Bingya Hou

Artificial Photosynthesis on TiO2-Passivated InP Nanopillars

Here, we report photocatalytic CO2 reduction with water to produce methanol using TiO2-passivated InP nanopillar photocathodes under 532 nm wavelength illumination. In addition to providing a stable photocatalytic surface, the TiO2-passivation layer provides substantial enhancement in the photoconversion efficiency through the introduction of O vacancies associated with the nonstoichiometric growth of TiO2 by atomic layer deposition. Plane wave-density functional theory (PW-DFT) calculations confirm the role of oxygen vacancies in the TiO2 surface, which serve as catalytically active sites in the CO2 reduction process. PW-DFT shows that CO2 binds stably to these oxygen vacancies and CO2 gains an electron (-0.897e) spontaneously from the TiO2 support. This calculation indicates that the O vacancies provide active sites for CO2 absorption, and no overpotential is required to form the CO2(-) intermediate. The TiO2 film increases the Faraday efficiency of methanol production by 5.7× to 4.79% under an applied potential of -0.6 V vs NHE, which is 1.3 V below the E(o)(CO2/CO2(-)) = -1.9 eV standard redox potential. Copper nanoparticles deposited on the TiO2 act as a cocatalyst and further improve the selectivity and yield of methanol production by up to 8-fold with a Faraday efficiency of 8.7%.

Artificial Photosynthesis on TiO 2 -Passivated InP Nanopillars

Here, we report photocatalytic CO2 reduction with water to produce methanol using TiO2-passivated InP nanopillar photocathodes under 532 nm wavelength illumination. In addition to providing a stable photocatalytic surface, the TiO2-passivation layer provides substantial enhancement in the photoconversion efficiency through the introduction of O vacancies associated with the nonstoichiometric growth of TiO2 by atomic layer deposition. Plane wave-density functional theory (PW-DFT) calculations confirm the role of oxygen vacancies in the TiO2 surface, which serve as catalytically active sites in the CO2 reduction process. PW-DFT shows that CO2 binds stably to these oxygen vacancies and CO2 gains an electron (-0.897e) spontaneously from the TiO2 support. This calculation indicates that the O vacancies provide active sites for CO2 absorption, and no overpotential is required to form the CO2(-) intermediate. The TiO2 film increases the Faraday efficiency of methanol production by 5.7× to 4.79% under an applied potential of -0.6 V vs NHE, which is 1.3 V below the E(o)(CO2/CO2(-)) = -1.9 eV standard redox potential. Copper nanoparticles deposited on the TiO2 act as a cocatalyst and further improve the selectivity and yield of methanol production by up to 8-fold with a Faraday efficiency of 8.7%.

Enhanced Photocatalytic Reduction of CO2 to CO through TiO2 Passivation of InP in Ionic Liquids

A robust and reliable method for improving the photocatalytic performance of InP, which is one of the best known materials for solar photoconversion (i.e., solar cells). In this article, we report substantial improvements (up to 18×) in the photocatalytic yields for CO2 reduction to CO through the surface passivation of InP with TiO2 deposited by atomic layer deposition (ALD). Here, the main mechanisms of enhancement are the introduction of catalytically active sites and the formation of a pn-junction. Photoelectrochemical reactions were carried out in a nonaqueous solution consisting of ionic liquid, 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM]BF4), dissolved in acetonitrile, which enables CO2 reduction with a Faradaic efficiency of 99% at an underpotential of +0.78 V. While the photocatalytic yield increases with the addition of the TiO2 layer, a corresponding drop in the photoluminescence intensity indicates the presence of catalytically active sites, which cause an increase in the electron-hole pair recombination rate. NMR spectra show that the [EMIM](+) ions in solution form an intermediate complex with CO2(-), thus lowering the energy barrier of this reaction.

Clamping instability and van der Waals forces in carbon nanotube mechanical resonators.

We investigate the role of weak clamping forces, typically assumed to be infinite, in carbon nanotube mechanical resonators. Due to these forces, we observe a hysteretic clamping and unclamping of the nanotube device that results in a discrete drop in the mechanical resonance frequency on the order of 5-20 MHz, when the temperature is cycled between 340 and 375 K. This instability in the resonant frequency results from the nanotube unpinning from the electrode/trench sidewall where it is bound weakly by van der Waals forces. Interestingly, this unpinning does not affect the Q-factor of the resonance, since the clamping is still governed by van der Waals forces above and below the unpinning. For a 1 μm device, the drop observed in resonance frequency corresponds to a change in nanotube length of approximately 50-65 nm. On the basis of these findings, we introduce a new model, which includes a finite tension around zero gate voltage due to van der Waals forces and shows better agreement with the experimental data than the perfect clamping model. From the gate dependence of the mechanical resonance frequency, we extract the van der Waals clamping force to be 1.8 pN. The mechanical resonance frequency exhibits a striking temperature dependence below 200 K attributed to a temperature-dependent slack arising from the competition between the van der Waals force and the thermal fluctuations in the suspended nanotube.

Enhanced photoluminescence in air-suspended carbon nanotubes by oxygen doping

We report photoluminescence (PL) imaging and spectroscopy of air-suspended carbon nanotubes (CNTs) before and after exposure to a brief (20 s) UV/ozone treatment. These spectra show enhanced PL intensities in 10 out of 11 nanotubes that were measured, by as much as 5-fold. This enhancement in the luminescence efficiency is caused by oxygen defects which trap excitons. We also observe an average 3-fold increase in the D-band Raman intensity further indicating the creation of defects. Previous demonstrations of oxygen doping have been carried out on surfactant-coated carbon nanotubes dissolved in solution, thus requiring substantial longer ozone/UV exposure times (∼15 h). Here, the ozone treatment is more efficient because of the surface exposure of the air-suspended CNTs. In addition to enhanced PL intensities, we observe narrowing of the emission linewidth by 3–10 nm. This ability to control and engineer defects in CNTs is important for realizing several optoelectronic applications such as light-emitting ...

Cross-plane Thermoelectric and Thermionic Transport across Au/ h -BN/Graphene Heterostructures

The thermoelectric voltage generated at an atomically abrupt interface has not been studied exclusively because of the lack of established measurement tools and techniques. Atomically thin 2D materials provide an excellent platform for studying the thermoelectric transport at these interfaces. Here, we report a novel technique and device structure to probe the thermoelectric transport across Au/h-BN/graphene heterostructures. An indium tin oxide (ITO) transparent electrical heater is patterned on top of this heterostructure, enabling Raman spectroscopy and thermometry to be obtained from the graphene top electrode in situ under device operating conditions. Here, an AC voltage V(ω) is applied to the ITO heater and the thermoelectric voltage across the Au/h-BN/graphene heterostructure is measured at 2ω using a lock-in amplifier. We report the Seebeck coefficient for our thermoelectric structure to be −215 μV/K. The Au/graphene/h-BN heterostructures enable us to explore thermoelectric and thermal transport on nanometer length scales in a regime of extremely short length scales. The thermoelectric voltage generated at the graphene/h-BN interface is due to thermionic emission rather than bulk diffusive transport. As such, this should be thought of as an interfacial Seebeck coefficient rather than a Seebeck coefficient of the constituent materials.

Plasmon Resonant Amplification of a Hot Electron-Driven Photodiode

We report plasmon resonant excitation of hot electrons in a photodetector based on a metal/oxide/metal (Au/Al2O3/graphene) heterostructure. In this device, hot electrons, excited optically in the gold layer, jump over the oxide barrier and are injected into the graphene layer, producing a photocurrent. To amplify this process, the bottom gold electrode is patterned into a plasmon resonant grating structure with a pitch of 500 nm. The photocurrent produced in this device is measured using 633-nm-wavelength light as a function of incident angle. We observe the maximum photocurrent at ±10° from normal incidence under irra-diation with light polarized parallel to the incident plane (p-polarization) and perpendicular to the lines on the grating, and a constant (angle-independent) photocurrent under irradiation with light polarized perpendicular to the incident plane (s-polarization) and parallel to the grating. These data show an amplification factor of 4.6× under resonant conditions. At the same angle (±10°), we also observe sharp dips in the photoreflectance corresponding to waveve-ctor matching between the incident light and the plasmon mode in the grating. In addition, finite-difference time-domain simulations predict sharp dips in the photoreflectance at ±10°, and the electric field intensity profiles show clear excitation of a plasmon resonant mode when illuminated with p-polarized light at this angle.

Plasmon resonant amplification of hot electron-driven photocatalysis

We report plasmon resonant excitation of hot electrons in a metal based photocatalyst in the oxygen evolution half reaction in aqueous solution. Here, the photocatalyst consists of a 100-nm thick Au film deposited on a corrugated silicon substrate. In this configuration, hot electrons photoexcited in the metal are injected into the solution, ultimately reversing the water oxidation reaction (O2 + 4H+ + 4e− ⇋ 2H2O) and producing a photocurrent. In order to amplify this process, the gold electrode is patterned into a plasmon resonant grating structure with a pitch of 500 nm. The photocurrent (i.e., charge transfer rate) is measured as a function of incident angle using 633 nm wavelength light. We observe peaks in the photocurrent at incident angles of ±9° from normal when the light is polarized parallel to the incident plane (p-polarization) and perpendicular to the lines on the grating. Based on these peaks, we estimate an overall plasmonic gain (or amplification) factor of 2.1× in the charge transfer rate. At these same angles, we also observe sharp dips in the photoreflectance, corresponding to the condition when there is wavevector matching between the incident light and the plasmon mode in the grating. No angle dependence is observed in the photocurrent or photoreflectance when the incident light is polarized perpendicular to the incident plane (s-polarization) and parallel to the lines on the grating. Finite difference time domain simulations also predict sharp dips in the photoreflectance at ±9°, and the electric field intensity profiles show clear excitation of a plasmon-resonant mode when illuminated at those angles with p-polarized light.We report plasmon resonant excitation of hot electrons in a metal based photocatalyst in the oxygen evolution half reaction in aqueous solution. Here, the photocatalyst consists of a 100-nm thick Au film deposited on a corrugated silicon substrate. In this configuration, hot electrons photoexcited in the metal are injected into the solution, ultimately reversing the water oxidation reaction (O2 + 4H+ + 4e− ⇋ 2H2O) and producing a photocurrent. In order to amplify this process, the gold electrode is patterned into a plasmon resonant grating structure with a pitch of 500 nm. The photocurrent (i.e., charge transfer rate) is measured as a function of incident angle using 633 nm wavelength light. We observe peaks in the photocurrent at incident angles of ±9° from normal when the light is polarized parallel to the incident plane (p-polarization) and perpendicular to the lines on the grating. Based on these peaks, we estimate an overall plasmonic gain (or amplification) factor of 2.1× in the charge transfer rate...

Enhanced thermoelectric efficiency in topological insulator Bi2Te3 nanoplates via atomic layer deposition-based surface passivation

We report in-plane thermoelectric measurements of Bi2Te3 nanoplates, a typical topological insulator with Dirac-like metallic surface states, grown by chemical vapor deposition. The as-grown flakes exposed to ambient conditions exhibit relatively small thermopowers around −34 μV/K due to unintentional surface doping (e.g., gas adsorption and surface oxidation). After removal of the unintentional surface doping and surface passivation by deposition of 30 nm of Al2O3 using atomic layer deposition (ALD), the Seebeck coefficient of these flakes increases by a factor of 5× to −169 μV/K. Here, we believe that the ALD-based surface passivation can prevent the degradation of the thermoelectric properties caused by gas adsorption and surface oxidation processes, thus, reducing the unintentional doping in the Bi2Te3 and increasing the Seebeck coefficient. The high surface-to-volume ratio of these thin (∼10 nm thick) nanoplates make them especially sensitive to surface doping, which is a common problem among nanomaterials in general. An increase in the sample resistance is also observed after the ALD process, which is consistent with the decrease in doping.We report in-plane thermoelectric measurements of Bi2Te3 nanoplates, a typical topological insulator with Dirac-like metallic surface states, grown by chemical vapor deposition. The as-grown flakes exposed to ambient conditions exhibit relatively small thermopowers around −34 μV/K due to unintentional surface doping (e.g., gas adsorption and surface oxidation). After removal of the unintentional surface doping and surface passivation by deposition of 30 nm of Al2O3 using atomic layer deposition (ALD), the Seebeck coefficient of these flakes increases by a factor of 5× to −169 μV/K. Here, we believe that the ALD-based surface passivation can prevent the degradation of the thermoelectric properties caused by gas adsorption and surface oxidation processes, thus, reducing the unintentional doping in the Bi2Te3 and increasing the Seebeck coefficient. The high surface-to-volume ratio of these thin (∼10 nm thick) nanoplates make them especially sensitive to surface doping, which is a common problem among nanomat...

Prevention of surface recombination by electrochemical tuning of TiO2-passivated photocatalysts

We present a systematic study of photoluminescence (PL) spectroscopy of TiO2-passivated GaAs as a function of electrochemical potential in an ionic liquid solution. We observe a 7X increase in the PL intensity as the GaAs transitions from accumulation to depletion due to the applied potential. We attribute this to the excellent control over the surface Fermi level enabled by the high capacitance of the electrochemical double layer and TiO2. This allows us to control the surface carrier concentration and corresponding non-radiative recombination rate. In addition to photoluminescence (PL) spectroscopy, we also measured the capacitance-potential (i.e., C-V) characteristics of these samples, which indicate flat band potentials that are consistent with these regimes of ion accumulation observed in the photoluminescence measurements. We have also performed electrostatic simulations of these C-V characteristics, which provide a detailed and quantitative picture of the conduction and valence band profiles and ch...