Influence of Shell Formation on Morphological Structure,Optical and Emission Intensity on Aqueous Dispersible NaYF4:Ce/Tb Nanoparticles

A highly water-dispersible NaYF₄:Ce/Tb (core), NaYF₄:Ce/Tb@NaYF₄(core/shell) and NaYF₄:Ce/Tb@NaYF₄@SiO₂ (core/shell/SiO₂) nanoparticles (NPs) were synthesized via a general synthesis approach. The growth of an inert NaYF₄ and silica shell (~14 nm) around the core-NPs resulted in an increase of the average size of the nanopaticles as well as broadening of their size distribution. The optical band-gap energy slightly decreases after shell formation due to the increase the crystalline size. To optimize the influence of shell formation a comparative analysis of photoluminescence properties (excitation, emission, and luminescence decay time) of the core, core/shell, and core/shell/SiO₂ NPs were measured. The emission intensity was significantly enhanced after inert shell formation around the surface of the core NPs. The Commission International de l’Eclairage chromaticity coordinates of the emission spectrum of core, core/shell, core/shell/SiO₂ NPs lie closest to the standard green color emission at 545 nm. By quantitative spectroscopic measurements of surface-modified core-NPs, it was suggested that encapsulation with inert and silica layers was found to be effective in retaining both luminescence intensity and dispersibility in aqueous environment. Considering the high aqueous dispersion and enhanced luminescence efficiency of the core-NPs make them an ideal luminescent material for luminescence bioimaging and optical biosensors.     

Magnetic Core/Shell Nanocomposites MgFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/SiO<Subscript>2</Subscript> for Biomedical Application: Synthesis and Properties

Magnetic core/shell (CS) nanocomposites (MNCs) are synthesized using a simple method, in which a magnesium ferrite nanoparticle (MgFe₂O₄) is a core, and an amorphous silicon dioxide (silica SiO₂) layer is a shell. The composition, morphology, and structure of synthesized particles are studied using X-ray diffraction, field emission electron microscopy, transmission electron microscopy (TEM), energy-dispersive spectroscopy (EDS), scattering electrophoretic photometer, thermogravimetric analysis (TGA), and Mössbauer spectroscopy. It is found that the MgFe₂O₄/SiO₂ MNC has the core/shell structure formed by the Fe?O–Si chemical bond. After coating with silica, the MgFe₂O₄/SiO₂ MNC saturation magnetization significantly decreases in comparison with MgFe₂O₄ particles without a SiO₂ shell. Spherical particles agglomerated from MgFe₂O₄ nanocrystallites ～9.6 and ～11.5 nm in size function as cores coated with SiO₂ shells ～30 and ～50 nm thick, respectively. The total size of obtained CS MNCs is ～200 and 300 nm, respectively. Synthesized CS MgFe₂O₄/SiO₂ MNCs are very promising for biomedical applications, due to the biological compatibility of silicon dioxide, its sizes, and the fact that the Curie temperature is in the region required for hyperthermal therapy, 320 K.     

Gold decorated NaYF<Subscript>4</Subscript>:Yb,Er/NaYF<Subscript>4</Subscript>/silica (core/shell/shell) upconversion nanoparticles for photothermal destruction of BE(2)-C neuroblastoma cells

Gold decorated NaYF₄:Yb,Er/NaYF₄/silica (core/shell/shell) upconversion (UC) nanoparticles (~70–80 nm) were synthesized using tetraethyl orthosilicate and chloroauric acid in a one-step reverse microemulsion method. Gold nanoparticles (~6 nm) were deposited on the surface of silica shell of these core/shell/shell nanoparticles. The total upconversion emission intensity (green, red, and blue) of the core/shell/shell nanoparticles decreased by ~31% after Au was deposited on the surface of silica shell. The upconverted green light was coupled with the surface plasmon of Au leading to rapid heat conversion. These UC/silica/Au nanoparticles were very efficient to destroy BE(2)-C cancer cells and showed strong potential in photothermal therapy.     

Influence of Surface Coating on Structural and Photoluminescent Properties of CaMoO4:Pr Nanoparticles

CaMoO₄:Pr(core), CaMoO₄:Pr@CaMoO₄ (core/shell) and CaMoO₄:Pr@CaMoO₄@SiO₂ (core/shell/shell) nanoparticles were synthesized using polyol method. X-ray diffraction (XRD), thermogravimatric analysis (TGA), UV–vis absorption, optical band gap energy analysis, Fourier transform infrared (FTIR), FT-Raman and photoluminescence (PL) spectroscopy were employed to investigate the structural and optical properties of the synthesized core and core/shell nanoparticles. The results of the XRD indicate that the obtained core, core/shell and core/shell/shell nanoparticles crystallized well at ~150 °C in ethylene glycol (EG) under urea hydrolysis. The growth of the CaMoO₄ and SiO₂ shell (~12 nm) around the CaMoO₄:Pr core nanoparticles resulted in an increase of the average size of the nanopaticles as well as in a broadening of their size distribution. These nanoparticles can be well-dispersed in distilled water to form clear colloidal solutions. The photoluminescence spectra of core, core/shell and core/shell/shell nanoparticles show the characteristic charge transfer emission band of MoO₄ ^2? (533 nm) and Pr³⁺ 4f²?→?4f², with multiple strong ³H₄?→?³P₂, ¹D₂?→?³H₄ and ³P₀?→?³?F₂ transitions located at ~490, 605 and 652 nm, respectively. The emission intensity of the CaMoO₄:Pr@CaMoO₄ core/shell and CaMoO₄:Pr@CaMoO₄@SiO₂ core/shell/shell nanoparticles increased ~4.5 and 1.7 times,respectively, with respect to those of CaMoO₄:Pr core nanoparticles. This indicates that a significant amount of nonradiative centers existing on the surface of CaMoO₄:Pr@CaMoO₄ core/shell nanoparticles can be eliminated by the shielding effect of CaMoO₄ shells.     

Synthesis and characterization of hollow nanoparticles of crystalline Gd<Subscript>2</Subscript>O<Subscript>3</Subscript>

Although Gd₂O₃ (gadolinia) nanoparticle is the subject of intense research interest due to its magnetic property as well as controllable emission wavelengths by doping of various lanthanide ions, it is known to be difficult to prepare monodisperse crystalline gadolinia nanoparticles because it requires high temperature thermal annealing process to enhance the crystallinity. In this article, we demonstrate the synthesis of hollow nanoparticles of crystalline Gd₂O₃ by employing poly(N-vinylpyrrolidone) (PVP) to stabilize the surface of Gd(OH)CO₃·H₂O nanoparticles and to successively form SiO₂ shell as a protecting layer to prevent aggregation during calcinations processes. Silica shells could be selectively removed after calcinations by a treatment with basic solution to give hollow nanoparticles of crystalline Gd₂O₃. The formation mechanism of hollow nanoparticles could be suggested based on several characterization results of the size and shape, and crystallinity of Gd₂O₃ nanoparticles by TEM, SEM, and XRD.     

Core/shell structured ZnO/SiO2 nanoparticles: Preparation, characterization and photocatalytic property

ZnO nanoparticles were prepared by a simple chemical synthesis route. Subsequently, SiO₂ layers were successfully coated onto the surface of ZnO nanoparticles to modify the photocatalytic activity in acidic or alkaline solutions. The obtained particles were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive spectrometry (EDS) and zeta potential. It was found that ultrafine core/shell structured ZnO/SiO₂ nanoparticles were successfully obtained. The photocatalytic performance of ZnO/SiO₂ core/shell structured nanoparticles in Rhodamine B aqueous solution at varied pH value were also investigated. Compared with uncoated ZnO nanoparticles, core/shell structured ZnO/SiO₂ nanoparticles with thinner SiO₂ shell possess improved stability and relatively better photocatalytic activity in acidic or alkaline solutions, which would broaden its potential application in pollutant treatment.     

A facile synthesis approach and impact of shell formation on morphological structure and luminescent properties of aqueous dispersible NaGdF<Subscript>4</Subscript>:Yb/Er upconversion nanorods

A general facile synthesis approach was used for fabrication of highly emissive aqueous dispersible hexagonal phase upconversion luminescent NaGdF₄:Yb/Er nanorods (core NRs) through metal complex decomposition process. An inert NaGdF₄ and porous silica layers were grafted surrounding the surface of each and every NRs to enhance their luminescence efficiency and colloidal dispersibility in aqueous environment. Optical properties in terms of band gap energy of core, core/shell, and silica-coated core/shell/SiO₂ nanorods were observed to investigate the influence of surface coating, which was gradually decreased after surface coating because of increase crystalline size after growth of inert and silica shells. The inert shell formation before silica surface grafting, upconversion luminescence intensity was greatly improved by about 20 times, owing to the effective surface passivation of the seed core and, therefore, protection of Er³⁺ ion in the core from the nonradiative decay caused by surface defects. Moreover, after silica coating, core/shell nanorods shows strong upconversion luminescence property similar to the hexagonal upconversion core NRs. It is expected that these NaGdF₄:Yb/Er@NaGdF₄@SiO₂ (core/shell/SiO₂) NRs including highly upconversion emissive and aqueous dispersible properties make them an ideal materials for various photonic-based potential applications such as in upconversion luminescent bioimaging, magnetic resonance imaging, and photodynamic therapy.

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Synthesis and characterization of mono-dispersed Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Er<Superscript>3+</Superscript>-coated SiO<Subscript>2</Subscript> nanoparticles by co-precipitation process

In this paper, a facile co-precipitation process for preparing mono-dispersed core–shell structure nanoparticles is reported. The 110 nm SiO₂ cores coated with an yttrium aluminum garnet (Y₃Al₅O₁₂) layer doped with Er³⁺ were synthesized and the influence of the concentration ratio of [urea]/[metal ions] on the final product was investigated. The structure and morphology of samples were characterized by the X-ray powder diffraction, Fourier transform IR spectroscopy and transmission electron microscopy, respectively. The results indicate that a layer of well-crystallized garnet Y₃Al₅O₁₂:Er³⁺ were successfully coated on the silica particles with the thickness of 20 nm. The near infrared and upconversion luminescent spectra of the SiO₂@Y₃Al₅O₁₂:Er³⁺ powders further confirm that a Y₃Al₅O₁₂:Er³⁺ coating layer has formed on the surface of silica spherical particles.     

Deposition of conductive TiN shells on SiO<Subscript>2</Subscript> nanoparticles with a fluidized bed ALD reactor

Conductive TiN shells have been deposited on SiO₂ nanoparticles (10–20 nm primary particle size) with fluidized bed atomic layer deposition using TDMAT and NH₃ as precursors. Analysis of the powders confirms that shell growth saturates at approximately 0.4 nm/cycle at TDMAT doses of >1.2 mmol/g of powder. TEM and XPS analysis showed that all particles were coated with homogeneous shells containing titanium. Due to the large specific surface area of the nanoparticles, the TiN shells rapidly oxidize upon exposure to air. Electrical measurements show that the partially oxidized shells are conducting, with apparent resistivity of approximately ~11 kΩ cm. The resistivity of the powders is strongly influenced by the NH₃ dose, with a smaller dose giving an order-of-magnitude higher resistivity.     

Light scattering calculations from Au and Au/SiO2 core/shell nanoparticles

Given the importance of the optical properties of Au and Au/SiO₂ core/shell nanoparticles, in this article we focus our attention on the light scattering properties of such systems and on a relative comparison. In particular, we report theoretical results of angle-dependent light scattering intensity and scattering efficiency for Au and Au/SiO₂ core/shell nanoparticles increasing the Au particle radius from 30 to 130 nm, and for Au/SiO₂ core/shell particles changing the core-to-shell sizes ratio. Finally, a comparison between the scattering efficiency of the Au and Au/SiO₂ core/shell nanoparticles is drawn. The results of this work can be used in the design of tunable efficiency light scattering devices (biological and molecular sensors, solar cells).     

Synthesis of water dispersible boron core silica shell (B@SiO<Subscript>2</Subscript>) nanoparticles

Water dispersible boron nanoparticles have great potential as materials for boron neutron capture therapy of cancer and magnetic resonance imaging, if they are prepared on a large scale with uniform size and shape and hydrophilic modifiable surface. We report the first method to prepare spherical, monodisperse, water dispersible boron core silica shell nanoparticles (B@SiO₂ NPs) suitable for aforementioned biomedical applications. In this method, 40 nm elemental boron nanoparticles, easily prepared by mechanical milling and carrying 10-undecenoic acid surface ligands, are hydrosilylated using triethoxysilane, followed by base-catalyzed hydrolysis of tetraethoxysilane, which forms a 10-nm silica shell around the boron core. This simple two-step process converts irregularly shaped hydrophobic boron particles into the spherically shaped uniform nanoparticles. The B@SiO₂ NPs are dispersible in water and the silica shell surface can be modified with primary amines that allow for the attachment of a fluorophore and, potentially, of targeting moieties.

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Optical and fluorescent properties of Y<Subscript>2</Subscript>O<Subscript>3</Subscript> sol–gel planar waveguides containing Tb<Superscript>3+</Superscript> doped nanocrystals

Terbium doped Y₂O₃ planar waveguides were fabricated by sol–gel process and dip-coating using yttrium acetate as precursor. Two different doping modes were compared, i.e. introduction in the sol of dispersed Tb³⁺ions from dissolved Tb(NO₃)₃, or of nanoparticles of Tb₂O₃ or [Y₂O₃:50% Tb] from an alcoholic suspension. The chemical and nanostructural properties were analyzed by infrared spectroscopy, transmission electron microscopy and X-ray diffraction. The Tb³⁺ fluorescence properties were studied as a function of temperature and atmosphere of the thermal treatments, and of the Tb³⁺ concentration. The fluorescence properties are discussed in relation to the quenching mechanisms induced by Tb⁴⁺ transformation, residual OH groups, and crystallites size and structure. Optical propagation losses of the Tb doped Y₂O₃ planar waveguides related to the doping modes and Tb³⁺ concentration are presented. Doping sol–gel films by nanoparticles is shown to be a valuable alternative to the conventional doping from dissolved terbium salt. PACS 81.21.Fw; 84.40.Az; 78.67.Bf     

Synthesis and characteristics of nano-size sandwich structure (Y,Gd)BO3: Eu3+ phosphors

The sandwich structure core–shell–shell nanospheres SiO₂@(Y,Gd)BO₃:Eu³⁺@SiO₂ (SiO₂@YGB@SiO₂) have been synthesized by depositing YGB nanoparticles on silica core surface through the precipitation method, followed by sol–gel processing of tetraethoxysilane (TEOS) to form smooth silica shell over the surface of YGB. The phosphors were characterized by X-ray diffraction (XRD), scanning electronic microscope (SEM), transmission electronic microscope (TEM) and photoluminescence spectra. The results showed that the phosphors with spherical morphology can be produced easily by assembling the core–shell or core–shell–shell structure, and the XRD patterns indicated that the crystallinity of YGB is weakened due to the core–shell structure, which resulting from the local site symmetry of Eu³⁺ was decreased. The photoluminescence properties of the product are compared with those of the pure YGB, the core–shell structure SiO₂@YGB and YGB@SiO₂. The emission intensity, relative luminous efficiency and Red/Orange values of phosphors are increased in the order SiO₂@YGB@SiO₂>SiO₂@YGB>YGB@SiO₂>YGB; and the chromaticity coordinates of the phosphors are shifted from orange of pure YGB to red of SiO₂@YGB@SiO₂.     

Photoluminescence of the nanosized xerogel Zn<Subscript>2</Subscript>SiO<Subscript>4</Subscript>:Mn<Superscript>2+</Superscript> in pores of anodic alumina

The photoluminescence properties of a composite material prepared by the introduction of the nanosized phosphor Zn₂SiO₄:Mn²⁺ into porous anodic alumina have been investigated. Scanning electron microscopy studies have revealed that Zn₂SiO₄:Mn²⁺ particles are uniformly distributed in 70% of the volume of the pore channels. The samples exhibit an intense luminescence in the range of 2.3–3.0 eV, which corresponds to the emission of different types of F centers in alumina. After the formation of Zn₂SiO₄:Mn²⁺ nanoparticles in the pores, an intense photoluminescence band is observed at 2.4 eV due to the ⁴T₁–⁶A₁ electronic transition within the 3d shell of the Mn²⁺ activator ion. It has been found that the maximum of the photoluminescence of Zn₂SiO₄:Mn²⁺ xerogel nanoparticles located in the porous matrix is shifted to higher energies, and the luminescence decay time decreases significantly.     

Synthesis of robust water-soluble ZnS:Mn/SiO2 core/shell nanoparticles

Water-soluble Mn doped ZnS (ZnS:Mn) nanocrystals synthesized by using 3-mercaptopropionic acid (MPA) as stabilizer were homogeneously coated with a dense silica shell through a multi-step procedure. First, 3-mercaptopropyl triethoxy silane (MPS) was used to replace MPA on the particle surface to form a vitreophilic layer for further silica deposition under optimal experimental conditions. Then a two-step silica deposition was performed to form the final water-soluble ZnS:Mn/SiO₂ core/shell nanoparticles. The as-prepared core/shell nanoparticles show little change in fluorescence intensity in a wide range of pH value.     

The influence of Fe,Cu, SiO<Subscript>2</Subscript>, TiO<Subscript>2</Subscript>, and Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles in aqueous solution on proton relaxation times

Measurements of proton nuclear spin-spin and spin-lattice relaxation times are applied for determining the concentration of solid-phase nanoparticles in nanofluids. This approach is tested for metal oxides SiO₂, TiO₂, Al₂O₃ and metal-carbon nanoparticles of 3d-metals Fe and Cu. It is shown that the sensitivity of the method for determining concentrations of 3d-metals is much higher than for oxides (by 2–4 orders of magnitude). It is revealed that measurement of the proton spin-spin relaxation time allows one to determine the concentration of Cu nanoparticles to 0.0001 mg/ml and that of Fe nanoparticles to 0.00001 mg/ml.     

Synthesis and magnetic properties of FeNi<Subscript>3</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> core-shell nanocomposites

In this study, FeNi₃/Al₂O₃ core-shell nanocomposites, where individual FeNi₃ nanoparticles were coated with a thin layer of alumina, were fabricated by a modified sol-gel method. Several physical characterizations were performed on the samples of FeNi₃/Al₂O₃ nanocomposites with different thickness of Al₂O₃ shell. The encapsulation of FeNi₃ nanoparticles with alumina stops FeNi₃ agglomeration during heat treatment, and prevents interaction among the closely spaced magnetic FeNi₃ nanoparticles. The Al₂O₃ insulating shell improves the soft magnetic properties of FeNi₃. The study of the complex permeability of the samples shows that the real part μ’ of the permeability of the sample with Al molar content of 20% (Al/(Fe+Ni)) is as high as 12, and independent of frequency up to at least 1 GHz. The tunneling magnetoresistance arising from the presence of the Al₂O₃ shell have also been studied.     

Thermostable photocatalytically active TiO<Subscript>2</Subscript> anatase nanoparticles

Anatase is the low-temperature (300–550 °C) crystalline polymorph of TiO₂ and it transforms to rutile upon heating. For applications utilizing the photocatalytic properties of nanoscale anatase at elevated temperatures (over 600 °C) the issue of phase stabilisation is of major interest. In this study, binary TiO₂/SiO₂ particles were synthesized by a flame aerosol process with TiCl₄ and SiCl₄ as precursors. The theoretical Si/Ti ratio was varied in the range of 0.7–1.3 mol/mol. The synthesized TiO₂/SiO₂ samples were heat treated at 900 and 1,000 °C for 3 h to determine the thermostability of anatase. Pyrogenic TiO₂ P25 (from Evonik/Degussa, Germany) widely applied as photocatalyst was used as non-thermostabilized reference material for comparison of photocatalytic activity of powders. Both the non-calcinated and calcinated powders were characterized by means of XRD, TEM and BET. Photocatalytic activity was examined with dichloroacetic acid (DCA) chosen as a model compound. It was found that SiO₂ stabilized the material retarding the collapse of catalyst surface area during calcination. The weighted anatase content of 85% remains completely unchanged even after calcination at 1,000 °C. The presence of SiO₂ layer/bridge as spacer between TiO₂ particles freezes the grain growth: the average crystallite size increased negligibly from 17 to 18 nm even during the calcination at 1,000 °C. Due to the stabilizing effect of SiO₂ the titania nanoparticles calcinated at 900 and 1,000 °C show significant photocatalytic activity. Furthermore, the increase in photocatalytic activity with calcination temperature indicates that the titania surface becomes more accessible either due to intensified cracking of the SiO₂ layer or due to enhanced transport of SiO₂ into the necks thus releasing additional titania surface.     

Synthesis of core–shell nanoparticles with a Pt nanoparticle core and a silica shell

A method to prepare a core–shell structure consisting of a Pt metal core coated with a silica shell (Pt(in)SiO₂) is described herein. A silica shell was grown on poly(vinylpyrrolidone) (PVP)-stabilized Pt nanoparticles 2–3 nm in size through hydrolysis and condensation reactions of tetraethyl orthosilicate (TEOS) in a water/ethanol mixture with ammonia as a catalyst. This process requires precise control of the reaction conditions to avoid the formation of silica particles containing multiple Pt cores and core-free silica. The length of PVP molecules, water content, concentration of ammonia and Pt nanoparticles in solution were found to significantly influence the core–shell structure. By optimizing these parameters, it was possible to prepare core–shell particles each containing a single Pt nanoparticle with a silica layer coating approximately 10 nm thick.     

Shape controlled quantum dot (QD)-decorated-mesoporous SiO<Subscript>2</Subscript> (m-SiO<Subscript>2</Subscript>/QD) hollow particles for photodynamic therapy

This work reported a novel kind of CdTe quantum dot (QD) decorated mesoporous SiO₂ (m-SiO₂/QD) hybrid hollow nanoparticles for carrying photodynamic therapy (PDT) reagent. Both rod-like and spherical nanoparticles were prepared by using different shaped templates. Due to the porous shell and hollow interior, the hybrid m-SiO₂/QD hollow nanorod with 360 nm long and 120 nm in diameter was selected for carrying zinc(II) phthalocyanine (ZnPc) photosensitizing molecules (61 mg/g) since the generated reactive ¹O₂ could be easily delivered out of the hollow particles through the porous shell (BET area 251 cm²/g). It was found that the m-SiO₂/QD-ZnPc hollow nanorods exhibited a good PDT activity and showed effective photocytotoxicity for the cancer cells. Because of the porous nature, fluorescence characteristic, and excellent storage ability, the m-SiO₂/QD hybrid hollow particles possessed broad potential in the fluorescent labeled PDT.

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Graphic abstract m-SiO₂/QD hybrid hollow particles with different morphologies could be successfully synthesized by using the templating method and they could be used as carriers for photodynamic therapy reagents.