Characterization of luminescent properties of ZnO:Er thin films prepared by rf magnetron sputtering

ZnO:Er thin films were deposited on c-plane sapphire substrates by rf magnetron sputtering and annealed at 700 °C under air and H₂ atmospheres for the luminescent improvement. The effects of sputtering parameters and the annealing conditions on visible and 1.54 μm IR emissions were investigated. Structural and luminescent properties strongly depended on the deposition conditions and annealing atmospheres. By tuning the excitation wavelength, ZnO:Er thin films exhibited a strong emission band at around 465 nm and a weak emission at 525 nm originated from the energy transition of ⁴I_15/2–⁴F_5/2 and ⁴I_15/2–²H_11/2, respectively, while 1.54 μm IR emissions due to ⁴I_15/2–⁴I_13/2 transition.     

Infrared luminescence in Er3+:Yb3Al5O12 bulk ceramics prepared by sol–gel method

Erbium doped and pure ytterbium aluminium garnet (YbAG, Yb₃Al₅O₁₂) bulk ceramics were successfully prepared by a chelating sol–gel route based on the polyesterification of ethylenediaminetetraacetic acid (EDTA) with triethanolamine (TEA). The gel decomposition and phase formation in precursor powders were studied using XRD and TG/DTA. Amorphous precursor was directly converted to YbAG phase after calcinations at 800 °C. The influence of intermediate grinding on microstructure and luminescent properties was investigated. The discrete luminescence bands of the ⁴I_13/2 → ⁴I_15/2 transition were observed in the infrared emission spectra of erbium doped samples. The lifetime of luminescence at 1530 nm was 2.82 ms and 1.82 ms for the doped samples. This may be attributed to the different efficiency of surface recombination channel, caused by different grain size distribution. Prepared samples are suitable as a standard for photoluminescence measuring of Er-doped YbAG thin films.     

Structural,optical, and spectroscopic properties of Er3+-doped TeO2–ZnO–ZnF2 glass-ceramics

Transparent fluorotellurite glass-ceramics have been obtained by heat treatment of precursor Er-doped TeO₂–ZnO–ZnF₂ glasses. ErF₃ nanocrystals nucleated in the glass-ceramics have a typical size of 45 ± 10 nm. Based on the Judd-Ofelt theory, the main radiative parameters for the ⁴I_13/2 → ⁴I_15/2 transition have been obtained. The split of the absorption and emission bands and the reduction of the Ω₂ parameter, as compared to the glass, confirm the presence of Er³⁺ ions in a crystalline environment in glass-ceramic samples. The analysis of the ⁴I_13/2 decays suggests that a fraction of Er³⁺ ions remains in a glass environment while the rest forms nanocrystals. For the glass-ceramics, intense red and green upconversion emissions were observed with an enhancement of the ⁴F_9/2 → ⁴I_15/2 red one compared to the glass sample. The temporal evolution of the red emission together with the excitation upconversion spectra suggests that energy transfer processes are responsible for the enhancement of the red emission.     

Efficient near-infrared to visible and ultraviolet upconversion in polycrystalline BiOCl:Er3+/Yb3+ synthesized at low temperature

Er³⁺/Yb³⁺ co-doped BiOCl poly-crystals were synthesized by the conventional solid state method at 500 °C, which exhibited good crystalline and low phonon energy. Under 980 nm excitation, the samples showed intense red upconversion (UC) luminescence (Er³⁺: ⁴F_9/2→⁴I_15/2) as well as other four UC emission bands, including ultraviolet (UV) emission at 380 nm, violet emission at 411 nm, green UC emissions at 525 and 545 nm and near-infrared (NIR) emission between 800 and 850 nm, corresponding to the transitions of ⁴G_11/2, ²H_9/2, ²H_11/2, ⁴S_3/2 and ⁴I_9/2→⁴I_15/2 of Er³⁺, respectively. Interestingly, including the violet and green UC emissions, the red one originated a nearly three-photon process in this system, and a possible UC mechanism was proposed for the enhanced red emission.     

Y2O3:Yb,Tm and Y2O3:Yb,Ho powders for low-temperature thermometry based on up-conversion fluorescence

Recently, trivalent rare earth doped materials have received significant attention due to the strong temperature dependence of the fluorescence emission of these materials, which can be useful in temperature sensing. Here, we investigated Y₂O₃ ceramic powders doped with Yb³⁺ and co-doped with either Tm³⁺ or Ho³⁺. The powders were obtained via spray pyrolysis at 900 °C and additionally thermally treated at 1100 °C for 24 h. Structural characterization using X-ray powder diffraction confirmed the cubic bixbyte structure. Scanning electron microscopy (SEM) revealed that the particles exhibit a uniform spherical morphology. The up-conversion emissions were measured using laser excitation at 978 nm, resulting in the following transitions: blue emission in the range of 450–500 nm, weak red emission in the range of 650–680 nm and near infrared emission in the range of 765–840 nm for Tm³⁺, as well as green emission centered at 550 nm and weak near infrared emission at 755 nm for the Ho³⁺ ions. In addition, the temperature dependence of the fluorescence intensity ratios of different Stark components was analyzed in the range of 10–300 K. Significant temperature sensitivity was detected for several components, with the largest value of 0.097 K^?1 related to the intensity ratio of I₅₃₆ and I₇₇₂ emissions observed for the Y₂O₃:Yb,Ho powder.     

Dielectric properties and bright red emission of Y3+/Eu3+-codoped ZrO2 thin films prepared by chemical solution deposition

We report on an effective combination of good dielectric properties with bright red emission in Y³⁺/Eu³⁺-codoped ZrO₂ thin films. The thin films were deposited on fused silica and Pt/TiO₂/SiO₂/Si substrates using a chemical solution deposition method. The crystal structure, surface morphology, electrical and optical properties of the thin films were investigated in terms of annealing temperature, and Y³⁺/Eu³⁺ doping content. The 5%Eu₂O₃–3%Y₂O₃–92%ZrO₂ thin film with 400 nm thickness annealed at 700 °C exhibits optimal photoluminescent properties and excellent electrical properties. Under excitation by 396 nm light, the thin film on fused silica substrate shows bright red emission bands centered at 593 nm and 609 nm, which can be attributed to the transitions of Eu³⁺ ions. Dielectric constant and dissipation factor of the thin films at 1 kHz are 30 and 0.01, respectively, and the capacitance density is about 65.5 nf/cm² when the bias electric field is less than 500 kV/cm. The thin films also exhibit a low leakage current density and a high optical transmittance with a large band gap.     

Gd-based oxyfluoride glass ceramics: Phase transformation,optical spectroscopy and upconverting temperature sensing

A series of precursor glasses with compositions of SiO₂-Al₂O₃-AlF₃-Na₂O- NaF-Gd₂O₃/GdF₃-YbF₃-ErF₃ were prepared and their crystallization behaviors were investigated. For the samples with high F content, meta-stable hexagonal GdF₃ nanocrystals were preferentially precipitated from glass matrix and decreasing F/O ratio induced phase transformation to cubic NaGdF₄ and finally to hexagonal NaGdF₄. Benefited from its multiple active sites, significant enhanced upconversion luminescence was achieved for Yb/Er co-doped glass ceramic containing hexagonal NaGdF₄ nanocrystals. Importantly, significant temperature-sensitive upconversion fluorescence intensity ratio between Er³⁺: ²H_11/2 → ⁴I_15/2 transition (520 nm) and ⁴S_3/2 → ⁴I_15/2 one (540 nm) was detected owing to the competitive radiation transitions from these two thermally coupled emitting-states. Furthermore, linear temperature-dependent fluorescence intensity ratio between Er³⁺: ⁴F_9/2 → ⁴I_15/2 transition (650 nm) to ⁴S_3/2 → ⁴I_15/2 one (540 nm) was achieved, showing the advantages of high sensitivity, superior signal discriminability as well as excellent thermal stability for temperature determination.     

1.53 µm luminescence properties of Er3+-doped K–Sr–Al phosphate glasses

Trivalent erbium (Er³⁺)-doped K–Sr–Al phosphate glasses were prepared and studied their spectroscopic properties as a function of Er₂O₃ concentration. Judd–Ofelt analysis has been carried out for 1.0 mol% Er₂O₃-doped phosphate glass and in turn radiative properties have been evaluated for the excited levels of Er³⁺ ion. The radiative lifetime for the ⁴I_13/2 level was found to be higher for the present glass when compared to other Er³⁺-doped glasses. The Er³⁺-doped glasses exhibit intense near infrared emission at 1.53 µm corresponds to ⁴I_13/2→⁴I_15/2 transition as well as green emission at 546 nm corresponding to ⁴S_3/2→⁴I_15/2 under 980 nm and 488 nm excitations, respectively. The emission cross-section spectrum for 1.0 mol% of Er₂O₃-doped glass has been evaluated using McCumber theory. The gain cross-section has been evaluated as a function of population inversion, which revealed that the lasing action would be achieved at 1.53 µm for a population inversion about 40%. Decay curves for the ⁴I_13/2 level were measured and lifetimes have been determined for the studied glasses. The results indicate that the present glasses could be useful for laser as well as optical amplifiers at 1.53 µm.     

Single-source-precursor synthesis of soft magnetic Fe3Si- and Fe5Si3-containing SiOC ceramic nanocomposites

We present here the single-source-precursor synthesis of Fe₃Si and Fe₅Si₃-containing SiOC ceramic nanocomposites and investigation of their magnetic properties. The materials were prepared upon chemical modification of a hydroxy- and ethoxy-substituted polymethylsilsesquioxane with iron (III) acetylacetonate (Fe(acac)₃) in different amounts (5, 15, 30 and 50 wt%), followed by cross-linking at 180 °C and pyrolysis in argon at temperatures ranging from 1000 °C to 1500 °C. The polymer-to-ceramic transformation of the iron-modified polysilsesquioxane and the evolution at high temperatures of the synthesized SiFeOC-based nanocomposite were studied by means of thermogravimetric analysis (TGA) coupled with evolved gas analysis (EGA) as well as X-ray diffraction (XRD). Upon pyrolysis at 1100 °C, the non-modified polysilsesquioxane converts into an amorphous SiOC ceramic; whereas the iron-modified precursors lead to Fe₃Si/SiOC nanocomposites. Annealing of Fe₃Si/SiOC at temperatures exceeding 1300 °C induced the crystallization of Fe₅Si₃ and β-SiC. The crystallization of the different iron-containing phases at different temperatures is considered to be a consequence of the in situ generation of a Fe–C–Si alloy within the materials during pyrolysis. Depending on the Fe and Si content in the alloy, either Fe₃Si and graphitic carbon (at 1000–1200 °C) or Fe₅Si₃ and β-SiC (at T > 1300 °C) crystallize. All SiFeOC-based ceramic samples were found to exhibit soft magnetic properties. Magnetization versus applied field measurements of the samples show a saturation magnetization up to 26.0 emu/g, depending on the Fe content within the SiFeOC-based samples as well as on the crystalline iron silicide phases formed during pyrolysis.     

Generation of a low temperature NO linkage isomer in a transition metal complex of group 9: K[IrCl5NO]

The [IrCl₅NO]^− 1 ion in the potassium salt can be partially transformed into a metastable state by light irradiation in the violet-near UV region at low temperature (77 K). The excitation process was followed by infrared spectroscopy, comparing the spectra before and after irradiation.A new band grew at 1812 cm^− 1 after irradiation with light in the 308–420 nm spectral region. The metastable state behavior is verified as this band decays upon heating the samples above 90 K or by subsequent irradiation using 450–680 nm light. The band at 1812 cm^− 1 was assigned to ν(NO) of metastable state 1 (or an IrON linkage isomer) for comparison with the band position reported for other transition metal nitrosyls. To our knowledge, this is the first generation of a M-ON linkage isomer reported for a nitrosyl of transition metal of group 9. Its behavior is similar to that observed in other nitrosyl complexes of group 8.     

Physical,thermal and ablative performance of CVI densified urethane-mimetic SiC preforms containing in situ grown Si3N4 whiskers

A two-step process has been developed for silicon carbide (SiC) coated polyurethane mimetic SiC preform containing silicon nitride (Si₃N₄) whiskers. SiC/Si₃N₄ preforms were prepared by pyrolysis/siliconization treatment at 1600 °C, of powder compacts containing rigid polyurethane, novolac and Si, forming a porous body with in situ grown Si₃N₄ whiskers. The properties were controlled by varying Si/C mole ratios such as 1–2.5. After densification using a chemical vapour infiltration, the resulting SiC/Si₃N₄/SiC composites showed excellent oxidation resistance, thermal conductivity of 4.32–6.62 Wm⁻¹ K⁻¹, ablation rate of 2.38 × 10⁻³ − 3.24 × 10⁻³ g cm⁻² s and a flexural strength 43.12–55.33 MPa for a final density of 1.39–1.62 gcm⁻³. The presence of a Si₃N₄ phase reduced the thermal expansion mismatch resulting in relatively small cracks and well-bonded layers even after ablation testing. This innovative two-step processing can provide opportunities for expanded design for using SiC/Si₃N₄/SiC composites being lightweight, inexpensive, homogeneous and isotropic for various high temperature applications.     

Luminescent and structural properties of manganese-doped zinc aluminate spinel nanocrystals

Manganese-doped zinc aluminate spinel (ZnAl₂O₄:Mn; Mn=0–6.0 mol%) phosphor nanoparticles were prepared by the sol–gel process. The effects of thermal annealing and dopant concentration on the structure, microstructure and luminescence of the powder phosphors were investigated. The X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) results confirmed that a single-phase spinel started to crystallize at around 600 °C for the investigated powders. On heating at 600–1200 °C, the powders had the average crystallite sizes of around 12–33 nm. The crystallite size and lattice constant increased as the doping level of Mn increased. FT-IR spectra exhibited only absorption bands of the AlO₆ octahedral groups, which suggested that the powder phosphors mainly crystallized in a normal spinel structure. Scanning electron microscopy (SEM) investigations showed the primary particle sizes were around 20–25 nm for the powders annealed at 1000 °C, and less than ca. 50 nm for those annealed at 1200 °C. Photoluminescence (PL) spectra under UV or visible light excitation exhibited a strong green emission band centered at 510 nm, corresponding to the typical ⁴T₁(⁴G)—⁶A₁(⁶S) transition of tetrahedral Mn²⁺ ions. The most intense PL emission was obtained by exciting at 458 nm. The PL intensity was significantly enhanced by the improved crystallinity and diminished OH^? groups. Optimum brightness occurred at a doping of 3.0 mol% Mn.     

Melt synthesis of Eu-doped oxide phosphors using arc-imaging furnace

To synthesize various complex oxide materials and their solid solutions, we applied a novel “melt-synthesis technique” rather than conventional solid-state reaction techniques. Rapid synthesis methods to develop those double oxides have been strongly anticipated. During melt synthesis, the mixture of oxides or their precursors is melted rapidly (1–60 s) in an arc-imaging furnace using strong light radiation. A spherical molten sample with multiple homogeneously mixed cations was solidified directly on a copper hearth with rapid cooling of ca. 10² °C/s.We studied the synthesis of A₂BO₄ type double oxides (AA′)₂BO₄ (A = Sr²⁺, Ca²⁺, A′ = La³⁺, Gd³⁺, Y³⁺, Eu³⁺, B = Al) using this method. Homogeneous samples with Eu³⁺ dopants were synthesized using liquid phase mixing in a few seconds, which is much faster than diffusions of ions in solid phase. Red fluorescence under the irradiation of ultraviolet light (254 and 365 nm) was observed. The excitation band shifted.     

Near-infrared luminescent properties and natural lifetime calculation of a novel Er3+ complex

In this communication, a novel Er³⁺ complex Er(PT)₃TPPO [PT = 1-phenyl-3-methyl-4-tert-butylbenzoyl-5-pyrazolone, TPPO = triphenyl phosphine oxide] is successfully synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. Its optical properties and the energy transfer process from the ligand PT to the Er³⁺ ion are investigated, the typical near-infrared (NIR) luminescence (centered at around 1530 nm) is attributed to the ⁴I_13/2 → ⁴I_15/2 transition of Er³⁺ ion which results from the efficient energy transfer from PT to Er³⁺ ion (an antenna effect). The wider full width at half maximum (78 nm) peaked at 1530 nm in the emission spectrum and the Judd–Ofelt theory calculation on the radiative properties suggest that Er(PT)₃TPPO should be a promising candidate for tunable lasers and planar optical amplifiers.     

Large size and low density SiOC aerogel monolith prepared from triethoxyvinylsilane/tetraethoxysilane

Crack-free silicon oxycarbide (SiOC) aerogel monolith was fabricated by pyrolysis of precursor aerogel prepared from triethoxyvinylsilane/tetraethoxysilane (VTES/TEOS) using sol-gel process and ambient drying. Effects of different precursors, the amount of base catalyst (NH₄OH) and the heating rate during pyrolysis on the properties such as monolithicity, bulk density, surface area and pore size distribution of aerogels were investigated. The results show that the crack-free SiOC aerogel can be easily obtained from VTES/TEOS as compared to that of methyltriethoxysilanes/tetraethoxysilane (MTES/TEOS) and phenyltriethoxysilanes/tetraethoxysilane (PhTES/TEOS) precursors. The influence of heating rate during pyrolysis process on shrinkage rate, ceramic yield and surface area of the SiOC aerogels could be ignored, while the variation in the amount of NH₄OH exerted a strong impact on the properties of SiOC aerogels. Increasing the amount of NH₄OH resulted in the decrease of bulk density and surface area of SiOC aerogels from 0.335 g/cm³ and 488 m²/g to 0.265 g/cm³ and 365 m²/g. The resultant SiOC aerogels exhibit high compressive strength (1.45–3.17 MPa). ²⁹Si MAS NMR spectra revealed the retention of Si-C bond in the SiOC aerogels after pyrolysis at 1000 °C. The present work demonstrates VTES/TEOS is a promising co-precursors to easily and low cost synthesize large size SiOC aerogel monolith.     

Luminescent properties of rare earth (Er,Yb) doped yttrium aluminium garnet thin films and bulk samples synthesised by an aqueous sol–gel technique

Yttrium aluminium garnet (YAG) powders and thin films deposited on silicon substrates were prepared by an aqueous sol–gel route using metal nitrates. The sol–gel process resulted in an amorphous gel, and the thermal decomposition and successive crystallization were characterized by thermal analysis and X-ray diffraction. Powders were prepared by heat treatment of the amorphous gel, while crack-free thin films of densely packed nano-crystalline particles were obtained on silicon substrates by dip-coating technique. Photoluminescence (PL) properties as well as up-conversion (anti-stoke emission) of Er, Yb co-doped YAG phosphors were investigated. Green (555 nm) and red (650 nm) photoluminescence up-conversion emissions arising due to ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions, respectively for Er³⁺ ion were observed. Photoluminescence and radiative life-times of the exited states of Er³⁺ in the visible and near IR ranges are also reported.     

Persistent photoluminescence emission from SrTa2O6:Pr3+ phosphor prepared at different temperatures

Phosphors with persistent emission are of interest for security and emergency signage, and medical diagnosis. Three SrTa₂O₆:Pr³⁺phosphor samples with persistent emission were prepared by solid state reaction at 1200, 1400 and 1500 °C. Structural crystallization was shown to improve with an increase in temperature as identified by X-ray diffraction. The scanning electron microscopy images showed that the particles of the phosphor were agglomerated and co-melting was induced by increasing the synthesis temperature. The ion distribution in the phosphors was determined using the time of flight secondary ion mass spectroscopy. The red emission was obtained from the D₂→³H₄ and the ³P₀→³H₆ transitions at 608 and 619 nm, respectively. The main absorption occurred at 225 nm (5.5 eV), and the band gap (E_g) calculations confirmed that it corresponds to band-to-band excitation. Another excitation due to charge transfer at 300 nm was also obtained which makes the phosphor suitable to be used in red light emitting diodes. The persistent emission time parameters (260–296 s) were calculated from the phosphorescence decay curves using the second order exponential decay equation. The corresponding electron trapping centers were determined using the thermoluminescence spectroscopy, and the activation energy was determined using the initial rise method.     

Scintillation,TSL and RPL properties of MgF2 transparent ceramic and single crystal

We have prepared MgF₂ transparent ceramics by spark plasma sintering (SPS) and investigated the scintillation and dosimeter properties compared with those of a single crystal. Under X-ray irradiation, a transparent ceramic showed scintillation with a broad feature over 300–600 nm with decay times of 310 and 1940 μs while the single crystal did not show such emission. It was found that MgF₂ show radio-photoluminescence (RPL), which is a generation of new luminescence center by ionizing radiation. The RPL was only observed in the transparent ceramic samples, which appeared as two emission bands peaking around 415 and 700 nm under 340±40 nm excitation. During the PL reading, the emission band at 415 nm effectively increased over 50 s. This result suggested that the RPL in MgF₂ shows a build-up phenomenon. From PL emission/excitation characteristics and decay time, it was suggested that the RPL peak around 415 nm was due to M(C_2h) center.     

Red-brown ceramic pigments based on chromium doped ferrian armalcolite,effect of mineralizers

A new red-brown ceramic pigment based on chromium-doped ferrian armalcolite have been synthesized and characterized. (MgFe)(Cr_xTi_3−xFe)O₁₀ powders (x=0–0.3) fired at 1200 °C crystallize ferrian armalcolite as the only crystalline phase detected. Samples fired at 1000 °C show red-brown shades in glazes that darken and bluish (b* turns to negative values) at 1200 °C. The x=0.2 sample fired at 1000 °C shows the best red colour (L*a*b*=49.5/15.2/10.3). Assignment of bands in the UV–Vis–NIR spectra is difficult due to the overlapping of Cr³⁺, Cr⁴⁺ and Fe³⁺ absorptions in octahedral coordination. Analysis of UV–Vis–NIR spectra of powders shows that these spectra are dominated by the strong absorption associated to Fe³⁺ ions in octahedral sites. In contrast, an intense band at 520 nm dominates the UV–Vis–NIR spectra of glazed samples, which should be associated to Cr⁴⁺ in octahedral coordination. This absorption increases when the amount of chromium increases, indicating that chromium is the real chromophore of the system. Finally, the weak shoulder at 600 nm and the double weak band at 700 nm, detected more evidently when chromium amount in sample increases, indicate the progressive presence of Cr³⁺ in octahedral sites. The entrance of Cr⁴⁺ in x=0.1 sample shrinks the crystalline cell, but when chromium amount in the samples increases, both Cr⁴⁺ and Cr³⁺enter simultaneously and the unit cell remains practically stable. The microstructure of the powders analysed by SEM microscopy indicates aggregates of 6–10 fine particles of 200–400 nm of diameter. The addition of mineralizers (boric acid, sodium perborate, NaF and a mixture BaF₂.4MgF₂) does not modify significantly the reactivity of the system; at 1000 °C hematite and rutile remain as residual crystalline phases, except in NaF additions where the crystallization of NaFeTi₃O₈ is detected. SEM-EDX mapping analyses of pigment powders confirm in all cases a homogeneous distribution of ions in the particles.     

Effective Pd/C catalyst for chlorobenzene and hexachlorobenzene hydrodechlorination by direct pyrolysis of sawdust impregnated with palladium nitrate

Two Pd/C catalysts were prepared by pyrolysis of Pd(NO₃)₂ impregnated sawdust. At equal pyrolysis time slow ramping with shorter isothermal heating resulted in 0.9 wt.% Pd/C-S1 sample comprising carbon support with some oxygen-containing moieties and Pd⁰ with 2.6 nm average particle size (APS) partially decorated with carbon shell, whereas fast temperature ramping and long isothermal heating provided 0.6 wt.% Pd/C-S2 containing Pd⁰ with 3.7 nm APS, with larger fraction of carbon decorated particles. Pd/C-S1 is slightly more efficient than Pd/C-S2 in gas phase chlorobenzene hydrodechlorination to benzene at 100–250 °C. Only Pd/C-S1 provides hexachlorobenzene hydrodechlorination in liquid phase due to lower APS and probably smaller PdC_x content.