Kinetics of Cr3+ to Cr4+ ion valence transformations and intra-lattice cation exchange of Cr4+ in Cr,Ca:YAG ceramics used as laser gain and passive Q-switching media.

This paper focuses on the kinetics of Cr4+ formation in Cr,Ca:YAG ceramics prepared by solid-state reaction sintering. The kinetics of Cr4+ formation was studied by annealing of Cr,Ca:YAG ceramics in ambient air under different temperatures at different times, resulting in the transformation of Cr3+ to Cr4+. The activation energy (Ea) of Cr3+ oxidation determined by the Jander model was 2.7 ± 0.2 eV, which is in good correlation with the activation energy of innergrain oxygen diffusion in the YAG lattice. It is concluded that Cr3+ to Cr4+ transformation in YAG ceramics is limited by oxygen diffusion through the grain body. It was established that in Cr,Ca:YAG ceramics, the intralattice cation exchange, in which the Cr4+ ions exchange positions with the Al3+ ions, switching from "A" to "D" sites, is faster than Cr3+ to Cr4+ oxidation. In the temperature range of 900-1300 °C, the reaction enthalpy of Al3+/Cr4+ ion exchange between octahedral "A" and tetrahedral "D" lattice sites is close to zero, and this exchange ratio is thermodynamically driven by entropy.

Structural and optical characterization of RbLaP4O12:Ln3+ (Ln3+ = Ce3+, Nd3+, Tm3+, or Yb3+).

In this work, for the first time, detailed structural and optical characterization of RbLaP4O12 doped with different concentrations of Ce3+, Nd3+, Tm3+, or Yb3+ ions is reported. The samples were obtained via a precipitation technique. Their structural characterization was performed using X-ray diffraction (XRD), and infrared and Raman spectroscopies. Following XRD data, the unit cell parameters of host lattices were calculated using Rietveld refinement. It was found that an increase in the dopant content leads to a decrease in the unit cell volume. The optical characterization of RbLaP4O12:Ln3+ was carried out by collecting absorption and emission spectra, as well as luminescence decay profiles. Following absorption spectra, the energy band gap of the studied matrix was determined. It was found that the broad absorption band located in the ultra-violet range, in most cases ascribed to charge transfer or f-d transitions, is in fact related to the absorption of the host lattice. The analysis of luminescence properties allowed us to investigate possible ways of depopulation emission levels of impurities.

Laser induced white emission generated by infrared excitation from Eu3+:Sr2CeO4 nanocrystals.

The laser induced white emission (LIWE) was observed from Eu3+:Sr2CeO4 nanocrystals. The samples were obtained in form of powders by the modified sol-gel route. The structure and morphology of the phosphors were investigated by powder X-ray diffraction and transmission electron microscope techniques. The intense LIWE occurred under reduced pressure and focused beam of near infrared laser excitation. The power and pressure dependencies exhibit evident threshold character typical for the avalanche effect. The photoconductivity of the Eu3+:Sr2CeO4 nanocrystals measured as a function of different powers of excitation source was analyzed.

Broadband anti-Stokes white emission of Sr2CeO4 nanocrystals induced by laser irradiation.

The laser induced white emission (LIWE) from Sr2CeO4 nanocrystals upon irradiation with a focused IR laser beam was investigated. It was observed to be a threshold phenomenon with its intensity increasing exponentially with the excitation power density. This process was investigated under double laser beam simultaneous excitation in the UV range leading to Stokes emission in the visible range and in the IR range leading to anti-Stokes LIWE. With increasing LIWE intensity, the Stokes emission intensity strongly decreased. The LIWE is accompanied by efficient photocurrent generation depending on laser excitation density followed by multiphoton absorption and ionization processes. Photoimpedance measurements showed a sharp increase of the dielectric constant by several orders of magnitude in the Sr2CeO4 nanocrystals during the LIWE process demonstrating a metallic-like behaviour. The mechanisms of LIWE include multiphoton absorption and ionization that lead to the creation of a coupled pair of Ce3+ and Ce4+ ions that allow for the intervalence charge transfer (IVCT) emission transitions in the white light range. A strong decrease of absorption band intensity of Sr2CeO4 with increasing LIWE intensity confirms the creation of (Ce3+, Ce4+) pairs.

Cytotoxic interactions of bare and coated NaGdF4:Yb(3+):Er(3+) nanoparticles with macrophage and fibroblast cells.

The lanthanide nano-compounds are well suited to serve as fluorescent and magnetic contrast agents and luminescent labels. Although they are considered as promising materials for bio-imaging and bio-sensors in vivo or in vitro, the amount of data is still insufficient for deep understanding the toxicity of these nanomaterials. This knowledge is of great importance in the light of growing use of the biofunctionalized nanoparticles, which raises some questions about safety of these materials. Despite lanthanide-doped NaGdF4 nanocrystals are considered as non-toxic, here we present the data showing the fatal effect of newly synthetized NaGdF4:Yb(3+):Er(3+) on chosen types of cells. Our studies were performed on two cell lines NIH3T3 fibroblasts, and RAW264.7 macrophages. Cytotoxic properties of NaGdF4:Yb(3+):Er(3+) nanoparticles and their biological effects were studied by assessing cell culture viability (MTS), proliferation and apoptosis. Bare NaGdF4:Yb(3+):Er(3+) nanocrystals were cytotoxic and induced apoptosis of both NIH3T3 and RAW264.7 cells. Their cytotoxicity was reduced by PEGylation, at the expense of minimizing direct interactions between the compound and the cell. On the other hand, coating with silica reduced cell death induced by Yb(3+):Er(3+) codoped NaGdF4 nanocrystals (but proliferation was still inhibited). The NH2-modified silica coated nanoparticles were clearly less cytotoxic than pristine nanoparticles, which suggests that both, silica and PEG coatings are reasonable approaches to decrease cytotoxicity of the nanocrystal labels. The silica and PEG shell, should also enable and simplify further bio-functionalization of these luminescent labels. The authors acknowledge the financial support from: Institute of Immunology and Experimental Therapy, Polish Academy of Sciences (IITD PAN) grant no. 3/15, Polish Ministry of Science and Higher Education, Grant N N507 499538 and from the Wroclaw Research Centre EIT+ within the project "The Application of Nanotechnology in Advanced Materials" - NanoMat (POIG.01.01.02-02-002/08) financed by the European Regional Development Fund (Operational Program Innovative Economy, 1.1.2).

Near infrared absorbing near infrared emitting highly-sensitive luminescent nanothermometer based on Nd(3+) to Yb(3+) energy transfer.

A new type of near infrared absorbing near infrared emitting (NANE) luminescent nanothermometer is presented, with a physical background that relies on efficient Nd(3+) to Yb(3+) energy transfer under 808 nm photo-excitation. The emission spectra of LiLa0.9-xNd0.1YbxP4O12 (x = 0.05, 0.1, 0.2, 0.3, 0.5) nanocrystals were measured in a wide 100-700 °C temperature range. The ratio between the Nd(3+) ((4)F3/2→(4)I9/2) and Yb(3+) ((2)F5/2→(2)F7/2) luminescence bands, and the thermometer sensitivity were found to be strongly dependent on the Yb(3+) concentration. These phenomenological relations were discussed in terms of the competition between three phenomena, namely (a) Nd(3+)→ Yb(3+) phonon assisted energy transfer, (b) Yb(3+)→ Nd(3+) back energy transfer and (c) energy diffusion between Yb(3+) ions. The highest sensitivity of the temperature measurement was found for x = 0.5 (LiLa0.4Nd0.1Yb0.5P4O12), which was equal to 4 × 10(-3) K(-1) at 330 K. In stark contrast to conventional approaches, the proposed phosphate host matrix allows for a high level of doping, and thus, owing to the negligible concentration quenching, the presented luminophores exhibit a high absorption cross section and bright emission. Moreover, such optical remote thermometers, whose excitation and emission wavelengths are weakly scattered or absorbed and fall into the optical transmission window of the skin, may therefore become a practical solution for biomedical applications, such as remote control of thermotherapy.

Synthesis and up-conversion luminescence of Er(3+) and Y b(3+) codoped nanocrystalline tetra- (KLaP4O12) and pentaphosphates (LaP5O14).

The up-converting nanocrystals of KLa0.95Er0.05Y bxP4O12 and La0.95-xEr0.05Y bxP5O14 were prepared using co-precipitation method. The spectroscopic properties of these materials were investigated in a function of Y b(3+) concentration. The up-conversion emission, power dependence of emission intensities, and the luminescence decay times were investigated. It was found that the green to red and (2)H11/2 → (4)I15/2 to (4)S3/2 → (4)I15/2 emission intensity ratio were strongly affected by the Y b(3+) concentration. Moreover, the order of up-conversion emission and threshold power rises up with Y b(3+) concentration for (4)S3/2 → (4)I15/2 transition. The luminescence decay time of the (4)S3/2 → (4)I15/2 emission increases with Y b(3+) concentration while the (4)F9/2 → (4)I15/2 emission is independent of dopant concentration. The influence of the Y b(3+) concentration on the up-conversion emission intensities was discussed in terms of concentration dependent hetero looped photon avalanche process. A comparison of the up-conversion properties of KLa0.95Er0.05Y bxP4O12 and La0.95-xEr0.05Y bxP5O14 nanocrystals was presented.

Influence of grain size on optical properties of Sr2CeO4 nanocrystals.

The absorption, excitation, and emission spectra of the Sr2CeO4 nanocrystals prepared by the modified sol-gel method were investigated. The impact of the average grain size of Sr2CeO4 nanocrystals on their optical properties was investigated. It was observed that with increasing the average grain size of Sr2CeO4 nanocrystals, the emission decay times decreased significantly. A similar behavior was observed for the emission quantum efficiencies and the Huang-Rhys factors. The grain size dependence of optical parameters of Sr2CeO4 nanocrystals was found well fitted by functions of the reciprocal of the grain diameter. It was shown that this dependence may be rationalized assuming that the correction for electric local field associated with effective refractive index affecting the spherical nanoparticle is governed by its shell.

Synthesis and luminescent properties of La(1-x)Nd(x)P5O14 nanocrystals.

La(1-x)Nd(x)P5O14 nanocrystals were synthesized using a coprecipitation method. Their structure and morphology were determined. The luminescence and excitation spectra of La(1-x)Nd(x)P5O14 nanocrystals were measured in the entire range of Nd(3+) concentration. It was found that the relative intensities of absorption transitions increased significantly with concentration due to the cooperative interactions. The effect of concentration on fluorescence transitions was investigated. It was found that the intensity of the (4)F3/2 → (4)I11/2 transition significantly increased with concentration relative to the resonant (4)F3/2 → (4)I9/2 transition almost three times due to strong reabsorption. The concentration quenching of fluorescence was discussed in terms of the Yokota-Tanimoto model.

Optimisation of ligand exchange towards stable water suspensions of crystalline NaYF4: Er3+, Yb3+ nanoluminophors.

NaYF4: 2%Er3+, 20%Yb3+ nanoparticles were synthesized through a wet chemical route. In order to transfer the nanoparticles from chloroform to aqueous solution an oleic acid to 3-mercaptopropionic acid ligand exchange process has been performed and optimized. The influence of temperature and atmosphere onto the NaYF4:2%Er3+, 20%Yb3+ nanoparticles water suspensions dispersibility and stability after replacing oleic acid with 3-mercaptopropionic acid ligands has been investigated. The results revealed an improvement of nanoparticles water suspension transparency and luminescence yield after ligand exchange process performed under inert atmosphere and at elevated temperature.

White emission of lithium ytterbium tetraphosphate nanocrystals.

An efficient anti-Stokes white broadband emission induced by 976 nm laser diode in lithium ytterbium tetraphosphate (LiYbP4O12) nanocrystals was investigated. The emission occurs at room temperature and atmospheric pressure. Its intensity demonstrates an evident threshold dependence on the temperature and excitation density characteristic to avalanche process. The white emission is accompanied by very efficient photoconductivity characterized by microampere photocurrent which increases with the fourth order of applied incident light power (~P4). We show that this emission is critically dependent on temperature and increases significantly in vacuum. It is concluded that the anti-Stokes white emission is associated with theYb3+- CT luminescence.