Tunable Optoelectronic Properties Research Articles

Space-confined solid-phase growth of two-domain 1T′-ReSe2 for tunable optoelectronics

Two-dimensional layered ReX2 (X = Se, S) has attracted researcher's great interest due to its unusual in-plane anisotropic optical and electrical properties and great potential in polarization-sensitive optoelectronic devices, while the clean, energy-saving, and ecological synthesis of highly crystalline ReSe2 with controlled domains remains challenging. Here, we develop a space-confined solid-phase approach for growing high-quality two-domain 1T′-ReSe2 with tunable optoelectronic properties by using pure Re powder as a Re precursor. The results show that ReSe2 can be grown at a temperature as low as 550 °C in a small-tube-assisted space-confined reactor, with its size and shape well-tailored via temperature control. A solid-phase two-domain ReSe2 growth mechanism is proposed, as evidenced by combining in situ optical monitoring, ex situ electron microscope, elemental mapping, and polarized optical imaging. Moreover, two-domain ReSe2 transistors are fabricated, which exhibit a switchable transport behavior between n-type and ambipolar character via grain boundary orientation control. This modulation phenomenon is attributed to the different doping levels between grain boundary and single domain. Furthermore, our two-domain ReSe2 photodetectors exhibit a highly gate-tunable current on–off ratio (with a maximum value of ∼8.2 × 103), a polarization-sensitive photo-response, and a high-speed response time (∼300 μs), exceeding most of the previously reported ReX2 photodetectors. Our work, thus, provides a low-consumption, energy-saving growth strategy toward high-quality, domain-controlled ReX2 for highly tunable and high-performance optoelectronics.

Band gap engineering and enhanced optoelectronic performance by varying dopant concentration in RbSr[formula omitted]Sn[formula omitted]Cl[formula omitted]: Ab-inito study

In the pursuit of eco-friendly solar cells, the exploration of lead-free perovskite halides has gained momentum. This study examines tin (Sn) doping effects on RbSrCl3, a lead-free perovskite, using density functional theory (DFT). Systematically varying Sn doping (25%, 50%, 75%, 100%), the research reveals consistent mechanical stability of the doped systems. Notably, an inverse relationship emerges: increased Sn dopant reduces bandgap values, enhancing visible range absorption of the hybrid perovskite materials which is crucial for solar efficiency. Extending simulations to 14 eV, optical properties like refractive index, absorption coefficient, and conductivity are explored offering a comprehensive understanding of the materials’ optical behavior. In summary, Sn-doped hybrid perovskite materials exhibit both mechanical stability and tunable optoelectronic properties, positioning them as promising candidates for solar cell technology. The study is a significant step in advancing environmentally conscious solar cell technologies for sustainable energy applications.

Biaxial strain tuned upconversion photoluminescence of monolayer WS2

Monolayer tungsten disulfide (1L-WS2) is a direct bandgap atomic-layered semiconductor material with strain tunable optical and optoelectronic properties among the monolayer transition metal dichalcogenides (1L-TMDs). Here, we demonstrate biaxial strain tuned upconversion photoluminescence (UPL) from exfoliated 1L-WS2 flakes transferred on a flexible polycarbonate cruciform substrate. When the biaxial strain applied to 1L-WS2 increases from 0 to 0.51%, it is observed that the UPL peak position is redshifted by up to 60 nm/% strain, while the UPL intensity exhibits exponential growth with the upconversion energy difference varying from − 303 to − 120 meV. The measured power dependence of UPL from 1L-WS2 under biaxial strain reveals the one photon involved multiphonon-mediated upconversion mechanism. The demonstrated results provide new opportunities in advancing TMD-based optical upconversion devices for future flexible photonics and optoelectronics.

Unveiling Valence State-Dependent Photocatalytic Water Splitting Activity and Photocathodic Behavior in Visible Light-Active Iridium-Doped BaTiO3.

Despite having favorable energetics and tunable optoelectronic properties, utilization of BaTiO3 (BTO) for photocatalytic reactions is limited by its absorption only in the ultraviolet region. To address this challenge, BTO is doped with iridium (Ir) to induce visible light absorption. The visible light-induced photocatalytic H2 generation efficiency is enhanced by 2 orders of magnitude on selective conversion of the Ir valence state from Ir4+ to Ir3+. To understand such intriguing behavior, valence state-dependent changes in the optoelectronic, structural, and surface properties and electronic band structure are comprehensively investigated. The effect of electron occupancy change between Ir4+ (t2g5 eg0) and Ir3+ (t2g6 eg0) and their energetic positions within the band gap is found to significantly influence H2 generation. Besides this, converting Ir4+ to Ir3+ enhanced the photocathodic current and lowered the onset potential. Results aid in designing photocatalysts to efficiently use low-energy photons for enhancing solar H2 production in these emerging BTO-based photocatalysts. Collectively, the observations made in this work highlight the promising application of Ir3+:BTO in z-scheme photocatalysis.

PtII(C^N)(N-donor ligand)Cl-type complexes with the four-coordinate organoboron unit and their optoelectronic properties

In this research, we have developed a series of PtII(C^N)(N-donor ligand)Cl-type phosphorescent complexes with the four-coordinate organoboron unit in the C^N ligand. Through shifting the coordinating position of the Pt(II) center from phenyl ring to pyridyl ring of the 2-phenylpyridine-type (ppy-type) four-coordinate organoboron unit, the variation of >50 nm in charge-transfer (CT) absorption band and >40 nm in phosphorescent wavelength can be observed in the synthesized PtII(C^N)(N-donor ligand)Cl-type complexes, indicating effective tuning of their photophysical properties incurred by the four-coordinate organoboron unit. In addition, based on the cyclic voltammetry result, obvious variation of electron density on the Pt(II) center of these PtII(C^N)(N-donor ligand)Cl-type phosphorescent complexes can also be observed. Critically, these PtII(C^N)(N-donor ligand)Cl-type complexes with the ppy-type four-coordinate organoboron unit can exhibit aggregation enhanced phosphorescent emission (AEPE) behavior. It seems that the hydrogen bonding among the N-donor ligands and water molecules can affect their AEPE response greatly, representing a new way to tune the AEPE behavior in the PtII(C^N)(N-donor ligand)Cl-type complexes. In the solution-processed organic light-emitting diodes (OLEDs), peak electroluminescent (EL) efficiencies of 15.3%, 10.3 cd A−1 and 9.8 lm W−1 have been achieved with EL at ca. 648 nm. These impressive results have provided key information for tuning optoelectronic properties of the PtII(C^N)(N-donor ligand)Cl-type complexes by the four-coordinate organoboron unit and N-donor ligand.

Halide Ion Mobility in Paired 2D Halide Perovskites: Ruddlesden–Popper Versus Dion–Jacobson Phases

Abstract2D lead halide perovskites with tunable optoelectronic properties through modulating inorganic components and organic spacer ligands represent a promising candidate in perovskite optoelectronics. However, an intrinsic soft lattice of perovskites gives rise to a vacancy‐mediated halide ion migration, which further affects the long‐term stability of materials as well as devices. Here, halide ion mobility is evaluated using two different 2D perovskites yielded with butylammonium (BA) for the Ruddlesden–Popper (RP) phase and butane‐1,4‐diamine (BDA) for the Dion–Jacobson (DJ) phase, respectively. By probing the halide ion migration kinetics in the physically paired 2D bromide and iodide perovskite films, the softer lattice (RP) shows a lower activation energy of 50.9 kJ mol−1 as compared to that of more rigid lattice (DJ) of 60.8 kJ mol−1. Given similar halide diffusion pathlength and halide mixing chemical potential, the binding mode (RP and DJ) can indeed dictate the overall halide ion stability. Understanding such halide ion mobility is important in designing perovskites with increased stability and performances at material and device levels.

Unraveling the Transformation from Type-II to Z-Scheme in Perovskite-Based Heterostructures for Enhanced Photocatalytic CO2 Reduction.

The ability to create perovskite-based heterostructures with desirable charge transfer characteristics represents an important endeavor to render a set of perovskite materials and devices with tunable optoelectronic properties. However, due to similar material selection and band alignment in type-II and Z-scheme heterostructures, it remains challenging to obtain perovskite-based heterostructures with a favorable electron transfer pathway for photocatalysis. Herein, we report a robust tailoring of effective charge transfer pathway in perovskite-based heterostructures via a type-II to Z-scheme transformation for highly efficient and selective photocatalytic CO2 reduction. Specifically, CsPbBr3/TiO2 and CsPbBr3/Au/TiO2 heterostructures are synthesized and then investigated by ultrafast spectroscopy. Moreover, taking CsPbBr3/TiO2 and CsPbBr3/Au/TiO2 as examples, operando experiments and theoretical calculations confirm that the type-II heterostructure could be readily transformed into a Z-scheme heterostructure through establishing a low-resistance Ohmic contact, which indicates that a fast electron transfer pathway is crucial in Z-scheme construction, as further demonstrated by CsPbBr3/Ag/TiO2 and CsPbBr3/MoS2 heterostructures. In contrast to pristine CsPbBr3 and CsPbBr3/TiO2, the CsPbBr3/Au/TiO2 heterostructure exhibits 5.4- and 3.0-fold enhancement of electron consumption rate in photocatalytic CO2 reduction. DFT calculations and in situ diffuse reflectance infrared Fourier transform spectroscopy unveil that the superior CO selectivity is attributed to the lower energy of *CO desorption than that of hydrogenation to *HCO. This meticulous design sheds light on the modification of perovskite-based multifunctional materials and enlightens conscious optimization of semiconductor-based heterostructures with desirable charge transfer for catalysis and optoelectronic applications.

Near-Infrared Absorbing Para-Azaquinodimethane Conjugated Polymers Synthesized via the Transition-Metal-Free Route toward Efficient Photothermal Conversion.

Conjugated polymers with strong absorption in the second near-infrared (NIR-II) window have multiple applications. However, the development of new type of NIR-II conjugated polymers via facile and green methods remains challenging. Herein, this work reports a mild and convenient transition-metal-free method to synthesize near-infrared absorbing quinoidal conjugated polymers containing para-azaquinodimethane (AQM) moieties. The AQM quinoidal conjugated polymers with unique molecular structures and tunable optoelectronic properties can be synthesized by combining the Knoevenagel polycondensation of aromatic dialdehyde monomers with commercially available 1,4-diacetyl-2,5-piperazinedione and the following alkylation reaction. The resultant polymer PQ-DPP shows remarkable NIR-II absorption with a narrow band gap of about 1.08eV. PQ-DPP nanoparticles exhibit high photothermal conversion efficiency of up to 48% under 1064nm laser irradiation (1W cm-2) endowing this polymer with potential in bio-related applications.

Time-resolved study of laser-induced phase separation in CsPb(IxBr1−x)3 perovskite under high pressure

Mixed-halide perovskites have attracted extensive interest with their broadly tunable bandgap and optoelectronic properties, which makes them ideal candidates for various solar cells and light-emitting diodes. However, the mixed-halide perovskites often encounter phase separation and degradation under light illumination, which prevents them from many optoelectronic applications. The study on the underlying mechanism and the controlling of the phase separation is crucial to improve the tailored properties for practical applications. Here, we report our systematical investigations of the time-resolved photoluminescence shift and crystal structure evolution on the nanocrystalline CsPb(IxBr1−x)3 perovskite under intense laser illumination and found the increasing contribution of bromine-rich phase over time. Furthermore, we subject the nanocrystalline CsPb(IxBr1−x)3 perovskite to a quasi-hydrostatic pressure environment and observed that the phase separation slows down quickly with increasing pressure and can be totally suppressed at a rather mild pressure below 0.2 GPa. These findings suggest the light-induced separation of the crystalline structure, and their optoelectronic properties can be largely suppressed, which provides a useful approach to overcome the problem caused by the intense light applications.

Data‐Driven Approach to Accelerate the Design of Halide Perovskite for Photovoltaic Application Using Electronic Properties as Descriptors

Perovskite solar cells (PSCs) have garnered remarkable attention for their efficiency and tunable optoelectronic properties. However, their instability to moisture and heat poses challenges. Traditional trial‐and‐error approaches for finding stable halide perovskites are inefficient due to the vast compositional possibilities within ABX3 perovskite structure. This study uses machine learning (ML) to predict bandgaps and photovoltaic parameters of PSCs, using a dataset of 447 data points containing chemical composition, bandgaps, and photovoltaic parameters. Various ML models including support vector regressor, random forest, gradient boost regressor, XGBoost, extratree Regressor, and AdaBoost Regressor have been used herein. Positional average elemental property (PAEP) approach is introduced to featurize the data. As ABX3 perovskite involves distinct A, B, and X sites, the proposed PAEP model captures site‐specific effects, enhancing model accuracy. The best model exhibits impressive r‐values of 0.98 for bandgap prediction and 0.86 for power conversion efficiency of PSCs. Elemental properties of B and X sites, such as ionization energy, electron affinity, and electronegativity, are found to be crucial features in the analysis by Shapley additive explanation. This study underscores the potential of ML in designing novel, stable, and efficient PSCs, offering a more efficient alternative to conventional trial‐and‐error methods.

Progress and development on the synthesis and application of two-dimensional molybdenum disulphide

Two-dimensional (2D) molybdenum disulphide (MoS2) stands out with its unique tunable bandgap and optoelectronic properties, making it a prime focus in transition metal dichalcogenides (TMDs) research. It has wide-ranging applications in energy storage, electronics, optoelectronics and high-performance sensing materials. Synthesis methods fall into top-down (chemical, mechanical and liquid-phase exfoliation) and bottom-up (physical vapour deposition, chemical layer deposition, atomic layer deposition and solvothermal/hydrothermal) categories. Choosing the right synthesis method is pivotal as it significantly impacts the material's properties and application potential. 2D MoS2, owing to its natural abundance, adaptability, adjustable bandgap and high surface-to-volume ratio, finds utility in various domains like energy storage, catalysis, composite and sensors. This review delves into recent progress, challenges and future prospects in 2D MoS2 synthesis and applications.

Composition-tunable transition metal dichalcogenide nanosheets via a scalable, solution-processable method.

The alloying of two-dimensional (2D) transition metal dichalcogenides (TMDs) is an established route to produce robust semiconductors with continuously tunable optoelectronic properties. However, typically reported methods for fabricating alloyed 2D TMD nanosheets are not suitable for the inexpensive, scalable production of large-area (m2) devices. Herein we describe a general method to afford large quantities of compositionally-tunable 2D TMD nanosheets using commercially available powders and liquid-phase exfoliation. Beginning with Mo(1-x)WxS2 nanosheets, we demonstrate tunable optoelectronic properties as a function of composition. We extend this method to produce Mo0.5W0.5Se2 MoSSe, WSSe, and quaternary Mo0.5W0.5SSe nanosheets. High-resolution scanning transmission electron microscopy (STEM) imaging confirms the atomic arrangement of the nanosheets, while an array of spectroscopic techniques is used to characterize the chemical and optoelectronic properties. This transversal method represents an important step towards upscaling tailored TMD nanosheets with a broad range of tunable optoelectronic properties for large-area devices.

Modeling-driven materials by design for conjugated polymers: insights into optoelectronic, conformational, and thermomechanical properties.

Conjugated polymers (CPs) have emerged as pivotal functional materials in the realm of flexible electronics and optoelectronic devices due to their unique blend of mechanical flexibility, solution processability, and tunable optoelectronic properties. This review synthesizes the latest molecular simulation-driven insights obtained from various multiscale modeling techniques, including quantum mechanics (QM), all-atomistic (AA) molecular dynamics (MD), coarse-grained (CG) modeling, and machine learning (ML), to elucidate the optoelectronic, structural, and thermomechanical properties of CPs. By integrating findings from our recent computational work with key experimental studies, we highlight the molecular mechanisms influencing the multifunctional performance of CPs. This comprehensive understanding aims to guide future research directions and applications in the modeling assisted design of high-performance CP-based materials and devices.

Viologen-based solution-processable ionic porous polymers for electrochromic applications.

Electrochromic porous thin films are promising for applications in smart windows and energy-efficient optical displays. However, their generally poor processing ability and excessive processing times remain grand challenges. Herein, we report the design and convenient synthesis of core-altered N-arylated viologens with aldehyde groups (πV-CHO) as new building blocks to prepare soluble, viologen-embedded ionic porous polymers. We also demonstrate that these polymers can be easily solution-processed by drop-coating to fabricate high-quality electrochromic films with tunable optoelectronic properties in a cost-effective fashion. The prepared films exhibit excellent electrochromic performance, including a low driving voltage (1.2-1.4 V), fast switching times (0.8-1.7 s), great coloration efficiency (73-268 cm2 C-1), remarkably high optical contrast up to 95.6%, long cycling stability, and tunable oxidation and reduction colors. This work sheds important light on a new molecular engineering approach to produce redox-active polymers with combined properties of intrinsic porosity, reversible and tunable redox activity, and solution processability. This provides the materials with an inherently broad utility in a variety of electrochemical devices for energy storage, sensors, and electronic applications.

In-plane Polarity Boosts Photocatalytic Overall Water Splitting in Two-Dimensional Covalent Organic Frameworks with Polarized Linkages

Benefiting from the modular nature and tunable optoelectronic properties, two-dimensional (2D) covalent organic frameworks (COFs) emerge as promising candidates for photocatalytic overall water splitting (OWS). However, the rapid recombination of...

Ultrafast charge transfer of stiboviologens for electrochromism and visible light-induced α-amino C(sp3)–H functionalization

Four stiboviologens (SbV2+) with tunable optoelectronic properties were synthesized. Stiboviologens exhibited ultrafast MLCT (metal-to-ligand charge transfer) processes and had great visible light catalytic performance.

Theoretical design of direct Z-scheme SnC/PtSe2 heterostructure with enhanced photocatalytic performance and tunable optoelectronic properties

Theoretical design of direct Z-scheme SnC/PtSe2 heterostructure with enhanced photocatalytic performance and tunable optoelectronic properties

Counterion chemistry of 5-halo (X: Cl, Br, I)-uracil derived carbon nitride: unlocking enhanced photocatalytic performance

This study presents the design of a halouracil doped polymeric carbon nitride photocatalyst with tunable optoelectronic properties and photoactivity.

Efficient tuning of optoelectronic properties of 1,6- and 1,7-disubstituted perylene diimides: agreement between theory and experiment

Both the 1,7- and 1,6-regioisomers of PDI may find applications in organic electronics as they exhibit similar yet unique properties, however, the purity of these regioisomers is crucial.

Enhanced stability and tunable optoelectronic properties of silicon–carbon monolayers by strain and surface functionalization

Exploring novel two-dimensional carbon-based materials with superior properties is of special importance for applications in nano-optoelectronics.