Photoinduced Enhancement Research Articles

Room-temperature relaxor ferroelectricity and photovoltaic effects in tin titanate directly deposited on a silicon substrate

We have studied ferroelectricity and photovoltaic effects in atomic layer deposited (ALD) 40-nm thick SnTiO$_{x}$ films deposited directly onto p-type (001)Si substrate. These films showed well-saturated, square and repeatable hysteresis loops with remnant polarization of 1.5 $\mu$C/cm$^{2}$ at room temperature, as detected by out-of-plane polarization versus electric field (P-E) and field cycling measurements. A photo-induced enhancement in ferroelectricity was also observed as the spontaneous polarization increased under white-light illumination. The ferroelectricity exhibits relaxor characteristics with dielectric peak shifting from ca. T = 600 K at f = 1 MHz to ca. 500 K at 100 Hz. Moreover, our films showed ferroelectric photovoltaic behavior under the illumination of a wide spectrum of light, from visible to ultraviolet regions. A combination of experiment and theoretical calculation provided optical band gap of SnTiO$_{x}$ films which lies in the visible range of white light spectra. Our study leads a way to develop green ferroelectric SnTiO$_{x}$ thin films, which are compatible to semiconducting processes, and can be used for various ferroelectric and dielectric applications.

Liposomes formed from photo-cleavable phospholipids: in situ formation and photo-induced enhancement in permeability.

Photocleavable liposomes were formed in situ through the coupling of an o-nitrobenzyl-containing azide tail precursor and an alkyne-functionalized lysolipid by the copper-catalyzed azide–alkyne cycloaddition (CuAAC) reaction. Inclusion of the photolabile o-nitrobenzyl-structure enables control over the permeability and morphology of the liposomes. Photolysis of the o-nitrobenzyl group changes the molecular structure of the photolabile phospholipids, inducing phase transitions and permeability increases in the bilayer membrane, ultimately disrupting the liposome entity.

Passive membrane penetration by ZnO nanoparticles is driven by the interplay of electrostatic and phase boundary conditions.

The internalization of nanoparticles through the biological membrane is of immense importance for biomedical applications. A fundamental understanding of the lipid specificity and the role of the membrane biochemical and physical forces at play in modulating penetration are lacking. The current understanding of nanoparticle-membrane interaction is drawn mostly from computational studies and lacks sufficient experimental evidence. Herein, using confocal fluorescence imaging and potentiometric dye-based fluorimetry, we first investigated the interaction of ZnONP in both multi-component and individual lipid membranes using cell-like giant unilamellar vesicles to dissect the lipid specificity; also, we investigated the changes in membrane order, anisotropy and hydrophobicity. ZnONP was found to interact with phosphatidylinositol and phosphatidylcholine head-group-containing lipids specifically. We further investigated the interaction of ZnONP with three physiologically relevant membrane conditions varying in composition and dipole potential. We found that ZnONP interaction leads to a photoinduced enhancement of the partial-to-complete phase separation depending upon the membrane composition and cholesterol content. Interestingly, while the lipid order of a partially-phase-separated membrane remained unchanged upon ZnONP crowding, a fully-phase-separated membrane showed an increase in the lipid order. Strikingly, ZnONP crowding induced a contrasting effect on the fluorescence anisotropy of the membrane upon binding to the two membrane conditions, in line with the measured diffusion coefficient. ZnONP seems to preferentially penetrate through the liquid disordered areas of the membrane and the boundaries of the phase-separated regions driven by the interplay between the electrostatics and phase boundary conditions, which are collectively dictated by the composition and ZnONP-induced lipid reorganization. The results may lead to a greater understanding of the interplay of membrane parameters and ZnONP interaction in driving passive penetration.

Photoinduced Enhancement of Excitonic Order.

We study the dynamics of excitonic insulators coupled to phonons using the time-dependent mean-field theory. Without phonon couplings, the linear response is given by the damped amplitude oscillations of the order parameter with a frequency equal to the minimum band gap. A phonon coupling to the interband transfer integral induces two types of long-lived collective oscillations of the amplitude, one originating from the phonon dynamics and the other from the phase mode, which becomes massive. We show that, even for small phonon coupling, a photoinduced enhancement of the exciton condensation and the gap can be realized. Using the Anderson pseudospin picture, we argue that the origin of the enhancement is a cooperative effect of the massive phase mode and the Hartree shift induced by the photoexcitation. We also discuss how the enhancement of the order and the collective modes can be observed with time-resolved photoemission spectroscopy.

Photo-induced persistent enhancement of dielectric permittivity in Zn:BaAl2O4

Photo-induced persistent enhancement of dielectric permittivity has been demonstrated in Ba(Al0.97Zn0.03)2O4−δ (BAZ) with a stuffed-tridymite-type structure under photo-irradiation with an energy of 3.4 eV (365 nm). The dielectric permittivity is enhanced by more than 20% and shows a weak frequency dependency. The dielectric loss (tanδ) shows only a slight increment for frequencies up to 1 MHz, indicating that the incremental change in dielectric permittivity of BAZ is not caused by photoconduction. This enhancement persists on termination of photo-irradiation. The results of this study suggest that the origin of the enhancement of dielectric permittivity is related to the dielectric response of the photo-excited dipole moments, which are composed of photo-excited electrons trapped in in-gap states and photo-excited holes generated in the valence band maximum. These findings shed light on the development of devices that can control dielectric properties by photo-irradiation.

Photo-Induced Performance Enhancement of Tantalum Nitride for Solar Water Oxidation

Summary The semiconductor/electrolyte interface plays important roles in defining the performance of photocatalysts but is poorly studied. Here, we report a surprising observation that unique reactions at this interface under photo-electrochemical (PEC) conditions lead to unusual performance enhancement of Ta 3 N 5 for solar water oxidation reactions. The enhancement was only observed when Co(OH) 2 was introduced as a water oxidation co-catalyst. Illumination and positive bias were also critical to the enhancement. It was proposed that O • radical formation induced by illumination results in the formation of Ta-O-Co bonds, which exhibit less severe Fermi-level pinning when compared with Ta-O-Ta bonds that are more commonly observed on bare Ta 3 N 5 under normal PEC conditions. When a high-performance oxygen evolution catalyst such as cobalt phosphate (Co-Pi) was added to the Ta 3 N 5 /Co(OH) 2 system, high photocurrent densities and good stability were achieved simultaneously.

Bi3TeBO9: electronic structure, optical properties and photoinduced phenomena

Improvement of the nonlinear optical properties, mainly photoinduced enhancement of effective second harmonic generation was observed in Bi3TeBO9 (BTBO) crystals under irradiation of two external UV laser beams. The effect is caused by an interaction of two coherent photoinducing beams of nitrogen laser with wavelength 371 nm near the Bi3TeBO9 fundamental edge, resulting in formation of additional anisotropy. To explain the observed phenomenon and establish the general features of the electronic structure, the band structure calculations, as well as electronic density of states, elastic properties and principal optical functions were simulated by means of the density functional theory approach. The comparison of the nonlinear optical properties with the conventional α-BIBO crystal shows that BTBO is a promising material for the fabrication of UV laser optical triggers.

High-Frequency Analysis of Effective Interactions and Bandwidth for Transient States after Monocycle Pulse Excitation of Extended Hubbard Model

Using a high-frequency expansion in periodically driven extended Hubbard models, where the strengths and ranges of density-density interactions are arbitrary, we obtain the effective interactions and bandwidth, which depend sensitively on the polarization of the driving field. Then, we numerically calculate modulations of correlation functions in a quarter-filled extended Hubbard model with nearest-neighbor interactions on a triangular lattice with trimers after monocycle pulse excitation. We discuss how the resultant modulations are compatible with the effective interactions and bandwidth derived above on the basis of their dependence on the polarization of photoexcitation, which is easily accessible by experiments. Some correlation functions after monocycle pulse excitation are consistent with the effective interactions, which are weaker or stronger than the original ones. However, the photoinduced enhancement of anisotropic charge correlations previously discussed for the three-quarter-filled organic conductor $\alpha$-(bis[ethylenedithio]-tetrathiafulvalene)$_2$I$_3$ [$\alpha$-(BEDT-TTF)$_2$I$_3$] in the metallic phase is not fully explained by the effective interactions or bandwidth, which are derived independently of the filling.

Enhancing the Photocatalytic Hydrogen Evolution Performance of a Metal/Semiconductor Catalyst through Modulation of the Schottky Barrier Height by Controlling the Orientation of the Interface

Construction of a metal-semiconductor heterojunction is a promising method to improve heterogeneous photocatalysis for various reactions. Although the structure and photocatalytic performance of such a catalyst system have been extensively studied, few reports have demonstrated the effect of interface orientation at the metal-semiconductor junction on junction-barrier bending and the electronic transport properties. Here, we construct a Pt/PbS heterojunction, in which Pt nanoparticles are used as highly active catalysts and PbS nanocrystals (NCs) with well-controlled shapes are used as light-harvesting supports. Experimental results show that the photoelectrocatalytic activities of the Pt/PbS catalyst are strongly dependent on the contacting facets of PbS at the junction. Pt/octahedral PbS NCs with exposed PbS(111) facets show the highest photoinduced enhancement of hydrogen evolution reaction activity, which is ∼14.38 times higher than that of the ones with only PbS(100) facets (Pt/cubic PbS NCs). This enhancement can further be rationalized by the different energy barriers of the Pt/PbS Schottky junction due to the specific band structure and electron affinity, which is also confirmed by the calculations based on density functional theory. Therefore, controlling the contacting interfaces of a metal/semiconductor material may offer an effective approach to form the desired heterojunction for optimization of the catalytic performance.

Photoinduced Enhancement of Anisotropic Charge Correlations on Triangular Lattices with Trimers

To explore nontrivial photoinduced modulations of charge correlations, we theoretically study photoinduced dynamics in quarter-filled extended Hubbard models with competing intersite repulsive interactions on triangular lattices with trimers, where the end points are crystallographically equivalent. The exact diagonalization method is used and the time-dependent Schr\"odinger equation is numerically solved during and after photoexcitation. Time-averaged double occupancy and intersite density-density correlations can be interpreted as due to effective on-site and intersite repulsive interactions, respectively, relative to transfer energies. In the case where the intersite repulsive interactions compete with each other, the anisotropy of their effective interactions can be enhanced with the help of the trimers, irrespective of whether the trimers are linear or bent. In particular, in the case where the arrangement of the trimers is close to that in $\alpha$-(bis[ethylenedithio]-tetrathiafulvalene)$_2$I$_3$ [$\alpha$-(BEDT-TTF)$_2$I$_3$] in the metallic phase, the effective on-site repulsion is enhanced relative to the transfer energies. The relevance of this theoretical finding to the experimentally observed optical freezing of charge motion is discussed.

Photo-stability and time-resolved photoluminescence study of colloidal CdSe/ZnS quantum dots passivated in Al2O3 using atomic layer deposition

We report photo-stability enhancement of colloidal CdSe/ZnS quantum dots (QDs) passivated in Al2O3 thin film using the atomic layer deposition (ALD) technique. 62% of the original peak photoluminescence (PL) intensity remained after ALD. The photo-oxidation and photo-induced fluorescence enhancement effects of both the unpassivated and passivated QDs were studied under various conditions, including different excitation sources, power densities, and environment. The unpassivated QDs showed rapid PL degradation under high excitation due to strong photo-oxidation in air while the PL intensity of Al2O3 passivated QDs was found to remain stable. Furthermore, recombination dynamics of the unpassivated and passivated QDs were investigated by time-resolved measurements. The average lifetime of the unpassivated QDs decreases with laser irradiation time due to photo-oxidation. Photo-oxidation creates surface defects which reduces the QD emission intensity and enhances the non-radiative recombination rate. From the comparison of PL decay profiles of the unpassivated and passivated QDs, photo-oxidation-induced surface defects unexpectedly also reduce the radiative recombination rate. The ALD passivation of Al2O3 protects QDs from photo-oxidation and therefore avoids the reduction of radiative recombination rate. Our experimental results demonstrated that passivation of colloidal QDs by ALD is a promising method to well encapsulate QDs to prevent gas permeation and to enhance photo-stability, including the PL intensity and carrier lifetime in air. This is essential for the applications of colloidal QDs in light-emitting devices.

Photoinduced Enhancement of the Charge Density Wave Amplitude.

Symmetry breaking and the emergence of order is one of the most fascinating phenomena in condensed matter physics. It leads to a plethora of intriguing ground states found in antiferromagnets, Mott insulators, superconductors, and density-wave systems. Exploiting states of matter far from equilibrium can provide even more striking routes to symmetry-lowered, ordered states. Here, we demonstrate for the case of elemental chromium that moderate ultrafast photoexcitation can transiently enhance the charge-density-wave (CDW) amplitude by up to 30% above its equilibrium value, while strong excitations lead to an oscillating, large-amplitude CDW state that persists above the equilibrium transition temperature. Both effects result from dynamic electron-phonon interactions, providing an efficient mechanism to selectively transform a broad excitation of the electronic order into a well-defined, long-lived coherent lattice vibration. This mechanism may be exploited to transiently enhance order parameters in other systems with coupled degrees of freedom.

Fluorescence Blinking and Photoactivation of All-Inorganic Perovskite Nanocrystals CsPbBr3 and CsPbBr2I.

Study of the emission behavior of all-inorganic perovskite nanocrystals CsPbBr3 and CsPbBr2I as a function of the excitation power employing fluorescence correlation spectroscopy and conventional techniques reveals fluorescence blinking in the microsecond time scale and photoinduced emission enhancement. The observation provides insight into the radiative and nonradiative deactivation pathways of these promising substances. Because both blinking and photoactivation processes are intimately linked to the charge separation efficiency and dynamics of the nanocrystals, these key findings are likely to be helpful in realizing the true potential of these substances in photovoltaic and optoelectronic applications.

Photoinduced enhancement of a triboelectric nanogenerator based on an organolead halide perovskite

We report a methylammonium lead triiodide (MAPbI3) perovskite-based photoenhanced triboelectric nanogenerator (TENG).

Photo-induced enhancement of the power factor of Cu2S thermoelectric films

Element doping is commonly used to adjust the carrier concentrations in semiconductors such as thermoelectric materials. However, the doping process unavoidably brings in defects or distortions in crystal lattices, which further strongly affects the physical properties of the materials. In this work, high energy photons have been used to activate the carriers in Cu2S thermoelectric films. As a result, the carrier concentrations, and the respective electrical conductivity as well as Seebeck coefficient are further changed. The photon-induced electrical transport properties are further analyzed utilizing a Parallel circuit model. Due to the realization of optimized carrier concentrations by photon activation, the power factor of Cu2S film is improved more than 900 times as compared with the dark data. As compared to the traditional doping process, the approach using photon activation can realize the tuning of carrier concentrations without affecting crystal lattice. This method provides an opportunity to investigate the intrinsic physical properties of semiconductor materials without involving traditional element doping process that usually brings in additional lattice defects or distortions.

Optical and electron paramagnetic resonance studies of the excited triplet states of UV-B absorbers: 2-ethylhexyl salicylate and homomenthyl salicylate.

The energy levels and lifetimes of the lowest excited triplet (T1) states of UV-B absorbers, 2-ethylhexyl salicylate (EHS) and homomenthyl salicylate (HMS), and their deprotonated anions (EHS(-) and HMS(-)) were determined through measurements of phosphorescence and electron paramagnetic resonance (EPR) spectra in rigid solutions at 77 K. The observed T1 energies of EHS and HMS are higher than those of butylmethoxydibenzoylmethane, the most widely used UV-A absorber, and octyl methoxycinnamate, the most widely used UV-B absorber. The T1 states of EHS, HMS, EHS(-) and HMS(-) were assigned to almost pure (3)ππ* state from the observed T1 lifetimes and zero-field splitting parameters. EHS and HMS with an intramolecular hydrogen bond show a photoinduced phosphorescence enhancement in ethanol at 77 K. The EPR signals of the T1 states of EHS and HMS also increase in intensity with UV-irradiation time (photoinduced EPR enhancement). The T1 lifetimes of EHS and HMS at room temperature were determined through triplet-triplet absorption measurements in ethanol. The quantum yields of singlet oxygen production by EHS and HMS were determined by using time-resolved near-IR phosphorescence.

Hexahedron Prism-Anchored Octahedronal CeO2: Crystal Facet-Based Homojunction Promoting Efficient Solar Fuel Synthesis.

An unprecedented, crystal facet-based CeO2 homojunction consisting of hexahedron prism-anchored octahedron with exposed prism surface of {100} facets and octahedron surface of {111} facets was fabricated through solution-based crystallographic-oriented epitaxial growth. The photocatalysis experiment reveals that growth of the prism arm on octahedron allows to activate inert CeO2 octahedron for an increase in phototocatalytic reduction of CO2 into methane. The pronounced photocatalytic performance is attributed to a synergistic effect of the following three factors: (1) band alignment of the {100} and {111} drives electrons and holes to octahedron and prism surfaces, respectively, aiming to reach the most stable energy configuration and leading to a spatial charge separation for long duration; (2) crystallographic-oriented epitaxial growth of the CeO2 hexahedron prism arm on the octahedron verified by the interfacial lattice fringe provides convenient and fast channels for the photogenerated carrier transportation between two units of homojuntion; (3) different effective mass of electrons and holes on {100} and {111} faces leads to high charge carrier mobility, more facilitating the charge separation. The proposed facet-based homojunction in this work may provide a new concept for the efficient separation and fast transfer of photoinduced charge carriers and enhancement of the photocatalytic performance.

Wavelength-dependent optical enhancement of superconducting interlayer coupling inLa1.885Ba0.115CuO4

We analyze the pump wavelength dependence for the photo-induced enhancement of interlayer coupling in La1.885Ba0.115CuO4, which is promoted by optical melting of the stripe order. In the equilibrium superconducting state (T < Tc = 13 K), in which stripes and superconductivity coexist, time-domain THz spectroscopy reveals a photo-induced blue-shift of the Josephson Plasma Resonance after excitation with optical pulses polarized perpendicular to the CuO2 planes. In the striped, non-superconducting state (Tc < T < T_SO = 40 K) a transient plasma resonance similar to that seen below Tc appears from a featureless equilibrium reflectivity. Most strikingly, both these effects become stronger upon tuning of the pump wavelength from the mid-infrared to the visible, underscoring an unconventional competition between stripe order and superconductivity, which occurs on energy scales far above the ordering temperature.

Photoinduced magnetization enhancement in two-dimensional weakly anisotropic Heisenberg magnets

By comparing the photo-induced magnetization dynamics in simple layered systems we show how light-induced modifications of the magnetic anisotropy directly enhance the magnetization. It is observed that the spin precession in (CH3NH3)2CuCl4, initiated by a light pulse, increases in amplitude at the critical temperature TC. The phenomenon is related to the dependence of the critical temperature on the axial magnetic anisotropy. The present results underline the possibility and the importance of the optical modifications of the anisotropy, opening new paths toward the control of the magnetization state for ultrafast memories.

The Effect of External Gaseous Environments on the Photoluminescence Intensity of Quantum‐Dimensional Composite System

The luminescence properties of the composite system based on colloidal CdSe/ZnS core shell quantum dots and GaAs nanowires under continuous laser irradiation are investigated. The phenomenon of photoinduced luminescence enhancement under various gaseous environments is shown. In addition to the previously reported mechanisms of the photoluminescence enhancement, a new one which is connected to the quantum dots losses of vibrational energy during the collisions with molecules of external gases is proposed.