Enhancement of NIR emission varying thulium of ZrO2:2Yb3+-xTm3+ nanoparticles by sonochemical method

A. Herrera-Rodríguez, T. López-Luke, G. Ramírez-García, Andrea Ceja-Fdez, Salvador Barrientos, Víctor Hugo Romero Arellano, J. Zárate-Medina
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Abstract

In this research, Yb3+ -Tm3+ co-doped ZrO2 nanoparticles (ZrO2:2Yb3+ -xTm3+; x=0.0125, 0.025, 0.05, 0.1, and 0.2 mol%) were synthesized using ethylenediamine and Pluronic F-127® as precipitating and surfactant agents, respectively, through a sonochemical method assisted by hydrothermal treatment and subsequent annealing as an innovative, simple, and fast route. Structural, morphological, and chemical characterization was determined by XRD, SEM, and FT-IR. The photoluminescent characterization was performed using a spectrometer with an excitation wavelength of 975 nm. The SEM technique confirms the formation of spherical and semispherical nanoparticles dispersed of sizes less than 110 nm. Furthermore, XRD results proved that the solids have monoclinic and tetragonal crystalline structure for undoped ZrO2 and the tetragonal phase was stabilized with Yb3+ -Tm3+ co-doped ZrO2. At the same time, FT-IR spectroscopy showed the functional groups corresponding to –OH residual, C-H, and C=C bonds due to surfactant agent remand and metallic oxide bonding of Zr-O, corresponding to the tetragonal crystal structure, principally. On the other hand, photoluminescent characterization exhibited upconversion (UC) emissions at 488, 656, and 800 nm due to 1G4→3H6, 1G4→3F4, and 3H4→3H6 transitions of Tm3+, respectively. These emissions increase in intensity due to the increment of Tm3+ concentration until 0.1mol%; lower and higher to this concentration, the photoluminescent intensity decrease. ZrO2:2Yb3+ -0.1Tm3+ nanoparticles showed the highest enhancement (144%) at 800 nm concerning the ZrO2:2Yb3+ -0.0125Tm3+ sample.
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声化学法增强ZrO2:2Yb3+-xTm3+纳米粒子的近红外发射
在本研究中,Yb3+ -Tm3+共掺杂ZrO2纳米粒子(ZrO2: 2yb3 + -xTm3+;x=0.0125, 0.025, 0.05, 0.1和0.2 mol%)分别以乙二胺和Pluronic F-127®为沉淀剂和表面活性剂,通过声化学方法辅助水热处理和随后的退火合成,这是一种创新,简单,快速的途径。通过XRD, SEM和FT-IR对其进行了结构,形态和化学表征。利用激发波长为975 nm的光谱仪进行光致发光表征。扫描电镜技术证实了球形和半球形纳米颗粒的形成,分散尺寸小于110 nm。此外,XRD结果表明,未掺杂ZrO2的固体具有单斜晶和四方晶结构,Yb3+ -Tm3+共掺杂ZrO2后,四方晶相稳定。同时,FT-IR光谱显示了表面活性剂残馀形成的-OH残馀、C- h、C=C键和Zr-O的金属氧化物成键所对应的官能团,主要为正方晶体结构。另一方面,由于Tm3+的1G4→3H6、1G4→3F4和3H4→3H6跃迁,Tm3+在488、656和800 nm处表现出上转换(UC)发射。当Tm3+浓度达到0.1mol%时,排放强度随浓度的增加而增加;该浓度越低,光致发光强度越低。ZrO2:2Yb3+ -0.0125Tm3+样品在800 nm处的增强幅度最大(144%)。
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