Mengjing Wang

Reversible Chemochromic MoO3 Nanoribbons through Zerovalent Metal Intercalation

Molybdenum trioxide (α-MoO3) is a 2D layered oxide with use in electrochromic and photochromic devices owing to its ability to reversibly change color between transparent and light blue with electrochemical or hydrogen intercalation. Despite its significant application potential, MoO3 performance is largely limited by the destructiveness of these intercalation techniques, insignificant coloration, and slow color response. We demonstrate a reversible chemochromic method, using intercalation of zerovalent metals into α-MoO3 nanoribbons (Sn, ∼2 at. %; Co, ∼4 at. %), to chemically alter MoO3 from transparent white to a deep blue indigo, resulting in enhanced coloration and chemically tunable optical properties. We present two strategies to reversibly tune the color response of MoO3 nanoribbons. Chromism can be reversed (i) by complete oxidative deintercalation with hydrogen peroxide or iodine or (ii) through a temperature-driven disorder-order phase transition of the intercalated zerovalent metal.

A Silicon-Based Two-Dimensional Chalcogenide: Growth of Si2Te3 Nanoribbons and Nanoplates

We report the synthesis of high-quality single-crystal two-dimensional, layered nanostructures of silicon telluride, Si2Te3, in multiple morphologies controlled by substrate temperature and Te seeding. Morphologies include nanoribbons formed by VLS growth from Te droplets, vertical hexagonal nanoplates through vapor-solid crystallographically oriented growth on amorphous oxide substrates, and flat hexagonal nanoplates formed through large-area VLS growth in liquid Te pools. We show the potential for doping through the choice of substrate and growth conditions. Vertical nanoplates grown on sapphire substrates, for example, can incorporate a uniform density of Al atoms from the substrate. We also show that the material may be modified after synthesis, including both mechanical exfoliation (reducing the thickness to as few as five layers) and intercalation of metal ions including Li(+) and Mg(2+), which suggests applications in energy storage materials. The material exhibits an intense red color corresponding to its strong and broad interband absorption extending from the red into the infrared. Si2Te3 enjoys chemical and processing compatibility with other silicon-based material including amorphous SiO2 but is very chemically sensitive to its environment, which suggests applications in silicon-based devices ranging from fully integrated thermoelectrics to optoelectronics to chemical sensors.

Dual Element Intercalation into 2D Layered Bi2Se3 Nanoribbons

We demonstrate the intercalation of multiple zero-valent atomic species into two-dimensional (2D) layered Bi2Se3 nanoribbons. Intercalation is performed chemically through a stepwise combination of disproportionation redox reactions, hydrazine reduction, or carbonyl decomposition. Traditional intercalation is electrochemical thus limiting intercalant guests to a single atomic species. We show that multiple zero-valent atoms can be intercalated through this chemical route into the host lattice of a 2D crystal. Intermetallic species exhibit unique structural ordering demonstrated in a variety of superlattice diffraction patterns. We believe this method is general and can be used to achieve a wide variety of new 2D materials previously inaccessible.

Polytypic phase transitions in metal intercalated Bi2Se3.

The temperature and concentration dependent phase diagrams of zero-valent copper, cobalt, and iron intercalated bismuth selenide are investigated using in situ transmission electron microscopy. Polytypic phase transitions associated with superlattice formation along with order-disorder transitions of the guest intercalant are determined. Dual-element intercalants of CuCo, CuFe, and CoFe-Bi2Se3 are also investigated. Hexagonal and striped domain formation consistent with two-dimensional ordering of the intercalant and Pokrovksy-Talapov theory is identified as a function of concentration. These studies provide a complete picture of the structural behavior of zero-valent metal intercalated Bi2Se3.

Temperature-driven disorder–order transitions in 2D copper-intercalated MoO3 revealed using dynamic transmission electron microscopy

We demonstrate two different classes of disorder–order phase transitions in two-dimensional layered nanomaterial MoO3 intercalated with ~9–15 atomic percent zero-valent copper using conventional in situ electron diffraction and dynamic transmission electron microscopy. Heating to ~325 °C on a time scale of minutes produces a superlattice consistent with the formation of a charge density wave stabilized by nanometer-scale ordering of the copper intercalant. Unlike conventional purely electronic charge-density-wave states which form, reform, and disappear on picosecond scales as the temperature is changed, once it forms the observed structure in Cu–MoO3 is stable indefinitely over a very large temperature range (30 °C to the decomposition temperature of 450 °C). Nanosecond-scale heating to ~380–400 °C produced a completely different structure, replacing the disordered as-fabricated Cu–MoO3 with a much more crystallographically ordered metastable state that, according to a precession electron diffraction reconstruction, resembles the original MoO3 lattice apart from an asymmetric distortion that appears to expand parts of the van der Waals gaps to accommodate the copper intercalant. Control experiments in Cu-free material exhibited neither transformation, thus it appears the copper is a necessary part of the phase dynamics. This work shows how the combination of high-density metal atom intercalation and heat treatment over a wide range of time scales can produce nanomaterials of high crystalline quality in unique structural states that cannot be accessed through other methods.

Ultrafast zero-bias photocurrent in GeS nanosheets

We have observed emission of terahertz radiation from photoexcited GeS nanosheets without external bias. We attribute the origin of terahertz pulse emission to the shift current resulting from inversion symmetry breaking in ferroelectric single- or few-layer GeS nanosheets. We find that the direction of the shift current, and the corresponding polarity of the emitted THz pulses is determined by the spontaneous polarization in the ferroelectric GeS nanosheets. Experimental observation of zero-bias photocurrents puts GeS nanosheets forth as a promising candidate material for applications in third generation photovoltaics based on shift current, or bulk photovoltaic effect.

Terahertz emission from 2D nanomaterials

Group-IV monochalcogenides belong to a family of 2D layered materials. Monolayers of group-IV monochalcogenides GeS, GeSe, SnS and SnSe have been theoretically predicted to exhibit a large shift current owing to a spontaneous electric polarization at room temperature. Using THz emission spectroscopy, we find that above band gap photoexcitation with ultrashort laser pulses results in emission of nearly single-cycle THz pulses due to a surface shift current in multi-layer, sub-μm to few- μm thick GeS and GeSe, as inversion symmetry breaking at the crystal surface enables THz emission by the shift current. Experimental demonstration of THz emission by the surface shift current puts this layered group-IV monochalcogenides forward as a candidate for next generation shift current photovoltaics, nonlinear photonic devices and THz sources.

Chemically Tunable Full Spectrum Optical Properties of 2D Silicon Telluride Nanoplates

Silicon telluride (Si2Te3) is a two-dimensional, layered, p-type semiconductor that shows broad near-infrared photoluminescence. We show how, through various means of chemical modification, Si2Te3 can have its optoelectronic properties modified in several independent ways without fundamentally altering the host crystalline lattice. Substitutional doping with Ge strongly red-shifts the photoluminescence while substantially lowering the direct and indirect band gaps and altering the optical phonon modes. Intercalation with Ge introduces a sharp 4.3 eV ultraviolet resonance and shifts the bulk plasmon even while leaving the infrared response and band gaps virtually unchanged. Intercalation with copper strengthens the photoluminescence without altering its spectral shape. Thus, silicon telluride is shown to be a chemically tunable platform of full spectrum optical properties promising for optoelectronic applications.