Solution‐Processed Flexible Broadband Photodetectors with Solution‐Processed Transparent Polymeric Electrode

Room‐temperature solution‐processed flexible photodetectors with spectral response from 300 to 2600 nm are reported. Solution‐processed polymeric thin film with transparency ranging from 300 to 7000 nm and superior electrical conductivity as the transparent electrode is reported. Solution‐processed flexible broadband photodetectors with a “vertical” device structure incorporating a perovskite/PbSe quantum dot bilayer thin film based on the above solution‐processed transparent polymeric electrode are demonstrated. The utilization of perovskite/PbSe quantum dot bilayer thin film as the photoactive layer extends spectral response to infrared region and boosts photocurrent densities in both visible and infrared regions through the trap‐assisted photomultiplication effect. Operated at room temperature and under an external bias of ‐1 V, the solution‐processed flexible photodetectors exhibit over 230 mA W^‐1 responsivity, over 1011 cm Hz1/2/W photodetectivity from 300 to 2600 nm and ≈70 dB linear dynamic ranges. It is also found that the solution‐processed flexible broadband photodetectors exhibit fast response time and excellent flexibility. All these results demonstrate that this work develop a facile approach to realize room‐temperature operated ultrasensitive solution‐processed flexible broadband photodetectors with “vertical” device structure through solution‐processed transparent polymeric electrode.     

Low‐Noise Multispectral Photodetectors Made from All Solution‐Processed Inorganic Semiconductors

Infrared, visible, and multispectral photodetectors are important components for sensing, security and electronics applications. Current fabrication of these devices is based on inorganic materials grown by epitaxial techniques which are not compatible with low‐cost large‐scale processing. Here, air‐stable multispectral solution‐processed inorganic double heterostructure photodetectors, using PbS quantum dots (QDs) as the photoactive layer, colloidal ZnO nanoparticles as the electron transport/hole blocking layer (ETL/HBL), and solution‐derived NiO as the hole transport/electron blocking layer (HTL/EBL) are reported. The resulting device has low dark current density of 20 nA cm^‐2 with a noise equivalent power (NEP) on the order of tens of picowatts across the detection spectra and a specific detectivity (D*) value of 1.2 × 10¹² cm Hz^1/2 W^‐1. These parameters are comparable to commercially available Si, Ge, and InGaAs photodetectors. The devices have a linear dynamic range (LDR) over 65 dB and a bandwidth over 35 kHz, which are sufficient for imaging applications. Finally, these solution‐processed inorganic devices have a long storage lifetime in air, even without encapsulation.     

Routes to Achieving High Quantum Yield Luminescence from Gas‐Phase‐Produced Silicon Nanocrystals

Plasma‐synthesized silicon nanocrystals with alkene ligands have shown the potential to exhibit high‐efficiency photoluminescence, but results reported in the literature have been inconsistent. Here, for the first time, the role of the immediate post‐synthesis “afterglow plasma” environment is explored. The significant impact of gas injection into the afterglow plasma on the photoluminescence efficiency of silicon nanocrystals is reprorted. Depending on the afterglow conditions, photoluminescence quantum yields of silicon nanocrystals synthesized under otherwise identical conditions can vary by a factor of almost five. It is demonstrated that achieving a fast quenching of the particle temperature and a high flux of atomic hydrogen to the nanocrystal surface are essential for a high photoluminescence quantum yield of the produced silicon nanocrystals.     

Silicon Nanocrystals in Liquid Media: Optical Properties and Surface Stabilization by Microplasma‐Induced Non‐Equilibrium Liquid Chemistry

Surface engineering of silicon nanocrystals directly in water or ethanol by atmospheric‐pressure dc microplasma is reported. In both liquids, microplasma processing stabilizes the optoelectronic properties of silicon nanocrystals. The microplasma treatment induces non‐equilibrium liquid chemistry that passivates the silicon nanocrystals surface with oxygen‐/organic‐based terminations. In particular, the microplasma treatment in ethanol drastically enhances the silicon nanocrystals photoluminescence intensity and causes a clear red‐shift (≈80 nm) of the photoluminescence maximum. The photoluminescence properties are stable after several days of storage in either ethanol or water. The surface chemistry induced by the microplasma treatment is analyzed and discussed.     

Solution‐Processed Low Threshold Vertical Cavity Surface Emitting Lasers from All‐Inorganic Perovskite Nanocrystals

Recently, newly engineered all‐inorganic cesium lead halide perovskite nanocrystals (IPNCs) (CsPbX₃, X = Cl, Br, I) are discovered to possess superior optical gain properties appealing for solution‐processed cost‐effective lasers. Yet, the potential of such materials has not been exploited for practical laser devices, rendering the prospect as laser media elusive. Herein, the challenging but practically desirable vertical cavity surface emitting lasers (VCSELs) based on the CsPbX₃ IPNCs, featuring low threshold (9 µJ cm^?2), directional output (beam divergence of ≈3.6°), and favorable stability, are realized for the first time. Notably, the lasing wavelength can be tuned across the red, green, and blue region maintaining comparable thresholds, which is promising in developing single‐source‐pumped full‐color visible lasers. It is fully demonstrated that the characteristics of the VCSELs can be versatilely engineered by independent adjustment of the cavity and solution‐processable nanocrystals. The results unambiguously reveal the feasibility of the emerging CsPbX₃ IPNCs as practical laser media and represent a significant leap toward CsPbX₃ IPNC‐based laser devices.     

Efficient Directed Energy Transfer through Size‐Gradient Nanocrystal Layers into Silicon Substrates

Spectroscopic evidence of directed excitonic energy transfer (ET) is presented through size‐gradient CdSe/ZnS nanocrystal quantum dot (NQD) layers into an underlying Si substrate. NQD monolayers are chemically grafted on hydrogen‐terminated Si surfaces via a self‐assembled monolayer of amine modified carboxy‐alkyl chains. Subsequent NQD monolayers are linked with short alkyldiamines. The linking approach enables accurate positioning and enhanced passivation of the layers. Two different sizes of NQDs (energy donors emitting at 545 nm, and energy acceptors emitting at 585 nm) are used in comparing different monolayer and bilayer samples grafted on SiO₂ and oxide‐free Si surfaces via time‐resolved photoluminescence measurements. The overall efficiency of ET from the top‐layer donor NQDs into Si is estimated to approach ≈90% through a combination of different energy relaxation pathways. These include sequential ET through the intermediate acceptor layer realized mainly via the non‐radiative mechanism and direct ET into the Si substrate realized by means of the radiative coupling. The experimental observations are quantitatively rationalized by the theoretical modeling without introducing any extraneous energy scavenging processes. This indicates that the linker‐assisted fabrication enables the construction of defect‐free, bandgap‐gradient multilayer NQD/Si hybrid structures suitable for thin‐film photovoltaic applications.     

High‐Performance Quantum‐Dot Light‐Emitting Diodes Using NiOx Hole‐Injection Layers with a High and Stable Work Function

Solution‐processed oxide thin films are actively pursued as hole‐injection layers (HILs) in quantum‐dot light‐emitting diodes (QLEDs), aiming to improve operational stability. However, device performance is largely limited by inefficient hole injection at the interfaces of the oxide HILs and high‐ionization‐potential organic hole‐transporting layers. Solution‐processed NiO_x films with a high and stable work function of ≈5.7 eV achieved by a simple and facile surface‐modification strategy are presented. QLEDs based on the surface‐modified NiO_x HILs show driving voltages of 2.1 and 3.3 V to reach 1000 and 10 000 cd m^?2, respectively, both of which are the lowest among all solution‐processed LEDs and vacuum‐deposited OLEDs. The device exhibits a T₉₅ operational lifetime of ≈2500 h at an initial brightness of 1000 cd m^?2, meeting the commercialization requirements for display applications. The results highlight the potential of solution‐processed oxide HILs for achieving efficient‐driven and long‐lifetime QLEDs.     

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.     

Mn2+‐Doped CdSe Quantum Dots: New Inorganic Materials for Spin‐Electronics and Spin‐Photonics

Recent advances in the chemistry of colloidal semiconductor nanocrystal doping have led to new materials showing fascinating physical properties of potential technological importance. This article provides an overview of efforts to dope one of the most widely studied colloidal semiconductor nanocrystal systems, CdSe quantum dots, with one of the most widely studied transition‐metal dopant ions, Mn²⁺, and describes the major new physical properties that have emerged following successful synthesis of this material. These properties include spin‐polarizable excitonic photoluminescence, magnetic circular dichroism, exciton storage, and excitonic magnetic polaron formation. A brief survey of parallel advances in the characterization of analogous self‐assembled Mn²⁺‐doped quantum dots grown by molecular beam epitaxy is also presented, and the physical properties of the colloidal quantum dots are shown to compare favorably with those of the self‐assembled quantum dots. The rich variety of physical properties displayed by colloidal Mn²⁺‐doped CdSe quantum dots highlights the attractiveness of this material for future fundamental and applied research.     

Unraveling the Gain Mechanism in High Performance Solution‐Processed PbS Infrared PIN Photodiodes

High gain and low dark current solution‐processed colloidal PbS quantum dots infrared (IR) PIN photodetectors with IR sensitivity up to 1500 nm are demonstrated. The low dark current is due to the P‐I‐N structure with both electron and hole blockers. The high gain in our IR photodiodes is due to the enhancement of electron tunneling injection through the 1,1‐bis[(di‐4‐tolylamino) phenyl]cyclohexane (TAPC) electron blocker under IR illumination resulting from a distorted electron blocking barrier in the presence of photo‐generated holes trapped in the TAPC electron blocker. It is further found that the trap states in the TAPC layer are generated by the Ag atoms penetrated in the TAPC layer during the thermal evaporation process. The resulting photodetectors have a high detectivity value of 7 × 10¹³ Jones, which is even higher than that of a commercial InGaAs photodiode.     

Luminescent Colloidal Dispersion of Silicon Quantum Dots from Microwave Plasma Synthesis: Exploring the Photoluminescence Behavior Across the Visible Spectrum

Aiming for a more practical route to highly stable visible photoluminescence (PL) from silicon, a novel approach to produce luminescent silicon nanoparticles (Si‐NPs) is developed. Single crystalline Si‐NPs are synthesized by pyrolysis of silane (SiH₄) in a microwave plasma reactor at very high production rates (0.1–10 g h^?1). The emission wavelength of the Si‐NPs is controlled by etching them in a mixture of hydrofluoric acid and nitric acid. Emission across the entire visible spectrum is obtained by varying the etching time. It is observed that the air oxidation of the etched Si‐NPs profoundly affects their optical properties, and causes their emission to blue‐shift and diminish in intensity with time. Modification of the silicon surface by UV‐induced hydrosilylation also causes a shift in the spectrum. The nature of the shift (red/blue) is dependent on the emission wavelength of the etched Si‐NPs. In addition, the amount of shift depends on the type of organic ligand on the silicon surface and the UV exposure time. The surface modification of Si‐NPs with different alkenes results in highly stable PL and allows their dispersion in a variety of organic solvents. This method of producing macroscopic quantities of Si‐NPs with very high PL stability opens new avenues to applications of silicon quantum dots in optoelectronic and biological fields, and paves the way towards their commercialization.     

Over 16.7% Efficiency Organic‐Silicon Heterojunction Solar Cells with Solution‐Processed Dopant‐Free Contacts for Both Polarities

Realization of synchronous improvement in optical management and electrical engineering is necessary to achieve high‐performance photovoltaic device. However, inherent challenges are faced in organic‐silicon heterojunction solar cells (HSCs) due to the poor contact property of polymer on structured silicon surface. Herein, a remarkable efficiency boost from 12.6% to over 16.7% in poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate)/n‐silicon (PEDOT:PSS/n‐Si) HSCs by independent optimization of hole‐/electron‐selective contacts only relying on solution‐based processes is realized. A bilayer PEDOT:PSS film with different functionalizations is utilized to synchronously realize conformal contact and effective carrier collection on textured Si surface, making the photogenerated carriers be well separated at heterojunction interface. Meanwhile, fullerene derivative is used as electron‐transporting layer at the rear n‐Si/Al interface to reduce the contact barrier. The study of carriers' transport and independent optimization on separately contacted layers may lead to an effective and simplified path to fabricate high‐performance organic‐silicon heterojunction devices.     

Fabrication of MAPbBr3 Single Crystal p‐n Photodiode and n‐p‐n Phototriode for Sensitive Light Detection Application

In this study, MAPbBr₃ single crystal (MSC) p‐n perovskite homojunction photodiode and n‐p‐n phototriode are successfully fabricated through controlled incorporation of Bi³⁺ ions in solution. Optoelectronic analysis reveals that the photodiode shows typical photovoltaic behavior and the best photovoltaic performance can be achieved when the n‐type MSC is grown in 0.3% Bi³⁺ feed solution. The as‐assembled p‐n MSC photovoltaic detector displays obvious sensitivity to 520 nm illumination, with a high responsivity of up to 0.62 A W^‐1 and a specific detectivity of 2.16 × 10¹² Jones, which surpass many those of MSC photodetectors previously reported. Further performance optimization can be realized by constructing an n‐p‐n phototriode using the same growth method. The photocurrent magnification rate of the as‐fabricated n‐p‐n phototriode can reach a maximum value of 2.9 × 10³. Meanwhile, a higher responsivity of 14.47 A W^‐1, specific detectivity of 4.67 × 10¹³ Jones, and an external quantum efficiency of up to 3.46 × 10³ are achieved under an emitter–collector bias of 8 V. These results confirm that the present p‐n and n‐p‐n MSC homojunctions are promising device configurations, which may find potential application in future optoelectronic devices and systems.     

Light Extraction Efficiency Enhancement of Colloidal Quantum Dot Light‐Emitting Diodes Using Large‐Scale Nanopillar Arrays

A colloidal quantum dot light‐emitting diode (QLED) is reported with substantially enhanced light extraction efficiency by applying a layer of large‐scale, low‐cost, periodic nanopillar arrays. Zinc oxide nanopillars are grown on the glass surface of the substrate using a simple, efficient method of non‐wetting templates. With the layer of ZnO nanopillar array as an optical outcoupling medium, a record high current efficiency (CE) of 26.6 cd/A is achieved for QLEDs. Consequently, the corresponding external quantum efficiency (EQE) of 9.34% reaches the highest EQE value for green‐emitting QLEDs. Also, the underlying physical mechanisms enabling the enhanced light‐extraction are investigated, which leads to an excellent agreement of the numerical results based on the mode theory with the experimental measurements. This study is the first account for QLEDs offering detailed insight into the light extraction efficiency enhancement of QLED devices. The method demonstrated here is intended to be useful not only for opening up a ubiquitous strategy for designing high‐performance QLEDs but also with respect to fundamental research on the light extraction in QLEDs.     

High Performance PbS Colloidal Quantum Dot Solar Cells by Employing Solution‐Processed CdS Thin Films from a Single‐Source Precursor as the Electron Transport Layer

CdS thin films are a promising electron transport layer in PbS colloidal quantum dot (CQD) photovoltaic devices. Some traditional deposition techniques, such as chemical bath deposition and RF (radio frequency) magnetron sputtering, have been employed to fabricate CdS films and CdS/PbS CQD heterojunction photovoltaic devices. However, their power conversion efficiencies (PCEs) are moderate compared with ZnO/PbS and TiO₂/PbS heterojunction CQD solar cells. Here, efficiencies have been improved substantially by employing solution‐processed CdS thin films from a single‐source precursor. The CdS film is deposited by a straightforward spin‐coating and annealing process, which is a simple, low‐cost, and high‐material‐usage fabrication process compared to chemical bath deposition and RF magnetron sputtering. The best CdS/PbS CQD heterojunction solar cell is fabricated using an optimized deposition and air‐annealing process achieved over 8% PCE, demonstrating the great potential of CdS thin films fabricated by the single‐source precursor for PbS CQDs solar cells.     

Organic and Inorganic Blocking Layers for Solution‐Processed Colloidal PbSe Nanocrystal Infrared Photodetectors

A PbSe solution‐processed nanocrystal‐based infrared photodetector incorporating carrier blocking layers is demonstrated, and significant reduction of dark current is achieved. Detectivity values close to 10¹² Jones are achieved by using poly[(9,9′‐dioctylfluorenyl‐2,7‐diyl)‐co‐(4,4′‐(N‐(4‐sec‐butyl))diphenylamine)] (TFB) and ZnO nanocrystals (NC) as the electron blocker and hole blocker, respectively. An improvement in lifetime is also observed in the devices with the ZnO NCs hole blocking layer.     

Porous NIR Photoluminescent Silicon Nanocrystals‐POSS Composites

Near infrared photoluminescent porous silicon nanocrystals(ncSi)‐polyhedral oligomeric silsesquioxanes (POSS) polymer composites are synthesized using a combination of thermal hydrosilylation and polymerization between Vinyl‐POSS and hydrogen‐terminated silicon nanocrystals (ncSi:H). The synthesized materials are characterized by IR, powder X‐ray diffraction and solid‐state nuclear magnetic resonance (NMR) (¹³C and ²⁹Si). The results demonstrate that the hydrosilylation–polymerization reaction proceeded to create chemically crosslinked Vinyl‐POSS‐ncSi composites in which the integrity of the POSS cages is maintained intact. Scanning electron microscope (SEM) results demonstrate that morphology of these materials depends on the weight ratio of ncSi:H to Vinyl‐POSS. Brunauer–Emmett–Teller surface area analyses establish that the composites have high surface areas ranging from 290.5 to 1047.2 m² g^?1 and pore volumes from 0.64 to 1.17 cm³ g^?1. The pore sizes range from 6.08 to 3.54 nm and are dependent on the weight ratio of Vinyl‐POSS to ncSi:H. Photoluminescence spectroscopy shows that the absolute quantum yield of the nanocomposites is not affected by the weight ratio of ncSi:H to Vinyl‐POSS. Thermal gravimetric analysis results show that the POSS polymer composites with ncSi have lower thermal stability in nitrogen atmosphere as compared with the pure Vinyl‐POSS polymer. It is envisioned that future applications for these composites will likely be found in the fields of advanced materials, gas adsorption media, and biomedicine.     

Fast,Air‐Stable Infrared Photodetectors based on Spray‐Deposited Aqueous HgTe Quantum Dots

The ability to detect near‐infrared and mid‐infrared radiation has spawned great interest in colloidal HgTe quantum dots (QDs). In contrast to the studies focused on extending the spectral range of HgTe QD devices, the temporal response, another figure of merit for photodetectors, is rarely investigated. In this work, a single layer, aqueous HgTe QD based photoconductor structure with very fast temporal response (up to 1 MHz 3 dB bandwidth) is demonstrated. The device is fabricated using a simple spray‐coating process and shows excellent stability in ambient conditions. The origin of the remarkably fast time response is investigated by combining light intensity‐dependent transient photocurrent, temperature‐dependent photocurrent, and field‐effect transistor (FET) measurements. The charge carrier mobility, as well as the energy levels and carrier lifetimes associated with the trap states in the QDs, are identified. The results suggest that the temporal response is dominated by a fast bimolecular recombination process under high light intensity and by a trap‐mediated recombination process at low light intensity. Interestingly, it was found that the gain and time response of aqueous HgTe QD‐based photoconductors can be tuned by controlling the QD size and surface chemistry, which provides a versatile approach to optimize the photodetectors with selectable sensitivity and operation bandwidth.     

A General Solvent Selection Strategy for Solution Processed Quantum Dots Targeting High Performance Light‐Emitting Diode

An all‐solution‐processed quantum dots (QDs) light emitting diode (QLED) consists of different layers deposited from various orthogonal solvents. Here, the authors develop a general solvent selection strategy to obtain orthogonal solubility properties as well as high film quality. It is found that a “poor” QDs film morphology with striation defects often occurs when the QDs film is deposited from “bad” solvent. A physical model is presented to rationalize the observed striation defects, and then a general solvent selection strategy is proposed to prevent both surface striation defects and the dissolving of the underlying layers by carefully choosing the “good” solvent for QDs. A compact QDs film can be fabricated without altering the original morphology of underlying functional layers in a QLED device, leading to significant device performance improvement. An external quantum efficiency of 15.45% is achieved in a green QLED with uniform emitting region. This solvent selection strategy provides a general way to deposit high quality films for most of the solution‐processed multilayer optoelectronic devices.