α-MoO3 Crystals Research Articles

Building nanoplatelet α-MoO3 films: A high quality crystal anisotropic 2D material for integration

The successful development of nanoplatelet α-MoO3 −films with wavelength-dependent in-plane and out-of-plane birefringence both in the visible and in the medium infrared is demonstrated. The films are prepared by a two-step process starting from structurally amorphous and continuous substoichiometric MoO3-X followed by isothermal annealing at low temperature (250 °C) to yield the formation of a dense network of large α-MoO3 2D nanoplatelets lying in-plane with no overlapping. These α-MoO3 crystals form a film with excellent thickness uniformity (20 nm) and are oriented with the [010] crystallographic direction parallel to the substrate normal. Finally, we report the film anisotropic optical complex refractive index, both parallel and perpendicular to the plane the full spectral range from 0.7 to 5 eV as determined by spectroscopic ellipsometry, and their characteristic in-plane phonon mode in the IR from FTIR measurements. These results show a promising pathway to the creation of highly functional anisotropic α-MoO3 2D films suitable for the development of integrated nanostructured photonic components.

Ultrafast In-Situ synthesis of flexible MoO3 anode in five seconds for High-Performance aqueous zinc ion hybrid capacitor

The efficient synthesis of high-performance α-MoO3 on flexible conductive substrates is crucial for enhancing its value in the field of energy storage. However, traditional synthesis methods currently employed often suffer from slow heating rates, intricate reaction processes involving multiple steps, sluggish reaction kinetics, high energy consumption, and prolonged preparation times, thereby hindering efficient production. Presented herein is a facile, ultrafast, and versatile approach utilizing microwave carbon thermal shock, a one-step reaction synthesis of α-MoO3 on carbon substrates within 5 s. During microwave carbon thermal shock, the precursor salt experiences an extremely rapid heating rate, swiftly decomposing to form small-sized α-MoO3 crystals. Simultaneously, this process promotes the oxidation of adjacent carbon sites, thereby imparting multi-scale defects and oxygen-containing functional groups to the resulting carbon cloth (CC). The exceptionally low reaction energy barriers and superior Gibbs free energy (ΔG) further substantiate the advantages of the microwave carbon thermal shock strategy over traditional synthesis methods in terms of both kinetics and thermodynamics. The air-assisted transient microwave carbonthermal shock (AMCTS) process circumvents high energy requirements, multistep reactions, and extended preparation times, endowing AMCTS-CC@MoO3 with remarkable flexibility and processability. In demonstrating its practical utility within zinc-ion hybrid micro capacitors, it exhibits outstanding specific capacitance (up to 2300mF cm−2) and mechanical stability. This air-assisted transient microwave thermal shock process provides an efficient route for ultrafast and low-cost synthesis of flexible zinc-ion anode materials.

Structure and photoluminescence of α-MoO3:Eu3+ microbelts

Phosphors of α-MoO3 with varying concentrations of Eu activator emitting an orange–red color were synthesized using a conventional solid-state reaction. The sintered pellets consisted of microbelts with a wide size distribution. The surface morphology became rough with an increase in the sintering temperature, which was attributed to a higher proportion of large and transparent nonluminous microbelts under ultraviolet light. Photoluminescence of 1 at.% Eu-doped α-MoO3 pellet sintered at 710 °C exhibited the strongest intensity. Ultrasonic vibrations caused the disruption of interlayer bonding and fragmentation in the horizontal direction of the α-MoO3 crystals, resulting in smaller belts with a thickness of 10–20 nm. The finely fragmented Eu-doped α-MoO3 microbelts dispersed in water retained luminescent properties under ultraviolet light with a wavelength of 254 nm. The report on the fabrication of emitting α-MoO3 micro/nanobelts through sintering and subsequent ultrasonication is promising for developing low-cost and large-area optical devices.

Anisotropic mechanical properties of α-MoO3 nanosheets.

The mechanical behaviors of 2D materials are fundamentally important for their potential applications in various fields. α-Molybdenum trioxide (α-MoO3) crystals with unique electronic, optical, and electrochemical properties, have attracted extensive attention for their use in optoelectronic and energy conversion devices. From a mechanical viewpoint, however, there is limited information available on the mechanical properties of α-MoO3. Here, we developed a capillary force-assisted peeling method to directly transfer α-MoO3 nanosheets onto arbitrary substrates. Comparatively, we could effectively avoid surface contamination arising from the polymer-assisted transfer method. Furthermore, with the help of an in situ push-to-pull (PTP) device during SEM, we systematically investigated the tensile properties of α-MoO3. The measured Young's modulus and fracture strengths along the c-axis (91.7 ± 13.7 GPa and 2.1 ± 0.9 GPa, respectively) are much higher than those along the a-axis (55.9 ± 8.6 GPa and 0.8 ± 0.3 GPa, respectively). The in-plane mechanical anisotropy ratio can reach ∼1.64. Both Young's modulus and the fracture strength of MoO3 show apparent size dependence. Additionally, the multilayer α-MoO3 nanosheets exhibited brittle fracture with interplanar sliding due to poor van der Waals interaction. Our study provides some key points regarding the mechanical properties and fracture behavior of layered α-MoO3 nanosheets.

Unique ghost surface phonon polaritons in biaxially hyperbolic materials.

We predicted peculiar ghost surface phonon polaritons in biaxially hyperbolic materials, where the two hyperbolic principal axes lie in the plane of propagation. We took the biaxially-hyperbolic α-MoO3 as one example of the materials to numerically simulate the ghost surface phonon polaritons. We found three unique ghost surface polaritons to appear in three enclosed wavenumber-frequency regions, respectively. These ghost surface phonon polaritons have different features from the surface phonon polaritons found previously, i.e., they are some hybrid-polarization surface waves composed of two coherent evanescent branch-waves in the α-MoO3 crystal. The interference of branch-waves leads to that their Poynting vector and electromagnetic fields both exhibit the oscillation-attenuation behavior along the surface normal, or a series of rapidly attenuated fringes. We found that the in-plane hyperbolic anisotropy and low-symmetric geometry of surface are the two necessary conditions for the existence of these ghost surface polaritons.

Investigating the effect of H+-ion irradiation on layered α-MoO3 flakes by defect engineering

Ion irradiation is a versatile and convenient tool for modifying the optical, electrical, and catalytic properties of two-dimensional (2D) materials through controlled induction of impurities and defects. The behavior of 2D materials under ion irradiation is interesting, which needs to be explored in the contest of their optoelectronic applications. In the present work, we have reported the effect of H+-ion irradiation on layered α-MoO3 flakes by defect engineering. Initially, the α-MoO3 crystals were synthesized using the physical vapor deposition technique followed by mechanical exfoliation of an as-grown crystal to obtain α-MoO3 flakes of different thicknesses. Then, the exfoliated flakes were exposed to H+-ion/proton irradiation with a fluence of 1 × 1016 ions/cm2 using a 30 keV source. After irradiation, new photoluminescence (PL) emission peaks were observed at different positions in the range of ∼2.4–1.9 eV, which was found to be absent in pristine flakes. Raman studies revealed non-uniform oxygen vacancy distribution in H+-ion irradiated α-MoO3 flakes, which affected the PL peak positions. Additionally, first-principle calculations and Bader charge analysis were performed to identify the origin of the new PL peaks. Our findings indicate that oxygen vacancies positioning at different locations of the α-MoO3 lead to the emergence of new absorption peaks within the range of ∼2.2–1.25 eV, which is consistent with our experimental findings. The present study gives insight into exploring the use of ion-irradiated α-MoO3 in optoelectronics applications with tunable properties.

Twist-tunable polaritonic nanoresonators in a van der Waals crystal

Optical nanoresonators are key building blocks in various nanotechnological applications (e.g., spectroscopy) due to their ability to effectively confine light at the nanoscale. Recently, nanoresonators based on phonon polaritons (PhPs)—light coupled to lattice vibrations—in polar crystals (e.g., SiC, or h-BN) have attracted much attention due to their strong field confinement, high quality factors, and their potential to enhance the photonic density of states at mid-infrared (mid-IR) frequencies, where numerous molecular vibrations reside. Here, we introduce a new class of mid-IR nanoresonators that not only exhibit the extraordinary properties previously reported, but also incorporate a new degree of freedom: twist tuning, i.e., the possibility of controlling their spectral response by simply rotating the constituent material. To achieve this result, we place a pristine slab of the van der Waals (vdW) α-MoO3 crystal, which supports in-plane hyperbolic PhPs, on an array of metallic ribbons. This sample design based on electromagnetic engineering, not only allows the definition of α-MoO3 nanoresonators with low losses (quality factors, Q, up to 200), but also enables a broad spectral tuning of the polaritonic resonances (up to 32 cm−1, i.e., up to ~6 times their full width at half maximum, FWHM ~5 cm−1) by a simple in-plane rotation of the same slab (from 0 to 45°). These results open the door to the development of tunable and low-loss IR nanotechnologies, fundamental requirements for their implementation in molecular sensing, emission or photodetection applications.

Launching and Manipulation of Higher-Order In-Plane Hyperbolic Phonon Polaritons in Low-Dimensional Heterostructures.

Hyperbolic phonon polaritons (HPhPs) are stimulated by coupling infrared (IR) photons with the polar lattice vibrations. Such HPhPs offer low-loss, highly confined light propagation at subwavelength scales with out-of-plane or in-plane hyperbolic wavefronts. For HPhPs, while a hyperbolic dispersion implies multiple propagating modes with a distribution of wavevectors at a given frequency, so far it has been challenging to experimentally launch and probe the higher-order modes that offer stronger wavelength compression, especially for in-plane HPhPs. In this work, the experimental observation of higher-order in-plane HPhP modes stimulated on a 3C-SiC nanowire (NW)/α-MoO3 heterostructure is reported where leveraging both the low-dimensionality and low-loss nature of the polar NWs, higher-order HPhPs modes within 2D α-MoO3 crystal are launched by the 1D 3C-SiC NW. The launching mechanism is further studied and the requirements for efficiently launching of such higher-order modes are determined. In addition, by altering the geometric orientation between the 3C-SiC NW and α-MoO3 crystal, the manipulation of higher-order HPhP dispersions as a method of tuning is demonstrated. This work illustrates an extremely anisotropic low dimensional heterostructure platform to confine and configure electromagnetic waves at the deep-subwavelength scales for a range of IR applications including sensing, nano-imaging, and on-chip photonics.

Trisodium citrate assisted morphological evolution of α-MoO3 via a facile hydrothermal route and its application to improve the corrosion resistance of zinc coating

ABSTRACT A facile trisodium citrate-assisted hydrothermal route was demonstrated for the synthesis of α-MoO3 nanostructures. Trisodium citrate concentration-dependent morphological evolution of α-MoO3 was achieved in hydrothermal process. The morphological evolution from nanorods to nanoplates was observed with increase in trisodium citrate concentration, owing to its shape directing effect by hindering the growth of α-MoO3 crystal along [001] direction. The time-dependent hydrothermal experimental results suggested that the formation and growth of α-MoO3 nanorods proceed through ‘Ostwald ripening-splitting’ mechanism. The synthesised α-MoO3 nanorods were successfully used to produce Zn – α-MoO3 coatings on mild steel using an acid sulphate bath, and the corrosion behaviour of the generated coatings was also investigated.

Embedding Co in perovskite MoO3 for superior catalytic oxidation of refractory organic pollutants with peroxymonosulfate

A cobalt (Co)-doped perovskite molybdenum trioxide (α-MoO3) catalyst (Co-MO) was synthesized by a facile pyrolysis strategy and used for degrading various organic contaminants via peroxymonosulfate (PMS) activation. The doped Co was inserted in the inter space between the octahedron [MoO6], facilitating the growth of the α-MoO3 crystal on the [010] direction. This unique structure accelerated the activation of PMS as the Co-MO could function as a carrier for electron transfer to facilitate the Co(II)/Co(III) cycle in the Co-MO/PMS system. As a result, the Co-MO/PMS system showed noticeable activity for removing 100% bisphenol A (BPA) under a broad conditions within 30 min. The radical quenching test and electron paramagnetic resonance analysis revealed that singlet oxygen (1O2) was the main active species for BPA degradation in the Co-MO/PMS system, while free radicals, such as O2•-, SO4•- and •OH, were also produced as the intermediate species. Furthermore, the carrier mechanism may enable the Co-MO/PMS system maintain relatively high performance during repeat use, and also excellent adaptability was revealed by the well function in various water matrices and high activity in degrading various refractory organic pollutants. Our findings pave a useful avenue for the rational design of novel cobalt-doped catalysts with high catalytic performance toward wide environmental applications.

Origins and cavity-based regulation of optical anisotropy of α-MoO3 crystal

Orthogonal α-MoO3 is one of the most common and air-stable compounds of molybdenum, holding the merits of wide bandgap, van der Waals (vdW) structure, biaxial symmetry and recently discovered hyperbolic topological transitions, which has drawn significant attention in developing novel nanophotonic and optoelectronic devices. Herein the broadband optical anisotropy, one of the most fundamental physical characteristics of α-MoO3 crystal, was systematically investigated using a combination of spectroscopic ellipsometry (SE) and reflectance difference spectroscopy (RDS). The centimeter-level high-quality α-MoO3 crystal was grown by modified physical vapor deposition. The optical refractive indices along three crystalline axes were precisely determined by SE in the broad spectral range (400–1600 nm), and then the in-plane and out-plane birefringence was analyzed. Both the intrinsic and resonant cavity modulated optical anisotropy of α-MoO3 was studied by polarization-resolved RDS, from which we find the physical origins of linear dichroism are dominated by electronical transitions along the c-axis. Furthermore, the external photonic cavity of SiO2 enables enhanced sensitivity to view electronical transitions and a high modulation ratio of optical anisotropy reached 30, which provides new opportunities to tune optical anisotropy for polarized photonic devices. Our results can help understand the physical origin of the highly optical anisotropy of α-MoO3 and establish an effective metrological tool to study other types of vdW crystals.

Real-space nanoimaging of hyperbolic shear polaritons in a monoclinic crystal.

Various optical crystals possess permittivity components of opposite signs along different principal directions in the mid-infrared regime, exhibiting exotic anisotropic phonon resonances. Such materials with hyperbolic polaritons-hybrid light-matter quasiparticles with open isofrequency contours-feature large-momenta optical modes and wave confinement that make them promising for nanophotonic on-chip technologies. So far, hyperbolic polaritons have been observed and characterized in crystals with high symmetry including hexagonal (boron nitride), trigonal (calcite) and orthorhombic (α-MoO3 or α-V2O5) crystals, where they obey certain propagation patterns. However, lower-symmetry materials such as monoclinic crystals were recently demonstrated to offer richer opportunities for polaritonic phenomena. Here, using scanning near-field optical microscopy, we report the direct real-space nanoscale imaging of symmetry-broken hyperbolic phonon polaritons in monoclinic CdWO4 crystals, and showcase inherently asymmetric polariton excitation and propagation associated with the nanoscale shear phenomena. We also introduce a quantitative theoretical model to describe these polaritons that leads to schemes to enhance crystal asymmetry via the damping loss of phonon modes. Ultimately, our findings show that polaritonic nanophotonics is attainable using natural materials with low symmetry, favouring a versatile and general way to manipulate light at the nanoscale.

Oxygen vacancies in oxidized and reduced vertically aligned α-MoO3 nanoblades

Oxidation states of MoO3 alter the electronic properties by several orders of magnitude. Oxygen vacancy-mediated intrinsic defects in vertically aligned α-MoO3 crystals are systematically tuned and their impact on optoelectronic properties analyzed.

Long-Lived Phonon Polaritons in Hyperbolic Materials.

Natural hyperbolic materials with dielectric permittivities of opposite signs along different principal axes can confine long-wavelength electromagnetic waves down to the nanoscale, well below the diffraction limit. Confined electromagnetic waves coupled to phonons in hyperbolic dielectrics including hexagonal boron nitride (hBN) and α-MoO3 are referred to as hyperbolic phonon polaritons (HPPs). HPP dissipation at ambient conditions is substantial, and its fundamental limits remain unexplored. Here, we exploit cryogenic nanoinfrared imaging to investigate propagating HPPs in isotopically pure hBN and naturally abundant α-MoO3 crystals. Close to liquid-nitrogen temperatures, losses for HPPs in isotopic hBN drop significantly, resulting in propagation lengths in excess of 8 μm, with lifetimes exceeding 5 ps, thereby surpassing prior reports on such highly confined polaritonic modes. Our nanoscale, temperature-dependent imaging reveals the relevance of acoustic phonons in HPP damping and will be instrumental in mitigating such losses for miniaturized mid-infrared technologies operating at liquid-nitrogen temperatures.

Structural evolutions of layered α-MoO3 crystals during rapid thermal annealing upon Pb-species at elevated temperatures

Structural evolutions of layered α-MoO3 crystals during rapid thermal annealing upon Pb-species at elevated temperatures

Chemical switching of low-loss phonon polaritons in \u03b1-MoO3 by hydrogen intercalation

Phonon polaritons (PhPs) have attracted significant interest in the nano-optics communities because of their nanoscale confinement and long lifetimes. Although PhP modification by changing the local dielectric environment has been reported, controlled manipulation of PhPs by direct modification of the polaritonic material itself has remained elusive. Here, chemical switching of PhPs in α-MoO3 is achieved by engineering the α-MoO3 crystal through hydrogen intercalation. The intercalation process is non-volatile and recoverable, allowing reversible switching of PhPs while maintaining the long lifetimes. Precise control of the intercalation parameters enables analysis of the intermediate states, in which the needle-like hydrogenated nanostructures functioning as in-plane antennas effectively reflect and launch PhPs and form well-aligned cavities. We further achieve spatially controlled switching of PhPs in selective regions, leading to in-plane heterostructures with various geometries. The intercalation strategy introduced here opens a relatively non-destructive avenue connecting infrared nanophotonics, reconfigurable flat metasurfaces and van der Waals crystals.

Recycling Molybdenum from Direct Coal Liquefaction Residue: A New Approach to Enhance Recycling Efficiency

In this paper, direct coal liquefaction residue was prepared from Shen-dong coal, and the solubility of the residue in five organic solvents was studied. Then, an experimental device was set up to recover molybdenum (Mo) compounds from the direct coal liquefaction residue after extraction, and the influences of sublimation temperature and duration on recycling efficiency were examined. The recycled Mo-based products were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), and a thermal analyzer. The results reveal that the optimum extraction conditions were obtained through ultrasonic extraction with a quinoline solvent and the highest recycling efficiency occurred for sublimation at 900 °C for 30 min. The recycled products are identified to be α-MoO3 crystals. Moreover, the α-MoO3 crystal is thermally stable before the temperature reaches its melting point.

Synthesis of lustering two-dimensional α-MoO3 van der Waals crystals by TiO2 assisted selective facet passivation

Large-sized α-MoO3 nanoplates with 10−100 μm were synthesized by introduction of titanium tetra isopropoxide as TiO2 precursor in hydrothermal solution chemistry. During the hydrothermal synthesis, the TiO2 can be selectively deposited on the (001) facets of h-MoO3 hexagonal rods and on the (001) and/or (010) facet of α-MoO3 re-growing crystals due to the small lattice mismatch between them. Owing to the TiO2 passivation of the surface of h-MoO3 rods, the h-MoO3 rods are changed to MoO3 tubes because the h-MoO3 are dissolved from the inner part of the TiO2 passivated h-MoO3 rods. The TiO2-passivated (001) facets of h-MoO3 rods act as templates for the re-growth of α-MoO3 and consequently produced rectangle-shaped α-MoO3 nanoplates. Simultaneously, the TiO2 passivated on the (001) and/or (010) facet of the re-growing α-MoO3 crystals inhibits the preferred crystal growth to [001] direction and promoted the crystal growth to [100] direction, thereby yielding plate-shaped α-MoO3. The small α-MoO3 nanoplates and rectangle-shaped ones are further grown to larger nanoplates by attachment process and/or continuous growth.

One-step synthesis of centimeter-size alpha-MoO3 with single crystallinity

By utilizing the convenient physical vapor deposition procedure, a simple and low-cost synthesis route is developed to fabricate high-quality orthorhombic MoO3 crystals with single crystallinity and significant size (bigger than 10 mm × 10 mm2). A combined characterization techniques of atomic force microscopy, X-ray photoelectron spectroscopy, synchrotron-based X-ray diffraction and Raman spectroscopy confirm the high quality of α-MoO3 crystal from the point view of both electronic and physical structures. Compared to previous reports in literature, we demonstrate herein a rather simplified one-step approach with only the MoO3 powder needed. In the end, corresponding electrochromic performance has also been tested which reveals high transmittance and remarkable optical properties which may broadens the potential applications of MoO3 single crystal in nanosensors, nanoelectronics and so on.

New Insights into Planar Defects in Layered α-MoO3 Crystals.

The observation of regular ( h0 l) planar defects in α-MoO3 crystals can be traced back to over 60 years ago. Two mechanisms have been proposed to interpret the formation of the planar defects. One is related to the diffusion of oxygen vacancies because of thermal-driven release of oxygen atoms in vacuum and the consequent crystallographic shear of α-MoO3. The other is associated with redox reactions of moisture and/or hydrocarbons that give rise to H xMoO3 precipitates. Here, we report that regularly spaced (302) planar defects can be introduced into α-MoO3 belt crystals by heating in liquid sulfur at 300 °C. These defects are undetectable by both atomic force microscopy and scanning electron microscopy at the crystal surface. Raman scattering enhancement and weakening have been observed for different phonon modes of α-MoO3 at the (302) planar defects as probed from the (010) surface. Their comparisons with the Raman scattering enhancements at the edges and the argon-plasma-induced Raman spectral evolutions of the as-grown α-MoO3 belt crystals provide new insights into the planar defects with regard to their formation and characteristics.