Revealing the Loss Mechanism of Chemically-Induced Hot Electron Transport.

Hot electrons are crucial for unraveling the intrinsic relationship between chemical reactions and charge transfer in heterogeneous catalysis. Significant research focused on real-time detection of reaction-driven hot electron flow (chemicurrent) to elucidate the energy conversion mechanisms, but it remains elusive because carrier generation contributes to only part of the entire process. Here, a theoretical model for quantifying the chemicurrent yield is presented by clarifying the contributions of hot carrier losses from the internal emission and multiple reflections. The experimental chemicurrent yield verifies our model with a reliable mean free path of hot electrons, emphasizing the importance of comprehensive consideration of the transport process besides hot electron generation. Moreover, Pt nanoparticles (NPs)-decorated Au/TiO2 is examined, showing the role of NPs-induced carrier losses in the performance of catalytic nanodiodes. These findings are expected to contribute to understanding the hot electron detection efficiency and designing nanodiodes with enhanced hot carrier flow and catalytic activity.

Catalytic Boosting by Surface-Plasmon-Driven Hot Electrons on Antenna-Reactor Schottky Nanodiodes.

Significant research has focused on enhancing catalytic performance through solar energy conversion, and the design of photocatalysis incorporating surface plasmons is drawing considerable attention as a highly competitive catalyst system. Although the hot electron process is the primary mechanism in plasmonic photocatalysis, the precise function of hot electron transport in catalytic reactions remains unclear due to the absence of direct measurement. Here, we demonstrate the intrinsic relationship between surface-plasmon-driven hot electrons and catalytic activity during hydrogen oxidation, utilizing catalytic Schottky nanodiodes (Pt/Ag/TiO2) for antenna-reactor plasmonic photocatalysis. The simultaneous and independent measurements of hot electron flow and catalytic turnover rate show that the plasmonic effect amplifies the flow of reaction-induced hot electrons (chemicurrent), leading to enhanced catalytic activity. Plasmonic photocatalytic performance can be controlled with light wavelengths, intensity, surface temperature, and structures. These results elucidate the hot electron flow on photocatalysis and offer improved strategies for efficient catalytic devices.

How Hot Electron Generation at the Solid-Liquid Interface Is Different from the Solid-Gas Interface.

Excitation of hot electrons by energy dissipation under exothermic chemical reactions on metal catalyst surfaces occurs at both solid-gas and solid-liquid interfaces. Despite extensive studies, a comparative operando study directly comparing electronic excitation by electronically nonadiabatic interactions at solid-gas and solid-liquid interfaces has not been reported. Herein, on the basis of our in situ techniques for monitoring energy dissipation as a chemicurrent using a Pt/n-Si nanodiode sensor, we observed the generation of hot electrons in both gas and liquid phases during H2O2 decomposition. As a result of comparing the current signal and oxygen evolution rate in the two phases, surprisingly, the efficiency of reaction-induced excitation of hot electrons increased by ∼100 times at the solid-liquid interface compared to the solid-gas interface. The boost of hot electron excitation in the liquid phase is due to the presence of an ionic layer lowering the potential barrier at the junction for transferring hot electrons.

Phase-dependent Friction on Exfoliated Transition Metal Dichalcogenides Atomic Layers.

The fundamental aspects of energy dissipation on 2-dimensional (2D) atomic layers are extensively studied. Among various atomic layers, transition metal dichalcogenides (TMDs) exists in several phases based on their lattice structure, which give rise to the different phononic and electronic contributions in energy dissipation. 2H and 1T' (distorted 1T) phase MoS2 and MoTe2 atomic layers exfoliated on mica substrate are obtained and investigated their nanotribological properties with atomic force microscopy (AFM)/ friction force microscopy (FFM). Surprisingly, 1T' phase of both MoS2 and MoTe2 exhibits ≈10 times higher friction compared to 2H phase. With density functional theory analyses, the friction increase is attributed to enhanced electronic excitation, efficient phonon dissipation, and increased potential energy surface barrier at the tip-sample interface. This study suggests the intriguing possibility of tuning the friction of TMDs through phase transition, which can lead to potential application in tunable tribological devices.

Surface Plasmon-Induced Hot Carriers: Generation, Detection, and Applications.

ConspectusDuring surface plasmon-mediated light-matter interactions, external energies on plasmonic metal nanostructures undergo energy dissipation via elastic e-e scattering, radiative luminescence, and nonradiative processes such as thermal relaxation (phonon) and electronic excitation (electron-hole pairs). In this process, surface plasmon decays dominantly through nonradiative recombination when the metal is smaller than 25 nm, forming hot carriers, including hot electrons and hot holes, with high kinetic energy of 1-3 eV. Although the ultrafast dynamics of hot carriers are on time scales ranging from femtoseconds to picoseconds, these fast-disappearing hot carriers can be collected as the steady-state photocurrent or chemicurrent by adopting the metal-semiconductor (M-S)-based platform for detecting hot carrier flow. Plasmonic hot carriers, especially as they convert to an electrochemical signal, are a promising topic, and their energy conversion mechanisms are being actively studied in the fields of renewable energy, optoelectronics, and photocatalysis. Recent studies have demonstrated that these hot carriers can both improve the performance of solar energy conversion and control the catalytic activity or selectivity by directly participating in the photoelectrochemical (PEC) reaction.In this Account, we describe the inherent relationship between hot carriers and surface plasmon as well as what role hot carriers play throughout the catalytic reaction. The recent experimental work and the theoretical analysis of in situ hot carrier generation on Au nanostructures were conducted with photoconductive atomic force microscopy and finite-difference time-domain (FDTD) simulations, respectively. We highlight the recent nanoscale visualization of hot carrier flow occurring through light-matter interactions and that the localized surface plasmon field surrounding the Au nanostructure leads to boosted hot carrier generation. In addition, we highlight the recent demonstration that plasmonic hot carriers prolong the lifetime of photoexcited carriers in the MAPbI3/Au/TiO2 hybrid nanodiode by the synergistic effect between plasmonic Au and perovskites. From this work, the solar-to-electron conversion performance of this nanodiode significantly increases due to the amplification of light absorption, which helps to design hybrid platforms for efficient hot carrier photovoltaics. We discuss the application of surface plasmon-driven hot electron generation, including hot electron-based photovoltaic devices and photocatalysts. We highlight the recent photoelectrochemical measurements on the Au/p-GaN heterostructures that are controlled by participating plasmonic hot carriers in the water splitting reaction. Furthermore, controlling the flow of both hot electrons and holes by developing hybrid platform configurations for hot carrier applications has promising opportunities for regulating the catalytic activities of hot carrier-based photocatalysis and improving the photoconversion efficiency of hot carrier-based optoelectronic devices.

Effect of Water Vapor on Oxidation Processes of the Cu(111) Surface and Sublayer.

Copper-based catalysts have different catalytic properties depending on the oxidation states of Cu. We report operando observations of the Cu(111) oxidation processes using near-ambient pressure scanning tunneling microscopy (NAP-STM) and near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS). The Cu(111) surface was chemically inactive to water vapor, but only physisorption of water molecules was observed by NAP-STM. Under O2 environments, dry oxidation started at the step edges and proceeded to the terraces as a Cu2O phase. Humid oxidation of the H2O/O2 gas mixture was also promoted at the step edges to the terraces. After the Cu2O covered the surface under humid conditions, hydroxides and adsorbed water layers formed. NAP-STM observations showed that Cu2O was generated at lower steps in dry oxidation with independent terrace oxidations, whereas Cu2O was generated at upper steps in humid oxidation. The difference in the oxidation mechanisms was caused by water molecules. When the surface was entirely oxidized, the diffusion of Cu and O atoms with a reconstruction of the Cu2O structures induced additional subsurface oxidation. NAP-XPS measurements showed that the Cu2O thickness in dry oxidation was greater than that in humid oxidation under all pressure conditions.

Trioctylphosphine Oxide (TOPO)-Assisted Facile Fabrication of Phosphorus-Incorporated Nanostructured Carbon Nitride Toward Photoelectrochemical Water Splitting with Enhanced Activity.

Designing nanostructured arrays of two-dimensional surfaces and interfaces is a versatile approach to increasing their photoelectrochemical activity. Here, phosphorus (P)-incorporated nanostructured carbon nitride (h-PCN) with an enlarged surface area is fabricated by employing trioctylphosphine oxide (TOPO) as a dopant precursor for visible-light-driven photoelectrochemical water splitting to produce hydrogen. The structural, morphological, and electronic properties of the photocatalyst have been characterized through various physicochemical techniques. We show that the incorporation of P into the g-C3N4 framework enhances light absorption over broad regimes, charge separation, and migration, as well as the specific surface area, showing excellent photocurrent enhancement (5.4 folds) in the cathodic direction as compared to bulk g-C3N4. Moreover, the photocathode shows 3.3-fold enhancement in current at zero biased potential. Without using any cocatalyst, the photoelectrodes produced 27 µmol h-1 of H2 and 13 µmol h-1of O2 with 95% faradic efficiency. The excellent photoelectrochemical behavior toward water-splitting reactions by the photoelectrode is attributed to the synergistic effect of P incorporation and active sites emerging from the nanostructured architecture of the material. This work demonstrates the facile fabrication of nanostructured P-incorporated g-C3N4 toward water-splitting reactions to produce hydrogen without using a cocatalyst in a simple and cost-effective way.

Lanthanum-catalysed synthesis of microporous 3D graphene-like carbons in a zeolite template.

Three-dimensional graphene architectures with periodic nanopores­reminiscent of zeolite frameworks­are of topical interest because of the possibility of combining the characteristics of graphene with a three-dimensional porous structure. Lately, the synthesis of such carbons has been approached by using zeolites as templates and small hydrocarbon molecules that can enter the narrow pore apertures. However, pyrolytic carbonization of the hydrocarbons (a necessary step in generating pure carbon) requires high temperatures and results in non-selective carbon deposition outside the pores. Here, we demonstrate that lanthanum ions embedded in zeolite pores can lower the temperature required for the carbonization of ethylene or acetylene. In this way, a graphene-like carbon structure can be selectively formed inside the zeolite template, without carbon being deposited at the external surfaces. X-ray diffraction data from zeolite single crystals after carbonization indicate that electron densities corresponding to carbon atoms are generated along the walls of the zeolite pores. After the zeolite template is removed, the carbon framework exhibits an electrical conductivity that is two orders of magnitude higher than that of amorphous mesoporous carbon. Lanthanum catalysis allows a carbon framework to form in zeolite pores with diameters of less than 1 nanometre; as such, microporous carbon nanostructures can be reproduced with various topologies corresponding to different zeolite pore sizes and shapes. We demonstrate carbon synthesis for large-pore zeolites (FAU, EMT and beta), a one-dimensional medium-pore zeolite (LTL), and even small-pore zeolites (MFI and LTA). The catalytic effect is a common feature of lanthanum, yttrium and calcium, which are all carbide-forming metal elements. We also show that the synthesis can be readily scaled up, which will be important for practical applications such as the production of lithium-ion batteries and zeolite-like catalyst supports.

Plasmonic hot carrier-driven photoelectrochemical water splitting on antenna-reactor Pt/Ag/TiO2 Schottky nanodiodes.

Plasmonic photoelectrochemical (PEC) water splitting has excited immense interest, as it can overcome the intrinsic limitations of semiconductors, in terms of light absorption, by the localized-surface plasmon resonances effect. Here, to get insight into the role of plasmonic hot carriers in plasmonic water splitting, a rational design of an antenna-reactor type Pt/Ag/TiO2 metal-semiconductor Schottky nanodiode was fabricated and used as a photoanode. Using the designed PEC cell system combined with the Pt/Ag/TiO2 nanodiode, we show that the plasmonic hot carriers excited from Ag were utilized for the oxygen (O2) evolution reaction and, consequently, had a decisive role in the enhancement of the photocatalytic efficiency. These results were supported by finite-difference time-domain simulations, and the faradaic efficiency was measured by the amount of actual gas produced. Therefore, this study provides a deep understanding of the dynamics and mechanisms of plasmonic hot carriers in plasmonic-assisted PEC water splitting.

Manipulation of hot electron flow on plasmonic nanodiodes fabricated by nanosphere lithography.

Energy conversion to generate hot electrons through the excitation of localized surface plasmon resonance (LSPR) in metallic nanostructures is an emerging strategy in photovoltaics and photocatalytic devices. Important factors for surface plasmon and hot electron generation are the size, shape, and materials of plasmonic metal nanostructures, which affect LSPR excitation, absorbance, and hot electron collection. Here, we fabricated the ordered structure of metal-semiconductor plasmonic nanodiodes using nanosphere lithography and reactive ion etching. Two types of hole-shaped plasmonic nanostructures with the hole diameter of 280 and 115 nm were fabricated on Au/TiO2Schottky diodes. We show that hot electron flow can be manipulated by changing the size of plasmonic nanostructures on the Schottky diode. We show that the short-circuit photocurrent changes and the incident photon-to-electron conversion efficiency results exhibit the peak shift depending on the structures. These phenomena are explicitly observed with finite difference time domain simulations. The capability of tuning the morphology of plasmonic nanostructure on the Schottky diode can give rise to new possibilities in controlling hot electron generation and developing novel hot-electron-based energy conversion devices.

Restructuring of Porphyrin Networks Driven by Self-Assembled Octanoic Acid Monolayer on Au(111).

We report time-dependent surface restructuring of bicomponent domain structures of 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine (H2OEP) and cobalt(II) 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine (CoOEP) (H2/Co OEP) driven by self-assembled octanoic acid on the surface of Au(111). Scanning tunneling microscopy (STM) visualized molecular adsorption/desorption and rearrangement of supramolecular architectures in real-time in a solution of octanoic acid. We found that unique domain structures emerged at an initial state guided by adsorbed octanoic acid on the Au surface. Moreover, the desorption of octanoic acid occurred in solution, leading to the surface restructuring of porphyrin molecular networks. This molecular evidence is well-manifested in the time-dependent phase transitions, monitored by in situ STM.

Direct Imaging of Surface Plasmon-Driven Hot Electron Flux on the Au Nanoprism/TiO2.

Direct measurement of hot electron flux from a plasmonic Schottky nanodiode is important for obtaining fundamental insights explaining the mechanism for electronic excitation on a surface. Here, we report the measurement of photoinduced hot electrons on a triangular Au nanoprism on TiO2 under incident light with photoconductive atomic force microscopy (pc-AFM), which is direct proof of the intrinsic relation between hot electrons and localized surface plasmon resonance. We find that the local photocurrent measured on the boundary of the Au nanoprism is higher than that inside the Au nanoprism, indicating that field confinement at the boundary of the Au nanoprism acts as a hot spot, leading to the enhancement of hot electron flow at the boundary. Under incident illumination with a wavelength near the absorption peak (645 nm) of a single Au nanoprism, localized surface plasmon resonance resulted in the generation of a higher photoinduced hot electron flow for the Au nanoprism/TiO2, compared with that at a wavelength of 532 nm. We show that the application of a reverse bias results in a higher photocurrent for the Au nanoprism/TiO2, which is associated with a lowering of the Schottky barrier height caused by the image force. These nanoscale measurements of hot electron flux with pc-AFM indicate efficient photon energy transfer mediated by surface plasmons in hot electron-based energy conversion.

Elongated Lifetime and Enhanced Flux of Hot Electrons on a Perovskite Plasmonic Nanodiode.

A fundamental understanding of hot electron transport is critical for developing efficient hot-carrier-based solar cells. There have been significant efforts to enhance hot electron flux, and it has been found that a key factor affecting the hot electron flux is the lifetime of the hot electrons. Here, we report a combined study of hot electron flux and the lifetime of hot carriers using a perovskite-modified plasmonic nanodiode. We found that perovskite deposition on a plasmonic nanodiode can considerably improve hot electron generation induced by photon absorption. The perovskite plasmonic nanodiode consists of MAPbI3 layers covering a plasmonic-Au/TiO2 Schottky junction that is composed of randomly connected Au nanoislands deposited on a TiO2 layer. The measured incident photon-to-electron conversion efficiency and the short-circuit photocurrent show a significantly improved solar-to-electrical conversion performance of this nanodiode. Such an improvement is ascribed to the improved hot electron flux in MAPbI3 caused by effective light absorption from near-field enhancement of plasmonic Au and the efficient capture of hot electrons from Au nanoislands via the formation of a three-dimensional Schottky interface. The relation between the lifetime and flux of hot electrons was confirmed by femtosecond transient absorption spectroscopy that showed considerably longer hot electron lifetimes in MAPbI3 combined with the plasmonic Au structure. These findings can provide a fundamental understanding of hot electron generation and transport in perovskite, which can provide helpful guidance to designing efficient hot carrier photovoltaics.

Enhanced hot electron generation by inverse metal-oxide interfaces on catalytic nanodiode.

Identifying the electronic behavior of metal-oxide interfaces is essential for understanding the origin of catalytic properties and for engineering catalyst structures with the desired reactivity. For a mechanistic understanding of hot electron dynamics at inverse oxide/metal interfaces, we employed a new catalytic nanodiode by combining Co3O4 nanocubes (NCs) with a Pt/TiO2 nanodiode that exhibits nanoscale metal-oxide interfaces. We show that the chemicurrent, which is well correlated with the catalytic activity, is enhanced at the inverse oxide/metal (CoO/Pt) interfaces during H2 oxidation. Based on quantitative visualization of the electronic transfer efficiency with chemicurrent yield, we show that electronic perturbation of oxide/metal interfacial sites not only promotes the generation of hot electrons, but improves catalytic activity.

Oxygen activation on the interface between Pt nanoparticles and mesoporous defective TiO2 during CO oxidation.

Platinum-based heterogeneous catalysts are mostly used in various commercial chemical processes because of their high catalytic activity, influenced by the metal/oxide interaction. To design rational catalysts with high performance, it is crucial to understand the relationship between the metal-oxide interface and the reaction pathway. Here, we investigate the role of oxygen defect sites in the reaction mechanism for CO oxidation using Pt nanoparticles supported on mesoporous TiO2 catalysts with oxygen defects. We show an intrinsic correlation between the catalytic reactivity and the local properties of titania with oxygen defects (i.e., Ti3+ sites). In situ infrared spectroscopy observations of the Pt/mesoporous TiO2-x catalyst indicate that an oxygen molecule bond can be activated at the perimeter between the Pt and an oxygen vacancy in TiO2 by neighboring CO molecules on the Pt surface before CO oxidation begins. The proposed reaction pathways for O2 activation at the Pt/TiO2-x interface based on density functional theory confirm our experimental findings. We suggest that this provides valuable insight into the intrinsic origin of the metal/support interaction influenced by the presence of oxygen vacancies, which clarifies the pivotal role played by the support.

In Situ Observations of UV-Induced Restructuring of Self-Assembled Porphyrin Monolayer on Liquid/Au(111) Interface at Molecular Level.

Porphyrin-derived molecules have received much attention for use in solar energy conversion devices, such as artificial leaves and dye-sensitized solar cells. Because of their technological importance, a molecular-level understanding of the mechanism for supramolecular structure formation in a liquid, as well as their stability under ultraviolet (UV) irradiation, is important. Here, we observed the self-assembled structure of free-base, copper(II), and nickel(II) octaethylporphyrin formed on Au(111) in a dodecane solution using scanning tunneling microscopy (STM). As evident in the STM images, the self-assembled monolayers (SAMs) of these three porphyrins on the Au(111) surface showed hexagonal close-packed structures when in dodecane solution. Under UV irradiation (λ = 365 nm), the porphyrin molecules in the SAM or the dodecane solution move extensively and form new porphyrin clusters on the Au sites that have a high degree of freedom. Consequently, the Au(111) surface was covered with disordered porphyrin clusters. However, we found that the porphyrin molecules decomposed under UV irradiation at 254 nm. Molecular-scale observation of the morphological evolution of the porphyrin SAM under UV irradiation can provide a fundamental understanding of the degradation processes of porphyrin-based energy conversion devices.

Graphene-Semiconductor Catalytic Nanodiodes for Quantitative Detection of Hot Electrons Induced by a Chemical Reaction.

Direct detection of hot electrons generated by exothermic surface reactions on nanocatalysts is an effective strategy to obtain insight into electronic excitation during chemical reactions. For this purpose, we fabricated a novel catalytic nanodiode based on a Schottky junction between a single layer of graphene and an n-type TiO2 layer that enables the detection of hot electron flows produced by hydrogen oxidation on Pt nanoparticles. By making a comparative analysis of data obtained from measuring the hot electron current (chemicurrent) and turnover frequency, we demonstrate that graphene's unique electronic structure and extraordinary material properties, including its atomically thin nature and ballistic electron transport, allow improved conductivity at the interface between the catalytic Pt nanoparticles and the support. Thereby, graphene-based nanodiodes offer an effective and facile way to approach the study of chemical energy conversion mechanisms in composite catalysts with carbon-based supports.

Thermal Evolution and Instability of CO-Induced Platinum Clusters on the Pt(557) Surface at Ambient Pressure.

Carbon monoxide (CO) is one of the most-studied molecules among the many modern industrial chemical reactions available. Following the Langmuir-Hinshelwood mechanism, CO conversion starts with adsorption on a catalyst surface, which is a crucially important stage in the kinetics of the catalytic reaction. Stepped surfaces show enhanced catalytic activity because they, by nature, have dense active sites. Recently, it was found that surface-sensitive adsorption of CO is strongly related to surface restructuring via roughening of a stepped surface. In this scanning tunneling microscopy study, we observed the thermal evolution of surface restructuring on a representative stepped platinum catalyst, Pt(557). CO adsorption at 1.4 mbar CO causes the formation of a broken-step morphology, as well as CO-induced triangular Pt clusters that exhibit a reversible disordered-ordered transition. Thermal instability of the CO-induced platinum clusters on the stepped surface was observed, which is associated with the reorganization of the repulsive CO-CO interactions at elevated temperature.

Hot-electron-mediated surface chemistry: toward electronic control of catalytic activity.

Energy dissipation at surfaces and interfaces is mediated by excitation of elementary processes, including phonons and electronic excitation, once external energy is deposited to the surface during exothermic chemical processes. Nonadiabatic electronic excitation in exothermic catalytic reactions results in the flow of energetic electrons with an energy of 1-3 eV when chemical energy is converted to electron flow on a short (femtosecond) time scale before atomic vibration adiabatically dissipates the energy (in picoseconds). These energetic electrons that are not in thermal equilibrium with the metal atoms are called "hot electrons". The detection of hot electron flow under atomic or molecular processes and understanding its role in chemical reactions have been major topics in surface chemistry. Recent studies have demonstrated electronic excitation produced during atomic or molecular processes on surfaces, and the influence of hot electrons on atomic and molecular processes. We outline research efforts aimed at identification of the intrinsic relation between the flow of hot electrons and catalytic reactions. We show various strategies for detection and use of hot electrons generated by the energy dissipation processes in surface chemical reactions and photon absorption. A Schottky barrier localized at the metal-oxide interface of either catalytic nanodiodes or hybrid nanocatalysts allows hot electrons to irreversibly transport through the interface. We show that the chemicurrent, composed of hot electrons excited by the surface reaction of CO oxidation or hydrogen oxidation, correlates well with the turnover rate measured separately by gas chromatography. Furthermore, we show that hot electron flows generated on a gold thin film by photon absorption (or internal photoemission) can be amplified by localized surface plasmon resonance. The influence of hot charge carriers on the chemistry at the metal-oxide interface are discussed for the cases of Au, Ag, and Pt nanoparticles on oxide supports and Pt-CdSe-Pt nanodumbbells. We show that the accumulation or depletion of hot electrons on metal nanoparticles, in turn, can also influence catalytic reactions. Mechanisms suggested for hot-electron-induced chemical reactions on a photoexcited plasmonic metal are discussed. We propose that the manipulation of the flow of hot electrons by changing the electrical characteristics of metal-oxide and metal-semiconductor interfaces can give rise to the intriguing capability of tuning the catalytic activity of hybrid nanocatalysts.

Work function engineering of SnO single crystal microplates with thermal annealing.

We synthesized black SnO single-crystal microplates via a sonochemical process and engineered the work function of the SnO microplates using thermal treatments. The as-synthesized SnO microplates have a wide (001) plane, as is clearly evident from TEM images and diffraction patterns. Surface potential measurements on the SnO microplates show that the work function changes as the annealing temperature increases. The TEM and XAS results after thermal treatments imply that the micro-sized SnO(001) single-crystals are stable up to about 400 °C in air, after which the surface starts to become locally oxidized. Consequently, the long-range ordering and lattice parameter of the SnO(001) single crystals started to change to make polycrystalline SnO2 at about 600 °C. These results demonstrate the ability to tune the work function of the microplates and suggest an intriguing way to engineer the electrical properties of nanostructures.