Charge Transport Characteristics Research Articles

The Molecular Nature of Redox-Conductive Metal-Organic Frameworks.

ConspectusRedox-conductive metal-organic frameworks (RC-MOFs) are a class of porous materials that exhibit electrical conductivity through a chain of self-exchange reactions between molecularly defined, neighboring redox-active units of differing oxidation states. To maintain electroneutrality, this electron hopping transport is coupled to the translocation of charge balancing counterions. Owing to the molecular nature of the redox active components, RC-MOFs have received increasing attention for potential applications in energy storage, electrocatalysis, reconfigurable electronics, etc. While our understanding of fundamental aspects that govern electron hopping transport in RC-MOFs has improved during the past decade, certain fundamental aspects such as questions that arise from the coupling between electron hopping and diffusion migration of charge balancing counterions are still not fully understood.In this Account, we summarize and discuss our group's efforts to answer some of these fundamental questions while also demonstrating the applicability of RC-MOFs in energy-related applications. First, we introduce general design strategies for RC-MOFs, fundamentals that govern their charge transport properties, and experimental diagnostics that allow for their identification. Selected examples with redox-active organic linkers or metallo-linkers are discussed to demonstrate how the molecular characteristics of the redox-active units inside RC-MOFs are retained. Second, we summarize experimental techniques that can be used to characterize charge transport properties in a RC-MOF. The apparent electron diffusion coefficient, Deapp, that is frequently determined in the field and obtained in large perturbation, transient experiments will be discussed and related to redox conductivity, σ, that is obtained in a steady state setup. It will be shown that both MOF-intrinsic (topology, pore size, and apertures) and experimental (nature of electrolyte, solvent) factors can have noticeable impact on electrical conductivity through RC-MOFs. Lastly, we summarize our progress in utilizing RC-MOFs as electrochromic materials, materials for harvesting minority carriers from illuminated semiconductors and within electrocatalysis. In the latter case, recent work on multivariate RC-MOFs in which redox active linkers are used to "wire" redox catalysts in the crystal interiors will be presented, offering opportunities to independently optimize charge transport and catalytic function.The ambition of this Account is to inspire the design of new RC-MOF systems, to aid their identification, to provide mechanistic insights into the governing ion-coupled electron hopping transport mode of conductivity, and ultimately to promote their applications in existing and emerging areas. With basically unlimited possibilities of molecular engineering tools, together with research in both fundamental and applied fields, we believe that RC-MOFs will attract even more attention in the future to unlock their full potential.

Theoretical prediction of holes and electrons mobility in coronene and perchlorocoronene crystals: Application of the Marcus–Jortner–Levich Theory

The study focused on theoretically predicting charge carrier mobilities in coronene and perchlorocoronene crystals using the Marcus–Levich–Jortner approach. By analyzing charge transfer integrals and considering hopping pathways, significant anisotropy in charge transfer was observed. Density functional theory (DFT) calculations at the B3LYP-D3/6-311++G(d,p) and ωB97X-D/6-311++G(d,p) levels were employed to assess the impact of normal modes on reorganization energies and charge transfer rates. Results indicated that perchlorination reduced mobility for both holes and electrons. Notably, maximum mobilities were observed at the melting points: 0.0120 cm2 V−1 s−1 for electrons and 0.0798 cm2 V−1 s−1 for holes in coronene at 455 K, and 0.0032 cm2 V−1 s−1 for electrons and 0.0426 cm2 V−1 s−1 for holes in perchlorocoronene at 560 K. This suggests that both crystals exhibit favorable charge transport characteristics near their respective melting points.

Impact of Structural Alterations from Chemical Doping on the Electrical Transport Properties of Conjugated Polymers.

Conjugated polymers (CPs) are widely used as conductive materials in various applications, with their conductive properties adjustable through chemical doping. While doping enhances the thermoelectric properties of CPs due to improved main-chain transport, overdoping can distort the polymer structure, increasing energy disorder and impeding intrinsic electrical transport. This study explored how different dopants affect the structural integrity and electrical transport properties of CPs. We found that dopants vary in their impact on CP structure, consequently altering their electrical transport capabilities. Specifically, ferric chloride (FeCl3)-doped indacenodithiophene-co-benzothiadiazole (IDTBT) shows superior electrical transport properties to triethyloxonium hexachloroantimonate (OA)-doped IDTBT due to enhanced backbone planarity and rigidity, which facilitate carrier transport and lower energetic disorder. These results highlight the critical role of dopant selection in optimizing CPs for advanced applications, suggesting that strategic dopant choices can significantly refine the charge transport characteristics of CPs, paving the way for their industrialization.

Nanoscale Graded Nitrogen-Doping of TiO2 via Pulsed Laser Deposition for Enhancing Charge Transfer in Perovskite Solar Cells.

An electron transport layer (ETL) for highly efficient perovskite solar cells (PSCs) should exhibit superior electrical transport properties and have its band levels aligned with interfacing layers to ensure efficient extraction of photo-generated carriers. Nitrogen-doped TiO2 (TiO2:N) is considered a promising ETL because it offers higher electrical conductivity compared to conventional ETLs made from spray-pyrolyzed TiO2. However, the application of highly doped TiO2:N in PSCs is often limited by the misalignment of energy band levels with adjacent layers and reduced optical transparency. In this study, a novel approach is introduced to enhance the charge transport characteristics and accurately align the electronic band alignment of TiO2:N layer through nanoscale doping level grading, achieved through the pulsed laser deposition (PLD) technique. The TiO2:N ETL with a graded doping profile can combine characteristics of both highly doped and lightly doped phases on each side. Furthermore, a nanoscale doping gradation, employing an ultrathin sub-layer structure with graded doping levels, creates a smoothly cascading band-level alignment that bridges the adjacent layers, enhancing the transport of photo-generated carriers. Consequently, this method leads to a substantial increase in the power conversion efficiency (PCE), exceeding 22%, which represents a relative improvement of 11% compared to traditional spray-pyrolyzed TiO2-based PSCs.

Viable Approach of Tuning Oxide Semiconductor Thin Films in Solution‐Processed Heterojunction Thin Films Transistors for Both Higher Performances and Stability

AbstractMetal‐oxide thin‐film transistors (TFTs) have garnered much attention because of their advantages such as high transparency, low leakage current, and low processing temperature. However, there is a need to continuously improve their mobility and bias stability for application to next‐generation advanced electronics. In this study, the thickness of bilayer semiconductors is finely controlled to enhance the charge transport characteristics and bias stability in solution‐processed heterojunction oxide TFTs. The thicknesses of the top and bottom layers in the bilayer are individually adjusted by controlling solution molarity. The introduction of a bilayer channel improved the electrical performance of oxide TFTs via effective charge transport. However, trap‐limited conduction becomes dominant in the bilayer with an excessively thick top layer, thereby leading to a significant reduction in mobility and positive bias stability. Meanwhile, although increasing the bottom layer thickness contributes to improved mobility and reliability, it causes a serious negative shift in threshold voltage (VTH). TFTs with an optimized bilayer structure show high mobility at a VTH close to 0 V and have particularly excellent positive bias stress stability. This study on bilayer channel thickness will be beneficial for developing advanced transistors with optimized bilayer or multilayer channels.

Structural, Morphological, Optical and Dielectric Studies of RE3+ Doped CoFe2O4

Cobalt ferrite nanoparticles, both undoped and Eu³⁺-doped, with the formula CoEuxFe2-xO4 (where x = 0.00 and 0.10), were produced using the citrate gel auto-combustion technique. X-ray diffraction confirmed the successful formation of the phase and the purity of the synthesized nanoparticles. The morphological analysis was conducted using scanning electron microscopy (SEM). The optical properties of cobalt ferrite were analyzed using UV-Vis spectrometer. Dielectric properties, such as the real part of the dielectric constant and loss tangent, were evaluated using an LCR meter. Doping cobalt ferrite nanoparticles with europium resulted in a significant improvement in charge storage and transport characteristics.

A novel photoelectrochemical based water splitting and uric acid biosensing using PLD grown In2Se3 thin films

By altering the deposition pressure during the film growth process using the pulsed laser deposition (PLD) technology, indium selenide (In2Se3) thin films have been optimized to produce their distinct phases. The phase purity, optical and morphological studies were carried out using XRD, Raman spectroscopy, XPS, UV–visible spectroscopy, AFM and FESEM measurements. A high absorption in the visible region is observed for In2Se3 thin films with suitable band edges for hydrogen evolution. Photoelectrochemical (PEC) activity for In2Se3 photoelectrodes having various phases was analyzed based on CV and I-t response. A good charge transport characteristics were observed using the EIS measurements on PLD grown In2Se3 thin films. The Mott–Schottky analysis for the charge carrier density, flat band potential, and depletion layer width was performed for the deposition pressure dependent phase formation and high performance for PEC water splitting conversion efficiency of 0.48 %, 0.57 % and 0.98 % corresponding to α-In2Se3, β-In2Se3 and γ-In2Se3 were observed, respectively. The as prepared In2Se3 thin films were employed for the detection of Uric Acid (UA) using the cyclic voltammetry (CV), differential pulse voltammetry (DPV) and chronoamperometry. The high sensitivity (0.38 mA/mM), selectivity and repeatability of the prepared biosensor demonstrates In2Se3 as potential candidate for the PEC based water splitting and biosensing application without the presence of an external mediator and can work in the self-powered mode.

Multiphasic titania photoanode: A facile phase assisted approach to enhance the photoelectrochemical and photovoltaic performance

A facile low-temperature method has been proposed and utilized to synthesize pristine and multiphasic titania. Increasing reactant acid content led to the phase transition of titania from pristine anatase to triphasic anatase-rutile-brookite mixed phase; then to biphasic anatase-rutile mixed phase and ultimately pristine rutile. Morphological differences between the samples led to different dye loading on the Dye Sensitized Solar Cell (DSSC) photoanodes, with anatase showing highest loading. However, the Electrochemical Impedance Spectroscopic (EIS) analyses revealed that the triphasic titania photoanode showed superior charge transport ability as evidenced by the lowest charge transfer resistance and highest carrier lifetime. This led to the triphasic DSSC showing a photoconversion efficiency of 4.23 % which is 45 % greater than the reference DP25 DSSC and 72 % better than that of the anatase DSSC despite having a 24 % lower dye loading. These factors suggest that the charge transport properties precede the dye loading capability of the photoanode in determining the DSSC performance. The intimate ternary interfacial junction between the anatase, rutile and brookite phases may be responsible for the enhanced charge transport properties of the triphasic titania. Thus, it is essential to ensure superior photoanode charge transport characteristics to enhance the DSSC performance.

Improved high temperature energy storage density and efficiency of polyimide nanocomposites via hindering charge and molecular motions

Electric vehicles and renewable energy consumption have huge demands for high-performance polymer dielectric capacitors. However, the resistivity and breakdown strength of existing polymer dielectrics deteriorate significantly at high temperatures, reducing the energy storage density and charge-discharge efficiency of capacitors below service requirements. The charge transport and molecular chain motion characteristics in linear polymers determine their conductivity, breakdown, and energy storage properties, but the quantitative relationship between them is not clear. An in-situ polymerization method was used to prepare polyimide/Al2O3 nanocomposites (PI/Al2O3 PNCs). Experimental results show that the resistivity, breakdown strength, energy storage density, and charge-discharge efficiency of PNCs increase initially and then decrease with increasing doping content, peaking at 3 wt%. The discharged energy density of PI/Al2O3-3 wt% PNCs at 180°C is 207.52 % higher than pure PI. A conductance-breakdown-energy storage co-simulation model based on charge transport and molecular chain displacement was used to simulate the voltage-current, breakdown, and energy storage characteristics of PNCs. The simulation results are consistent with the experiments. Comparative studies between simulation and experiments show that the independent interface zone between nanofillers and PI hinders charge transport and molecular chain movement, reducing electric field distortion and molecular chain spacing, thereby improving high-temperature breakdown and energy storage performance of PNCs.

Interfacial Engineering for Controlled Crystal Mosaicity in Single-Crystalline Perovskite Films.

Organic-inorganic hybrid perovskites have attracted significant attention for optoelectronic applications due to their efficient photoconversion properties. However, grain boundaries and irregular crystal orientations in polycrystalline films remain issues. This study presents a method for producing crystalline-orientation-controlled perovskite single-crystal films using retarded solvent evaporation. It is shown that single-crystal films, grown via inverse temperature crystallizationwithin a confined space, exhibit enhanced optoelectronic property. Using interfacial polymer layer, this method produces high-quality perovskite single-crystalline films with varying crystal orientations. Density functional theory calculations confirm favorable adsorption energies for (110) surfaces with methylammonium iodide and PbI2 terminations on poly(3-hexylthiophene), and stronger adsorption for (224) surfaces with I and methylammonium terminations on polystyrene, influenced by repulsive forces between the thiophene group and the perovskite surface. The correlation between charge transport characteristics and perovskite single-crystalline properties highlights potential advancements in perovskite optoelectronics, improving device performance and reliability.

Advancements in non‐fullerene acceptors for organic solar cells: Brief review of research trends

AbstractIn the last few decades, fullerene‐based acceptors have been extensively utilized in organic solar cells (OSCs). However, OSCs based on fullerenes suffer from low photocurrent and photovoltage due to their poor light absorption capacity and limited tunability of energy levels, which impedes efficiency improvements. Recently, non‐fullerene acceptors (NFAs) have enabled rapid progress in OSCs, owing to their favorable properties such as strong light absorption, facile energy level tuning, and improved charge transport characteristics. These features have led to rapid efficiency enhancements. This review discusses the latest research trends related to NFAs, covering several factors that can be applied in the development of NFAs. Finally, we suggest prospects and challenges for high‐performance NFA‐based OSCs on the path to commercialization.

Exploring the Charge-Transport and Optical Characteristics of Organic Doublet Radicals: A Theoretical and Experimental Study with Photovoltaic Applications.

Herein, we present a series of stable radicals containing a trityl carbon-centered radical moiety exhibiting interesting properties. The radicals demonstrate the most blue-shifted anti-Kasha doublet emission reported so far with high color purity (full width at half-maximum of 46 nm) and relatively high photoluminescence quantum yields of deoxygenated toluene solutions reaching 31%. The stable radicals demonstrate equilibrated bipolar charge transport with charge mobility values reaching 10-4 cm2/V·s at high electric fields. The experimental results in combination with the results of TD-DFT calculations confirm that the blue emission of radicals violates the Kasha rule and originates from higher excited states, whereas the bipolar charge transport properties are found to stem from the particularity of radicals to involve the same molecular orbital(s) in electron and hole transport. The radicals act as the efficient materials for interlayers, passivating interfacial defects and enhancing charge extraction in PSCs. Consequently, this leads to outstanding performance of PSC, with power conversion efficiency surpassing 21%, accompanied by a remarkable increase in open-circuit voltage and exceptional stability.

Synergistic charge-transfer dynamics of rigid fused and unfused backbone with donors lead to promising photovoltaic properties of diazaborinine-based chromophores

Herein, a series of diazaborinin based derivatives (FABD1–FABD8) having D-π-D configuration was designed by inserting different types of rigid fused and unfused π-bridges into reference molecule (FABR) to explore their photovoltaic characteristics. To determine the optoelectronic and charge transport characteristics of these analogues, DFT/TD-DFT based calculations were conducted at the MPW1PW91/6-31G (d,p) level. For this, various analyses were performed such as transition density matrix (TDM), global reactivity parameters (GRP), open-circuit voltage (Voc), optical properties (UV–Vis), binding energy (Eb), hole-electron and frontier molecular orbital (FMO) energies. Their insights indicate that a rigid fused π-bridge greatly lowers the band gap as compared to an unfused π-spacers. Particularly, FABD7 showed the lowest energy gap of 2.20 eV owing to the presence of a rigid fused central core as compared to FABR with a band gap of 2.65 eV. Similarly, the entitled designed derivatives demonstrated a redshift absorption in the range of 585.7–704.6 nm while FABR is reported with 558.7 nm in the solvent phase. Furthermore, these derivatives displayed significant Voc with blending of PC61BM acceptor. This observation was also supported by DOS and TDM based insights. Interestingly, FABD7 seemed as a viable photovoltaic material due to its strong optical properties and small band gaps. These results uncover that the designed chromophores may be considered as efficient to enhance the performance of OSCs.

Rational Construction of Two-Dimensional Conjugated Metal-Organic Frameworks (2D c-MOFs) for Electronics and Beyond.

ConspectusTwo-dimensional conjugated metal-organic frameworks (2D c-MOFs) have emerged as a novel class of multifunctional materials, attracting increasing attention due to their highly customizable chemistry yielding programmable and unprecedented structures and properties. In particular, over the past decade, the synergistic relationship between the conductivity and porosity of 2D c-MOFs has paved the way toward their widespread applications. Despite their promising potential, the majority of 2D c-MOFs have yet to achieve atomically precise crystal structures, hindering the full understanding and control over their electronic structure and intrinsic charge transport characteristics. When modulating the charge transport properties of two-dimensional layered framework materials, decoupling the charge transport processes within and in between layers is of paramount importance, yet it represents a significant challenge. Unfortunately, 2D c-MOFs systems developed so far have failed to address such a major research target, which can be achieved solely by manipulating charge transport properties in 2D c-MOFs. 2D c-MOFs offer a significant advantage over organic radical molecules and covalent organic frameworks: polymerization through oxidative coordination is a viable route to form "spin-concentrated assemblies". However, the role of these spin centers in charge transport processes is still poorly understood, and the intrinsic dynamics and properties of these spins have seldom been investigated. Consequently, overcoming these challenges is essential to unlock the full potential of 2D c-MOFs in electronics and other related fields, as a new type of quantum materials.In this Account, we summarize and discuss our group's efforts to achieve full control at the atomic level over the structure of 2D c-MOFs and their applications in electronics and spintronics, thereby providing distinct evidence on 2D c-MOFs as a promising platform for exploring novel quantum phenomena. First, we unravel the key role played by the rational design of the ligands to decrease the boundary defects, achieve atomically precise large single crystals, and investigate the intrinsic charge transport properties of 2D c-MOFs. The advantages and disadvantages of the current structural elucidation strategies will be discussed. Second, the fundamental challenge in 2D c-MOF charge transport studies is to decouple the in-plane and interlayer charge transport pathways and achieve precise tuning of the charge transport properties in 2D c-MOFs. To address this challenge, we propose a design concept for the second-generation conjugated ligands, termed "programmable conjugated ligands", to replace the current first-generation ligands which lack modifiability as they mainly consist of sp2 hybridization atoms. Our efforts also extend to controlling the spin dynamics properties of 2D c-MOFs as "spin concentrated assemblies" using a bottom-up strategy.We hope this Account provides enlightening fundamental insights and practical strategies to overcome the major challenges of 2D c-MOFs for electronics and spintronics. Through the rational design of structural modulation within the 2D plane and interlayer interactions, we are committed to making significant steps forward for boosting the functional complexity of this blooming family of materials, thereby opening clear perspectives toward their practical application in electronics with the ultimate goal of inspiring further development of 2D c-MOFs and unleashing their full potential as an emerging quantum material.

Enhancing conductivity in polymers: The role of metal ions in conducting polymer systems

AbstractAs metal ion inclusion has a substantial effect on conducting polymer's mechanical, optical, and electrical properties, it has attracted a lot of attention. This article delves into the complex role of metal ions in conducting polymers, explaining how they affect functionality, structural stability, and conductivity enhancement. The review starts with a synopsis of conducting polymers and doping processes before diving into the particular ways that metal ions interact with polymer matrices to alter their electronic structure and charge transport characteristics. The importance of characterization techniques in comprehending the structure–property correlations is highlighted in the discussion of metal‐ion doped conducting polymer studies. In addition, the paper looks at the uses of conducting polymers doped with metal ions in numerous sectors, including energy storage, electronics, and sensors. The difficulties in attaining accurate control over doping concentrations and guaranteeing stability over an extended period are discussed, as well as potential avenues for future development in this area. This review offers important insights into the development and optimization of functional materials for a variety of applications by thoroughly investigating the function of metal ions in conducting polymers.

Unveiling the potential of TPA-based molecules to tune the optoelectronic properties and enhance the efficiency of dye-sensitized solar cells.

The world's energy and environmental requirements are changing due to rapid population growth and industrial growth, and solar cells can be used to meet these demands. Dye-sensitized solar cells (DSSCs) are solar cells in which energy conversion occurs via a process similar to photosynthesis in plants. DSSC development is still in its infancy. DSSCs can operate under cloudy conditions and indirect sunlight and have attracted considerable attention due to their low cost and high efficiency. We designed two metal-free TPA-based dyes (Dye2 and Dye3) based on the reference dye Mg207 (Dye1) by increasing the donor strength of the molecule, as such dyes have shown enhanced efficiency in DSSCs. Moreover, the triphenylamine (TPA) moiety has been demonstrated to be a good donor that prevents charge recombination. Intramolecular charge transfer (ICT) from the donor to acceptor moiety was found in the sensitizers, and electrons were promoted to the conduction band (CB) of the TiO2 semiconductor. The negative binding energy of the dye@TiO2 clusters indicated that dye adsorption on the semiconductor surface was stable. The double donor increased the electron injection and electronic coupling constants in Dye2 and Dye3, indicating that these newly designed dyes have superior charge injection capacity. Accordingly, the efficiencies of DSSCs with Dye2 and Dye3 were 9.77% and 9.62%, respectively, and substitution with the TPA unit at the -R1 and -R2 positions in Dye1 resulted in better power conversion compared to the parent compound (9.09%). Increased donor strength improved photovoltaic performance by increasing current density and light-harvesting efficiency. This is a good molecular design approach for preparing targeted donor- -acceptor (D- -A) organic dyes with high DSSC efficiency. To predict the charge transport and optoelectronic characteristics of the TPA dyes, quantum chemical calculations were carried out using Gaussian16. The ground-state (S0) optimized geometries of the sensitizers were computed by utilizing DFT at the B3LYP/6-31G** level. The absorption spectra ( max) were computed by employing TD-DFT with various functionals (B3LYP, PBE1PBE, CAM-B3LYP, and BHandHLYP) in the gas and solvent (DCM) phases. Among the studied functionals, BHandHLYP was found to be best at successfully reproducing the experimental data. Thus, the absorption spectra of the newly designed dyes and dye@TiO2 were calculated at the BHandHLYP/6-31G** level. The dye@TiO2 cluster optimizations were carried out at the B3LYP/6-31G**(LANL2DZ) level.

Porous two-dimensional CuSe@BiOI isotype heterojunction with highly exposed (1 0 2) facets for efficient photoelectrocatalytic CO2 reduction and photodetection

Using photoelectrochemical technology to construct efficient photoelectric materials has aroused extensive research interest. In this study, we propose a two-dimensional porous CuSe@BiOI isotype heterojunction photocathode for CO2 reduction to formic acid. The heterojunction was constructed by the epitaxial growth of high-quality oriented BiOI nanosheets onto the porous CuSe framework. The CuSe framework as a template to ensure the formation of the (102) facets of BiOI and the isotropic charge transport characteristics of the (102) surface greatly improve the efficiency of charge separation and transfer. This CuSe@BiOI isotype heterojunction electrode can efficiently reduce CO2 to formic acid with a selectivity of up to 80.5 % in 0.5 M potassium bicarbonate aqueous solution. Meanwhile,the performance of the photodetector based on CuSe@BiOI heterostructure is 6.97 × 1011 Jones and a response rate of 87.13 mA W−1. This finding provides a new approach to designing stable heterojunction photoelectrocatalysts with isotropy.

Synthesis of Thionated Perylenediimides: State of the Art and First Investigations of an Alternative to Lawesson's Reagent.

Perylenediimides (PDIs) are composed of a central perylene ring, on which are grafted two imide groups at the peri positions. Thionated PDIs are characterized by the substitution of one or more oxygen atoms of these imide functions with sulfur atoms. This structural modification alters the electronic properties with a redshift of the optical absorption accompanied by modification of the charge transport characteristics compared to their non-thionated counterparts. These properties make them suitable candidates for applications in optoelectronic devices, such as organic light-emitting diodes and organic photovoltaics. Moreover, the presence of sulfur atom(s) can favor the promotion of reactive oxygen species production for photodynamic and photothermal therapies. These thionated PDIs can be synthesized through the post-functionalization of PDIs by using a sulfurizing reagent. Nevertheless, the main drawbacks remain the difficulties in adjusting the degree of thionation and obtaining tri- and tetrathionated PDIs. Up to now, this thionation reaction has been described almost exclusively using Lawesson's reagent. In the current study, we present our first investigations into an alternative reagent to enhance selectivity and achieve a greater degree of thionation. The association of phosphorus pentasulfide with hexamethyldisiloxane (Curphey's reagent) clearly demonstrated higher reactivity compared with Lawesson's reagent to attain multi-thionated PDIs.

Plasmonic effect of metal nanoparticles on the photocatalytic properties of TiO2/rGO composite

A comparative study of the plasmon effect of Ag and Au nanoparticles on TiO2/rGO nanocomposite was carried out. The synthesis of Au and Ag nanoparticles was carried out by laser ablation. The morphology and structure of the nanocomposites were studied by EDA, HRTEM, XRD and Raman spectroscopy. It was shown that the absorption capacity of the nanocomposite material was increased in the visible range of the spectrum when Ag and Au nanoparticles were added to TiO2/rGO. This leads to an increase in their photocatalytic activity. The photocurrent generated by NC/Au 10−11 films is in 3.8 times and NC/Ag 10−12 is in 2 times higher compared to pure TiO2/rGO film. Similar results were obtained from experimental data on the dyes photodegradation. In the presence of plasmon nanoparticles a significant enhancement in the electrical properties of the TiO2/rGO nanocomposite was recorded. The charge carrier transfer resistance in nanocomposites was decreased by almost ∼7 times for NC/Au,10−11 and ∼4 times for NC/Ag,10−12 films compared to pure TiO2/rGO. In addition, for nanocomposites with Ag or Au nanoparticles, a decrease in the effective electron lifetime was observed. The data obtained allow us to conclude that plasmonic NPs have a synergistic effect in TiO2/rGO nanocomposites, which consists in modifying both their light-harvesting properties and charge-transport characteristics. The results obtained can be used for the design of materials with improved photocatalytic and optoelectronic characteristics.

Enhancing dye-sensitized solar cell performance: Optimizing Cu2ZnSnS4/ZnCo2O4 nanocomposites as efficient and cost-effective counter electrodes

This study investigates the utilization of Cu2ZnSnS4/ZnCo2O4 (CZTS/ZCO) nanocomposites prepared through hydrothermal and combustion methods as counter electrodes in Dye-Sensitized Solar Cells (DSSCs). Different ratios of Cu2ZnSnS4 and ZnCo2O4 were explored, and comprehensive analyses were conducted using X-ray Diffraction (XRD), Transmission Electron Microscopy (TEM), High-Resolution TEM (HRTEM), Brunauer–Emmett–Teller (BET) surface area analysis, Raman Spectroscopy, Electrochemical Impedance Spectroscopy (EIS), cyclic voltammetry (CV), Tafel analysis, Field Emission Scanning Electron Microscopy (FESEM), and Incident Photon-to-Electron Conversion Efficiency (IPCE), alongside long-term stability assessments. The CZTS:ZCO ratio of 2:1 exhibited the highest efficiency, reaching 8.81 %, with an open-circuit voltage of 729 mV, short-circuit current of 17.80 mAcm−2, and a fill factor of 67.9 %. This surpasses the efficiency of the reference Pt cell (8.42 %), which had an open-circuit voltage of 735 mV, short-circuit current of 17.16 mAcm−2, and a fill factor of 66.8 %. The average crystallite sizes for the main peaks of CZTS and ZCO samples were estimated to be 19.8 and 16.7 nm, respectively. The crystallite size can significantly affect the charge transfer and conductivity in the counter electrode during electrochemical processes; the presence of nanocrystals with these sizes can notably enhance the electrochemical properties and conductivity of the synthesized samples. Raman analysis results indicate that no additional phases or secondary phases such as ZnS and CuSnS3 have formed in the kesterite CZTS structure, and the crystal has formed as a single phase. Additionally, the F2g modes in the Raman spectrum of ZCO indicate tetrahedral units in the spinel ZCO structure, and the A1g modes represent octahedral structures in this phase, indicating the formation of suitable ZCO phase. The superior performance of the CZTS/ZCO nanocomposite can be attributed to its enhanced crystalline structure, superior charge transport characteristics, and improved electrocatalytic behaviours.