Particle-size-dependent upconversion luminescence of NaYF4: Yb,Er nanoparticles in organic solvents and water at different excitation power densities

Nano Research - A systematic study of the luminescence properties of monodisperse β-NaYF4: 20% Yb3+, 2% Er3+ upconversion nanoparticles (UCNPs) with sizes ranging from 12–43 nm is...     

Room-temperature facile synthesis of hexagonal NaYF4 and NaYF4: Yb,Er powder without any organic additives and its upconversion fluorescence properties

Based on the structure difference between cubic and hexagonal phases, a facile method was designed for the synthesis of pure hexagonal phase β-NaYF₄ and β-NaYF₄: Yb, Er powder at room temperature and ambient pressure. In the whole process, neither any organic additives, nor high temperature and high pressure were involved that indicated an environmentally friendly technology. The optimal synthesis conditions for hexagonal phase at room temperature is the pH value between 5.0 and 6.5, the amorphous Y (OH) ₃ as Y precursor and the F^?/Y³⁺ molar ratio equal to 6:1. A possible preparation mechanism based on the difference between the coordination structure of the hexagonal and the cubic phases was also proposed. It is found that the as prepared powder of the hexagonal phase can emit red upconversion luminescence with a high R/G ratio, which is significantly different from the light emitted by the usually synthesized hexagonal phase. This method can also provide a new perspective for studying the sustainable synthesis of rare earth compounds.     

Synthesis of monodisperse NaYF4:Yb, Tm@SiO2 nanoparticles with intense ultraviolet upconversion luminescence

In this paper, the NaYF4:Yb, Tm upconversion (UC) nanoparticles (NPs) were synthesized using a solvothermal approach, and the core-shell structured NaYF4:Yb, Tm@SiO2 NPs, coated with a thin layer of SiO2 on the surface of the NaYF4:Yb, Tm NPs, were prepared by a typical St?ber method. X-ray diffraction (XRD), transmission electron microscopy (TEM), and luminescence spectroscopy were applied to characterize these samples. The obtained core-shell structured NaYF4:Yb, Tm@SiO2 NPs exhibited a perfect spherical morphology with narrow size distribution and smooth surfaces. Under 980 nm excitation, NaYF4:Yb, Tm and NaYF4:Yb, Tm@SiO2 samples showed intense ultraviolet UC luminescence, which originated from the 1D2 --> 3H6, 1I6 --> 3F4 transitions of Tm3+. These NPs have great potential for applications as fluorescent labels, imaging probes, optical storage, photodynamic therapy (PDT) in deep tissue, and solid-state lasers.     

Synthesis and upconversion luminescence of NaYF4:Yb, Tm/TiO2 core/shell nanoparticles with controllable shell thickness

NaYF4:Yb, Tm/TiO2 core/shell nanoparticles were synthesized by a two-step method. First, the NaYF4:Yb, Tm nanocrystals were prepared using solvothermal technology; then, TiO2 shells were deposited on the nanocrystals by the hydrolysis of titanium ethoxide (TEOT) to form core/shell structures. By controlling the reaction time, we can adjust the thickness of TiO2 shell and thereby the weight percentage of TiO2 in the core/shell nanoparticles. The effect of shell thickness on the upconversion fluorescence of NaYF4:Yb, Tm nanocrystals was investigated in detail.     

Rapid microwave-enhanced hydrothermal synthesis and shape evolution of uniform NaGdF(4):Yb, Er (Tm/Ho) nanocrystals with upconversion and paramagnetic properties

An efficient microwave-enhanced hydrothermal synthesis strategy was developed for the rapid synthesis of β-NaGdF(4):Ln(3+) (Ln?=?Yb, Er/Tm/Ho) nanocrystals (NCs) with multicolour upconversion luminescence and paramagnetic properties. It has been found that the uniform β-NaGdF(4):Ln(3+) NCs could be rapidly formed within a few minutes at 160?°C and the shape of the NCs can be manipulated from uniform rod-like to spherical just by tuning the initial reactants' concentration. In comparison to conventional hydrothermal routes, a burst homogeneous nucleation and higher growth rate as well as enhanced dimensional homogeneity of the NaGdF(4):Ln(3+) was achieved in microwave synthesis. A microwave-heating-based classical crystallization mode and surfactant-assisted anisotropic growth mechanism were proposed for the formation of β-NaGdF(4):Ln(3+) NCs.     

Effect of homogeneous coating on K+-doped NaGdF4:Er3+,Yb3+ upconversion materials

Journal of Materials Science: Materials in Electronics - The K+-doped (Na1?xKx)GdF4:Er3+,Yb3+ upconversion materials were successfully synthesized by solvothermal method. The doping of K+ was...     

纳米NaYF4:Er3+,Yb3+上转换材料的合成及其性质研究

采用溶胶-凝胶法在水相合成了纳米NaYF_4:Er~(3 ),Yb~(3 )上转换材料,980nm红外激光照射下,肉眼可观察到明亮的上转换发光。实验研究了铒、镱掺杂浓度及焙烧温度对材料合成的影响。所合成的纳米材料呈圆球形、颗粒均匀、分散性好,平均粒径70nm,可应用于生物标记。     

Selective synthesis and upconversion luminescence of GdF3 and NaGdF4 nano/submicro-crystals doped with Yb3+/Ho3+

Journal of Materials Science: Materials in Electronics - In this work, GdF3 and NaGdF4 nano/submicro-crystals are selectively synthesized via a simple hydrothermal method. By merely adjusting the...     

A novel strategy for improving upconversion luminescence of NaYF4：Yb, Er nanocrystals by coupling with hybrids of silver plasmon nanostructures and poly（methyl methacrylate） photonic crystals

The coupling of upconversion nanophosphors （UCNPs） with the surface plasmonic resonance （SPR） of noble metals is a promising way to improve luminescent efficiency of UCNPs; however, it is still a challenge to achieve stable, reproducible and effective upconversion luminescence （UCL） enhancement through such coupling. In this work, we present a novel strategy to improve UCL of NaYF4：ybB,Er3. UCNPs, by combining the near-field coupling of SPR of silver and the far-field coupling of poly（methyl methacrylate） （PMMA） opal photonic crystals （OPCs） with the UCNPs. In order to control the effective interaction distance between the UCNPs and the SPR, a porous silver film consisting of randomly distributed silver nanoparticles （NPs） （〉 100 nm） was prepared which demonstrated strong SPR over a broad wavelength range, and its coupling to the UCNPs was found to be much stronger than that of a dense film. In the far-field coupling of OPCs, the photonic stop band （PSB） of the PMMA OPCs was tuned to 980 nm, matching exactly the excitation light. By modulating the particle size of the UCNPs, and the direction and excitation power of the incident light, a maximum enhancement of 60-fold was observed, which is an important advance for metaMnduced UCL enhancement systems.     

Upconversion in NaYF(4):Yb, Er nanoparticles amplified by metal nanostructures

Upconversion (UC) fluorescence in NaYF(4):Yb, Er nanoparticles amplified by metal nanostructures was compared in two nanostructure geometries: gold nanoshells surrounding nanoparticles and silver nanostructures adjacent to the nanoparticles, both placed on a dielectric silica surface. Enhanced UC luminescence signals and modified lifetimes induced by these two metals were observed in our study. The UC luminescence intensities of green and red emissions were enhanced by Ag nanostructures by a factor of approximately 4.4 and 3.5, respectively. The corresponding UC lifetimes were reduced ～ 1.7-fold and ～ 2.4-fold. In NaYF(4):Yb, Er nanoparticles encapsulated in gold nanoshells, higher luminescence enhancement factors were obtained (～9.1-fold for the green emission and ～ 6.7-fold for the red emission). However, the Au shell coating extended the red emission by a factor of 1.5 and did not obviously change the lifetime of green emission. The responsible mechanisms such as plasmonic enhancement and surface effects are discussed.     

NaYF4:Er3+和NaYF4:Yb3+/Er3+上转换荧光纳米晶的制备与表征

以EDTA为螯合剂,采用络合共沉淀法合成了NaYF4:Er3+和NaYF4:Yb3+/Er3+纳米晶.分别采用XRD、SEM、荧光分光光度计对合成的样品进行了结构、形貌和上转换荧光分析.XRD结果表明,制备的NaYF4:Er3+和NaYF4:Yb3+/Er3+均为纯立方相;SEM结果显示,制备的NaYF4:Er3+和NaYF4: Yb3+/Er3+晶粒粒径都在100nm左右,与NaYF4:Er3+相比,NaYF4:Yb3+/Er3+晶粒尺寸分布更均匀,分散性更好,符合作为荧光标记材料的要求;上转换荧光分析表明,在980nm激光器激发下,NaYF4:Yb3+/Er3+的发光强度比NaYF4:Er3+提高了1个数量级.     

Synthesis of BaMoO4:Er/Yb particles by an MAM method and their upconversion photoluminescence properties

Er³⁺-doped BaMoO₄ (BaMoO₄:Er³⁺) and Er³⁺/Yb³⁺ co-doped BaMoO₄ (BaMoO₄:Er³⁺/Yb³⁺) particles were successfully synthesized by a cyclic microwave-assisted metathetic (MAM) method, and show fine and homogeneous morphology with particle sizes of 0.5–1 μm. At 980-nm excitation, BaMoO₄:Er³⁺ and BaMoO₄:Er³⁺/Yb³⁺ particles exhibited a strong 525-nm emission band and a weak 550-nm emission band in the green region. The Raman spectrum of BaMoO₄:Er³⁺/Yb³⁺ particles indicated the appearance of additional peaks at higher frequencies (390 and 505 cm⁻¹) and at lower frequencies (218 and 255 cm⁻¹).     

Controllable synthesis of NaYF(4) : Yb,Er upconversion nanophosphors and their application to in vivo imaging of Caenorhabditis elegans

β-NaYF(4) : Yb,Er upconversion nanoparticles (UCNPs) can emit bright green fluorescence under near-infrared (NIR) light excitation which is safe to the body and can penetrate deeply into tissues. The application of UCNPs in biolabeling and imaging has received great attention recently. In this work, β-NaYF(4) : Yb,Er UCNPs with an average size of 35 nm, uniformly spherical shape, and surface modified with amino groups were synthesized by a one-step green solvothermal approach through the use of room-temperature ionic liquids as the reactant, co-solvent and template. The as-prepared UCNPs were introduced into Caenorhabditis elegans (C. elegans) to achieve successful in vivo imaging. We found that longer incubation time, higher UCNP concentration and smaller UCNP size can make the in vivo fluorescence of C. elegans much brighter and more continuous along their body. The worms have no apparent selectivity on ingestion of the UCNPs capped with different capping ligands while having similar size and shape. The next generation of worms did not show fluorescence under excitation. In addition, low toxicity of the nanoparticles was demonstrated by investigating the survival rates of the worms in the presence of the UCNPs. Our work demonstrates the potential application of the UCNPs in studying the biological behavior of organisms, and lays the foundation for further development of the UCNPs in the detection and diagnosis of diseases.     

Synthesis and upconversion luminescence properties of Yb/Er codoped BaGd2(MoO4)4 powder

Synthesis and upconversion luminescence properties of the new BaGd₂(MoO₄)₄:Yb³⁺,Er³⁺ phosphor were reported in this paper. The phosphor powder was obtained by the traditional high temperature solid-state method, and its phase structure was characterized by the XRD pattern. Based on the upconversion luminescence properties studies, it is found that, under 980 nm semiconductor laser excitation, BaGd₂(MoO₄)₄:Yb³⁺,Er³⁺ phosphor exhibits intense green upconversion luminescence, which is ascribed to ²H_11/2 → ⁴I_15/2 and ⁴S_3/2 → ⁴I_15/2 transition of Er³⁺. While the observed much weaker red emission is due to the non-radiative relaxation process of ⁴S_3/2 → ⁴F_9/2 and ⁴F_9/2 → ⁴I_15/2 transition originating from the same Er³⁺. The concentration quenching effects for both Yb³⁺ and Er³⁺ were found, and the optimum doping concentrations of 0.5 mol% Yb³⁺ and 0.08 mol% Er³⁺ in the new BaGd₂(MoO₄)₄ Gd³⁺ host were established.     

Up-conversion luminescence of the NaYF4:Yb3+,Er3+ nanomaterials prepared with the solvothermal synthesis

Up-converting NaYF₄:Yb³⁺,Er³⁺ (x_Yb: 0.20, x_Er: 0.02) nanomaterials were prepared with a microwave assisted solvothermal synthesis to study how the synthesis parameters affect the structure and up-conversion luminescence of the materials and thus their usability as labels in biomedical applications. The purity of the materials was studied with Fourier transform infra-red (FT-IR) spectroscopy and the particle size and morphology with transmission electron microscopy (TEM). The crystal structure was characterized with X-ray powder diffraction (XPD) and the crystallite sizes were calculated with the Scherrer formula. Up-conversion luminescence and luminescence decays were studied with near infra-red (NIR) laser excitation at 970 nm.The presence of the oleic acid was observed in the FT-IR spectra. The TEM images showed small quasi-spherical nanoparticles as well as long nanorods. The XPD measurements revealed that both cubic and hexagonal forms of NaYF₄ were present in the materials. The crystallite sizes ranged from ca. 20 to over 150 nm for the cubic and hexagonal phases, respectively. The characteristic up-conversion luminescence of Er³⁺ in red (640–685 nm; ⁴F_9/2 → ⁴I_15/2) and green (515–560 nm; ²H_11/2, ⁴S_3/2 → ⁴I_15/2 transitions) wavelengths was observed. The most intense luminescence and the longest luminescence emission lifetime were obtained with the material annealed for 12 h at 177 °C with 1.8 MPa pressure due to the predominance of the well-crystallized hexagonal form of NaRF₄ (R: Y, Yb, Er).     

水溶性NaYF4:Yb,Er纳米颗粒的溶剂热合成及其上转换发光性能

稀土上转换发光纳米材料具有极好的生物应用前景,但其应用的前提是能制备出水溶性、发光效率高的稀土纳米材料.以乙二醇为溶剂、稀土氯化物和NaP为反应物,采用简易的溶剂热法一步制备出水溶性的NaYF4:Yb,Er纳米颗粒.NaYF4:Yb,Er样品以粒径为25~40nm的球形颗粒为主,同时含有少量直径为25~40nm、长度为50～100nm的虫状纳米颗粒.该样品具有立方相结构,样品表面上的乙二醇配体使其能够很好地分散于水中.在980nm激光器激发下,NaYF4:Yb,Er纳米颗粒水溶液展现了强的黄绿色上转换发光.因此该样品拥有良好的生物应用潜力.     

高发光效率的亲水性NaYF4:Yb/Er纳米晶的制备

以不同比例的乙二醇和水作为混合溶剂,稀土氯化物和NaF为反应物,采用简易的溶剂热法一步制备出亲水性的NaYF4:Yb/Er纳米晶.用透射电子显微镜、X射线粉末衍射、红外吸收以及发光光谱等测试方法对产物的形貌、物相结构、表面配体和荧光性能进行了表征.结果表明,制备的纳米晶形貌比较均一,主要为立方相和六方相的混合相.随着溶剂中含水量由0%增加到50%,纳米晶尺寸变大,六方相NaYF4:Yb/Er含量增加,纳米晶的发光强度增加;进一步增加含水量时,尽管纳米晶尺寸变大,六方相含量也相应增加,但是其发光强度降低,可能是由于配体减少引起纳米晶表面缺陷增加,导致发光淬灭.     

An efficient and user-friendly method for the synthesis of hexagonal-phase NaYF(4):Yb, Er/Tm nanocrystals with controllable shape and upconversion fluorescence

Hexagonal-phase NaYF(4):Yb, Er/Tm nanocrystals are the best IR-to-visible upconverting materials to date, but user-friendly methods for making pure hexagonal-phase NaYF(4):Yb, Er/Tm nanocrystals with upconversion fluorescence are still lacking. Most of the methods reported so far require excess fluoride reactants in a high-temperature reaction which are very unfriendly to users and raise safety concerns. In this work, an efficient and user-friendly method was developed for the synthesis of uniform hexagonal-phase NaYF(4):Yb, Er/Tm nanocrystals with upconversion fluorescence, by forming small solid-state crystal nuclei and further growth and ripening of the nuclei. NaYF(4):Yb, Er/Tm nanoplates, nanospheres and nanoellipses were also selectively produced by varying the concentration of the surfactant. All the nanocrystals showed strong upconversion fluorescence, and fluorescence from the nanoplates was observed even when the laser power density was reduced to about 50?mW?cm(-2). These nanocrystals have great potential for use in biology and medicine as fluorescent labels or imaging probes.