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Development of infrared sensors using energy transfer/energy upconversion processes: Study of laser excited fluorescence in rare Earth ion doped crystals

A summary is presented of the spectroscopic study of three systems: LaF3:Ho(3+), LaF3:Er(3+) and CaF2:Nd(3+). When the D levels of Ho(3+) in LaF3 were resonantly excited with a laser beam of 640 nm, upconverted emissions were detected from J (416 nm), F (485 nm), and E (546 nm) levels. Energy upconverted emissions were also observed from F and E levels of Ho(3+) when the material was excited with an 800 nm near infrared laser. When the D levels of Er(3+) in LaF3 were resonantly excited with a laser beam of 637 nm, upconverted emissions were detected from the E (540 nm) and P (320, 400, and 468 nm) levels. Energy upconverted emissions were also observed from F, E, and D levels of Er(3+) when the material was resonantly excited with an 804 nm near infrared laser. When the D levels of Nd(3+) in CaF2 were resonantly excited with a laser beam of 577 nm, upconverted emissions were detected from the L (360 and 382 nm), K (418 nm), and I (432 nm) levels. Very weak upconverted emissions were detected when this system was irradiated with a near infrared laser. The numbers in parentheses are the wavelengths of the emissions.

Nash-Stevenson, S. K.↗

Development of flashlamp-pumped Q-switched Ho:Tm:Cr:YAG lasers for mid-infrared LIDAR application

A flashlamp-pumped 2.1 micron Ho:Tm:Cr:YAG laser was studied for both normal mode and Q-switched operations under a wide variety of experimental conditions in order to optimize performance. Laser output energy, slope efficiency, threshold and pulselength were determined as a function of operating temperature, output mirror reflectivity, input electrical energy and Q-switch opening time. The measured normal-mode laser thresholds of a Ho(3+) (0.45 atomic percent):Tm(3+) (2.5 atomic percent):Cr(3+) (0.8 atomic percent):YAG crystal ranged form 26 to 50 J between 120 and 200 K with slope efficiencies up to 0.36 percent with a 60 percent reflective output mirror. Under Q-switched operation the slope efficiency was 90 percent of the normal-mode result. Development of solid state lasers with Ho(3+), Tm(3+) and/or Er(3+) doped crystals has been pursued by NASA for eye-dafe mid-infrared LIDAR (light detection and ranging) application. As a part of the project, the authors have been working on evaluating Ho(3+):Tm(3+):Cr(3+):YAG crystals for normal-mode and Q-switched 2.1 micron laser operations in order to determine an optimum Tm(3+) concentration under flashlamp pumping conditions. Lasing properties of the Ho(3+) in the mid-infrared region have been studied by many research groups since the early 1960's. However, the technology of those lasers is still premature for lidar application. In order to overcome the inefficiency related to narrow absorption bands of the Ho(3+), Tm(3+) and Er(3+), the erbium has been replaced by chromium. The improvement in flashlamp-pumped Ho(3+) laser efficiency has been demonstrated recently by several research groups by utilizing the broad absorption spectrum of Cr(3+) which covers the flashlamp's emission spectrum. Efficient energy transfer to the Tm(3+) and then the Ho(3+) occurs subsequently. It is known that high Tm(3+) concentration and low Ho(3+) concentration are preferred to achieve a quantum efficiency approaching two and to avoid large reabsorption losses. However, determination of the optimum Tm(3+) concentration required to ensure efficient energy transfer from Cr(3+) to Tm(3+) and from Tm(3+) to Ho(3+) has not been made in the Ho:Tm:CR:YAG crystal. The results obtained so far are given.

Choi, Young S.↗

A process for preparing an assembly of an article and a soluble polyimide which resists dimensional change, delamination, and debonding when exposed to changes in temperature

An assembly of an article and a polyimide is prepared. The assembly resists dimensional change, delamination, or debonding when exposed to changes in temperature. An article is provided. A soluble polyimide resin solution having a low coefficient of thermal expansion (CTE) was prepared by dissolving the polyimide in solvent and adding a metal ion-containing additive to the solution. Examples of the additive are: Ho(OOCCH3), Er(NPPA)3, TmCl3, and Er(C5H7O2)3. The soluble polyimide resin is combined with the article to form the assembly.

Stoakley, Diane M.↗

New laser materials for laser diode pumping

The potential advantages of laser diode pumped solid state lasers are many with high overall efficiency being the most important. In order to realize these advantages, the solid state laser material needs to be optimized for diode laser pumping and for the particular application. In the case of the Nd laser, materials with a longer upper level radiative lifetime are desirable. This is because the laser diode is fundamentally a cw source, and to obtain high energy storage, a long integration time is necessary. Fluoride crystals are investigated as host materials for the Nd laser and also for IR laser transitions in other rare earths, such as the 2 micron Ho laser and the 3 micron Er laser. The approach is to investigate both known crystals, such as BaY2F8, as well as new crystals such as NaYF8. Emphasis is on the growth and spectroscopy of BaY2F8. These two efforts are parallel efforts. The growth effort is aimed at establishing conditions for obtaining large, high quality boules for laser samples. This requires numerous experimental growth runs; however, from these runs, samples suitable for spectroscopy become available.

Jenssen, H. P.↗

The reliability of the small-core Lanthanide effective core potentials

The reliability of the small-core Lanthanide effective core potentials (ECP) is tested using MF and MF(3), for M=Eu, Gd, Tb, and Yb and the atomic excitation energies for Pr, Nd, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb. In some case the ECP and all-electron (AE) results are in good agreement, while in others there are significant difference. The difference are much larger when the segmented basis set is used in conjunction with the ECP than when the atomic natural orbital (ANO) basis set is used. The study of the atoms suggests that problems for lanthanide containing molecules are associated with poor atomic excitation energies in the ECP treatment and even using the ANO basis set does not completely solve the problem. We note that the problem appears to be more severe for density functional approaches than for traditional correlation methods. We suggest that additional studies and new effective core potentials may be required for the Lanthanide atoms.

effective core potentials, atomic excitation, atom↗

Growth and characterization of materials for tunable lasers in the near infrared spectral region

During this reporting period, work proceeded in two directions. The first was the development of crystal growth procedures for rare earth doped LiYF4 crystals. The procedures for growth and pre-growth treatment of starting materials for undoped LiYF4 crystals were established and good optical quality materials were grown. A significant amount of time was spent trying to establish the optimum growth parameters for Yb(3+)-doped crystals. Unfortunately, it has proven difficult to obtain large size boules of high optical quality crystals of LiYF4 with doping concentrations of Yb(3+) of several percent. Because of these problems, this research is to be changed to attempt doping with other trivalent rare earth ions such as Ho, Er, and Tm. The second research area was investigating the potential of LiNbO3:Mg,Cr and LiNbO3:Mg,Cr,Yb as possible laser materials. The results are summarized.

Powell, Richard C.↗

Development of Field-Controlled Smart Optic Materials (ScN, AlN) with Rare Earth Dopants

The purpose of this investigation is to develop the fundamental materials and fabrication technology for field-controlled spectrally active optics that are essential for industry, NASA, and DOD applications such as: membrane optics, filters for LIDARs, windows for sensors, telescopes, spectroscopes, cameras, flat-panel displays, etc. ScN and AlN thin films were fabricated on c-axis Sapphire (0001) or quartz substrate with the RF and DC magnetron sputtering. The crystal structure of AlN in fcc (rocksalt) and hcp (wurtzite) were controlled. Advanced electrical characterizations were performed, including I-V and Hall Effect Measurement. ScN film has a free carrier density of 5.8 x 10(exp 20)/per cubic centimeter and a conductivity of 1.1 x 10(exp 3) per centimeter. The background ntype conductivity of as-grown ScN has enough free electrons that can readily interact with the photons. The high density of free electrons and relatively low mobility indicate that these films contain a high level of shallow donors as well as deep levels. Also, the UV-Vis spectrum of ScN and AlN thin films with rare earth elements (Er or Ho) were measured at room temperature. Their optical band gaps were estimated to be about 2.33eV and 2.24eV, respectively, which are obviously smaller than that of undoped thin film ScN (2.4eV). The red-shifted absorption onset gives direct evidence for the decrease of band gap (Eg) and the energy broadening of valence band states are attributable to the doping. As the doped elements enter the ScN crystal lattices, the localized band edge states form at the doped sites with a reduction of Eg. Using a variable angle spectroscopic ellipsometer, the decrease in refractive index with applied field is observed with a smaller shift in absorption coefficient.

Kim, Hyun-Jung↗

Stratospheric Tracers of Atmospheric Transport (STRAT) Campaign: ER-2 Participation

The NASA Stratospheric Tracers of Atmospheric Transport (STRAT) mission was initiated to advance knowledge of the major transport mechanisms of the upper troposphere-lower stratosphere. This is the region of the atmosphere within which exchange processes take place that critically determine the response of the climate system and ozone distribution to changing conditions triggered by the release of chemicals at the surface. The mission series that extended from October 1995 to November 1997 was extremely successful. The scientific advances that emerged from that mission include analyses of: (1) troposphere-to-stratosphere transport in the lowermost stratosphere from measurements of H2O, CO2, N2O, and O3; (2) the effects of tropical cirrus clouds on the abundance of lower stratospheric ozone; (3) the role of HO(sub x) in super- and subsonic aircraft exhaust plumes; and (4) dehydration and denitrification in the arctic polar vortex during the 1995-96 winter. The abstracts from published papers are included.

Anderson, James G.↗

Stratospheric Tracers of Atmospheric Transport (STRAT) Campaign: ER-2 Participation

The NASA Stratospheric Tracers of Atmospheric Transport (STRAT) mission was initiated to advance knowledge of the major transport mechanisms of the upper troposphere-lower stratosphere. This is the region of the atmosphere within which exchange processes take place that critically determine the response of the climate system and ozone distribution to changing conditions triggered by the release of chemicals at the surface. The mission series that extended from October 1995 to November 1997 was extremely successful. The scientific advances that emerged from that mission include analyses of: (1)troposphere-to-stratosphere transport in the lowermost stratosphere from measurements of H2O, CO2, N2O, and O3; (2) the effects of tropical cirrus clouds on the abundance of lower stratospheric ozone; and (3) the role of HO(x) in super- and subsonic aircraft exhaust plumes; and dehydration and denitrification in the arctic polar vortex during the 1995-96 winter.

Anderson, James G.↗

Rare Earth Garnet Selective Emitter

Thin film Ho-YAG and Er-YAG emitters with a platinum substrate exhibit high spectral emittance in the emission band (epsilon(sub lambda) approx. = 0.75, sup 4)|(sub 15/2) - (sup 4)|(sub 13/2),for Er-YAG and epsilon(sub lambda) approx. = 0.65, (sup 5)|(sub 7) - (sup 5)|(sub 8) for Ho-YAG) at 1500 K. In addition, low out-of-band spectral emittance, epsilon(sub lambda) less than 0.2, suggest these materials would be excellent candidates for high efficiency selective emitters in thermophotovoltaic (TPV) systems operating at moderate temperatures (1200-1500 K). Spectral emittance measurements of the thin films were made (1.2 less than lambda less than 3.0 microns) and compared to the theoretical emittances calculated using measured values of the spectral extinction coefficient. In this paper we present the results for a new class of rare earth ion selective emitters. These emitters are thin sections (less than 1 mm) of yttrium aluminum garnet (YAG) single crystal with a rare earth substitutional impurity. Selective emitters in the near IR are of special interest for thermophotovoltaic (TPV) energy conversion. The most promising solid selective emitters for use in a TPV system are rare earth oxides. Early spectral emittance work on rare earth oxides showed strong emission bands in the infrared (0.9 - 3 microns). However, the emittance outside the emission band was also significant and the efficiency of these emitters was low. Recent improvements in efficiency have been made with emitters fabricated from fine (5 - 10 microns) rare earth oxide fibers similar to the Welsbach mantle used in gas lanterns. However, the rare earth garnet emitters are more rugged than the mantle type emitters. A thin film selective emitter on a low emissivity substrate such as gold, platinum etc., is rugged and easily adapted to a wide variety of thermal sources. The garnet structure and its many subgroups have been successfully used as hosts for rare earth ions, introduced as substitutional impurities, in the development of solid state laser crystals. Doping, dependent on the particular ion and crystal structure, may be as high as 100 at. % (complete substitution of yttrium ion with the rare earth ion). These materials have high melting points, 1940 C for YAG (Yttrium Aluminum Garnet), and low emissivity in the near infrared making them excellent candidates for a thin film selective emitter. As previously stated, the spectral emittance of a rare earth emitter is characterized by one or more well defined emission bands. Outside the emission band the emittance(absorptance) is much lower. Therefore, it is expected that emission outside the band for a thin film selective emitter will be dominated by the emitter substrate. For an efficient emitter (power in the emission band/total emitted power) the substrate must have low emittance, epsilon(sub S). This paper presents normal spectral emittance, epsilon(sub lambda), measurements of holmium(Ho) and erbium (Er) doped YAG thin film selective emitters at (1500 K), and compares those results with the theoretical spectral emittance.

Lowe, Roland A.↗

HW Virginis - A short period eclipsing binary containing an sdB star

Simultaneous photometry of the binary star HW Vir, a detached system with an orbital period of 2 h 48 min is described. The new UBVR light curves obtained using the Wilson-Devinney code are found to constrain the orbital inclination of the system within the narrow range of 80.6 +/-0.2 deg. The temperature of the primary star is between 29,000 and 36,000 K, and the temperature of the secondary star is near 3,700 K. The possible masses and radii of the two stars are calculated using the published amplitude of the radial velocity curve of the primary star, 87.9 +/-4.8 km/s. It is found that, for the primary star log g1 is greater than 4.8 and less than or equal to 5.8. From the temperature and gravity of the primary star, its distance is found to be in the range between 42 and 151 pc. It is suggested that the system will begin mass transfer when the orbital period has decreased enough to bring the secondary star into contact with its Roche lobe.

Wood, Janet H.↗