Simas Sakirzanovas

Synthesis and optical properties of Li3Ba2La3(MoO4)8:Eu3+ powders and ceramics for pcLEDs

A series of polycrystalline Li3Ba2La3−xEux(MoO4)8 samples were prepared by the conventional solid-state reaction. The phase formation of the samples was investigated by X-ray diffraction measurements. The luminescence spectra and decay curves were studied as a function of Eu3+ concentration and temperature. It turned out that the optical band gap of the undoped molybdates is at 3.65 eV. The quantum efficiency (QE) of the Eu3+ doped luminescent materials increases with increasing Eu3+ concentration and almost 100% QE was obtained for those samples doped with 70, 80, or 90% Eu3+. A sample containing 100% Eu3+ showed solely a slight decrease in quantum efficiency. The luminous efficacy (LE) was 330 and 312 lm Wopt−1 for the 10 and 100% Eu3+ doped samples, respectively. The decrease of LE values is caused by a slight shift of the colour point to the red spectral range with increasing Eu3+ content. Temperature dependent measurements revealed that Li3Ba2Eu3(MoO4)8 loses only 15% of efficiency up to 400 K, which demonstrates that the investigated phosphors are attractive for application in pcLEDs.

Luminescence and luminescence quenching of highly efficient Y2Mo4O15:Eu3+ phosphors and ceramics

A good LED phosphor must possess strong enough absorption, high quantum yields, colour purity, and quenching temperatures. Our synthesized Y2Mo4O15:Eu3+ phosphors possess all of these properties. Excitation of these materials with near-UV or blue radiation yields bright red emission and the colour coordinates are relatively stable upon temperature increase. Furthermore, samples doped with 50% Eu3+ showed quantum yields up to 85%, what is suitable for commercial application. Temperature dependent emission spectra revealed that heavily Eu3+ doped phosphors possess stable emission up to 400 K and lose half of the efficiency only at 515 K. In addition, ceramic disks of Y2Mo4O15:75%Eu3+ phosphor with thickness of 0.71 and 0.98 mm were prepared and it turned out that they efficiently convert radiation of 375 and 400 nm LEDs to the red light, whereas combination with 455 nm LED yields purple colour.

Optically Clear and Resilient Free-Form µ-Optics 3D-Printed via Ultrafast Laser Lithography

We introduce optically clear and resilient free-form micro-optical components of pure (non-photosensitized) organic-inorganic SZ2080 material made by femtosecond 3D laser lithography (3DLL). This is advantageous for rapid printing of 3D micro-/nano-optics, including their integration directly onto optical fibers. A systematic study of the fabrication peculiarities and quality of resultant structures is performed. Comparison of microlens resiliency to continuous wave (CW) and femtosecond pulsed exposure is determined. Experimental results prove that pure SZ2080 is ∼20 fold more resistant to high irradiance as compared with standard lithographic material (SU8) and can sustain up to 1.91 GW/cm2 intensity. 3DLL is a promising manufacturing approach for high-intensity micro-optics for emerging fields in astro-photonics and atto-second pulse generation. Additionally, pyrolysis is employed to homogeneously shrink structures up to 40% by removing organic SZ2080 constituents. This opens a promising route towards downscaling photonic lattices and the creation of mechanically robust glass-ceramic microstructures.

Sol–gel (combustion) synthesis and characterization of different alkaline earth metal (Ca, Sr, Ba) stannates

In this study, monophasic strontium and barium stannate (SrSnO3, Sr2SnO4, BaSnO3, Ba2SnO4) powders were synthesized by means of environmentally friendly aqueous sol–gel technique under neutral conditions. However, it was established that the successful sol–gel synthesis of appropriate calcium stannates (CaSnO3 and Ca2SnO4) can be performed only at acidic sol–gel processing conditions. Moreover, the influence of nature of alkaline earth metal source on the phase purity of different metal stannates was evaluated. The thermal behaviour of Ca–Sn–O, Sr–Sn–O and Ba–Sn–O precursor gels was investigated by TG-DSC measurements. The phase purity, crystallization peculiarities and microstructural evolution of the sol–gel derived alkaline earth metal stannate powders were studied by XRD and SEM measurements.

CHARACTERIZATION OF CERIUM-DOPED YTTRIUM ALUMINIUM GARNET NANOPOWDERS SYNTHESIZED VIA SOL-GEL PROCESS

In this work the sol-gel process was used to prepare Ce-doped yttrium aluminium garnet (Y 3 A l 5 O 12, YAG) samples. The synthesis products were characterized by infrared spectroscopy (IR), X-ray powder diffraction analysis (XRD), and transmission electron microscopy (TEM). The particle size and luminescence properties of synthesized samples were also determined. The XRD patterns of Y 3 A l 5 O 12:Ce samples showed that phase purity of garnets depends on the synthesis temperature and concentration of dopant. The YAG:Ce samples calcined at 1000°C showed the formation of single-phase YAG in the whole doping range (from 0 up to 10 mol% of Ce). However, during calcination at 1300°C the formation of CeO2 as an impurity phase at >4 mol% of Ce was observed. The mean particle size of Y 3 A l 5 O 12:Ce sample (4 mol% of Ce) synthesized at 1300°C was determined to be approximately 180–280 nm. The luminescence properties of Ce-doped YAG also depend on cerium concentration in the samples. The highest emission (λ ex = 450nm) intensity was determined for Y 3 A l 5 O 12:Ce samples doped by 5–6 mol% of Ce.

Synthesis and Optical Properties of Li3Ba2La3(MoO4)8:Sm 3+ Powders for pcLEDs

A series of Sm3+-activated molybdates Li3Ba2(La1−xSmx)3(MoO4)8 with 0<̲x<̲1 (0% to 100% Sm3+) have been prepared by the conventional solid-state synthesis method, and their optical properties were investigated. Reflection, excitation and emission spectra were recorded and put in relation to the various [Xe]4 f 5 → [Xe]4 f 5 transitions of Sm3+. The positions of the charge transfer bands of Sm3+ and Mo6+ were resolved by Gaussian peak fitting. Emission spectra recorded at 100 K revealed the Stark sublevels of the Sm3+ energy levels. Time-dependent emission measurements of the 4G5/2 →6H9/2 transition were performed to disentangle the influence of temperature and activator concentration on the decay constants. The results are discussed in the context of the structure of the host material. Sm3+ occupies two different crystallographic sites at higher activator concentrations, which results in a bi-exponential decay curve. Temperature-dependent emission spectra were recorded to determine the thermal quenching behavior of the material. Internal and external quantum efficiencies (IQE and EQE) have been calculated. The IQE is independent of temperature, while the emission intensity strongly decreases at temperatures higher than 400 K. It is concluded that the photon escape efficiency in Li3Ba2La3(MoO4)8 correlates with temperature. An EQE of 44% was achieved for the 2% Sm3+ sample, which is comparatively high for Sm3+. Color points and luminous efficacies were calculated. The color point is independent of the Sm3+ concentration, but a blue-shift was observed with increasing temperature. This shift may be caused by lattice expansion and a subsequent decrease of spin-orbit coupling. Graphical Abstract Synthesis and Optical Properties of Li3Ba2La3(MoO4)8:Sm3+ Powders for pcLEDs

Synthesis and functionalization of NaGdF4:Yb,Er@NaGdF4 core–shell nanoparticles for possible application as multimodal contrast agents

Upconverting nanoparticles (UCNPs) are promising, new imaging probes capable of serving as multimodal contrast agents. In this study, monodisperse and ultrasmall core and core–shell UCNPs were synthesized via a thermal decomposition method. Furthermore, it was shown that the epitaxial growth of a NaGdF4 optical inert layer covering the NaGdF4:Yb,Er core effectively minimizes surface quenching due to the spatial isolation of the core from the surroundings. The mean diameter of the synthesized core and core–shell nanoparticles was ≈8 and ≈16 nm, respectively. Hydrophobic UCNPs were converted into hydrophilic ones using a nonionic surfactant Tween 80. The successful coating of the UCNPs by Tween 80 has been confirmed by Fourier transform infrared (FTIR) spectroscopy. Scanning electron microscopy (SEM), powder X-ray diffraction (XRD), photoluminescence (PL) spectra and magnetic resonance (MR) T1 relaxation measurements were used to characterize the size, crystal structure, optical and magnetic properties of the core and core–shell nanoparticles. Moreover, Tween 80-coated core–shell nanoparticles presented enhanced optical and MR signal intensity, good colloidal stability, low cytotoxicity and nonspecific internalization into two different breast cancer cell lines, which indicates that these nanoparticles could be applied as an efficient, dual-modal contrast probe for in vivo bioimaging.

Photochemical synthesis of CeO2 nanoscale particles using sodium azide as a photoactive material: effects of the annealing temperature and polyvinylpyrrolidone addition

A novel and simple method for CeO2 nanoscale particle synthesis in aqueous solutions via a photochemical route is reported in this paper. To this end, CeCl3·7H2O or Ce(NO3)3·6H2O was used as a Ce precursor, while NaN3 was chosen as the photoactive compound. Synthesis was carried out without any surfactants or by using polyvinylpyrrolidone (PVP). The synthesized samples were subsequently thermally treated at different temperatures between 100 and 900 °C. XRD patterns and Raman spectra indicated that CeO2 samples possess the fluorite structure. TEM analysis revealed that synthesis without surfactants leads to formation of highly agglomerated particles, while adding PVP to the primary solution resulted in decreased agglomeration and reduced particle size. The particle size was calculated from XRD and Raman line broadening and confirmed by TEM analysis. The average crystallite size for the unheated samples prepared without surfactant was hardly radiation exposure dependent and varied from 6.5 to 8.9 nm. Even smaller particles (3.3–7.0 nm) were formed by using PVP. It turned out that an increase of the calcination temperature causes significant crystallite growth. A strong interaction between CeO2 nanoparticles and PVP was revealed by TG analysis. The UV/VIS absorption spectra showed a strong absorption below 400 nm (3.10 eV) with a well-defined absorption peak at around 295–320 nm. The estimated band gap (Eg) of the obtained nanoscale particles was in the range of 2.90–3.57 eV, i.e. the values are higher than that of a bulk CeO2 powder (Eg = 3.19 eV), except for the sample calcined at 900 °C.

Stereophotography and spatial surface reconstruction using scanning electron microscopy images

Abstract Three-dimensional reconstruction technique to fully characterize structural performance of solid materials is suggested. The three-dimensional sample data out of the SEM images taken from different angles were extrapolated, measured and interpreted. In stereometry, the technique of three dimensional SEM imaging is fairly straightforward. Selected specimen area is photographed using SEM imaging tools from two different angles. Tilting is performed using standard SEM manipulation tools. In some cases, the specimen must be rotated to such a position, in which the tilting is done on visual ordinate axis. The resulting images are combined in pairs using any three-dimensional anaglyph software available to produce an anaglyph image, which, in turn, can be analyzed using standard 3D glasses. To achieve finer results, extrapolation of spatial data was done from three or more sample images using visual reconstruction software applications. This technique for recovering spatial data from the SEM pictures (structure-from-motion) is the VisualSFM software, which is an application for spatial reconstruction using structure from sample motion. Using VisualSFM, the images are analyzed for matching points and the camera angle is guessed for each image. Any number of additional viewports can be added to VisualSFM software. Based on this input, a surface is reconstructed where the matching points intersect and a colour value is assigned. The software produces a cloud of points, which has to be processed externally. Freely available software, such as MeshLab can be used to join the point cloud to a mesh and, as a second step of reconstruction, apply surface properties to the mesh polygons. The gold particles were selected as model material for the spatial 3D surface reconstruction.

Upconverting nanocrystals as luminescent temperature probes for local-heating imaging during direct laser writing 3D nanolithography

Luminescence measurements of upconverting nanocrystals (UCNCs) dispersed in SZ2080 prepolymer being pro- cessed by direct laser writing (DLW) nanopolymerization technique are presented. Er3+ ions doped β-NaYbF4 and Er3+,Yb3+ co-doped β-NaGdF4 core and core-shell UCNCs were prepared by a thermal decomposition method. The ratio of the 2H11/2 → 4I15/2 and 4S3/2 → 4I15/2 emission intensities under λ = 975 nm excitation was confirmed to follow Boltzmann-type distribution in the temperature range from 20 °C to 200 °C and enabled a self-referenced optical readout of the sample temperature changes. Variation of thermally-coupled spectral bands fluorescence intensity ratio (FIR) was observed while prepolymer being processed under typical DLW conditions (1030 nm, 300 fs, 200 kHz, NA = 0.8) and Epulse varying from below modification threshold to the optical breakdown. Average fitted temperature changes around polymerized voxel measured ∆T1 < 30 °C within polymerization window and increases up to ∆T2~100 °C in overexposing regime.