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Functionalization of CDs leads to energy structure change and a HOMO level shift of up to 0.9 eV.

A comprehensive review on Hg chalcogenide colloidal quantum dot infrared photodetectors, with the essential progress of synthesis methods, property control, device engineering, focus plane array integration and innovative applications.

Close attention to the interfaces of solution-processed metal halide perovskite-based light-emitting devices (LEDs) is crucial for their optimal performance. Solution processing of these devices typically leads to the formation of van der Waals interfaces with a weak connection between different functional layers, leaving great room for improvement in charge transport through strengthening of the interlayer interaction. Here, we have realized a hydrogen-bond-assisted interface that makes use of ultrasmall amine-terminated carbon dots to enhance the interaction between the hole transport layer made of PEDOT:PSS and the hybrid lead bromide perovskite emitting layer, which not only promotes the hole injection efficiency but also orients the quasi-2D perovskite crystals penetrating the vertical direction of the device without any, or very few, horizontal grain boundaries, which has a profound effect on the photophysical and transport properties of the emitting layer. As a result, LEDs based on quasi-2D perovskites show up to 24.5% external quantum efficiency, 80 000 cd m

The Bi3+ and Te4+ co-doping strategy and in situ growth regulation via external oxygen vacancies were applied to Cs2AgInCl6 nanocrystals, resulting in a high photoluminescence quantum yield of 34%, as a consequence of restrained Ag/In vacancies.

A Purcell factor of 2.6, obtained by matching the emission wavelength of phosphor with the Mie scattering resonance of TiO2 nanoparticles, and small stokes shift improve the effective solar reflectance of fluorescent cooling coatings by up to ∼4%.

Hybrid methylammonium lead iodide (MAPbI

Lead-free perovskite quantum dots (QDs) have been widely investigated for optoelectronic devices because of their excellent electrical and optical properties. However, optoelectronic devices based on such lead-free perovskites still have much lower performance than those made of Pb-based counterparts. Herein, we developed a lead-free photodetector with an enhanced broadband spectral response ranging from 300 to 630 nm. By balancing plasmonic near-field enhancement and surface energy quenching through precisely controlling the thickness of Al2O3 spacer between the CsSnBr3 QDs and silver nanoparticle membrane, the photodetector with 5 nm thick Al2O3 experiences a maximum photocurrent enhancement of 6.5-fold at 410 nm, with a responsivity of 62.3 mA/W and detectivity of 4.27 × 1011 Jones. Moreover, its photocurrent shows a negligible decrease after 100 cycles of bending, which is ascribed to the tension-offset induced by the self-assembled nanoparticle membrane. The proposed plasmonic membrane enhancement provides a great potential for high-performance perovskite optoelectronic devices.

Metal halide perovskites are highly attractive for lighting applications, but the multiexcitonic emission processes in these crystals are largely unexplored. This study presents an investigation of Sb3+-doped Cs2ZrCl6 perovskite crystals that display double luminescence due to the intrinsic host self-trapped excitons (denoted as host STEs) and dopant-induced extrinsic self-trapped excitons (denoted as dopant STEs), respectively. Steady-state and transient-state spectroscopy reveal that the host and dopant STEs can be independently charged at specific energies. Density functional theory calculations confirm that the multiexcitonic emission stems from minimal interactions between the host and dopant STEs in the zero-dimensional crystal lattice. By selective excitation of different STEs through precise control of excitation wavelength, we further demonstrate dynamic color tuning in the Cs2ZrCl6:Sb3+ crystals. The color kinetic feature offers exciting opportunities for constructing multicolor light-emitting devices and encrypting multilevel optical codes.

Doping and compositional tuning of Cs(2)AInCl(6) (A = Ag, Na) double perovskite nanocrystals (PNCs) is considered a promising strategy toward the development of light-emitting sources for applications in solution-processed optoelectronic devices. Oleic acid and oleylamine are by far the most often used surface capping ligands for PNCs. However, the undesirable desorption of these ligands due to proton-exchange reaction during isolation and purification processing results in colloidal and structural instabilities. Thus, the improvement of colloidal and optical stability of PNCs represents one of the greatest challenges in the field. Here, we report a trioctylphosphine-mediated synthesis and purification method toward Sb-alloyed Cs2NaInCl6 PNCs with excellent stability and optical features. Nuclear magnetic resonance spectroscopy enabled one to explain the role of trioctylphosphine and to reveal the reaction mechanism during crystal nucleation and growth. Under the optimized reaction conditions, in situ-generated trioctylphosphonium chloride and benzoyl trioctylphosphonium chloride serve as highly reactive halide sources, while benzoyl trioctylphosphonium and oleylammonium cations together with the oleate anion serve as surface capping ligands, which are bound strongly to the PNC surface. The tightly bound ionic pair of oleylammonium oleate and benzoyl trioctylphosphonium chloride/oleate ligands allows one to obtain monodispersed bright-blue-emitting PNCs with high photoluminescence quantum yields exceeding 50% at an optimum Sb content (0.5%), which also exhibit long-term colloidal stability. The approach based on dual cationic ligand passivation of double PNCs opens the doors for applications in other systems with a potential to achieve higher stability along with superior optical properties. Web of Science 13 40 47859 47845

The co-doping of double perovskites is a useful approach in terms of improving their stability and photoluminescence quantum yield. Herein, Bi

It is important to reveal the luminescence mechanisms of carbon dots (CDs). Herein, CDs with two types of optical centers are synthesized from citric acid in formamide by a solvothermal method, and show high photoluminescence quantum yield reaching 42%. Their green/yellow emission exhibits pronounced vibrational structure and high resistance toward photobleaching, while broad red photoluminescence is sensitive to solvents, temperature, and UV-IR. Under UV-IR, the red emission is gradually bleached due to the photoinduced dehydration of the deprotonated surface of CDs in dimethyl sulfoxide, while this process is hindered in water. From the analysis of steady-state and time-resolved photoluminescence and transient absorption data together with density functional theory calculations, the green/ yellow emission is assigned to conjugated sp

Near-infrared persistent luminescent (or afterglow) nanoparticles with the biologically appropriate size are promising materials for background-free imaging applications, while the conventional batch synthesis hardly allows for reproducibility in controlling particle size because of the random variations of reaction parameters. Here, highly efficient chemistry was matched with an automated continuous flow approach for directly synthesizing differently sized ZnGa2O4:Cr3+ (ZGC) nanoparticles exhibiting long persistent luminescence. The key flow factors responsible for regulating the particle formation process, especially the high pressure-temperature and varied residence time, were investigated to be able to tune the particle size from 2 to 6 nm and to improve the persistent luminescence. Upon silica shell encapsulation of the nanoparticles accompanied by an annealing process, the persistent luminescence of the resulting particles was remarkably enhanced. High-fidelity automated flow chemistry demonstrated here offers an alternative for producing ZGC nanoparticles and will be helpful for other compositionally complex metal oxide nanoparticles.

Metal halide perovskites combine excellent electronic and optical properties, such as defect tolerance and high photoluminescence efficiency, with the benefits of low-cost, large-area, solution-based processing. Composition- and dimension-tunable properties of perovskites have already been utilized in bright and efficient light-emitting diodes (LEDs). At the same time, there are still great challenges ahead to achieving operational and spectral stability of these devices. In this review, the origins of instability of perovskite materials, and reasons for their degradation in LEDs are considered. Then, strategies for improving the stability of perovskite materials are reviewed, such as compositional engineering, dimensionality control, defect passivation, suitable encapsulation matrices, and fabrication of core/shell perovskite nanocrystals. For improvement of the operational stability of perovskite LEDs, the use of inorganic charge-transport layers, optimization of charge balance, and proper thermal management are considered. The review is concluded with a detailed account of the current challenges and a perspective on the key approaches and opportunities on how to reach the goal of stable, bright, and efficient perovskite LEDs.

Shell growth around nanocrystal cores is the most efficient way to passivate their surface in order to improve their stability and optical properties. Due to the different atomic arrangements and c...

Halide perovskite nanocrystals are a family of nanomaterials with a high prospect for use in light-emitting devices, lasers, and quantum optics, which makes their integration into photonic circuits...

Dissolution of intermediate sodium polysulfides (Na2Sx; 4≤x≤8) is a crucial obstacle for the development of room-temperature sodium-sulfur (Na-S) batteries. One promising strategy to avoid this issue is to load short-chain sulfur (S2-4), which could prohibit the generation of soluble polysulfides during the sodiation process. Herein, unlike in the previous reported cases where short-chain sulfur was stored by confinement within a small-pore-size (≤0.5 nm) carbon host, we report a new strategy to generate short-chain sulfur in larger pores (>0.5 nm) by the synergistic catalytic effect of CoS2 and appropriate pore size. Based on density functional theory calculations, we predict that CoS2 can serve as a catalyst to weaken the S-S bond in the S8 ring structure, facilitating the formation of short-chain sulfur molecules. By experimentally tuning the pore size of the CoS2-based hosts and comparing their performances as cathodes in Na-S and Li-S batteries, we conclude that such a catalytic effect depends on the proximity of sulfur to CoS2. This avoids the generation of soluble polysulfides and results in superior electrochemical properties of the composite materials introduced here for Na-S batteries. As a result, the optimized CoS2/N-doped carbon/S electrode showed excellent electrochemical performance with high reversible specific capacities of 488 mA h g-1 (962 mA h g(s)-1) after 100 cycles (0.1 A g-1) and 403 mA h g-1 after 1000 cycles (1 A g-1) with a superior rate performance (262 mA h g-1 at 5.0 A g-1).

We report the phase transfer in heavy-metal-free ZnSe nanorods (NRs) from hexagonal wurtzite (WZ) to cubic zinc-blende (ZB) phases. This phase transformation is mediated by Cu(I) ions under thermal...

Highly fluorescent carbon nanoparticles called carbon dots (CDs) have been the focus of intense research due to their simple chemical synthesis, nontoxic nature, and broad application potential including optoelectronics, photocatalysis, biomedicine, and energy-related technologies. Although a detailed elucidation of the mechanism of their photoluminescence (PL) remains an unmet challenge, the CDs exhibit robust, reproducible, and environment-sensitive PL signals, enabling us to monitor selected chemical phenomena including phase transitions or detection of ultralow concentrations of molecular species in solution. Herein, we report the PL turn-off/on behavior of aqueous CDs allowing the reversible monitoring of the water-ice phase transition. The bright PL attributable to molecular fluorophores present on the CD surface was quenched by changing the liquid aqueous environment to solid phase (ice). Based on light-induced electron paramagnetic resonance (LEPR) measurements and density functional theory (DFT) calculations, the proposed kinetic model assuming the presence of charge-separated trap states rationalized the observed sensitivity of PL lifetimes to the environment. Importantly, the PL quenching induced by freezing could be suppressed by adding a small amount of alcohols. This was attributed to a high tendency of alcohol to increase its concentration at the CD/solvent interface, as revealed by all-atom molecular dynamics simulations. Based on this behavior, a fluorescence "turn-on" alcohol sensor for exhaled breath condensate (EBC) analysis has been developed. This provided an easy method to detect alcohols among other common interferents in EBC with a low detection limit (100 ppm), which has a potential to become an inexpensive and noninvasive clinically useful diagnostic tool for early stage lung cancer screening.

Quasi-two-dimensional (quasi-2D) Ruddlesden–Popper (RP) perovskites such as BA2Csn–1PbnBr3n+1 (BA = butylammonium, n > 1) are promising emitters, but their electroluminescence performance is limited by a severe non-radiative recombination during the energy transfer process. Here, we make use of methanesulfonate (MeS) that can interact with the spacer BA cations via strong hydrogen bonding interaction to reconstruct the quasi-2D perovskite structure, which increases the energy acceptor-to-donor ratio and enhances the energy transfer in perovskite films, thus improving the light emission efficiency. MeS additives also lower the defect density in RP perovskites, which is due to the elimination of uncoordinated Pb2+ by the electron-rich Lewis base MeS and the weakened adsorbate blocking effect. As a result, green light-emitting diodes fabricated using these quasi-2D RP perovskite films reach current efficiency of 63 cd A−1 and 20.5% external quantum efficiency, which are the best reported performance for devices based on quasi-2D perovskites so far., Owing to large exciton binding energy, quasi-2D perovskite is promising for light-emitting application, yet inhomogeneous phases distribution limits the potential. Here, the authors improve the performance by using MeS additive to regulate the phase distribution and to reduce defect density in the films.

Lead–halide perovskite nanocrystals are an attractive class of materials since they can be easily fabricated, their optical properties can be tuned all over the visible spectral range, and they possess high emission quantum yields and narrow photoluminescence linewidths. Doping perovskites with lanthanides is one of the ways to widen the spectral range of their emission, making them attractive for further applications. Herein, we summarize the recent progress in the synthesis of ytterbium-doped perovskite nanocrystals in terms of the varying synthesis parameters such as temperature, ligand molar ratio, ytterbium precursor type, and dopant content. We further consider the dependence of morphology (size and ytterbium content) and optical parameters (photoluminescence quantum yield in visible and near-infrared spectral ranges) on the synthesis parameters. The developed open-source code approximates those dependencies as multiple-parameter linear regression and allows us to estimate the value of the photoluminescence quantum yield from the parameters of the perovskite synthesis. Further use and promotion of an open-source database will expand the possibilities of the developed code to predict the synthesis protocols for doped perovskite nanocrystals.

Solid-state color-saturated blue emitters are an essential part of light-emitting diodes (LEDs) and high-definition displays, and lead halide perovskite nanomaterials are one such type of emitter. ...

The optical properties of chemically synthesized carbon dots (CDs) can be widely tuned via doping and surface modification with heteroatoms such as nitrogen, which results in a range of potential applications. Herein, two most commonly used synthesis approaches, namely, solvothermal and microwave-assisted thermal treatments, have been used for the preparation of CDs from phloroglucinol using three different nitrogen containing solvents, namely, ethylenediamine, dimethylformamide, and formamide. Based on the analysis of the morphology and optical properties, we demonstrate the tenability of the CD appearance from amorphous or well-carbonized spherical particles to onion-like ones, which is controlled by solvent polarity, whereas the thermal treatment conditions mostly influence the degree of N-doping and the nature of emissive centers of CDs formed. The findings of this study expand the toolkit of the available CDs with variable morphology and energy structure.

Since chirality is one of the phenomena often occurring in nature, optically active chiral compounds are important for applications in the fields of biology, pharmacology, and medicine. With this in mind, chiral carbon dots (CDs), which are eco-friendly and easy-to-obtain light-emissive nanoparticles, offer great potential for sensing, bioimaging, enantioselective synthesis, and development of emitters of circularly polarized light. Herein, chiral CDs have been produced via two synthetic approaches using a chiral amino acid precursor L/D-cysteine: (i) surface modification treatment of achiral CDs at room temperature and (ii) one-pot carbonization in the presence of chiral precursor. The chiral signal in the absorption spectra of synthesized CDs originates not only from the chiral precursor but from the optical transitions attributed to the core and surface states of CDs. The use of chiral amino acid molecules in the CD synthesis through carbonization results in a substantial (up to 8 times) increase in their emission quantum yield. Moreover, the synthesized CDs show two-photon absorption which is an attractive feature for their potential bioimaging and sensing applications.

Size- and shape-tunable colloidal semiconductor nanocrystals are among the most promising materials for photoelectrochemical water splitting. However, in-depth insights into dimension-dependent charge carrier separation and transport for colloidal semiconductor NCs are still lacking in the contemporary literature. Herein, we experimentally compared photoelectrochemical performance of heavy-metal-free ZnSe nanodots and nanorods with the same cubic structure (zinc blende), similar volumes, and similar absorption edge positions and performed density functional theory (DFT) calculations to study the correlation between the dimension and the electronic structures of ZnSe dots and rods. To eliminate the influence of the different deposition amount of NRs and NDs on each phtoanode, we quantified an average photocurrent density contribution of each single ZnSe dot and rod to be 5 × 10

We introduce a hierarchical nanostructure of CoS2/N-doped carbon@MoS2 comprising two transition-metal sulfides CoS2 and MoS2, with enhanced sodium storage performance in sodium-ion batteries. A micron-sized Co metal-organic framework (MOF) is transformed into a CoS2/N-doped carbon composite, followed by a solvothermal growth of MoS2 nanosheets on the surface. The resulting composite material offers several specific advantages for sodium storage: (i) accelerated sodium-ion diffusion kinetics due to its heterogeneous interface; (ii) shortened ion diffusion path and exposed active sites for sodium storage due to its hierarchical nanosheet architecture; and (iii) homogeneous nitrogen doping of the MOF-derived carbon, which is beneficial for electronic conductivity. Due to these merits, this composite exhibits excellent electrochemical performance with a specific capacity of 596 mAh g-1 after 100 cycles at 0.1 A g-1 and 395 mAh g-1 at 5.0 A g-1.

Carbon dots are luminescent carbonaceous nanoparticles that can be endowed with chiral properties, making them particularly interesting for biomedical applications due to their low cytotoxicity and facile synthesis. In recent years, synthetic efforts leading to chiral carbon dots with other attractive optical properties such as two-photon absorption and circularly polarized light emission have flourished. We start this review by introducing examples of molecular chirality and its origins and providing a summary of chiroptical spectroscopy used for its characterization. Then approaches used to induce chirality in nanomaterials are reviewed. In the main part of this review we focus on chiral carbon dots, introducing their fabrication techniques such as bottom-up and top-down chemical syntheses, their morphology, and optical/chiroptical properties. We then consider emerging applications of chiral carbon dots in sensing, bioimaging, and catalysis, and conclude this review with a summary and future challenges.

Relatively weak red photoluminescence of carbon dots (CDots) is a major challenge on the way to their successful implementation in biological and optoelectronic devices. We present a theoretical analysis of the interaction among the surface emission centers of CDots, showing that it may determine efficiency of the red photoluminescence of CDots. Based on the previous experimental studies, it is assumed that the optical response of the CDots is determined by the molecule-like subunits of polycyclic aromatic hydrocarbons (PAHs) attached to the CDots' surface. Three characteristic types of coupling of these PAH subunits are considered: non-interacting monomers, noncovalently bound dimers, and covalently bound dimers with two, three, or four carbon linkers. We demonstrate that the CDots' photoluminescence broadens, redshifts, and weakens by 2 orders of magnitude when the free monomers are substituted by the covalently bridged centers. These and other results of our study show that the realization of CDots with many weakly interacting surface emission centers may constitute an efficient way to achieve their efficient red photoluminescence, which is highly desirable for biological and optoelectronic applications.