Measurement of a solid-state triple point at the metal-insulator transition in VO2.

First-order phase transitions in solids are notoriously challenging to study. The combination of change in unit cell shape, long range of elastic distortion and flow of latent heat leads to large energy barriers resulting in domain structure, hysteresis and cracking. The situation is worse near a triple point, where more than two phases are involved. The well-known metal-insulator transition in vanadium dioxide, a popular candidate for ultrafast optical and electrical switching applications, is a case in point. Even though VO2 is one of the simplest strongly correlated materials, experimental difficulties posed by the first-order nature of the metal-insulator transition as well as the involvement of at least two competing insulating phases have led to persistent controversy about its nature. Here we show that studying single-crystal VO2 nanobeams in a purpose-built nanomechanical strain apparatus allows investigation of this prototypical phase transition with unprecedented control and precision. Our results include the striking finding that the triple point of the metallic phase and two insulating phases is at the transition temperature, Ttr = Tc, which we determine to be 65.0 ± 0.1 °C. The findings have profound implications for the mechanism of the metal-insulator transition in VO2, but they also demonstrate the importance of this approach for mastering phase transitions in many other strongly correlated materials, such as manganites and iron-based superconductors.

Effects of Thickness on the Metal-Insulator Transition in Free-Standing Vanadium Dioxide Nanocrystals.

Controlling solid state phase transitions via external stimuli offers rich physics along with possibilities of unparalleled applications in electronics and optics. The well-known metal-insulator transition (MIT) in vanadium dioxide (VO2) is one instance of such phase transitions emerging from strong electronic correlations. Inducing the MIT using electric field has been investigated extensively for the applications in electrical and ultrafast optical switching. However, as the Thomas-Fermi screening length is very short, for considerable alteration in the material's properties with electric field induced MIT, crystals below 10 nm are needed. So far, the only way to achieve thin crystals of VO2 has been via epitaxial growth techniques. Yet, stress due to lattice mismatch as well as interdiffusion with the substrate complicate the studies. Here, we show that free-standing vapor-phase grown crystals of VO2 can be milled down to the desired thickness using argon ion-beam milling without compromising their electronic and structural properties. Among our results, we show that even below 4 nm thickness the MIT persists and the transition temperature is lowered in two-terminal devices as the crystal gets thinner. The findings in this Letter can be applied to similar strongly correlated materials to study quantum confinement effects.

Visualization of one-dimensional diffusion and spontaneous segregation of hydrogen in single crystals of VO2.

Hydrogen intercalation in solids is common, complicated, and very difficult to monitor. In a new approach to the problem, we have studied the profile of hydrogen diffusion in single-crystal nanobeams and plates of VO2, exploiting the fact that hydrogen doping in this material leads to visible darkening near room temperature connected with the metal-insulator transition at 65 °C. We observe hydrogen diffusion along the rutile c-axis but not perpendicular to it, making this a highly one-dimensional diffusion system. We obtain an activated diffusion coefficient, [Formula: see text] applicable in metallic phase. In addition, we observe dramatic supercooling of the hydrogen-induced metallic phase and spontaneous segregation of the hydrogen into stripes implying that the diffusion process is highly nonlinear, even in the absence of defects. Similar complications may occur in hydrogen motion in other materials but are not revealed by conventional measurement techniques.

Ion transport induced room-temperature insulator-metal transition in single-crystalline Cu2Se.

Cu2Se is a superionic conductor above 414 K, with ionic conductivities reaching that of molten salts. The superionic behavior results from hopping Cu ions between different crystallographic sites within the Se scaffold. However, the properties of Cu2Se below 414 K are far less known due to experimental limitations imposed by the bulk or polycrystalline samples that have been available so far. Here, we report the synthesis of ultra-thin, large-area single crystalline Cu2Se samples using a chemical vapor deposition method. The as-synthesized Cu2Se crystals exhibit optically and electrically detectable and controllable robust phases at room temperature and above. We demonstrate that Cu ion vacancies can be manipulated to induce an insulator-metal transition, which exhibits 6 orders of magnitude change in the electrical resistance of two terminal devices, accompanied by an optical change in the phase configuration. Our experiments show that the high mobility of the liquid-like Cu ion vacancies in Cu2Se causes macroscopic ordering in the Cu vacancies. Consequently, phase distribution over the crystals is not dictated by the diffusive motion of the ions but by the local energy minima formed due to the phase transition. As a result, long-range vacancy ordering of the crystal below 414 K becomes optically observable at a micrometer scale. This work demonstrates that Cu2Se could be a prototypical system where long-range ordering properties can be studied via electrical and optical methods.

Plasmon-enhanced photoresponse of single silver nanowires and their network devices.

The photo-bolometric effect is critically important in optoelectronic structures and devices employing metallic electrodes with nanoscale features due to heating caused by the plasmonic field enhancement. One peculiar case is individual silver nanowires (Ag NWs) and their networks. Ag NW-networks exhibit excellent thermal, electrical, and mechanical properties, providing a simple yet reliable alternative to common flexible transparent electrode materials used in optoelectronic devices. To date, there have been no reports on the photoresponse of Ag NWs. In this study, we show that single Ag NWs and networks of such Ag NWs possess a significant, intrinsic photoresponse, thanks to the photo-bolometric effect, as directly observed and measured using scanning photocurrent microscopy. Surface plasmon polaritons (SPPs) created at the contact metals or plasmons created at the nanowire-metal structures cause heating at the junctions where a plasmonic field enhancement is possible. The local heating of the Ag NWs results in negative photoconductance due to the bolometric effect. Here an open-circuit response due to the plasmon-enhanced Seebeck effect was recorded at the NW-metal contact junctions. The SPP-assisted bolometric effect is found to be further enhanced by decorating the Ag NWs with Ag nanoparticles. These observations are relevant to the use of metallic nanowires in plasmonic applications in particular and in optoelectronics in general. Our findings may pave the path for plasmonics-enabled sensing without spectroscopic detection.

Real time optical observation and control of atomically thin transition metal dichalcogenide synthesis.

Understanding the mechanisms involved in chemical vapour deposition (CVD) synthesis of atomically thin transition metal dichalcogenides (TMDCs) requires precise control of numerous growth parameters. All the proposed mechanisms and their relationship with the growth conditions are inferred from characterising intermediate formations obtained by stopping the growth blindly. To fully understand the reaction routes that lead to the monolayer formation, real time observation and control of the growth are needed. Here, we demonstrate how a custom-made CVD chamber that allows real time optical monitoring can be employed to study the reaction routes that are critical to the production of the desired layered thin crystals in salt assisted TMDC synthesis. Our real time observations reveal the reaction between the salt and the metallic precursor to form intermediate compounds which lead to the layered crystal formation. We identified that both the vapour-solid-solid and vapour-liquid-solid growth routes are in an interplay. Furthermore, we demonstrate the role H2 plays in the salt-assisted WSe2 synthesis. Finally, we observed the synthesis of the MoSe2/WSe2 heterostructures optically, and elucidated the conditions required for both lateral and vertical heterostructure syntheses.

Photoresponse of a strongly correlated material determined by scanning photocurrent microscopy.

The generation of a current by light is a key process in optoelectronic and photovoltaic devices. In band semiconductors, depletion fields associated with interfaces separate long-lived photo-induced carriers. However, in systems with strong electron-electron and electron-phonon correlations it is unclear what physics will dominate the photoresponse. Here, we investigate photocurrent in VO(2), an exemplary strongly correlated material known for its dramatic metal-insulator transition at T(c) ≈ 68 °C, which could be useful for optoelectronic detection and switching up to ultraviolet wavelengths. Using scanning photocurrent microscopy on individual suspended VO(2) nanobeams we observe a photoresponse peaked at the metal-insulator boundary but extending throughout both insulating and metallic phases. We determine that the response is photothermal, implying efficient carrier relaxation to a local equilibrium in a manner consistent with strong correlations. Temperature-dependent measurements reveal subtle phase changes within the insulating state. We further demonstrate switching of the photocurrent by optical control of the metal-insulator boundary arrangement. Our work shows the value of applying scanning photocurrent microscopy to nanoscale crystals in the investigation of strongly correlated materials, and the results are relevant for designing and controlling optoelectronic devices employing such materials.