B.M. Nagabhushana

Combustion synthesis, characterization and Raman studies of ZnO nanopowders

Spherical shaped ZnO nanopowders (14-50 nm) were synthesized by a low temperature solution combustion method in a short time <5 min. Rietveld analysis show that ZnO has hexagonal wurtzite structure with lattice constants a=3.2511(1) Å, c=5.2076(2) Å, unit cell volume (V)=47.66(5) (Å)(3) and belongs to space group P63mc. SEM micrographs reveal that the particles are spherical in shape and the powders contained several voids and pores. TEM results also confirm spherical shape, with average particle size of 14-50 nm. The values are consistent with the grain sizes measured from Scherrers method and Williamson-Hall (W-H) plots. A broad UV-vis absorption spectrum was observed at ∼375 nm which is a characteristic band for the wurtzite hexagonal pure ZnO. The optical energy band gap of 3.24 eV was observed for nanopowder which is slightly lower than that of the bulk ZnO (3.37 eV). The observed Raman peaks at 438 and 588 cm(-1) were attributed to the E(2) (high) and E(1) (LO) modes respectively. The broad band at 564 cm(-1) is due to disorder-activated Raman scattering for the A(1) mode. These bands are associated with the first-order Raman active modes of the ZnO phase. The weak bands observed in the range 750-1000 cm(-1) are due to small defects.

CaTiO3:Eu3+ red nanophosphor: low temperature synthesis and photoluminescence properties.

Nanoparticles of Eu3+ doped (1-9 mol%) CaTiO3 were prepared using low temperature (500°C) solution combustion technique using metal nitrates as precursors and urea as fuel. The powder X-ray diffraction patterns of the as-formed products show single orthorhombic phase. The crystallite size was estimated using Scherrers method and found to be in the range 40-45 nm. The effect of Eu3+ ions on luminescence characteristics of CaTiO3 was studied and the results were discussed in detail. The phosphors exhibit bright red emission upon 398 nm excitation. The characteristic emission peaks recorded at ∼540, 593, 615, 653, 696 and 706 nm (5D0→7Fj=0,1,2,3,4,5) were attributed to Eu3+ ions. The electronic transition corresponding to 5D0→7F2 (615 nm) was stronger than the magnetic dipole transition 5D0→7F1 of Eu3+ ions (596 nm). The CIE chromaticity co-ordinates were calculated from emission spectra, the values (x,y) very close to NTSC standard value of red emission. Therefore, the present phosphors were highly useful for display applications.

Synthesis, structural and luminescence studies of magnesium oxide nanopowder.

Nanoparticles of magnesium oxide (MgO) have been prepared by low temperature solution combustion and hydrothermal method respectively. Powder X-ray diffraction (PXRD) patterns of MgO samples prepared by both the methods show cubic phase. The Scanning Electron Microscopy (SEM) studies reveal, the combustion derived product show highly porous, foamy and fluffy in nature than hydrothermally derived sample. The optical absorption studies of MgO show surface defects in the range 250-300 nm. The absorption peak at ∼290 nm might be due to F-centre. Photoluminescence (PL) studies were carried upon exciting at 290 nm. The sample prepared via combustion method show broad emission peak centred at ∼395 nm in the bluish-violet (3.14 eV) region. However, in hydrothermal prepared sample show the emission peaks at 395 and 475 nm. These emission peaks were due to surface defects present in the sample since nanoparticles exhibits large surface to volume ratio and quantum confinement effect.

Effect of different fuels on structural, thermo and photoluminescent properties of Gd2O3 nanoparticles

Gd(2)O(3) nanoparticles (27-60 nm) have been synthesized by the low temperature solution combustion method using citric acid, urea, glycine and oxalyl dihydrazide (ODH) as fuels in a short time. The structural and luminescence properties have been carried out using powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), Raman, UV-Vis, photoluminescence (PL) and thermoluminescence (TL) techniques. The optical band gap values were estimated for as formed and 800 °C calcined samples. The band gap values in as-formed and calcined samples were found to be in the range 4.89-5.59 eV. It is observed that, the band gap values are lower for as-formed products and it has been attributed to high degree of structural defects. However, in calcined samples, structure becomes more order with reduced structure defects. Upon 270 nm excitation, deep blue UV-band at ~390nm along with blue (420-482 nm), green (532 nm) and red emission (612 nm) was observed. The 390 nm emission peak may be attributed to recombination of delocalized electron close to the conduction band with a single charged state of surface oxygen vacancy. TL measurements were carried out on Gd(2)O(3) prepared by different fuels by irradiating with γ-rays (1 kGy). A well resolved glow peak at 230 °C was observed for all the samples. It is observed that TL intensity is found to be higher in for urea fuel when compared to others. From TL glow curves the kinetic parameters were estimated using Chens peak shape method and results are discussed in detail.

Enhanced photoluminescence of Gd2O3:Eu3+ nanophosphors with alkali (M = Li+, Na+, K+) metal ion co-doping

Gd(1.95)Eu(0.04)M(0.01)O(3) (M=Li(+), Na(+), K(+)) nanophosphors have been synthesized by a low temperature solution combustion (LSC) method. Powder X-ray diffraction pattern (PXRD), scanning electron microscopy (SEM), UV-vis and photoluminescence (PL) measurements were carried out to characterize their structural and luminescent properties. The excitation and emission spectra indicated that the phosphor could be well excited by UV light (243 nm) and emit red light about 612 nm. The effect of alkali co-dopant on PL properties has been examined. The results showed that incorporation of Li(+), Na(+) and K(+) in to Gd(2)O(3):Eu(3+) phosphor would lead to a remarkable increase of photoluminescence. The PL intensity of Gd(2)O(3):Eu(3+) phosphor was improved evidently by co-doping with Li(+) ions whose radius is less than that of Gd(3+) and hardly with Na(+), K(+) whose radius is larger than that of Gd(3+). The effect of co-dopants on enhanced luminescence was mainly regarded as the result of a suitable local distortion of crystal field surrounding the Eu(3+) activator. These results will play an important role in seeking some more effective co-dopants.

Synthesis, characterization and photoluminescence properties of CaSiO3:Eu3+ red phosphor

CaSiO3:Eu3+ (1-5 mol%) red emitting phosphors have been synthesized by a low-temperature solution combustion method. The phosphors have been well characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and optical spectroscopy. PXRD patterns reveal monoclinic CaSiO3 phase can be obtained at 900°C. The SEM micrographs show the crystallites with irregular shape, mostly angular. Upon 254 nm excitation, the phosphor show characteristic fluorescence 5D0→7FJ (J=0, 1, 2, 3, 4) of the Eu3+ ions. The electronic transition located at 614 nm corresponding to 5D0→7F2 of Eu3+ ions, which is stronger than the magnetic dipole transition located at 593 nm corresponding to 5D0→7F1 of Eu3+ ions. Different pathways involved in emission process have been studied. Concentration quenching has been observed for Eu3+ concentration>4 mol%. UV-visible absorption shows an intense band at 240 nm in undoped and 270 nm in Eu3+ doped CaSiO3 which is attributed to oxygen to silicon (O-Si) ligand-to-metal charge-transfer (LMCT) band in the SiO3(2-) group. The optical energy band gap is widened with increase of Eu3+ ion dopant.

CdSiO3:Pr3+ nanophosphor: Synthesis, characterization and thermoluminescence studies

A series of Pr(3+) (1-9 mol%) doped CdSiO(3) nanophosphors have been prepared for the first time by a low temperature solution combustion method using oxalyldihydrizide (ODH) as a fuel. The final product was characterized by Powder X-ray diffraction (PXRD), Fourier Transform Infrared Spectroscopy (FTIR), scanning electron microscopy (SEM), and UV-Vis spectroscopy. The average crystallite size was calculated using Debye-Scherrers formula and Williamson-Hall (W-H) plots and found to be in the range 31-37 nm. The optical energy band gap (E(g)) of undoped for Pr(3+) doped samples were estimated from Tauc relation which varies from 5.15-5.36 eV. Thermoluminescence (TL) properties of Pr(3+) doped CdSiO(3) nanophosphor has been investigated using γ-irradiation in the dose range 1-6 kGy at a heating rate of 5 °C s(-1). The phosphor shows a well resolved glow peak at ∼171 °C along with shouldered peak at 223 °C in the higher temperature side. It is observed that TL intensity increase with increase of Pr(3+) concentration. Further, the TL intensity at 171 °C is found to be increase linearly with increase in γ-dose which is highly useful in radiation dosimetry. The kinetic parameters such as activation energy (E), frequency factor (s) and order of kinetics was estimated by Luschiks method and the results are discussed.

Investigation of structural and luminescence properties of Ho3+ doped YAlO3 nanophosphors synthesized through solution combustion route

YAlO3:Ho(3+) (1-5mol%) nanophosphors have been prepared by solution combustion route using oxalyl dihydrazide (ODH) as a fuel. The final product was well characterized by powder X-ray diffraction (PXRD), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), UV-Vis, etc. PXRD patterns confirm the formation of highly crystalline orthorhombic phase structure. SEM and TEM studies show the particles are dumbbell shape, highly agglomerated and nano-size (∼30nm). The direct energy band gap (Eg) values estimated from Taucs relation were found to be in the range 5.76-5.99eV. Photoluminescence (PL) studies show green (540 and 548nm) and red (645 and 742nm) emissions upon excited at 452nm wavelength. The emission peaks at ∼742 and 645nm was associated with the transitions of (5)F4→(5)I7 and (5)F5→(5)I8 respectively. The higher energy bands located at 540 and 548nm were associated with (5)F4, (5)S2→(5)I8 transitions. Thermoluminescence (TL) studies of γ-irradiated YAlO3:Ho(3+) (1-5mol%) show two glow peaks at 223 and 325°C recorded at a heating rate of 2.5°Cs(-1). The 223°C glow peak follow linear behavior up to 1kGy and after that, it showed sub-linearity. Up to 1kGy, the phosphor is quite useful in radiation dosimetry. The kinetic parameters (E, b and s) were estimated from glow peak shape method. The CIE coordinate values lies within the green region. Therefore, the present phosphors may have potential application in WLEDs as green phosphor.

YAlO3:Cr3+ nanophosphor: synthesis, photoluminescence, EPR, dosimetric studies.

YAlO(3):Cr(3+) (0.1 mol%) nanophosphor has been synthesized by low temperature solution combustion method. The X-ray diffraction studies reveal an orthorhombic structure. Transmission electron microscopy reveals that the particles are spherical in shape with nano-size ~40-65 nm. Electron paramagnetic resonance (EPR) spectrum shows a resonance signal with effective g value at g=1.978 which can be attributed to the exchange coupled Cr(3+) ion pairs in weakly distorted sites. The photoluminescence spectrum shows an intense doublet at 677 nm and 694 nm (R lines) assigned to spin-forbidden (2)E(g)→(4)A(2)(g) transition of Cr(3+) ions. EPR and PL studies reveal that the Cr(3+) ions occupy Al(3+) sites in YAlO(3). The interesting feature reported in this work concerns the linearity with gamma dose in the wide range (0.1-6 kGy). Prominent TL glow peaks at 226 °C and 346 °C were observed for both γ and UV-rays respectively. It is observed that the peaks at 226 °C and 346 °C eventually show a linear response up to 5 kGy which makes them a candidate for high dose dosimetry of ionizing radiation. The kinetic parameters namely activation energy (E), order of kinetics (b), frequency factor (s) of undoped and Cr doped samples were determined using Chens glow peak shape method and the results are discussed in detail.

EPR, thermo and photoluminescence properties of ZnO nanopowders.

Nanocrystalline ZnO powders have been synthesized by a low temperature solution combustion method. The photoluminescence (PL) spectrum of as-formed and heat treated ZnO shows strong violet (402, 421, 437, 485 nm) and weak green (520 nm) emission peaks respectively. The PL intensities of defect related emission bands decrease with calcinations temperature indicating the decrease of Zn(i) and V(o)(+) caused by the chemisorptions of oxygen. The results are correlated with the electron paramagnetic resonance (EPR) studies. Thermoluminescence (TL) glow curves of gamma irradiated ZnO nanoparticles exhibit a single broad glow peak at ∼343°C. This can be attributed to the recombination of charge carriers released from the surface states associated with oxygen defects, mainly interstitial oxygen ion centers. The trapping parameters of ZnO irradiated with various γ-doses are calculated using peak shape method. It is observed that the glow peak intensity increases with increase of gamma dose without changing glow curve shape. These two characteristic properties such as TL intensity increases with gamma dose and simple glow curve structure is an indication that the synthesized ZnO nanoparticles might be used as good TL dosimeter for high temperature application.