GaAs Mid-IR Electrically Tunable Metasurfaces.

In this work, we explore III-V based metal-semiconductor-metal structures for tunable metasurfaces. We use an epitaxial transfer technique to transfer a III-V thin film directly on metallic surfaces, realizing III-V metal-semiconductor-metal (MSM) structures without heavily doped semiconductors as substitutes for metal layers. The device platform consists of gold metal layers with a p-i-n GaAs junction. The target resonance wavelength can be tuned by modifying the geometry of the top metal grating on the GaAs, while systematic resonance tunability has been shown through the modulation of various carrier concentration injections in the mid-IR range. Electrically tunable metasurfaces with multilevel biasing can serve as a fundamental building block for electrically tunable metasurfaces. We believe that our demonstration can contribute to understanding the optical tuning of III-V under various biased conditions, inducing changes in metasurfaces.

Monolithic III-V on Metal for Thermal Metasurfaces.

It has been proposed that metal-semiconductor-metal (MSM) structures can be used to tune the absorptivity of a metasurface at infrared wavelengths. Indium arsenide (InAs) is a low-band-gap, high-electron-mobility semiconductor that may enable rapid index tuning for dynamic control over the infrared spectrum. However, direct growth of III-V thin films on top of metals has typically resulted in small-grain, polycrystalline materials that are not amenable to high-quality devices. Previously, epitaxial wafers were used for this purpose. However, the epitaxial constraints required that InAs be used for both the tuning layer and the bottom "metallic" layer, limiting the range of accessible designs. In this work, we show a demonstration of direct growth of single-crystalline InAs on metal to build tunable absorbers/emitters in the infrared regime. The growth was carried out at a temperature of 300 °C by the low temperature templated liquid phase (LT-TLP) method. The size of InAs single-crystalline mesas is ∼2500 µm2, enabling the desired device sizes. The proposed growth and device enable scalable and tunable infrared devices for various thermal-photonic applications.

Tunable Onset of Hydrogen Evolution in Graphene with Hot Electrons.

Here, we show that the turn-on voltage for the hydrogen evolution reaction on a graphene surface can be tuned in a semiconductor-insulator-graphene (SIG) device immersed in a solution. Specifically, it is shown that the hydrogen evolution reaction (HER) onset for the graphene can shift by >0.8 V by application of a voltage across a graphene-Al2O3-silicon junction. We show that this shift occurs due to the creation of a hot electron population in graphene due to tunneling from the Si to graphene. Through control experiments, we show that the presence of the graphene is necessary for this behavior. By analyzing the silicon, graphene, and solution current components individually, we find an increase in the silicon current despite a fixed graphene-silicon voltage, corresponding to an increase in the HER current. This additional silicon current appears to directly drive the electrochemical reaction, without modifying the graphene current. We term this current "direct injection current" and hypothesize that this current occurs due to electrons injected from the silicon into graphene that drives the HER before any electron-electron scattering occurs in the graphene. To further determine whether hot electrons injected at different energies could explain the observed total solution current, the nonequilibrium electron dynamics was studied using a 2D ensemble Monte Carlo Boltzmann transport equation (MCBTE) solver. By rigorously considering the key scattering mechanisms, we show that the injected hot electrons can significantly increase the available electron flux at high energies. These results show that semiconductor-insulator-graphene devices are a platform which can tune the electrochemical reaction rate via multiple mechanisms.

High Quantum Efficiency Hot Electron Electrochemistry.

Using hot electrons to drive electrochemical reactions has drawn considerable interest in driving high-barrier reactions and enabling efficient solar to fuel conversion. However, the conversion efficiency from hot electrons to electrochemical products is typically low due to high hot electron scattering rates. Here, it is shown that the hydrogen evolution reaction (HER) in an acidic solution can be efficiently modulated by hot electrons injected into a thin gold film by an Au-Al2O3-Si metal-insulator-semiconductor (MIS) junction. Despite the large scattering rates in gold, it is shown that the hot electron driven HER can reach quantum efficiencies as high as ∼85% with a shift in the onset of hydrogen evolution by ∼0.6 V. By simultaneously measuring the currents from the solution, gold, and silicon terminals during the experiments, we find that the HER rate can be decomposed into three components: (i) thermal electron, corresponding to the thermal electron distribution in gold; (ii) hot electron, corresponding to electrons injected from silicon into gold which drive the HER before fully thermalizing; and (iii) silicon direct injection, corresponding to electrons injected from Si into gold that drive the HER before electron-electron scattering occurs. Through a series of control experiments, we eliminate the possibility of the observed HER rate modulation coming from lateral resistivity of the thin gold film, pinholes in the gold, oxidation of the MIS device, and measurement circuit artifacts. Next, we theoretically evaluate the feasibility of hot electron injection modifying the available supply of electrons. Considering electron-electron and electron-phonon scattering, we track how hot electrons injected at different energies interact with the gold-solution interface as they scatter and thermalize. The simulator is first used to reproduce other published experimental pump-probe hot electron measurements, and then simulate the experimental conditions used here. These simulations predict that hot electron injection first increases the supply of electrons to the gold-solution interface at higher energies by several orders of magnitude and causes a peaked electron interaction with the gold-solution interface at the electron injection energy. The first prediction corresponds to the observed hot electron electrochemical current, while the second prediction corresponds to the observed silicon direct injection current. These results indicate that MIS devices offer a versatile platform for hot electron sources that can efficiently drive electrochemical reactions.

High-Speed Growth of ZnO Nanorods in Preheating Condition Using Microwave-Assisted Growth Method.

In this study, we present the microwave-assisted growth (MAG) of ZnO nanorods (ZNRs) using a preheating hydrothermal method under tailored preheating and postheating growth conditions. The perimeters such as solution concentration, preheating time, and postheating time, were changed to optimize ZNR growth and the growth was carried out in a domestic 850 watt microwave oven. Preheated solution was utilized as an accelerator to increase the aspect ratio of the ZNRs and reduce the fabrication time. Because of a long fabrication time and limited length in the conventional MAG method, preheating condition was used for efficient growth of nanorods through homogeneous nucleation in the solution and then heterogeneous nucleation of the formed ZNRs on seeded substrate during postheating process. The nanostructures were characterized with scanning electron microscopy to look at the morphology and dimensions. Dimensions of ZNRs kept on increasing as the molar concentration went higher. Preheating time highly affected the morphology, dimensions, and aspect ratio of ZNRs and postheating time not only ensured the stability of ZNRs with substrate due to heterogeneous nucleation process but also influenced the morphology of ZNRs.