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.

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.

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.

Effect of chloride ions' introduction on structural, thermal stability, and spectroscopic properties in Yb3+Er3+-codoped germanate-bismuth-lead glasses

Yb3+Er3+-codoped chloride-modified germanate-bismuth-lead glasses have been synthesized by the conventional melting and quenching method. Structural and thermal stability properties have been obtained on the basis of the Raman spectra and differential thermal analysis, which indicate that the PbCl2 addition has an important influence on the phonon density of states, maximum phonon energy, and thermal stability of host glasses. The Judd-Ofelt intensity parameters and quantum efficiencies were calculated on the basis of the Judd-Ofelt theory and lifetime measurements. For the 1.53 mu m emission band, the full widths at the half-maximum increase and peak wavelengths are blueshifted with increasing PbCl2 content. Moreover, the effect of the PbCl2 addition on the phonon density of states, OH- content, and upconversion luminescence has been discussed and evaluated. Our results reveal that, with increasing PbCl2 content, the decrease of phonon density and OH- content contributes more to the enhanced upconversion emissions than that of maximum phonon energy. (c) 2005 Optical Society of America

Fluorescence lifetime increasing with F- ions into ytterbium-doped germanium-lead-tellurite glasses

The effects of F- ions in a germanium-lead-tellurite glass system oil the spectral and potential laser properties of the Yb3+ are investigated. The absorption spectra, lifetimes, the emission cross-sections and the minimum pump intensities of the glass system with and without F- ions have been measured and calculated. The results show that the fluorescence lifetime and the minimum pump intensity of Yb3+ ions increase evidently, which indicates that germanium lead-oxyfluoride tellurite glass is a promising laser host matrix for high power generation. FT-IR spectra were used to analyse the effect of F- ions on OH- groups in this glass system. Analysis demonstrates that addition of fluoride removes the OH- groups and results in improvement of fluorescence lifetime of Yb3+.

Infrared-to-visible upconversion fluorescence of Er3+-doped novel lithium-barium-lead-bismuth glass

Er3+-doped lithium-barium-lead-bismuth glass for developing upconversion lasers has been fabricated and characterized. The Judd-Ofelt intensity parameters Omega(t) (t = 2, 4, 6), calculated based on the experimental absorption spectrum and Judd-Ofelt theory, were found to be Omega(2) = 3.05 x 10(-20) cm(2), Omega(4) = 0.95 x 10(-20) cm(2), and Omega(6) = 0.39 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 at room temperature. The upconversion mechanisms are discussed based on 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 intense upconversion processes. The intense upconversion luminescence of Er3+-doped lithium-barium-lead-bismuth glass may be a potentially useful material for developing upconversion optical devices. (c) 2004 Elsevier B.V. All rights reserved.

Intense frequency upconversion fluorescence of Er3+/Yb3+-codoped novel potassium-barium-strontium-lead-bismuth glasses

Er3+/Yb3+-codoped potassium-barium-strontium-lead-bismuth glasses for developing potential upconversion lasers have been fabricated and characterized. Based on the results of energy transfer efficiency, the optimal Yb3+/Er3+ concentration ratio is found to be 5:1. Intense green and red emissions centered at 525, 546, and 657 run, 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 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 long-lived I-4(11/2) level is supposed to serve as the intermediate state responsible for the upconversion processes. (c) 2004 Elsevier B.V. All rights reserved.

Novel lithium-barium-lead-bismuth glasses

New lithium-barium-lead-bismuth glasses with low OH- concentration have been obtained. The role of the different components in the glass formation has been explored from the thermal, density, and refractive index measurements. The T-g, T-x, and T-x-T-g values of these glasses are in the range of 358-400, 453-575, and 87-197 degreesC, respectively. The densities (p) and refractive indices of these glasses are mainly affected by Bi2O3 and PbO contents. A wide transmitting window from visible to infrared (IR) regions for some compositions of these glasses has been observed, which makes them appealing candidates for different optical applications such as upconverting phosphors, new laser materials, optical waveguides, and crystal-free fibre drawing. (C) 2004 Elsevier B.V. All rights reserved.

Structural and upconversion fluorescence properties of Er3+/Yb3+-codoped lead-free germanium-bismuth glass

We study the structural and infrared-to-visible upconversion fluorescence properties of Er3(+)/Yb3+-codoped lead-free germanium-bismuth glass. The structure of lead-free germanium-bismuth-lanthanum glass is investigated by peak-deconvolution of Raman spectroscopy. Intense green and red emissions centred at 525, 546, and 657nm, corresponding to the transitions H-2(11/2) -> (IT15/2)-I-4 -> S-4(3/2) -> 4I(15/2), and F-4(9/2) -> I-4(15/2), respectively, are observed at room temperature. The quadratic dependence of the 525, 546, and 657nm emissions on excitation power indicates that a two-photon absorption process occurs under 975nm excitation.

Structural and upconversion fluorescence properties of Er3+/Yb3+-codoped oxychloride lead-germanium-bismuth glass

Structural and infrared-to-visible upconversion fluorescence properties of Er3+/Yb3+-codoped oxychloride lead-germanium-bismuth glass have been studied. The Raman spectrum investigation indicates that PbCl2 plays an important role in the formation of glass network, and has an important influence on the upconversion luminescence owing to lower phonon energy. Intense green and red emissions centered at 525, 546, and 657 nm, corresponding to the transitions H-2(11/2)-->I-4(15/2,) I-4(3/2)-->I-4(15/2), and F-4(9/2)-->I-4(15/2), respectively, were observed at room temperature. 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. (C) 2004 Elsevier Ltd. All rights reserved.

Green and red upconversion luminescence in ytterbium-sensitized erbrium-doped novel lead-free germanium bismuth lanthanum glass

Structural and infrared-to-visible upconversion fluorescence properties in ytterbium-sensitized erbrium-doped novel lead-free germanium bismuth-lanthanum glass have been studied. The structure of lead-free germanium-bismuth-lanthanum glass was investigated by peak-deconvolution of Raman spectrum, and the structural information was obtained from the peak wavenumbers. Intense green and red emissions centered at 525, 546, and 657 nm, corresponding to the transitions 2H(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 at room temperature. 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. This novel lead-free germanium-bismuth-lanthanum glass with low maximum phonon energy (similar to 751 cm(-1)) can be used as potential host material for upconversion lasers. (c) 2005 Published by Elsevier B.V.

Up-conversion luminescence analysis in ytterbium-sensitized erbium-doped oxide-halide tellurite and germanate-niobic-lead glasses

Ytterbium-sensitized erbium-doped oxide-halide tellurite and germanate-niobic-lead glasses have been synthesized by conventional melting method. 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 simultaneously observed at room temperature in these glasses. The quadratic dependence of the 525, 546 and 657 nm emissions on excitation power indicates that a two-photon absorption process occurs. Tellurite glass showed a weaker up-conversion emission than germanate-niobic-lead glass, which is inconsistent with the prediction from the difference of maximum phonon energy between tellurite and germanate-mobic-lead glasses. In this paper, Raman spectroscopy was employed to investigate the origin of the difference in up-conversion luminescence in the two glasses. Compared with phonon side-band spectroscopy, Raman spectroscopy extracts more information including both phonon energy and phonon density. Our results reveal that the phonon density and the maximum phonon energy of host glasses are both important factors in determining the up-conversion efficiency. (c) 2005 Elsevier B.V. All rights reserved.

Effects of Yb ion concentration on the spectral properties of lead silica glasses

The spectral properties in different concentration of Yb ions (0.5-5 mol%)-doped silica glasses are explored in this paper. The glasses are prepared by traditional melting method. The absorption spectra and the fluorescent lifetime (tau(f)) are measured at room temperature and low temperature (18 K). The stimulated cross-section (sigma(emi)) and potential laser properties (beta(min), I-sat, I-min) are calculated based on the absorption spectra. The absorption cross-section (sigma(abs)) are in the range 1.08 x 10(-20) - 1.18 x 10(-20) cm(2) in different glasses, the fluorescence lifetime (tau(f)) change from 1.9 to 1.2 ms with the increase of Yb3+ concentration. The potential laser properties indicate that lead silica glass is a good host for highly Yb ion doping glass. (c) 2005 Elsevier B.V. All rights reserved.