Localized thermal emission from topological interfaces.

The control of thermal radiation by shaping its spatial and spectral emission characteristics plays a key role in many areas of science and engineering. Conventional approaches to tailoring thermal emission using metamaterials are hampered both by the limited spatial resolution of the required subwavelength material structures and by the materials' strong absorption in the infrared. In this work, we demonstrate an approach based on the concept of topology. By changing a single parameter of a multilayer coating, we were able to control the reflection topology of a surface, with the critical point of zero reflection being topologically protected. The boundaries between subcritical and supercritical spatial domains host topological interface states with near-unity thermal emissivity. These topological concepts enable unconventional manipulation of thermal light for applications in thermal management and thermal camouflage.

Synergistic Improvement in the Thermal Conductivity of Hybrid Boron Nitride Nanotube/Nanosheet Epoxy Composites.

Epoxy composites with excellent thermal properties are highly promising for thermal management applications in modern electronic devices. In this work, we report the enhancement of the thermal conductivity of two different nanocomposites, using epoxy resins LY564 (epoxy 1) and LY5052 (epoxy 2), by incorporating multiwalled boron nitride nanotubes (BNNT) and boron nitride nanosheets (BNNS) as fillers. The synergistic interaction between the 1D BNNT and 2D BNNS allows for improved thermal conductivity via several different mechanisms. The highest thermal conductivity was measured at a loading of 1/30 wt % of BNNT/BNNS, resulting in values of 2.6 and 3.4 Wm-1 K-1, respectively, for each epoxy matrix. This improvement is attributed to the formation of a three-dimensional heat flow path formed through intercalation of the nanotubes between the BNNS. The thermal conductivity of the epoxy 1 and 2 nanocomposites improved by 940 and 1500%, respectively, making them suitable as thermal interface materials in electronic applications requiring electrical resistivity.

Optimization of thermoelectric properties of carbon nanotube veils by defect engineering.

Carbon nanotubes (CNTs), with their combination of excellent electrical conductivity, Seebeck coefficient, mechanical robustness and environmental stability are highly desired as thermoelectric (TE) materials for a wide range of fields including Internet of Things, health monitoring and environmental remediation solutions. However, their high thermal conductivity (κ) is an obstacle to practical TE applications. Herein, we present a novel method to reduce the κ of CNT veils, by introducing defects, while preserving their Seebeck coefficient and electrical conductivity. Solid-state drawing of a CNT veil embedded within two polycarbonate films generates CNT veil fragments of reducing size with increasing draw ratio. A successive heat treatment, at above the polycarbonate glass-to-rubber transition temperature, spontaneously reconnects the CNT veils fragments electrically but not thermally. Stretching to a draw ratio of 1.5 and heat repairing at 170 °C leads to a dramatic 3.5-fold decrease in κ (from 46 to 13 W m-1 K-1), in contrast with a decrease in electrical conductivity of only 26% and an increase in Seebeck coefficient of 10%. To clarify the mechanism of reduction in thermal conductivity, a large-scale mesoscopic simulation of CNT veils under uniaxial stretching has also been used. This work shows that defect engineering can be a valuable strategy to optimize TE properties of CNT veils and, potentially, other thermoelectric materials.

Reversible Ionic Liquid Intercalation for Electrically Controlled Thermal Radiation from Graphene Devices.

Using graphene as a tunable optical material enables a series of optical devices such as switchable radar absorbers, variable infrared emissivity surfaces, or visible electrochromic devices. These devices rely on controlling the charge density on graphene with electrostatic gating or intercalation. In this paper, we studied the effect of ionic liquid intercalation on the long-term performance of optoelectronic devices operating within a broad infrared wavelength range. Our spectroscopic and thermal characterization results reveal the key limiting factors for the intercalation process and the performance of the infrared devices, such as the electrolyte ion-size asymmetry and charge distribution scheme and the effects of oxygen. Our results provide insight for the limiting mechanism for graphene applications in infrared thermal management and tunable heat signature control.

Localized X-ray photoelectron impedance spectroscopy (LoXPIS) for capturing charge dynamics of an ionic liquid electrolyte within an energy storage device.

Many electrochemical devices are based on the fundamental process of ion migration and accumulation on surfaces. Complex interplay of molecular properties of ions and device dimensions control the entire process and define the overall dynamics of the system. Particularly, for ionic liquid-based electrolytes it is often not clear which property, and to what extent, contributes to the overall performance of the device. Herein we use X-ray photoelectron spectroscopy (XPS) while the device is under electrical bias. Such a procedure reveals localized electrical potential developments, through binding energy shifts of the atomic core levels, in a chemically specific fashion. Combining it with square-wave AC modulation, the information can also be extended to time domain, and we investigate devices configured as a coplanar capacitor, with an ionic liquid as the electrolyte, in macro-dimensions. Our analysis reveals that a nonlinear voltage profile across the device emerges from spatially non-uniform electrical double layer formation on electrode surfaces. Interestingly the coplanar capacitor has an extremely slow time response which is particularly controlled by IL film thickness. XPS measurements can capture the ion dynamics in the tens of seconds to microseconds range, and reveal that ionic motion is all over the device, including on metallic electrode regions. This behavior can only be attributed to motion in more than one dimension. The ion dynamics can also be faithfully simulated by using a modified PNP equation, taking into account steric effects, and device dimensions. XPS measurements on two devices with different dimensions corroborated and validated the simulation results. The present results propose a new experimental approach and provide new insights into the dynamics of ions across electrochemical devices.

Strong Coupling of Carbon Quantum Dots in Liquid Crystals.

Carbon quantum dots (CDs) have recently received a tremendous amount of interest owing to their attractive optical properties. However, CDs have broad absorption and emission spectra limiting their application ranges. We herein, for the first time, show synthesis of water-soluble red emissive CDs with a very narrow line width (∼75 meV) spectral absorbance and hence demonstrate strong coupling of CDs and plasmon polaritons in liquid crystalline mesophases. The excited state dynamics of CDs has been studied by ultrafast transient absorption spectroscopy, and CDs display very stable and strong photoluminescence emission with a quantum yield of 35.4% and a lifetime of ∼2 ns. More importantly, we compare J-aggregate dyes with CDs in terms of their absorption line width, photostability, and ability to do strong coupling, and we conclude that highly fluorescent CDs have a bright future in the mixed light-matter states for emerging applications in future quantum technologies.

Topological engineering of terahertz light using electrically tunable exceptional point singularities.

The topological structure associated with the branch point singularity around an exceptional point (EP) can provide tools for controlling the propagation of light. Through use of graphene-based devices, we demonstrate the emergence of EPs in an electrically controlled interaction between light and a collection of organic molecules in the terahertz regime at room temperature. We show that the intensity and phase of terahertz pulses can be controlled by a gate voltage, which drives the device across the EP. Our electrically tunable system allows reconstruction of the Riemann surface associated with the complex energy landscape and provides topological control of light by tuning the loss imbalance and frequency detuning of interacting modes. Our approach provides a platform for developing topological optoelectronics and studying the manifestations of EP physics in light-matter interactions.

Multispectral Graphene-Based Electro-Optical Surfaces with Reversible Tunability from Visible to Microwave Wavelengths.

Optical materials with colour-changing abilities have been explored for display devices1, smart windows2,3, or modulation of visual appearance4-6. The efficiency of these materials, however, has strong wavelength dependence, which limits their functionality to a specific spectral range. Here, we report graphene-based electro-optical devices with unprecedented optical tunability covering the entire electromagnetic spectrum from the visible to microwave. We achieve this non-volatile and reversible tunability by electro-intercalation of lithium into graphene layers in an optically accessible device structure. This unique colour-changing capability, together with area-selective intercalation, inspires fabrication of new multispectral devices, including display devices and electro-optical camouflage coating. We anticipate that these results provide realistic approaches for programmable smart optical surfaces with a potential utility in many scientific and engineering fields such as active plasmonics and adaptive thermal management.

Electrically Controlled Thermal Radiation from Reduced Graphene Oxide Membranes.

We demonstrate a fabrication procedure of hybrid devices that consist of reduced graphene oxide films supported by porous polymer membranes that host ionic solutions. We find that we can control the thermal radiation from the surface of reduced graphene oxide through a process of electrically driven reversible ionic intercalation. Through a comparative analysis of the structural, chemical, and optical properties of our reduced graphene oxide films, we identify that the dominant mechanism leading to the intercalation-induced reduction of light emission is Pauli blocking of the interband recombination of charge carriers. We inspect the capabilities of our devices to act as a platform for the electrical control of mid-infrared photonics by observing a bias-induced reduction of apparent temperature of hot surfaces visualized through an infrared thermal camera.

Topological plasmonic waveguides in triharmonic metal gratings.

We study topological surface-plasmon-polaritons at optical frequencies in tri-harmonic diffraction gratings formed at a metal-dielectric interface. The latter are shown to well approximate a bipartite Kronig-Penney model. Topologically protected localised modes are then predicted to occur at the edges of the grating and at defects formed by the combination of two mirror antisymmetric corrugations, whose bulk invariant is a step-wise varying Zak phase in both cases. An interesting special case wherein the defect state is in-fact forbidden is also observed that reveals the fragility of such states despite their topological nature.

Large Rabi splitting of mixed plasmon-exciton states in small plasmonic moiré cavities.

We report on exciton-plasmon coupling in metallic moiré cavities, both numerically and experimentally. Moiré cavities fabricated using double exposure laser interference lithography were filled with a molecular dye, J-aggregate. Polarization-dependent spectroscopic reflection measurements supported by simulations reveal strong coupling of organic dye excitons with cavity modes of the plasmonic moiré cavities. An anti-crossing at zero detuning, a clear indication of strong coupling, has been observed when the excitonic absorption band resonates with the cavity mode. Large Rabi splitting energies owing to the strong coupling of plasmons and excitons are clearly observed.

Graphene-Enabled Adaptive Infrared Textiles.

Interactive clothing requires sensing and display functionalities to be embedded on textiles. Despite the significant progress of electronic textiles, the integration of optoelectronic materials on fabrics remains as an outstanding challenge. In this Letter, using the electro-optical tunability of graphene, we report adaptive optical textiles with electrically controlled reflectivity and emissivity covering the infrared and near-infrared wavelengths. We achieve electro-optical modulation by reversible intercalation of ions into graphene layers laminated on fabrics. We demonstrate a new class of infrared textile devices including display, yarn, and stretchable devices using natural and synthetic textiles. To show the promise of our approach, we fabricated an active device directly onto a t-shirt, which enables long-wavelength infrared communication via modulation of the thermal radiation from the human body. The results presented here provide complementary technologies which could leverage the ubiquitous use of functional textiles.

Chemically addressed switching measurements in graphene electrode memristive devices using in situ XPS.

The memristor has been the topic of heated research activity since the Pt/TiO2/TiOx/Pt structure was reported by Hewlett-Packard Labs. The characteristics of memristors such as the pinched hysteresis loops and time and input signal-dependent memristance are due to the drift of positively charged oxygen vacancies in the TiOx layer. While different modes of switching behaviour have been characterized, observing the switching as it happens with in situ measurements using X-ray photoelectron spectroscopy (XPS) can allow a better understanding of the device operation. The setup used in this work enables the application of voltage signals of different frequencies and amplitudes and observing the hysteresis seen in the I-V plane through chemical addressing. The measurements were conducted on Pt/TiO2/TiOx/graphene structures. The single layer graphene, utilized as a top electrode, effectively acts as a transparent electrode in that the layer beneath it can be observed to a depth of ∼10 nm in XPS. This allows for the observation of the changes in the binding energies of C 1s, Ti 2p and O 1s. By comparing the variation in the binding energy of Ti 2p to that of C 1s, and observing how the variation changes for different excitation signals (at different frequency and amplitudes), it is possible to inspect the effect of the oxygen vacancy drift. We employed a variety of input signals with varying frequency and amplitudes in order to test the memristive devices thoroughly: sine wave, triangular wave and DC bias. Graphene has been attracting attention due to its intriguing optoelectronic properties. This study utilizes graphene as a transparent top electrode for in situ measurements in XPS to observe chemically-addressed memristive hysteresis while an excitation signal is being applied to the device.

Graphene mode-locked femtosecond Alexandrite laser.

We report for the first time, to the best of our knowledge, graphene mode-locked operation of a femtosecond Alexandrite laser at 750 nm. A multipass-cavity configuration was employed to scale the output energy and to eliminate spectral/Q-switching instabilities. By using a monolayer graphene saturable absorber, mode locking could be obtained. With 5 W of pump at 532 nm, nearly transform-limited, 65 fs pulses with a time-bandwidth product of 0.319 were generated. The mode-locked laser operated at a pulse repetition rate of 5.56 MHz and produced 8 mW output power, corresponding to a pulse energy and peak power of 1.4 nJ and 22 kW, respectively. These experiments further show that graphene can be used to initiate mode locking at wavelengths as low as 750 nm.

Graphene-Based Adaptive Thermal Camouflage.

In nature, adaptive coloration has been effectively utilized for concealment and signaling. Various biological mechanisms have evolved to tune the reflectivity for visible and ultraviolet light. These examples inspire many artificial systems for mimicking adaptive coloration to match the visual appearance to their surroundings. Thermal camouflage, however, has been an outstanding challenge which requires an ability to control the emitted thermal radiation from the surface. Here we report a new class of active thermal surfaces capable of efficient real-time electrical-control of thermal emission over the full infrared (IR) spectrum without changing the temperature of the surface. Our approach relies on electro-modulation of IR absorptivity and emissivity of multilayer graphene via reversible intercalation of nonvolatile ionic liquids. The demonstrated devices are light (30 g/m2), thin (<50 µm), and ultraflexible, which can conformably coat their environment. In addition, by combining active thermal surfaces with a feedback mechanism, we demonstrate realization of an adaptive thermal camouflage system which can reconfigure its thermal appearance and blend itself with the varying thermal background in a few seconds. Furthermore, we show that these devices can disguise hot objects as cold and cold ones as hot in a thermal imaging system. We anticipate that, the electrical control of thermal radiation would impact on a variety of new technologies ranging from adaptive IR optics to heat management for outer space applications.

NLL-Assisted Multilayer Graphene Patterning.

The range of applications of diverse graphene-based devices could be limited by insufficient surface reactivity, unsatisfied shaping, or null energy gap of graphene. Engineering the graphene structure by laser techniques can adjust the transport properties and the surface area of graphene, providing devices of different nature with a higher capacitance. Additionally, the created periodic potential and appearance of the active external/inner/edge surface centers determine the multifunctionality of the graphene surface and corresponding devices. Here, we report on the first implementation of nonlinear laser lithography (NLL) for multilayer graphene (MLG) structuring, which offers a low-cost, single-step, and high-speed nanofabrication process. The NLL relies on the employment of a high repetition rate femtosecond Yb fiber laser that provides generation of highly reproducible, robust, uniform, and periodic nanostructures over a large surface area (1 cm2/15 s). NLL allows one to obtain clearly predesigned patterned graphene structures without fabrication tolerances, which are caused by contacting mask contamination, polymer residuals, and direct laser exposure of the graphene layers. We represent regularly patterned MLG (p-MLG) obtained by the chemical vapor deposition method on an NLL-structured Ni foil. We also demonstrate tuning of chemical (wettability) and electro-optical (transmittance and sheet resistance) properties of p-MLG by laser power adjustments. In conclusion, we show the great promise of fabricated devices, namely, supercapacitors, and Li-ion batteries by using NLL-assisted graphene patterning. Our approach demonstrates a new avenue to pattern graphene for multifunctional device engineering in optics, photonics, and bioelectronics.

Electrically switchable metadevices via graphene.

Metamaterials bring subwavelength resonating structures together to overcome the limitations of conventional materials. The realization of active metadevices has been an outstanding challenge that requires electrically reconfigurable components operating over a broad spectrum with a wide dynamic range. However, the existing capability of metamaterials is not sufficient to realize this goal. By integrating passive metamaterials with active graphene devices, we demonstrate a new class of electrically controlled active metadevices working in microwave frequencies. The fabricated active metadevices enable efficient control of both amplitude (>50 dB) and phase (>90°) of electromagnetic waves. In this hybrid system, graphene operates as a tunable Drude metal that controls the radiation of the passive metamaterials. Furthermore, by integrating individually addressable arrays of metadevices, we demonstrate a new class of spatially varying digital metasurfaces where the local dielectric constant can be reconfigured with applied bias voltages. In addition, we reconfigure resonance frequency of split-ring resonators without changing its amplitude by damping one of the two coupled metasurfaces via graphene. Our approach is general enough to implement various metamaterial systems that could yield new applications ranging from electrically switchable cloaking devices to adaptive camouflage systems.

Femtosecond pulse generation from a Ti3+:sapphire laser near 800 nm with voltage reconfigurable graphene saturable absorbers.

We experimentally show that a voltage-controlled graphene-gold supercapacitor saturable absorber (VCG-gold-SA) can be operated as a fast saturable absorber with adjustable linear absorption at wavelengths as low as 795 nm. This was made possible by the use of a novel supercapacitor architecture, consisting of a high-dielectric electrolyte sandwiched between a graphene and a gold electrode. The high-dielectric electrolyte allowed continuous, reversible adjustment of the Fermi level and, hence, the optical loss of the VCG-gold-SA up to the visible wavelengths at low bias voltages of the order of a few volts (0-2 V). The fast saturable absorber action of the VCG-gold-SA and the bias-dependent reduction of its loss were successfully demonstrated inside a femtosecond Ti3+:sapphire laser operating near 800 nm. Dispersion compensation was employed by using dispersion control mirrors and a prism pair. At a bias voltage of 1.2 V, the laser operated with improved power performance in comparison with that at zero bias, and the VCG-gold-SA initiated the generation of nearly transform-limited pulses as short as 48 fs at a pulse repetition rate of 131.7 MHz near 830 nm. To the best of our knowledge, this represents the shortest wavelength where a VCG-gold-SA has been employed as a mode locker with adjustable loss.

In-Situ XPS Monitoring and Characterization of Electrochemically Prepared Au Nanoparticles in an Ionic Liquid.

Gold nanoparticles (Au NPs) have been electrochemically prepared in situ and in vacuo using two different electrochemical device configurations, containing an ionic liquid (IL), N-N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide, that serves both as reaction and as stabilizing media for the NPs. It was observed in both devices that Au NPs were created using an anodically triggered route. The created Au NPs are relatively small (3-7 nm) and reside within the IL medium. X-ray photoelectron spectroscopy is utilized to follow not only the formation of the NPs but also their charging/discharging properties, by monitoring the charging shifts of the Au4f peak representing the electrodes and also the Au NPs as well as the F1s peak of the IL after polarizing one of the electrodes. Accordingly, DC polarization across the electrodes leads to a uniform binding energy shift of F1s of the IL along with that of Au4f of the NPs within. Moreover, this shift corresponds to only half of the applied potential. AC polarization brings out another dimension for demonstrating further the harmony between the charging/discharging property of the IL medium and the Au NPs in temporally and laterally resolved fashions. Polarization of the electrodes result in perfect spectral separation of the Au4f peaks of the NPs from those of the metal in both static (DC) and in time- and position-dependent (AC) modes.

Generation of sub-20-fs pulses from a graphene mode-locked laser.

We demonstrate, what is to our knowledge, the shortest pulses directly generated to date from a solid-state laser, mode locked with a graphene saturable absorber (GSA). In the experiments, a low-threshold diode-pumped Cr3+:LiSAF laser was used near 850 nm. At a pump power of 275 mW provided by two pump diodes, the Cr3+:LiSAF laser produced nearly transform-limited, 19-fs pulses with an average output power of 8.5 mW. The repetition rate was around 107 MHz, corresponding to a pulse energy and peak power of 79 pJ and 4.2 kW, respectively. Once mode locking was initiated with the GSA, stable, uninterrupted femtosecond pulse generation could be obtained. In addition, the femtosecond output of the laser could be tuned from 836 nm to 897 nm with pulse durations in the range of 80-190 fs. We further performed detailed mode locking initiation tests across the full cavity stability range of the laser to verify that pulse generation was indeed started by the GSA and not by Kerr lens mode locking.