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.

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.

Diffusion-Controlled Epitaxy of Large Area Coalesced WSe2 Monolayers on Sapphire.

A multistep diffusion-mediated process was developed to control the nucleation density, size, and lateral growth rate of WSe2 domains on c-plane sapphire for the epitaxial growth of large area monolayer films by gas source chemical vapor deposition (CVD). The process consists of an initial nucleation step followed by an annealing period in H2Se to promote surface diffusion of tungsten-containing species to form oriented WSe2 islands with uniform size and controlled density. The growth conditions were then adjusted to suppress further nucleation and laterally grow the WSe2 islands to form a fully coalesced monolayer film in less than 1 h. Postgrowth structural characterization demonstrates that the WSe2 monolayers are single crystal and epitaxially oriented with respect to the sapphire and contain antiphase grain boundaries due to coalescence of 0° and 60° oriented WSe2 domains. The process also provides fundamental insights into the two-dimensional (2D) growth mechanism. For example, the evolution of domain size and cluster density with annealing time follows a 2D ripening process, enabling an estimate of the tungsten-species surface diffusivity. The lateral growth rate of domains was found to be relatively independent of substrate temperature over the range of 700-900 °C suggesting a mass transport limited process, however, the domain shape (triangular versus truncated triangular) varied with temperature over this same range due to local variations in the Se/W adatom ratio. The results provide an important step toward atomic level control of the epitaxial growth of WSe2 monolayers in a scalable process that is suitable for large area device fabrication.

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.

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.

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.

Metal-Insulator Transition of Single-Crystal V2O3 through van der Waals Interface Engineering.

Strongly correlated electron materials harbor interesting materials physics, such as high-Tc superconductivity, colossal magnetoresistance, and metal-insulator transition. These physical properties can be greatly influenced by the dimensionality and geometry of the hosting materials and their interaction strengths with underlying substrates. In a classic strongly correlated oxide vanadium sesquioxide (V2O3), the coexistence of a metal-insulator and paramagnetic-antiferromagnetic transitions at ∼150 K makes this material an excellent platform for exploring basic physics and developing future devices. So far, most studies have been focused on epitaxial thin films in which the strongly coupled substrate has a pronounced effect on V2O3, leading to the observations of intriguing phenomena and physics. In this work, we unveil the kinetics of a metal-insulator transition of V2O3 single-crystal sheets at nano and micro scales. We show the presence of triangle-like alternating metal/insulator phase patterns during phase transition, which is drastically different from the epitaxial film. The observation of single-stage metal-insulator transition in V2O3/graphene compared to the multistage in V2O3/SiO2 evidence the importance of sheet-substrate coupling. Harnessing the freestanding form of the V2O3 sheet, we show that the phase transition of V2O3 sheet can generate a large dynamic strain to monolayer MoS2 and tune its optical property based on the MoS2/V2O3 hybrid structure. The demonstration of the capability in tuning phase transition kinetics and phase patterns using designed hybrid structure of varied sheet-substrate coupling strengths suggests an effective knob in the design and operation of emerging Mott devices.

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.

Air stability of low-temperature dehydrogenation of Pd-decorated Mg blades.

We demonstrated that Pd-decorated Mg blades are air-stable for hydrogen storage with a low desorption temperature of 373 K. Pd-catalyst-decorated Mg blades were prepared by 64° oblique incident angle thermal deposition on a rotatable substrate with the rotation axis perpendicular to the substrate. The hydrogen desorption from Pd-decorated Mg blades was performed and recorded by temperature-programmed desorption (TPD) for repeated hydrogenation­dehydrogenation cycles. The near-surface structural and compositional changes were characterized in situ by reflection high energy electron diffraction (RHEED). The Mg blades were intentionally exposed to air at elevated temperatures (333 or 358 K) between certain cycles. It was found that the degradation of the storage capacity was affected weakly by the air exposure at moderate temperatures. The kinetics of the hydrogen desorption was sensitive to air exposure but recoverable through a replenishment of fresh catalyst Pd on the surface of the oxidized Mg blades.

Flexo-photovoltaic effect in MoS2.

The theoretical Shockley-Queisser limit of photon-electricity conversion in a conventional p-n junction could be potentially overcome by the bulk photovoltaic effect that uniquely occurs in non-centrosymmetric materials. Using strain-gradient engineering, the flexo-photovoltaic effect, that is, the strain-gradient-induced bulk photovoltaic effect, can be activated in centrosymmetric semiconductors, considerably expanding material choices for future sensing and energy applications. Here we report an experimental demonstration of the flexo-photovoltaic effect in an archetypal two-dimensional material, MoS2, by using a strain-gradient engineering approach based on the structural inhomogeneity and phase transition of a hybrid system consisting of MoS2 and VO2. The experimental bulk photovoltaic coefficient in MoS2 is orders of magnitude higher than that in most non-centrosymmetric materials. Our findings unveil the fundamental relation between the flexo-photovoltaic effect and a strain gradient in low-dimensional materials, which could potentially inspire the exploration of new optoelectronic phenomena in strain-gradient-engineered materials.

Tunable 2D Group-III Metal Alloys.

Chemically stable quantum-confined 2D metals are of interest in next-generation nanoscale quantum devices. Bottom-up design and synthesis of such metals could enable the creation of materials with tailored, on-demand, electronic and optical properties for applications that utilize tunable plasmonic coupling, optical nonlinearity, epsilon-near-zero behavior, or wavelength-specific light trapping. In this work, it is demonstrated that the electronic, superconducting, and optical properties of air-stable 2D metals can be controllably tuned by the formation of alloys. Environmentally robust large-area 2D-Inx Ga1- x alloys are synthesized byConfinement Heteroepitaxy (CHet). Near-complete solid solubility is achieved with no evidence of phase segregation, and the composition is tunable over the full range of x by changing the relative elemental composition of the precursor. The optical and electronic properties directly correlate with alloy composition, wherein the dielectric function, band structure, superconductivity, and charge transfer from the metal to graphene are all controlled by the indium/gallium ratio in the 2D metal layer.

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.

Vanadium disulfide flakes with nanolayered titanium disulfide coating as cathode materials in lithium-ion batteries.

Unlike the vast majority of transition metal dichalcogenides which are semiconductors, vanadium disulfide is metallic and conductive. This makes it particularly promising as an electrode material in lithium-ion batteries. However, vanadium disulfide exhibits poor stability due to large Peierls distortion during cycling. Here we report that vanadium disulfide flakes can be rendered stable in the electrochemical environment of a lithium-ion battery by conformally coating them with a ~2.5 nm thick titanium disulfide layer. Density functional theory calculations indicate that the titanium disulfide coating is far less susceptible to Peierls distortion during the lithiation-delithiation process, enabling it to stabilize the underlying vanadium disulfide material. The titanium disulfide coated vanadium disulfide cathode exhibits an operating voltage of ~2 V, high specific capacity (~180 mAh g-1 @200 mA g-1 current density) and rate capability (~70 mAh g-1 @1000 mA g-1), while achieving capacity retention close to 100% after 400 charge-discharge steps.

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.

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.

Revealing the Crystalline Integrity of Wafer-Scale Graphene on SiO2/Si: An Azimuthal RHEED Approach.

The symmetry of graphene is usually determined by a low-energy electron diffraction (LEED) method when the graphene is on the conductive substrates, but LEED cannot handle graphene transferred to SiO2/Si substrates due to the charging effect. While transmission electron microscopy can generate electron diffraction on post-transferred graphene, this method is too localized. Herein, we employed an azimuthal reflection high-energy electron diffraction (RHEED) method to construct the reciprocal space mapping and determine the symmetry of wafer-size graphene both pre- and post-transfer. In this work, single-crystalline Cu(111) films were prepared on sapphire(0001) and spinel(111) substrates with sputtering. Then the graphene was epitaxially grown on single-crystalline Cu(111) films with a low pressure chemical vapor deposition. The reciprocal space mapping using azimuthal RHEED confirmed that the graphene grown on Cu(111) films was single-crystalline, no matter the form of the monolayer or multilayer structure. While the Cu(111) film grown on sapphire(0001) may occasionally consist of 60° in-plane rotational twinning, the reciprocal space mapping revealed that the in-plane orientation of graphene grown atop was not affected. The proposed method for checking the crystalline integrity of the post-transferred graphene sheets is an important step in the realization of the graphene as a platform to fabricate electronic and optoelectronic devices.

Biaxially textured Al film growth on CaF2 nanostructures toward a method of preparing single-crystalline Si film on glass substrates.

We report the room temperature growth of biaxially textured Al films and further demonstrate the use of these Al films in preparing single-crystalline Si layers on glass substrates. The formation of the biaxial texture in Al film relies on the existence of the CaF(2) buffer layer prepared using oblique angle physical vapor deposition, which consists of single-crystalline nanorods with caps that are in the form of inverted nanopyramids. The single-crystalline Si film was obtained upon crystallization of the amorphous Si film deposited through physical evaporation on the biaxially textured Al film. This method of preparing single-crystalline Si film on glass substrate is potentially attractive for being employed in silicon technology and in fabrication of low-cost electronic devices.