Electron-hole Pair Excitations Research Articles

Optical and Other Measurement Techniques of Carrier Lifetime in Semiconductors

In this paper, various methods for characterization of semiconductor charge carrier lifetime are reviewed and an optical technique is described in detail. This technique is contactless, all-optical and based upon measurements of free carrier absorption transients by an infrared probe beam following electron-hole pair excitation by a pulsed laser beam. Main features are a direct probing of the excess carrier density coupled with a homogeneous carrier distribution within the sample, enabling precision studies of different recombination mechanisms. The method is capable of measuring the lifetime over a broad range of injections (10 13 -10 18 cm -3 ) probing the minority carrier lifetime, the high injection lifetime and Auger recombination, as well as the transition between these ranges. Performance and limitations of the technique, such as lateral resolution, are addressed while application of the technique for lifetime mapping and effects of surface recombination are also outlined. Results from detailed studies of the injection dependence yield good agreement with the Shockley-Read-Hall theory, whereas the coefficient for Auger recombination shows an apparent shift to a higher value, with respect to the traditionally accepted value, at carrier densities below 2×10 17 cm -3 . Data also indicate an increased value of the coefficient for bimolecular recombination from the generally accepted value. Measurement on an electron irradiated wafer and wafers of exceptionally high carrier lifetimes are also discussed within the framework of different recombination mechanisms.

Vibrational deexcitation and rotational excitation of H2 and D2 scattered from Cu(111): Adiabatic versus non-adiabatic dynamics

We have studied survival and rotational excitation probabilities of H(2)(v(i) = 1, J(i) = 1) and D(2)(v(i) = 1, J(i) = 2) upon scattering from Cu(111) using six-dimensional (6D) adiabatic (quantum and quasi-classical) and non-adiabatic (quasi-classical) dynamics. Non-adiabatic dynamics, based on a friction model, has been used to analyze the role of electron-hole pair excitations. Comparison between adiabatic and non-adiabatic calculations reveals a smaller influence of non-adiabatic effects on the energy dependence of the vibrational deexcitation mechanism than previously suggested by low-dimensional dynamics calculations. Specifically, we show that 6D adiabatic dynamics can account for the increase of vibrational deexcitation as a function of the incidence energy, as well as for the isotope effect observed experimentally in the energy dependence for H(2)(D(2))/Cu(100). Furthermore, a detailed analysis, based on classical trajectories, reveals that in trajectories leading to vibrational deexcitation, the minimum classical turning point is close to the top site, reflecting the multidimensionally of this mechanism. On this site, the reaction path curvature favors vibrational inelastic scattering. Finally, we show that the probability for a molecule to get close to the top site is higher for H(2) than for D(2), which explains the isotope effect found experimentally.

Plasmon Emission Quantum Yield of Single Gold Nanorods as a Function of Aspect Ratio

We report on the one-photon photoluminescence of gold nanorods with different aspect ratios. We measured photoluminescence and scattering spectra from 82 gold nanorods using single-particle spectroscopy. We found that the emission and scattering spectra closely resemble each other independent of the nanorod aspect ratio. We assign the photoluminescence to the radiative decay of the longitudinal surface plasmon generated after fast interconversion from excited electron-hole pairs that were initially created by 532 nm excitation. The emission intensity was converted to the quantum yield and was found to approximately exponentially decrease as the energy difference between the excitation and emission wavelength increased for gold nanorods with plasmon resonances between 600 and 800 nm. We compare this plasmon emission to its molecular analogue, fluorescence.

Mapping of Electron-Hole Excitations in the Charge-Density-Wave System1T−TiSe2Using Resonant Inelastic X-Ray Scattering

In high-resolution resonant inelastic x-ray scattering at the Ti L edge of the charge-density-wave system 1T-TiSe(2), we observe sharp low energy loss peaks from electron-hole pair excitations developing at low temperature. These excitations are strongly dispersing as a function of the transferred momentum of light. We show that the unoccupied bands close to the Fermi level can effectively be probed in this broadband material. Furthermore, we extract the order parameter of the charge-density-wave phase from temperature-dependent measurements.

Superhydrophilic TiO2 surfaces generated by reactive oxygen treatment

The authors show that superhydrophilic TiO2 can be obtained without irradiation of the surface with ultraviolet (UV) light and concomitant excitation of electron-hole pairs. The authors demonstrate that the treatment of TiO2 surfaces with reactive oxygen species generated by air plasma removes the surface organic contaminants, leading to almost 0° contact-angle wetting of the surface. The superhydrophilicity can be explained by the positive spreading coefficient calculated using the effective surface tensions. Our results point toward UV-light irradiation as an indirect cause of the superhydrophilicity of TiO2 and support the hypothesis that this property arises from a self-cleaning effect based on the photo-oxidation and decomposition of organic contaminants at the surface.

Charge Transport in Charge-Ordered States of Two-Dimensional Organic Conductors, α-(BEDT-TTF)2I3 and α'-(BEDT-TTF)2IBr2

Electric conductance and dielectric constant have been measured in the charge-ordered states of the quasi two-dimensional organic conductors α-(BEDT-TTF) 2 I 3 and α'-(BEDT-TTF) 2 IBr 2 to understand the charge transport mechanism. The current–voltage ( I – V ) characteristics show a strong nonlinear behavior, which is qualitatively explained by the transport of individual carriers thermally excited from the charge-ordered states in BEDT-TTF layers. The discrepancy with the simulation based on the thermal activation model at low temperatures is likely due to quantum tunneling through the potential barrier. The dielectric constants show a large difference between the in-plane and out-of-plane directions of the samples, showing a highly two-dimensional nature of Coulomb potential. The temperature dependence of dielectric constant is ascribed to the polarization effect of the thermally excited electron–hole pairs, consistent with the model of nonlinear I – V characteristics. All these features are qualitativ...

Competition between Electron and Phonon Excitations in the Scattering of Nitrogen Atoms and Molecules off Tungsten and Silver Metal Surfaces

We investigate the role played by electron-hole pair and phonon excitations in the interaction of reactive gas molecules and atoms with metal surfaces. We present a theoretical framework that allows us to evaluate within a full-dimensional dynamics the combined contribution of both excitation mechanisms while the gas particle-surface interaction is described by an ab initio potential energy surface. The model is applied to study energy dissipation in the scattering of N(2) on W(110) and N on Ag(111). Our results show that phonon excitation is the dominant energy loss channel, whereas electron-hole pair excitations represent a minor contribution. We substantiate that, even when the energy dissipated is quantitatively significant, important aspects of the scattering dynamics are well captured by the adiabatic approximation.

Time-dependent density functional theory for strong electromagnetic fields in crystalline solids

We apply the coupled dynamics of time-dependent density functional theory and Maxwell equations to the interaction of intense laser pulses with crystalline silicon. As a function of electromagnetic field intensity, we see several regions in the response. At the lowest intensities, the pulse is reflected and transmitted in accord with the dielectric response, and the characteristics of the energy deposition are consistent with two-photon absorption. The absorption process begins to deviate from that at laser intensities of $\ensuremath{\sim}$${10}^{13}$ W/cm${}^{2}$, where the energy deposited is of the order of 1 eV per atom. Changes in the reflectivity are seen as a function of intensity. When it passes a threshold of about $3\ifmmode\times\else\texttimes\fi{}{10}^{12}$ W/cm${}^{2}$, there is a small decrease. At higher intensities, above $2\ifmmode\times\else\texttimes\fi{}{10}^{13}$ W/cm${}^{2}$, the reflectivity increases strongly. This behavior can be understood qualitatively in a model treating the excited electron-hole pairs as a plasma.

Optical cavity cooling of mechanical modes of a semiconductor nanomembrane

A novel mechanism for cooling nanomechanical objects has now been demonstrated. Optically excited electron–hole pairs produce a mechanical stress that damps the motion of a gallium arsenide membrane. In this way, the nanoscale resonator is cooled from room temperature to 4 K.

Continuous-distribution puddle model for conduction in trilayer graphene

An insulator-to-metal transition is observed in trilayer graphene based on the temperature dependence of the resistance under different applied gate voltages. At small gate voltages the resistance decreases with increasing temperature due to the increase in carrier concentration resulting from thermal excitation of electron-hole pairs. At large gate voltages excitation of electron-hole pairs is suppressed, and the resistance increases with increasing temperature because of the enhanced electron-phonon scattering. We find that the simple model with overlapping conduction and valence bands, each with quadratic dispersion relations, is unsatisfactory. Instead, we conclude that impurities in the substrate that create local puddles of higher electron or hole densities are responsible for the residual conductivity at low temperatures. The best fit is obtained using a continuous distribution of puddles. From the fit the average of the electron and hole effective masses can be determined.

Vibrational cooling, heating, and instability in molecular conducting junctions: full counting statistics analysis

We study current-induced vibrational cooling, heating, and instability in a donor-acceptor rectifying molecular junction using a full counting statistics approach. In our model, electron-hole pair excitations are coupled to a given molecular vibrational mode which is either harmonic or highly anharmonic. This mode may be further coupled to a dissipative thermal environment. Adopting a master equation approach, we confirm the charge and heat exchange fluctuation theorem in the steady-state limit, for both harmonic and anharmonic models. Using simple analytical expressions, we calculate the charge current and several measures for the mode effective temperature. At low bias, we observe the effect of bias-induced cooling of the vibrational mode. At higher bias, the mode effective temperature is higher than the environmental temperature, yet the junction is stable. Beyond that, once the vibrational mode (bias-induced) excitation rate overcomes its relaxation rate, instability occurs. We identify regimes of instability as a function of voltage bias and coupling to an additional phononic thermal bath. Interestingly, we observe a reentrant behavior where an unstable junction can properly behave at a high enough bias. The mechanism for this behavior is discussed.

Enhanced photovoltaic response of the first polyoxometalate-modified zinc oxide photoanode for solar cell application

A photovoltaic electrode consisting of polyoxometalate (SiW12) and zinc oxide (ZnO) was fabricated on indium tin oxide (ITO) glass by one-step electrodeposition. The addition of SiW12 strongly influences the morphology and crystallographic orientation of the ZnO. The photovoltaic properties of the ZnO film and the SiW12–ZnO composite films were investigated via solar cell assembly. Both transient photocurrent and current–voltage curve measurements demonstrate that the photocurrent and power conversion efficiency of the SiW12–ZnO composite film were markedly enhanced in comparison with that of the ZnO film. Based on the results of fluorescence quenching measurements, the enhanced photovoltaic effect should be attributed to the occurrence of the photoinduced electron transfer between polyoxometalate and ZnO, which increases the efficient dissociation of excited electron–hole pairs (excitons).

Towards chemically accurate simulation of molecule–surface reactions

This perspective addresses four challenges facing theorists whose aim is to make quantitatively accurate predictions for reactions of molecules on metal surfaces, and suggests ways of meeting these challenges, focusing on dissociative chemisorption reactions of H(2), N(2), and CH(4). Addressing these challenges is ultimately of practical importance to a more accurate description of overall heterogeneously catalysed reactions, which play a role in the production of more than 90% of man-made chemicals. One challenge is to describe the interaction of a molecule with a metal surface with chemical accuracy, i.e., with errors in reaction barrier heights less than 1 kcal mol(-1). In this framework, the potential of a new implementation of specific reaction parameter density functional theory (SRP-DFT) will be discussed, with emphasis on applications to reaction of H(2) with metal surfaces. Two additional challenges are to come up with improved descriptions of the effects of phonons and electron-hole pairs on reaction of molecules like N(2) on metal surfaces. Phonons can be tackled using sudden approximations in quantum dynamics, and through Ab Initio Molecular Dynamics (AIMD) calculations using classical dynamics. To additionally achieve an accurate description of the effect of electron-hole pair excitation on dissociative chemisorption within a classical dynamics framework, it may be possible to combine AIMD with electronic friction. The fourth challenge we will consider is how to achieve an accurate quantum mechanical description of the dissociative chemisorption of a polyatomic molecule, like methane, on a metal surface. A method of potential interest is the Multi-Configuration Time-Dependent Hartree (MCTDH) method.

Temperature dependence of ultrafast phonon dynamics in graphite

Nonequilibrium optical phonons are generated in graphite following the excitation of electron-hole pairs with a femtosecond laser pulse. Their energy relaxation is probed by means of terahertz pulses. We find that the hot-phonon lifetime increases by a factor of 2 when the sample temperature decreases from 300 to 5 K. These results suggest that the energy relaxation in graphite at room temperature and above is dominated by the anharmonic decay of hot A1′ phonons at the K point into acoustic phonons with energies of about 10 meV.

Size-Dependent Non-FRET Photoluminescence Quenching in Nanocomposites Based on Semiconductor Quantum Dots CdSe/ZnS and Functionalized Porphyrin Ligands

We review recent experimental work to utilize the size dependence of the luminescence quenching of colloidal semiconductor quantum dots induced by functionalized porphyrin molecules attached to the surface to describe a photoluminescence (PL) quenching process which is different from usual models of charge transfer (CT) or Foerster resonant energy transfer (FRET). Steady-state and picosecond time-resolved measurements were carried out for nanocomposites based on colloidal CdSe/ZnS and CdSe quantum dots (QDs) of various sizes and surfacely attached tetra-mesopyridyl-substituted porphyrin molecules (“Quantum Dot-Porphyrin” nanocomposites), in toluene at 295 K. It was found that the major part of the observed strong quenching of QD PL in “QD-Porphyrin” nanocomposites can neither be assigned to FRET nor to photoinduced charge transfer between the QD and the chromophore. This PL quenching depends on QD size and shell and is stronger for smaller quantum dots: QD PL quenching rate constants scale inversely with the QD diameter. Based on the comparison of experimental data and quantum mechanical calculations, it has been concluded that QD PL quenching in “QD-Porphyrin” nanocomposites can be understood in terms of a tunneling of the electron (of the excited electron-hole pair) followed by a (self-) localization of the electron or formation of trap states. The major contribution to PL quenching is found to be proportional to the calculated quantum-confined exciton wave function at the QD surface. Our findings highlight that single functionalized molecules can be considered as one of the probes for the complex interface physics and dynamics of colloidal semiconductor QD.

Factors in the Metal Doping of BiVO4 for Improved Photoelectrocatalytic Activity as Studied by Scanning Electrochemical Microscopy and First-Principles Density-Functional Calculation

Metal doping of the metal oxide photoelectrocatalyst, BiVO4, dramatically increases its activity for water oxidation. Scanning electrochemical microscopy (SECM) was used to screen various dopants for their photoelectrochemical performance and to optimize the used dopant material concentrations with this photocatalyst. For example, adding Mo to W-doped BiVO4 enhanced the performance. The photocatalytic activity was examined on larger electrodes by means of photoelectrochemical and electrochemical measurements. The developed photoelectrocatalyst, W- and Mo-doped BiVO4, shows a photocurrent for water oxidation that is more than 10 times higher than undoped BiVO4. Factors that affect performance are discussed, and enhanced separation of excited electron–hole pairs by doping onto the semiconductor is suggested by first-principles density-functional theory (DFT) calculations. Distortion of the crystal structure of monoclinic scheelite-like BiVO4 by addition of W and Mo doping predicted by DFT is also revealed b...

Quantum electronic mechanisms of atomic rearrangements during growth of hard carbon films

Considering that diamond can grow without combination of pressure and heat, other effects in addition to ion impact thermal spikes effects must exist, which are ruling the growth of diamond and ta-C films (tetrahedral amorphous carbon). A newly proposed quantum electronic activation model for the diamond and diamond-like atomic rearrangement of carbon atoms appears to be confirmed by various elder and more recently published experimental results. It is based on various types of effects producing activation energy, before producing heat. Thus, it is possible to excite electron–hole pairs, which during their diffusion produce some transversal transient polarization, which under specific conditions can result in a new metastable atomic structure. This article focuses on published work on atomic rearrangements, which have been observed during annealing of diamond and some kinds of DLC (diamond-like carbon) coatings, such as a-C:H and a-CNx coatings. These atomic rearrangements were explained by using essentially Raman spectroscopy results, which are reviewed in this article, before being discussed with additional new proposed aspects on fundamentals to consider and which have been up dated in their interpretation. The considered atomic rearrangement model appears then also to be in agreement with some formerly discussed catalytic effects, which under specific conditions, favorize the growth of diamond and more diamond-like carbon films. It is expected that this new quantum electronic atomic rearrangement model will not be limited only to diamond, ta-C and DLC materials.

Laserlike Vibrational Instability in Rectifying Molecular Conductors

We study the damping of molecular vibrations due to electron-hole pair excitations in donor-acceptor (D-A) type molecular rectifiers. At finite voltage additional nonequilibrium electron-hole pair excitations involving both electrodes become possible, and contribute to the stimulated emission and absorption of phonons. We point out a generic mechanism for D-A molecules, where the stimulated emission can dominate beyond a certain voltage due to the inverted position of the D and A quantum resonances. This leads to current-driven amplification (negative damping) of the phonons similar to laser action. We investigate the effect in realistic molecular rectifier structures using first-principles calculations.

Photocatalytic oxidation of organic dyes with nanostructured zinc dioxide modified with silver metals

Silver-doped nano-ZnO samples with different Ag loadings were prepared by a one-spot solvothermal method. The structure, physico-chemical and optical properties of the products are characterized by using X-ray diffraction (XRD), transmission electron microscope (TEM), energy dispersive X-ray analysis (EDS), diffuse reflectance spectroscopy (DRS) and photoluminescence spectra (PL). The photocatalytic activity of the as-prepared samples was examined by using photocatalytic oxidation of methyl orange (MO) as a model reaction, and the effects of the noble metal content on the photocatalytic activity were investigated. The results indicated that the photocatalytic activity of ZnO nanoparticles can be greatly improved by depositing appropriate amount of noble metal on their surface as electron scavengers. In addition, a key mechanism was proposed in order to account for the enhanced activity. The enhancement for the photocatalytic activities can be attributed to the interaction between Ag particles and ZnO, which made Ag particles act as electron traps to effectively separate the excited electron-hole pairs.

State-to-state dynamics at the gas-liquid metal interface: Rotationally and electronically inelastic scattering of NO[2Π1/2(0.5)] from molten gallium

Jet cooled NO molecules are scattered at 45° with respect to the surface normal from a liquid gallium surface at E(inc) from 1.0(3) to 20(6) kcal/mol to probe rotationally and electronically inelastic scattering from a gas-molten metal interface (numbers in parenthesis represent 1σ uncertainty in the corresponding final digits). Scattered populations are detected at 45° by confocal laser induced fluorescence (LIF) on the γ(0-0) and γ(1-1) A(2)Σ ← X(2)Π(Ω) bands, yielding rotational, spin-orbit, and λ-doublet population distributions. Scattering of low speed NO molecules results in Boltzmann distributions with effective temperatures considerably lower than that of the surface, in respectable agreement with the Bowman-Gossage rotational cooling model [J. M. Bowman and J. L. Gossage, Chem. Phys. Lett. 96, 481 (1983)] for desorption from a restricted surface rotor state. Increasing collision energy results in a stronger increase in scattered NO rotational energy than spin-orbit excitation, with an opposite trend noted for changes in surface temperature. The difference between electronic and rotational dynamics is discussed in terms of the possible influence of electron hole pair excitations in the conducting metal. While such electronically non-adiabatic processes can also influence vibrational dynamics, the γ(1-1) band indicates <2.6 × 10(-4) probability for collisional formation of NO(v = 1) at surface temperatures up to 580 K. Average translational to rotational energy transfer is compared from a hard cube model perspective with previous studies of NO scattering from single crystal solid surfaces. Despite a lighter atomic mass (70 amu), the liquid Ga surface is found to promote translational to rotational excitation more efficiently than Ag(111) (108 amu) and nearly as effectively as Au(111) (197 amu). The enhanced propensity for Ga(l) to transform incident translational energy into rotation is discussed in terms of temperature-dependent capillary wave excitation of the gas-liquid metal interface.