Simultaneous structure and luminescence property control of barium carbonate nanocrystals through small amount of lanthanide doping

Rare earth doping has been widely applied in many functional nanomaterials with desirable properties and functions,which would have a significant effect on the growth process of the materials.However,the controlling strategy is limited into high concentration of lanthanide doping,which produces concentration quenching of the lanthanide ion luminescence with an increase in the Ln^(3+)concentration,resulting in lowering the fluorescence quantum yield of lanthanide ion.Herein,for the first time,we demonstrate simultaneous control of the structures and luminescence properties of BaCO_3nanocrystals via a small amount of Tb^(3+)doping strategy.In fact,Tb^(3+)would partially occupy Ba^(2+)sites,resulting in the changes to the structures of the BaCO_3nanocrystals,which is primarily determined by charge modulation,including the contributions from the surfaces of crystal nuclei and building blocks.These structurally modified nanocrystals exhibit tunable luminescence properties,thus emerging as potential candidates for photonic devices such as light-emitting diodes and color displays.

Prolonging charge-separation states by doping lanthanide-ions into {001}/{101} facets-coexposed TiO_(2) nanosheets for enhancing photocatalytic H_(2) evolution

Ultrathin TiO_(2)nanosheets with coexposed{001}/{101}facets have attracted considerable attention because of their high photocatalytic activity.However,the charge-separated states in the TiO_(2)nanosheets must be extended to further enhance their photocatalytic activity for H_(2)evolution.Herein,we present a successful attempt to selectively dope lanthanide ions into the{101}facets of ultrathin TiO_(2)nanosheets with coexposed{001}/{101}facets through a facile one-step solvothermal method.The lanthanide doping slightly extended the light-harvesting region and markedly improved the charge-separated states of the TiO_(2)nanosheets as evidenced by UV-vis absorption and steady-state/transient photoluminescence spectra.Upon simulated sunlight irradiation,we observed a 4.2-fold enhancement in the photocatalytic H_(2)evolution activity of optimal Yb^(3+)-doped TiO_(2)nanosheets compared to that of their undoped counterparts.Furthermore,when Pt nanoparticles were used as cocatalysts to reduce the H_(2)overpotential in this system,the photocatalytic activity enhancement factor increased to 8.5.By combining these results with those of control experiments,we confirmed that the extended charge-separated states play the main role in the enhancement of the photocatalytic H_(2)evolution activity of lanthanide-doped TiO_(2)nanosheets with coexposed{001}/{101}facets.

Fabrication and Characterization of Lanthanide-TiO2 Nanotube Composites

Titanium dioxide (TiO2) doped with neodymium (Nd) and/or Gadolinium (Gd) rare-earth elements were fabricated into nanotubes via the hydrothermal method in a KOH solution and in-situ doping. Titanium dioxide nanotubes (TNTs) and in-situ Nd-doped and/or Gd-doped TNTs were characterized with transmission and scanning electron microscopy, energy-dispersive X-ray analysis, X-ray diffraction, Raman spectroscopy, and Fourier-transform infrared spectroscopy. Morphologies indicated a network of aggregated nanotubes. The phase and composition analyses revealed that the lanthanide TNTs had anatase phases with Nd and/or Gd nanoparticles in the TNT lattice. The nanoparticles were uniformly deposited on the surface because of hydroxyl groups on the TNT surfaces, resulting in a very high loading density. The outer diameter and the length of the TNTs increased with doping. The mechanisms for the formation of multiwall TNTs are discussed.

Relationship between Crystal Structure and Luminescence Properties of (Y_(0.96-x)Ln_xCe_(0.04))_3Al_5O_(12) (Ln=Gd, La, Lu) Phosphors

The doping effects of La^3＋, Gd^3＋ and Lu^3＋ on the crystal structure and luminescence properties of （Yo96-x LnxCe0.04）3Al5O12（Ln = Gd, La, Lu） phosphors were studied. The X-ray diffraction patterns presented that with the inerease of the doping concentrations of La^3＋ and Gd^3＋ ions, the d-value of （Y0.96-xLnxCe0.04）3Al5O12 （Ln = Gd, La） inereased and the larger the doping ion, the stronger the effect would be. The doping amount causing phase transition in （Y0.96-xLnxCe0.04）3Al5O12 decreased with the inerease of the ionic radii of the doping lanthanide ions （La^3＋： 0.106 nm, Gd^3＋： 0. 094 nm, Lu^3＋ ： 0.083 nm）. The bigger doping ion of Gd^3＋ made the emission of （Y0.96-xGdxCe0.04）3Al5O12 move to red spectral region, but the smaller one of Lu^3＋ made it blue.

Photoluminescence and Ce^(3+)→Tb^(3+)→Eu^(3+) Energy Transfer Processes of the Ce^(3+)/Tb^(3+)/Eu^(3+)-doped β-NaYF_(4) Phosphors with Broadened Excitation Spectrum

Ce^(3+)/Tb^(3+) co-doped and Ce^(3+)/Tb^(3+)/Eu^(3+) tri-doped β-NaYF_(4) photoluminescent microcrystals using oleic acid as surfactant were synthesized using the solvothermal method.Their microstructural characteristics and photoluminescence properties were investigated in detail.They have the shape of hexagonal prism bipyramids with uniform particle size,which decreases with the concentrations of Tb^(3+) and Eu^(3+).The energy transfer processes of both the Ce^(3+)→Tb^(3+) and the Ce^(3+)→Tb^(3+)→Eu^(3+) were systematically studied.Compared with Eu^(3+) or Tb^(3+) single-doped β-NaYF_(4) microcrystals,the sensitization by Ce^(3+) for the photoluminescence of Tb^(3+) and Eu^(3+) leads to a broad excitation spectral bandwidth in the ultraviolet (UV) range.Meanwhile,the corresponding optical absorption efficiency is greatly enhanced.High energy transfer efficiencies have been observed from Ce^(3+) to Tb^(3+) and from Tb^(3+) to Eu^(3+).

Brightening heavily doped upconversion nanoparticles by tuning characteristics of core-shell structures

Heavily doped upconversion nanoparticles(UCNPs)potentially have exceptional photon upconversion abilities that are promising for diverse applications,such as lasing and super-resolution microscopy.However,heavily doped UCNPs typically can only offer mediocre upconversion luminescence intensity,and there still lacks general guidelines for the design and synthesis of heavily doped UCNPs.Herein,in order to boost the upconversion luminescence of heavily doped UCNPs,we studied the influence of characteristics of the core-shell structure on heavily doped UCNPs'upconversion luminescence.We find that some empirical guidelines derived from conventional UCNPs are not suitable for heavily doped UCNPs.Using NaYbF_(4):Tm@NaYF_(4) core-shell UCNPs with a high concentration of Yb_(3+)as a representative,our studies reveal that a rather thick inert NaYF4 shell is needed to protect the UCNPs from surface quenching,and the upconversion luminescence may undergo the cooperative sensitization process,which should be due to the highly concentrated Yb~(3+)dopant.In addition,the upconversion luminescence of heavily doped NaYbF4:Tm UCNPs exhibits no obvious dependence on the type of inert shell.Furthermore,our results show that confining both Yb~(3+)and Tm~(3+)dopants in a thin layer(known as theδ-doping strategy)does not work well in the heavily doped UCNPs.Accordingly,we propose a NaYbF_(4):Tm@NaYbF_(4)@NaYF_(4) core-shell-shell structure to enhance the luminescence of heavily doped UCNPs,by weakening the dissipation of excitation energy and strengthening the absorption.These findings should be helpful to establish general design principles for developing the brightest possible UCNPs that can meet the requirements of various applications.

(Sm/Eu/Tm)^(3+) doped tantalum semiconductor system for photovoltaic and electrochemical functionality amplification

This work reports the synthesis,characterization,and energy focused applications of the novel lanthanides co-doped tantalum pentoxide hetero-system(Sm^(3+)-Eu^(3+)-Tm^(3+):Ta_(2)O_(5)).Ln^(3+)-doped Ta_(2)O_(5) express excellent opto-electronic features reflected by the narrow band gap energy of 3.87 eV.Different vibrations confirm the presence of Ta-O-Ta and Ta-O bonds.The synthesized system possesses orthorhombic geometry with 59.46 nm particle size.With the smoother and compact morphology,the synthesized material succeeds in augmenting the performance of different systems aimed at energy applications.Fully ambient perovskite solar cell device fabricated with the Ln^(3+)-doped Ta_(2)O_(5) as an electron transport layer excels in achieving an efficiency and fill factor of 14.17% and 76% under artificial sun.This device was marked by the negligible hysteresis behavior showing profound photovoltaic performance.The electrochemical activity of the Ln^(3+)-doped Ta_(2)O_(5) decorated electrode was evaluated for electrical charge storage potential with pseudocapacitive behavior,With the highest specific capacitance of 355.39 F/g and quicker ionic diffusion rate,the designed electrode excels conventionally used materials.Electro-catalysis of water with Ln^(3+)-doped Ta_(2)O_(5) material indicates its capacity for H_(2) production with the lowest overpotential and Tafel slope values of 148 and 121.2 mV/dec,while the O_(2) generation is comparatively lower.With the stable electrochemical output,this rare earth modified material has the potential to replace conventionally used environmentally perilous and costly materials.