Multimode Luminescence with Temperature and Energy Level Synergistic Dependence in Rare Earth Halide DPs for Advanced Multifunctional Applications.

Rare-earth halide double perovskites (DPs) have attracted extensive attention due to their excellent optoelectronic performance. However, the correlation between luminescence performance, crystal structure, and temperature, as well as the inherent energy transfer mechanism, is not well understood. Herein, Lanthanide ions (Ln3+: Nd3+ or Dy3+) as the co-dopants are incorporated into Sb3+ doped Cs2NaYbCl6 DPs to construct energy transfer (ET) models to reveal the effects of temperature and energy levels of rare earth on luminescence and ET. The different excited state structures of Sb3+-Ln3+ doped Cs2NaYbCl6 DPs at different temperatures and relative positions of energy levels of rare earth synergistically determine the physical processes of luminescence. These multi-mode luminescent materials exhibit good performance in anti-counterfeiting, NIR imaging, and temperature sensing. This work provides new physical insights into the effects of temperature and energy levels of rare earth on the energy transfer mechanism and related photophysical process.

Excited State Regulated Emission in Hybrid Indium Halides via Crystal Structure Switch.

Organic-inorganic metal halides have become one of the most promising materials in the next generation of optoelectronic applications due to their high charge carrier mobility and tunable band gaps. In this study, Sb:PA6InCl9 and Sb:PA4NaInCl8 single crystals were prepared through evaporation crystallization, respectively. Due to the different degrees of lattice distortions, the highly efficient yellow emission in Sb:PA6InCl9 at 610 nm and the green emission in Sb:PA4NaInCl8 at 545 nm were achieved by regulation of the excited state, respectively. By introducing additional sodium ions in the post-treatment, we found that the zero-dimensional Sb:PA6InCl9 could rapidly convert into a two-dimensional layered structure of Sb:PA4NaInCl8, thus resulting in a novel green/yellow emission switch. This work guides the structural and performance control of organic-inorganic hybrid In-based metal halides and offers broad prospects for luminescent switching in anticounterfeiting applications.

Weakening Ligand-Liquid Affinity to Suppress the Desorption of Surface-Passivated Ligands from Perovskite Nanocrystals.

The interfacial migration of surface-bound ligands highly affects the colloidal stability and optical quality of semiconductor nanocrystals, of which the underlying mechanism is not fully understood. Herein, colloidal CsPbBr3 perovskite nanocrystals (PNCs) with fragile dynamic equilibrium of ligands are taken as the examples to reveal the important role of balancing ligand-solid/solvent affinity in suppressing the desorption of ligands. As a micellar surfactant, glycyrrhizic acid (GA) with bulky hydrophobic and hydrophilic groups exhibits a relatively smaller diffusion coefficient (∼440 µm2/s in methanol) and weaker ligand-liquid affinity than that of conventional alkyl amine and carboxy ligands. Consequently, hydrophilic GA-passivated PNCs (PNCs-GA) show excellent colloidal stability in various polar solvents with dielectric constant ranging from 2.2 to 32.6 and efficient photoluminescence with a quantum yield of 85.3%. Due to the suppressed desorption of GA, the morphological and optical properties of PNCs-GA are well maintained after five rounds purification and two months long-term storage. At last, hydrophilic PNCs-GA are successfully patterned through inkjet- and screen-printing technology. These findings offer deep insights into the interfacial chemistry of colloidal NCs and provide a universal strategy for preparing high-quality hydrophilic PNCs.

Component Engineering to Tailor the Structure and Optical Properties of Sb-Doped Indium-Based Halides.

Controlling the structure of halide perovskites through component engineering, and thus revealing the changes in luminescence properties caused by the conversion of crystal structure, is of great significance. Herein, we report a controllable synthetic strategy of three-dimensional (3D) Cs2KInCl6 and zero-dimensional (0D) (Cs/K)2InCl5(H2O) halide perovskites by changing the Cs/K feed ratio. 3D Cs2KInCl6 double perovskites are obtained at the Cs/K feed ratio of 1:1, while 0D (Cs/K)2InCl5(H2O) perovskites are formed at the Cs/K feed ratio of 2:1. Further, a reversible crystal structure transformation between 3D Cs2KInCl6 double perovskites and 0D (Cs/K)2InCl5(H2O) perovskites can be achieved by subsequent addition of metal-salt precursors. In addition, the emission efficiency of two perovskite structures can be greatly boosted by breaking the forbidden transition through Sb doping, and as a result, a novel green/yellow reversible emission switch is generated. Meanwhile, the relationship between perovskite structure and luminescence mechanism has been systematically revealed. These environmentally stable halide perovskites have great potential to be applied in optoelectronic devices.

Thermal and photo stability of all inorganic lead halide perovskite nanocrystals.

Inorganic lead halide perovskite (ILHP) nanocrystals (NCs) show great potential in solid state lighting and next generation display technology due to their excellent optical properties. However, almost all ILHP NCs are still facing the problem of unstable luminescence properties caused by heating and/or UV illumination. Further improving the thermal and photo stability of ILHP NCs has become the most urgent challenge for their practical application. This Perspective review specifically focuses on the thermal and photo stability of ILHP NCs, discusses and analyzes the factors that affect the thermal and photo stability of ILHP NCs from the perspective of surface ligands and structure composition, summarizes the current strategies to improve the thermal and photo stability of ILHP NCs, and presents the key challenges and perspectives on the research for the improvement of thermal and photo stability of ILHP NCs.

Surface polarons and optical micro-cavity modulated broad range multi-mode emission of Te-doped CdS nanowires.

The optical confinement and strong carrier coupling within a semiconductor nanostructure cavity are crucial for the modulation of emission properties. Fundamental understanding of the light-matter interaction in a low dimensional system is important. In this paper, we synthesized high-quality hexagonal Te-doped CdS nanowires by two-step chemical vapor deposition and investigated systematically the doping concentration, temperature, excitation power, excitation wavelength dependent Raman, photoluminescence and carrier lifetime decay. Scanning electron microscopy, energy dispersive x-ray spectrometry and x-ray diffraction confirmed Te-doping in the as-prepared samples. The strong surface optical (SO) phonon mode is observed in the micro-Raman spectra of an individual Te-CdS nanowire, which is unsuitable in large-sized structures. In situ micro-photoluminescence (µ-PL) characterization shows dominant confined defect state emission with whispering gallery mode (WGM) characteristics. The emission peak position shifts under increased excitation power, demonstrating the inelastic scattering by bound carriers. In addition, the short wavelength emission modes are dominant at a low temperature (80 K) while the long wavelength emission modes are dominant at a high temperature (300 K) due to different recombination processes contributing to the WGM resonant bands, which was also confirmed by the time-resolved PL measurement. All these results reflect strong coupling between the surface evanescent-wave in the WGM cavity and the SO phonon/polaron, which will facilitate the rational tailoring of surface/interface relevant properties for nanophotonic device applications.

Optically programmable encoder based on light propagation in two-dimensional regular nanoplates.

We design an efficient optically controlled microdevice based on CdSe nanoplates. Two-dimensional CdSe nanoplates exhibit lighting patterns around the edges and can be realized as a new type of optically controlled programmable encoder. The light source is used to excite the nanoplates and control the logical position under vertical pumping mode by the objective lens. At each excitation point in the nanoplates, the preferred light-propagation routes are along the normal direction and perpendicular to the edges, which then emit out from the edges to form a localized lighting section. The intensity distribution around the edges of different nanoplates demonstrates that the lighting part with a small scale is much stronger, defined as '1', than the dark section, defined as '0', along the edge. These '0' and '1' are the basic logic elements needed to compose logically functional devices. The observed propagation rules are consistent with theoretical simulations, meaning that the guided-light route in two-dimensional semiconductor nanoplates is regular and predictable. The same situation was also observed in regular CdS nanoplates. Basic theoretical analysis and experiments prove that the guided light and exit position follow rules mainly originating from the shape rather than material itself.

Aqueous synthesis of Cu-doped ZnCdS/ZnS core/shell nanocrystals with a new and highly reactive sulfur source.

A new sulfur precursor with a highly reactive chemical nature was prepared with S powder and NaBH4 at the high temperature of 180 °C in a closed autoclave and made it possible to carry out the synthesis of high quality metal sulfide nanocrystals (NCs) with diverse composition and structure. Using this new sulfur source, we demonstrated aqueous synthesis of colloidal Cu-doped ZnCdS NCs (d-dots) with pure, color-tunable photoluminescence (PL) in a wide spectral range (from 517 to 650 nm) based on the 'co-nucleation doping' strategy. The influences of the various experimental variables, including Cd/Zn ratio, Cu-doping concentration, pH value and amount of mercaptopropionic acid (MPA), on the optical properties of Cu-doped ZnCdS NCs were systematically investigated. Furthermore, highly efficient and stable dopant emission from Cu:ZnCdS/ZnS core/shell d-dots with PL quantum yield as high as 40% was achieved by the deposition of a ZnS shell around the bare Cu:ZnCdS cores; this is the highest reported to date for aqueous doped NCs. The optical properties and structure of the d-dots were characterized by UV-vis absorption spectra, PL spectra, x-ray photoelectron spectroscopy, powder x-ray diffraction, and transmission electron microscopy. The experimental results indicated that this facile synthesis route would provide a versatile approach for the preparation of other water-soluble sulfide NCs.

Efficient white light emitting diodes based on Cu-doped ZnInS/ZnS core/shell quantum dots.

We report the fabrication of efficient white light-emitting diodes (WLEDs) based on Cu : ZnInS/ZnS core/shell quantum dots (QDs) with super large Stokes shifts. The composition-controllable Cu : ZnInS/ZnS QDs with a tunable emission from deep red to green were prepared by a one-pot noninjection synthetic approach. The high performance Cu : ZnInS QD-WLEDs with the colour rendering index up to 96, luminous efficacy of 70-78 lm W(-1), and colour temperature of 3800-5760 K were successfully fabricated by integration of red and green Cu-doped QDs. Negligible energy transfer between Cu-doped QDs was clearly found by measuring the photoluminescence lifetimes of the QDs, consistent with the small spectral overlap between QD emission and absorption. The experimental results indicated low toxic Cu : ZnInS/ZnS QDs could be suitable for solid state lighting.

The luminescence modulation of rare earth-doped/containing lead-free double perovskites toward multifunctional applications: a review.

Lead-free double perovskites (DPs) with superior environmental stability and high defect tolerance have attracted considerable attention and exhibit great promise in photodetectors, solar cells, lighting devices, etc. However, achieving optical modulation and high photoluminescence quantum yield using this kind of material remains a challenge. Rare earth ions feature abundant energy levels and outstanding photophysical properties. Incorporating rare earth ions into lead-free DPs is an effective strategy to improve their optical performances, which have great effects on night-vision and light emitting diodes. Consequently, in this mini-review, we summarize the synthesis methods, optical properties, issues, and multifunctional applications of lead-free DPs described in recent years. The performances of DPs can be modulated via rare earth doping, which involves the extension of luminescence range, the improvement of PLQY, the realization of multi-mode excitation, and the regulation of luminescence color. We hope that this review will provide some insights into luminescence modulation and applications of lead-free DPs.

Temperature-Dependent Photoluminescence from Well-Resolved Excited State Structures in Rare-Earth-Based Double Perovskites.

Lead-free halide double perovskites (DPs) have become a research hotspot in the field of photoelectrons due to their unique optical properties and flexible compositional tuning. However, the reports on the optical properties of DPs primarily concentrate on the room temperature state and only exhibit single emission band. Here, we synthesized Cs2NaYCl6:Sb3+, Dy3+ DPs by a solvothermal method to realize white light emission with photoluminescence (PL) quantum yield as high as 70.7%. The energy-transfer process from self-trapped excitons (STEs) to Dy3+ ions was revealed by optical characterization and theoretical simulation calculations. Interestingly, we observed the double-emission from low-energy STE emission of Sb3+ ions and Dy3+ emission at low temperatures, and the double-emission is consistent with the asymmetric doublet feature of the 3P1 → 1S0 transition split into two minima. The PL spectra further showed that the fluorescence intensity ratios of Dy3+ ions at 580 and 680 nm were strongly temperature-dependent, and the relative sensitivity is up to 1.79% K-1 at 360 K. Moreover, the near-infrared and radiation luminescence properties indicated that the Cs2NaYCl6:Sb3+, Dy3+ DPs also have good prospects for night vision and radiation detection, as well as the great potential for applications in solid-state illumination and optical temperature measurement.

Alkaline surface treatment and time-resolved reading of mn-doped nanocrystal signal transducer for enhanced bioassay sensitivity.

Recently, Mn-doped semiconductor nanocrystals (NCs) with high brightness, long lifetimes, and low-energy excitation are emerging for time-resolved luminescence biosensing/imaging. Following our previous work on Mn-doped NCs, in this work we developed poly(styrene-co-maleic anhydride) (PSMA)-encapsulated Mn-doped AgZnInS/ZnS NCs as signal transducers for immunoassay of capsular polysaccharide (CPS), a surface antigen and also a biomarker of Burkholderia pseudomallei which causes a fatal disease called melioidosis. To enhance the assay sensitivity, a surface treatment for PSMA-encapsulated NCs (NC-probes) was performed to promote the presence of carboxyl groups that help conjugate more anti-CPS antibodies to the surface of NC-probes and thus enhance bioassay signals. Meanwhile, time-resolved reading on the luminescence of NC-probes was adopted to minimize the assay background autofluorescence. Both strategies essentially enhance the assay signal-to-background ratio (or equivalently the assay sensitivity) by increasing the signal and decreasing the background, respectively. Through performing and comparing immunoassays with different NC-probes (with and without surface treatment) and different signal reading methods (time-resolved reading and non-time-resolved reading), it was proven that the immunoassay adopting surface-treated NC-probes and time-resolved reading achieved a lower limit-of-detection (LOD) than the ones adopting non-surface-treated NC-probes or non-time-resolved reading. Moreover, the achieved LOD is comparable to the LOD of immunoassay using enzyme horseradish peroxidase as a signal transducer.

Effective Energy Transfer Boosts Emission of Rare-Earth Double Perovskites: The Bridge Role of Sb(III) Doping.

Halide perovskites have attracted considerable interest due to their excellent photoelectric properties. In this study, we synthesized Sb3+-doped Cs2NaTbCl6 using a solvothermal method to investigate its tunable photoelectric properties and low toxicity. Upon Sb3+ ion doping, the photoluminescence yield (PLQY) of Cs2NaTbCl6 significantly increased from ∼1.7 to ∼47%. The introduced Sb3+ ions with ns2 electronic configuration expanded the rare-earth element's absorption cross section, broke intrinsic forbidden transitions, and suppressed nonradiative recombination. Additionally, the codoping of Sb3+ and Mn2+ facilitated efficient energy transfer, resulting in highly efficient photoluminescence. The PLQY of 1%Sb3+,3%Mn2+:Cs2NaTbCl6 reached a remarkable 85.8%, marking the highest reported value for rare-earth double perovskites in the visible light region. This study highlights the vital role of Sb(III) doping as a bridging agent to enhance the emission in rare-earth double perovskites.

Temperature-Dependent Reversible Optical Properties of Mn-Based Organic-Inorganic Hybrid (C8H20N)2MnCl4 Metal Halides.

Organic-inorganic metal halides (OIMHs) have abundant optical properties and potential applications, such as light-emitting diodes, displays, solar cells, and photodetectors. Herein, we report zero-dimensional Mn-based OIMH (C8H20N)2MnCl4 single crystals synthesized by a simple slow evaporation method, which exhibit intense green emission at 520 nm originating from 4T1-6A1 transition of Mn2+ ions. Large organic cations in the crystal structure result in the isolated [MnCl4]2- tetrahedrons, and the closest Mn-Mn distance reaches 9.07 Å, which effectively inhibits the migration of excitation energy between adjacent Mn2+ emission centers, thus achieving a high quantum yield (∼87%) and a long photoluminescence (PL) lifetime (3.42 ms). The different optical and structural properties at low and high temperatures are revealed by temperature-dependent PL and X-ray diffraction spectra. The PL spectra and lifetimes under the heating and cooling processes indicate that the optical property transitions are reversible at 220/240 K. Our work provides a promising strategy for building multifunctional optoelectronic materials and insights into the understanding convertible photophysical properties from isomers of metal halides.

Photocatalytic CO2 Reduction Coupled with Oxidation of Benzyl Alcohol over CsPbBr3@PANI Nanocomposites.

Herein, we successfully prepare conductive polyaniline (PANI)-encapsulated CsPbBr3 perovskite nanocrystals (PNCs) that demonstrate much improved photocatalytic performance and stability toward the CO2 reduction reaction (CRR) coupled with oxidation of benzyl alcohol (BA) to benzaldehyde. Due to the acid-base interaction between CO2 and PANI, CO2 molecules are selectively adsorbed on PANI in the form of carbamate. As a result, the rate of production of CO (rCO) reaches 26.1 µmol g-1 h-1 with a selectivity of 98.1%, which is in good agreement with the rate of oxidation (∼27.0 µmol g-1 h-1) of BA. Such a high reduction/oxidation rate is enabled by the fast electron transfer (∼2.2 ps) from PNCs to PANI, as revealed by femtosecond transient absorption spectroscopy. Moreover, because of the benefit of the encapsulation of PANI, no significant decrease in rCO is observed in a 10 h CRR test. This work offers insight into how to simultaneously achieve improved photocatalytic performance and stability of CsPbX3 PNCs.

Facile synthesis of Mn-doped ZnS nanocrystals and determination of critical temperature for lattice diffusion process.

High-quality Mn:ZnS doped nanocrystals (d-dots) with photoluminescence (PL) quantum yield (QY) of 50-70% have been synthesized based on nucleation-doping strategy by choosing 1-dodecanethiol (DDT) as the capping ligand. Controlling the growth of small-sized MnS core nanoclusters was successfully achieved by changing the injection temperature of sulfur precursor, the growth time of MnS nuclei, and the amount of DDT. Furthermore, MnS/ZnS core/shell d-dots with a diffusion layer at the interface between the MnS core and the ZnS shell were fabricated through an overcoating of the ZnS shell layer on the presynthesized MnS core nanoclusters. The resulting monodisperse d-dots exhibited spherical shape with a zinc-blende crystal structure. The critical temperature for lattice diffusion of Mn ions in the ZnS host lattice was determined to be about 260 degrees C by annealing the presynthesized and purified Mn:ZnS d-dots.

Review of Mn-Doped Semiconductor Nanocrystals for Time-Resolved Luminescence Biosensing/Imaging.

Colloidal semiconductor nanocrystals (NCs) have been developed for decades and are widely applied in biosensing/imaging. However, their biosensing/imaging applications are mainly based on luminescence-intensity measurement, which suffers from autofluorescence in complex biological samples and thus limits the biosensing/imaging sensitivities. It is expected for these NCs to be further developed to gain luminescence features that can overcome sample autofluorescence. On the other hand, time-resolved luminescence measurement utilizing long-lived-luminescence probes is an efficient technique to eliminate short-lived autofluorescence of samples while recording time-resolved luminescence of the probes for signal measurement after pulsed excitation from a light source. Despite time-resolved measurement being very sensitive, the optical limitations of many of the current long-lived-luminescence probes cause time-resolved measurement to be generally performed in laboratories with bulky and costly instruments. In order to apply highly sensitive time-resolved measurement for in-field or point-of-care (POC) testing, it is essential to develop probes possessing high brightness, low-energy (visible-light) excitation, and long lifetimes of up to milliseconds. Such desired optical features can significantly simplify the design criteria of time-resolved measurement instruments and facilitate the development of low-cost, compact, sensitive instruments for in-field or POC testing. Mn-doped NCs have recently been in rapid development and provide a strategy to solve the challenges faced by both colloidal semiconductor NCs and time-resolved luminescence measurement. In this review, we outline the major achievements in the development of Mn-doped binary and multinary NCs, with emphasis on their synthesis approaches and luminescence mechanisms. Specifically, we demonstrate how researchers approached these obstacles to achieve the aforementioned desired optical properties on the basis of the progressive understanding of Mn emission mechanisms. Afterward, we review representative applications of Mn-doped NCs in time-resolved luminescence biosensing/imaging and present the potential of Mn-doped NCs in advancing time-resolved luminescence biosensing/imaging for in-field or POC testing.

Green Triplet Self-Trapped Exciton Emission in Layered Rb3Cd2Cl7:Sb3+ Perovskite: Comparison with RbCdCl3:Sb3.

Metal halide materials have recently sparked intense research because of their excellent photophysical properties and chemical stability. For example, RbCdCl3:Sb3+ exhibits broad emission at about 600 nm with a high photoluminescence quantum yield (PLQY) over 91% and double emission bands with bright white color. Herein, we obtained a novel Rb and Cd layered perovskite Rb3Cd2Cl7 doped with Sb3+, which gives luminescence at 525 nm with a large Stokes shift of 200 nm, originating from a self-trapped exciton (STE). Its PLQY is 57.47%, but its low-temperature PLQY becomes much higher at the same wavelength. When Rb3Cd2Cl7:Sb3+ and RbCdCl3:Sb3+ were compared, the two classes of quantum confinement effects by Rb and Cd ions in the lattice were identified to describe their electronic states and different optical properties. These results suggest that properties of Sb-doped cadmium halides could be modified by the structure type and local atomic confinement to find applications as promising luminescent materials for optoelectronic devices.

Tunable Green Light-Emitting CsPbBr3 Based Perovskite-Nanocrystals-in-Glass Flexible Film Enables Production of Stable Backlight Display.

Despite recent advances in producing perovskite-nanocrystals-in-glass (PNG) for display application, it remains challenging to achieve ultrapure and large-area CsPbBr3 PNG-based flexible films with tunable green emission. Herein, we report a facile strategy to produce flexible film containing CsPbBr3 PNG. Specifically, the achievement of CsPbBr3 PNG with tunable green emissions (517-528 nm) is realized by elaborate regulation of the glass precursor concentration and thermal treatment temperature by an in situ growth method. With the integration of red-light-emitting CsPbBrxI3-x PNG powder, the color gamut of as-prepared white-light-emitting sources can cover up to 126.27% of the NTSC 1953 standard and 93.9% of the Rec. 2020 standard. Notably, flexible and large-area white-light-emitting films can be readily obtained by sandwiching and gluing mixed PNG powders between two layers of hydrophobic and transparent PET films. Intriguingly, as-prepared PNG films exhibit excellent hydrothermal, photostability, and long-term operation stability, making them promising for practical ultrahigh-definition displays.

Highly efficient green InP-based quantum dot light-emitting diodes regulated by inner alloyed shell component.

InP-based quantum dot light-emitting diodes (QLEDs), as less toxic than Cd-free and Pb-free optoelectronic devices, have become the most promising benign alternatives for the next generation lighting and display. However, the development of green-emitting InP-based QLEDs still remains a great challenge to the environmental preparation of InP quantum dots (QDs) and superior device performance. Herein, we reported the highly efficient green-emitting InP-based QLEDs regulated by the inner alloyed shell components. Based on the environmental phosphorus tris(dimethylamino)phosphine ((DMA)3P), we obtained highly efficient InP-based QDs with the narrowest full width at half maximum (~35 nm) and highest quantum yield (~97%) by inserting the gradient inner shell layer ZnSexS1-x without further post-treatment. More importantly, we concretely discussed the effect and physical mechanism of ZnSexS1-x layer on the performance of QDs and QLEDs through the characterization of structure, luminescence, femtosecond transient absorption, and ultraviolet photoelectron spectroscopy. We demonstrated that the insert inner alloyed shell ZnSexS1-x provided bifunctionality, which diminished the interface defects upon balancing the lattice mismatch and tailored the energy levels of InP-based QDs which could promote the balanced carrier injection. The resulting QLEDs applying the InP/ZnSe0.7S0.3/ZnS QDs as an emitter layer exhibited a maximum external quantum efficiency of 15.2% with the electroluminescence peak of 532 nm, which was almost the highest record of InP-based pure green-emitting QLEDs. These results demonstrated the applicability and processability of inner shell component engineering in the preparation of high-quality InP-based QLEDs.