Transparent Barium Phosphate glasses embedded with rare-earth ions and silver were made by the melt quenching technique. Glasses were characterized by measuring absorption, emission spectra and lifetime measurements. From the emission measurements chromaticity diagrams were generated. Color coordinates and color temperature were estimated. The glass sample with silver was subjected to heat treatment to induce nanoparticles. Effect of heat treatment on luminescence measurements was analyzed.
A few different sodium borate glasses were made with various combinations of dopants ions, Sm3+, Dy3+, Tb3+ and Ag+. Absorption, and fluorescence spectral data of these samples were recorded. Chromaticity diagrams were plotted to measure color coordinates and color temperature. Samples were subjected to heat treatments above the glass transition temperature, to induce silver nanoparticles. Heat treated samples revealed a large enhancement in luminescence under 405 nm diode laser excitation and a relatively weaker enhancement under 375 nm laser excitation, which indicates the influence of plasmonic effect.
A few different Sodium borate glasses were made by the melt quenching technique. A sodium borate glass embedded with Dy3+ revealed white color when excited by a diode laser. A chromaticity diagram was developed which revealed color coordinates to be x=0.403 and y=0.426 for 375 nm diode laser excitation. A glass that was embedded with Dy3+, and Sm3+ revealed warm white light under diode laser excitation. However, another glass embedded with Dy3+, Sm3+, and Tb3+ revealed warm white light whose color coordinates are x=0.375 and y=0.455 and the coordinated color temperature is 5173 K.
We investigated terbium doped halide crystals. These materials were investigated by exposing them to blue and violet diode laser sources. Optical spectroscopy and lifetime measurements are performed for unambiguous assignment of spectral transitions and detect quenching phenomenon, if any. Terbium doped halide crystals revealed bright white light under low power diode laser excitation. Chromaticity diagrams are developed from spectral measurements. Color coordinates and color temperature are estimated. Our measurements indicate that terbium-doped fluorides are suitable for white-light generation under diode laser excitation.
Absorption spectrum of Er3+-dopedCaF2 revealed absorption peaks at 255, 365, 379, 407, 441, 449, 487, 522, 539, 652, and 798 nm. When the sample was excited with an 802-nm near-infrared laser, it revealed emissions at 390, 415, 462, 555, 665, and 790 nm due to stepwise excitation and energy transfer upconversion processes. The absorption and emission peaks are identified with Er3+ spectral transitions. The sample color appears to be either white or green under near-infrared laser excitation. Emission color was found to be dependent on the pump laser wavelength used and laser power. Excitation spectral recordings were made by tuning the pump laser wavelength. Excited state lifetimes are measured to analyze the data. Color coordinates and color temperatures are measured for 802- and 405-nm laser excitations. Our studies indicate that this sample is useful for solid-state lighting applications.
Sodium borate glass embedded with Tb3+, Sm3+ and Dy3+ was made by the melt quenching technique. The resulting glass is highly transparent. Absorption, and emission spectral measurements are performed. Under a diode laser excitation the glass emitted warm white light. Lifetimes of the excited levels are measured. CIE color co-ordinates and color temperature are measured.
CaF2 is a cubic material and Erbium enters the lattice in triply ionized state. Erbium occupies Ca sites in the material. Defects occur in the material because a trivalent dopant ion replaces a divalent host ion. Er3+ occupies several different sites. Absorption spectrum of Er3+-doped CaF2 revealed absorption peaks at 255, 365, 379, 407, 441, 449, 487, 522, 539, 652 and 798 nm. When the sample was excited with an 800 nm near-infrared laser it revealed emissions at 390, 415, 462, 555, 665 and 790 nm. The absorption and emission peaks are identified with Er3+ spectral transitions. The sample color appears to be either white or green under near-infrared laser excitation. Emission color was found to be dependent on the pump laser wavelength used and laser power. Excitation spectral recordings were made by tuning the pump laser wavelength. The sample emission appears to be white under near-infrared excitation as well as violet laser excitation. Excited state lifetimes are measured to analyze the data. Our studies indicate that this sample is useful in solid state lighting applications.
White light emission characteristics of Dy3+ -doped CaF2, KPb2Cl5 and KPb2Br5 are investigated. Absorption, emission and lifetime measurements of these samples are performed to analyze the data. All these materials revealed bright white light under 405 nm diode laser excitation.
ZnSe doped with Cr2+ was analyzed by EDS, XPS and Micro-Raman spectroscopy techniques. EDS and XPS
analysis revealed that chromium concentration is more than 2% and there are additional impurities, Ga, Ti, and Ta.
EDS measurements did not reveal any variation in chromium concentration when a line scan was performed over a
200 μm distance. XPS analysis indicated that the sample surface is inhomogeneous. Photoluminescence was
acquired by exciting the sample with 325 nm laser beam. Photoluminescence revealed charge transfer bands.
Micro-Raman study revealed the LO, TO and 2TA modes at 252, 205 and 140 cm-1. Under 488 or 514.5 nm
excitation background luminescence was predominant due to excitation of Cr2+ electrons into the conduction band.
However, 632.8 nm laser excitation revealed, strong Raman signals. Raman data were acquired by exciting the
sample on the grain boundary and inside the domain. The ratio of LO and TO peak intensities changed randomly
when data were acquired from different points on the grain boundary indicating the presence of random strain in the
material. When Raman data were acquired from different points on the sample surface for comparison, it revealed
that the LO mode was distorted as well as broadened whereas the TO mode intensity increased. This was due to the
presence of local modes induced by the sample inhomogeneity and the interaction of the holes with the LO mode.
Glasses embedded with Dysprosium and Samarium were made by the melt quenching technique. Dy3+ -doped glasses exhibited bright white luminescence under 10 mW of 405 nm diode laser excitation. Color rending index of the glass was improved by adding Sm3+ as a co-dopant to the glass. Spectroscopic results of the glasses are discussed.
Under 405 nm diode laser excitation Europium doped Lanthanum fluoride glows bright white and revealed numerous wavelengths in the blue, green and red regions of the electromagnetic spectrum. These lines were emitted from 5DJ (J=0, 1, 2 and 3) to 7FJ (J=0, 1, 2, 3, 4, 5, and 6) levels. For the same excitation conditions Europium doped Calcium fluoride glows white with abundant blue emission and some yellow light. These materials appear to be promising candidates for solid state white light sources. Emission characteristics are described in detail.
Silver doped sodium borate glass was made by the melt quenching technique. As made glass, did not
reveal any absorption transitions in the visible or ultraviolet region. Differential scanning calorimeter was used to
measure glass transition temperature. Heat treated glass revealed absorption peak at 410 nm due to surface plasmon
resonance. Under violet laser excitation the glass revealed emission at 450 - 620 nm, whose lifetimes are more than
30μs. Under near resonant excitation it revealed intense Raman scattering. We also made multielement oxide
glasses co-doped with silver and Er3+ and performed spectroscopic studies. Energy upconversion was observed
from Er3+ at 415 nm in a 2% Ag co-doped oxide glass but not in other glasses. Infrared to visible upconversion
studies were performed in all these glasses under near-infrared laser excitation. 2% Ag doped glass exhibited
enhanced upconversion signals from erbium than that of other glasses.
A 915 nm T:Sapphire laser was used to excite luminescence from Yb3+ doped YAG crystal. The excited ions undergo
nonradiative relaxation followed by strong emission at 1030 nm. The heating produced by the nonradiative relaxation
increases the sample temperature. A Mach-Zehnder interferometer was setup with 514.5 nm Ar+ laser beam. Laser
heating causes the interferometer fringes to move. A mathematical formula was developed to estimate the change in
sample temperature from the fringe count. When 300mW Ti:Sapphire laser beam was focused through the YAG:Yb3+crystal its temperature increased by 6.9°C. This technique works equally well to measure the solid sample temperature
changes in laser cooling studies.
Excited rare-earth ions relax radiatively and non-radiatively. The non-radiative relaxation rate and hence the lifetime of the excited level exhibit temperature dependence. These materials can be used to sense temperature below the melting point of the crystal. We have developed calibration standards using rare-earth ion doped crystals. The sensitivity of the technique and the applicable temperature range depends on the ionic energy levels and the type of crystal. We will discuss some of the results obtained in rare-earth ion doped fluoride and oxide crystals.
Lead magnesium niobate-lead titanate,
Pb(Mg, Nb)O3-PbTiO3 is a piezoelectric, ferroelectric crystal at room temperature with large electromechanical coefficient. The crystals were grown by PbO-B2O3 flux method. Typically the crystals were colorless and transparent, but a small fraction of them were Brown/reddish colored and show interesting photoluminescence (PL) properties. The PL studies were conducted under XeCl (308nm) excitation and under Argon Ion (Ar+) laser excitation. The excitation with 308nm gave broad PL centered at 500nm and intense emission at 710nm. The emission at 710nm in colorless crystals is very weak. The excitation with Ar+ laser coinciding with electronic absorption in brown samples gave rich and sharp PL particularly with 514.5 nm excitation. The PL with
514.5nm-Ar+ laserexcitation, consisted of intense anti stokes emission in addition to intense red and near infrared emission, is a result of photo-transfer optically stimulated luminescence (PT-OSL). This involved electron-hole recombination at photoinduced
magnetic polaron site. The PL emissions and the centers identified are the followings: 718nm emission due to magnetic polaron and 360nm emission due to cooperative emission from two polarons, Fe-R line at 660nm due to Fe3+ coupled to a cation; 380nm and 399nm due to Pb2+ clusters and Nb5+ center; 630 and 860 nm due to 6p→6s transition of Pb3+ and 760nm due to isolated Fe3+ ions. Raman spectrum of brown samples revealed the presence of nano particles/wires of orthorhombic β PbO. The FTIR spectrum gives evidence of significant amount of hydroxyl impurity.
Fluorescence lifetime sensing is useful to measure temperature in harsh environments. We implemented the technique
using samarium doped materials. The sample was exposed to a pulsed laser beam and the resulting lifetime was
measured. A plot of lifetime versus temperature exhibited a linear dependence. A small change in temperature produced
a significant change in lifetime, which is important in measuring temperature accurately. This technique is an alternative
when conventional techniques are not suitable.
Optical spectra of Pr3+ doped fiber was recorded under dye laser and Ar+ laser excitation. Fluorescence was observed from 1D2 and 3P0 levels. In addition to that emission was also observed at 280 to 300 nm due to cooperative emission.
Two-photon absorption phenomena are useful for the generation of short wavelength radiation. When the same atom absorbs IR and visible photons it generates uv/visible energy. Such two-photon absorption phenomena in certain rare-earth ion doped materials have been implemented in our laboratory. The importance of these studies in fibers will be discussed. Infrared quantum counter studies in Eu, Tb, Ho, Er, and Pr doped fibers are proposed for future work.
Step-wise two-photon excitation studies are useful for the development of upconversion lasers and infrared quantum counter devices. Our recent experimental results on erbium doped materials revealed efficient violet upconversion emission under diode laser excitation. Latest experiments on infrared quantum counter studies are also discussed. Different energy upconversion phenomena and the upconversion laser development are also reviewed in detail. A discussion is given on the estimation of excited state absorption cross sections.
High-resolution spectroscopic studies of Eu3+ doped Y2SiO5 revealed certain new aspects, which were not known in the past. Our studies indicate that europium occupies several distinct sites in this host material. Temporal evolution revealed unusual behavior.
When a praseodymium doped fluoride fiber was pumped with a 587 nm dye laser that resonantly excited the 1D2 level of Pr3+, we detected energy upconversion signals at 492 and 522 nm from the 3P0,1 levels. We also observed violet upconversion signals at 356, 382 and 413 nm. Anti Stokes Raman signals were observed at 3500 - 4200 cm-1 away from the laser beam.
Green upconversion signals were observed from the 5S2 levels of holmium ion under 2 mW HeNe laser excitation. Under a dye laser or Ar+ laser excitation, we also observed blue upconversion signals from 3H6, 5G4 and 5G5 levels in addition to the green and red signals.
Interferometry is an essential field of optical metrology and is adapted in many applications in optics, crystal growth, and industry. Crystal growth rate is one of the critical parameters for the growth of optical quality single crystals. A laser interferometry technique has been developed and applied successfully for crystal growth rate measurement from solution. A He-Ne laser at the wavelength of 633 nm with an output power of 1.5 mW was used in this experiment. The beam was incident on the crystal growing from solution. As the crystal is growing, the path length of the front and back surface reflected beams changes hence the phase factor of the detector output signal changes continuously. This phase change is directly related to the growth of crystal. The growth rate of the LAP crystal was found to be 6.5 plus or minus 0.1 nm/s. A Mach-Zehnder interferometer, also, has been applied to study the variation of concentration at the interface of the growing crystal from solution.
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