Frequency upconversion properties of Er3+/Yb3+-codoped lead-germanium-bismuth oxide glasses

The frequency upconversion properties of Er3+/Yb3+-codoped heavy metal oxide lead-germanium-bismuth oxide glasses under 975 mn excitation are investigated. Intense green and red emission bands centered at 536, 556 and 672 run, corresponding to the H-2(1/2) --> I-4(15/2), S-4(3/2) --> I-4(15/2) and F-4(9/2) -->I-4(15/2) transitions of Er3+, respectively, were simultaneously observed at room temperature. The influences of PbO on upconversion intensity for the green (536 and 556 nm) and red (672 nm) emissions were compared and discussed. The optimized rare earth doping ratio of Er3+ and Yb3+, is 1:5 for these glasses, which results in the stronger upconversion fluorescence intensities. The dependence of intensities of upconversion emission on excitation power and possible upconversion mechanisms were evaluated and analyzed. The structure of glass has been investigated by means of infrared (IR) spectral analysis. The results indicate that the Er3+/Yb3+-codoped heavy metal oxide lead-germanium-bismuth oxide glasses may be a potential materials for developing upconversion fiber optic devices. (C) 2006 Published by Elsevier Ltd.

Absolute oscillator strengths for iron, copper, cadmium and gold measured by the atomic beam method

Absolute f-values for 7 transitions in the first spectra of 4 elements have been measured using the atomic beam absorption technique. The equivalent widths of the absorption lines are measured with a photoelectric scanner and the atomic beam density is determined by continuously weighing a part of it with a sensitive automatic microbalance. The complete theory is presented and corrections are calculated to cope with gas absorption by the deposit on the microbalance pan and atoms which do not stick to the pan. An additional correction for the failure of the assumption of effusive flow in the formation of the atomic beam at large densities has been measured experimentally.

The following f-values were measured:

Fe: f_λ3720 = 0.0430 ± 8%

Cu: f_λ3247 = 0.427 ± 4.5%, f_λ3274 = 0.206 ± 4.7%, f_λ2492 = 0.0037 ± 9%

Cd: f_λ3261 = 0.00190 ± 7%, f_λ2288 = 1.38 ± 12%

Au: f_λ2428 = 0.283 ± 5.3%

Comparison with other accurately measured f-values, where they exist, shows agreement within experimental errors.

Metallogenic Provinces of the Southwestern United States and Northern Mexico

Some of the metallogenic provinces of the southwestern United States and northern Mexico are defined by the geographic distribution of trace elements in the primary sulfide minerals chalcopyrite and sphalerite. The elements investigated include antimony, arsenic, bismuth, cadmium, cobalt, gallium, germanium, indium, manganese, molybdenum, nickel, silver, tellurium, thallium, and tin. Of these elements, cobalt, gallium, germanium, indium, nickel, silver, and tin exhibit the best defined geographic distribution.

The data indicate that chalcopyrite is the preferred host for tin and perhaps molybdenum; sphalerite is the preferred host for cadmium, gallium, germanium, indium, and manganese; galena is the preferred host for antimony, bismuth, silver, tellurium, and thallium; and pyrite is the preferred host for cobalt, nickel, and perhaps arsenic. With respect to the two minerals chalcopyrite and sphalerite, antimony, arsenic, molybdenum, nickel, silver, and tin prefer chalcopyrite; and bismuth, cadmium, cobalt, gallium, germanium, indium, manganese, and thallium prefer sphalerite. This distribution probably is the result of the interaction of several factors, among which are these: the various radii of the elements, the association due to chemical similarities of the major and trace elements, and the degree of ionic versus covalent and metallic character of the metal-sulfur bonds in chalcopyrite and sphalerite. The type of deposit, according to a temperature classification, appears to be of minor importance in determining the trace element content of chalcopyrite and sphalerite.

A preliminary investigation of large single crystals of sphalerite and chalcopyrite indicates that the distribution within a single crystal of some elements such as cadmium in sphalerite and indium and silver in chalcopyrite is relatively uniform, whereas the distribution of some other elements such as cobalt and manganese in sphalerite is somewhat less uniform and the distribution of tin in sphalerite is extremely erratic. The variations in trace element content probably are due largely to variations in the composition of the fluids during the growth of the crystals, but the erratic behavior of tin in sphalerite perhaps is related to the presence of numerous cavities and inclusions in the crystal studied.

Maps of the geographic distribution of trace elements in chalcopyrite and sphalerite exhibit three main belts of greater than average trace element content, which are called the Eastern, Central, and Western belts. These belts are consistent in trend and position with a beltlike distribution of copper, gold, lead, zinc, silver, and tungsten deposits and with most of the major tectonic features. However, there appear to be no definite time relationships, for as many as four metallogenic epochs, from Precambrian to late Tertiary, are represented by ore deposits within the Central belt.

The evidence suggests that the beltlike features have a deep seated origin, perhaps in the sub-crust or outer parts of the mantle, and that the deposits within each belt might be genetically related through a beltlike compositional heterogeneity in the source regions of the ores. Hence, the belts are regarded as metallogenic provinces.

Spontaneous and stimulated light emission due to radiative recombination in forward biased lead telluride P-N junctions

Since the discovery in 1962 of laser action in semiconductor diodes made from GaAs, the study of spontaneous and stimulated light emission from semiconductors has become an exciting new field of semiconductor physics and quantum electronics combined. Included in the limited number of direct-gap semiconductor materials suitable for laser action are the members of the lead salt family, i.e . PbS, PbSe and PbTe. The material used for the experiments described herein is PbTe . The semiconductor PbTe is a narrow band- gap material (E_g = 0.19 electron volt at a temperature of 4.2°K). Therefore, the radiative recombination of electron-hole pairs between the conduction and valence bands produces photons whose wavelength is in the infrared (λ ≈ 6.5 microns in air).

The p-n junction diode is a convenient device in which the spontaneous and stimulated emission of light can be achieved via current flow in the forward-bias direction. Consequently, the experimental devices consist of a group of PbTe p-n junction diodes made from p –type single crystal bulk material. The p - n junctions were formed by an n-type vapor- phase diffusion perpendicular to the (100) plane, with a junction depth of approximately 75 microns. Opposite ends of the diode structure were cleaved to give parallel reflectors, thereby forming the Fabry-Perot cavity needed for a laser oscillator. Since the emission of light originates from the recombination of injected current carriers, the nature of the radiation depends on the injection mechanism.

The total intensity of the light emitted from the PbTe diodes was observed over a current range of three to four orders of magnitude. At the low current levels, the light intensity data were correlated with data obtained on the electrical characteristics of the diodes. In the low current region (region A), the light intensity, current-voltage and capacitance-voltage data are consistent with the model for photon-assisted tunneling. As the current is increased, the light intensity data indicate the occurrence of a change in the current injection mechanism from photon-assisted tunneling (region A) to thermionic emission (region B). With the further increase of the injection level, the photon-field due to light emission in the diode builds up to the point where stimulated emission (oscillation) occurs. The threshold current at which oscillation begins marks the beginning of a region (region C) where the total light intensity increases very rapidly with the increase in current. This rapid increase in intensity is accompanied by an increase in the number of narrow-band oscillating modes. As the photon density in the cavity continues to increase with the injection level, the intensity gradually enters a region of linear dependence on current (region D), i.e. a region of constant (differential) quantum efficiency.

Data obtained from measurements of the stimulated-mode light-intensity profile and the far-field diffraction pattern (both in the direction perpendicular to the junction-plane) indicate that the active region of high gain (i.e. the region where a population inversion exists) extends to approximately a diffusion length on both sides of the junction. The data also indicate that the confinement of the oscillating modes within the diode cavity is due to a variation in the real part of the dielectric constant, caused by the gain in the medium. A value of τ ≈ 10^-9 second for the minority- carrier recombination lifetime (at a diode temperature of 20.4°K) is obtained from the above measurements. This value for τ is consistent with other data obtained independently for PbTe crystals.

Data on the threshold current for stimulated emission (for a diode temperature of 20. 4°K) as a function of the reciprocal cavity length were obtained. These data yield a value of J’_th = (400 ± 80) amp/cm² for the threshold current in the limit of an infinitely long diode-cavity. A value of α = (30 ± 15) cm^-1 is obtained for the total (bulk) cavity loss constant, in general agreement with independent measurements of free- carrier absorption in PbTe. In addition, the data provide a value of n_s ≈ 10% for the internal spontaneous quantum efficiency. The above value for n_s yields values of t_b ≈ τ ≈ 10^-9 second and t_s ≈ 10^-8 second for the nonradiative and the spontaneous (radiative) lifetimes, respectively.

The external quantum efficiency (n_d) for stimulated emission from diode J-2 (at 20.4° K) was calculated by using the total light intensity vs. diode current data, plus accepted values for the material parameters of the mercury- doped germanium detector used for the measurements. The resulting value is n_d ≈ 10%-20% for emission from both ends of the cavity. The corresponding radiative power output (at λ = 6.5 micron) is 120-240 milliwatts for a diode current of 6 amps.

Isotope shift studies in the rare earths and lead

Isotope shifts of K_α1 x-ray transitions were measured for the Neodymium isotopes Nd 142, 143, 144, 145, 146, 148 and 150, the Samarium isotopes Sm 147, 148, 149, 150, 152 and 154, the Gadolinium isotopes Gd 154, 155, 156, 157, 158 and 160, the Dysprosium isotopes Dy 162 and 164, the Erbium isotopes Er 166, 168 and 170, the Hafnium isotopes Hf 178 and 180 and the Lead isotopes Pb 204, 206, 207 and 208. A curved crystal Cauchois spectrometer was used. The analysis of the measurement furnished the variation of the mean square charge radius of the nucleus, δ˂r²˃, for 23 isotope pairs. The experimental results were compared with theoretical values from nuclear models. Combining the x-ray shifts and the optical shifts in Nd and Sm yielded the optical mass shifts. An anomaly was observed in the odd-even shifts when the optical and the x-ray shifts were plotted against each other.

Preparation, characterization and gas sensing properties of lead tetra-(tert-butyl)-5,10,1 5,20-tetraazaporphyrin spin-coating films

A spin-coated film of lead tetra-(tert-butyl)-5,10,15,20-tetraazaporphyrin complex (PbTAP(t-Bu)(4)) was obtained and characterized by IR spectra, absorption spectra and atomic force microscopy. The response and recovery characteristics of the film to NH3, NO2 and C2H5OH vapor were investigated at room temperature. In addition, the reversibility and stability of the film to NH3 were also studied. The results indicate that the PbTAP(t-Bu)(4) derivative can be exploited as an NH3 sensor at room temperature. (c) 2007 Elsevier B.V. All rights reserved.

Structural role of fluoride in aluminophosphate sol-gel glasses: High-resolution double-resonance NMR studies

The local structure of Na-Al-P-O-F glasses, prepared by a novel sol-gel route, was extensively investigated by advanced solid-state NMR techniques. Al-21{F-19} rotational echo double resonance (REDOR) results indicate that the F incorporated into aluminophosphate glass is preferentially bonded to octahedral Al units and results in a significant increase in the concentration of six-coordinated aluminum. The extent of Al-F and Al-O-P connectivities are quantified consistently by analyzing Al-27{P-31} and Al-21{F-19} REDOR NMR data. Two distinct types of fluorine species were identified and characterized by various F-19{Al-27}, F-19{Na-23}, and F-19{P-31} double resonance experiments, which were able to support peak assignments to bridging (Al-F-Al, -140 ppm) and terminal (Al-F, -170 ppm) units. On the basis of the detailed quantitative dipole-dipole coupling information obtained, a comprehensive structural model for these glasses is presented, detailing the structural speciation as a function of composition.

Intense frequency upconversion fluorescence of Er3+/Yb3+ co-doped lithium-strontium-lead-bismuth glasses

Infrared-to-visible upconversion fluorescence of Er(3+)/Yb(3+) co-doped lithium-strontium-lead-bismuth (LSPB) glasses for developing potential upconversion lasers has been studied under 975-nm excitation. Based on the results of energy transfer efficiency and upconversion spectra, the optimal Yb(3+)-Er(3+) concentration ratio is found to be 5:1. Intense green and red emissions centered at 525, 546, and 657 nm, corresponding to the transitions 2H_(11/2)-->4I_(15/2), 4S_(3/2)-->4I_(15/2), and 4F_(9/2)-->4I_(15/2), respectively, were observed. The quadratic dependence of the 525-, 546-, and 657-nm emissions on excitation power indicates that a two-photon absorption process occurs under 975-nm excitation. The high-populated 4I_(11/2) level is supposed to serve as the intermediate state responsible for the upconversion processes. The intense upconversion luminescence of Er(3+)/Yb(3+) co-doped LSPB glasses may be a potentially useful material for developing upconversion optical devices.

Effect of OH- on upconversion luminescence of Er3(+)-doped oxyhalide tellurite glasses

The Raman spectra, infrared spectra and upconversion luminescence spectra were studied, and the effect mechanism of OH- groups on the upconversion luminescence of Er3+-doped oxyhalide tellurite glasses was analyzed. The results show that the phonon energy of lead chloride tellurite (PCT) glass was lower than that of lead fluoride tellurite (PFT) glass, but upconversion luminescence intensity of Er3+-doped PFT glass was higher than that of Er3+-doped PCT glass. The analysis considers that it was attributed mainly to the effect of OH- groups. The lower the absorption coefficient of the OH- groups, the higher the fluorescence lifetime of Er3+, and as a result the higher upconversion luminescence intensity of Er3+. In this work, the effect of OH groups on the upconversion luminescence of Er3+ was bigger than that of the phonon energy. (c) 2005 Elsevier Inc. All rights reserved.

Efficient frequency upconversion emission in Er3+-doped novel strontium lead bismuth glass

Er3+ -doped strontium lead bismuth glass for developing upconversion lasers has been fabricated and characterized. The Judd-Ofelt intensity parameters Omega(1) (t = 2,4,6), calculated based on the experimental absorption spectrum and Judd-Ofelt theory, were found to be Omega(2) = 2.95 x 10(-20), Omega(4) = 0-91 X 10(-20), and Omega(6) = 0.36 x 10(-20) cm(2). Under 975 nm excitation, intense green and red emissions centered at 525, 546, and 657 nm, corresponding to the transitions H-2(11/2) --> I-4(15/2), S-4(3/2) I-4(15/2), and F-4(9/2) --> I-4(15/2) respectively were observed. The upconversion mechanisms are discussed based oil the energy matching and quadratic dependence on excitation power, and the dominant mechanisms are excited state absorption and energy transfer upconversion for the green and red emissions. The long-lived I-4(11/2) level is supposed to serve as the intermediate state responsible for the upconversion processes. (C) 2004 Published by Elsevier B.V.