High Concentration Of Free Electrons Research Articles

High-Performance Sensing Platform Based on Morphology/Lattice Collaborative Control of Femtosecond-Laser-Induced MXene-Composited Graphene.

Flexible sensors based on laser-induced graphene (LIG) are widely used in wearable personal devices, with the morphology and lattice arrangement of LIG the key factors affecting their performance in various applications. In this study, femtosecond-laser-induced MXene-composited graphene (LIMG) is used to improve the electrical conductivity of graphene by incorporating MXene, a 2D material with a high concentration of free electrons, into the LIG structure. By combining pump-probe detection, laser-induced breakdown spectroscopy (LIBS), and density functional theory (DFT) calculations, the morphogenesis and lattice structuring principles of LIMG is explored, with the results indicating that MXene materials are successfully embedded in the graphene lattice, altering both their morphology and electrical properties. The structural sparsity and electrical conductivity of LIMG composites (up to 3187 Sm-1) are significantly enhanced compared to those of LIG. Based on these findings, LIMG has been used in wearable electronics. LIMG electrodes are used to detect uric acid, with a minimum detection limit of 2.48µM. Additionally, LIMG-based pressure and bending sensors have been successfully used to monitor human limb movement and pulse. The direct in situ femtosecond laser patterning synthesis of LIMG has significant implications for developing flexible wearable electronic sensors.

Fluorine-doped ATO NCs with enhanced LSPR effect for smart windows with adaptive solar modulation

Smart windows with excellent near-infrared (NIR) light shielding capacity and controlled visible light transmittance are expected to reduce building energy consumption and improve indoor comfort. However, the ability of current thermochromic materials to regulate solar gain with the tunable extinction of phase-change materials is still far from optimum. In this work, an fluorine (F)-doped ATO (FATO) nanocrystals (NCs) are designed as a photothermal material to optimize the solar modulation of thermochromic hydrogels. F ion doping can modify the electronic structure of ATO, resulting in a high concentration of oxygen vacancies and free electrons, thereby enhancing the NIR absorption performance and photothermal conversion performance of the ATO NCs. On this premise, the designed smart window based on FATO NCs and thermochromic hydrogels exhibits the remarkable features of excellent NIR shielding, high initial visible transmittance and fast response speed. The window is capable of shielding 99.5% of the solar radiation from 300 to 2500 nm and permitting 75.0% of initial visible light. Moreover, the simulated indoor temperature of the smart window was 17.2 °C lower compared with the black one, demonstrating potentials in practical application of building energy saving.

Transparent Conducting Amorphous IZO Thin Films: An Approach to Improve the Transparent Electrode Quality.

It is common knowledge that using different oxygen contents in the working gas during sputtering deposition results in fabrication of indium zinc oxide (IZO) films with a wide range of optoelectronic properties. It is also important that high deposition temperature is not required to achieve excellent transparent electrode quality in the IZO films. Modulation of the oxygen content in the working gas during RF sputtering of IZO ceramic targets was used to deposit IZO-based multilayers in which the ultrathin IZO unit layers with high electron mobility (μ-IZO) alternate with ones characterized by high concentration of free electrons (n-IZO). As a result of optimizing the thicknesses of each type of unit layer, low-temperature 400 nm thick IZO multilayers with excellent transparent electrode quality, indicated by the low sheet resistance (R ≤ 8 Ω/sq.) with high transmittance in the visible range (T¯ > 83%) and a very flat multilayer surface, were obtained.

Plasmon assisted Ti3C2Tx grafting and surface termination tuning for enhancement of flake stability and humidity sensing performance.

Humidity sensors play a critical role in monitoring human activities, environmental health, food processing and storage, and many other fields. Recently, some 2D materials, particularly MXenes, have been considered as promising candidates for creating humidity sensors because of their high surface area, surface-to-bulk ratio, and excellent conductivity, arising from the high concentration and mobility of free electrons. In this work, we propose the plasmon-assisted surface modification and termination tuning of common MXene (Ti3C2Tx) to enhance their response to humidity and increase their stability against oxidation. Hydrophobic (-C6H4-CF3) and hydrophilic (-C6H4-COOH) chemical moieties were covalently grafted to the Ti3C2Tx surface using plasmon-mediated diazonium chemistry. In situ Grazing-Incidence Wide-Angle X-ray Scattering (GIWAXS) measurements, performed at different humidity levels indicate that surface modification significantly affects penetration of water molecules in Ti3C2Tx films. As a result, the sensitivity of the flakes to the presence of water molecules was significantly altered. Additionally, proposed surface grafting commonly proceeds on the less stable MXene surface sites, where flake oxidation commonly initiates. As a result of the modification, such "weak" and more chemically active sites were blocked and Ti3C2Tx stability was significantly enhanced.

Preparation of High-Performance Metal-Free UV/Near Infrared-Shielding Films for Human Skin Protection.

A series of metal-free UV/near infrared (NIR)-shielding coatings are successfully fabricated by shielded cathodic arc plasma evaporation (CAPE) and substrate-biased RF magnetron sputtering processes. The UV/NIR-shielding coatings comprising quarter-wave stacks of TiO2/SiO2 multilayers and high-conductivity sputter-deposited ITO films with a thickness in the range of 200–600 nm could block IRA and IRB radiations, respectively. The total thicknesses of UV/near infrared-shielding films are in the range from 375 nm to 1513.8 nm. The anatase-phase TiO2 films with absorption edge located at ~375 nm were deposited by shielded CAPE at ~100 °C. Further, the well-crystallized ITO films were found to have high free-electron concentrations (1.12 × 1021 cm−3), resulting in strong absorption of IRB due to the plasmon resonance absorption. The optimal optical design and ITO film thickness were investigated, and the TiO2(SiO2/TiO2)3 multilayer combined with an ITO film thickness of 400 nm was found to provide a high NIR-shielding rate of 94.8%, UVB to UVA-shielding rate of 92.7%, and average visible light transmittance of 68.1%. Further, human skin cells protected by a UV/NIR-shielding coating showed significantly decreased reactive oxygen species generation and inflammatory cytokine expression as compared to those of unprotected cells. The results demonstrate that the development of multifunction coatings have potential for transparent heat insulation windows and human skin protection against UV/IR radiations.

Constructing on-demand photoreversible mono/multi-color switching fabrics with plasmonic in-doped ZnO catalyzed systems

Photoreversible color switching fabrics have attracted much interest by using plasmonic semiconductor-catalyzed systems with simultaneous high photocatalytic and photothermal effects, while such kinds of semiconductors are rarely reported. In this work, with ZnO as a model, we report the tuning of plasmonic performances of ZnO nanocrystals by doping various concentrations of indium ions through a solvothermal route. Indium doping not only confers size evolution but also incorporates ZnO lattices with a high concentration of free electrons that result in extended plasmonic photoabsorption, simultaneously achieving high photocatalytic and photothermal performances. The plasmonic In-doped ZnO nanocrystals, along with redox dyes, can be conveniently utilized for the design of a series of novel semiconductor-catalyzed color switching systems, including mono-color (red, green, blue) and multi-color switching (red, yellow, blue) systems, which rapidly respond to 365 nm light for photocatalytic discoloration and 980 nm light-induced photothermal heating for recoloration (in air). Furthermore, with methylcellulose as the polymer matrix, the plasmonic In-doped ZnO catalyzed systems can be further processed into switchable fabrics/papers, exhibiting excellent mono/multi-color response features. Based on the manipulation of the interactions between light and plasmonic semiconductor-catalyzed systems, the rewritable fabrics/papers exhibit a broad range of highly reversible photochromic features, showing great potential for application as advanced sensors and rewritable media.

Free electron nonlinearities in heavily doped semiconductors plasmonics

Heavily doped semiconductors have emerged as tunable low-loss plasmonic materials at mid-infrared frequencies. In this article we investigate nonlinear optical phenomena associated with high concentration of free electrons. We use a hydrodynamic description to study free electron dynamics in heavily doped semiconductors up to third-order terms, which are usually negligible for noble metals. We find that cascaded third-harmonic generation due to second-harmonic signals can be as strong as direct third-harmonic generation contributions even when the second-harmonic generation efficiency is zero. Moreover, we show that when coupled with plasmonic enhancement free electron nonlinearities could be up to two orders of magnitude larger than conventional semiconductor nonlinearities. Our study might open a new route for nonlinear optical integrated devices at mid-infrared frequencies.

Metal-induced n+/n homojunction for ultrahigh electron mobility transistors

A self-organized n+/n homojunction is proposed to achieve ultrahigh performance of thin film transistors (TFTs) based on an amorphous (Zn,Ba)SnO3 (ZBTO) semiconductor with sufficiently limited scattering centers. A deposited Al layer can induce a highly O-deficient (n+) interface layer in the back channel of a-ZBTO without damaging the front channel layer via the formation of a metal-oxide interlayer between the metal and back channel. The n+ layer can significantly improve the field-effect mobility by providing a relatively high concentration of free electrons in the front n-channel ZBTO, where the scattering of carriers is already controlled. In comparison with a Ti layer, the Al metal layer is superior, as confirmed by first-principles density functional theory (DFT) calculations, due to the stronger metal-O bonds, which make it easier to form a metal oxide AlOx interlayer through the removal of oxygen from ZBTO. The field-effect mobility of a-ZBTO with an Al capping layer can reach 153.4 cm2/Vs, which is higher than that of the pristine device, i.e., 20.8 cm2/Vs. This result paves the way for the realization of a cost-effective method for implementing indium-free ZBTO devices in various applications, such as flat panel displays and large-area electronic circuits.

Improved surface-enhanced Raman scattering (SERS) sensitivity to molybdenum oxide nanosheets via the lightning rod effect with application in detecting methylene blue

MoO2 nanomaterials show a superior surface-enhanced Raman scattering (SERS) property due to their high concentration of free electrons and low resistivity. However, the physical process of semiconductor-based SERS is still elusive because there are many factors that affect the local electromagnetic field intensity and the subsequent Raman intensity of the molecules in close proximity to the semiconductor nanomaterials. Herein, we investigate the important contribution of surface morphology to molybdenum oxide SERS. The MoO3/MoO2 nanosheets (NSs) are synthesized by oxidizing MoO2 NS, and the surface roughness of MoO3 can be controlled through adjusting the oxidization time. Compared with the MoO2 NS before oxidization, the MoO3/MoO2 NSs exhibit a much stronger SERS signal, which favors their application as a SERS substrate to detect trace amounts of methylene blue molecules. The minimum detectable concentration is up to 10−9 M and the maximum enhancement factor is about 1.4 × 105. Meanwhile, excellent signal reproducibility is also observed using the MoO3/MoO2 NSs as the SERS substrate. A simulated electric field distribution shows that a stronger electric field enhancement is formed due to the lightning rod effect in the gap of corrugated MoO3 NSs. These results demonstrate that the surface topography of molybdenum oxide may play a more important role than their oxidation state in SERS signal enhancement.

Prediction of Potential Barrier at Crystallite Boundaries in Poly- and Nanocrystalline Semiconductors

The distribution of the potential and the parameters of the potential barrier for electrons in semiconductor crystallite is numerically calculated. The calculations are made in a spherical crystallite with uniformly distributed surface states and uniformly distributed donors. It is considered in the calculations that the surface charge is screened both by the ionized donors and on free electrons; the contibution of free electrons should not be neglected in semiconductors with a high concentration of free electrons. It is demonstrated that the height of the potential barrier depends non-monotonically on the concentration of the donors in the crystallite. Moreover, in the curve of the height of the potential barrier as a function of the concentration of the donors, it is possible to highlight two segments corresponding to the cases of the complete and partial depletion of the crystallite. The height of the potential barrier increases with the concentration of the donors in the first segment and decreases in the second segment. It is established that the height of the potential barrier increases with the increase in the concentration of the surface states. The possibility of the existence of surface potential barriers in nano- and polycrystalline metal-oxide semiconductors, which are applied as a sensitive layer of gas sensors, is estimated. It is concluded that if the crystallite radius in metal-oxide semiconductors does not exceed 10 nm the sensor’s sensitivity to gas could hardly be attributed to the usual barrier model. It is demonstrated that shape of crystallite and the contribution of free electrons to screening of surface charge have to be taken into account to calculation of width of potential barrier.

Free-electron effects on the optical absorption of the hybrid perovskite CH3NH3PbI3 from first principles

Hybrid organic-inorganic perovskites, such as methyl-ammonium lead tri-iodide (MAPbI$_3$), are interesting candidates for efficient absorber materials in next-generation solar cells, partly due to an unusual combination of low exciton binding energy and strong optical absorption. Excitonic effects in this material have been subject to debate both for experiment and theory, indicating a need for better understanding of the screening mechanisms that act upon the electron-hole interaction. Here we use cutting-edge first-principles theoretical spectroscopy, based on density-functional and many-body perturbation theory, to study atomic geometries, electronic structure, and optical properties of three MAPbI$_3$ polymorphs and find good agreement with earlier results and experiment. We then study the influence of free electrons on the electron-hole interaction and show that this explains consistently smaller exciton binding energies, compared to those in the material without free electrons. Interestingly, we also find that the absorption line shape strongly resembles that of the spectrum without free electrons up to high free electron concentrations. We explain this unexpected behavior by formation of Mahan excitons that dominate the absorption edge, making it robust against free-electron induced changes observed in other semiconductors.

Calculation of the grain potential barrier in the poly− and nanocrystalline semiconductors

The distribution of potential and parameters of potential barrier in semiconductor crystallite was calculated numerically. The calculation was carried out in spherical crystallite with evenly distributed donors and surface states. The calculation assumed that the surface charge is screened by both ionized donors and free electrons, the contribution of which cannot be neglected in semiconductors with high concentration of free electrons. The height of potential barrier is shown to nonmonotonically depend on the concentration of donors. The dependence of height of potential barrier on the concentration of donors may be divided into two part. One part of dependence describes the fully depleted crystallite and the second part describes the party depleted crystallite. On the first part the height of potential barrier increases with the donor concentration but on the second part the height of potential barrier decreases. The height of the potential barrier increases with increasing of concentration of surface states. The possibility of existing of potential barriers is estimated in nano− and polycrystalline metal oxide semiconductors used as sensitive layers of gas sensors. It is concluded that if the radius of crystal grains in metal oxide semiconductors does not exceed 10 nm, the explanation of the sensitivity of the sensor to gas by using a commonly barrier model seems unlikely. It is demonstrated that shape of crystallite and the contribution of free electrons to screening of surface charge have to be taken into account to calculation of width of potential barrier.

Controlled Formation of Defective Shell on TiO2 (001) Facets for Enhanced Photocatalytic CO2 Reduction

AbstractDefective black TiO2 has attracted considerable attention as photocatalyst for highly efficient solar energy conversion. However, it still remains a challenge to understand the basic role of defective shell on the basis of crystal facet engineering, due to the difficulty in generating defects merely on a specific facet. Herein, we develop a novel strategy to precisely control the formation of defective shell only on {001} facets of TiO2 nanocrystals due to the anisotropic effect of the crystal facets, which enables the investigation of defective shell on a specific facet to be achieved. It is found that the defective shell, middle interface layer and crystalline core together constitute a homojunction (TiO2‐homojunction). The defective shell of TiO2‐homojunction realizes the effective spatial separation of photogenerated electrons and holes. Moreover, the presence of Ti3+ ion and oxygen vacancies in defective shell can induce high free electron concentration and serve as active sites to promote the adsorption and activation of CO2 molecules. As a result, the TiO2‐homojunction exhibits significant photocatalytic behavior for CO2 reduction in a gas‐solid system. More interestingly, the position of redox reaction is reversed due to the controlled formation of defective shell, where {001} facets act as reduction sites and {101} facets as oxidation sites during photocatalytic process.

Electronic excitations stabilized by a degenerate electron gas in semiconductors

Excitons in semiconductors and insulators consist of fermionic subsystems, electrons and holes, whose attractive interaction facilitates bound quasiparticles with quasi-bosonic character. In the presence of a degenerate electron gas, such excitons dissociate due to free carrier screening. Despite their absence, we found pronounced emission traces in the below-band-edge region of bulk, germanium-doped GaN up to a temperature of 100 K, mimicking sharp spectral features at high free electron concentrations (3.4E19–8.9E19 cm−3). Our interpretation of the data suggests that a degenerate, three-dimensional electron gas stabilizes a novel class of quasiparticles, which we name collexons. These many-particle complexes are formed by exchange of electrons with the Fermi gas. The potential observation of collexons and their stabilization with rising doping concentration is enabled by high crystal quality due to the almost ideal substitution of host atoms with dopants.

β-In2S3 for photovoltaic devices: investigation of the native point defects with ab initio first-principle calculations

Herein, we report a theoretical investigation based on DFT calculations devoted to the nature of charge carriers in the β-In2S3 material used as buffer in chalcopyrite thin-film solar cells. Our simulations led to unambiguous results concerning the incapability for this material to be a p-type semiconductor. Furthermore, it is demonstrated that the insertion of indium into a Td interstitial site seems to be the driving force leading to a natural n-type conductivity. Our calculations took into account different atmospheres in order to be directly comparable with experimental data. In particular, the competitive InS structure was considered. It is shown that the S-poor condition strongly lesser the defect formation energy and should be privileged to achieve high free electron concentrations for potential applications.

Investigation of Dual-Ion Beam Sputter-Instigated Plasmon Generation in TCOs: A Case Study of GZO.

The use of the high free-electron concentration in heavily doped semiconductor enables the realization of plasmons. We report a novel approach to generate plasmons in Ga:ZnO (GZO) thin films in the wide spectral range of ∼1.87-10.04 eV. In the grown GZO thin films, dual-ion beam sputtering (DIBS) instigated plasmon is observed because of the formation of different metallic nanoclusters are reported. Moreover, formation of the nanoclusters and generation of plasmons are verified by field emission scanning electron microscope, electron energy loss spectra obtained by ultraviolet photoelectron spectroscopy, and spectroscopic ellipsometry analysis. Moreover, the calculation of valence bulk, valence surface, and particle plasmon resonance energies are performed, and indexing of each plasmon peaks with corresponding plasmon energy peak of the different nanoclusters is carried out. Further, the use of DIBS-instigated plasmon-enhanced GZO can be a novel mean to improve the performance of photovoltaic, photodetector, and sensing devices.

High ionospheric activity effects on LatPos RTK network performance in Latvia

Fast and reliable coordinate determination with GNSS in real time is the main objective of continuous operating reference system (CORS) network users. To provide services for coordinate determination, Network-based Real Time Kinematic (NRTK) system called “LatPos” has been established and operated in Latvia since 2006. One of the factors, affecting the performance of LatPos system services, is activity of ionosphere. Ionosphere is a region of the earth’s atmosphere, from about 60 kilometers up to 1000 km above the earth’s surface, in which there is a high concentration of free electrons, spatially variated, affected by space weather, seasonal and solar cycle changes.Ionospheric activity conditions depending on mentioned factors can be analyzed by LatPos system data. Some data processing strategies has been developed and LatPos RTK network performance results obtained, during different ionospheric activity conditions. This paper focused on both segments: the NRTK performance and the rover receiver coordinate determination possibilities in field when high ionospheric activity occurs.

Influence of RF power on the opto-electrical and structural properties of gallium-doped zinc oxide thin films

GZO thin films were succesfully deposited onto n-Si and glass substrates by RF magnetron sputtering at room temperature. The structural, morphological and opto-electrical properties of the films were investigated in terms of RF power, using various methods such as XRD, AFM, SEM, EDX, XPS, SIMS, UV–Vis–NIR spectroscopy and Hall effect measurements. The achieved results revealed that the all films have highly c-axis (002) oriented polycrystalline structure with high transmittance in Vis and high reflectance in NIR region as well as good conductivity. Meanwhile, surface of the films was uniform, compact and crack-free. With incerasing of RF power, it was seen that crystallinity of the films improved and the grain size became larger. It was also observed that optical band gap of the films was increased to the order of 0.15 eV as well as decreasing the resistivity to the order of 6.38 Ω cm with increasing RF power from 100 to 200 W. Deposited film at 200 W, which can be optimum sputtering power for coating GZO films, having high concentration of free electrons and lowest resistivity exhibited the highest IR reflectivity (~55%) in NIR region. In addition, deposited GZO films at this power have larger particle size and highly optical transmittance (~87%) in visible region. Obtained both of optical and electrical results suggested that the deposited GZO films can be used in low thermal emissivity coating for energy efficient glass and the UV-blocking layer as well as transparent conductive oxide electrode for flexible opto-electronic devices.

Highly doped InP as a low loss plasmonic material for mid-IR region.

We study plasmonic properties of highly doped InP in the mid-infrared (IR) range. InP was grown by metal-organic vapor phase epitaxy (MOVPE) with the growth conditions optimized to achieve high free electron concentrations by doping with silicon. The permittivity of the grown material was found by fitting the calculated infrared reflectance spectra to the measured ones. The retrieved permittivity was then used to simulate surface plasmon polaritons (SPPs) propagation on flat and structured surfaces, and the simulation results were verified in direct experiments. SPPs at the top and bottom interfaces of the grown epilayer were excited by the prism coupling. A high-index Ge hemispherical prism provides efficient coupling conditions of SPPs on flat surfaces and facilitates acquiring their dispersion diagrams. We observed diffraction into symmetry-prohibited diffraction orders stimulated by the excitation of surface plasmon-polaritons in a periodically structured epilayer. Characterization shows good agreement between the theory and experimental results and confirms that highly doped InP is an effective plasmonic material aiming it for applications in the mid-IR wavelength range.

Indium-doped ZnO nanowires with infrequent growth orientation, rough surfaces and low-density surface traps

Indium-doped ZnO nanowires have been prepared by vapor transport deposition. With increasing In content, the growth orientation of the nanowires switches from [100] to infrequent [023] and the surface becomes rough. No surface-related exciton emission is observed in these nanowires. The results indicate that large surface-to-volume ratio, high free electron concentration, and low density of surface traps can be achieved simultaneously in ZnO nanowires via In doping. These unique properties make In-doped ZnO nanowire a potential material for photocatalysis application, which is demonstrated by the enhanced photocatalytic degradation of Rhodamine B.