Distribution Of Charge Carriers Research Articles

Charge Dynamics and Defect States under “Spot‐Light”: Spectroscopic Insights into Halide Perovskite Solar Cells

Halide perovskite solar cells (PSCs) have shown remarkable power conversion efficiencies. However, the inherent defect issues of perovskite materials still limit their performance and long‐term stability, resulting in lifespans far from commercial standards. With their noninvasive approach to probing the electronic and vibrational properties of materials, spectroscopic techniques have become crucial tools for uncovering and understanding defect states and complex charge carrier dynamics in halide perovskites. This review explores the application of various advanced spectroscopic techniques in PSCs to elucidate the complex behaviors of charge carriers within PSCs. These techniques reveal detailed temporal and spatial distributions of charge carriers, enabling precise analysis of defect impacts and interfacial charge transfer processes. By integrating spectroscopic data, it is possible to more accurately identify and mitigate defect‐induced nonradiative recombination and charge transfer, thereby enhancing the stability and efficiency of PSCs. This comprehensive spectroscopic understanding is crucial for developing innovative technologies to accelerate the commercial viability of PSCs.

Effective Model Reduction Scheme for the Electronic Structure of Highly Doped Semiconducting Polymers.

Highly doped organic polymers have emerged as prominent candidates within novel technological disciplines, yet the fundamental correlation between structure and charge transport characteristics still remains missing. Toward this objective, an efficient model reduction scheme for highly doped polymer chains is developed considering the paradigmatic case of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS). The reduced model accounts for the chemical and structural details of the conducting polymer chain in addition to the long-range Coulombic interactions between charge carriers (holes) and dopant ions and the Coulombic repulsion between holes residing on the PEDOT chain. The model is shown to reproduce the intrachain hole-density profile of bulk polymer chains within a mean-field description. Furthermore, and critically, the model is adept at determining the energy distribution of doped PEDOT samples that in effect, influences the hole distribution among polymer chains. The hole distribution so obtained broadly upholds the approximation of a homogeneous charge-carrier distribution in doped polymers commonly found in the literature. In addition, it is observed that the spin configuration of the charge carriers dictates the energetics of the doped chains while it is a critical function of the chain length, carrier density, and disorder parameters.

Enhanced Schottky barrier engineering in silver-doped TiO2/p-Si heterojunctions: Insights into electrical behavior and charge carrier dynamics

Heterojunctions were fabricated through the deposition of silver-doped Titanium dioxide (Ag–TiO2) onto p-type crystalline silicon, employing the sol-gel technique. Electrical characterization was conducted with varying Ag concentrations. The investigation revealed that the Schottky barriers at each interface (Ag/TiO2 and Si/Ag), along with the built-in potential at the TiO2/p-Si junction, increase proportionally with the Ag concentration. This observed trend was attributed to the reduction in the TiO2 bandgap due to Ag incorporation, resulting in a concurrent shift in both valence and conduction bands. Consequently, there is a growth of the conduction energy discontinuity and a reduction in the valence one, facilitating hole diffusion while impeding electron transfer across the depletion layer. Furthermore, the introduction of Ag leads to a decrease in both electron and hole concentrations. However, Ag incorporation within the TiO2 matrix manifests as nanoparticles and clusters, resulting in a nonhomogeneous distribution of charge carriers across the sample. Impedance analysis indicates an increase in device resistance and a decrease in effective capacitance.

Transient Electroluminescence Spectroscopy in Planar Electroluminescent Devices

AbstractThe emergence of planar electroluminescent diodes (including polymer light‐emitting diodes, organic light‐emitting diodes, quantum‐dot light‐emitting diodes, and perovskite light‐emitting diodes) is causing a revolution in displays, lighting, and wearable electronic devices. Continuous advancement in the comprehension and management of charge carrier dynamics in these devices has led to several significant breakthroughs, including diodes with ultrahigh luminance, memory devices, and amplified spontaneous emission. Transient electroluminescence (TrEL) spectroscopy is a relative powerful technology to investigate charge dynamics, including transport, distribution, and storage of charge carriers, in electrically‐driven planar light‐emitting diodes (LEDs). The aim of this review is to revisit the principle and applications of TrEL spectroscopy in planar electroluminescent diodes, and to evaluate the reliability of various parameters extracted using this technology. A particular focus is on electroluminescence response time, charge‐carrier transport and storage, and exciton species. First, the principle and equipment system of the TrEL, as well as specific attention during TrEL measurements are described in detail, following by the applications TrEL spectroscopy in planar LEDs. Further development on the TrEL technology is discussed in the third section. Finally, a summary and outlook for the TrEL are shown and challenges faced by the TrEL spectroscopy are also highlighted.

Exciton-Phonon Coupling in Single ZnCdSe-Dot/CdS-Rod Nanocrystals with Engineered Band Gaps from Type-II to Type-I.

Exciton-phonon coupling limits the homogeneous emission line width of nanocrystals. Hence, a full understanding of this is crucial. In this work, we statistically investigate exciton-phonon coupling by performing single-particle spectroscopy on colloidal Zn1-x Cd x Se/CdS and CdSe/CdS dot-in-rod nanocrystals at cryogenic temperatures (T ≈ 10 K). In situ cation exchange enables us to analyze different band alignments and, thereby, different charge-carrier distributions. We find that the relative intensities of the longitudinal optical S- and Se-type phonon replicas correlate with the charge-carrier distribution. Our experimental findings are complemented with quantum mechanical calculations within the effective mass approximation that hint at the relevance of surface charges.

Bulk photovoltaic effect in ferroelectric nematic liquid crystals.

The bulk photovoltaic (BPV) effect in ferroelectric liquid crystals is of increasing scientific interest owing to its great potential for light-energy conversion. The ferroelectric nematic phase exhibits a huge spontaneous polarization that can be aligned to a preferred direction. In this Letter, we investigate the tensorial properties of the BPV effect in the planarly aligned ferroelectric nematic phase of the liquid crystalline material RM734. A steady-state short-circuit photocurrent of ~160 pA and an open-circuit photovoltage of ~50 mV were observed in a cell with a thickness of 5.5 µm under the illumination of ultraviolet light without any bias voltage. Based on the photocurrent measurements in different electrode configurations, the non-zero elements of the BPV tensor were obtained. The BPV effect is attributed to the combination of the spontaneous polarization and the asymmetric distribution of photoinduced charge carriers. This study not only provides an understanding of the bulk PV mechanism in soft ferroelectrics but also promises a wide range of unprecedented, to the best of our knowledge, benefits for light harvesting to engineer marketable photovoltaic devices.

Monte Carlo simulation of initial and volume ion recombination correction factor in plane parallel ionization chambers exposed to ion beams

Objective. Accurate reference dosimetry with ionization chambers (ICs) relies on correcting for various influencing factors, including ion recombination. Theoretical frameworks, such as the Boag and Jaffe theories, are conventionally used to describe the ion recombination correction factors. Experimental methods are time consuming, the applicability may be limited and, in some cases, impractical to be used in clinical routine. The development of simulation tools becomes necessary to enhance the understanding of recombination under circumstances that may differ from conventional use. Before progressing, it is crucial to benchmark novel approaches to calculate ion recombination losses under known conditions. In this study, we introduce and validate a versatile simulation tool based on a Monte Carlo scheme for calculating initial and volume ion recombination correction factors in air-filled ICs exposed to ion beams with clinical dose rates. Approach. The simulation includes gaussian distribution of ion positions to model the distribution of charge carriers along the chamber volume. It accounts for various physical transport effects, including drift, diffusion, space charge screening and free electron fraction. To compute ion recombination, a Monte Carlo scheme is used due to its versatility in multiple geometries, without exhibiting convergence problems associated with numerically solved procedures. Main results. The code is validated in conventional dose rates against Jaffe’s theory for initial recombination and Boag’s theory for volume recombination based on parameters derived from experimental data including proton, helium and carbon ion beams measured with a plane parallel IC. Significance. The simulation demonstrates excellent agreement, typically 0.05% or less relative difference with the theoretical and experimental data. The current code successfully predicts ion recombination correction factors, in a large variety of ion beams, including different temporal beam structures.

Photoluminescence of dense arrays of InGaPAs/InGaAs quantum dots formed by substitution of group V elements

One drawback of self-organized quantum dots is their low optical gain. The development of new shaping methods that would allow higher gain, for example, due to a higher surface density of the QD array, remains an important task to date. In the present work, arrays of quantum dots have been formed by substituting phosphorous atoms with arsenic ones in a thin InGaP epilayer. Based on transmission electron microscopy data, the surface density was estimated to be about 1.3 × 1012 cm−2, which is one of the highest values for quantum dots on GaAs. The influence of an additional InGaAs epilayer (quantum well) on the luminescence properties of quantum dots was investigated in a wide temperature range and different optical pumping levels. It was found that placing the quantum well under the layer of quantum dots has little effect on the central emission wavelength, while quantum dots covered with the InGaAs demonstrate a strong red shift of the luminescence spectrum. A transition from a nonequilibrium to an equilibrium distribution of charge carriers over quantum-dot states, related to the lateral transport of charge carriers over quantum dot array, similar to that previously observed in In(Ga)As Stranski-Krastanow quantum dots, was revealed. This is manifested in a change in temperature dependencies of the linewidth and peak position of the photoluminescence band. For the structures under study, this transition occurs at a temperature of about 125 K. Rapid thermal annealing of the structures allows to increase the integrated photoluminescence intensity of quantum dots up to 4 times, while the maximum of the spectrum remains almost unchanged, provided that the annealing temperature does not exceed 620 °C.

Negative corona discharge strategy for efficient quantum dot light-emitting diodes.

In colloid quantum dot light-emitting diodes (QLEDs), the control of interface states between ZnO and quantum dots (QDs) plays a vital role. We present a straightforward and efficient method using a negative corona discharge to modify the QD film, creating a dipole moment at the interface of QDs and magnesium-doped ZnO (ZnMgO) for balanced charge carrier distribution within the QDs. This process boosts external quantum efficiencies in red, green, and blue QLEDs to 17.71%, 14.53%, and 9.04% respectively. Notably, optimized devices exhibit significant enhancements, especially at lower brightness levels (1000 to 10,000 cd·m-2), vital for applications in mobile displays, TV screens, and indoor lighting.

Distance Dependence of the Energy Transfer Mechanism in WS_{2}-Graphene Heterostructures.

We report on the mechanism of energy transfer in Van der Waals heterostructures of the two-dimensional semiconductor WS_{2} and graphene with varying interlayer distances, achieved through spacer layers of hexagonal boron nitride (h-BN). We record photoluminescence and reflection spectra at interlayer distances between 0.5 and 5.8nm (0-16 h-BN layers). We find that the energy transfer is dominated by states outside the light cone, indicative of a Förster transfer process, with an additional contribution from a Dexter process at 0.5nm interlayer distance. We find that the measured dependence of the luminescence intensity on interlayer distances above 1nm can be quantitatively described using recently reported values of the Förster transfer rates of thermalized charge carriers. At smaller interlayer distances, the experimentally observed transfer rates exceed the predictions and, furthermore, depend on excess energy as well as on excitation density. Since the transfer probability of the Förster mechanism depends on the momentum of electron-hole pairs, we conclude that, at these distances, the transfer is driven by nonrelaxed charge carrier distributions.

Scavenging Energy and Information through Dynamically Regulating the Electrical Double Layer

AbstractThe electrical double layer (EDL) between solids and liquids serves as the primary interface for ionic‐electronic coupling and is pivotal in nanoscale phenomena, governing electric field effects, ion transport, surface interactions, etc. Dynamically regulating the EDL through mechanical or electrostatic methods can influence charge carrier behavior, thereby impacting energy scavenging and storage processes. This regulation enabled efficient energy scavenging by governing ionic migration and optimizing charge carrier concentration at the interface, presenting a novel avenue to achieve efficient energy and information flow. Here, various scavenging energy and information devices through dynamically regulating the EDL are systematically reviewed. They are classified into three groups by regulating the distribution and movement of charge carriers throughout the entire EDL, diffuse layer, and Debye length range. The review provided a comprehensive overview of the operating principles, influencing factors, output characteristics, and typical applications, along with a discussion on future challenges. This holistic examination offers researchers valuable insights for evaluating their applicability in various scenarios.

Modeling of semiconductor heterostructures for energy converters and sensors

A set of modeling programs for constructing a sequence of energy zones of heterojunctions is presented for analyzing the distribution of charge carriers in the heterostructure and internal characteristics, for describing the processes of charge transfer and accumulation. Wolfram Mathematica analytical system and Delphi programming language were used. The main elements of materials are semiconductors, metals of contact structures and injection regions of nonequilibrium carriers. The programs allow determining the structural characteristics of materials, active zones and spatial charge regions, calculating quasi-Fermi levels and built-in potentials, as well as the efficiency of heterostructures in general and for separation-charge collection, charge accumulation, determining the type of metallization of barrier or ohmic contact.

A novel dual-parameter proximity and touch sensor using SiO2 nanoparticles and NaCl with commercial acrylic-based encapsulation

This study shows the development and analysis of a novel capacity proximity sensor (CPS) based on a sensing layer made up of a mixture of silicon dioxide nanoparticles (SiO2) and sodium chloride (NaCl), and an encapsulation layer based on a commercial acrylic-based varnish. The encapsulated and non-encapsulated proximity sensors were characterised using impedance spectroscopy (IS), revealing that the resulting impedimetric and capacitance responses exhibit different sensitivities and working sensing ranges. The non-encapsulated sensor presents impedimetric and maximum capacitive sensitivities of 0.0775 cm−1 and -0.9831 cm−1, respectively, within a 2–14 cm sensing range. In contrast, the encapsulated CPS shows maximum impedimetric and capacitive sensitivities of 0.3447 cm−1 and −3.349 cm−1, respectively, and an operation sensing range of 0–3 cm. The results show a 75% decrease in the total sensing range that could be attributed to: (i) a reduction of the effective sensing area due to a reduction of the roughness as demonstrated by SEM analysis, (ii) insulation effects limiting the impact of the material under test (MUT) on the charge carriers distribution, and (iii) decreased charge carrier density involved in the sensing process. Despite the reduced operational range, the encapsulation layer maintains the dual-parameter sensing capabilities, preserves the integrity of the sensing layer, and enables its dual functionality as a proximity and touch sensor. The reported comparison between the encapsulated and non-encapsulated CPSs highlights the effects of the encapsulation layer. The encapsulated version introduces a simple, fast, and cost-effective novel approach for developing CPSs that outperforms some reported CPSs in terms of reliability due to its dual-parameter sensing capability and sensitivity.

Overcoming the Unfavorable Effects of "Boltzmann Tyranny:" Ultra-Low Subthreshold Swing in Organic Phototransistors via One-Transistor-One-Memristor Architecture.

Organic phototransistors (OPTs), as photosensitive organic field-effect transistors (OFETs), have gained significant attention due to their pivotal roles in imaging, optical communication, and night vision. However, their performance is fundamentally limited by the Boltzmann distribution of charge carriers, which constrains the average subthreshold swing (SSave ) to a minimum of 60mV/decade at room temperature. In this study, an innovative one-transistor-one-memristor (1T1R) architecture is proposed to overcome the Boltzmann limit in conventional OFETs. By replacing the source electrode in an OFET with a memristor, the 1T1R device exploits the memristor's sharp resistance state transitions to achieve an ultra-low SSave of 18mV/decade. Consequently, the 1T1R devices demonstrate remarkable sensitivity to photo illumination, with a high specific detectivity of 3.9 × 109 cm W-1 Hz1/2 , outperforming conventional OPTs (4.9 × 104 cm W-1 Hz1/2 ) by more than four orders of magnitude. The 1T1R architecture presents a potentially universal solution for overcoming the detrimental effects of "Boltzmann tyranny," setting the stage for the development of ultra-low SSave devices in various optoelectronic applications.

Growth Control of InP/ZnSe Heterostructured Nanocrystals.

The morphology of heterostructured semiconductor nanocrystals (h-NCs) dictates the spatial distribution of charge carriers and their recombination dynamics and/or transport, which are the main performance indicators of photonic applications utilizing h-NCs. The inability to control the morphology of heterovalent III-V/II-VI h-NCs composed of heavy-metal-free elements hinders their practical use. As a case study of III-V/II-VI h-NCs, the growth control of ZnSe epilayers on InP NCs is demonstrated here. The anisotropic morphology in InP/ZnSe h-NCs is attributed to the facet-dependent energy costs for the growth of ZnSe epilayers on different facets of InP NCs, and effective chemical means for controlling the growth rates of ZnSe on different surface planes are demonstrated. Ultimately, this article capitalizes on the controlled morphology of InP/ZnSe h-NCs to expand their photophysical characteristics from stable and pure emission to environment-sensitive one, which will facilitate their use in a variety of photonic applications.

Impact of crystallinity and grain density on the charge-carrier distribution and transport in organic semiconductors

The crystalline and amorphous phases often coexist in the organic active layers of their electronic devices, which further undergo morphological changes over time. Understanding of the characteristics of the microscopic processes in polycrystalline organic films is essential for optimizing organic semiconductors and their devices, particularly in the context of flexible electronics. Here, we systematically investigate the charge-carrier distributions and transport in polycrystalline organic films, focusing on the impact of the crystallinity and grain density. These polycrystalline morphology data were generated from an efficient Monte Carlo method, which were then incorporated into molecular-level device simulations that can describe the microscopic charge-transport processes. These results demonstrate the distributions and transport characteristics of charge carriers in different phases of the polycrystalline organic semiconductor films, as well as the influencing factors. Importantly, we show that the influence of a polycrystalline morphology becomes more pronounced at low driving voltages, which has been the subject of significant research efforts. Our study also revealed a decrease in mobility at low crystallinities, a phenomenon that was not previously anticipated.

Pattern-illumination time-resolved phase microscopy and its applications for photocatalytic and photovoltaic materials.

Pattern-illumination time-resolved phase microscopy (PI-PM) is a technique used to study the microscopic charge carrier dynamics in photocatalytic and photovoltaic materials. The method involves illuminating a sample with a pump light pattern, which generates charge carriers and they decay subsequently due to trapping, recombination, and transfer processes. The distribution of photo-excited charge carriers is observed through refractive index changes using phase-contrast imaging. In the PI-PM method, the sensitivity of the refractive index change is enhanced by adjusting the focus position, the method takes advantage of photo-excited charge carriers to observe non-radiative processes, such as charge diffusion, trapping in defect/surface states, and interfacial charge transfer of photocatalytic and photovoltaic reactions. The quality of the image sequence is recovered using various informatics calculations. Categorizing and mapping different types of charge carriers based on their response profiles using clustering analysis provides spatial information on charge carrier types and the identification of local sites for efficient and inefficient photo-induced reactions, providing valuable information for the design and optimization of photocatalytic materials such as the cocatalyst effect.

Carrier modulation of one-dimensional MAPbxSr1-x(IyCl1-y)3 core-shell perovskite nanowires.

Low dimensional hybrid organic-inorganic perovskites (HOIPs) have become one of the most promising materials in solar cells, photodetectors, and lasers due to their low exciton binding energy, high bipolar carrier mobility, and long carrier lifetime. The effective separation and collection of photo-generated electrons and holes have always been crucial for a perovskite as a working medium for optoelectronic devices. However, the surface state of pristine perovskite nanowires causes recombination of electrons and holes at the edge of the energy band, leading to deactivation of charge carriers. In this work, we constructed MAPbxSr1-xI3 core-shell nanowires, which adjust the band gap and control the spatial distribution of charge carriers by changing the Pb composition ratio, achieving spontaneous separation of electron-hole pairs to avoid surface recombination. In addition, MAPbxSr1-x(IyCl1-y)3 core-shell nanowires with different component ratios (x, y) can be constructed by further doping the Cl element, and the spatial distribution of charge carriers in the nanowires can be flexibly manipulated to achieve exchange between type-I and type-II band alignment orders. This study provides a feasible method for enhancing the carrier separation of organic-inorganic hybrid perovskites and improving the performance of optoelectronic devices.

Size onset of metallic behavior in neutral aluminum clusters.

The excited state lifetimes of neutral (Al)n clusters up to ∼1 nm in diameter in size, where n ≤ 43, are systematically measured with femtosecond time-resolved mass spectrometry. The onset of metallic behavior is identified as a distinct change in the relaxation behavior initiated with single ultraviolet (400 nm) photon excitation. The experimentally measured excited state lifetimes gradually decrease with size for small molecular scale clusters (n < 10) before becoming indistinguishable for larger clusters (n > 9), where the measurements are comparable to electron-lattice relaxation time of bulk Al (∼300 fs). Particularly intense, or magic, Aln clusters do not exhibit any significant excited state lifetime behavior. Time-dependent density functional theory quantify the excited state properties and are presented to show that dynamics are strongly tied to the excited state charge carrier distributions and overlap, rather than detailed changes related to changes in the cluster's electronic and geometric structure. The consistency in excited state lifetimes for clusters larger than n = 9 is attributed to the hybridization of the s- and p-orbitals as well as increasing delocalization. Al3 exhibits unique temporal delay in its transient behavior that is attributed to a transition from triangular ground state to linear structure upon excitation.

Odnovremennoe nablyudenie tsiklotronnogo rezonansa dyrok i elektronov v dvoynoy kvantovoy yame HgTe/CdHgTe v usloviyakh effekta “opticheskogo zatvora”

Spectral studies of the photoconductivity in the temperature range of T = 5–70 K, as well as studies of the magneto-absorption and magnetotransport at T = 4.2 K, have been performed in a HgTe/CdHgTe heterostructure with a double quantum well under an “optical gate” effect. Studies of magneto-absorption spectra under the controlled optical exposure have made it possible to observe absorption lines caused by both the cyclotron resonances of electrons and holes simultaneously. The coexistence of electrons and holes in the HgTe/CdHgTe double quantum well with a relatively large bandgap (~80 meV) indicates the appearance of a strongly inhomogeneous light-induced distribution of charge carriers in the plane of the structure. Experimental results obtained clearly demonstrate disadvantages of the control of the Fermi level positions in heterostructures with HgTe/CdHgTe quantum wells by means of the optical gate.