Highly Confined and Tunable Hyperbolic Phonon Polaritons in Van Der Waals Semiconducting Transition Metal Oxides

2D van der Waals (vdW) layered polar crystals sustaining phonon polaritons (PhPs) have opened up new avenues for fundamental research and optoelectronic applications in the mid‐infrared to terahertz ranges. To date, 2D vdW crystals with PhPs are only experimentally demonstrated in hexagonal boron nitride (hBN) slabs. For optoelectronic and active photonic applications, semiconductors with tunable charges, finite conductivity, and moderate bandgaps are preferred. Here, PhPs are demonstrated with low loss and ultrahigh electromagnetic field confinements in semiconducting vdW α‐MoO₃. The α‐MoO₃ supports strong hyperbolic PhPs in the mid‐infrared range, with a damping rate as low as 0.08. The electromagnetic confinements can reach ≈λ₀/120, which can be tailored by altering the thicknesses of the α‐MoO₃ 2D flakes. Furthermore, spatial control over the PhPs is achieved with a metal‐ion‐intercalation strategy. The results demonstrate α‐MoO₃ as a new platform for studying hyperbolic PhPs with tunability, which enable switchable mid‐infrared nanophotonic devices.     

Thermochromes VO2 als Architekturglasbeschichtung

VO₂ undergoes at 68°C a temperature induced insulator‐metal phase transition. Especially the transmission of infrared radiation changes. Therefore VO₂ can be used as an intelligent sun protection coating. The physical mechanisms of the phase transition will be described as well as the properties of the material. Also the possibilities to change the properties of a VO₂‐coating with regard to an application will be pointed out.     

Launching Phonon Polaritons by Natural Boron Nitride Wrinkles with Modifiable Dispersion by Dielectric Environments

Interference‐free hyperbolic phonon polaritons (HPPs) excited by natural wrinkles in a hexagonal boron nitride (hBN) microcrystal are reported both experimentally and theoretically. Although their geometries are off‐resonant with the excitation wavelength, the wrinkles compensate for the large momentum mismatch between photon and phonon polariton, and launch the HPPs without interference. The spatial feature of wrinkles is about 200 nm, which is an order of magnitude smaller than resonant metal antennas at the same excitation wavelength. Compared with phonon polaritons launched by an atomic force microscopy tip, the phonon polaritons launched by wrinkles are interference‐free, independent of the launcher geometry, and exhibit a smaller damping rate (γ ≈ 0.028). On the same hBN microcrystal, in situ nanoinfrared imaging of HPPs launched by different mechanisms is performed. In addition, the dispersion of HPPs is modified by changing the dielectric environments of hBN crystals. The wavelength of HPPs is compressed twofold when the substrate is changed from SiO₂ to gold. The findings provide insights into the intrinsic properties of hBN‐HPPs and demonstrate a new way to launch and control polaritons in van der Waals materials.     

Ultra-High Interfacial Thermal Conductance via Double hBN Encapsulation for Efficient Thermal Management of 2D Electronics

Heat dissipation is a major limitation of high-performance electronics. This is especially important in emerging nanoelectronic devices consisting of ultra-thin layers, heterostructures, and interfaces, where enhancement in thermal transport is highly desired. Here, ultra-high interfacial thermal conductance in encapsulated van der Waals (vdW) heterostructures with single-layer transition metal dichalcogenides MX₂ (MoS₂, WSe₂, WS₂) sandwiched between two hexagonal boron nitride (hBN) layers is reported. Through Raman spectroscopic measurements of suspended and substrate-supported hBN/MX₂/hBN heterostructures with varying laser power and temperature, the out-of-plane interfacial thermal conductance in the vertical stack is calibrated. The measured interfacial thermal conductance between MX₂ and hBN reaches 74 ± 25 MW m⁻² K⁻¹, which is at least ten times higher than the interfacial thermal conductance of MX₂ in non-encapsulation structures. Molecular dynamics (MD) calculations verify and explain the experimental results, suggesting a full encapsulation by hBN layers is accounting for the high interfacial conductance. This ultra-high interfacial thermal conductance is attributed to the double heat transfer pathways and the clean and tight vdW interface between two crystalline 2D materials. The findings in this study reveal new thermal transport mechanisms in hBN/MX₂/hBN structures and shed light on building novel hBN-encapsulated nanoelectronic devices with enhanced thermal management.     

Recent progresses on physics and applications of vanadium dioxide

As a strongly correlated electron material, vanadium dioxide (VO₂) has been a focus of research since its discovery in 1959, owing to its well-known metal–insulator transition coupled with a structural phase transition. Recent years have witnessed both exciting discoveries in our understanding of the physics of VO₂ and developments in new applications of VO₂-related materials. In this article, we review some of these recent progresses on the phase transition mechanism and dynamics, phase diagrams, and imperfection effects, as well as growth and applications of VO₂. Our review not only offers a summary of the properties and applications of VO₂, but also provides insights into future research of this material by highlighting some of the challenges and opportunities.     

Study on a terahertz modulator based on metamaterial with photoinduced vanadium dioxide film

Abstract

Applying the photoexcitation characteristics of vanadium dioxide (VO₂), a dynamic resonant terahertz (THz) modulation with the combination of a VO₂ film and a metamaterial was suggested to realize THz wave active manipulation. The designed metamaterial with structured copper rings arrays can realize a passband from 0.776 to 1.045 THz. When insulator–metal phase transition in VO₂ thin film, which is deposited on the other surface of the metamaterial substrate, is induced by optical pumping, the metamaterial/VO₂ film hybrid structure behaves as an absorber with absorption rates of 90% at 0.88 THz and the transmission energy decrease to less than 3%. Therefore, about 78% modulation depth and more than 250 GHz modulation bandwidth have been reached under the photoinducing. The simulation results illustrate the promise of using phase transition materials for efficient broadband fast response modulators for THz waves.     

Electrically Driven Reversible Phase Changes in Layered In2Se3 Crystalline Film

An unconventional phase‐change memory (PCM) made of In₂Se₃, which utilizes reversible phase changes between a low‐resistance crystalline β phase and a high‐resistance crystalline γ phase is reported for the first time. Using a PCM with a layered crystalline film exfoliated from In₂Se₃ crystals on a graphene bottom electrode, it is shown that SET/RESET programmed states form via the formation/annihilation of periodic van der Waals' (vdW) gaps (i.e., virtual vacancy layers) in the stack of atomic layers and the concurrent reconfiguration of In and Se atoms across the layers. From density functional theory calculations, β and γ phases, characterized by octahedral bonding with vdW gaps and tetrahedral bonding without vdW gaps, respectively, are shown to have energy bandgap value of 0.78 and 1.86 eV, consistent with a metal‐to‐insulator transition accompanying the β‐to‐γ phase change. The monolithic In₂Se₃ layered film reported here provides a novel means to achieving a PCM based on melting‐free, low‐entropy phase changes in contrast with the GeTe–Sb₂Te₃ superlattice film adopted in interfacial phase‐change memory.     

Characteristics of CeOx–VO2 composite thin films synthesized by sol–gel process

Pure vanadium dioxide (VO₂) and CeOx–VO₂ (1.5 < x < 2) composite thin films were grown on muscovite substrate by inorganic sol–gel process using vanadium pentaoxide and cerium(III) nitrate hexahydrate powder as precursor. The crystalline structure, morphology and phase transition properties of the thin films were systematically investigated by X-ray diffraction, Raman, X-ray photoelectron spectroscopy, FE-SEM and optical transmission measurements. High quality of the VO₂ and CeOx–VO₂ composite films were obtained, in which the relative fractions of +4 valence state vanadium were above 70 % though the concentrations of cerium reached 9.77 at %. However, much of cerium compounds were formed at the edge of grains and the addition of cerium resulted in more clearly defined grain boundaries as shown in SEM images. Meanwhile, the composite films exhibited excellent phase transition properties and the infrared transmittance decreased from about 70 to 10 % at λ = 4 μm bellow and above the metal–insulator phase transition temperature. The metal–insulator phase transition temperatures were quite similar with about 66 °C of the pure VO₂ and CeOx–VO₂ composite thin films. But hysteresis widths increased with more addition of cerium, due to the limiting effect of grain boundaries on the propagation of the phase transition. Particularly, the CeOx–VO₂ composite film with an addition of 7.82 at % Ce showed a largest hysteresis width with about 20.6 °C. In addition, the thermochromic performance of visible transmittance did not change obviously with more addition of cerium.     

二氧化钒薄膜智能窗的研究进展

二氧化钒具有良好的半导体-金属相变特性,在常温下,二氧化钒的晶体结构为单斜晶系结构(M相),随着温度的升高达到相变温度,二氧化钒的晶型变成四方晶红石结构(R相),当温度降低到相变温度时,二氧化钒的晶型又变回单斜晶系结构(M相)。这种典型可逆热色特征,使二氧化钒成为当前建筑用智能窗材料的最佳选择。综述了近些年来制备VO_2薄膜的几种常用方法,并针对VO_2薄膜在热色智能窗应用方面存在的主要问题,从掺杂和复合薄膜结构两方面总结了提高VO_2薄膜性能的改进工艺,为推进VO_2薄膜智能窗的进一步研究提供了依据。     

Manipulation and Steering of Hyperbolic Surface Polaritons in Hexagonal Boron Nitride

Hexagonal boron nitride (hBN) is a natural hyperbolic material that supports both volume‐confined hyperbolic polaritons and sidewall‐confined hyperbolic surface polaritons (HSPs). In this work, efficient excitation, control, and steering of HSPs are demonstrated in hBN through engineering the geometry and orientation of hBN sidewalls. By combining infrared nanoimaging and numerical simulations, the reflection, transmission, and scattering of HSPs are investigated at the hBN corners with various apex angles. It is also shown that the sidewall‐confined nature of HSPs enables a high degree of control over their propagation by designing the geometry of hBN nanostructures.     

Tunable Modal Birefringence in a Low‐Loss Van Der Waals Waveguide

van der Waals (vdW) crystals are promising candidates for integrated phase retardation applications due to their large optical birefringence. Among the two major types of vdW materials, the hyperbolic vdW crystals are inherently inadequate for optical retardation applications since the supported polaritonic modes are exclusively transverse‐magnetic (TM) polarized and relatively lossy. Elliptic vdW crystals, on the other hand, represent a superior choice. For example, molybdenum disulfide (MoS₂) is a natural uniaxial vdW crystal with extreme elliptic anisotropy in the frequency range of optical communication. Both transverse‐electric (TE) polarized ordinary and TM polarized extraordinary waveguide modes can be supported in MoS₂ microcrystals with suitable thicknesses. In this work, low‐loss transmission of these guided modes is demonstrated with nano‐optical imaging at the near‐infrared (NIR) wavelength (1530 nm). More importantly, by combining theoretical calculations and NIR nanoimaging, the modal birefringence between the orthogonally polarized TE and TM modes is shown to be tunable in both sign and magnitude via varying the thickness of the MoS₂ microcrystal. This tunability represents a unique new opportunity to control the polarization behavior of photons with vdW materials.     

Controllable Magnetic Proximity Effect and Charge Transfer in 2D Semiconductor and Double-Layered Perovskite Manganese Oxide van der Waals Heterostructure

Optically generated excitonic states (excitons and trions) in transition metal dichalcogenides are highly sensitive to the electronic and magnetic properties of the materials underneath. Modulation and control of the excitonic states in a novel van der Waals (vdW) heterostructure of monolayer MoSe₂ on double-layered perovskite Mn oxide ((La_0.8Nd_0.2)_1.2Sr_1.8Mn₂O₇) is demonstrated, wherein the Mn oxide transforms from a paramagnetic insulator to a ferromagnetic metal. A discontinuous change in the exciton photoluminescence intensity via dielectric screening is observed. Further, a relatively high trion intensity is discovered due to the charge transfer from metallic Mn oxide under the Curie temperature. Moreover, the vdW heterostructures with an ultrathin h-BN spacer layer demonstrate enhanced valley splitting and polarization of excitonic states due to the proximity effect of the ferromagnetic spins of Mn oxide. The controllable h-BN thickness in vdW heterostructures reveals a several-nanometer-long scale of charge transfer as well as a magnetic proximity effect. The vdW heterostructure allows modulation and control of the excitonic states via dielectric screening, charge carriers, and magnetic spins.     

Compositional and metal-insulator transition characteristics of sputtered vanadium oxide thin films on yttria-stabilized zirconia

Vanadium dioxide (VO₂) thin films have been shown to undergo a rapid electronic phase transition near 70 °C from a semiconductor to a metal, making it an interesting candidate for exploring potential application in high speed electronic devices such as optical switches, tunable capacitors, and field effect transistors. A critical aspect of lithographic fabrication in devices utilizing electric field effects in VO₂ is the ability to grow VO₂ over thin dielectric films. In this article, we study the properties of VO₂ grown on thin films of Yttria-Stabilized Zirconia (YSZ). Near room temperature, YSZ is a good insulator with a high dielectric constant ($\epsilon _{\rm r} > 25$\epsilon _{\rm r} > 25). We demonstrate the sputter growth of polycrystalline VO₂ on YSZ thin films, showing a three order resistivity transition near 70 °C with transition and hysteresis widths of approximately 7 °C each. We examine the relationship between chemical composition and transition characteristics of mixed phase vanadium oxide films. We investigate changes in composition induced by low temperature post-deposition annealing in oxidizing and reducing atmospheres, and report their effects on electronic properties.     

Voltage- and current-activated metal–insulator transition in VO2-based electrical switches: a lifetime operation analysis

Abstract

Vanadium dioxide is an intensively studied material that undergoes a temperature-induced metal–insulator phase transition accompanied by a large change in electrical resistivity. Electrical switches based on this material show promising properties in terms of speed and broadband operation. The exploration of the failure behavior and reliability of such devices is very important in view of their integration in practical electronic circuits. We performed systematic lifetime investigations of two-terminal switches based on the electrical activation of the metal–insulator transition in VO₂ thin films. The devices were integrated in coplanar microwave waveguides (CPWs) in series configuration. We detected the evolution of a 10 GHz microwave signal transmitted through the CPW, modulated by the activation of the VO₂ switches in both voltage- and current-controlled modes. We demonstrated enhanced lifetime operation of current-controlled VO₂-based switching (more than 260 million cycles without failure) compared with the voltage-activated mode (breakdown at around 16 million activation cycles). The evolution of the electrical self-oscillations of a VO₂-based switch induced in the current-operated mode is a subtle indicator of the material properties modification and can be used to monitor its behavior under various external stresses in sensor applications.     

Ramp‐Reversal Memory and Phase‐Boundary Scarring in Transition Metal Oxides

Transition metal oxides are complex electronic systems that exhibit a multitude of collective phenomena. Two archetypal examples are VO₂ and NdNiO₃, which undergo a metal–insulator phase transition (MIT), the origin of which is still under debate. Here this study reports the discovery of a memory effect in both systems, manifested through an increase of resistance at a specific temperature, which is set by reversing the temperature ramp from heating to cooling during the MIT. The characteristics of this ramp‐reversal memory effect do not coincide with any previously reported history or memory effects in manganites, electron‐glass or magnetic systems. From a broad range of experimental features, supported by theoretical modelling, it is found that the main ingredients for the effect to arise are the spatial phase separation of metallic and insulating regions during the MIT and the coupling of lattice strain to the local transition temperature of the phase transition. We conclude that the emergent memory effect originates from phase boundaries at the reversal temperature leaving “scars” in the underlying lattice structure, giving rise to a local increase in the transition temperature. The universality and robustness of the effect shed new light on the MIT in complex oxides.     

Tailoring Materials for Mottronics: Excess Oxygen Doping of a Prototypical Mott Insulator

The Mott transistor is a paradigm for a new class of electronic devices—often referred to by the term Mottronics—which are based on charge correlations between the electrons. Since correlation‐induced insulating phases of most oxide compounds are usually very robust, new methods have to be developed to push such materials right to the boundary to the metallic phase in order to enable the metal–insulator transition to be switched by electric gating. Here, it is demonstrated that thin films of the prototypical Mott insulator LaTiO₃ grown by pulsed laser deposition under oxygen atmosphere are readily tuned by excess oxygen doping across the line of the band‐filling controlled Mott transition in the electronic phase diagram. The detected insulator to metal transition is characterized by a strong change in resistivity of several orders of magnitude. The use of suitable substrates and capping layers to inhibit oxygen diffusion facilitates full control of the oxygen content and renders the films stable against exposure to ambient conditions. These achievements represent a significant advancement in control and tuning of the electronic properties of LaTiO_3+x thin films making it a promising channel material in future Mottronic devices.     

Electro-Optic Upconversion in van der Waals Heterostructures via Nonequilibrium Photocarrier Tunneling

Ultrafast interlayer charge transfer is one of the most distinct features of van der Waals (vdW) heterostructures. Its dynamics competes with carrier thermalization such that the energy of nonthermalized photocarriers may be harnessed by band engineering. In this study, nonthermalized photocarrier energy is harnessed to achieve near-infrared (NIR) to visible light upconversion in a metal–insulator–semiconductor (MIS) vdW heterostructure tunnel diode consisting of few-layer graphene (FLG), hexagonal boron nitride (hBN), and monolayer tungsten disulfide (WS₂). Photoexcitation of the electrically biased heterostructure with 1.58 eV NIR laser in the linear absorption regime generates emission from the ground exciton state of WS₂, which corresponds to upconversion by ≈370 meV. The upconversion is realized by electrically assisted interlayer transfer of nonthermalized photoexcited holes from FLG to WS₂, followed by formation and radiative recombination of excitons in WS₂. The photocarrier transfer rate can be described by Fowler–Nordheim tunneling mechanism and is electrically tunable by two orders of magnitude by tuning voltage bias applied to the device. This study highlights the prospects for realizing novel electro-optic upconversion devices by exploiting electrically tunable nonthermalized photocarrier relaxation dynamics in vdW heterostructures.     

Controlling Photoluminescence Enhancement and Energy Transfer in WS2:hBN:WS2 Vertical Stacks by Precise Interlayer Distances

2D semiconducting transition metal dichalcogenides (TMDs) are endowed with fascinating optical properties especially in their monolayer limit. Insulating hBN films possessing customizable thickness can act as a separation barrier to dictate the interactions between TMDs. In this work, vertical layered heterostructures (VLHs) of WS₂:hBN:WS₂ are fabricated utilizing chemical vapor deposition (CVD)‐grown materials, and the optical performance is evaluated through photoluminescence (PL) spectroscopy. Apart from the prohibited indirect optical transition due to the insertion of hBN spacers, the variation in the doping level of WS₂ drives energy transfer to arise from the layer with lower quantum efficiency to the other layer with higher quantum efficiency, whereby the total PL yield of the heterosystem is increased and the stack exhibits a higher PL intensity compared to the sum of those in the two WS₂ constituents. Such doping effects originate from the interfaces that WS₂ monolayers reside on and interact with. The electron density in the WS₂ is also controlled and subsequent modulation of PL in the heterostructure is demonstrated by applying back‐gated voltages. Other influential factors include the strain in WS₂ and temperature. Being able to tune the energy transfer in the VLHs may expand the development of photonic applications in 2D systems.     

In situ nanomechanical behaviour of coexisting insulating and metallic domains in VO<Subscript>2</Subscript> microbeams

Measuring the electrical and mechanical responses of coexisting phases at nanoscale provides a platform to engineer micro-/nanoscale pattern of metallic and insulating domains with control over properties to make novel devices. Here, we employ several in situ characterization techniques, namely Raman, optical imaging and electrical measurements, to identify the phase coexistence of metallic and insulating domains. Further, we performed site-specific in situ nanoindentation to address the spatial variation in nanomechanical properties in vanadium dioxide (VO₂) single-crystal microbeams in proximity to metal–insulator transition temperature. We also investigated load or contact depth dependence on elastic modulus at various temperatures to avoid the interference of indentation size effect on nanomechanical properties across the phase transition. The obtained results confirm the abrupt increase in elastic modulus (~17 GPa) and nanohardness (1 GPa) across the transition from monoclinic (insulator) to rutile (metal) phase.     

Oxygen pressure dependent VO2 crystal film preparation and the interfacial epitaxial growth study

High quality VO₂ crystal films have been prepared on sapphire substrates by pulsed laser deposition method and the effects of oxygen pressure on the crystal phase structure are investigated. Results indicate that the phases and microstructures of VO₂ films are strongly sensitive to oxygen pressure. High oxygen pressure tends to form coarse B-VO₂ nanocrystals while low pressure favors a flat M1-VO₂ film epitaxial growth. X-ray diffraction φ-scan patterns confirm the [020] epitaxial growth orientation of the M1-VO₂ film and the in-plane lattice epitaxial relationship at the interface is also examined. Raman spectra indicate that M1-VO₂ phase has much stronger Raman scattering modes than B-VO₂, and the clear phonon modes further confirm the idea stoichiometry of VO₂ crystal film. Infrared transmittance spectra as the function of temperature are recorded and the results show that M1-VO₂ crystal films undergo a distinct infrared transmittance variation across metal insulator transition boundary, while B-VO₂ exhibits negligible thermochromic switching properties in the temperature range concerned. The pronounced phase transition behavior of the M1-VO₂ crystal film makes it a promising candidate for optical filter/switch and smart window applications in the future.