relaxed and straight, is not fully adequate to describe the realistic 1D structure, which is extremely sensitive to perturbations such as external force or boundary conditions.

Direct Observation of Band Structure Modifications in Nanocrystals of CsPbBr3 Perovskite.

We investigate the variation of the bandgap energy of single quantum dots of CsPbBr3 inorganic halide perovskite as a function of size and shape and upon embedding within an ensemble. For that purpose, we make use of valence-loss electron spectroscopy with Z-contrast annular dark-field (ADF) imaging in a state-of-the-art low-voltage monochromatic scanning transmission electron microscope. In the experiment, energy absorption is directly mapped onto individual quantum dots, whose dimensions and location are simultaneously measured to the highest precision. In that way, we establish an intimate relation between quantum dot size and even shape and its bandgap energy on a single object level. We explicitly follow the bandgap increase in smaller quantum dots due to quantum confinement and demonstrate that it is predominantly governed by the smallest of the three edges of the cuboidal perovskite dot. We also show the presence of an effective coupling between proximal dots in an ensemble, leading to band structure modification. These unique insights are directly relevant to the development of custom-designed quantum structures and solids which will be realized by purposeful assemblage of individually characterized and selected quantum dots, serving as building blocks.

Carbon Nanotubes as Electrically Active Nanoreactors for Multi-Step Inorganic Synthesis: Sequential Transformations of Molecules to Nanoclusters and Nanoclusters to Nanoribbons.

In organic synthesis, the composition and structure of products are predetermined by the reaction conditions; however, the synthesis of well-defined inorganic nanostructures often presents a significant challenge yielding nonstoichiometric or polymorphic products. In this study, confinement in the nanoscale cavities of single-walled carbon nanotubes (SWNTs) provides a new approach for multistep inorganic synthesis where sequential chemical transformations take place within the same nanotube. In the first step, SWNTs donate electrons to reactant iodine molecules (I2), transforming them to iodide anions (I(-)). These then react with metal hexacarbonyls (M(CO)6, M = Mo or W) in the next step, yielding anionic nanoclusters [M6I14](2-), the size and composition of which are strictly dictated by the nanotube cavity, as demonstrated by aberration-corrected high resolution transmission electron microscopy, scanning transmission electron microscopy, and energy dispersive X-ray spectroscopy. Atoms in the nanoclusters [M6I14](2-) are arranged in a perfect octahedral geometry and can engage in further chemical reactions within the nanotube, either reacting with each other leading to a new polymeric phase of molybdenum iodide [Mo6I12]n or with hydrogen sulfide gas giving rise to nanoribbons of molybdenum/tungsten disulfide [MS2]n in the third step of the synthesis. Electron microscopy measurements demonstrate that the products of the multistep inorganic transformations are precisely controlled by the SWNT nanoreactor with complementary Raman spectroscopy revealing the remarkable property of SWNTs to act as a reservoir of electrons during the chemical transformation. The electron transfer from the host nanotube to the reacting guest molecules is essential for stabilizing the anionic metal iodide nanoclusters and for their further transformation to metal disulfide nanoribbons synthesized in the nanotubes in high yield.

Weaving of organic threads into a crystalline covalent organic framework.

A three-dimensional covalent organic framework (COF-505) constructed from helical organic threads, designed to be mutually weaving at regular intervals, has been synthesized by imine condensation reactions of aldehyde functionalized copper(I)-bisphenanthroline tetrafluoroborate, Cu(PDB)2(BF4), and benzidine (BZ). The copper centers are topologically independent of the weaving within the COF structure and serve as templates for bringing the threads into a woven pattern rather than the more commonly observed parallel arrangement. The copper(I) ions can be reversibly removed and added without loss of the COF structure, for which a tenfold increase in elasticity accompanies its demetalation. The threads in COF-505 have many degrees of freedom for enormous deviations to take place between them, throughout the material, without undoing the weaving of the overall structure.

Inelastic electron irradiation damage in hexagonal boron nitride.

We present a study of the inelastic effects caused by electron irradiation in monolayer hexagonal boron nitride (h-BN). The data was obtained through in situ experiments performed inside a low-voltage aberration-corrected transmission electron microscope (TEM). By using various specialized sample holders, we study defect formation and evolution with sub-nanometer resolution over a wide range of temperatures, between -196 and 1200 °C, highlighting significant differences in the geometry of the structures that form. The data is then quantified, allowing insight into the defect formation mechanism, which is discussed in comparison with the potential candidate damage processes. We show that the defect shapes are determined by an interplay between electron damage, which we assign to charging, and thermal effects. We additionally show that this damage can be avoided altogether by overlapping the samples with a monolayer of graphene, confirming this for h-BN and providing a way to overcome the well-known fragility of h-BN under the electron beam.

Structure and local chemical properties of boron-terminated tetravacancies in hexagonal boron nitride.

Imaging and spectroscopy performed in a low-voltage scanning transmission electron microscope are used to characterize the structure and chemical properties of boron-terminated tetravacancies in hexagonal boron nitride. We confirm earlier theoretical predictions about the structure of these defects and identify new features in the electron energy-loss spectra of B atoms using high resolution chemical maps, highlighting differences between these areas and pristine sample regions. We correlate our experimental data with calculations which help explain our observations.

Resolution enhancement at a large convergence angle by a delta corrector with a CFEG in a low-accelerating-voltage STEM.

Resolution reduction by a diffraction limit becomes severe with an increase in the wavelength of an electron at a relatively low accelerating voltage. For maintaining atomic resolution at a low accelerating voltage, a larger convergence angle with aberration correction is required. The developed aberration corrector, which compensates for higher-order aberration, can expand the uniform phase angle. Sub-angstrom imaging of a Ge [112] specimen with a narrow energy spread obtained by a cold field emission gun at 60 kV was performed using the aberration corrector. We achieved a resolution of 82 pm for a Ge-Ge dumbbell structure image by high angle annular dark-field imaging.

Evidence for active atomic defects in monolayer hexagonal boron nitride: a new mechanism of plasticity in two-dimensional materials.

We report the formation and motion of 4|8 (square-octagon) defects in monolayer hexagonal boron nitride (h-BN). The 4|8 defects, involving less-favorable B-B and N-N bonds, are mobile within the monolayer at high sample temperature (∼ 1000 K) under electron beam irradiation. Gliding of one or two atomic rows along the armchair direction is suggested to be the origin of the defect motion. This represents a completely new mechanism of plasticity in two-dimensional materials.

Development of Cs and Cc correctors for transmission electron microscopy.

Novel spherical aberration (Cs) and chromatic aberration (Cc) correctors, which correct aberrations using a new principle, were developed. The asymmetric Cs correctors were designed for use in the probe- and image-forming systems at 300 kV to diminish undesired parasitic aberrations. The correctors composed of non-equivalent multipoles connecting with a demagnifying transfer doublet in the system. The axial aberrations were corrected well up to the fifth order except 6-fold astigmatism (A(6)) experimentally. Next, we developed superior Cs correctors for probe- and image-forming systems of low voltage microscope that uses triple dodecapoles to correct 6-fold astigmatism (A(6)). An important feature of this system is the rotation of the 3-fold astigmatism azimuth at the second dodecapole. The optimum rotation of the three hexapole fields for the compensation of A(6) was derived from theoretical calculations. The experimental results confirmed the compensation of A(6) and the third-order Cs. Finally, a unique Cc corrector, which utilized the concave lens effect formed by a long quadrupole field, was designed. The performance of the Cc corrector was investigated using a 30-kV transmission electron microscope. The results confirmed that Cc correction was achieved.