Anisotropic Heavy-Metal-Free Semiconductor Nanocrystals: Synthesis, Properties, and Applications.

Heavy-metal (Cd, Hg, and Pb)-containing semiconductor nanocrystals (NCs) have been explored widely due to their unique optical and electrical properties. However, the toxicity risks of heavy metals can be a drawback of heavy-metal-containing NCs in some applications. Anisotropic heavy-metal-free semiconductor NCs are desirable replacements and can be realized following the establishment of anisotropic growth mechanisms. These anisotropic heavy-metal-free semiconductor NCs can possess lower toxicity risks, while still exhibiting unique optical and electrical properties originating from both the morphological and compositional anisotropy. As a result, they are promising light-emitting materials in use various applications. In this review, we provide an overview on the syntheses, properties, and applications of anisotropic heavy-metal-free semiconductor NCs. In the first section, we discuss hazards of heavy metals and introduce the typical heavy-metal-containing and heavy-metal-free NCs. In the next section, we discuss anisotropic growth mechanisms, including solution-liquid-solid (SLS), oriented attachment, ripening, templated-assisted growth, and others. We discuss mechanisms leading both to morphological anisotropy and to compositional anisotropy. Examples of morphological anisotropy include growth of nanorods (NRs)/nanowires (NWs), nanotubes, nanoplatelets (NPLs)/nanosheets, nanocubes, and branched structures. Examples of compositional anisotropy, including heterostructures and core/shell structures, are summarized. Third, we provide insights into the properties of anisotropic heavy-metal-free NCs including optical polarization, fast electron transfer, localized surface plasmon resonances (LSPR), and so on, which originate from the NCs' anisotropic morphologies and compositions. Finally, we summarize some applications of anisotropic heavy-metal-free NCs including catalysis, solar cells, photodetectors, lighting-emitting diodes (LEDs), and biological applications. Despite the huge progress on the syntheses and applications of anisotropic heavy-metal-free NCs, some issues still exist in the novel anisotropic heavy-metal-free NCs and the corresponding energy conversion applications. Therefore, we also discuss the challenges of this field and provide possible solutions to tackle these challenges in the future.

Interfacial Passivation Engineering for Highly Efficient Quantum Dot Light-Emitting Diodes via Aromatic Amine-Functionalized Dipole Molecules.

Blue quantum dot (QD) light-emitting diodes (QLEDs) exhibit unsatisfactory operational stability and electroluminescence (EL) properties due to severe nonradiative recombination induced by large numbers of dangling bond defects and charge imbalance in QD. Herein, dipolar aromatic amine-functionalized molecules with different molecular polarities are employed to regulate charge transport and passivate interfacial defects between QD and the electron transfer layer (ETL). The results show that the stronger the molecular polarity, especially with the -CF3 groups possessing a strong electron-withdrawing capacity, the more effective the defect passivation of S and Zn dangling bonds at the QD surface. Moreover, the dipole interlayer can effectively reduce electron injection into QD at high current density, enhancing charge balance and mitigating Joule heat. Finally, blue QLEDs exhibit a peak external quantum efficiency (EQE) of 21.02% with an operational lifetime (T50 at 100 cd m-2) exceeding 4000 h.

Low-Temperature Cross-Linked Hole Transport Layer for High-Performance Blue Quantum-Dot Light-Emitting Diodes.

Quantum-dot light-emitting diodes (QLEDs), a kind of promising optoelectronic device, demonstrate potential superiority in next-generation display technology. Thermal cross-linked hole transport materials (HTMs) have been employed in solution-processed QLEDs due to their excellent thermal stability and solvent resistance, whereas the unbalanced charge injection and high cross-linking temperature of cross-linked HTMs can inhibit the efficiency of QLEDs and limit their application. Herein, a low-temperature cross-linked HTM of 4,4'-bis(3-(((4-vinylbenzyl)oxy)methyl)-9H-carbazol-9-yl)-1,1'-biphenyl (DV-CBP) with a flexible styrene side chain is introduced, which reduces the cross-linking temperature to 150 °C and enhances the hole mobility up to 1.01 × 10-3 cm2 V-1 s-1. More importantly, the maximum external quantum efficiency of 21.35% is successfully obtained on the basis of the DV-CBP as a cross-linked hole transport layer (HTL) for blue QLEDs. The low-temperature cross-linked high-mobility HTL using flexible side chains could be an excellent alternative for future HTL development.

Charge Carrier Regulation for Efficient Blue Quantum-Dot Light-Emitting Diodes Via a High-Mobility Coplanar Cyclopentane[b]thiopyran Derivative.

The performance of blue quantum dot light-emitting diodes (QLEDs) is limited by unbalanced charge injection, resulting from insufficient holes caused by low mobility or significant energy barriers. Here, we introduce an angular-shaped heteroarene based on cyclopentane[b]thiopyran (C8-SS) to modify the hole transport layer poly-N-vinylcarbazole (PVK), in blue QLEDs. C8-SS exhibits high hole mobility and conductivity due to the π···π and S···π interactions. Introducing C8-SS to PVK significantly enhanced hole mobility, increasing it by 2 orders of magnitude from 2.44 × 10-6 to 1.73 × 10-4 cm2 V-1 s-1. Benefiting from high mobility and conductivity, PVK:C8-SS-based QLEDs exhibit a low turn-on voltage (Von) of 3.2 V. More importantly, the optimized QLEDs achieve a high peak power efficiency (PE) of 7.13 lm/W, which is 2.65 times that of the control QLEDs. The as-proposed interface engineering provides a novel and effective strategy for achieving high-performance blue QLEDs in low-energy consumption lighting applications.

In Situ Local Band Engineering of Monolayer Graphene Using Triboelectric Plasma.

Graphene, a promising material with excellent properties, suffers from a major limitation in electronics due to its zero bandgap. The gas molecules adsorption has proven to be an effective approach for band regulation, which usually requires a harsh environment. Here, O2 - ions produced with triboelectric plasma are used for in situ regulation of graphene, and the switching ratio can reach 1010. The O2 - ions physical adsorption will reduce the Fermi-level (EF) of graphene. As the EF of graphene is lower than the lowest unoccupied molecular orbital (LUMO) level of O2-, the adsorption of O2 - changes from uniform physical adsorption to local chemical adsorption, thereby realizing the semiconductor properties of graphene. The local graphene bandgap is calculated to be 83.4 meV by the variable-temperature experiment. Furthermore, annealing treatment can restore to 1/10 of the initial conductance. The C─O bond formed by O2 - adsorption has low bond energy and is easy to desorb, while the C═O bond formed by adsorption on defects and edges has higher bond energy and is difficult to desorb. The study proposes a simple in situ method to investigate the microscopic process of O2 - adsorption on the graphene surface, demonstrating a new perspective for local energy band engineering of graphene.

Harnessing Natural Evaporation for Electricity Generation using MOF-Based Nanochannels.

Functionalized nanochannels can convert environmental thermal energy into electrical energy by driving water evaporation. This process involves the interaction between the solid-liquid interface and the natural water evaporation. The evaporation-driven water potential effect is a novel green environmental energy capture technology that has a wide range of applications and does not depend on geographical location or environmental conditions, it can generate power as long as there is water, light, and heat. However, suitable materials and structures are needed to harness this natural process for power generation. MOF materials are an emerging field for water evaporation power generation, but there are still many challenges to overcome. This work uses MOF-801, which has high porosity, charged surface, and hydrophilicity, to enhance the output performance of evaporation-driven power generation. It can produce an open circuit voltage of ≈2.2 V and a short circuit current of ≈1.9 µA. This work has a simple structure, easy preparation, low-cost and readily available materials, and good stability. It can operate stably in natural environments with high practical value.

Phase Engineering Reinforced Energy Transfer for High-Performance Blue Perovskite Light-Emitting Diodes.

Layered metal-halide perovskites, a category of self-assembled quantum wells, are of paramount importance in emerging photonic sources, such as lasers and light-emitting diodes (LEDs). Despite high trap density in two-dimensional (2D) perovskites, efficient non-radiative energy funneling from wide- to narrow-bandgap components, sustained by the Förster resonance energy transfer (FRET) mechanism, contributes to efficient luminescence by light or electrical injection. Herein, it is demonstrated that bandgap extension of layered perovskites to the blue-emitting regime will cause sluggish and inefficient FRET, stemming from the tiny spectral overlap between different phases. Motivated by the importance of blue LEDs and inefficient energy transfer in materials with phase polydispersity, wide-bandgap quasi-2D perovskites with narrow phase distribution, improved crystallinity, and the pure crystal orientation perpendicular to the charge transport layer are developed. Based on this emitter, high-performance blue perovskite LEDs with improved electroluminescence (EL) external quantum efficiency (EQE) of 7.9% at 478 nm, a narrow full width at half-maximum (FWHM) of 22 nm and a more stable EL spectra are achieved. These results provide an important insight into spectrally stable and efficient blue emitters and EL devices based on perovskites.

Light and voltage dual-modulated volatile resistive switching in single ZnO nanowires.

A single ZnO nanowire device with volatile resistive switching behavior has been prepared. Different from traditional resistive switching devices, such ZnO nanowire devices do not exhibit resistive switching behaviors under a single bias voltage, and appear resistive switching behavior under the combined action of light stimuli and bias voltage. Through the demonstration of the time-dependent hysteresis curve and atmosphere-dependent hysteresis loop of the resistive switching devices, it is believed that under the resistive switching process, ultraviolet illumination can increase the carrier concentration and modulate the barrier depletion structure, and external bias voltage can ionize the surface state. They work together to modulate the switching process of the devices. Such light stimuli and bias voltage dual-modulated resistive switching device enables optical control and may thus be considered for sensory applications or optically tunable memories.

Conventional and pulsed hybrid triboelectric nanogenerator with tunable output time and wider impedance matching range.

Sliding grating-structured triboelectric nanogenerators (SG-TENGs) can multiply transferred charge, reduce open-circuit voltage, and increase short-circuit current, which have wide application prospects in self-powered systems. However, conventional SG-TENGs have an ultrahigh internal equivalent impedance, which reduces the output voltage and energy under low load resistances (<10 MΩ). The Pulsed SG-TENGs can reduce the equivalent impedance to near zero by introducing a synchronously triggered mechanical switch (STMS), but its limited output time causes the incomplete charge transfer under high load resistances (>1 GΩ). In this paper, a conventional and pulsed hybrid SG-TENG (CPH-SG-TENG) is developed through rational designing STMS with tunable width and output time. The matching relationship among grid electrode width, contactor width of STMS, sliding speed, and load resistance has been studied, which provides a feasible solution for simultaneous realization of high output energy under small load resistances and high output voltage under high load resistances. The impedance matching range is extended from zero to at least 10 GΩ. The output performance of CPH-SG-TENG under low and high load resistances are demonstrated by passive power management circuit and arc discharge, respectively. The general strategy using tunable STMS combines the advantages of conventional and pulsed TENGs, which has broad application prospects in the fields of TENGs and self-powered systems.

Size Engineering of Trap Effects in Oxidized and Hydroxylated ZnSe Quantum Dots.

Environmentally friendly blue-emitting ZnSe quantum dots (QDs) are in high demand for next-generation light-emitting devices. Yet, they suffer longstanding optical instability issues under aerobic conditions. Herein, we have demonstrated the existence of oxidization or hydroxylation on the QD surface when QDs are subjected to oxygen exposure, which potentially introduces highly localized in-gap states. Those states result in a dense number of surface-related, weak-intensity "dark" exciton states at the emission edge. Remarkably, there exists a critical diameter (Dc ≈ 8.5 nm) at which the deepest trap level reaches resonance with the highest occupied molecular orbital state. Beyond this critical diameter, the effects of those trap states are minimized, and the emission edge is dominated by high-intensity, bulk-to-bulk-like "bright" exciton states. The present work provides a novel strategy for designing highly stable QD emitters via size engineering, which are broadly applicable to other closely related QD systems.

Highly efficient near-infrared light-emitting diodes based on Zn:CuInSe2/ZnS//ZnS quantum dots with double shell engineering.

Near-infrared (NIR) quantum dot-based light-emitting diodes (QLEDs) developed rapidly in the fields of biomedical applications, telecommunications, sensing and diagnostics. However, it remains an enormous challenge for the synthesis of high-quality NIR QD materials with low toxicity or non-toxicity, high photoluminescence (PL) quantum yields (QYs) and high stability. Herein, we used a facile method to synthesize large-sized (8 nm) and thick-shell NIR Zn:CuInSe2/ZnS//ZnS QDs by engineering a double ZnS shell. The resulting NIR QDs exhibited high PL QYs of 80%, and excellent photochemical stability, which could be ascribed to the decreased lattice mismatch of the core/shell interface by the introduced Zn element into CuInSe2 cores and the energetic defect passivation of the double ZnS shell engineering. Furthermore, the high-quality Zn:CuInSe2/ZnS//ZnS QDs based LEDs exhibited the maximum external quantum efficiency (EQE) of 3.0%, 4.0% and 2.5% for PL peaks located at 705, 719 and 728 nm, respectively. This efficiency is comparable to that of the outstanding PbS- and InAs-based NIR QLEDs, as well as the avoidance of toxic heavymetal and/or hazardous reagents in this work. The synthesized high-quality Zn:CuInSe2/ZnS//ZnS QDs could be expected to promote the potential applications of heavy-metal-free QDs in the NIR fields.

Power management strategy for unidirectional current pulsed triboelectric nanogenerator.

Power management circuit (PMC) can efficiently store the output energy of pulsed triboelectric nanogenerator (Pulsed-TENG). Unidirectional current Pulsed-TENG (UP-TENG) has the advantage of without using rectifier bridge. However, the energy storage efficiency is limited for large capacitors at low capacitor voltage (<10 V). To solve this problem, PMC is optimized here. Firstly, rectifier diode is used to reduce the energy loss. Energy storage efficiency of PMC using rectifier diode (D-PMC) is higher than that of conventional PMC. Then, appropriate inductor is used to further form the optimized PMC (O-PMC), which reduces the energy loss of inductor. Results show that O-PMC using 100µH inductor has the highest energy storage efficiency. The actual test energy storage efficiency of O-PMC is 30.6%, which 3.4 times higher than that of D-PMC. Finally, an external capacitor is connected to electrodes of UP-TENG to form the EUP-TENG, which improves charging speed and output voltage of O-PMC. O-PMC using EUP-TENG can stably power calculator at low motion frequencies. O-PMC can be widely used in self-powered systems.

Bulk-like ZnSe Quantum Dots Enabling Efficient Ultranarrow Blue Light-Emitting Diodes.

Blue-emitting heavy-metal free QDs simultaneously exhibiting photoluminescence quantum yield close to unity and narrow emission line widths are essential for next-generation electroluminescence displays, yet their synthesis is highly challenging. Herein, we develop the synthesis of blue-emitting QDs by growing a thin shell of ZnS on ZnSe cores with their size larger than bulk Bohr diameter. The bulk-like size of ZnSe cores enables the emission to locate in the blue region with a narrow emission width close to its intrinsic peak width. The obtained bulk-like ZnSe/ZnS core/shell QDs display high quantum yield of 95% and extremely narrow emission width of ∼9.6 nm. Moreover, the bulk-like size of ZnSe cores reduces the energy level difference between QDs and adjacent layers in LEDs and improves charge transport. The LEDs fabricated with these high-quality QDs show bright pure blue emission with an external quantum efficiency of 12.2% and a relatively long operating lifetime.

Quantum dot light-emitting diodes with high efficiency at high brightness via shell engineering.

Quantum dot light-emitting diodes (QD-LEDs) have made great development in the performance. However, the efficiency droop at high brightness limits their applications in daylight displays and outdoor lightings. Herein, we systematically regulate the shell structure and composition, and the results indicate that CdSe-based QDs with ZnSe interlayer and thinner ZnSeS outermost layer as emitting layers (EML) enable high-performance QD-LEDs. Accordingly, the devices exhibit peak external quantum efficiency (EQE) of 22.9% with corresponding brightness of 67,840 cd/m2, and this efficiency can be still maintained > 90% of the maximum value even at 100,000 cd/m2, which satisfies the requirements for high-brightness display and lighting applications. This strong performance is mainly attributed to the ZnSe/ZnSeS graded shell that smooths the injection barrier between QD EML and the adjacent hole transport layers (HTL), and then improves the hole injection and charge injection balance, in particular at the high luminance and/or at high current density.

The water droplet with huge charge density excited by triboelectric nanogenerator for water sterilization.

Water is one of the most essential resources for the survival of human beings and all other living things. For the point of daily use, water sterilization has enormous social and economic significance, especially for remote and undeveloped areas. Here, we developed a self-powered water sterilization device, which consists of a rotating-disk freestanding triboelectric-layer mode triboelectric nanogenerator (RF-TENG), a voltage-multiplying circuit, and a water droplet control system. The output voltage of the RF-TENG is boosted by a voltage-multiplying circuit and then utilized to charge water droplet. When the rotation rate of the RF-TENG is 300 rpm, the output voltage of a six-fold voltage-multiplying circuit can reach 9319 V, and a 62.50µl water droplet can be positively charged to 6320 nC at the flow rate of 0.31 ml min-1. The charge density and electric filed of the water droplet can reach 101.12 nCµl-1and 11.28 kV cm-1, respectively. The charged water droplet can killE. coliandS. aureusquickly and efficiently through electroporation mechanism. With the advantages of low cost, simple in fabrication and usage, portability, and etc, the self-powered water sterilization device has wide application prospects in remote and undeveloped areas.

Improved thermal/chemical stability of flexible Ag NWs/Chitosan composite electrode integrated by chemical welding and sequential protection for better PV performance.

An integration strategy of chemical welding and subsequent protection was demonstrated to address silver nanowires (Ag NWs)-based issues. Preferentially, a halogenated salt of NaCl solution was used to stimulate the junction welding thus to reduce the junction resistance, by virtue of the autocatalytic redox of Ag atoms with halogen ions and dissolved oxygen molecules. Subsequently, chitosan, possessing the biocompatible, degradable, environmentally friendly non-toxic features, was embedded to protect Ag NWs. With these two steps, the composite electrode consisting Ag NWs and chitosan reaches a lowest sheet resistance of ∼8 Ω, with a transmittance over 80% at 550 nm, along with high thermal and chemical stabilities, accompanying with excellent flexibility. Besides, it also prompts a synergistic improvement when pioneered in Cu(In, Ga)Se2(CIGS) device as a transparent conductive electrode. It yields a power conversion efficiency of 6.6%, with 32% improvement relative to that bare Ag NWs, and 85% of the conventional one. Our findings present a new strategy for addressing instable/inefficient Ag NWs-based devices, driving their rapid development and its practical applications.

A robust all-inorganic hybrid energy harvester for synergistic energy collection from sunlight and raindrops.

As a new concept of the device, a hybrid energy harvester integrated with a water droplet triboelectric nanogenerator (WD-TENG) and a solar cell has been reported to convert raindrop energy and solar energy into electricity. However, organic triboelectric layers are usually utilized in previous studies that might be decomposed under long-term UV irradiation, resulting in degradation of the hybrid energy harvester. In this work, a fully inorganic hybrid energy harvester is demonstrated. Superhydrophobic SiO2 film is introduced to the system as both the triboelectric layer of the WD-TENG and the anti-reflective layer of the solar cell, which could increase the power conversion efficiency (PCE) of the solar cell from 15.17% to 15.71%. Meanwhile, WD-TENG with the SiO2 triboelectric layer could collect energies from rain droplets. This superhydrophobic SiO2 film could effectively reduce the dependence of the tilt angle for the WD-TENG and bring up self-cleaning performance for the hybrid energy harvester. Moreover, this fully inorganic architecture could enhance the stability of the hybrid energy harvester, making it a promising strategy in practical applications.

The recent progress of triboelectric nanogenerator-assisted photodetectors.

Since 2012, triboelectric nanogenerator (TENG) has attracted significant interest from researchers in the field of energy conversion due to its unique output characteristics of high voltage, pulse and low current. In addition, recent advancements have demonstrated that photodetection platforms based on TENG exhibit great advantages such as being simple, low-cost, portable, with high sensitivity, high response, etc, and are environment friendly. Here, this article provides a comprehensive review on the state-of-the-art photodetectors based on TENG in recent years, and a detailed introduction to the structural design and potential mechanisms. It mainly focuses on self-powered photodetectors (including photodetectors as a load resistance of a TENG and photosensitive materials such as tribo-layer of TENG) and the modulation of photodetectors based on TENG (including utilizing the voltage of TENG as well as triboelectric microplasma). Finally, we put forward some perspectives and outlook, including structure engineering and mechanism guidance, for the future development of simple, high-performance and portable photodetectors based on TENG.

Quantum dot light-emitting diodes with an Al-doped ZnO anode.

A study of hybrid ZnCdSeS/ZnS quantum dot light-emitting diodes (QLEDs) device fabricated with indium tin oxide-free transparent electrodes is presented. Al-doped zinc oxide (AZO) prepared by magnetron sputtering is adopted in anode transparent electrodes for green QLEDs with different sputtering pressures. A Kelvin probe force microscopy measurement showed that AZO has a work function of approximately 5.0 eV. The AZO/poly(ethylene-dioxythiophene)/polystyrenesulfonate (PEDOT:PSS) interface can be adjusted by the sputtering pressures, which was confirmed by hole-only devices. AZO films with low surface roughness can form a good AZO/PEDOT:PSS interface, which can increase the holes' injection, and result in an improved charge balance. The maximum current efficiency, luminance, and external quantum efficiency of the optimized QLED devices under a sputtering pressure of 1 mTorr can achieve values of 50.75 cd A-1, 102 500 cd m-2, and 12.94%, respectively.

AgNWs/AZO composite electrode for transparent inverted ZnCdSeS/ZnS quantum dot light-emitting diodes.

Fully transparent inverted quantum dot light-emitting diodes (QLEDs) were fabricated by incorporating a Ag-nanowire-based anode. Aluminum-doped zinc oxide (ZnO:Al, AZO) was inserted by atomic layer deposition and reduced the sheet resistance by promoting adhesion of Ag nanowires (AgNWs) film and increasing its chemical stability towards oxygen. The performance of the QLEDs was optimal when the thickness of AZO was 20 nm. The current efficiency of the fully transparent inverted QLEDs integrated with the AgNWs/AZO anode reached 15.33 cd A-1. The main peak wavelength and optical transmittance of the inverted QLEDs were 530 nm and 75.66%, respectively. This discovery is expected to provide a basic method for the production of flexible displays with full transparency by AgNWs-based electrodes.