Velocity Map Imaging Photoelectron Spectroscopy of Silver Iodide Aerosol Particles.

The valence band electronic structure of isolated silver iodide nanoparticles (AgI NP) was investigated by vacuum-ultraviolet aerosol photoelectron spectroscopy using the velocity map imaging technique (VUV VMI-PES). The VUV VMI-PES results were obtained for polydisperse aerosol produced by aggregation of hydrocolloid of silver iodide particles 8 - 15 nm in size. The ionization energy of the AgI particles was found to be 6.0 ± 0.1 eV with respect to the vacuum level. The DFT calculations showed that the main contribution to the density of AgI electronic states in the valence region originates from I 5p orbitals. The dependence of the asymmetry parameter on the electron energy showed that the value of the characteristic energy loss of excited photoelectrons was 2.7 eV, which coincided with the band gap of the nanomaterial.

Ab-initio calculations of temperature dependent electronic structures of inorganic halide perovskite materials.

Despite wide interest in halide perovskite materials, it is still challenging to accurately calculate their electronic structure and its temperature dependence. In this work, we present ab-initio calculations of the temperature dependence of the electronic structure of CsPbX3 materials (X = Cl, Br or I) in the cubic form and of the zero temperature electronic structure of the orthorhombic phase of these materials. Phonon-induced temperature dependent band energy renormalization was calculated within the framework of Allen-Heine-Cardona theory, where we exploited the self-consistent procedure to determine both the energy level shifts and their broadenings. The phonon spectrum of the materials was obtained using the self-consistent phonon method since standard density functional perturbation theory calculations in harmonic approximation yield phonon modes with imaginary frequencies due to the fact that the cubic structure is not stable at zero temperature. Our results suggest that low energy phonon modes mostly contribute to phonon-induced band energy renormalization. The calculated values of the band gaps at lowest temperature where the material exhibits a cubic structure are in good agreement with experimental results from the literature. The same is the case for the slope of the temperature dependence of the band gap for the CsPbI3 material where reliable experimental data are available in the literature. We also found that phonon-induced temperature dependence of the band gap is most pronounced for the conduction band minimum and valence band maximum, while other bands exhibit a weaker dependence.

Spectral Functions of the Holstein Polaron: Exact and Approximate Solutions.

It is generally accepted that the dynamical mean field theory gives a good solution of the Holstein model, but only in dimensions greater than two. Here, we show that this theory, which becomes exact in the weak coupling and in the atomic limit, provides an excellent, numerically cheap, approximate solution for the spectral function of the Holstein model in the whole range of parameters, even in one dimension. To establish this, we make a detailed comparison with the spectral functions that we obtain using the newly developed momentum-space numerically exact hierarchical equations of motion method, which yields electronic correlation functions directly in real time. We crosscheck these conclusions with our path integral quantum Monte Carlo and exact diagonalization results, as well as with the available numerically exact results from the literature.

High-Resolution Doppler and Azimuth Estimation and Target Detection in HFSWR: Experimental Study.

In this paper, we present a new high-resolution algorithm for primary signal processing in High Frequency Surface Wave Radar (HFSWR). The algorithm has been developed to achieve and improve primary signal processing performance in existing HFSWR radars in terms of radar target detection. The proposed algorithm is based on a high-resolution estimate of the Range-Doppler (RD-HR) map using given number of frames in the selected integration period. RD-HR maps are formed at every antenna in receive antenna array. Target detection is based on an RD-HR map averaged across all the antennas. Azimuth estimation is performed by a high-resolution MUSIC-type algorithm that is executed for all detections we found in the RD-HR map. The existence of strong Bragg's lines in the RD-HR map complicates the detection process but the contrast of the RD-HR map as well as the detectability of targets on the RD-HR map is significantly better compared to the RD-FFT map used by many existing radars, such as WERA.

Performance Limits of Direct Wideband Coherent 3D Localization in Distributed Massive MIMO Systems.

We address the accuracy of wideband direct position estimation of a radio transmitter via a distributed antenna array in 5G cellular systems. Our derivations are based only on the presence of spatially coherent line-of-sight (LoS) signal components, which is a realistic assumption in small cells, especially in the mmWave range. The system model considers collocated time and phase synchronized receiving front-ends with antennas distributed in 3D space at known locations and connected to the front-ends via calibrated coaxial cables or analog radio-frequency-over-fiber links. Furthermore, the signal model assumes spherical wavefronts. We derive the Cramér-Rao bounds (CRBs) for two implementations of the system: with (a) known signals and (b) random Gaussian signals. The results show how the bounds depend on the carrier frequency, number of samples used for estimation, and signal-to-noise ratios. They also show that increasing the number of antennas (such as in massive MIMO systems) considerably improves the accuracy and lowers the signal-to-noise threshold for localization even for non-cooperative transmitters. Finally, our derivations show that the square roots of the bounds are two to three orders of magnitude below the carrier wavelength for realistic system parameters.

Direct Wideband Coherent Localization by Distributed Antenna Arrays.

We address wideband direct coherent localization of a radio transmitter by a distributed antenna array in a multipath scenario with spatially-coherent line-of-sight (LoS) signal components. Such a signal scenario is realistic in small cells, especially indoors in the mmWave range. The system model considers collocated time and phase synchronized receiving front-ends with antennas distributed in 3D space at known locations connected to the front-ends via calibrated coaxial cables or analog radio frequency over fiber links. The signal model assumes spherical wavefronts. We propose two ML-type algorithms (for known and unknown transmitter waveforms) and a subspace-based SCM-MUSIC algorithm for wideband direct coherent position estimation. We demonstrate the performance of the methods by Monte Carlo simulations. The results show that even in multipath environments, it is possible to achieve localization accuracy that is much better (by two to three orders of magnitude) than the carrier wavelength. They also suggest that the methods that do not exploit knowledge of the waveform have mean-squared errors approaching the Cramér-Rao bound.

Effects of thermal disorder on the electronic structure of halide perovskites: insights from MD simulations.

The effects of thermal disorder on the electronic properties of organic/inorganic halide perovskites were investigated using ab initio molecular dynamics simulations. It was generally found that band gap variations due to effects of thermal disorder are the largest in materials with the smallest lattice constant. The factors that may lead to departure from this trend include the degree of rotational and translational motion of the organic cation and the strength of its dipole. It was found that the contribution of the flexible organic part to the band gap variations is considerably smaller than the contribution of the inorganic part of the material. The results of our simulations indicate that band gap variations in halide perovskites fall within the range exhibited in inorganic semiconductors.

Effects of thermal disorder on the electronic properties of ordered polymers.

The effects of thermal disorder on the electronic properties of crystalline polymers were investigated. Atomic configurations of the material were obtained using classical Monte Carlo simulations at room temperature, while electronic structure calculations were performed using the density functional theory based charge patching method and the overlapping fragment method. We investigated two different stable configurations of crystalline poly(3-hexylthiophene) (P3HT) and calculated the density of electronic states and the wave function localisation. We found that the effect of disorder in side chains is more pronounced in the more stable configuration of P3HT than in the other one due to the larger conformational freedom of side chains. The results show that disorder in main chains has a strong effect on the electronic structure and leads to the localisation of the wave functions of the highest states in the valence band, similar to localisation that occurs in amorphous polymers. The presence of such states is one possible origin of thermally activated electrical transport in ordered polymers at room temperature.

Toward an ideal polymer binder design for high-capacity battery anodes.

The dilemma of employing high-capacity battery materials and maintaining the electronic and mechanical integrity of electrodes demands novel designs of binder systems. Here, we developed a binder polymer with multifunctionality to maintain high electronic conductivity, mechanical adhesion, ductility, and electrolyte uptake. These critical properties are achieved by designing polymers with proper functional groups. Through synthesis, spectroscopy, and simulation, electronic conductivity is optimized by tailoring the key electronic state, which is not disturbed by further modifications of side chains. This fundamental allows separated optimization of the mechanical and swelling properties without detrimental effect on electronic property. Remaining electronically conductive, the enhanced polarity of the polymer greatly improves the adhesion, ductility, and more importantly, the electrolyte uptake to the levels of those available only in nonconductive binders before. We also demonstrate directly the performance of the developed conductive binder by achieving full-capacity cycling of silicon particles without using any conductive additive.

A comparative study of electronic properties of disordered conjugated polymers.

The comparison of hole density of states (DOS) and hole mobilities of several organic polymer based systems was performed to gain insight into the main factors that determine the electrical properties of conjugated polymers. The DOS and the mobility of the systems under investigation were evaluated using an atomistic multiscale procedure. The results suggest that the irregularities in the shape of the polymer chains increase the diagonal disorder, while alkyl side chains act as spacers that reduce the diagonal disorder which originates from long range electrostatic interactions. Intrachain electronic coupling in relatively ordered polymers narrows the tail of the DOS, while in less ordered polymers it represents the additional component of disorder and widens the tail of the DOS. The width of the DOS tail was confirmed to be an important factor that determines the activation energy for charge carrier transport. However, it is not the only factor since the system with a smaller width of the DOS tail can have a larger activation energy due to, for example, smaller wave function overlap between transport states.

Electron-phonon coupling in crystalline organic semiconductors: microscopic evidence for nonpolaronic charge carriers.

We consider electron-phonon coupling in crystalline organic semiconductors, using naphthalene for our case study. Employing a first-principles approach, we compute the changes in the selfconsistent Kohn-Sham potential corresponding to different phonon modes and go on to obtain the carrier-phonon coupling matrix elements (vertex functions). We then evaluate perturbatively the quasiparticle spectral residues for electrons at the bottom of the lowest unoccupied (LUMO), and holes at the top of the highest occupied (HOMO), band, obtaining Z(e) ≈ 0.74 and Z(h) ≈ 0.78, respectively. Along with the widely accepted notion that the carrier-phonon coupling strengths in polyacenes decrease with increasing molecular size, our results provide strong microscopic evidence for the previously conjectured nonpolaronic nature of bandlike carriers in these systems.

Electrical transport properties of oligothiophene-based molecular films studied by current sensing atomic force microscopy.

Using conducting probe atomic force microscopy (CAFM) we have investigated the electrical conduction properties of monolayer films of a pentathiophene derivative on a SiO(2)/Si-p+ substrate. By a combination of current-voltage spectroscopy and current imaging we show that lateral charge transport takes place in the plane of the monolayer via hole injection into the highest occupied molecular orbitals of the pentathiophene unit. Our CAFM data suggest that the conductivity is anisotropic relative to the crystalline directions of the molecular lattice.

The role of disorder on the electronic structure of conjugated polymers. The case of poly-2,5-bis(phenylethynyl)-1,3,4-thiadiazole.

Insight into the electronic structure of disordered poly-2,5-bis(phenylethynyl)-1,3,4-thiadiazole in an amorphous region, in comparison to an ideal two-planar cofacial oligomer system, is pursued. The atomic structure of the amorphous polymer was obtained from classical molecular dynamics. It was subsequently used to calculate the electronic states and inter- and intrachain electronic coupling integrals using the density functional theory based charge patching method. The interchain electronic coupling integrals in the amorphous system were found to be an order of magnitude smaller than in the ordered system with similar distances between the chains. The results also suggest that the electronic structure of the whole system cannot be understood as a collection of the electronic structures of individual chains. The band gap of the whole system is significantly smaller than the band gaps of individual chains. This decrease originates from the disordered long range electrostatic potential created by the dipole moments of polymer repeat units, which should be minimized if one seeks good transport properties.

Overlapping fragments method for electronic structure calculation of large systems.

We present a method for the calculation of the electronic structure of systems that contain tens of thousands of atoms. The method is based on the division of the system into mutually overlapping fragments and the representation of the single-particle Hamiltonian in the basis of eigenstates of these fragments. In practice, for the range of the system size that we studied (up to tens of thousands of atoms), the dominant part of the calculation scales linearly with the size of the system when all the states within a fixed energy interval are required. The method is highly suitable for making good use of parallel computing architectures. We illustrate the method by applying it to diagonalize the single-particle Hamiltonian obtained using the density functional theory based charge patching method in the case of amorphous alkane and polythiophene polymers.

Nonequilibrium Thermodynamics of Charge Separation in Organic Solar Cells.

This work presents a novel theoretical description of the nonequilibrium thermodynamics of charge separation in organic solar cells (OSCs). Using stochastic thermodynamics, we take realistic state populations derived from the phonon-assisted dynamics of electron-hole pairs within photoexcited organic bilayers to connect the kinetics with the free energy profile of charge separation. Hereby, we quantify for the first time the difference between nonequilibrium and equilibrium free energy profile. We analyze the impact of energetic disorder and delocalization on free energy, average energy, and entropy. For a high disorder, the free energy profile is well-described as equilibrated. We observe significant deviations from equilibrium for delocalized electron-hole pairs at a small disorder, implying that charge separation in efficient OSCs proceeds via a cold but nonequilibrated pathway. Both a large Gibbs entropy and large initial electron-hole distance provide an efficient charge separation, while a decrease in the free energy barrier does not necessarily enhance charge separation.

Charge carrier motion in disordered conjugated polymers: a multiscale Ab initio study.

We developed an ab initio multiscale method for simulation of carrier transport in large disordered systems, based on direct calculation of electronic states and electron-phonon coupling constants. It enabled us to obtain the never seen before rich microscopic details of carrier motion in conjugated polymers, which led us to question several assumptions of phenomenological models, widely used in such systems. The macroscopic mobility of disordered poly(3-hexylthiophene) (P3HT) polymer, extracted from our simulation, is in agreement with experimental results from the literature.

Electronic structure of disordered conjugated polymers: polythiophenes.

Electronic structure of disordered semiconducting conjugated polymers was studied. Atomic structure was found from a classical molecular dynamics simulation, and the charge patching method was used to calculate the electronic structure with the accuracy similar to the one of density functional theory in local density approximation. The total density of states, the local density of states at different points in the system, and the wave functions of several states around the gap were calculated in the case of poly(3-hexylthiophene) (P3HT) and polythiophene (PT) systems to gain insight into the origin of disorder in the system, the degree of carrier localization, and the role of chain interactions. The results indicated that disorder in the electronic structure of alkyl-substituted polythiophenes comes from disorder in the conformation of individual chains, while in the case of polythiophene there is an additional contribution due to disorder in the electronic coupling between the chains. Each of the first several wave functions in the conduction and valence band of P3HT is localized over several rings of a single chain. It was shown that the localization can be caused in principle both by ring torsions and chain bending; however, the effect of ring torsions is much stronger. PT wave functions are more complicated due to larger interchain electronic coupling and are not necessarily localized on a single chain.

Naturally safe: Cellular noise for document security.

Modern document protection relies on the simultaneous combination of many optical features with micron and submicron structures, whose complexity is the main obstacle for unauthorized copying. In that sense, documents are best protected by the diffractive optical elements generated lithographically and mass-produced by embossing. The problem is that the resulting security elements are identical, facilitating mass-production of both original and counterfeited documents. Here, we prove that each butterfly wing-scale is structurally and optically unique and can be used as an inimitable optical memory tag and applied for document security. Wing-scales, exhibiting angular variability of their color, were laser-cut and bleached to imprint cryptographic information of an authorized issuer. The resulting optical memory tag is extremely durable, as verified by several century-old insect specimens still retaining their coloration. The described technique is simple, amenable to mass-production, low cost and easy to integrate within the existing security infrastructure.

Position estimation with a millimeter-wave massive MIMO system based on distributed steerable phased antenna arrays.

In this paper, we propose a massive MIMO (multiple-input-multiple-output) architecture with distributed steerable phased antenna subarrays for position estimation in the mmWave range. We also propose localization algorithms and a multistage/multiresolution search strategy that resolve the problem of high side lobes, which is inherent in spatially coherent localization. The proposed system is intended for use in line-of-sight indoor environments. Time synchronization between the transmitter and the receiving system is not required, and the algorithms can also be applied to a multiuser scenario. The simulation results for the line-of-sight-only and specular multipath scenarios show that the localization error is only a small fraction of the carrier wavelength and that it can be achieved under reasonable system parameters including signal-to-noise ratios, antenna number/placement, and subarray apertures. The proposed concept has the potential of significantly improving the capacity and spectral/energy efficiency of future mmWave massive MIMO systems.

Investigation of carrier confinement in direct bandgap GeSn/SiGeSn 2D and 0D heterostructures.

Since the first demonstration of lasing in direct bandgap GeSn semiconductors, the research efforts for the realization of electrically pumped group IV lasers monolithically integrated on Si have significantly intensified. This led to epitaxial studies of GeSn/SiGeSn hetero- and nanostructures, where charge carrier confinement strongly improves the radiative emission properties. Based on recent experimental literature data, in this report we discuss the advantages of GeSn/SiGeSn multi quantum well and quantum dot structures, aiming to propose a roadmap for group IV epitaxy. Calculations based on 8-band k∙p and effective mass method have been performed to determine band discontinuities, the energy difference between Γ- and L-valley conduction band edges, and optical properties such as material gain and optical cross section. The effects of these parameters are systematically analyzed for an experimentally achievable range of Sn (10 to 20 at.%) and Si (1 to 10 at.%) contents, as well as strain values (-1 to 1%). We show that charge carriers can be efficiently confined in the active region of optical devices for experimentally acceptable Sn contents in both multi quantum well and quantum dot configurations.