Multi-functionality of fluorescent nanocrystals in glass ceramics

Thermal processing of as-made fluorozirconate glasses, which were additionally doped with rare-earth and chlorine ions, results in the formation of fluorescent nanocrystals therein. For medical applications, the glasses were doped with divalent europium ions as the fluorescent rare-earth ion, while trivalent neodymium was used to develop up-conversion systems. The samples were annealed up to 290 °C to initiate the growth of hexagonal or orthorhombic phase BaCl₂ nanocrystals therein. Upon annealing some of the rare-earth ions were incorporated into the BaCl₂ nanocrystals leading to enhanced fluorescence properties. The particle diameters were in the range of a few nanometers to several tens of nanometers.     

Aqueous Synthesis of Water-Soluble L-Cysteine-Modified Cadmium Sulfide Doped with Silver Ion/Zinc Sulfide Nanocrystals

The water-soluble silver ion-doped cadmium sulfide nanocrystals were synthesized by a co-precipitation technique in aqueous solution using L-cysteine as surface modifier, and then L-cysteine-modified cadmium sulfide doped with silver ion/zinc sulfide core/shell nanocrystals were prepared by zinc sulfide epitaxial coated on surface of silver ion-doped cadmium sulfide nanocrystals. The crystal structure, morphology, and spectral properties of cadmium sulfide doped with silver ion/zinc sulfide nanocrystals were characterized by X-ray power diffraction, transmission electron microscope, infrared spectrum, and photoluminescence spectrum. The results show that the photoluminescence quantum yield of cadmium sulfide doped with silver ion/zinc sulfide nanocrystals is improved greatly after doped with silver ion and coated with zinc sulfide shell. The cysteine modified on the surface of cadmium sulfide doped with silver ion/zinc sulfide nanocrystals renders the nanocrystals water-soluble and biocompatible.     

La、Ce掺杂ZnO纳米晶的发光特性

共沉淀法制备了稀土镧、铈掺杂的ZnO半导体纳米晶。X射线衍射(XRD)结果表明:掺杂的ZnO纳米晶为六方纤锌矿结构,随掺杂浓度增加ZnO粒径减小。对铈掺杂纳米ZnO,以波长380nm激发,在443nm处出现了半峰宽较窄的强的蓝光发射峰;镧掺杂ZnO纳米晶则为从418~610nm的多峰宽带发射。     

Ni2+掺杂和卤素空位填充协同抑制CsPbBr3纳米晶体中的离子迁移

卤化铅钙钛矿(LHPs)由于具有优异的光电性能和制备成本低等优点,已成为新一代光电器件的有力候选材料。然而,缺陷造成的离子迁移会导致LHPs纳米晶的晶体结构解离分解。因此,稳定性成为LHPs实际应用中亟待解决的问题。本文旨在研究镍离子替位掺杂及卤素空位填补对CsPbBr3纳米晶中的离子迁移抑制作用。通过离子迁移活化能的测定和高分辨透射电镜的原位观察,分析了前驱体掺杂剂对加强LHPs稳定性的作用原理。首先,选用乙酰丙酮镍和溴化镍作为掺杂剂,合成了掺杂LHPs纳米晶。其次,通过吸收-荧光光谱,X射线衍射,X射线光电子衍射,透射电子显微镜等测试手段对掺杂样品的光学及化学组成进行分析。最后,通过纳米晶薄膜电导率的温度依赖关系计算出其离子迁移活化能,并结合高分辨电镜原位观察纳米晶在高能电子束辐照下的形貌演变过程,揭示了不同掺杂剂对合成掺杂LHPs稳定性的影响。实验结果表明:Ni²⁺掺杂CsPbBr3样品的离子迁移活化能相较本征CsPbBr3样品(0.07 eV)有显著提升,其中乙酰丙酮镍掺杂样品的离子迁移活化能为0.238 eV,溴化镍掺杂样品的离子迁移活化能为0.487 eV。另外,电子束辐照测试表明溴化镍掺杂钙钛矿晶体表现出更高的结构稳定性,这主要归因于掺杂的Ni²⁺对卤素的强结合和卤素填补空位缺陷的协同钝化作用。Ni²⁺掺杂和卤素空位填充协同可以有效抑制卤化物钙钛矿纳米晶体中的离子迁移。     

Upconversion luminescence and magnetic properties of ligand-free monodisperse lanthanide doped BaGdF5 nanocrystals

Lanthanide (Ln=Yb³⁺, Er³⁺and Tm³⁺) doped monodisperse oleate-capped BaGdF₅ nanocrystals with a mean diameter of approximately 18 nm were prepared via liquid-solid-solution method. The cell parameter of the as-prepared cubic BaGdF₅ nanocrystals is 5.884 Å, which is different from the reported 6.023 Å (JCPDS 24-0098). When excited by a 980 nm laser, these Ln³⁺ doped nanocrystals exhibit multi-color up-conversion (UC) emissions including blue, yellow and white, by precisely adjusting the dopant concentration of Yb³⁺, Er³⁺ and Tm³⁺. The oleate ligands capped on the surface of the as-synthesized products, which can be conversed from hydrophobic to hydrophilic along with certain extent of weakening of UC intensity, can be moved by the acid treatment process. The measured field dependence of magnetization (M-H curves) of the BaGdF₅ nanocrystals shows excellent paramagnetism. At room temperature, the magnetization of BaGd_0.798Yb_0.2Tm_0.002F₅ nanocrystals is 0.9165 emu/g and the magnetic mass susceptibility reaches 6.11×10⁻⁵ emu g⁻¹ Oe⁻¹ at 15 kOe. Our results indicate that these bi-functional hydrophilic Ln³⁺ doped BaGdF₅ nanocrystals have potential applications in color displays, bioseparation and optical-magnetic dual modal nanoprobes in biomedical imaging.     

Spectral-luminescent characteristics of fluorophosphate glasses with zinc sulfide nanocrystals

Fluorophosphate glasses doped with ZnS are studied. The properties of ZnS nanocrystals formed are determined using X-ray-diffraction analysis and optical spectroscopy. The size and the band-gap width of these crystals are determined by the Tauc method. It is shown that ZnS nanocrystals luminesce in the visible spectral region with a low (2–3%) absolute quantum yield.     

掺杂Mn2+的浓度对CdS纳米颗粒光致发光的影响

采用反胶束法,合成了硅土包裹的掺有不同浓度的Mn2 的CdS纳米颗粒.高分辨电镜表明这些颗粒的直径小于5 nm.仅仅改变Mn2 的掺杂浓度,研究了这些颗粒的光致发光谱和光致发光激发谱,结果表明:Mn2 浓度的大小对掺杂CdS纳米颗粒的发光产生了重要的影响.通过电子顺磁共振谱的测量和分析揭露了Mn2 浓度影响这些掺杂颗粒发光效率的原因.     

Local structure investigation of (Co,Cu) co-doped ZnO nanocrystals and its correlation with magnetic properties

Pure, Co doped and (Co, Cu) co-doped ZnO nanocrystals have been prepared by wet chemical route at room temperature to investigate the effect of Cu doping in Co doped ZnO nanocrystals . The nanocrystals have initially been characterized by X-ray diffraction, FTIR, Raman, optical absorption and EPR spectroscopy and the results were corroborated with DFT based electronic structure calculations. Magnetic properties of the samples have been investigated by studying their magnetic hysteresis behavior and temperature dependence of susceptibilities. Finally the local structure at the host and dopant sites of the nanocrystals have been investigated by Zn, Co and Cu K edges EXAFS measurements with synchrotron radiation to explain their experimentally observed magnetic properties.     

Ce~(3+)掺杂LiLuF_4氟氧微晶玻璃的发光性质

通过熔融法以及热处理,制备了Ce~(3+)掺杂含Li Lu F_4纳米晶的透明氟氧微晶玻璃。XRD结果表明,玻璃中析出的晶相为Li Lu F_4,其晶粒大小随热处理温度的升高和时间的延长而变大。在330 nm紫外光激发下,Ce~(3+)掺杂的氟氧玻璃和Li Lu F4微晶玻璃的发射为一峰值波长为370 nm的宽带光谱。微晶玻璃的发光强度显著高于未经过热处理的基础玻璃,并且随着热处理温度的升高及时间的延长,微晶玻璃的发光逐渐增强。微晶玻璃的370 nm发射的荧光寿命均长于基础玻璃的。     

Structure and intense UV up-conversion emissions in RE3+-doped sol–gel glass-ceramics containing KYF4 nanocrystals

Transparent nano-glass-ceramics containing KYF₄ nanocrystals were successfully obtained by the sol–gel method, doped with Eu³⁺ and co-doped with Yb³⁺ and Tm³⁺ ions. Precipitation of cubic KYF₄ nanocrystals was confirmed by X-ray diffraction and high-resolution transmission electron microscope images. Excitation and emission spectra let us to discern between ions into KYF₄ nanocrystals and those remaining in a glassy environment, supplemented with time-resolved photoluminescence decays, that also clearly reveal differences between local environments. Unusual high-energy up-conversion emissions in the UV range were obtained in Yb³⁺–Tm³⁺ co-doped samples, and involved mechanisms were discussed. The intensity of these high-energy emissions was analyzed as a function of Yb³⁺ concentration, heat treatment temperature of precursor sol–gel glasses and pump power, determining the optimum values for potential optical applications as highly efficient UV up-conversion materials in UV solid-state lasers.     

Surface effect of nanocrystals doped with rare earth ions enriched on surface and its application in upconversion luminescence

By employing a certain proportion of hydrogen peroxide, ammonia, ammonium fluoride, and ethylene diamine tetraacetic acid (EDTA) as precipitator, well-crystallized LaOF:Eu3+ and LaOF:Yb3+, Er3+ nanocrystals are synthe- sized by using the chemical co-precipitation method. The structural properties of these samples are characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FTIR) spectra. The results show that all the samples have an average size below 70 nm, which decreases gradually with the increase of the EDTA content, and a certain number of EDTA molecules are coupled with doped ions on the surfaces of nanocrystals. Most of the doped ions are proved to be enriched on the surfaces of nanocrystals and surrounded by the high energy vibration groups and bonds in EDTA molecules. The observed differences in upconversion emission spectrum among the different LaOF:Yb3+, Er3+ nanocrystals are explained by the different two-photon upconversion mechanisms. Especially, in the LaOF:Yb3+, Er3+ nanocrystals with EDTA, the two-photon processes that contain several special cross-relaxation processes are introduced to analyse the corresponding upconversion mechanisms.     

Dopant induced morphology changes in ZnO nanocrystals

Zinc oxide (ZnO) nanocrystals doped with different groups of impurities, e.g., Li, Na, Cu, Pr and Mg synthesized by solid-state reaction method under similar conditions exhibit different morphology. XRD showed monophasic wurtzite structure but change in lattice parameters and Zn-O bond length indicates incorporation of dopant ion in ZnO lattice. The morphology of ZnO nanocrystals exhibited striking dependence on type of dopant ion with the shape changing from nanorods, spherical to petal like particles. Photoluminescence (PL) shows pronounced UV emission and negligible visible emission for Li, Na and Cu doped ZnO nanocrystals with peak positions coinciding with that of undoped ZnO. Whereas signature emission of Pr³⁺ ion as well as broad visible emission from Mg doped ZnO revealed the role of intra gap metastable states formed by the dopant ion in the emission process.     

Room temperature magnetism of Fe doped CdS nanocrystals

Undoped and Fe doped CdS nanocrystals with Fe content of 2–5 at% of average crystallite size 1.2–2 nm have been obtained using chemical co-precipitation method with 2-mercaptoethonal as capping agent at 80 °C. X-ray diffraction (XRD) results showed that the undoped CdS nanocrystals were in mixed phase of cubic and hexagonal, where as the doped CdS nanocrystals were in hexagonal phase. Room-temperature ferromagnetism has been observed in Fe-doped CdS nanocrystals. Magnetic studies indicated diamagnetism in undoped, ferromagnetism in lightly doped (2 and 3 at%) and paramagnetism in samples of higher Fe content (4 and 5 at%). The substitutional incorporation of Fe³⁺ ion in Cd²⁺ sites was reflected in structural and electron paramagnetic resonance (EPR) measurements. Isolated as well as interacting Fe³⁺ ions are observed in EPR.     

Preparation and luminescence of water soluble poly (N-vinyl-2-pyrrolidone)/LaF3:Eu nanocrystals

Lanthanide-doped luminescent nanocrystals have great potential as biological luminescent labels, but their use has been limited because of most of these nanocrystals are hydrophobic. In this work, water soluble LaF₃:Eu³⁺ down-conversion nanocrystals were prepared by encapsulated individual nanocrystals with polyvinylpyrrolidone (PVP). Their morphology, surface structure and luminescence properties were explored in detail. The results indicate that these nanocrystals can be readily dispersed in water, forming a stable and transparent colloidal solution. The colloidal solution displayed unique red luminescence with high emission intensity under ultraviolet excitation. These results suggest that these nanocrystals have great potential as luminescent labeling materials for biological applications.     

Frequency-conversion properties of Eu doped chlorophosphate glass ceramics containing CaCl2 nanocrystals

Eu³⁺ ion doped chlorophosphate glass ceramics containing nanocrystals were successfully prepared, and their spectroscopic characterizations were done using absorption, excitation and emission spectra. For the crystallized samples, X-ray diffraction (XRD) and transmission electron microscopy (TEM) experiments evidenced the formation of CaCl₂ nanocrystals. The absorption and emission spectra investigations indicate that a considerable amount of Eu³⁺ ions was trapped in CaCl₂ nanocrystals, and therefore an efficient up- and down-frequency conversion was observed. The comparative spectroscopic studies of Eu³⁺ doped samples suggest that the investigated glass ceramics systems are potentially applicable as frequency-conversion photonics devices.     

Microstructural study of thin films of 5 mol% gadolinia doped ceria prepared by pulsed laser ablation

Microstructural characterization of thin films of 5 mol% gadolinia doped ceria films deposited by pulsed laser ablation in the energy range 100–600 mJ/pulse has been investigated, as deposited films were found to be nanocrystalline with preferred orientation. X-ray diffraction analysis revealed that the size of the nanocrystals of doped ceria does not vary significantly with increasing laser energy, whereas transmission electron microscopy study showed a uniform distribution of nanocrystal of 8–10 nm for energies ≤200 mJ/pulse and nanocrystals embedded in a large crystalline matrix of doped ceria for energies in the range 400–600 mJ/pulse. Although the laser-ablated films were totally free from secondary phases, lattice imaging of the large grained doped ceria showed growth-induced defects, such as dislocations and ledges.     

Optimal conditions for exciting long-lived photon echo signals in impurity nanocrystals

The specific features of the formation of long-lived photon echo signals in dielectric nanocrystals doped with rare earth ions have been considered. It is shown that the optimal situation for observing long-lived photon echo signals in impurity nanocrystals is the absence of resonance between the vibrational modes of the nanomatrix and the impurity-ion electronic transitions, contributing to the spin-phonon relaxation.     

Spectroscopic study of local thermal effect in transparent glass ceramics containing nanoparticles

Local thermal effect influencing the fluorescence of triply ionized rare earth ions doped in nanocrystals is studied with laser spectroscopy and theory of thermal transportation for transparent oxyfluoride glass ceramics containing nanocrystals. The result shows that the local temperature of the nanocrystals embedded in glass matrices is much higher than the environmental temperature of the sample. It is suggested that the temperature-dependent thermal energy induced by the light absorption must be considered when the theory of thermal transportation is applied to the study of local thermal effect.     

Effect of surface defects on radiative interband recombination in silicon nanocrystals highly doped with hydrogen-like impurities

The role of surface defects at the Si nanocrystal boundary during the process of interband radiative recombination is studied in the case in which nanocrystals are doped with hydrogen-like impurities with shallow energy levels. It is shown that, in the case of a nonpassivated surface with a large number of dangling bonds, the rate of radiative transitions in nanocrystals doped with donors can be larger than that in nondoped crystallites. On the other hand, doping with acceptors leads to a decrease in the rate of transitions. In the case of a completely passivated surface, the recombination rate remains almost unchanged irrespective of the type of dope.     

Strong segregation of doped ions in Y2SiO5:Pr3+ nanocrystals

Strong temperature controlled segregation of doped ions in Y₂SiO₅:Pr³⁺ nanocrystals detected by spectroscopic techniques is reported. The elastic interactions stimulate Pr³⁺ segregation thus leading to non-uniform distribution of doped ions, pair formation and, as a consequence, to abnormal low threshold of luminescence concentration quenching for Y₂SiO₅:Pr³⁺ nanocrystals.