Giant pyroelectricity in nanomembranes.

Pyroelectricity describes the generation of electricity by temporal temperature change in polar materials1-3. When free-standing pyroelectric materials approach the 2D crystalline limit, how pyroelectricity behaves remained largely unknown. Here, using three model pyroelectric materials whose bonding characters along the out-of-plane direction vary from van der Waals (In2Se3), quasi-van der Waals (CsBiNb2O7) to ionic/covalent (ZnO), we experimentally show the dimensionality effect on pyroelectricity and the relation between lattice dynamics and pyroelectricity. We find that, for all three materials, when the thickness of free-standing sheets becomes small, their pyroelectric coefficients increase rapidly. We show that the material with chemical bonds along the out-of-plane direction exhibits the greatest dimensionality effect. Experimental observations evidence the possible influence of changed phonon dynamics in crystals with reduced thickness on their pyroelectricity. Our findings should stimulate fundamental study on pyroelectricity in ultra-thin materials and inspire technological development for potential pyroelectric applications in thermal imaging and energy harvesting.

Liquid-Phase van der Waals Epitaxy of a Few-Layer and Unit-Cell Thick Ruddlesden-Popper Halide Perovskite.

2D Ruddlesden-Popper (RP) halide perovskites with natural multiple quantum well structures are an ideal platform to integrate into vertical heterostructures, which may introduce plentiful intriguing optoelectronic properties that are not accessible in a single bulk crystal. Here, we report liquid-phase van der Waals epitaxy of a 2D RP hybrid perovskite (4,4-DFPD)2PbI4 (4,4-DFPD is 4,4-difluoropiperidinium) on muscovite mica and fabricate a series of perovskite-perovskite vertical heterostructures by integrating it with a second 2D RP perovskite R-NPB [NPB = 1-(1-naphthyl)ethylammonium lead bromide] sheets. The grown (4,4-DFPD)2PbI4 nanobelt array can be multiple layers to unit-cell thin and are crystallographically aligned on the mica substrate. An interlayer photo emission in this R-NPB/(4,4-DFPD)2PbI4 heterostructure with a lifetime of about 25 ns at 120 K has been revealed. Our demonstration of epitaxial (4,4-DFPD)2PbI4 array grown on mica via liquid-phase van der Waals epitaxy provides a paradigm to prepare orderly distributed 2D RP hybrid perovskites for further integration into multiple heterostructures. The discovery of a new interlayer emission in the R-NPB/(4,4-DFPD)2PbI4 heterostructure enriches the basic understanding of interlayer charge transition in halide perovskite systems.

A Reconfigurable Remotely Epitaxial VO2 Electrical Heterostructure.

The reconfigurability of the electrical heterostructure featured with external variables, such as temperature, voltage, and strain, enabled electronic/optical phase transition in functional layers has great potential for future photonics, computing, and adaptive circuits. VO2 has been regarded as an archetypal phase transition building block with superior metal-insulator transition characteristics. However, the reconfigurable VO2-based heterostructure and the associated devices are rare due to the fundamental challenge in integrating high-quality VO2 in technologically important substrates. In this report, for the first time, we show the remote epitaxy of VO2 and the demonstration of a vertical diode device in a graphene/epitaxial VO2/single-crystalline BN/graphite structure with VO2 as a reconfigurable phase-change material and hexagonal boron nitride (h-BN) as an insulating layer. By diffraction and electrical transport studies, we show that the remote epitaxial VO2 films exhibit higher structural and electrical quality than direct epitaxial ones. By high-resolution transmission electron microscopy and Cs-corrected scanning transmission electron microscopy, we show that a graphene buffered substrate leads to a less strained VO2 film than the bare substrate. In the reconfigurable diode, we find that the Fermi level change and spectral weight shift along with the metal-insulator transition of VO2 could modify the transport characteristics. The work suggests the feasibility of developing a single-crystalline VO2-based reconfigurable heterostructure with arbitrary substrates and sheds light on designing novel adaptive photonics and electrical devices and circuits.

Chemical reaction induced carrier localization in nanometer-thin Al/Ru, Al/Co, and Al/Mo superlattices.

It is well-known that the electrical conductivity of a metallic film reduces dramatically when the film becomes very thin. This effect is mainly attributed to surface scattering of the conducting carriers. In a multilayer structure, interface scattering also reduces the conductance, but chemical reactions at the interfaces can have equal or bigger effects. The extent of chemically induced carrier localization at the metallic interfaces has not been explored or reported. We have grown superlattices consisting of nm-thin, alternating Al and transition-metal layers (Al/Ru, Al/Co and Al/Mo) by magnetron sputtering, and measured the electrical conductance of the superlattices in-situ during the growth. We observed a sharp conductance drop at the start of each transition metal layer and a pause in conduction increase at the start of each Al layer, neither of which is predicted by the surface scattering model. We show that these abnormal conductance changes can be explained by localization of Al free carriers at the interfaces to facilitate the formation of intermetallic bonds. The magnitude of the measured conductance drops suggests that one monolayer of compound is formed at each interface at room temperature. Annealing the superlattices to 300 °C caused a modest decrease in conductance, attributed to further chemical reactions. In contrast, a superlattice involving two fully miscible transition metals, Ru and Co, exhibited no carrier localization, resulting in a conductance more than three times that of superlattices containing Al layers.

Traditional Semiconductors in the Two-Dimensional Limit.

Interest in two-dimensional materials has exploded in recent years. Not only are they studied due to their novel electronic properties, such as the emergent Dirac fermion in graphene, but also as a new paradigm in which stacking layers of distinct two-dimensional materials may enable different functionality or devices. Here, through first-principles theory, we reveal a large new class of two-dimensional materials which are derived from traditional III-V, II-VI, and I-VII semiconductors. It is found that in the ultrathin limit the great majority of traditional binary semiconductors studied (a series of 28 semiconductors) are not only kinetically stable in a two-dimensional double layer honeycomb structure, but more energetically stable than the truncated wurtzite or zinc-blende structures associated with three dimensional bulk. These findings both greatly increase the landscape of two-dimensional materials and also demonstrate that in the double layer honeycomb form, even ordinary semiconductors, such as GaAs, can exhibit exotic topological properties.

Remote epitaxy of copper on sapphire through monolayer graphene buffer.

In this work, we show that remote heteroepitaxy can be achieved when Cu thin film is grown on single crystal, monolayer graphene buffered sapphire(0001) substrate via a thermal evaporation process. X-ray diffraction and electron backscatter diffraction data show that the epitaxy process forms a prevailing Cu crystal domain, which is remotely registered in-plane to the sapphire crystal lattice below the monolayer graphene, with the (111) out-of-plane orientation. As a poor metal with zero density of states at its Fermi level, monolayer graphene cannot totally screen out the stronger charge transfer/metallic interactions between Cu and substrate atoms. The primary Cu domain thus has good crystal quality as manifested by a narrow crystal misorientation distribution. On the other hand, we show that graphene interface imperfections, such as bilayers/multilayers, wrinkles and interface contaminations, can effectively weaken the atomic interactions between Cu and sapphire. This results in a second Cu domain, which directly grows on and follows the graphene hexagonal lattice symmetry and orientation. Because of the weak van der Waals interaction between Cu and graphene, this domain has inferior crystal quality. The results are further confirmed using graphene buffered spinel(111) substrate, which indicates that this remote epitaxial behavior is not unique to the Cu/sapphire system.

Initial bridges between two ribosomal subunits are formed within 9.4 milliseconds, as studied by time-resolved cryo-EM.

Association of the two ribosomal subunits during the process of translation initiation is a crucial step of protein synthesis. The two subunits (30S and 50S) of the bacterial 70S ribosome are held together by 12 dynamic bridges involving RNA-RNA, RNA-protein, and protein-protein interactions. The process of bridge formation, such as whether all these bridges are formed simultaneously or in a sequential order, is poorly understood. To understand such processes, we have developed and implemented a class of microfluidic devices that mix two components to completion within 0.4 ms and spray the mixture in the form of microdroplets onto an electron microscopy grid, yielding a minimum reaction time of 9.4 ms before cryofixation. Using these devices, we have obtained cryo-EM data corresponding to reaction times of 9.4 and 43 ms and have determined 3D structures of ribosomal subunit association intermediates. Molecular analyses of the cryo-EM maps reveal that eight intersubunit bridges (bridges B1a, B1b, B2a, B2b, B3, B7a, B7b, and B8) form within 9.4 ms, whereas the remaining four bridges (bridges B2c, B4, B5, and B6) take longer than 43 ms to form, suggesting that bridges are formed in a stepwise fashion. Our approach can be used to characterize sequences of various dynamic functional events on complex macromolecular assemblies such as ribosomes.

Photon Transport in One-Dimensional Incommensurately Epitaxial CsPbX3 Arrays.

One-dimensional nanoscale epitaxial arrays serve as a great model in studying fundamental physics and for emerging applications. With an increasing focus laid on the Cs-based inorganic halide perovskite out of its outstanding material stability, we have applied vapor phase epitaxy to grow well aligned horizontal CsPbX3 (X: Cl, Br, or I or their mixed) nanowire arrays in large scale on mica substrate. The as-grown nanowire features a triangular prism morphology with typical length ranging from a few tens of micrometers to a few millimeters. Structural analysis reveals that the wire arrays follow the symmetry of mica substrate through incommensurate epitaxy, paving a way for a universally applicable method to grow a broad family of halide perovskite materials. The unique photon transport in the one-dimensional structure has been studied in the all-inorganic Cs-based perovskite wires via temperature dependent and spatially resolved photoluminescence. Epitaxy of well oriented wire arrays in halide perovskite would be a promising direction for enabling the circuit-level applications of halide perovskite in high-performance electro-optics and optoelectronics.

Vertically Oriented Arrays of ReS2 Nanosheets for Electrochemical Energy Storage and Electrocatalysis.

Transition-metal dichalcogenide (TMD) nanolayers show potential as high-performance catalysts in energy conversion and storage devices. Synthetic TMDs produced by chemical-vapor deposition (CVD) methods tend to grow parallel to the growth substrate. Here, we show that with the right precursors and appropriate tuning of the CVD growth conditions, ReS2 nanosheets can be made to orient perpendicular to the growth substrate. This accomplishes two important objectives; first, it drastically increases the wetted or exposed surface area of the ReS2 sheets, and second, it exposes the sharp edges and corners of the ReS2 sheets. We show that these structural features of the vertically grown ReS2 sheets can be exploited to significantly improve their performance as polysulfide immobilizers and electrochemical catalysts in lithium-sulfur (Li-S) batteries and in hydrogen evolution reactions (HER). After 300 cycles, the specific capacity of the Li-S battery with vertical ReS2 catalyst is retained above 750 mA h g(-1), with only ∼0.063% capacity decay per cycle, much better than the baseline battery (without ReS2), which shows ∼0.184% capacity decay per cycle under the same test conditions. As a HER catalyst, the vertical ReS2 provides very small onset overpotential (<100 mV) and an exceptional exchange-current density (∼67.6 µA/cm(2)), which is vastly superior to the baseline electrode without ReS2.

Effects of nanoscale surface roughness on the resistivity of ultrathin epitaxial copper films.

The knowledge on the influence of surface roughness and the electron-phonon (el-ph) interaction on electrical transport properties of nanoscale metal films is important from both fundamental and technological points of view. Here we report a study of the temperature dependent electron transport properties of nanoscale copper films by measuring temperature dependent electrical resistivity with thickness ranging from 4 to 500 nm. We show that the residual resistivity, which is temperature independent, can be described quantitatively using both measured vertical surface root-mean-square roughness and lateral correlation length in the nanoscale, with no adjustable parameter, by a recent quasi-classical model developed by Chatterjee and Meyerovich (2010 Phys. Rev. B 81 245409-10). We also demonstrate that the temperature dependent component of the resistivity can be described using the Bloch-Grüneisen equation with a thickness dependent el-ph coupling constant and a thickness dependent Debye temperature. We show that the increase of the el-ph coupling constant with the decrease of film thickness gives rise to an enhancement of the temperature dependent component of the resistivity.

Gas-Assisted Annular Microsprayer for Sample Preparation for Time-Resolved Cryo-Electron Microscopy.

Time-resolved cryo electron microscopy (TRCEM) has emerged as a powerful technique for transient structural characterization of isolated biomacromolecular complexes in their native state within the time scale of seconds to milliseconds. For TRCEM sample preparation, microfluidic device [9] has been demonstrated to be a promising approach to facilitate TRCEM biological sample preparation. It is capable of achieving rapidly aqueous sample mixing, controlled reaction incubation, and sample deposition on electron microscopy (EM) grids for rapid freezing. One of the critical challenges is to transfer samples to cryo-EM grids from the microfluidic device. By using microspraying method, the generated droplet size needs to be controlled to facilitate the thin ice film formation on the grid surface for efficient data collection, while not too thin to be dried out before freezing, i.e., optimized mean droplet size needs to be achieved. In this work, we developed a novel monolithic three dimensional (3D) annular gas-assisted microfluidic sprayer using 3D MEMS (MicroElectroMechanical System) fabrication techniques. The microsprayer demonstrated dense and consistent microsprays with average droplet size between 6-9 µm, which fulfilled the above droplet size requirement for TRCEM sample preparation. With droplet density of around 12-18 per grid window (window size is 58×58 µm), and the data collectible thin ice region of >50% total wetted area, we collected ~800-1000 high quality CCD micrographs in a 6-8 hour period of continuous effort. This level of output is comparable to what were routinely achieved using cryo-grids prepared by conventional blotting and manual data collection. In this case, weeks of data collection process with the previous device [9] has shortened to a day or two. And hundreds of microliter of valuable sample consumption can be reduced to only a small fraction.

Vertically Aligned One-Dimensional Crystal-Structured Sb2Se3 for High-Efficiency Flexible Solar Cells via Regulating Selenization Kinetics.

Recently, antimony selenide (Sb2Se3) has exhibited an exciting potential for flexible photoelectric applications due to its unique one-dimensional (1D) chain-type crystal structure, low-cost constituents, and superior optoelectronic properties. The 1D structure endows Sb2Se3 with a strong anisotropy in carrier transport and a lasting mechanical deformation tolerance. The control of the crystalline orientation of the Sb2Se3 film is an essential requirement for its device performance optimization. However, the current state-of-the-art Sb2Se3 devices suffer from unsatisfactory orientation control, especially for the (001) orientation, in which the chains stand vertically. Herein, we achieved an unprecedented control of the (001) orientation for the growth of the Sb2Se3 film on a flexible Mo-coated mica substrate by balancing the collision rate and kinetic energy of Se vapor particles with the surface of Sb film by regulating the selenization kinetics. Based on this (001)-oriented Sb2Se3 film, a high efficiency of 8.42% with a record open-circuit voltage (VOC) of 0.47 V is obtained for flexible Sb2Se3 solar cells. The vertical van der Waals gaps in the (001) orientation provide favorable diffusion paths for Se atoms, which results in a Se-rich state at the bottom of the Sb2Se3 film and promotes the in situ formation of the MoSe2 interlayer between Mo and Sb2Se3. These phenomena contribute to a back-surface field enhanced absorber layer and a quasi-Ohmic back contact, improving the device's VOC and the collection of carriers. This method provides an effective strategy for the orientation control of 1D materials for efficient photoelectric devices.

Nanostructured porous silicon films for terahertz optics.

A simple technique is reported to create 31 and 45 µm thick, graded-index Si films in the form of nanospirals on a Si substrate using a dynamic, oblique angle deposition technique. We show that the success in producing such a thick, nanostructured film without delamination from the Si substrate is primarily due to the nano-porous nature of the film which effectively eliminates the stress generated during growth. Effective refractive indices of 1.9 and 2.1 were extracted from the terahertz time-domain reflectivity data, which correspond to 57% and 51% porosity for the 31 and 45 µm thick films, respectively. The gradient of porosity through the film was modeled to describe quantitatively the terahertz reflectance data in the 0.2-2.0 THz regime.

Functionally strain-graded nanoscoops for high power Li-ion battery anodes.

Lithium-ion batteries show poor performance for high power applications involving ultrafast charging/discharging rates. Here we report a functionally strain-graded carbon-aluminum-silicon anode architecture that overcomes this drawback. It consists of an array of nanostructures each comprising an amorphous carbon nanorod with an intermediate layer of aluminum that is finally capped by a silicon nanoscoop on the very top. The gradation in strain arises from graded levels of volumetric expansion in these three materials on alloying with lithium. The introduction of aluminum as an intermediate layer enables the gradual transition of strain from carbon to silicon, thereby minimizing the mismatch at interfaces between differentially strained materials and enabling stable operation of the electrode under high-rate charge/discharge conditions. At an accelerated current density of ∼51.2 A/g (i.e., charge/discharge rate of ∼40C), the strain-graded carbon-aluminum-silicon nanoscoop anode provides average capacities of ∼412 mAh/g with a power output of ∼100 kW/kg(electrode) continuously over 100 charge/discharge cycles.

Mechanism for the formation of isolated poly(p-xylylene) fibrous structures under shadowing growth.

Because of the low sticking coefficient, conventional parylene deposition is known to achieve the conformal coating on corrugated or patterned surfaces. However, recently, it has been shown that in contrary to the conformal coating, extremely nonconformal and isolated fibrous parylene structures can be formed on surfaces if it is deposited at an oblique angle using a directional flux. We demonstrate that directional flux can create a high local vapor pressure facing the flux, while the reflection of monomers because of a small sticking coefficient would generate a background vapor pressure. The parylene oblique angle deposition is a combination of the shadowing growth and a much slower conformal coating process, which together give rise to the isolated fibrous structure.

Orientation-Controlled Large-Area Epitaxial PbI2 Thin Films with Tunable Optical Properties.

Lead iodide (PbI2) as a layered material has emerged as an excellent candidate for optoelectronics in the visible and ultraviolet regime. Micrometer-sized flakes synthesized by mechanical exfoliation from bulk crystals or by physical vapor deposition have shown a plethora of applications from low-threshold lasing at room temperature to high-performance photodetectors with large responsivity and faster response. However, large-area centimeter-sized growth of epitaxial thin films of PbI2 with well-controlled orientation has been challenging. Additionally, the nature of grain boundaries in epitaxial thin films of PbI2 remains elusive. Here, we use mica as a model substrate to unravel the growth mechanism of large-area epitaxial PbI2 thin films. The partial growth leading to uncoalesced domains reveals the existence of inversion domain boundaries in epitaxial PbI2 thin films on mica. Combining the experimental results with first-principles calculations, we also develop an understanding of the thermodynamic and kinetic factors that govern the growth mechanism, which paves the way for the synthesis of high-quality large-area PbI2 on other substrates and heterostructures of PbI2 on single-crystalline graphene. The ability to reproducibly synthesize high-quality large-area thin films with precise control over orientation and tunable optical properties could open up unique and hitherto unavailable opportunities for the use of PbI2 and its heterostructures in optoelectronics, twistronics, substrate engineering, and strain engineering.

Passive Microfluidic device for Sub Millisecond Mixing.

We report the investigation of a novel microfluidic mixing device to achieve submillisecond mixing. The micromixer combines two fluid streams of several microliters per second into a mixing compartment integrated with two T- type premixers and 4 butterfly-shaped in-channel mixing elements. We have employed three dimensional fluidic simulations to evaluate the mixing efficiency, and have constructed physical devices utilizing conventional microfabrication techniques. The simulation indicated thorough mixing at flow rate as low as 6 µL/s. The corresponding mean residence time is 0.44 ms for 90% of the particles simulated, or 0.49 ms for 95% of the particles simulated, respectively. The mixing efficiency of the physical device was also evaluated using fluorescein dye solutions and FluoSphere-red nanoparticles suspensions. The constructed micromixers achieved thorough mixing at the same flow rate of 6 µL/s, with the mixing indices of 96% ± 1%, and 98% ± 1% for the dye and the nanoparticle, respectively. The experimental results are consistent with the simulation data. The device demonstrated promising capabilities for time resolved studies for macromolecular dynamics of biological macromolecules.

Growth front smoothing effects in extremely high pressure vapor deposition.

Recent experimental chemical vapor depositions of silicon at extreme pressures of ~ 50 MPa (~ 500 atm) have been observed to generate remarkably smooth surfaces not predicted by low-pressure deposition models. In this paper, we propose an anti-shadowing mechanism where the collision of particles within the valleys of the surface growth front leads to smoothening. We conduct Monte Carlo simulations to simulate the evolution of film roughness at pressures between 1 and 50 MPa. We observe that surface roughness approaches an asymptotic invariant value that follows power law behavior as a function of pressure. The film thickness at which invariance begins is shown to have a similar power law behavior with respect to pressure. Our simulated results compare favorably with recent experimental observations and provide insight into the fundamental mechanisms underlying film evolution at pressures between one and hundreds of atmospheres.

High-Crystallinity Epitaxial Sb2Se3 Thin Films on Mica for Flexible Near-Infrared Photodetectors.

The V-VI binary chalcogenide, Sb2Se3, has attracted considerable attention for its applications in thin film optoelectronic devices because of its unique 1D structure and remarkable optoelectronic properties. Herein, we report an Sb2Se3 thin film epitaxially grown on a flexible mica substrate through a relatively weak (van der Waals) interaction by vapor transport deposition. The epitaxial Sb2Se3 thin films exhibit a single (120) out-of-plane orientation and a 0.25° full width at half-maximum of (120) rocking curve in X-ray diffraction, confirming the high crystallinity of the epitaxial films. The Sb2Se3(120) plane is epitaxially aligned on mica(001) surface with the in-plane relationship of Sb2Se3[2̅10]//mica[010] and Sb2Se3[001]//mica[100]. Compared to the photodetector made of a nonepitaxial Sb2Se3 film, the photocurrent of the epitaxial Sb2Se3 film photodetector is almost doubled. Furthermore, because of the flexibility and high sensitivity of the epitaxial Sb2Se3 film photodetector on mica, it has been successfully employed to detect the heart rate of a person. These encouraging results will facilitate the development of epitaxial Sb2Se3 film-based devices and potential applications in wearable electronics.