Victor V. Atuchin

Linear structural evolution induced tunable photoluminescence in clinopyroxene solid-solution phosphors.

Clinopyroxenes along the Jervisite (NaScSi2O6) – Diopside (CaMgSi2O6) join have been studied, and a solid-solution of the type (Na1−xCax)(Sc1−xMgx)Si2O6 has been identified in the full range of 0 ≤ x ≤ 1. The powder X-ray patterns of all the phases indicate a structural similarity to the end compounds and show smooth variation of structural parameters with composition. The linear structural evolution of iso-structural (Na1−xCax)(Sc1−xMgx)Si2O6 solid-solutions obeying Vegards rule has also been examined and verified by high resolution transmission electron microscopy (HRTEM). The continuous solid-solutions show the same structural type, therefore the photoluminescence spectra of Eu2+ doped samples possess the superposition of spectral features from blue-emitting component (CaMgSi2O6:Eu2+) and yellow-emitting one (NaScSi2O6:Eu2+). This indicates that the spectroscopic properties of (Na1−xCax)(Sc1−xMgx)Si2O6 clinopyroxene solid-solutions are in direct relations with structural parameters, and it is helpful for designing color-tunable photoluminescence with predetermined parameters.

New Yellow-Emitting Whitlockite-type Structure Sr1.75Ca1.25(PO4)2:Eu2+ Phosphor for Near-UV Pumped White Light-Emitting Devices

New compound discovery is of interest in the field of inorganic solid-state chemistry. In this work, a whitlockite-type structure Sr1.75Ca1.25(PO4)2 newly found by composition design in the Sr3(PO4)2-Ca3(PO4)2 join was reported. Crystal structure and luminescence properties of Sr1.75Ca1.25(PO4)2:Eu(2+) were investigated, and the yellow-emitting phosphor was further employed in fabricating near-ultraviolet-pumped white light-emitting diodes (w-LEDs). The structure and crystallographic site occupancy of Eu(2+) in the host were identified via X-ray powder diffraction refinement using Rietveld method. The Sr1.75Ca1.25(PO4)2:Eu(2+) phosphors absorb in the UV-vis spectral region of 250-430 nm and exhibit an intense asymmetric broadband emission peaking at 518 nm under λex = 365 nm which is ascribed to the 5d-4f allowed transition of Eu(2+). The luminescence properties and mechanism are also investigated as a function of Eu(2+) concentration. A white LED device which is obtained by combining a 370 nm UV chip with commercial blue phosphor and the present yellow phosphor has been fabricated and exhibit good application properties.

Pressure-Stimulated Synthesis and Luminescence Properties of Microcrystalline (Lu,Y)3Al5O12:Ce3+ Garnet Phosphors

The Lu2.98Ce0.01Y0.01Al5O12 and Y2.99Ce0.01Al5O12 phosphors were synthesized by solid state reaction at temperature 1623 K and pressure 1.5 × 10(7) Pa in (95% N2 + 5% H2) atmosphere. Under the conditions, the compounds crystallize in the form of isolated euhedral partly faceted microcrystals ∼19 μm in size. The crystal structures of the Lu2.98Ce0.01Y0.01Al5O12 and Y2.99Ce0.01Al5O12 garnets have been obtained by Rietveld analysis. The photoluminescence (PL) and X-ray excited luminescence (XL) spectra obtained at room temperature indicate broad asymmetric bands with maxima near 519 and 540 nm for Y2.99Ce0.01Al5O12 and Lu2.98Ce0.01Y0.01Al5O12, respectively. The light source was fabricated using the powder Lu2.98Ce0.01Y0.01Al5O12 phosphor and commercial blue-emitting n-UV LED chips (λ(ex) = 450 nm). It is found that the CIE chromaticity coordinates are (x = 0.388, y = 0.563) with the warm white light emission correlated color temperature (CCT) of 6400 K and good luminous efficiency of 110 lm/W.

Enhanced optical constants of nanocrystalline yttrium oxide thin films

Yttrium oxide (Y2O3) films with an average crystallite-size (L) ranging from 5 to 40 nm were grown by sputter-deposition onto Si(100) substrates. The optical properties of grown Y2O3 films were evaluated using spectroscopic ellipsometry measurements. The size-effects were significant on the optical constants and their dispersion profiles of Y2O3 films. A significant enhancement in the index of refraction (n) is observed in well-defined Y2O3 nanocrystalline films compared to that of amorphous Y2O3. A direct, linear L-n relationship found for Y2O3 films suggests that tuning optical properties for desired applications can be achieved by controlling the size at the nanoscale dimensions.

Surface crystallography and electronic structure of potassium yttrium tungstate

Structural and electronic characteristics of KY(WO4)2 (KYW) (010) crystal surfaces have been studied using reflection high-energy electron diffraction (RHEED) and x-ray photoelectron spectroscopy (XPS). The results indicate that the crystal structure and chemical composition of the mechanically polished pristine surface is stoichiometrically well maintained as expected for KYW crystals. Combined measurements of RHEED and XPS as a function of 1.5 keV Ar+ ion irradiation of the KYW (010) surfaces indicate amorphization, partial loss of potassium atoms, and partial transformation of chemical valence state of tungsten from W6+ to a lower valence state, W0 state predominantly, which induces electronic states at the top of valence band.

Structure evolution and photoluminescence of Lu3(Al,Mg)2(Al,Si)3O12:Ce3+ phosphors: new yellow-color converters for blue LED-driven solid state lighting

This paper reports the development of new phosphors using the chemical unit cosubstituting solid solution design strategy. Starting from Lu3Al5O12, the Al3+–Al3+ couple in respective octahedral and tetrahedral coordination was simultaneously substituted by a Mg2+–Si4+ pair forming the Lu3(Al2−xMgx)(Al3−xSix)O12:Ce3+ (x = 0.5–2.0) series; as a result, the CeO8 polyhedrons were compressed and the emission got red-shifted from green to yellow together with the broadening. The evolution of, the unit cell, the local structural geometry as well as the optical properties of Ce3+ in these garnet creations, in response to the gradual Mg–Si substitution for Al–Al, were studied by combined techniques of structural refinement and luminescence measurements. The new composition Lu2.97Ce0.03Mg0.5Al4Si0.5O12 was comprehensively evaluated regarding its potential application in blue LED-driven solid state white lighting: the maximum emission is at 550 nm under λex = 450 nm; the internal and external quantum efficiencies can reach 85% and 49%, respectively; a 1-phosphor-converted wLED lamp fabricated using the as-prepared phosphor exhibits the luminous efficacy of 105 lm W−1, the correlated color temperature of 6164 K and the color rendering index (Ra) of 75.6. The new solid solution composition series is open for further optimization to enhance the competence for commercial consideration.

Cation Substitution Dependent Bimodal Photoluminescence in Whitlockite Structural Ca3–xSrx(PO4)2:Eu2+ (0 ≤ x ≤ 2) Solid Solution Phosphors

Cation substitution dependent tunable bimodal photoluminescence behavior was observed in the Ca3-xSrx(PO4)2:Eu(2+) (0 ≤ x ≤ 2) solid solution phosphors. The Rietveld refinements verified the phase purity and whitlockite type crystal structure of the solid solutions. The tunable photoluminescence evolution was studied as a function of strontium content, over the composition range 0.1 ≤ x ≤ 2. In addition to the emission band peak at 416 nm in Ca3(PO4)2:Eu(2+), the substitution of Ca(2+) by Sr(2+) induced the emerging broad-band peak at 493-532 nm. A dramatic red shift of the emission peak located in the green-yellow region was observed on an increase of x in the samples with 0.75 ≤ x ≤ 2.00. The two emission bands could be related to the EuOn-Ca9 and EuOn-Ca9-xSrx emitting blocks, respectively. The values for the two kinds of emitting blocks in the solid solutions can be fitted well with the observed intensity evolution of the two emission peaks.

Spectroscopic ellipsometry characterization of the optical properties and thermal stability of ZrO2 films made by ion-beam assisted deposition

The optical properties, interface structure, and thermal stability of the ZrO2 films grown on Si(100) were investigated in detail. A 2nm thick interfacial layer (IL) is formed at the ZrO2–Si interface for the as-grown ZrO2. The optical constants of ZrO2 films and IL correspond to amorphous-ZrO2 and amorphous-SiO2, respectively. The oxidation and IL growth at 900°C, as a function of annealing time, exhibit a two-step behavior with a slow and a fast growth-rate zones. The transition from a zone of slow to fast rate is attributed to structurally modified ZrO2 facilitating the faster oxygen transport to the ZrO2∕Si interface.

Calcium and strontium thiobarbiturates with discrete and polymeric structures

Three new alkaline earth metal complexes, [Ca2(H2O)8(μ2-HTBA-O,O′)2(HTBA-O)2] (1), [Ca(H2O)5(HTBA-O)2]·2H2O (2), and [Sr(H2O)4(μ2-HTBA-O,S)2]n (3) (H2TBA = 2-thiobarbituric acid, C4H4N2O2S), were synthesized and characterized by FT-IR spectroscopy, TG-DSC, and single-crystal and powder X-ray diffraction analysis. The single-crystal X-ray diffraction data revealed that 1 and 2 are discrete structures, whereas 3 is a polymer. In 1 and 2, Ca2+ is seven-coordinate and forms a monocapped trigonal prism. In 1, the prisms are pairwise connected with the assistance of two [μ2-HTBA-O,O′]− ligands. In 3, Sr2+ is coordinated by four monodentate HTBA− via S or O donors and four waters, with the formation of a distorted square antiprism. The antiprisms are connected by μ2-O,S bridging HTBA−. Hydrogen bonding involving coordinated water and π–π interactions plays an important role in construction of the supramolecular 3-D structures in 1–3. Infrared spectroscopic data supported the structural data. The thermal stability of 1–3 decreases in the order 1 > 2 > 3. Dehydration of 1–3 was a multi-step process, followed by exothermic oxidative degradation of the 2-thiobarbiturate moiety between 290 and 800 °C.

The formation and structural parameters of new double molybdates RbLn(MoO4)2 (Ln = Pr, Nd, Sm, Eu)

The structures of double molybdates with general compositions ALn(MoO4)2 (A – alkaline metals, Cu or Tl) have been considered and compared. It has been shown that the ionic radii ratio RLn/RA is a key factor governing crystal symmetry. Different structure fields in ALn(MoO4)2 (A = Li+, Na+, K+, Cu+, Rb+, Ag+, Cs+, Tl+) molybdates have been defined as a function of element composition.