Engineering the Exciton Dissociation in Quantum‐Confined 2D CsPbBr3 Nanosheet Films

Recent years have witnessed a rapid development of all‐inorganic halide perovskite in optoelectronic devices. Ultrathin 2D CsPbBr₃ nanosheets (NSs) with large lateral dimensions have demonstrated exceptional photophysical properties because of their analogous exciton electronic structure to quantum wells. Despite the incredible progress on device performance, the photophysics and carrier transportation parameters of quantum‐confined CsPbBr₃ NSs are lacking, and the fundamental understanding of the exciton dissociation mechanism is far less developed. Here, a ligands rearrangement mechanism is proposed to explain why annealed NS films have an increased charge transfer rate and a decreased exciton binding energy and lifetime, prompting tunneling as a dominant way of exciton dissociation to separate photogenerated excitons between neighboring NSs. This facile but efficient method provides a new insight to manipulate perovskite nanocrystals coupling. Moreover, ultrathin 2D CsPbBr₃ NS film is demonstrated to have a enhanced absorption cross section and high carrier mobility of 77.9 cm² V^?1 s^?1, contributing to its high responsivity of 0.53 A W^?1. The photodetector has a long‐term stability up to three months, which are responsible for reliable perovskite‐based device performance.     

High Hole Mobility in Long‐Range Ordered 2D Lead Sulfide Nanocrystal Monolayer Films

Coupling between colloidal semiconductor nanocrystals (NCs) with long‐range order is critical for designing advanced nanostructures with controlled energy flow and charge carrier transport. Herein, under the premise of keeping long‐range order in 2D NC monolayer, its native organic ligands are exchanged with halogen ions in situ at the liquid–air interface to enhance the coupling between NCs. Further treatments on the films with dimethyl sulfoxide, methanol, or their mixture effectively improve carrier mobility of the devices. The devices show repeatable enhanced p‐type transport behavior with hole mobility of up to 0.224 ± 0.069 cm² V^?1 s^?1, the highest value reported for lead sulfide NC solids without annealing treatment. Thanks to accurate control over the surface of NCs as well as the structure of NC film, the ordered NC monolayer film of high hole mobility suggests great potentials for making reliable high performance devices.     

All-Inorganic CsPbBr3 Perovskite Nanocrystals/2D Non-Layered Cadmium Sulfide Selenide for High-Performance Photodetectors by Energy Band Alignment Engineering

Perovskites have attracted intensive attention as promising materials for the application in various optoelectronic devices due to their large light absorption coefficient, high carrier mobility, and long charge carrier diffusion length. However, the performance of the pure perovskite nanocrystals-based device is extremely restricted by the limited charge transport capability due to the existence of a large number of the grain boundary between perovskite nanocrystals. To address these issues, a high-performance photodetector based on all-inorganic CsPbBr₃ perovskite nanocrystals/2D non-layered cadmium sulfide selenide heterostructure has been demonstrated through energy band engineering with designed typed-II heterostructure. The photodetector exhibits an ultra-high light-to-dark current ratio of 1.36 × 10⁵, a high responsivity of 2.89 × 10² A W⁻¹, a large detectivity of 1.28 × 10¹⁴ Jones, and the response/recovery time of 0.53s/0.62 s. The enhancement of the optoelectronic performance of the heterostructure photodetector is mainly attributed to the efficient charge carrier transfer ability between the all-inorganic CsPbBr₃ perovskites and 2D cadmium sulfide selenide resulting from energy band alignment engineering. The charge carriers’ transfer dynamics and the mechanism of the CsPbBr₃ perovskites/2D non-layered nanosheets interfaces have also been studied by state-state PL spectra, fluorescence lifetime imaging microscopy, time-resolved photoluminescence spectroscopy, and Kelvin probe force microscopy measurements.     

Reversible Transformation between CsPbBr3 Perovskite Nanowires and Nanorods with Polarized Optoelectronic Properties

CsPbX₃ (X = Cl, Br, I) perovskite nanowires and nanorods are important 1D and quasi 1D semiconductor nanomaterials. They have shown significant prospect in optic and optoelectronic applications, especially for their adaptability to flexible devices, good carrier transport performance, polarized absorption, and emission properties. Due to the high dependence of the property to the morphology, it is crucial to develop synthesis methods with continuous diameter and length tunability of the 1D/quasi 1D perovskites. In this report, a feasibly room temperature synthesis method was developed for ultrathin CsPbX₃(X = Cl, Br, I) perovskite nanowires. By aging the CsPbBr₃ nanowires (≈2*500 nm) under ambient condition with proper concentration and time, the nanowires are transformed to nanorods with controllable diameter and length. Reversibly, the nanorods can be transformed back to nanowires. Equilibrium mechanism is adopted to understand the morphology evolution, and hopefully could be generally applied to many other nano materials. The polarized optoelectronic properties of the nanowires and nanorods are interpreted by a model based on the two-channel anisotropies measurement. Polarized light detectors constructed by oriented assembled nanowires are fabricated to demonstrate their application potentials.     

Exploring the Origin of the Temperature‐Dependent Behavior of PbS Nanocrystal Thin Films and Solar Cells

Temperature‐dependent studies of the electrical and optical properties of cross‐linked PbS nanocrystal (NC) solar cells can provide deeper insight into their working mechanisms. It is demonstrated that the overall effect of temperature on the device efficiency originates from the temperature dependence of the open‐circuit voltage and the short‐circuit current, while the fill factor remains approximately constant. Extensive modeling provides signs of band‐like transport in the inhomogeneously coupled NC active layer and shows that the charge transport is dominated by diffusion. Moreover, via low temperature absorption and photoluminescence (PL) measurements, it is shown that the optical properties of PbS thin films before and after benzenedithiol (BDT) treatment exhibit very distinct behavior. After BDT treatment, both the optical density (OD) and PL are shifted to lower energies, indicating the occurrence of electronic wave function overlap between adjacent NCs. Decrease of the temperature leads to additional red‐shift of the OD and PL spectra, which is explained by the well‐known temperature dependence of the PbS NCs' bandgap. Moreover, BDT treated PbS NCs show unusual properties, such as decrease of the PL signal and broadening of the spectra at low temperatures. These features can be attributed to the partial relaxation of the quantum confinement and the opening of new radiative and nonradiative pathways for recombination at lower temperatures due to the presence of trap states.     

Coordinatable and High Charge‐Carrier‐Mobility Water‐Soluble Conjugated Copolymers for Effective Aqueous‐Processed Polymer–Nanocrystal Hybrid Solar Cells and OFET Applications

A water‐soluble conjugated polymer (WCP) poly[(3,4‐dibromo‐2,5‐thienylene vinylene)‐co‐(p‐phenylene‐vinylene)] (PBTPV), containing thiophene rings with high charge‐carrier mobility and benzene rings with excellent solubility is designed and prepared through Wessling polymerization. The PBTPV precursor can be easily processed by employing water or alcohols as the solvents, which are clean, environmentally friendly, and non‐toxic compared with the highly toxic organic solvents such as chloroform and chlorobenzene. As a novel photoelectric material, PBTPV presents excellent hole‐transport properties with a carrier mobility of 5 × 10^?4 cm² V^?1 s^?1 measured in an organic field‐effect transistor device. By integrating PBTPV with aqueous CdTe nanocrystals (NCs) to produce the active layer of water‐processed hybrid solar cells, the devices exhibit effective power conversion efficiency up to 3.3%. Moreover, the PBTPV can form strong coordination interactions with the CdTe NCs through the S atoms on the thiophene rings, and effective coordination with other nanoparticles can be reasonably expected.     

High Optical Gain of Solution-Processed Mixed-Cation CsPbBr3 Thin Films towards Enhanced Amplified Spontaneous Emission

A solution-processed thin film made of all-inorganic CsPbBr₃ perovskite is a promising candidate for low-cost and flexible green-color lasers. However, the amplified spontaneous emission (ASE) of solution-processed CsPbBr₃ films still experiences a high threshold owing to poor morphology and insufficient optical gain. Here, a multiple-cation doping strategy is demonstrated to develop compact, smooth thin films of Cs_0.87(FAMA)_0.13PbBr₃/(NMA)₂PbBr₄ (FA: formamidinium; MA: methylammonium; NMA: naphthylmethylammonium) with a record high net modal optical gain of ≈ 3030 cm⁻¹ and low propagation loss of 1.0 cm⁻¹. The FA and MA cations improve the crystallization kinetics to form continuous films, and the NMA cations reduce the grain dimension, increase film dispersibility/uniformity, and enhance spatial confinement to promote optical gain. Room-temperature ASE is demonstrated under a low threshold of ≈ 3.8  µ J cm⁻² without degradation after four months of storage in glove box or excitation by 3 × 10⁷ laser pulses. These findings provide insights into enhancing the optical gain and lowering the threshold of perovskite lasers in terms of molecular synthesis and microstructure engineering.     

Formamidinium‐Based Dion‐Jacobson Layered Hybrid Perovskites: Structural Complexity and Optoelectronic Properties

Layered hybrid perovskites have emerged as a promising alternative to stabilizing hybrid organic–inorganic perovskite materials, which are predominantly based on Ruddlesden‐Popper structures. Formamidinium (FA)‐based Dion‐Jacobson perovskite analogs are developed that feature bifunctional organic spacers separating the hybrid perovskite slabs by introducing 1,4‐phenylenedimethanammonium (PDMA) organic moieties. While these materials demonstrate competitive performances as compared to other FA‐based low‐dimensional perovskite solar cells, the underlying mechanisms for this behavior remain elusive. Here, the structural complexity and optoelectronic properties of materials featuring (PDMA)FA_n–1Pb_nI_3n+1 (n = 1–3) formulations are unraveled using a combination of techniques, including X‐ray scattering measurements in conjunction with molecular dynamics simulations and density functional theory calculations. While theoretical calculations suggest that layered Dion‐Jacobson perovskite structures are more prominent with the increasing number of inorganic layers (n), this is accompanied with an increase in formation energies that render n > 2 compositions difficult to obtain, in accordance with the experimental evidence. Moreover, the underlying intermolecular interactions and their templating effects on the Dion‐Jacobson structure are elucidated, defining the optoelectronic properties. Consequently, despite the challenge to obtain phase‐pure n > 1 compositions, time‐resolved microwave conductivity measurements reveal high photoconductivities and long charge carrier lifetimes. This comprehensive analysis thereby reveals critical features for advancing layered hybrid perovskite optoelectronics.     

Core/Shell Perovskite Nanocrystals: Synthesis of Highly Efficient and Environmentally Stable FAPbBr3/CsPbBr3 for LED Applications

Lead halide perovskite nanocrystals (PeNCs) are promising materials for applications in optoelectronics. However, their environmental instability remains to be addressed to enable their advancement into industry. Here the development of a novel synthesis method is reported for monodispersed PeNCs coated with all inorganic shell of cesium lead bromide (CsPbBr₃) grown epitaxially on the surface of formamidinium lead bromide (FAPbBr₃) NCs. The formed FAPbBr₃/CsPbBr₃ NCs have photoluminescence in the visible range 460–560 nm with narrow emission linewidth (20 nm) and high optical quantum yield, photoluminescence quantum yield (PLQY) up to 93%. The core/shell perovskites have enhanced optical stability under ambient conditions (70 d) and under ultraviolet radiation (50 h). The enhanced properties are attributed to overgrowth of FAPbBr₃ with all‐inorganic CsPbBr₃ shell, which acts as a protective layer and enables effective passivation of the surface defects. The use of these green‐emitting core/shell FAPbBr₃/CsPbBr₃ NCs is demonstrated in light‐emitting diodes (LEDs) and significant enhancement of their performance is achieved compared to core only FAPbBr₃‐LEDs. The maximum current efficiency observed in core/shell NC LED is 19.75 cd A^‐1 and the external quantum efficiency of 8.1%, which are approximately four times and approximately eight times higher, respectively, compared to core‐only devices.     

Flexible and Self‐Powered Lateral Photodetector Based on Inorganic Perovskite CsPbI3–CsPbBr3 Heterojunction Nanowire Array

Self‐powered perovskite photodetectors mainly adopt the vertical heterojunction structure composed of active layer, electron–hole transfer layers, and electrodes, which results in the loss of incident light and interfacial accumulation of defects. To address these issues, a self‐powered lateral photodetector based on CsPbI₃–CsPbBr₃ heterojunction nanowire arrays is designed on both a rigid glass and a flexible polyethylene naphthalate substrate using an in situ conversion and mask‐assisted electrode fabrication method. Through adding the polyvinyl pyrrolidone and optimizing the concentration of precursors under the pressure‐assisted moulding process, both the crystallinity and stability of perovskite nanowire array are improved. The nanowire array–based lateral device shows a high responsivity of 125 mA W^?1 and a fast rise and decay time of 0.7 and 0.8 ms under a self‐powered operation condition. This work provides a new strategy to fabricate perovskite heterojunction nanoarrays towards self‐powered photodetection.     

Facile Fabrication of PbS Nanocrystal:C60 Fullerite Broadband Photodetectors with High Detectivity

Hybrid PbS nanocrystal/C₆₀ fullerite photodetectors are fabricated using a simple one‐step drop casting procedure onto pre‐patterned interdigitated electrodes. The devices exhibit a broad spectral response from the near UV through to the near infrared yielding a detectivity, D*, of above 10¹⁰ Jones from 400 nm to ≈1050 nm. The ability to further extend the spectral response to wavelengths ≈1350 nm in the near infrared via tuning of the PbS nanocrystal diameter is also demonstrated. The dynamic responses of the devices are presented, exhibiting a fast photocurrent rise time (<40 ns) followed by a long bi‐exponential decay with characteristic lifetimes of τ₁ = 5.3 μs ± 0.1 μs and τ₂ = 37.8 μs ± 0.7 μs. These devices, which have a detectivity approaching that of commercial detectors, a broader spectral response, and a fast rise time, offer an attractive low‐cost solution for large‐area broadband photodetectors.     

Poly(catecholamine) Coated CsPbBr3 Perovskite Microlasers: Lasing in Water and Biofunctionalization

Lead halide perovskite (LHP) is a promising material for various optoelectronic applications. Surface coating on particles is a common strategy to improve their functionality and environmental stability, but LHP is not amenable to most coating chemistries because of its intrinsic weakness against polar solvents. Here, a novel method of synthesizing LHP microlasers in a super-saturated polar solvent using sonochemistry and applying various functional coatings on individual microlasers in situ is described. Cesium lead bromine perovskite (CsPbBr₃) microcrystals, capped with organic poly-norepinephrine (pNE) layers, are synthesized. The catechol group of pNE coordinates to bromine-deficient lead atoms, forming a defect-passivating and diffusion-blocking shell. The pNE layer enhances the material lifetime of CsPbBr₃ in water by 2000-fold, enabling bright luminescence and lasing from single microcrystals in water. Furthermore, the pNE shell permits biofunctionalization with proteins, small molecules, and lipid bilayers. Luminescence from CsPbBr₃ microcrystals is sustained in water over 1 h and observed in live cells. The functionalization method may enable new applications of LHP laser particles in water-rich environments.     

Sustainable and Self‐Enhanced Electrochemiluminescent Ternary Suprastructures Derived from CsPbBr3 Perovskite Quantum Dots

Lead halide perovskite quantum dots (QDs) are promising electrochemiluminescence (ECL) nanoemitters due to their fascinating photophysical properties. However, due to their poor structural stability against the external environment, the trade‐off between their colloidal stability and carrier injection/transport efficiency is a major challenge in the advancement of perovskite‐based ECL technology. In this work, intense and stable ECL from CsPbBr₃ (CPB) QDs is achieved by simultaneously encapsulating CPB QDs and coreactant (CoR) into in situ generated SiO₂ matrix via hydrolysis of tetramethyl orthosilicate. The well‐designed architecture of the as‐obtained CPB‐CoR@SiO₂ nanocomposites (NCs) guarantees not only greatly improved stability thanks to the peripheral SiO₂ protecting matrix, but also efficient self‐enhanced ECL between CPB and the intra‐coreactants. Consequently, by elaborately selecting the CoR molecules with different tertiary/secondary amines and functional groups, multifold higher (up to 10.2 times) ECL efficiencies are obtained for the CPB‐CoR@SiO₂ NCs alone in reference to the standard Ru(bpy)₃²⁺/tri‐n‐propylamine system. This work provides an efficient design strategy for obtaining stable and highly efficient ECL from perovskite QDs, and offers a new perspective for the development and application of perovskite‐based ECL system.     

High Bulk Electron Mobility Diketopyrrolopyrrole Copolymers with Perfluorothiophene

The question of designing high electron mobility polymers by increasing the planarization using diffusive nonbonding heteroatom interactions in diketopyrrolopyrrole polymers is addressed in this. For this, three different diketopyrrolo[3,4‐c]pyrrole (DPP) derivatives with thienyl‐, 2‐pyridinyl‐, and phenyl‐flanked cores are copolymerized with an electron‐rich thiophene unit as well as an electron‐deficient 3,4‐difluorothiophene unit as comonomer to obtain diverse polymeric DPPs which vary systematically in their structures. The crystallinity differs significantly with clear trends on varying both flanking unit and comonomer. The optical gap and energy levels depend more on the nature of the flanking aryl units rather than on fluorination. Additionally, the charge transport properties are compared using different methods to differentiate between interface or orientation effects and bulk charge carrier transport. In organic field effect transistor devices with very high electron as well as hole mobilities (up to 0.6 cm² V^?1 s^?1) are obtained and fluorination leads to a more pronounced n‐type nature in all polymers, resulting in ambipolar behavior in otherwise p‐type materials. In contrast, space‐charge limited current measurements show a strong influence of the flanking units only on electron mobilities. Especially, the elegant synthetic strategy of combining pyridyl flanking units with difluorothiophene as the comonomer culminates in a record bulk electron mobility of 4.3 × 10^?3 cm² V^?1 s^?1 in polymers.     

Reversible Photoinduced Phase Segregation and Origin of Long Carrier Lifetime in Mixed‐Halide Perovskite Films

Mixed‐halide hybrid perovskite semiconductors have attracted tremendous attention as a promising candidate for efficient photovoltaic and light‐emitting devices. However, these perovskite materials may undergo phase segregation under light illumination, thus affecting their optoelectronic properties. Here, photoexcitation induced phase segregation in triple‐cation mixed‐halide perovskite films that yields to red‐shift in the photoluminescence response is reported. It is demonstrated that photoexcitation induced halide migration leads to the formation of smaller bandgap iodide‐rich and larger bandgap bromide‐rich domains in the perovskite film, where the phase segregation rate is found to follow the excitation power‐density as a power law. Results confirm that charge carrier lifetime increases due to the trapping of photoexcited carriers in the segregated smaller bandgap iodide‐rich domains. Interestingly, these photoinduced changes are fully reversible and thermally activated when the excitation power is turned off. A significant difference in activation energies for halide ion migration is observed during phase segregation and recovery process. Additionally, the emission linewidth broadening is investigated as a function of temperature which is governed by the exciton–optical phonon coupling. The mechanism of photoinduced phase segregation is interpreted based on exciton–phonon coupling strength in both mixed and demixed (segregated) states of perovskite films.     

All‐Inorganic Perovskite Nanocrystals for High‐Efficiency Light Emitting Diodes: Dual‐Phase CsPbBr3‐CsPb2Br5 Composites

A dual‐phase all‐inorganic composite CsPbBr₃‐CsPb₂Br₅ is developed and applied as the emitting layer in LEDs, which exhibited a maximum luminance of 3853 cd m^–2, with current density (CE) of ≈8.98 cd A^–1 and external quantum efficiency (EQE) of ≈2.21%, respectively. The parasite of secondary phase CsPb₂Br₅ nanoparticles on the cubic CsPbBr₃ nanocrystals could enhance the current efficiency by reducing diffusion length of excitons on one side, and decrease the trap density in the band gap on the other side. In addition, the introduction of CsPb₂Br₅ nanoparticles could increase the ionic conductivity by reducing the barrier against the electronic and ionic transport, and improve emission lifetime by decreasing nonradiative energy transfer to the trap states via controlling the trap density. The dual‐phase all‐inorganic CsPbBr₃‐CsPb₂Br₅ composite nanocrystals present a new route of perovskite material for advanced light emission applications.     

Highly Luminescent Covalently Linked Silicon Nanocrystal/Polystyrene Hybrid Functional Materials: Synthesis,Properties, and Processability

Silicon nanocrystals (SiNCs) have received much attention because of their exquisitely tunable photoluminescent response, biocompatibility, and the promise that they may supplant their CdSe quantum dot counterparts in many practical applications. One attractive strategy that promises to extend and even enhance the utility of SiNCs is their incorporation into NC/polymer hybrids. Unfortunately, methods employed to prepare hybrid materials of this type from traditional compound semiconductor (e.g., CdSe) quantum dots are not directly transferable to SiNCs because of stark differences in surface chemistry. Herein, the preparation of chemically resistant SiNC/polystyrene hybrids exhibiting exquisitely tunable photoluminescence is reported and material processability is demonstrated by preparing micro and nanoscale architectures.     

Optoelectronic Properties of Quasi‐Linear,Self‐Assembled Platinum Complexes: Pt–Pt Distance Dependence

Charge‐carrier mobilities of various self‐assembled platinum complexes were measured by time‐resolved microwave conductivity techniques in the temperature range –80 to +100 °C. Eight compounds were investigated in the present study, including the original Magnus' green salt ([Pt(NH₃)₄][PtCl₄]) and derivatives with the general structure [Pt(NH₂R)₄][PtCl₄], where R denotes an alkyl side chain. In one instance, the chlorines were substituted with bromines. For these complexes, which all consist of a linear backbone of platinum atoms with Pt–Pt distances, d, varying from 3.1 to ≥ 3.6 Å, a strong, inverse correlation was found between d and the one‐dimensional charge‐carrier mobility, Σμ_1D. The highest value of Σμ_1D at room temperature was observed for R = (S)‐3,7‐dimethyloctyl (dmoc) with Σμ_1D ≥ 0.06 cm² V^–1 s^–1. Almost all materials exhibited a charge‐carrier mobility that was relatively independent of the temperature over the range studied. One exceptional compound (R = (R)‐2‐ethylhexyl) showed a pronounced negative temperature dependence of the charge‐carrier mobility; upon decreasing the temperature from +100 °C to –80 °C the charge‐carrier mobility increased by a factor of about ten.     

Highly Sensitive Temperature Sensor: Ligand‐Treated Ag Nanocrystal Thin Films on PDMS with Thermal Expansion Strategy

Highly sensitive temperature sensors are designed by exploiting the interparticle distance–dependent transport mechanism in nanocrystal (NC) thin films based on a thermal expansion strategy. The effect of ligands on the electronic, thermal, mechanical, and charge transport properties of silver (Ag) NC thin films on thermal expandable substrates of poly(dimethylsiloxane) (PDMS) is investigated. While inorganic ligand‐treated Ag NC thin films exhibit a low temperature coefficient of resistance (TCR), organic ligand‐treated films exhibit extremely high TCR up to 0.5 K^?1, which is the highest TCR exhibited among nanomaterial‐based temperature sensors to the best of the authors' knowledge. Structural and electronic characterizations, as well as finite element method simulation and transport modeling are conducted to determine the origin of this behavior. Finally, an all‐solution based fabrication process is established to build Ag NC‐based sensors and electrodes on PDMS to demonstrate their suitability as low‐cost, high‐performance attachable temperature sensors.     

Interfacial‐Tunneling‐Effect‐Enhanced CsPbBr3 Photodetectors Featuring High Detectivity and Stability

Inorganic halide perovskite (HP)‐based photodetectors (PDs) have exhibited fast response speed and high responsivity, but with low detectivity due to the high dark current of devices. Additionally, the intrinsic instability of HPs and interface deterioration originating from ion migration inhibit their practical applications severely. A tunneling organic layer is introduced to solve both these problems. Light‐induced charge carriers can flow across the interfacial (poly(methyl methacrylate), PMMA) layer with appropriate thickness via the Fowler–Nordheim tunneling effect. Due to the effective control of dark current, the photo‐/dark‐current ratio reaches a giant value of 2.13 × 10⁸, and the peak detectivity is as high as 1.24 × 10¹³ Jones. With such superiority, light signal as weak as 244 pW is accurately imaged by a PD array. Additionally, the hydrophobic organic layer inhibits the destruction of HPs caused by moisture and ion migration induced interface reaction, and negligible response attenuation is observed during continuous work in a humid environment for 48 h. This heterojunction structure design provides a new strategy to enhance the performance and stability of perovskite‐based photoelectric and photovoltaic devices.