- NSF-PAR ID:
- Date Published:
- Journal Name:
- Journal of Materials Chemistry C
- Page Range / eLocation ID:
- 7285 to 7294
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
Fluorides are promising host materials for optical applications. This paper reports the photoluminescent (PL) and cathodoluminescent (CL) characteristics of barium hexafluorogermanate BaGeF 6 nanowires codoped with Ce 3+ , Tb 3+ and Sm 3+ rare earth ions, produced by a solvothermal route. The synthesized BaGeF 6 nanowires exhibit uniform morphology and size distribution. X-ray diffraction divulges the one-dimensional growth of crystalline BaGeF 6 structure, with the absence of any impurity phases. Visible luminescence is recorded from the nanowires in green and red regions, when the nanowires are codoped with Ce 3+ /Tb 3+ , and Ce 3+ /Tb 3+ /Sm 3+ , respectively, under a UV excitation source. The PL emission from the codoped BaGeF 6 nanowires, when excited by a 254 nm source, originates from the efficient energy transfer bridges between Ce 3+ , Tb 3+ and Sm 3+ ions. The decay time of the visible luminescent emission from the nanowires is in the order of subnanoseconds, being one of the shortest decay time records from inorganic scintillators. The CL emission from the BaGeF 6 nanowires in the tunable visible range reveals their potential use for the detection of high-energy radiation. The PL emissions are sensitive to H 2 O 2 at low concentrations, enabling their high-sensitivity detection of H 2 O 2 using BaGeF 6 nanowires. A comparison with BaSiF 6 nanowires is made in terms of decay time and its sensitivity towards H 2 O 2 .more » « less
null (Ed.)Development of new host materials containing heavy elements for radiation detection is highly desirable. In this work, dibarium octafluorohafnate, Ba 2 HfF 8 , doped with rare-earth ions, was synthesized as cube-shaped nanocrystals via a facile hydrothermal method. The host lattice contains two Ba 2+ crystallographic sites, and dopants on these sites exhibit site-dependent photoluminescence (PL), cathodoluminescence (CL) and X-ray excited radioluminescence (RL) characteristics. Single doping contents were optimized as 25 mol% Tb 3+ and 5 mol% Eu 3+ . In Ba 2 HfF 8 :Tb 3+ –Eu 3+ codoped nanocrystals, preferrable occupation of Eu 3+ and Tb 3+ at two different Ba 2+ sites in the host lattice was observed. The nanocubes exhibited enhanced emissions over micron sized particles. In PL, the presence of Tb 3+ ions significantly enhanced the emission intensity of Eu 3+ ions due to energy transfer from the Tb 3+ to Eu 3+ ions, while under high-energy irradiation in CL or RL, Tb 3+ emission was intensified. X-ray induced RL with afterglow in seconds was observed. It was found that the codoped sample showed higher sensitivity than the singly doped sample, indicating that codoping is an effective strategy to develop a scintillator with this host structure for high-energy radiation detection.more » « less
Compared to halides Cs2HfX6(X = Cl, Br, I) with a vacancy‐ordered cubic double perovskite structure, the halide Cs2HfF6(CHF), with a hexagonal Bravais lattice, possesses a higher mass density and chemical stability for radiation detection. Luminescence properties and energy transfer mechanisms of rare‐earths‐doped CHF materials are studied here. The structure of CHF is identified as a new type of vacancy‐ordered hexagonal perovskite, with the same type of building blocks of the double perovskite but stacked with single layers. Density‐functional theory calculations reveal a large bandgap of CHF. A broad emission is observed from the pristine CHF host, which is suggested to be associated with self‐trapped excitons (STEs). A series of rare‐earths‐doped materials are designed utilizing the STE emissions, and efficient energy transfers from STEs and Tb3+to Eu3+are achieved for tunable emissions. The codoped material shows stable emission under X‐ray irradiation, with 10.2% reduction from its initial emission intensity, associated with possible structural evolution by radiation‐induced deformation of the soft host. The radiation responses of singly and codoped materials are evaluated, and the codoped material is found to be more sensitive to the radiation energy than the singly doped or pristine CHF for radiation detection.
Unveiling the underlying mechanisms of properties of functional materials, including the luminescence differences among similar pyrochlores A2B2O7, opens new gateways to select proper hosts for various optoelectronic applications by scientists and engineers. For example, although La2Zr2O7(LZO) and La2Hf2O7(LHO) pyrochlores have similar chemical compositional and crystallographic structural features, they demonstrate different luminescence properties both before and after doped with Eu3+ions. Based on our earlier work, LHO‐based nanophosphors display higher photo‐ and radioluminescence intensity, higher quantum efficiency, and longer excited state lifetime compared to LZO‐based nanophosphors. Moreover, under electronic O2−→Zr4+/Hf4+transition excitation at 306 nm, undoped LHO nanoparticles (NPs) have only violet blue emission, whereas LZO NPs show violet blue and red emissions. In this study, we have combined experimental and density functional theory (DFT) based theoretical calculation to explain the observed results. First, we calculated the density of state (DOS) based on DFT and studied the energetics of ionized oxygen vacancies in the band gaps of LZO and LHO theoretically, which explain their underlying luminescence difference. For Eu3+‐doped NPs, we performed emission intensity and lifetime calculations and found that the LHOE NPs have higher host to dopant energy transfer efficiency than the LZOE NPs (59.3% vs 24.6%), which accounts for the optical performance superiority of the former over the latter. Moreover, by corroborating our experimental data with the DFT calculations, we suggest that the Eu3+doping states in LHO present at exact energy position (both in majority and minority spin components) where oxygen defect states are located unlike those in LZO. Lastly, both the NPs show negligible photobleaching highlighting their potential for bioimaging applications. This current report provides a deeper understanding of the advantages of LHO over LZO as an advanced host for phosphors, scintillators, and fluoroimmunoassays.
null (Ed.)Controlled energy transfer has been found to be one of the most effective ways of designing tunable and white photoluminescent phosphors. Utilizing host emission to achieve the same would lead to a new dimension in the design strategy for novel luminescent materials in solid state lighting and display devices. In this work, we have achieved controlled energy transfer by suppressing the host to dopant energy transfer in La 2 Hf 2 O 7 :Eu 3+ nanoparticles (NPs) by co-doping with uranium ions. Uranium acts as a barrier between the oxygen vacancies of the La 2 Hf 2 O 7 host and Eu 3+ doping ions to increase their separation and reduce the non-radiative energy transfer between them. Density functional theory (DFT) calculations of defect formation energy showed that the Eu 3+ dopant occupies the La 3+ site and the uranium ion occupies the Hf 4+ site. Co-doping the La 2 Hf 2 O 7 :Eu 3+ NPs with uranium ions creates negatively charged lanthanum and hafnium vacancies making the system highly electron rich. Formation of cation vacancies is expected to compensate the excess charge in the U and Eu co-doped La 2 Hf 2 O 7 NPs suppressing the formation of oxygen vacancies. This work shows how one can utilize the full color gamut in the La 2 Hf 2 O 7 :Eu 3+ ,U 6+ NPs with blue, green and red emissions from the host, uranium and europium, respectively, to produce near perfect white light emission.more » « less