Photoelectronic Applications Research Articles

Highly Diffusive Nonluminescent Carriers in Hybrid Phase Lead Triiodide Perovskite Nanowires

AbstractCrystal structural rearrangements unavoidably introduce defects into materials, where even these small changes in local lattice structure could arouse a prominent impact on the overall nature of crystals. Contrary to the traditional notion that defects obstruct carrier transport, herein, we report a promoted transport mechanism of nonluminescent carriers in single‐crystalline CH3NH3PbI3 nanowires (1345.2 cm2 V−1 s−1, about a 14‐fold improvement), enabled by the phase transition induced defects (PTIDs). Carriers captured by PTIDs evade both the radiative and non‐radiative recombinations during the incomplete tetragonal‐to‐orthorhombic phase transition at low temperatures, forming a specific nonluminescent state that exhibits an efficient long‐distance transport and thereby realize a prominent enhancement of photocurrent responsivity for photodetector applications. The findings provide broader insights into the carrier transport mechanism in perovskite semiconductors and have significant implications for their rational design for photoelectronic applications at varied operating temperatures.

Highly Diffusive Nonluminescent Carriers in Hybrid Phase Lead Triiodide Perovskite Nanowires.

Crystal structural rearrangements unavoidably introduce defects into materials, where even these small changes in local lattice structure could arouse a prominent impact on the overall nature of crystals. Contrary to the traditional notion that defects obstruct carrier transport, herein, we report a promoted transport mechanism of nonluminescent carriers in single-crystalline CH3NH3PbI3 nanowires (1345.2 cm2 V-1 s-1, about a 14-fold improvement), enabled by the phase transition induced defects (PTIDs). Carriers captured by PTIDs evade both the radiative and non-radiative recombinations during the incomplete tetragonal-to-orthorhombic phase transition at low temperatures, forming a specific nonluminescent state that exhibits an efficient long-distance transport and thereby realize a prominent enhancement of photocurrent responsivity for photodetector applications. The findings provide broader insights into the carrier transport mechanism in perovskite semiconductors and have significant implications for their rational design for photoelectronic applications at varied operating temperatures.

High Sensitivity Of Nanocrystalline SnO2-Y2O3 Thin Films Based UV-Detector Prepared Using Chemical Bath Deposition

Nanocrystalline Tin dioxide - Yttrium oxide (NC SnO2-Y2O3) thin film was effectively created by employing the chemical bath deposition approach on SiO2/Si substrates. X-ray diffraction, field emission scanning electron microscopy [FESEM], and energy-dispersive X-ray spectroscopy were used to analyze the structural and the surface morphology of the annealed sample at 500°C for two hours in air. When annealed at 500°C, the SnO2-Y2O3 film crystallized was accomplished with a tetragonal rutile structure. The nanocrystalline SnO2 thin film was effectively employed as a UV photodetector device (UV PDs). A UV photo detector based on nanocrystalline SnO2-Y2O3 film showed 2988% sensitivity when exposed to a 360 nm wavelength (6 mW/cm2) at an applied voltage of 3 V. In contrast, the responsivity value was 3.247 A/W. The rise and full times were determined by calculating to be 0.663 s and 0.436 s, respectively. The excellent performance of the device could be correlated with high surface-to-volume proportions including its elevated crystal performance. Given its outstanding stability and reliability, the nanocrystalline SnO2-Y2O3 thin film sensor is the optimum option for commercially photo-electronic applications.

γ‐Valerolactone Enabling Spontaneously Inhibited Iodide Oxidation for High‐Quality Perovskite Single Crystal Fabrication

AbstractThe iodide precursor oxidation has persistently plagued solution grown iodine‐based perovskite single crystals (IPSCs) that inevitably introduce undesirable triiodide ion (I3−) defects and severely hindering crystal quality, despite IPSCs having garnered remarkable progress in multifarious photoelectronic applications. In this work, the spontaneously inhibited iodide oxidation is discovered in an eco‐friendly solvent, γ‐Valerolactone (GVL), and demonstrates a universal solution approach for fabricating high‐quality IPSCs. Compared to the routine γ‐Butyrolactone (GBL) system, GVL provides a lowered growth temperature and a significantly broadened inverse temperature operation window, thereby improving the theoretical utilization rate of perovskite precursors up to 88.6%. More importantly, due to its higher open‐ring hydrolysis energy, GVL can spontaneously inhibit the iodide precursors oxidation without any additional reductant and therefore effectively prevent the forming I3− defects. Typically, the as‐fabricated MAPbI3 single crystal possesses an extremely low trap density of 3.57 × 108 cm−3 and a high carrier mobility‐lifetime (µτ) product of 2.74 × 10−3 cm2 V−1, which enables its photodetection capabilities to be on a par with the state‐of‐art MAPbI3 single crystal photodetectors. This work paves an efficacious and green pathway for high‐quality IPSC fabrication toward advanced optoelectronic utilizations.

Layer-dependent transport and optoelectronic properties in 2D all-inorganic Ruddlesden–Popper perovskite Cs2PbBr4

In recent years, two-dimensional (2D) all-inorganic Ruddlesden–Popper (RP) perovskites have attracted significant research attention. In this study, the electronic and carrier transport properties of 2D layered RP perovskite Cs2PbBr4 are studied by DFT calculations. The carrier mobility of the RP perovskite Cs2PbBr4 layers are studied based on deformation-potential (DP) theory. We found that the carrier mobility in 2D Cs2PbBr4 layers are enhanced as the number of layers increases. For trilayer Cs2PbBr4 the electron mobility reaches 7588.7 cm2V−1s−1, which is much higher than the widely studied bulk MAPbI3 (1500 cm2V−1s−1). In addition, the exciton binding energies are also calculated. Our work proves that the 2D RP perovskite Cs2PbBr4 layers are potential candidates for the photoelectronic devices applications.

Advancements in Optoelectronics: Harnessing the Potential of 2D Violet Phosphorus

AbstractRecently, 2D violet phosphorus (VP), a new kind of allotrope of phosphorus has attained significant attention owing to its remarkable electronic, optical, and magnetic characteristics. Tunable, large direct bandgap, high charge carrier mobility, and large optical absorption make it a potential candidate for realizing photoelectronic applications. VP demonstrates unique electronic structure, chemical stability, strong light‐matter interaction, and thermal stability that can be utilized for assembling intelligent photoelectronic devices. This review article provides comprehensive investigations of the latest synthesis techniques employed to develop the VP including its structural characterizations, stability, and degradation mechanisms. Furthermore, this review demonstrates the diverse applications of VP in optoelectronics, including photodetectors, polarization detection, imaging systems, neuromorphic optoelectronic devices, and many others. Finally, challenges and future research directions associated with the VP in terms of optoelectronics are discussed. Overall, as presented, the review offers an extensive study of VP, covering its synthesis, structural insights mechanisms, and applications in optoelectronics with the aim of stimulating further research and development in this growing field.

MoO3 with the Synergistic Effect of Sulfur Doping and Oxygen Vacancies: The Influence of S Doping on the Structure, Morphology, and Optoelectronic Properties.

Molybdenum trioxide (MoO3) is an attractive semiconductor. Thus, bandgap engineering toward photoelectronic applications is appealing yet not well studied. Here, we report the incorporation of sulfur atoms into MoO3, using sulfur powder as a source of sulfur, via a self-developed hydrothermal synthesis approach. The formation of Mo-S bonds in the MoO3 material with the synergistic effect of sulfur doping and oxygen vacancies (designated as S-MoO3-x) is confirmed using Fourier-transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance (EPR). The bandgap is tuned from 2.68 eV to 2.57 eV upon sulfur doping, as confirmed by UV-VIS DRS spectra. Some MoS2 phase is identified with sulfur doping by referring to the photoluminescence (PL) spectra and electrochemical impedance spectroscopy (EIS), allowing significantly improved charge carrier separation and electron transfer efficiency. Therefore, the as-prepared S-MoO3-x delivers a sensitive photocurrent response and splendid cycling stability. This study on the synergistic effect of sulfur doping and oxygen vacancies provides key insights into the impact of doping strategies on MoO3 performance, paving new pathways for its optimization and development in relevant fields.

Ion Migration in Metal Halide Perovskites: Characterization Protocols and Physicochemical Mechanisms.

Metal halide perovskites (MHPs) have demonstrated considerable promise for a range of photoelectronic applications owing to their prominent photophysical properties. However, MHPs suffer from remarkable ion migration under illumination and bias voltage, which generally poses operational instability of MHP-based devices and restricts their practicality. While numerous chemical strategies have been proposed for manipulating ion migration dynamics, the relevant mechanistic research relatively lags behind, which is nevertheless imperative for guiding ion migration engineering. In this perspective, we first review the well-established experimental techniques for characterizing ion migration in MHP films and photovoltaic devices. For the sake of gaining insights into the underlying mechanism, we also present a series of physical models that elucidate the dynamics of ion migration and the coupling interaction between ions and charge carriers in MHP photovoltaics. Finally, we identify several crucial areas for future investigation, with the aim of advancing both the fundamental and applied research on high-efficiency and high-stability MHP materials and devices.

Insight into stable, concentrated radicals from sulfur-functionalized alkyne-rich crystalline frameworks and application in solar-to-vapor conversion

Organic radicals feature versatile unpaired electrons key for photoelectronic and biomedical applications but remain difficult to access in stable concentrated forms. We disclose easy generation of stable, concentrated radicals from various alkynyl phenyl motifs, including 1) sulfur-functionalized alkyne-rich organic linkers in crystalline frameworks; 2) the powders of these molecules alone; 3) simple diethynylbenzenes. For Zr-based framework, the generation of radical-rich crystalline framework was achieved by thermal annealing in the range of 300–450 °C. For terminal alkynes, electron paramagnetic resonance signals (EPR, indicative of free radicals) arise after air exposure or mild heating (e.g., 70 °C). Further heating (e.g., 150 °C for 3 h) raises the radical concentrations up to 3.30 mol kg−1. For more stable internal alkynes, transformations into porous radical solids can also be triggered, albeit at higher temperatures (e.g., 250–500 °C). The resulted radical-containing solids are porous, stable to air as well as heat (up to 300–450 °C) and exhibit photothermal conversion and solar-driven water evaporation capacity. The formation of radicals can be ascribed to extensive alkyne cyclizations, forming defects, dangling bonds and the associated radicals stabilized by polycyclic π-systems.

Biocompatible Perovskite Nanocrystals with Enhanced Stability for White Light-Emitting Diodes.

Recently emerged lead halide perovskite CsPbX3 (X = Cl, Br, and I) nanocrystals (PNCs) have attracted tremendous attention due to their excellent optical properties. However, the poor water stability, unsatisfactory luminescence efficiency, disappointing lead leakage, and toxicity have restricted their practical applications in photoelectronics and biomedical fields. Herein, a controllable encapsulated strategy is investigated to realize CsPbX3 PNCs/PVP @PMMA composites with superior luminescence properties and excellent biocompatibility. Additionally, the synthesized CsPbBr3 and CsPbBr0.6I2.4 PNCs/PVP@PMMA structures exhibit green and red emissions with a maximal photoluminescence quantum yield (PLQY) of about 70.24% and 98.26%, respectively. These CsPbX3 PNCs/PVP@PMMA structures show high emission efficiency, excellent stability after water storage for 18 months, and low cytotoxicity at the PNC concentration at 500 μg mL-1. Moreover, white light-emitting diode (WLED) devices based on mixtures of CsPbBr3 and CsPbBr0.6I2.4 PNCs/PVP@PMMA perovskite structures are investigated, which exhibit excellent warm-white light emissions at room temperature. A flexible manipulation method is used to fabricate the white light emitters based on these perovskite composites, providing a fantastic platform for fabricating solid-state white light sources and full-color displays.

Pressure-triggered intense natural white emission via controllable distortions of antimony chloride dimers

Zero-dimensional (0D) hybrid metal halides (HMHs), featured with unique self-trapped exciton (STE) emissions, are emerging photoluminescence (PL) materials for photoelectronic applications. Compared with metal-halogen monomers, dimeric units in 0D HMHs possess more structural flexibility and less spatial confinement of excitons, creating new opportunities for PL engineering. Herein, high pressure is employed on 0D (C3H12N2)2Sb2Cl10 to controllably distort inter- and intra-octahedral structures within [Sb2Cl10]4− dimers. Intense natural white emission is achieved with dramatically increased photoluminescence quantum yield from less than ≈1% to 74.2 %. The high-pressure emission of (C3H12N2)2Sb2Cl10 is proven to originate from the STE recombination from triplet states with varied emission equilibrium, as well as the promoted excitonic trapping with restrained nonradiative recombination. This work offers valuable insights into the structure effects on STE emission and the transition mechanisms of metal-halogen dimers, which are crucial for developing novel metal halides for illumination.

Adaptive maleimide-fused macrocyclic clamps: Synthesis, structures, and complexations with polycyclic aromatic hydrocarbons

The photoactive macrocyclic molecules attract attention because of their important roles in supramolecular chemistry as well as photoelectronic applications. Herein, two D-A conjugated macrocycles containing two maleimide nodes have been successfully obtained via an one-pot cascade reaction of Perkin and imidization condensations. Owing to the incorporation of two bulky 1,4-dimethoxybenzene moieties at the narrow maleimide corners, the obtained conjugated macrocycles have been equipped with two adaptive clamps, which can adjust to the guest sizes to capture the guest molecules. Interestingly, the co-crystallization with larger-sized polycyclic aromatic hydrocarbons (PAHs) leads to the 1:1 host-guest complexes, while with smaller-sized solvents results in the 1:2 complexes. Furthermore, the rotatable 1,4-dimethoxybenzene moieties endowed such macrocyclic fluorophores with pronounced solvatochromic and aggregation-induced emission enhancement (AIEE) phenomena.

Fabrication of Single-Crystal Violet Phosphorus Flakes For Ultrasensitive Photodetection.

Violet phosphorus (VP) has attracted a lot of attention for its unique physicochemical properties and emerging potential in photoelectronic applications. Although VP has a van der Waals (vdW) structure similar to that of other 2D semiconductors, direct synthesis of VP on a substrate is still challenging. Moreover, optoelectronic devices composed of transfer-free VP flakes have not been demonstrated. Herein, a bismuth-assisted vapor phase transport technique is designed to grow uniform single-crystal VP flakes on the SiO2/Si substrate directly. The size of the crystalline VP flakes is an order of magnitude larger than that of previous liquid-exfoliated samples. The photodetector fabricated with the VP flakes shows a high responsivity of 12.5 A W-1 and response/recovery time of 3.82/3.03ms upon exposure to 532nm light. Furthermore, the photodetector shows a small dark current (<1 pA) that is beneficial to high-sensitivity photodetection. As a result, the detectivity is 1.38×1013 Jones that is comparable with that of the vdW p-n heterojunction detector. The results reveal the great potential of VP in optoelectronic devices as well as the CVT technique for the growth of single-crystal semiconductor thin films.

Defect and doping properties of sliding ferroelectric γ-InSe for photovoltaic applications

Layered van der Waals (vdw) materials have been proposed as light-absorbing materials for photovoltaic applications. InSe is a layered vdw semiconductor with ultra-high carrier mobility, strong charge transfer ability, super deformability, thermoelectricity, and optoelectronic properties. Its γ phase, or γ-InSe, was greatly stabilized by doping recently, which also exhibits sliding ferroelectricity. In this study, we propose that γ-phase InSe (γ-InSe), which was recently synthesized in a high-quality bulk phase, could be an excellent light-absorbing material candidate. Based on the first-principles simulations, bulk γ-InSe is found to possess suitable bandgap, decent absorption, and low effective mass. The investigation of defect properties reveals the major defect types, defect levels, and deep-level defects that could possibly harm the efficiency, and the deep-level defects can be significantly suppressed under Se-rich conditions. In addition, γ-InSe is intrinsically n-type, which can be tuned into weak p-type by Zn and Cd doping. We also identify the defect types of Y and Bi doping, which have been experimentally used to adjust the mechanical property of γ-InSe, and find that Y interstices could play an important role in improving the stiffness of γ-InSe. Our study provides theoretical insights for photovoltaic and other photoelectronic applications based on this interesting ferroelectric layered vdw material.

Promoting the carrier mobility of Nb2SiTe4 through cation coordination engineering

Ternary two-dimensional (2D) monoclinic Nb2SiTe4 has garnered significant attention for its potential applications in anisotropic photoelectronics. Yet, its intrinsic indirect bandgap nature and low hole mobility, attributed to the short Nb–Nb dimer configurations, hinder the efficient photogenerated carrier separation and transport. In this Letter, using density functional theory calculations, we demonstrate the interlayer intercalation of Si results in the formation of a metastable orthorhombic Nb2SiTe4 structure devoid of detrimental short Nb–Nb dimers. Notably, this Si intercalation leads to a remarkable reduction of hole effective masses of orthorhombic Nb2SiX4 (X = S, Se, and Te), a crucial factor for achieving high carrier mobility. Taking the orthorhombic Nb2SiTe4 monolayer as an example, the calculated hole mobility (&amp;gt;100 cm2 V−1 s−1) is comparable in magnitude to the respectable hole mobility observed in multiple layers of the monoclinic Nb2SiTe4. To simultaneously enhance electron and hole mobility, we establish a van der Waals junction between the monoclinic and orthorhombic Nb2SiTe4 structures, achieving high and comparable carrier mobilities. The Nb2SiTe4 junction exhibits a nearly direct bandgap of 0.35 eV, rendering it suitable for infrared light harvesting. Furthermore, carriers within the Nb2SiTe4 junction become spatially separated across different layers, resulting in an intrinsic built-in electric field, which is superior for efficient photo-generated charge separation and decreases the potential nonradiative carrier recombination. Our findings highlight the impact of cation coordination engineering on the electronic and optical properties of 2D Nb2SiTe4 and provide a feasible solution to achieve better carrier transport in low-dimensional photovoltaic functionalities.

Autonomous nanomanufacturing of lead-free metal halide perovskite nanocrystals using a self-driving fluidic lab.

Lead-based metal halide perovskite (MHP) nanocrystals (NCs) have emerged as a promising class of semiconducting nanomaterials for a wide range of optoelectronic and photoelectronic applications. However, the intrinsic lead toxicity of MHP NCs has significantly hampered their large-scale device applications. Copper-base MHP NCs with composition-tunable optical properties have emerged as a prominent lead-free MHP NC candidate. However, comprehensive synthesis space exploration, development, and synthesis science studies of copper-based MHP NCs have been limited by the manual nature of flask-based synthesis and characterization methods. In this study, we present an autonomous approach for the development of lead-free MHP NCs via seamless integration of a modular microfluidic platform with machine learning-assisted NC synthesis modeling and experiment selection to establish a self-driving fluidic lab for accelerated NC synthesis science studies. For the first time, a successful and reproducible in-flow synthesis of Cs3Cu2I5 NCs is presented. Autonomous experimentation is then employed for rapid in-flow synthesis science studies of Cs3Cu2I5 NCs. The autonomously generated experimental NC synthesis dataset is then utilized for fast-tracked synthetic route optimization of high-performing Cs3Cu2I5 NCs.

Vapor-phase methods for synthesizing metal-organic framework thin films

&lt;p&gt;Due to their unique structures and exceptional physical and chemical properties, metal-organic framework (MOF) materials have garnered extensive attention in various fields, including catalysis, separations, sensing, and optics. Compared with powders or bulk MOF materials, MOF thin films exhibit large vertical and horizontal dimensions, higher specific surface areas, and abundant active sites and undergo facile combination with other functional centers for adsorption/separation, catalysis, and photoelectronic device applications. Among the methods used in preparing MOF thin films, the vapor phase approach enables more effective growth of MOF films with controllable thicknesses, uniformity, and compatibility; thus, it has attracted significant interest. This extensive review presents four vapor-phase approaches for preparing MOF thin films: the steam-assisted conversion method, vapor-phase transformations of metal oxide templates, vapor-phase linker exchange, and the atomic layer deposition/molecular layer deposition method. We summarize the advantages and disadvantages of these different vapor-phase-based methods for thin-film preparation, aiming to promote their use in precise and controllable surface syntheses.&lt;/p&gt;

Electronic Structure and Optical Property of 2D MgPX3 (X = S and Se) Monolayer by Density Functional Theory

2D metal phosphorus trichalcogenides (MgPX3) have attracted tremendous research interests in spintronic, electrocatalytic, and photoelectronic applications due to their unique magnetic and optical properties. Herein, a systematical investigation on the electronic structures and optical properties of 2D MgPX3 (X = S and Se) monolayers is performed by density functional theory. Owing to small cleavage energy, 2D MgPX3 monolayers can be obtained by mechanical exfoliation with an excellent structure stability of 2D MgPX3 monolayers demonstrated by elastic tensor, phonon dispersion, and molecular dynamics, respectively. 2D MgPX3 behaves as a direct bandgap semiconductor with a strong optical absorption in UV range whereas a weak adsorption near the band edge, demonstrated by both single‐ and quasiparticle approximations. Upon analyses on transition dipole moment along with the wave function symmetry, the weak optical absorption is attributed to the parity‐forbidden effect where the wave functions almost show the same parity between top valence band and bottom conduction band. The findings indicate that 2D MgPX3 monolayers hold promise as candidate materials for flexible UV photoelectronics devices and provide a theoretical insight into the optical properties of 2D semiconductors.

Methylammonium-Based Quasi-Two-Dimensional Perovskite Single Crystals for Highly Sensitive X-ray Detection and Imaging.

The strategy of introducing large organic cations into three-dimensional perovskites could reduce the dimensionality of perovskites to form quasi-two-dimensional (quasi-2D) perovskites, resulting in increased stability and reduced detection limits due to less ion migration. Herein, a quasi-2D perovskite single crystal (BDA)(MA)2Pb3Br10 (BDA = NH3C4H8NH3, MA = CH3NH3) with a layered structure was grown by the temperature-cooling solution method. The X-ray detector based on the (BDA)(MA)2Pb3Br10 single crystal has a sensitivity as high as 1984 μC Gy-1 cm-2 at 55.6 V/mm, and it could detect X-rays as low as 28.12 nGy s-1 at 22.2 V/mm. In addition, the X-ray imaging system based on the single-crystal device easily distinguishes between metals and plastics and exhibits a spatial resolution estimated as 250 μm, indicating the feasibility of (BDA)(MA)2Pb3Br10 crystals for X-ray imaging. This research offers a method for the design of quasi-2D layered perovskites and enhances photoelectronic applications in X-ray inspection and imaging.

Construction of metallo-complexes with 2,2′:6′,2″-terpyridine substituted triphenylamine in different modified positions and their photophysical properties

The stable coordinated metallo-complexes based on 2,2′:6′,2″-terpyridine (tpy) and its derivatives have been widely researched for various wide-ranging applications in photoelectronics, catalysis, sensor, photoluminescence, and so on. However, the most reported studies ignored the comprehensive comparison between structures modified by different positions and photoluminescence. Herein, we design a series of metallo-complexes which were assembled with tpy substituted triphenylamine (TPA) at different positions and metal ions and explored their photophysical properties. In the solution state, MLE2 based on the 5,5″-positions modification showed the highest PLQYs and PL intensity. With the increase of solvent polarity, MLB2 exhibit the largest redshift. In the solid state, from MLA2 to MLE2, the emission colours are gradually red-shifted from yellow to red. The findings in this work may pave a new way to design functional metallo-complexes, not just for PL properties.