The origin of the Cosmic Diffuse Gamma-ray (CDG) background in the 0.3 to 30 MeV energy range is a mystery that has persisted for 50 years. The best existing measurements have large systematic uncertainties, and the latest theoretical models based on emission from active galactic nuclei and supernovae differ significantly from these data below 1 MeV. The Mini Astrophysical MeV Background Observatory (MAMBO) is a new CubeSat mission under development at Los Alamos National Laboratory with the goal of making high-quality measurements of the MeV CDG to help solve this puzzle. The concept is motivated by the fact that, since the MeV CDG is relatively bright, only a small detector is required to make high-quality measurements of it. Indeed, the sensitivity of space-based gamma-ray instruments to the MeV CDG is limited not by size, but by the locally generated instrumental background produced by interactions of energetic particles in spacecraft materials. Comparatively tiny CubeSat platforms provide a uniquely quiet environment relative to previous gamma-ray science missions. The MAMBO mission will provide the best measurements ever made of the MeV CDG spectrum and angular distribution, utilizing two key innovations: 1) low instrumental background on a 12U CubeSat platform; and 2) an innovative shielded spectrometer design that simultaneously measures signal and background. Los Alamos is partnering with commercial vendors for the 12U CubeSat bus and ground station network, which we expect will become a new paradigm for low-cost, fast-turnaround space science missions. We present calibration and test results for the payload and simulations of the expected scientific return.
A composite fast neutron detector module based on the 6Li(n,α) 3H reaction in 6Li-enriched GS20® scintillating glass has been engineered to be compact, robust, and tunable. The solid scintillating composite consists of only three components, all commercially sourced, and can be optically coupled to silicon photomultipliers (SiPMs) to create a highly capable and portable neutron detector module. The composite provides moderation of incident fast neutrons through an optically transparent organic matrix and achieves high gamma rejection by the use of small scintillating particles. The performance of the module was assessed by measurements of the die-away time and the sensitivity to both gammas and neutrons. Controlled scintillation light losses enable determination of the neutron capture location along the length of the cylindrical composite. Optical raytracing was used to predict the light-transport efficiencies and the longitudinal position dependency of scintillation events within the module. These assessments indicate that this module can be effective in the detection of nuclear material for nonproliferation, safeguards and security applications, and in fundamental and applied science.
The origin of the cosmic diffuse gamma-ray (CDG) background in the 0.3–10 MeV energy range is a mystery that has persisted for over 40 years. The Mini Astrophysical MeV Background Observatory (MAMBO) is a new CubeSat mission under development at Los Alamos National Laboratory with the goal of addressing this longstanding puzzle. The concept is motivated by the fact that, since the MeV CDG is relatively bright, only a small detector is required to make high-quality measurements of it. Indeed, the sensitivity of space-based gamma-ray instruments to the CDG is limited not by size, but by the locally generated instrumental background produced by interactions of energetic particles in spacecraft materials. Comparatively tiny CubeSat platforms provide a uniquely quiet environment relative to previous MeV gamma-ray science missions. The MAMBO mission will provide the best measurements ever made of the MeV CDG spectrum and angular distribution, utilizing two key innovations: 1) low instrumental background on a 12U CubeSat platform; and 2) an innovative shielded spectrometer design that simultaneously measures signal and background. Los Alamos is partnering with commercial vendors for the 12U CubeSat bus and ground station network, which we expect will become a new paradigm for low-cost, fast-turnaround space science missions. We describe the MAMBO instrument and mission concept in detail and present the expected scientific return.
Radiographic imaging represents a vital capability within non-destructive assessment, quality control and fundamental science. This study focuses on Gd2O2S:Tb3+ based scintillating composites incorporated into pixelated-metallic aperture screens, attached to amorphous silicon-based flat panels. Performance metrics are explored through coupled MCNP6- FRED simulations; here, scintillation light transport is investigated as a function of pixelated screen geometry and optical characteristics. For the first time, we demonstrate image acquisition with a 100 micron thick pixelated metallic aperture screen. The results demonstrate promising improvements to x-ray interaction rates while maintaining image quality.
The origin of the cosmic diffuse gamma-ray (CDG) background in the 0.3 – 30 MeV energy range is a mystery that has persisted for over 40 years. The Mini Astrophysical MeV Background Observatory (MAMBO) is a CubeSat mission motivated by the fact that, since the MeV CDG is relatively bright, only a small detector is required to make high-quality measurements of it. Indeed, the sensitivity of space-based gamma-ray instruments to the CDG is limited not by size, but by the locally generated instrumental background produced by interactions of energetic particles in spacecraft materials. Comparatively tiny CubeSat platforms provide a uniquely quiet environment relative to previous gamma-ray science missions. The MAMBO mission will provide the best measurements ever made of the MeV CDG spectrum and angular distribution, utilizing two key innovations: 1) low instrumental background on a 12U CubeSat platform; and 2) an innovative shielded spectrometer design that simultaneously measures signal and background. Enabling technologies include the use of compact silicon photomultipliers (SiPMs) for scintillator readout, and a tagged calibration source for real-time gain adjustment. We describe the MAMBO instrument, readout, commercial 12U bus systems, and mission concept in detail, including simulations and laboratory measurements demonstrating the key measurement concept.
Hyperspectral imaging with sufficient resolution and sensitivity for scientifically useful space-based mapping of trace gases has long required large and expensive satellite instruments. Miniaturizing this capability to a CubeSat configuration is a major challenge, but opens up more agile and far less expensive observing strategies. A major step in this direction is our development of NACHOS, an ultra-compact (1.5U instrument, 3U complete CubeSat) hyperspectral imager covering the 300-500nm spectral range in 400 channels. Here we describe laboratory and field performance characterization of this new instrument. Laboratory tests demonstrate spatial and spectral resolutions of <0.8 mrad and 1.3 nm, respectively, with good resolution of the spectral lines of our SO2 and NO2 target gases. Outdoor field tests under realistic illumination conditions provide real-world signal-to-noise benchmarks, and yield hyperspectral images displaying high quality solar and atmospheric spectra. To estimate on-orbit gas retrieval sensitivities, we computationally implanted plumes of varying concentrations into acquired hyperspectral datacubes. Applying our adaptive matched filter gas-retrieval algorithms to the generated scene, we predict NACHOS will be able to distinguish 35 and 7 ppm⋅m plumes of SO2 and NO2 (respectively) with high sensitivity; a capability well-suited to address scientific goals related to monitoring both passive SO2 degassing from volcanoes and NO2 emissions from anthropogenic sources. Lastly, we will show findings from thermal and vibrational environmental tests, performed in preparation for a scheduled early-2022 launch, demonstrating the extremely robust spectrometer design is well-suited for satellite-based deployment.
The Nano-satellite Atmospheric Chemistry Hyperspectral Observation System (NACHOS) is a high-throughput (f/2.9), high spectral resolution (~1.3 nm optical resolution, 0.6 nm sampling) Offner-design hyperspectral imager operating in the 300-500 nm spectral region. The 1.5U instrument payload (1U optical system, 0.5U electronics module) is hosted by a 1.5U LANL-designed CubeSat bus to comprise a 3U complete satellite. Spectroscopically similar to NASA’s Ozone Monitoring Instrument (OMI), which provides wide-field global mapping of ozone and other gases at coarse spatial resolution, NACHOS fills the complementary niche of targeted measurements at much higher spatial resolution. With 350 across-track spatial pixels and a 15-degree across-track field of view, NACHOS will provide spectral imaging at roughly 0.4 km per pixel from 500 km altitude. NACHOS incorporates highly streamlined gas-retrieval algorithms for rapid onboard processing, alleviating the need to routinely downlink massive hyperspectral data cubes. We will discuss the instrument design, challenges in achieving mechanical robustness to launch vibration in such a compact instrument, the onboard calibration system, and gas-retrieval data downlink strategy. We will also discuss potential science missions, including monitoring of NO2 as an easily detected proxy for anthropogenic fossil-fuel greenhouse gases, monitoring lowlevel SO2 degassing at pre-eruptive volcanoes, H2CO from wildfires, and characterization of aerosols. The long-term vision is for a many-satellite constellation that could provide both high spatial resolution and frequent revisits for selected targets of interest. As an initial technology demonstration of this vision, the NACHOS project is currently slated to launch two CubeSats in early 2022.
High purity is a fundamental requirement to enable laser-cooling-grade materials. The vertical Bridgman method is well suited for crystal growth on the few-grams scale, which is compatible with purification techniques that aim to exceed the typical 99.999% to 99.9999% purity of commercial precursor materials. Here, we present advances in the Bridgman crystal growth of cooling-grade LLF:Yb single crystals in a radio-frequency heated furnace. Optical spectroscopy, cooling efficiency, and power cooling characterization are reported. COMSOL simulations were used to investigate the thermal gradient inside the crucible as the crystal growth proceeds.
In radiation balanced lasers, anti-Stokes fluorescence is used to minimize the heat generated by the quantum defect and other non-radiative processes. Thermo-optics distortions can be minimized, enabling the scaling to high power. Here, experimental results of radiation balanced operation in various disk gain materials (i.e. YLF:Yb and LLF:Yb ) are presented. Different multipass pumping schemes are investigated for pump beam area scaling towards high power CW operation. Laser cavity design and thermal management issues are also discussed.
The origin of the cosmic diffuse gamma-ray (CDG) background in the 0.3 – 30 MeV energy range is a mystery that has persisted for over 40 years. The Mini Astrophysical MeV Background Observatory (MAMBO) is a CubeSat mission concept motivated by the fact that, since the MeV CDG is relatively bright, only a small detector is required to make highquality measurements of it. Indeed, the sensitivity of space-based gamma-ray instruments to the CDG is limited not by size, but by the locally generated instrumental background produced by interactions of energetic particles in spacecraft materials. Comparatively tiny CubeSat platforms provide a uniquely quiet environment relative to previous gamma-ray science missions. The MAMBO mission will provide the best measurements ever made of the MeV CDG spectrum and angular distribution, utilizing two key innovations: 1) low instrumental background on a 12U CubeSat platform; and 2) an innovative shielded spectrometer design that simultaneously measures signal and background. We describe the MAMBO instrument and mission concept in detail, including simulations and laboratory measurements demonstrating the key measurement concept.
We report on the Bridgman crystal growth of Yb3+-doped LiLuF4 (LLF:Yb) for radiation balanced laser (RBL) applications. Crystals were grown on both radio-frequency (RF) heated and resistively heated furnaces starting from the binary fluorides LiF, LuF3, and YbF3. Graphite crucibles were found to introduce excessive amounts of carbon contamination, while glassy carbon crucibles offered significantly better results. In a preliminary experiment, a LLF:Yb crystal grown by this method showed laser-induced cooling when excited at 1055 nm with 810 mW in a setup with the crystal in air and measuring the temperature change by a thermal camera.
The role of pump saturation in high-power optical refrigeration is investigated. Employing both Z-scan and intensity-dependent PL techniques, we measure the pump saturation intensity in Yb:YLF versus the temperature. We find that the absorption efficiency, and consequently the cooling efficiency can be limited at cryogenic temperatures under power scaling (when substantial heat lift is desired) unless multi-pass pumping schemes are tailored to control the average pump intensity inside the crystal.
Optical refrigeration of Yb:YLF crystals is used to cool an arbitrary payload (HgCdTe IR sensor) for the first time to below 135K in a completely vibration free environment. This milestone is made possible by the design and fabrication of a specialty thermal link that efficiently shields the payload from the intense fluorescence while sustaining frequent thermal cycling. We also show the latest advances in the design and implementation of novel thermal links that promise sub-100K payload temperatures. This investigation considers thermal link materials that are CTE-matched to YLF and includes rigorous optical and thermal modeling under various geometries.
Single crystals of LiYF4 (YLF) and LiLuF4 (LLF) doped with Yb3+, Tm3+, or Ho3+ are attractive materials for enabling radiation balanced lasers (RBLs) operating in the 1–2 μm wavelength range. High material purity and short growth times are critical for exploring and optimizing the performance of these materials. We show that the Bridgman growth method can yield single crystals within ~1 week and requiring only a few grams of the respective starting materials. We report on progress growing YLF and LLF crystals by the vertical Bridgman method and discuss the challenges posed by the incongruent melting properties of YLF. The congruently-melting LLF is found to be an attractive candidate material for RBL applications.
The technological advances introduced by additive manufacturing techniques have significantly improved the ability to generate functional composites with a wide variety of mechanical and optical properties. Progress in the additive manufacturing of scintillating particle composites could enable new capabilities that span applications in nuclear nonproliferation, nuclear energy and basic science. The present work focuses on developing capabilities for additively manufacturing scintillating particle composites where successful implementation could enable cost-effective highperformance detectors for a wide range of applications. The results demonstrate the optical and response characteristics of arranged scintillating glass particle composites that are optically transparent, mechanically robust and respond to incident fast neutrons.
Optical refrigeration of rare-earth-doped solids has reached the boiling point of argon, 87 K, and is expected to cool to that of nitrogen, 77 K, in the near future. This technology is poised to pave the way to compact, reliable, and vibrationfree all-solid-state optical cryocoolers. By attaching the Yb:YLF cooling crystal to a cold finger via a double 90° kink thermal link, we have cooled a silicon temperature sensor to below 151 K. An advanced design of the thermal link and the clamshell surrounding the cooled assembly successfully controlled the flow of heat and radiation to allow cooling of a payload to cryogenic temperatures. Key elements of the design were a low-absorption thermal link material, an optimized thermal link geometry, and a spectrally-selective coating of the clamshell.
Radiation-balanced lasers (RBL) combine solid-state optical refrigeration and lasing in one material to enable a net zero thermal load that allows for favorable scaling to high laser powers. A high-performance RBL material, therefore, has to first qualify as a high-performance laser-cooling material. This necessitates exquisite material purity in order to achieve the required near-unity external quantum efficiency and low background absorption. Solvent extraction, ion exchange, and electrochemical treatment of aqueous solutions or melts are some of the techniques available for the purification of starting materials used in the growth of RBL crystals. Scaling these methods to the 100s of gram scale needed for traditional Czochralski crystal growth while maintaining parts-per-billion level impurity concentrations however has proven challenging in several past efforts. In contrast, we have previously shown solvent extraction and electrochemical treatment to be effective on the several gram scale. This creates a need for exploring alternative methods for growing optical-cooling-grade fluoride crystals on the small scale. We will present results on growing Yb-doped YLiF4 (YLF) and LuLiF4 (LLF) single crystals using the vertical Bridgman method. The external quantum efficiency and background absorption of these samples will be reported and discussed in the context of RBL.
Optical refrigeration of rare-earth doped crystals has exceptional qualities that can be used for building a compact and vibration-free all-solid-state optical cooler. Estimating the lowest achievable temperature and cooling power of such a device requires accurate measurements of external quantum efficiency, mean fluorescence wavelength, and parasitic absorption. Here we discuss temperature dependent measurements of these parameters for a high quality Yb:YLF sample by performing a LITMoS test (Laser Induced Temperature Modulation Spectrum) combined with contact-free differential luminescence thermometry. These measurements are challenging at low temperatures, but by integrating these two methods, we can perform LITMoS test at any temperature.
Many application areas, including space-based and compact fieldable devices, use scintillator systems that require high quantum efficiency and small size, weight, and power consumption (SWAP). Advancements in semiconductor readout devices, such as silicon Avalanche Photodiodes (APD) provide a low SWAP alternative to conventional photomultiplier tubes (PMTs) and provide larger quantum efficiency over a broader spectral range. Direct replacement of PMTs by APDs can degrade system performance because the optimal detection sensitivity of APDs (~700 nm) is poorly matched to the emission of most scintillators (~300-500 nm). Wavelength-shifters can mitigate this performance degradation, however there are many parameters that must be optimized. We will describe our generalized method of applying layers of wavelength shifting dyes to scintillators coupled with state-of-the-art APD readout devices. We will present recent results using single dye layers (YSO:Ce), multiple dye layers (LiCaF:Ce), neutron sensitive scintillators (LiCaF:Ce), and hygroscopic scintillators (CsI:Na) to provide a robust proof of concept of this method for other high performance scintillators (e.g. LaBr3 and CLYC). Improvements in the measured light collection efficiency and energy resolution are supported by photoluminescence, radioluminescence, and absolute quantum efficiency measurements.
Optical refrigeration by laser irradiation of YLiF4:Yb3+ (YLF:Yb) crystals has been shown to be strongly deteriorated by impurities, which absorb energy at the laser wavelength, and relax non-radiatively, negating cooling produced from anti-Stokes fluorescence. We aim to increase the efficiency of optical refrigeration through materials purification. We start with the purest sources commercially available and process them in a cleanroom environment. Our method proceeds through electrochemical purification, separating out the transition metal impurities by their redox potentials, and can be scaled up to produce the amounts of material needed for crystal growth.
The performance of a solid-state optical refrigerator is the result of a complex interplay of numerous optical and thermal parameters. We present a first preliminary study of an optical cryocooler using ray-tracing techniques. A numerical optimization identified a non-resonant cavity with astigmatism. This geometry offered more efficient pump absorption by the YLF:10%Yb laser-cooling crystal compared to non-resonant cavities without astigmatism that have been pursued experimentally so far. Ray tracing simulations indicate that ~80% of the incident pump light can absorbed for temperatures down to ~100 K. Calculations of heat loads, cooling power, and net payload heat lift are presented. They show that it is possible to cool a payload to a range of 90–100 K while producing a net payload heat lift of 80 mW and 300 mW when pumping a YLF:10%Yb crystal with 20 W and 50 W at 1020 nm, respectively. This performance is suited to cool HgCdTe infrared detectors that are used for sensing in the 8–12 μm atmospheric window. While the detector noise would be ~6× greater at 100 K than at 77 K, the laser refrigerator would introduce no vibrations and thus eliminate sources of microphonic noise that are limiting the performance of current systems.
Solid-state optical refrigeration is an emerging cooling technology that can provide vibration free and reliable refrigeration to cryogenic temperatures in a lightweight and compact device. The technology has matured over the past two decades and is currently being considered for applications where the mechanical vibrations, limited reliability, or insufficient portability of existing cooling technologies pose challenges. Possible applications include satellite-borne infrared imaging, laser metrology, and gamma-ray spectroscopy as well as high-reliability cooling of semiconductors and high-temperature superconductors. The best results achieved so far have been in cooling rare-earth-doped solids, especially materials doped with ytterbium. We discuss the fundamental physical principles of solid-state laser cooling, the resulting material and device design requirements, and the estimated payload heat lift of an optical cryocooler.
The role of transition-metal impurities in Yb3+-doped YLiF4 (YLF) laser-cooling crystals is studied. Divalent 3d transition-metal ions, in particular Fe2+, are found to have strong absorptions at the laser cooling pump wavelength and degrade the cooling efficiency by introducing background absorption. A set of eight substitutional and chargecompensated defects that form upon introduction of 1+, 2+, and 3+ transition-metal ions into the YLF crystal lattice is proposed. A calculation of solution energies for each defect type and for a range of 3d ions is carried out. It indicates that divalent 3d ions preferentially substitute for Y3+ accompanied by a fluoride vacancy for charge compensation. An electron paramagnetic resonance (EPR) study of a YLF crystal identifies Fe2+ in the crystal lattice, in agreement with the elemental analysis and the computational results. A strategy for purifying the YF3, LiF, and YbF3 starting materials for the YLF:Yb crystal growth is discussed. Chelate-assisted solvent extraction purification with pyrrolidine dithiocarbamate (APDC) for Y, Li, and Yb as well as ethylenediaminetetraacetic acid (EDTA) for Li was carried out.
Heat switches are a key enabling element of efficient refrigerators that are based on the electrocaloric effect. We
demonstrate a new concept for a heat switch that is based on micro-scale electrohydrodynamic (EHD) flows in thin
layers of dielectric fluids. In this device, convective flow of the fluid is controlled by applying an electric field across the
fluid layer. This creates a heat switch that can be cycled between a “closed” state with efficient convective heat transport and an “open” state with less efficient conductive heat transport. Substantial switching of the thermal transport coefficient was achieved in 500 μm thick layers of commercial hydrofluoroethers and bias voltages of typically 390 V. The efficacy of the heat switch varied by almost four orders of magnitude for different biasing schemes. The highest efficacy was achieved by biasing a patterned strip electrode and using a planar ground electrode. A preliminary experiment found a thermal conductivity contrast of 4.7±1.1 for the switch in the closed vs. open state. We also characterize the electrocaloric response of commercial multilayer ceramic chip capacitors and show that they can serve as serve as a useful surrogate material for first-generation electrocaloric refrigerators until higher performing multilayer structures of ferroelectric polymers are available.
In recent years, composite scintillators consisting of nanosize inorganic crystals in an organic matrix have been
actively developed. Ideally these scintillators would have efficiency and resolution similar to inorganic crystals,
but at the same time would be inexpensive and easy to manufacture. In order to make composite scintillators
optically transparent, McKigney et al. finds that nanosize inorganic crystals should be used in order to reduce
optical scattering. One way to produce these nanosize inorganic crystals is through wet milling, where inorganic
crystals are ground with microsize beads in an organic solvent to achieve size reduction. Milling is relatively
simple in terms of preparation and equipment; however, milling is also known to introduce defects into the
ground material. Therefore, a new light yield measurement technique is developed to evaluate the degree to
which milling alters the light yield of the milled inorganic crystals. In this work, the light yield measurement
technique is applied to samples containing BaFCl:Eu inorganic crystals milled in a tributyl phosphate (TBP)
and cyclohexane mixture.
The total crystal-field splitting of the 2F7/2 ground-state multiplet of Yb3+ critically determines the cooling efficiency of an optical refrigerator. Crystals with a small 2F7/2 splitting maintain a sizeable thermal population of the initial state of the pumped crystal-field transition at low temperatures, leading to a workable laser-cooling efficiency in the application-relevant cryogenic regime below 120 K. A comprehensive review of the crystal-field splitting of (2S+1)L(J) multiplets in rare-earth-doped fluoride crystals is presented. The concept of crystal-field strength is used to predict the splitting of the 2F7/2 ground-state multiplet from other fluoride crystals doped with other rare earth ions. The analysis correctly predicts the typical 350-450 cm-1 total splitting of 2F7/2 in fluorides, but the accuracy of the method is found to be rather limited. LiKYF5, K2YF5, and Cs2KLnF6 are predicted to have large 2F7/2 splittings that are unfavorable for laser cooling. KY3F10, YLiF4, LuLiF4, and GdLiF4 are among the group of crystals expected to have small 2F7/2 splittings and currently appear to be the most promising hosts for laser cooling with Yb3+. LiBiF4:Yb3+ may have a <350 cm-1 2F7/2 splitting and warrants further study.
The status of optical refrigeration of rare-earth-doped solids is reviewed, and the various factors that limit the
performance of current laser-cooling materials are discussed. Efficient optical refrigeration is possible in materials for
which hωmax < Ep/8, where hωmax is the maximum phonon energy of the host material and Ep is the pump energy for
the rare-earth dopant. Transition-metal and OH- impurities at levels >100 ppb are believed to be the main reason for the
limited laser-cooling performance in current materials. The many components of doped ZBLAN glass pose particular
processing challenges. Binary fluoride glasses such as YF3-LiF are considered as alternatives to ZBLAN, and the
crystalline system KPb2Cl5 :Dy3+ is identified as a prime candidate for high-efficiency laser cooling.
Significant progress has been made in synthesizing and characterizing ultra-pure, rare-earth-doped ZIBLAN (ZrF4-InF3-
BaF2-LaF3-AlF3-NaF) glass capable of laser refrigeration. Yb3+-doped ZIBLAN glass was produced from fluoride
precursors which were individually purified by solvent extraction and subsequently treated with hydrofluoric gas at
elevated temperatures to remove oxygen impurities. We have developed two-band differential luminescence
thermometry (TBDLT) as a new non-invasive, spectroscopic technique to evaluate the intrinsic quality of Yb3+ doped
laser-cooling samples. TBDLT measures changes in the local temperature upon laser excitation via the small changes in
the 2F5/2→2F7/2 fluorescence spectrum. Two commercial band pass filters in combination with a balanced dual InGaAs
photodetector are used to select and integrate regions of interest in the fluorescence spectrum with sub-millisecond
resolution. The TBDLT technique successfully finds the zero-crossing temperature (ZCT), which is the minimum
temperature to which a Yb3+ doped sample can cool, independent of surface heating. ZCT is a useful measure for the
presence of impurities and the overall quality of the laser-cooling material. Favorable laser cooling results were obtained
for several 1% Yb3+-doped glasses with varying degrees of purity.
The fluorozirconate glass ZBLAN:1%Yb3+ was synthesized, for the first time, from fluoride precursors that were
individually purified by solvent extraction and hydrofluoric (HF) gas treatment. The synthesis used aqueous solutions of
high-purity commercial precursors that were subjected to ultra-filtration followed by solvent extraction using ammonium
pyrrolidine dithiocarbamate (APDC) and methyl-isobutyl-ketone (MIBK). The purified metal fluorides were precipitated
and treated in hot HF gas to remove water, hydroxyl (OH-), and oxide impurities. ZBLAN:1%Yb3+ was fabricated from
these precursors by melting under inert atmosphere, yielding glasses with excellent mechanical properties and having a
clear, bubble-free, and crystallite-free matrix. The effect of adding 0.5 mol% of In3+ as an oxidizer to suppress the
reduction of Zr4+ and the accompanying formation of black precipitates was studied. We found evidence for an oxidizer
concentration threshold of ~0.8 mol%. Glasses made from purified fluorides formed black precipitates even with the
addition of 0.5 mol% In3+, while glasses made from commercial fluorides did not. In the latter, additional oxidizers were
likely present in the form of transition-metal impurities. An In3+ oxidizer concentration of >0.8 mol% is expected to
eliminate the black precipitates in purified glasses and to yield ZBLAN:Yb3+ glass for efficient laser cooling.
A quantitative description of optical refrigeration in Yb3+-doped ZBLAN glass in the presence of transition-metal and
OH impurities is presented. The model includes the competition of radiative processes with energy migration, energy
transfer to transition-metal ions, and multiphonon relaxation. The cooling efficiency is sensitive to the presence of both
3d metal ions with absorption in the near infrared and high-frequency vibrational impurities such as OH. The calculation
establishes maximum impurity concentrations for different operating temperatures and finds Cu2+, Fe2+, Co2+, Ni2+, and
OH to be the most problematic species. Cu2+ in particular has to be reduced to <2 ppb, and Fe2+, Co2+, Ni2+, and OH have
to be reduced to 10-100 ppb for a practical ZBLAN:Yb3+ optical cryocooler to operate at 100-150 K.
A quantitative description of optical refrigeration in rare-earth doped solids in the presence of impurities is presented. The model includes the competition of radiative processes with energy migration, energy transfer to transition-metal ions, and multiphonon relaxation. The cooling efficiency is sensitive to the presence of both 3d metal ions with absorption in the near infrared and high-frequency vibrational impurities such as OH. A case study of ZBLAN:Yb3+ identifies Cu2+, Fe2+, Co2+, and OH as the most problematic species and establishes a 1-10 ppm upper limit for each of these impurities for a practical ZBLAN:Yb3+ optical cryocooler operating at
100-150 K to become feasible. The model results form the basis for an advanced strategy for the synthesis of high-purity ZBLAN:Yb3+ that exploits the potential of available purification techniques in an aqueous intermediate step. Such
high-performance ZBLAN:Yb3+ is expected to enable optical cryocoolers with ~1% overall efficiency at 120 K and find use in a wide range of applications that require highly reliable, noise-free, and vibration-free cooling of electronic and opto-electronic components.
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