RESUMEN

Although organic-inorganic hybrid one-dimensional (1D) lead halide postperovskites (LHPPs) have been reported to show white luminescence and tunable photoluminescence quantum yield (PLQY), their structure-property relationships are not fully understood. Here, we used Mn2+ to test the doping effect on the luminescence of two 1D-LHPPs compounds, namely, {TETA[Pb2Br6]}n 1 and {TETA[Pb2Cl6]}n 2, where TETA = triethylenetetrammonium. We found the pristine compounds show yellowish (551 nm) and bluish (447 nm) emission for 1 and 2, respectively, nanosecond excitation lifetimes (4.17 ns for 1 and 2.29 ns for 2) and low PLQYs (4.65 and 3.57% for 1 and 2, respectively). By fine-doping the Mn2+ ions to ca. 8% the PLQYs for 1 and 2 are maximized to 24 and 25% for 1 and 2, respectively. Upon the increasing Mn2+ dopant, the emission wavelengths can also vary gradually from 551 to 615 nm and from 447 to 660 nm for 1 and 2, respectively, covering almost the whole visible-light range, and the excitation lifetimes are enhanced to microseconds (0.77 µs for 1 and 0.39 µs for 2), owing to the more spin-forbidden d-d transition (4T1-6A1) component from the Mn2+ ions present in the photoluminescence spectra. Moreover, these Mn2+-doped 1D-LHPPs demonstrate high structural and optical stability in humid and high-temperature environments. Hence, such doped materials can be fabricated into a UV-pumped white light-emitting diode, rendering the potential application for solid-state lighting and display systems.

RESUMEN

Here, this study reports single-band red upconversion emission in ß-Ba2ScAlO5: Yb3+/Er3+ phosphor by doping Mn2+. The optimum concentration of Mn2+ ions in ß-Ba2ScAlO5: Yb3+/Er3+ phosphor was 0.20. The intensity of red and green emissions is increased by 27.4 and 19.3 times, respectively. Compared with the samples without Mn2+ ions, the red-green integral strength ratio of ß-Ba2ScAlO5: Yb3+/Er3+/Mn2+ sample was significantly increased by 28.4 times, reaching 110.9. The UCL mechanism was explored by analyzing the down-conversion luminescence spectra, absorption spectra, UCL spectra, and upconversion fluorescence lifetime decay curves of Yb3+/Er3+/Mn2+ co-doped ß-Ba2ScAlO5. The enhancement of upconversion red light is achieved through energy transfer between defect bands and Er3+ ions, as well as energy transfer between Mn2+ ions and Er3+ ions. In addition, the Mn2+ doped ß-Ba2ScAlO5: Yb3+/Er3+ red UCL phosphors have great potential for ambient temperature sensing in the 298-523 K temperature range. The maximum sensitivity of ß-Ba2ScAlO5: Yb3+/Er3+/Mn2+ phosphor as a temperature sensor at 523 K is 0.0247 K-1.

RESUMEN

Typical layered transition-metal chalcogenide materials, especially MoS2, are gradually attracting widespread attention as aqueous Zn-ion battery (AZIB) cathode materials by virtue of their two-dimensional structure, tunable band gap, and abundant edges. The metastable phase 1T-MoS2 exhibits better electrical conductivity, electrochemical activity, and zinc storage capacity compared to the thermodynamically stable 2H-MoS2. However, 1T-MoS2 is still limited by the phase stability and layered structure destruction for AZIB application. Thus, a three-dimensional interconnected network heterostructure (Mn-MoS2/MXene) consisting of Mn2+-doped MoS2 and MXene with a high percentage of 1T phase (82.9%) was synthesized by hydrothermal methods and investigated as the cathode for AZIBs. It was found that S-Mn-S covalent bonds between MoS2 interlayers and Ti-O-Mo bonds at heterogeneous interfaces can act as "electron bridges" to facilitate electron and charge transfer. And the doping of Mn2+ and the combination of MXene not only expanded the interlayer spacing of MoS2 but also maintained the metastable structure of 1T-MoS2 nanosheets, acting to reduce the activation energy for Zn2+ intercalation and enhance specific capacity. The obtained Mn-MoS2/MXene contains more 1T-MoS2 and provides an improved specific capacity of 191.7 mAh g-1 at 0.1 A g-1. Compared with Mn-MoS2 and pure MoS2, it also exhibits enhanced cycling stability with a capacity retention of 80.3% after 500 cycles at 1 A g-1. Besides, the conductivity of Mn-MoS2/MXene is significantly improved, which induces a lower activation energy of the zinc ions during intercalation/deintercalation.

RESUMEN

Halide perovskite has been widely studied as a new generation of photoelectronic materials. However, their thermal and humidity-induced emission quenching have greatly limited their utility and reliability. Here, we report a hexagonal Mn2+ -doped CsCdCl3 perovskite crystal that possesses stable photoluminescence (PL) at both high temperature and humidity. The room temperature long-persistent luminescence (LPL) of the single crystals lasts up to 1480 s and can be adjusted by changing the concentration of Mn2+ ion doping. The characteristic emission of d-d transition of Mn2+ is realized, and the photoluminescence quantum yield (PLQY) is up to 91.4 %, it can maintain more than 90 % of the initial PL spectral integral area at 150 °C (423 K). High humid stability PL can be achieved more than 75 % of the initial PL intensity after 55 days of immersion in water. These excellent properties show the application prospect of the LPL material in lighting indication and anti-counterfeiting.

RESUMEN

Mn2+-doped semiconductor nanocrystals with tuned location and concentration of Mn2+ ions can yield diverse coupling regimes, which can highly influence their optical properties such as emission wavelength and photoluminescence (PL) lifetime. However, investigation on the relationship between the Mn2+ concentration and the optical properties is still challenging because of the complex interactions of Mn2+ ions and the host and between the Mn2+ ions. Here, atomically flat ZnS nanoplatelets (NPLs) with uniform thickness were chosen as matrixes for Mn2+ doping. Using time-resolved (TR) PL spectroscopy and density functional theory (DFT) calculations, a connection between coupling and PL kinetics of Mn2+ ions was established. Moreover, it is found that the Mn2+ ions residing on the surface of a nanostructure produce emissive states and interfere with the change of properties by Mn2+-Mn2+ coupling. In a configuration with suppressed surface contribution to the optical response, we show the underlying physical reasons for double and triple exponential decay by DFT methods. We believe that the presented doping strategy and simulation methodology of the Mn2+-doped ZnS (ZnS:Mn) system is a universal platform to study dopant location- and concentration-dependent properties also in other semiconductors.

RESUMEN

Doping Mn2+ into CsPbCl3 nanocrystals (NCs) yields strong orange emission, while the related emission in Mn2+ doped CsPbBr3 NCs is impaired seriously. This is mainly ascribed to back energy transfer from the Mn2+ dopant to the host. Doping Mn2+ into perovskites with multiple-quantum-well (MQW) structures may address this issue, where the energy funnels ensure a rapid energy transfer process, and thus resulting in a high photoluminescence quantum yield (PLQY). Here, we have developed an Ag+ assisted Mn2+ doping method in which Mn2+ can be easily doped into Br-based MQW perovskites. In this MQW perovskites, both nanoplatelets (NPLs) and NCs were formed simultaneously, where efficient energy transfer occurred from the NPLs with a higher energy bandgap to the NCs with a smaller energy bandgap, and then to the Mn2+ dopants. White lighting solution with a PLQY up to 98% has been acquired by altering the experimental parameters, such as reaction time and the Pb-to-Mn feed ratio. The successful doping of Mn2+ into CsPbBr3 host has great significance and shows promising application for next-generation white lighting.

RESUMEN

Lead halide perovskites hold promise for photovoltaics, lasers, and light-emitting diode (LED) applications, being known as light-harvesting or -emitting materials. Here we show that colloidal lead halide CsPbCl3 perovskite quantum dots (PQDs), when incorporating divalent manganese (Mn2+) ions, are able to produce spin-paired singlet oxygen molecules with over-unit quantum yield (∼1.08) in air conditions. Our mechanistic studies and atomic-level density functional theory calculations endorse an energy-migration-mediated quantum cutting process favoring multiple singlet oxygen generation (MSOG), in which one exciton-activated bulk Mn2+ ion (∼2.0 eV) inside the nanocrystal migrates its energy among the Mn2+ sublattice to two surface Mn2+ defect states (∼1.0 eV), followed by nonradiative energy transfers to two surrounding oxygen molecules. Moreover, superhydrophobicization of MSOG PQDs through silica-mediated polystyrene encapsulation prevents them from disintegrating in aqueous medium, enabling photodegradation of methyl orange at a rate even higher than that of the canonical titanium oxide photocatalyst. The observation of ultraefficient singlet oxygen generation in PQDs has implications for fields ranging from photodynamic therapy to photocatalytic applications.

RESUMEN

All-inorganic semiconductor perovskite quantum dots (QDs) with outstanding optoelectronic properties have already been extensively investigated and implemented in various applications. However, great challenges exist for the fabrication of nanodevices including toxicity, fast anion-exchange reactions, and unsatisfactory stability. Here, the ultrathin, core-shell structured SiO2 coated Mn2+ doped CsPbX3 (X = Br, Cl) QDs are prepared via one facile reverse microemulsion method at room temperature. By incorporation of a multibranched capping ligand of trioctylphosphine oxide, it is found that the breakage of the CsPbMnX3 core QDs contributed from the hydrolysis of silane could be effectively blocked. The thickness of silica shell can be well-controlled within 2 nm, which gives the CsPbMnX3 @SiO2 QDs a high quantum yield of 50.5% and improves thermostability and water resistance. Moreover, the mixture of CsPbBr3 QDs with green emission and CsPbMnX3 @SiO2 QDs with yellow emission presents no ion exchange effect and provides white light emission. As a result, a white light-emitting diode (LED) is successfully prepared by the combination of a blue on-chip LED device and the above perovskite mixture. The as-prepared white LED displays a high luminous efficiency of 68.4 lm W-1 and a high color-rendering index of Ra = 91, demonstrating their broad future applications in solid-state lighting fields.

RESUMEN

Photoelectrochemical (PEC) biosensing with semiconductor quantum dots (QDs) has received great attention because it integrates the advantages of both photo-excitation and electrochemical detection. During the photon-to-electricity conversion in PEC processes, electron-hole (charge) separation competes with electron-hole recombination, and the net effect essentially determines the performance of PEC biosensors. Herein, we propose a new approach for slowing down electron-hole recombination to increase charge separation efficiency for PEC biosensor development. Through doping with Mn(2+) , a pair of d bands ((4) T1 and (6) A1 ) is inserted between the conduction and valence bands of CdS QDs, which alters the electron-hole separation and recombination dynamics, allowing the generation of long-lived charge carriers with ms-scale lifetime that decay about 10(4) -10(5) -fold more slowly than in the case of undoped QDs. Photocurrent tests indicated that Mn(2+) doping resulted in an approximately 80 % increase in photocurrent generation compared with undoped CdS QDs. For application, the Mn-doped CdS QDs were coated on the surface of a glassy carbon electrode and functionalized with a cell surface carbohydrate-specific ligand (3-aminophenylboronic acid). In this way, a sensitive cytosensor for K562 leukemia cells was constructed. Moreover, the sugar-specific binding property of 3-aminophenylboronic acid allowed the electrode to serve as a switch for the capture and release of cells. This has been further explored with a view to developing a reusable PEC cytosensing platform.

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