Harnessing Pb-S Interactions for Long-Term Water Stability in Cesium Lead Halide Perovskite Nanocrystals.

Lead halide perovskite nanocrystals (LHP NCs) have garnered attention as promising light-harvesting materials for optoelectronics and photovoltaic devices, attributed to their impressive optoelectronic properties. However, their susceptibility to moisture-induced degradation has hindered their practical applications. Despite various encapsulation strategies, challenges persist in maintaining their stability and optoelectronic performance simultaneously. Here, a ligand exchange approach is proposed using (11-mercaptoundecyl)-N,N,N-trimethylammonium bromide (MUTAB) to enhance the stability and dispersibility of CsPbBr3 (CPB) NCs in aqueous environments. MUTAB enables effective surface passivation of the CPB NCs via robust Pb-S interactions at the S-terminal while concurrently directing water molecules through the unbound cationic N-terminal or vice versa, ensuring water dispersibility and stability. Spectroscopic analysis confirms retained structural and optical integrity post-ligand exchange. Crucially, MUTAB-bound CPB NCs exhibit sustained charge transfer properties, demonstrated by aqueous colloidal oxidation reactions. This ligand exchange strategy offers a promising pathway for advancing LHP NCs toward practical optoelectronic and photocatalytic applications.

Ligands in Lead Halide Perovskite Nanocrystals: From Synthesis to Optoelectronic Applications.

Ligands are indispensable for perovskite nanocrystals (NCs) throughout the whole lifetime, as they not only play key roles in the controllable synthesis of NCs with different sizes and shapes, but also act as capping shell that affects optical properties and electrical coupling of NCs. Establishing a systematic understanding of the relationship between ligands and perovskite NCs is significant to enable many potential applications of NCs. This review mainly focuses on the influence of ligands on perovskite NCs. First of all, the ligands-dominated size and shape control of NCs is discussed. Whereafter, the surface defects of NCs and the bonding between ligands and perovskite NCs are classified, and corresponding post-treatment of surface defects via ligands is also summarized. Furthermore, advances in engineering the ligands towards the high performance of optoelectronic devices based on perovskite NCs, including photodetector, solar cell, light emitting diode (LED), and laser, and finally to potential challenges are also discussed.

Performance Improvement of Lead-Based Halide Perovskites through B-Site Ion-Doping Strategies.

Owing to their excellent properties, lead halide perovskites have attracted extensive attention in the photoelectric field. Presently, the certified power conversion efficiency of perovskite solar cells has reached 25.7%, the specific detectivity of perovskite photodetectors has exceeded 1014 Jones, and the external quantum efficiency of perovskite-based light-emitting diode has exceeded 26%. However, their practical applications are limited by the inherent instability induced by the perovskite structure due to moisture, heat, and light. Therefore, one of the widely used strategies to address the issue is to replace partial ions of the perovskites with ions of smaller radii to shorten the bond length between halides and metal cations, improving the bond energy and enhancing the perovskite stability. Particularly, the B-site cation in the perovskite structure can affect the size of eight cubic octahedrons and their gap. However, the X-site can only affect four such voids. This review comprehensively summarizes the recent progress in B-site ion-doping strategies for lead halide perovskites and provides some perspectives for further performance improvements.

Donor:Acceptor Janus Nanoparticle-Based Films as Photoactive Layers: Control of Assembly and Impact on Performance of Devices.

Water-processable organic semiconductor nanoparticles (NPs) are considered promising materials for the next-generation of optoelectronic applications due to their controlled size, internal structure, and environmentally friendly processing. Reasonably, the controllable assembly of donor:acceptor (D:A) NPs on large areas, quality, and packing density of deposited films, as well as layer morphology, will influence the effectiveness of charge transfer at an interface and the final performance of designed optoelectronic devices.This work represents an easy and effective approach for designing self-assembled monolayers of D:A NPs. In this self-assembly procedure, the NP arrays are prepared on a large scale (2 × 2 cm2 ) at the air/water interface with controlled packing density and morphology. Due to the unique structure of individual D:A Janus particles and their assembled arrays, the Janus nanoparticle (JNP)-based device exhibits an 80% improvement of electron mobility and more balanced charge extraction compared to the conventional core-shell NP-based device. An outstanding performance of polymer solar cells with over 5% efficiency is achieved after post-annealing treatment of assembled arrays, representing one of the best results for NP-based organic photovoltaics. Ultimately, this work provides a new protocol for processing water-processable organic semiconductor colloids and future optoelectronic fabrication.

Preparation of Dye Semiconductors via Coupling Polymerization Catalyzed by Two Catalysts and Application to Transistor.

Organic dye semiconductors have received increasing attention as the next generation of semiconductors, and one of their potential applications is as a core component of organic transistors. In this study, two novel diketopyrrolopyrrole (DPP) dye core-based materials were designed and separately prepared using Stille coupling reactions under different palladium catalyst conditions. The molecular weights and elemental compositions were tested to demonstrate that both catalysts could be used to successfully prepare materials of this structure, with the main differences being the weight-average molecular weight and the dispersion index. PDPP-2Py-2Tz I with a longer conjugation length exhibited better thermodynamic stability than the counterpart polymer PDPP-2Py-2Tz II. The intrinsic optical properties of the polymers were relatively similar, while the electrochemical tests showed small differences in their energy levels. The polymers obtained with different catalysts displayed similar and moderate electron mobility in transistor devices, while PDPP-2Py-2Tz I possessed a higher switching ratio. Our study provides a comparison of such dye materials under different catalytic conditions and also demonstrates the great potential of dye materials for optoelectronic applications.

Preparation of Multicolour Solid Fluorescent Carbon Dots for Light-Emitting Diodes Using Phenylethylamine as a Co-Carbonization Agent.

Carbon dots (CDs), as a new type of photoluminescent nanomaterial, have attracted extensive attention in various fields because of their unique luminescence properties. However, CDs will exhibit fluorescence quenching in the solid state or aggregate state, which limits their application. In this paper, a unique strategy is proposed to regulate solutions to achieve multicolour fluorescence of CDs in the solid state. We report the successful preparation of orange, green and blue solid fluorescent CDs using citric acid, urea and phenylethylamine as precursors and methanol, ethanol and water as solvents, respectively. The solid-state fluorescence of CDs may be caused by the linkage of the phenylethyl structure to the surface of CDs during formation, which effectively disperses the CDs and prevents π-π interactions between graphitized nuclei. Meanwhile, multicolour solid fluorescent CDs are realized by adjusting the solvent in the preparation process. Based on the excellent fluorescence properties of CDs, orange, green and blue light-emitting diodes (LEDs) are prepared. A white LED (WLED) can be obtained by mixing the three colours of solid fluorescent CDs, which shows the application potential of CDs in display lighting equipment.

Photoelectric and Self-Assembly Properties of Tetrasubstituted Pyrene Discotic Derivatives.

To investigate the self-assembly behavior of π-conjugated ethynyl-pyrene discotic derivatives, a series of ethynyl-pyrene discotic materials were designed and synthesized by Sonogashira coupling reaction. The π-conjugated structures were characterized by 1H-NMR, IR spectroscopy, and elemental analysis. The optical properties of the discotic materials were examined by UV/Vis spectra and fluorescence emission spectra. The band gap of each compound was calculated by cyclic voltammetry with UV/Vis spectroscopy. Interestingly, the substituted groups in the four symmetrical positions did affect the self-assembly properties of as-resulted nano/micro structures. Under the same conditions, compounds 4a-4d could be self-assembled into different morphologies such as micro-tubes (for 4a), micro-wires (for 4b and 4c), and micro-grain crystals (for 4d). All of the results indicated that the discotic materials have the potential for optoelectronic applications.

Functional Carbazole-Fullerene Complexes: A New Perspective of Carbazoles Acting as Nano-Octopus to Capture Globular Fullerenes.

Fullerene host-guest constructs have attracted increasing attention owing to their molecular-level hybrid arrangements. However, the usage of simple carbazolic derivatives to bind with fullerenes is rare. In this research, three novel carbazolic derivatives, containing a tunable bridging linker and carbazole units for the capturing of fullerenes, are rationally designed. Unlike the general concave-convex interactions, fullerenes could interact with the planar carbazole subunits to form 2-dimensional hexagonal/quadrilateral cocrystals with alternating stacking patterns of 1 : 1 or 1 : 2 stoichiometry, as well as the controllable fullerene packing modes. At the meanwhile, good electron-transporting performances and significant photovoltaic effects were realized when a continuous C60⋅⋅⋅ C60 interaction channel existed. The results indicate that the introduction of such carbazolic system into fullerene receptor would provide new insights into novel fullerene host-guest architectures for versatile applications.

Excellent optoelectronic applications and electrical transport behavior of the n-WO3nanostructures/p-diamond heterojunction: a new perspective.

Nanostructured n-type metal oxides/p-type boron-doped diamond heterojunctions have demonstrated a typical rectification feature and/or negative differential resistance (NDR) potentially applied in wide fields. Recently, the fabrication and electronic transport behavior of n-WO3nanorods/p-diamond heterojunction at high temperatures were studied by Wanget al(2017Appl. Phys. Lett.110052106), which opened the door for optoelectronic applications that can operate at high-temperatures, high-power, and in various harsh environments. In this perspective, an overview was presented on the future directions, challenges and opportunities for the optoelectronic applications based on the n-WO3nanostructures/p-diamond heterojunction. We focus, in particular, on the prospects for its high temperature NDR, UV photodetector, field emission emitters, photocatalyst and optical information storage for a wide range of new optoelectronic applications.

Pyrene-Benzimidazole Derivatives as Novel Blue Emitters for OLEDs.

Three novel small organic heterocyclic compounds: 2-(1,2-diphenyl)-1H-benzimidazole-7-tert-butylpyrene (compound A), 1,3-di(1,2-diphenyl)-1H-benzimidazole-7-tert-butylpyrene (compound B), and 1,3,6,8-tetra(1,2-diphenyl)-1H-benzimidazolepyrene (compound C) were synthesized and characterized for possible applications as blue OLED emitters. The specific molecular design targeted decreasing intermolecular aggregation and disrupting crystallinity in the solid-state, in order to reduce dye aggregation, and thus obtain efficient pure blue photo- and electroluminescence. Accordingly, the new compounds displayed reasonably high spectral purity in both solution- and solid-states with average CIE coordinates of (0.160 ± 0.005, 0.029 ± 0.009) in solution and (0.152 ± 0.007, 0.126 ± 0.005) in solid-state. These compounds showed a systematic decrease in degree of crystallinity and intermolecular aggregation due to increasing steric hindrance, as revealed using powder X-ray diffraction analysis and spectroscopic studies. An organic light-emitting diode (OLED) prototype fabricated using compound B as the non-doped emissive layer displayed an external quantum efficiency (EQE) of 0.35 (±0.04)% and luminance 100 (±6) cd m-2 at 5.5 V with an essentially pure blue electroluminescence corresponding to CIE coordinates of (0.1482, 0.1300). The highest EQE observed from this OLED prototype was 4.3 (±0.3)% at 3.5 V, and the highest luminance of 290 (±10) cd m-2 at 7.5 V. These values were found comparable to characteristics of the best pure blue OLED devices based on simple fluorescent small-molecule organic chromophores.

Recent Advances and Optoelectronic Applications of Lead-Free Halide Double Perovskites.

Organic-inorganic metal halide perovskites (most notably CH3 NH3 PbI3 ) have demonstrated remarkable physical attributes for photovoltaic and diverse optoelectronic applications, whereas concerns about toxicity owing to the use of lead in the chemical composition still motivate further exploration of new, nontoxic candidates. Lead-free halide double perovskites (HDPs), designed by the rational chemical substitution of Pb2+ with other nontoxic candidate elements, have recently attracted interest as a fascinating alternative to their Pb-based counterparts. Herein, recent advances in crystal structures, physical properties, and versatile optoelectronic applications of lead-free HDPs, such as solar cells, photodetectors, X-ray detectors, and light-emitting diodes, are reviewed. Perspectives to improve the physical and photoelectric properties of existing HDP materials are also discussed and will favor future development of new, lead-free HDP candidates.

Photophysical Properties of some 1,3,4-Oxadiazole Derivatives Containing Phenolphtalein, Fluorene and Bisphenol A Units.

The photophysical properties of the three 1,3,4-oxadiazole derivatives containing fluorene (Ox-FL); fluorene and phenolphtaleine (Ox-FL-FF); or fluorene and bisphenol A (Ox-FL-BPA) moieties in the main chain were investigated by the fluorescence and absorption spectroscopy in different solvents and in the solid state. The electronic absorption spectra included a strong absorption band located in the 270-395 nm region, with a maxima around at 302 nm. The fluorescence excitation spectra were also characterized by one broad band, appearing in the wavelength range of 220-340 nm. All samples displayed the emission bands around 356-373 nm and exhibit high quantum yields ranged from 31.61 to 90.77%, in chloroform solution. The sensitivity of the emission spectra on medium characteristics (polarity, acidity and basicity) were evaluated by using the Catalan solvent scale and the fluorescence titration with a dilute acid solution.

Targeting Compact and Ordered Emitters by Supramolecular Dynamic Interactions for High-performance Organic Ambient Phosphorescence.

Purely organic room-temperature phosphorescence (RTP) materials have received intense attention due to their fascinating optical properties and advanced optoelectronic applications. The promotion of intersystem crossing (ISC) and minimalization of nonradiative dissipation under ambient conditions are key prerequisites for realizing high-performance organic RTP; However, the ISC process is generally inefficient for organic fluorogens and the populated triplet excitons are always too susceptible to be well stabilized by conventional means. Particularly, organizing organic fluorophores into compact and ordered entities by supramolecular dynamic interactions has proven to be a newly-emerged strategy to boost the ISC process greatly and suppress the non-radiative relaxations immensely, facilitating the population and stabilization of triplet excitons to access high-performance organic RTP. Consequently, well-defined organic emitters enable robust RTP emission even in the solution state, thus greatly extending the applications. Here, this review is focused on a timely and brief introduction to recent progress in tailoring ordered high-performance RTP emitters by supramolecular dynamic interactions. Their typical preparation strategies, optoelectronic properties, and applications are thoroughly summarized. In the summary section, key challenges and perspectives of this field are highlighted to suggest potential directions for future study.

A Holistic Review of C = C Crosslinkable Conjugated Molecules in Solution-Processed Organic Electronics: Insights into Stability, Processibility, and Mechanical Properties.

Solution-processable organic conjugated molecules (OCMs) consist of a series of aromatic units linked by σ-bonds, which present a relatively freedom intramolecular motion and intermolecular re-arrangement under external stimulation. The cross-linked strategy provides an effective platform to obtain OCMs network, which allows for outstanding optoelectronic, excellent physicochemical properties, and substantial improvement in device fabrication. An unsaturated double carbon-carbon bond (C = C) is universal segment to construct crosslinkable OCMs. In this review, the authors will set C = C cross-linkable units as an example to summarize the development of cross-linkable OCMs for solution-processable optoelectronic applications. First, this review provides a comprehensive overview of the distinctive chemical, physical, and optoelectronic properties arising from the cross-linking strategies employed in OCMs. Second, the methods for probing the C = C cross-linking reaction are also emphasized based on the perturbations of chemical structure and physicochemical property. Third, a series of model C = C cross-linkable units, including styrene, trifluoroethylene, and unsaturated acid ester, are further discussed to design and prepare novel OCMs. Furthermore, a concise overview of the optoelectronic applications associated with this approach is presented, including light-emitting diodes (LEDs), solar cells (SCs), and field-effect transistors (FETs). Lastly, the authors offer a concluding perspective and outlook for the improvement of OCMs and their optoelectronic application via the cross-linking strategy.

Macrocyclic Compounds: Metal Oxide Particles Nanocomposite Thin Films Deposited by MAPLE.

Nanocomposite films based on macrocyclic compounds (zinc phthalocyanine (ZnPc) and 5,10,15,20-tetra(4-pyridyl) 21H,23H-porphyrin (TPyP)) and metal oxide nanoparticles (ZnO or CuO) were deposited by matrix-assisted pulsed laser evaporation (MAPLE). 1,4-dioxane was used as a solvent in the preparation of MAPLE targets that favor the deposition of films with a low roughness, which is a key feature for their integration in structures for optoelectronic applications. The influence of the addition of ZnO nanoparticles (~20 nm in size) or CuO nanoparticles (~5 nm in size) in the ZnPc:TPyP mixture and the impact of the added metal oxide amount on the properties of the obtained composite films were evaluated in comparison to a reference layer based only on an organic blend. Thus, in the case of nanocomposite films, the vibrational fingerprints of both organic compounds were identified in the infrared spectra, their specific strong absorption bands were observed in the UV-Vis spectra, and a quenching of the TPyP emission band was visible in the photoluminescence spectra. The morphological analysis evidenced agglomerated particles on the composite film surface, but their presence has no significant impact on the roughness of the MAPLE deposited layers. The current density-voltage (J-V) characteristics of the structures based on the nanocomposite films deposited by MAPLE revealed the critical role played by the layer composition and component ratio, an improvement in the electrical parameters values being achieved only for the films with a certain type and optimum amount of metal oxide nanoparticles.

Advancement of Physical and Photoelectrochemical Properties of Nanostructured CdS Thin Films toward Optoelectronic Applications.

CdS thin films were grown on an FTO substrate at different temperatures, employing the low-cost hydrothermal method. All the fabricated CdS thin films were studied using XRD, Raman spectroscopy, SEM, PL spectroscopy, a UV-Vis spectrophotometer, photocurrent, Electrochemical Impedance Spectroscopy (EIS), and Mott-Schottky measurements. According to the XRD results, all the CdS thin films were formed in a cubic (zinc blende) structure with a favorable (111) orientation at various temperatures. The Scherrer equation was used to determine the crystal size of the CdS thin films, which varied from 25 to 40 nm. The SEM results indicated that the morphology of thin films seems to be dense, uniform, and tightly attached to the substrates. PL measurements showed the typical green and red emission peaks of CdS films at 520 nm and 705 nm, and these are attributable to free-carrier recombination and sulfur vacancies or cadmium vacancies, respectively. The optical absorption edge of the thin films was positioned between 500 and 517 nm which related to the CdS band gap. For the fabricated thin films, the estimated Eg was found to be between 2.50 and 2.39 eV. According to the photocurrent measurements, the CdS thin films grown were n-type semiconductors. As indicated by EIS, resistivity to charge transfer (RCT) decreased with temperature, reaching its lowest level at 250 °C. Flat band potential and donor density were found to fluctuate with temperature, from 0.39 to 0.76 V and 4.41 × 1018 to 15.86 × 1018 cm-3, respectively, according to Mott-Schottky measurements. Our results indicate that CdS thin films are promising candidates for optoelectronic applications.

Optoelectronic properties and applications of two-dimensional layered semiconductor van der Waals heterostructures: perspective from theory.

Van der Waals heterostructures (vdWHs) which combine two different materials together have attracted extensive research attentions due to the promising applications in optoelectronic and electronic devices, the investigations from theoretical simulations can not only predict the novel properties and the interfacial coupling, but also provide essential guidance for experimental verification and fabrications. This review summarizes the recent theoretical studies on electronic and optical properties of two-dimensional semiconducting vdWHs. The characteristics of different band alignments are discussed, together with the optoelectronic modulations from external fields and the promising applications in solar cells, tunneling field-effect transistors and photodetectors. At the end of the review, the further perspective and possible research problems of the vdWHs are also presented.

Band offset trends in IV-VI layered semiconductor heterojunctions.

The band offsets between semiconductors are significantly associated with the optoelectronic characteristics and devices design. Here, we investigate the band offset trends of few-layer and bulk IV-VI semiconductors MX and MX2(M = Ge, Sn; X = S, Se, Te). For common-cation (anion) systems, as the atomic number increases, the valence band offset of MX decreases, while that of MX2has no distinct change, and the physical origin can be interpreted using band coupling mechanism and atomic potential trend. The band edges of GeX2system straddle redox potentials of water, making them competitive candidates for photocatalyst. Moreover, layer number modulation can induce the band offset of GeSe/SnS and GeSe2/GeS2heterojunction undergoing a transition from type I to type II, which makes them suitable for optoelectronic applications.

Optical Modification of 2D Materials: Methods and Applications.

2D materials are under extensive research due to their remarkable properties suitable for various optoelectronic, photonic, and biological applications, yet their conventional fabrication methods are typically harsh and cost-ineffective. Optical modification is demonstrated as an effective and scalable method for accurate and local in situ engineering and patterning of 2D materials in ambient conditions. This review focuses on the state of the art of optical modification of 2D materials and their applications. Perspectives for future developments in this field are also discussed, including novel laser tools, new optical modification strategies, and their emerging applications in quantum technologies and biotechnologies.

Lead-Free Perovskite Photodetectors: Progress, Challenges, and Opportunities.

State-of-the-art photodetectors which apply hybrid perovskite materials have emerged as powerful candidates for next-generation light sensing. Among them, lead-based ones are the most popular beyond doubt on account of their unique and superior optoelectronic properties. Nevertheless, trade-off toward commercialization exists between nontoxicity and high performance, with the poor stability of lead-based perovskites, indicating that it is indispensable to substitute lead with nontoxic element meanwhile bringing about a comparable figure of merit of photodetectors and relatively long-term stability. Herein, recent advances in lead-free perovskite photodetectors are reviewed, analyzing the principle while designing new materials and highlighting some remarkable progress, which are comparable, even superior, to lead-based photodetectors. Furthermore, their potential strategy in optical communication, image sensing, narrowband photodetection, etc., is examined and a perspective on developing new materials and photodetectors with superior properties for more practical applications is provided.