Effect of silica coating on the structural and luminescent properties of Sm3+/Yb3+ or Tm3+/Yb3+ co-doped TiO2 nanoparticles

The luminescent characteristics of spherical titanium dioxide (TiO₂) nanoparticles (NP's) doped with Sm³⁺/Yb³⁺ and Tm³⁺/Yb³⁺ with and without a silica coating were analyzed. These nanoparticles were synthesized using the spray pyrolysis technique and coated with silica through a wet chemical process. The Sm³⁺/Tm³⁺ and Yb³⁺ doping induces a triphasic poly-crystalline structure of rutile and anatase TiO₂ and a Sm₂Ti₂O₇/Tm₂Ti₂O₇ cubic phase. A Williamson-Hall analysis was used to monitor the tensions of the NP's crystallites at the various doping concentrations and with addition of the silica shell. The luminescent spectra presented the characteristic emission peaks for the electronic energy levels transitions of the Sm³⁺/Tm³⁺ and Yb³⁺ ions. The Sm³⁺/Yb³⁺ co-doped NP's showed a maximum emission peak in the visible region at 612 nm, associated with ⁴G_5/2 → ⁶H_7/2 transitions of the Sm³⁺ ions. The IR emission peak at 973 nm (²F_5/2 → ²F_7/2) pertaining to Yb³⁺. For the combination of Tm³⁺/Yb³⁺, two emissions associated with Tm³⁺ ions were observed at 440 nm (¹D₂ → ³F₄) and 806 nm (³H₄ → ³H₆). The emission at 973 nm (²F_5/2 → ²F_7/2) is correlated to the Yb³⁺ ions. Silica coating of the NP's resulted in luminescence emission intensity increase of about 4 times.     

Effect of crystalline fraction on upconversion luminescence in Er3+/Yb3+ Co-doped NaYF4 oxyfluoride glass-ceramics

The crystalline fraction were adjusted MgO concentration and the corresponding effect on upconversion (UC) luminescence in Er³⁺/Yb³⁺ co-doped NaYF₄ oxyfluorode glass-ceramics was investigated. With increase of MgO and the content of Na₂O reduced, the internal network structure of the glass became compact, which made the size of NaYF₄ nanocrystals unchanged, while the average distance between the nanocrystals increased significantly. Crystal growth is limited with the glass network, keeping the crystal size not changed. SNM-1 glass ceramics samples show a predominant red up-conversion emission under near infrared excitation at 980 nm, while a predominant green emission is observed in the SNM-3 samples. In this paper, it was indicated that it changed the effect of glass network modifier MgO in the glass structure. The possible mechanism responsible for the color variation of UC in Er³⁺/Yb³⁺ co-doped was discussed.     

Tb3+/Yb3+ co-doped Y2O3 upconversion transparent ceramics: Fabrication and characterization for IR excited green emission

Tb³⁺/Yb³⁺ co-doped Y₂O₃ transparent ceramics were fabricated by vacuum sintering of the pellets (prepared from nanopowders by uniaxial pressing) at 1750 °C for 5 h. Zr⁴⁺ and La³⁺ ions were incorporated in Tb³⁺/Yb³⁺ co-doped Y₂O₃ nanoparticle to reduce the formation of pores which limits the transparency of ceramic. An optical transmittance of ∼80% was achieved in ∼450 to 2000 nm range for 1 mm thick pellet which is very close to the theoretical value by taking account of Fresnel’s correction. High intensity luminescence peak at 543 nm (green) was observed in these transparent ceramics under 976 and 929 nm excitations due to Yb–Tb energy transfer upconversion.     

Tm~(3+)/Yb~(3+)共掺氟氧玻璃的光谱性质

制备了Tm3+/Yb3+共掺杂的20GaF3-15InF3-17CdF2-15ZnF2-10SnF2-3P2O5-(20-x-y)PbF2-xTmF3-yYbF3(x=0.2～2,y=1～4)系列玻璃。室温下,通过其吸收光谱,运用Judd-Ofelt理论计算了样品的强度参量Ωt(t=2,4,6)、自发辐射几率、荧光分支比和荧光寿命等光谱参数。研究发现,增加Tm3+掺入量对Ω2影响不大,Ω4、Ω6的值有增大的趋势。在980nm激发下的荧光光谱中,观察到5个上转换发射峰,其中发光较强的464nm的蓝光是三光子过程,650nm的红光和800nm的红外光是双光子过程,并讨论了其上转换发光机理和Tm3+、Yb3+掺杂浓度对发光强度的影响。     

Phase evolution in Bi2O3:Yb3+/Er3+ nanoparticles with nearly single-band red upconversion luminescence

Bi₂O₃:Yb³⁺/Er³⁺ nanoparticles with flower-like morphology were easily synthesized by urea-assisted coprecipitation reactions. The influences of calcination temperature and doping concentration on the crystal phase structures of Bi₂O₃ and Bi₂O₃:x%Yb³⁺/2%Er³⁺ (x = 0–30) were systematically investigated by XRD analysis. The experimental results revealed that lanthanide doping could effectively improve the thermal stability of Bi₂O₂CO₃ samples, and the monoclinic-to-tetragonal-to-cubic phase transitions of Bi₂O₃ were implemented by controlling calcination temperatures and introducing smaller lanthanide ions (Ln³⁺) into the host lattices. Based on the analysis of TG and DSC curves, we found that the fundamental reason for this phase transition was the different stabilities of each crystalline phase under different doping conditions. Upon 980 nm laser excitation, Bi₂O₃:x%Yb³⁺/2%Er³⁺ samples presented near single-band red upconversion emission owing to the efficient energy reabsorption of the Bi₂O₃ host to Er³⁺ emission.     

Visible green upconversion luminescence of Er3+/Yb3+/Li+ co-doped CaWO4 particles

The upconversion (UC) luminescence of Li⁺/Er³⁺/Yb³⁺ co-doped CaWO₄ phosphors is investigated in detail. Single crystallized CaWO₄:Li⁺/Er³⁺/Yb³⁺ phosphor can be obtained, co-doped up to 25.0/5.0/20.0 mol% (Li⁺/Er³⁺/Yb³⁺) by solid-state reaction. Under 980 nm excitation, CaWO₄:Li⁺/Er³⁺/Yb³⁺ phosphor exhibited strong green UC emissions visible to the naked eye at 530 and 550 nm induced by the intra-4f transitions of Er³⁺ (²H_11/2,⁴S_3/2→⁴I_15/2). The optimum doping concentrations of Yb³⁺/Li⁺ for the highest UC luminescence were verified to be 10/15 mol%, and a possible UC mechanism that depends on the pumping power is discussed in detail.     

基于Er3+/Yb3+掺杂的上转换玻璃陶瓷材料的制备和性能

采用熔融-晶化法在ZnO-Al2 O3-SiO2系玻璃陶瓷的基础上,用GeO2取代部分SiO2成功制备出Er3+/Yb3+共掺ZnO-Al2 O3-GeO2-SiO2系玻璃陶瓷,并通过对样品的硬度及上转换荧光测试分析确定了GeO2的最佳取代量为7.5wt％.研究发现在980 nm波长光的激发下,样品产生了绿色(524 nm、546 nm)和红色(659 nm)上转换发光,且当Er3+/Yb3+掺杂比为2.5:6.5时样品上转换荧光强度最强.     

Power dependent upconversion in Er3+/Yb3+ co-doped BiNbO4 phosphors

In the present article, optical properties and energy upconversion in Er³⁺/Yb³⁺ co-doped BiNbO₄ matrix were investigated. The BiNbO₄ matrix was prepared using the solid-state reaction method. X-ray diffraction of the matrix shows that the crystal structure is consistent with ICSD code 74338. The grain distribution and the behavior of doping with Er³⁺ and Yb³⁺ on the sample surface were obtained by scanning electron microscope. Raman spectral characterization was carried out to examine the behavior of the vibrational modes of the samples. Upconversion emissions in the visible region at 484.5, 522, 541.5 and 670.5 nm in the matrices BiNbO₄:Er,Yb and BiNbO₄:Er were observed and analyzed as a function of 980 nm laser excitation power and rare-earth doping concentration. The results show that BiNbO₄ is a promising host material for efficient upconversion phosphors.     

Bioactivity and up-conversion luminescence characteristics of Yb3+/Tb3+ co-doped bioglass system

The present study elaborates the bioactive and optical features of Yb³⁺/Tb³⁺ co-doped bio-active glass. Three different combinations with assorted elemental concentrations were investigated. The amorphous nature of bioglass devoid of crystalline phases until 700 °C has been confirmed through XRD analysis. The results from Raman and FT-IR accomplished the presence of Si–O–Si broad vibrational modes typical of amorphous glass and further the characteristic PO₄ vibrations were also confirmed. The up-conversion luminescence studies revealed the typical Tb³⁺ emission excited at 976 nm. The mechanism that involved in the up-conversion and energy transfer emission phenomena were discussed. Morphological features of SBF immersed specimen affirm the formation of apatite layer by the spherical spongy agglomerates observed over the surface.     

Temperature self-monitoring photothermal nano-particles of Er3+/Yb3+ Co-doped zircon-tetragonal BiVO4

Self-monitored photo-thermal therapy (PTT) still faces huge challenge in cancer treatment, which aims to realize the real-time temperature reading during the course of optical heating. Exploiting new-type photo-thermal therapeutic agent (PTA) with thermometric function is considered to be one of effective methods to fulfill self-monitored PTT. In this work, spindle-like zircon-tetragonal (z-t) phase BiVO₄:Yb³⁺/Er³⁺ up-conversion (UC) nano-particles as self-monitored PTAs were prepared through the combination of co-precipitation and hydrothermal method. Under 980 nm laser diode excitation, real-time thermometry was accomplished by monitoring thermo-responsive emission intensity ratio of Er³⁺ (²H_11/2/⁴S_3/2 → ⁴I_15/2) transitions. Meanwhile, the photo-thermal conversion effect associated with UC process was trigged via the non-radiative transition channels. Considering the balance between UC emission intensity and heat generation, the optimal sample composition was determined as BiVO₄:20%Yb³⁺/3%Er³⁺. Their maximum absolute sensitivity (S_a) reached 0.0125 K^-1 at 460 K as the thermometer and the ability of photo-thermal conversion up to 3.32 K cm²/W as PTAs. Their potential applications in controlled subcutaneous photo-thermal treatment were estimated through ex vivo experiments. Results provided a new choice for nano-materials to realize real-time temperature feedback in the single host material (z-t BiVO₄) during the course of PTT.     

Pr3+:Y2SiO5/TiO2上转换复合膜光催化性能

为解决悬浮相TiO₂粉体处理水中污染物后难以分离和回收利用的缺点并进一步提高纳米TiO₂对太阳光的利用率,采用溶胶-凝胶法制备了Pr³⁺:Y₂SiO₅粉体、TiO₂薄膜以及Pr³⁺:Y₂SiO₅/TiO₂复合膜。利用XRD、SEM等表征方法对样品进行表征。重点考察了Pr³⁺:Y₂SiO₅/TiO₂复合材料薄膜对亚甲基蓝的光催化降解效率与镀膜层数等因素的关系。结果发现涂覆5层Pr³⁺:Y₂SiO₅/TiO₂复合膜时,降解率可高达95.7%,其对应的第2次和第3次降解率分别为82.46%和74.94%;随着Pr³⁺:Y₂SiO₅/TiO₂复合膜薄膜面积的增加降解率先增加后降低,使用8张薄膜时降解率最高达96.43%;增加光照强度有利于提高降解率,但当光照强度增加到100 W时,降解率达到稳定值96.18%;随着初始浓度的增加,降解率逐渐降低。     

CaO对提高Er3+/Yb3+共掺ZrO2上转换发光效率的研究

采用固相反应法在1000℃烧结得到了Er3 +/Yb3共掺杂ZrO2-CaO粉末样品,样品在980 nm激发下发射较强的绿红光,发射光谱显示三个主要发射峰,中心波长依次为658nm、544 nm和530 nm,文中利用速率方程讨论了样品的上转换发光与抽运功率的关系,对绿红光的上转换发光途径进行了分析.通过XRD检测发现...     

Temperature dependent upconversion properties of Yb3+:Ho3+ co-doped Gd2O3 nanoparticles prepared by pulsed laser ablation in water

Yb³⁺:Ho³⁺ co-doped Gd₂O₃ nanoparticles were successfully synthesized by pulsed laser ablation in water under different laser energy. The phase structure, morphology, crystallization and upconversion photoluminescence properties of obtained samples were investigated using X-Ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and photoluminescence spectra. The mechanism of the upconversion process was discussed based on the energy level diagram and power dependent upconversion emission. Upconversion mechanisms and thermal effects caused by absorption of excitation laser were discussed. Temperature dependent green and red emissions of Yb³⁺:Ho³⁺ co-doped Gd₂O₃ nanoparticles under the excitation of 980 nm were investigated in the low temperature range of 130 K–280 K. Non-radiative decay rate theory was used to explain the difference of quenching rates of green and red emissions. A further study on temperature sensing properties based on fluorescence intensity ratio (FIR) of green and red emissions was carried out. The FIR as a function of temperature can be well fitted by the model based on the thermal quenching theory. The relative sensitivity reaches its maximum value of 0.804% K⁻¹ at 216 K.     

Preparation of Er3+/Yb3+ co-doped zeolite-derived silica glass and its upconversion luminescence property

A novel upconversion luminescence transparent glass has been successfully synthesized from Er³⁺/Yb³⁺ co-doped zeolite powder by Spark Plasma Sintering (SPS) method through the order–disorder transition process. XRD was used to detect the order–disorder transition process of each phase after SPS. These zeolite-derived silica glasses showed enhanced upconversion luminescence under the excitation of 980 nm diode laser, which was caused by the change of phonon energy according to the results of Raman spectrum, and the corresponding energy transfer mechanism was also discussed in detail.     

Preparation and luminescent properties of Tb3+ doped Y2O2SO4 microflakes

Abstract

Tb³⁺ doped Y₂O₂SO₄ (Y₂O₂SO₄:Tb³⁺) microflakes were prepared by a combination method of electrospinning and calcination. The two-dimensional microflakes had smooth surface and high radial/axial ratio. Crystal structures of the Y₂O₂SO₄:Tb³⁺ microflakes resulted in layer by layer growth in axial direction. A possible formation mechanism was proposed on the basis of experimental results, which indicated that poly(vinyl pyrrolidone) played the role of the nanostructure directing template and revealed the growth priority in radial direction. The microflakes showed a favourable fluorescent property symbolised by the characteristic green emission (541 nm) resulting from the ⁵D₄→⁷F₅ transition of Tb³⁺ ions under 229 nm ultraviolet excitation. The maximum intensity of Tb³⁺ emission of the Y₂O₂SO₄:Tb³⁺ microflakes was 2·3 times stronger than that of the Y₂O₂SO₄:Tb³⁺ bulk powders with the same doping concentration.     

不同冷却方式对Er3+/Yb3+共掺BaF2粉末上转换发光效率的影响

采用液氮制冷和空冷两种冷却方式制备了不同烧结温度的系列相同配方Er3+/Yb3+共掺杂BaF2粉末.与同一烧结温度采用空冷制得的样品相比较,液氮制冷可将样品的上转换荧光强度提高20倍.各样品的XRD图谱表明,经两种方式冷却后样品的晶体结构没有明显区别,但采用液氮制冷制得样品的BaF2平均晶格常数a和样品中Yb2O3含量均较采用空冷制得样品的相应参数略有减小,由此可知液氮制冷有利于更多稀土离子替代基质材料中的Ba2+成为发光中心,提高了样品的上转换发光效率.     

Effect of Ce dopant on upconversion and temperature sensing performances in homogeneous ultrasmall Y2O3:Yb3+/Ho3+ nanoparticles through flame aerosol synthesis

Flame aerosol synthesis (FAS) is an excellent strategy for continuous, fast, and mass production of small-size upconversion nanoparticles (UCNPs), which have high potential applications in fields like biological imaging, colour display and optical temperature sensing. However, flame-made UCNPs have received less attention, and relevant studies are limited. Herein, for the first time, we successfully fabricated cerium (Ce)-doped homogeneous ultrasmall Y₂O₃:Yb³⁺/Ho³⁺ UCNPs using a liquid-fed FAS method. Ce was doped to improve the upconversion luminescence (UCL) of the Y₂O₃:Yb³⁺/Ho³⁺ UCNPs. The overall UCL intensity was enhanced ～77.9-fold for an optimal concentration of 20 mol% Ce-doped UCNPs, compared with the UCNPs without Ce doping with a relatively homogeneous ultrasmall size of 8–10 nm. Further studies confirmed that both trivalent (Ce³⁺) and tetravalent (Ce⁴⁺) simultaneously exist in the Y₂O₃ hosts and are critical in enhancing the UCL properties. In addition, the fluorescence intensity ratio (FIR) method was used to evaluate the thermal properties of the fabricated UCNPs. Ce doping significantly improved the thermal sensitivity of Y₂O₃:Yb³⁺/Ho³⁺ UCNPs. An excellent relative sensitivity (S_R) of 0.622% K^?1 at 598 K was obtained for flame-made UCNPs doped with 20 mol% Ce.     

Concentration effects on the upconversion luminescence in Ho3+/Yb3+ co-doped NaGdTiO4 phosphor

Ho³⁺/Yb³⁺ co-doped NaGdTiO₄ phosphors were synthesized by a solid-state reaction method. The upconversion (UC) luminescence characteristics excited by 980 nm laser diode were systematically investigated. Bright green UC emission centered at 551 nm accompanied with weak red and near infrared (NIR) UC emissions centered at 652 and 761 nm were observed. The dependence of UC emission intensity on excitation power density showed that all of green, red and NIR UC emissions are involved in two-photon process. The UC emission mechanisms were discussed in detail. Concentration dependence studies indicated that Ho³⁺ and Yb³⁺ concentrations had significant influences on UC luminescence intensity and the intensity ratio of the red UC emission to that of the green one. Rate equations were established based on the possible UC mechanisms and a theoretical formula was proposed to describe the concentration dependent UC emission. The UC luminescence properties of the presented material was evaluated by comparing with commercial NaYF₄:Er³⁺, Yb³⁺ phosphor, and our sample showed a high luminescence efficiency and good color performance, implying potential applications in a variety of fields.     

Synthesis of NaYF4:Yb3+, Er3+ upconversion nanoparticles in normal microemulsions

An interface-controlled reaction in normal microemulsions (water/ethanol/sodium oleate/oleic acid/n-hexane) was designed to prepare NaYF4:Yb3+, Er3+ upconversion nanoparticles. The phase diagram of the system was first studied to obtain the appropriate oil-in-water microemulsions. Transmission electron microscopy and X-ray powder diffractometer measurements revealed that the as-prepared nanoparticles were spherical, monodisperse with a uniform size of 20 nm, and of cubic phase with good crystallinity. Furthermore, these nanoparticles have good dispersibility in nonpolar organic solvents and exhibit visible upconversion luminescence of orange color under continuous excitation at 980 nm. Then, a thermal treatment for the products was found to enhance the luminescence intensity. In addition, because of its inherent merit in high yielding and being economical, this synthetic method could be utilized for preparation of the UCNPs on a large scale.     

Tuning size and up-conversion luminescence of CeO2:Yb3+/Er3+ nanoparticles through lanthanide doping

Particle size is a critical parameter in up-conversion luminescence tuning and application research. In this study, CeO₂:Yb³⁺/Er³⁺ nanospheres were synthesized via coprecipitation. The average size of these nanospheres gradually decreased as the Yb³⁺ doping concentration increased, which might be attributed to the influence of Yb³⁺ doping on the growth rate of nanospheres by surface charge repulsion. Upon exciting these nanospheres using a 980-nm laser, the corresponding up-conversion red-green emission intensity ratio gradually increased as the Yb³⁺ doping concentration increased, which might be ascribed to two reasons: the strengthened ⁴S_3/2 → ⁴F_9/2 nonradiative relaxation process and the enhanced Er³⁺ → Yb³⁺ energy back-transfer process. To assess the influence of the nonradiative relaxation process on the up-conversion emission red-green ratios, the down-conversion emission spectra and decay curves of CeO₂:x%Yb³⁺/2%Er³⁺ nanospheres that were excited by a 520 nm laser were investigated. To validate how the particle size affects the up-conversion emission, CeO₂:x%Lu³⁺/2%Yb³⁺/2%Er³⁺ nanospheres of various sizes were synthesized by substituting optically active Yb³⁺ using optically inert Lu³⁺. The corresponding up-conversion emission spectra and decay curves were investigated. The experimental results enhanced our understanding of how lanthanide doping affects the up-conversion luminescence tuning of Er³⁺, offering great potential to regulate the morphology and optical properties of the up-conversion luminescence nanoparticles.