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.

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.

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.

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.

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.

A chiral switchable photovoltaic ferroelectric 1D perovskite.

Spin and valley degrees of freedom in materials without inversion symmetry promise previously unknown device functionalities, such as spin-valleytronics. Control of material symmetry with electric fields (ferroelectricity), while breaking additional symmetries, including mirror symmetry, could yield phenomena where chirality, spin, valley, and crystal potential are strongly coupled. Here we report the synthesis of a halide perovskite semiconductor that is simultaneously photoferroelectricity switchable and chiral. Spectroscopic and structural analysis, and first-principles calculations, determine the material to be a previously unknown low-dimensional hybrid perovskite (R)-(-)-1-cyclohexylethylammonium/(S)-(+)-1 cyclohexylethylammonium) PbI3. Optical and electrical measurements characterize its semiconducting, ferroelectric, switchable pyroelectricity and switchable photoferroelectric properties. Temperature dependent structural, dielectric and transport measurements reveal a ferroelectric-paraelectric phase transition. Circular dichroism spectroscopy confirms its chirality. The development of a material with such a combination of these properties will facilitate the exploration of phenomena such as electric field and chiral enantiomer-dependent Rashba-Dresselhaus splitting and circular photogalvanic effects.

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.

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.

Publisher Correction: Carrier lifetime enhancement in halide perovskite via remote epitaxy.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Carrier lifetime enhancement in halide perovskite via remote epitaxy.

Crystallographic dislocation has been well-known to be one of the major causes responsible for the unfavorable carrier dynamics in conventional semiconductor devices. Halide perovskite has exhibited promising applications in optoelectronic devices. However, how dislocation impacts its carrier dynamics in the 'defects-tolerant' halide perovskite is largely unknown. Here, via a remote epitaxy approach using polar substrates coated with graphene, we synthesize epitaxial halide perovskite with controlled dislocation density. First-principle calculations and molecular-dynamics simulations reveal weak film-substrate interaction and low density dislocation mechanism in remote epitaxy, respectively. High-resolution transmission electron microscopy, high-resolution atomic force microscopy and Cs-corrected scanning transmission electron microscopy unveil the lattice/atomic and dislocation structure of the remote epitaxial film. The controlling of dislocation density enables the unveiling of the dislocation-carrier dynamic relation in halide perovskite. The study provides an avenue to develop free-standing halide perovskite film with low dislocation density and improved carried dynamics.

Remote Phononic Effects in Epitaxial Ruddlesden-Popper Halide Perovskites.

Despite their weak nature, van der Waals (vdW) interactions have been shown to effectively control the optoelectronic and vibrational properties of layered materials. However, how vdW effects exist in Ruddlesden-Popper layered halide perovskites remains unclear. Here we reveal the role of interlayer vdW force in Ruddlesden-Popper perovskite in regulating phase-transition kinetics and carrier dynamics based on high-quality epitaxial single-crystalline (C4H9NH3)2PbI4 flakes with controlled dimensions. Both substrate-perovskite epitaxial interaction and interlayer vdW interaction play significant roles in suppressing the structural phase transition. With reducing flake thickness from ∼100 to ∼20 nm, electron-phonon coupling strength decreases by ∼30%, suggesting the ineffectiveness of phonon confinement of the natural quantum wells. Therefore, the conventional understanding that vdW perovskite is equivalent to a multiple quantum well has to be substantially amended due to significant nonlocal phononic effects in the layered crystal, where intralayer interaction is not drastically different from the interlayer force.

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.

Coherent Phonon Transport Measurement and Controlled Acoustic Excitations Using Tunable Acoustic Phonon Source in GHz-sub THz Range with Variable Bandwidth.

We experimentally demonstrated a narrowband acoustic phonon source with simultaneous tunabilities of the centre frequency and the spectral bandwidth in the GHz-sub THz frequency range based on photoacoustic excitation using intensity-modulated optical pulses. The centre frequency and bandwidth are tunable from 65 to 381 GHz and 17 to 73 GHz, respectively. The dispersion of the sound velocity and the attenuation of acoustic phonons in silicon dioxide (SiO2) and indium tin oxide (ITO) thin films were investigated using the acoustic phonon source. The sound velocities of SiO2 and ITO films were frequency-independent in the measured frequency range. On the other hand, the phonon attenuations of both of SiO2 and ITO films showed quadratic frequency dependences, and polycrystalline ITO showed several times larger attenuation than those in amorphous SiO2. In addition, the selective excitation of mechanical resonance modes was demonstrated in nanoscale tungsten (W) film using acoustic pulses with various centre frequencies and spectral widths.

van der Waals Epitaxy of Antimony Islands, Sheets, and Thin Films on Single-Crystalline Graphene.

Antimony (Sb) nanostructures, including islands, sheets, and thin films, of high crystallinity were epitaxially grown on single-crystalline graphene through van der Waals interactions. Two types of graphene substrates grown by chemical vapor deposition were used, the as-grown graphene on Cu(111)/ c-sapphire and the transferred graphene on SiO2/Si. On the as-grown graphene, deposition of ultrathin Sb resulted in two growth modes and associated morphologies of Sb. One was Sb islands grown in Volmer-Weber (VW) mode, and the other was Sb sheets grown in Frank-van der Merve (FM) mode. In contrast, only Sb islands grown in VW mode were found in a parallel growth experiment on the transferred graphene. The existence of Sb sheets on the as-grown graphene was attributed to the remote epitaxy between Sb and Cu underneath the graphene. In addition, Sb thin films were grown on both the as-grown and transferred graphene substrates. Both films indicated high quality, and no significant difference can be found between these two films. This work unveiled two epitaxial alignments between Sb(0001) and graphene, namely, Sb [101̅0]∥graphene [10] for Sb islands and Sb [21̅1̅0]∥graphene [10] for Sb sheets. For Sb thin films on graphene, the epitaxial alignment followed that of Sb islands, implying that Sb thin films originated from the continued growth of Sb islands. Last, Raman spectroscopy was used to probe the state of graphene under ultrathin Sb. No strain, doping, or disorder was found in the graphene postgrowth of Sb. The knowledge of the interface formation between ultrathin Sb and graphene provides a valuable foundation for future research on van der Waals heterostructures between antimonene and graphene.

Defect-engineered epitaxial VO2±Î´ in strain engineering of heterogeneous soft crystals.

The success of strain engineering has made a step further for the enhancement of material properties and the introduction of new physics, especially with the discovery of the critical roles of strain in the heterogeneous interface between two dissimilar materials (for example, FeSe/SrTiO3). On the other hand, the strain manipulation has been limited to chemical epitaxy and nanocomposites that, to a large extent, limit the possible material systems that can be explored. By defect engineering, we obtained, for the first time, dense three-dimensional strongly correlated VO2±Î´ epitaxial nanoforest arrays that can be used as a novel "substrate" for dynamic strain engineering, due to its metal-insulator transition. The highly dense nanoforest is promising for the possible realization of bulk strain similar to the effect of nanocomposites. By growing single-crystalline halide perovskite CsPbBr3, a mechanically soft and emerging semiconducting material, onto the VO2±Î´, a heterogeneous interface is created that can entail a ~1% strain transfer upon the metal-insulator transition of VO2±Î´. This strain is large enough to trigger a structural phase transition featured by PbX6 octahedral tilting along with a modification of the photoluminescence energy landscape in halide perovskite. Our findings suggest a promising strategy of dynamic strain engineering in a heterogeneous interface carrying soft and strain-sensitive semiconductors that can happen at a larger volumetric value surpassing the conventional critical thickness limit.

Utilizing van der Waals Slippery Interfaces to Enhance the Electrochemical Stability of Silicon Film Anodes in Lithium-Ion Batteries.

High specific capacity anode materials such as silicon (Si) are increasingly being explored for next-generation, high performance lithium (Li)-ion batteries. In this context, Si films are advantageous compared to Si nanoparticle based anodes since in films the free volume between nanoparticles is eliminated, resulting in very high volumetric energy density. However, Si undergoes volume expansion (contraction) under lithiation (delithiation) of up to 300%. This large volume expansion leads to stress build-up at the interface between the Si film and the current collector, leading to delamination of Si from the surface of the current collector. To prevent this, adhesion promotors (such as chromium interlayers) are often used to strengthen the interface between the Si and the current collector. Here, we show that such approaches are in fact counter-productive and that far better electrochemical stability can be obtained by engineering a van der Waals "slippery" interface between the Si film and the current collector. This can be accomplished by simply coating the current collector surface with graphene sheets. For such an interface, the Si film slips with respect to the current collector under lithiation/delithiation, while retaining electrical contact with the current collector. Molecular dynamics simulations indicate (i) less stress build-up and (ii) less stress "cycling" on a van der Waals slippery substrate as opposed to a fixed interface. Electrochemical testing confirms more stable performance and much higher Coulombic efficiency for Si films deposited on graphene-coated nickel (i.e., slippery interface) as compared to conventional nickel current collectors.

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.

Single-Crystal Graphene-Directed van der Waals Epitaxial Resistive Switching.

Graphene has been broadcasted as a promising choice of electrode and substrate for flexible electronics. To be truly useful in this regime, graphene has to prove its capability in ordering the growth of overlayers at an atomic scale, commonly known as epitaxy. Meanwhile, graphene as a diffusion barrier against atoms and ions has been shown in some metal-graphene-dielectric configurations for integrated circuits. Guided by these two points, this work explores a new direction of using graphene as a bifunctional material in an electrochemical metallization memory, where graphene is shown to (i) order the growth of a low-ionicity semiconductor ZnS single-crystalline film and (ii) regulate the ion migration in the resistive switching device made of Cu/ZnS/graphene/Cu structures. The ZnS film is confirmed to be van der Waals epitaxially grown on single-crystal graphene with X-ray structural analysis and Raman spectroscopy. Charge transport studies with controlled kinetic parameters reveal superior ion regulating characteristic of graphene in this ZnS-based resistive switching device. The demonstration of the first graphene-directed epitaxial wide band gap semiconductor resistive switching suggests a possible and promising route toward flexible memristors.