We are exploring the potential of Praseodymium (Pr³+) as a dopant in low-phonon chloride hosts, CsCdCl3 and CsPbCl3. Pr3+ possesses favorable absorption bands (3H4 → 3F3,4) in the ~1.5 µm range, amendable to efficient laser diode or fiber laser pumping, as well as group of energy levels with energy gaps enabling mid-IR emissions in the 3-5 micron wavelength range of practical interest. In this work, spectroscopic investigation of Pr3+ aimed to also determine whether the “three-for-one” processes boosting the efficiency of mid-IR emission can be observed in these new materials. Detailed spectroscopic results including Judd-Ofelt analysis, transitions cross-sections, and fluorescence dynamics will be discussed and their potential for efficient mid-IR laser operation will be evaluated.
With the goal of developing new mid-IR lasers, Rare Earth doped low-phonon sulfide-based chalcogenide glasses are being explored for their potential as sources emitting at ~3-microns. Such low phonon energy materials are necessary to minimize competing non-radiative decay processes such as multi-phonon relaxation (MPR). This work presents the results of a comprehensive spectroscopic study comparing the 3-micron laser potential of three different RE ions (Dy3+, Ho3+, and Er3+) doped into sulfide-based chalcogenide glass. Spectroscopic results will focus on absorption, fluorescence, and decay characteristics. From these measurements, laser relevant parameters such as cross sections and radiative lifetimes are calculated.
In this work, we present the results of our recent spectroscopic investigation on Dy3+-doped Ga2Ge5S13 (Dy:GGS) glass, aiming to explore its potential for mid-infrared (3-5 µm) laser applications. Under 910 nm excitation, the studied Dy:GGS glass displayed broad emission bands centered at ~2.9 µm and ~4.35 µm corresponding to 6H13/2 --> 6H15/2 and 6H11/2 --> 6H13/2, respectively. The measured fluorescence decay time of the 6H11/2 manifold (upper laser level for 4.35 µm laser transition) was found to be in the millisecond range, demonstrating similarity to other sulfide glasses doped with Dy3+. Spectroscopic results and data modeling including the temperature dependent emission and decay dynamics, concentration dependent studies, Judd-Ofelt analysis, and transition cross-sections, will be presented.
The optical properties of rare-earth (RE) activated materials have been extensively investigated for their potential as solid-state laser gain media. More recently, mid-IR gain and lasing from RE3+ (Tb3+, Pr3+, Ce3+) doped low-phonon selenide-based chalcogenide glasses have sparked further development of this class of materials which have shown lifetimes on the order of millisecond for mid-IR transitions. In this work, mid-IR (3 - 5 micron) spectroscopic study was performed on the Ho3+ doped low-phonon sulfide and selenide-based chalcogenides glasses as well as indium fluoride glasses, which were prepared by melt quenching technique.
With the goal of developing new mid-IR laser sources, Rare-earth doped low-phonon crystals and sulfide-based chalcogenide glasses are being explored. Low maximum phonon energy materials are necessary to minimize competing non-radiative decay processes such as multi-phonon relaxation (MPR). This work presents the results of a comprehensive mid-IR spectroscopic study on Dy3+ doped sulfide-based chalcogenide glasses, as well as comparative results from similarly doped chloride and fluoride crystals. Spectroscopic results will focus on absorption, fluorescence, and decay characteristics. From these measurements, laser relevant parameters such as cross sections and radiative lifetimes are calculated.
All material types are being considered, from crystals to ceramics and glasses, with focus on those RE3+ hosts with low maximum energy. In this work, a comparative study was performed on the mid-IR (3-5 um) spectroscopic properties of erbium doped in low-phonon fluoride (BaF2) and chloride (CsCdCl3) crystals as well as sulphide (Ga2Ge5S13) glasses. Among the studied materials, Er3+:CsCdCl3 showed the longest 4I9/2 emission lifetime of ~11 ms whereas the ~ 46 us observed from Er3+:BaF2 was the shortest 4I9/2 lifetime. These results reflect the reduced nonradiative rates through multiphonon relaxation in chloride crystals. Spectroscopic results and data modeling including the temperature dependent emission and decay dynamics, Judd-Ofelt analysis, and transition cross-sections will be presented.
In recent years, ceramic sesquioxide materials have emerged as a promising alternative to crystalline laser hosts for near- and mid-infrared laser applications. Ceramics offer a number of manufacturing advantages over crystals including lower fabrication temperatures and the amenability to forming much larger size samples. In this work, a number of RE ions, doped into multiple sesquioxide hosts, are spectroscopically characterized in order to assess their potential for near- and mid-infrared laser applications. Characterization methods included absorption and fluorescence spectroscopy as well as decay dynamics, all measured as functions of temperature. The results are analyzed in order to determine the best laser gain media in the near- and mid-infrared spectral regions.
A large number of rare-earth (RE) activated materials have been investigated to develop new solid state infrared (IR) laser sources for potential applications in atmospheric sensing, material processing, laser remote sensing, medicine, and free space communications. RE3+-doped low-phonon chalcogenide glasses have shown efficient mid-IR emission as well as lasing at room temperature. In this work, we report the results of a comparative study of mid-IR spectroscopic properties of RE3+ doped chalcogenide glasses (e.g. GaGeX (X= S, Se)) aimed at exploring their potential for efficient mid-IR laser operation.
The development of mid-IR lasers faces some unique challenges when striving to achieve the highest efficiency and power output. Most critical among these challenges is luminescence quenching of the relatively closely-spaced upper and lower laser levels, usually occurring through the process of multi-phonon relaxation. This quenching can be mitigated by using gain materials with small maximum phonon energies. In this work, mid-IR spectroscopic characterization of RE3+ doped cesium cadmium chloride (CsCdCl3) crystals was performed. The transition probabilities of RE3+ ions using Judd-Ofelt analysis as well as the multiphonon non-radiative transition rates in RE3+:CsCdCl3 were estimated. Obtained experimental results, inclusive of temperature dependent absorption and fluorescence studies, transition cross-sections, and fluorescence dynamics, were interpreted from the standpoint of optimization for diode-pumped ~3-5 um laser development.
Laser hosts with low maximum phonon energies decrease multiphonon-relaxation (MPR) rates, which enables rare earth emission transitions in the mid-IR region. In this work, a comparative study of mid-IR (3-5 µm) spectroscopic properties on Ho3+ ions doped in various low-phonon fluoride (LaF3, BaF2, NaYF4) and chloride (KPb2Cl5, CsCdCl3, CsPbCl3) based crystals were explored. Experimental results of the mid-IR emission properties using both steady-state and time-resolved fluorescence spectroscopy will be presented. Several laser relevant spectroscopic parameters for the 3.9 µm mid-IR emission of all the studied crystals were determined and compared.
The increased interest in lasers operating in the mid-infrared spectral region has prompted the development of new gain materials with low maximum phonon energy. Fluorites (calcium fluoride [CaF2], strontium fluoride [SrF2], and barium fluoride [BaF2]) have emerged as promising laser host crystals due to their low phonon energies, high thermal conductivities, and ability to incorporate RE dopants. Dy3+ has been studied in CaF2 and SrF2 but its spectroscopic properties are largely unexplored in BaF2. In this work, dysprosium-doped barium fluoride was explored for its mid-infrared laser potential in the 3-μm spectral region. Results of absorption and fluorescence measurements were used to generate stimulated-emission cross sections, and the gain characteristics were determined at both room temperature and 77 K.
Extending solid-state laser technology to longer wavelengths is difficult because the transitions that lead to mid-IR emission experience strong competition from the multiphonon-relaxation (MPR) which reduces the emission quantum efficiency. In this work, a comparative study of mid-IR (3-5 μm) spectroscopic properties on RE3+ ions doped in various low-phonon fluoride and chloride based crystals were explored. Obtained experimental results, including temperature dependent absorption and fluorescence, transition cross-sections, and fluorescence dynamics are discussed and the potential for efficient laser operation is evaluated. Ultimately, the chloride materials demonstrated more favorable laser parameters than the fluoride materials, including significantly longer upper laser level lifetimes.
The mid-infrared fluorescence properties of erbium (Er) doped low-phonon ternary chloride-based crystals (KPb2Cl5, Cs2HfCl6, CsPbCl3, CsCdCl3) have been investigated. All crystals were grown by vertical Bridgman technique. Following optical excitations at 805 nm and 660 nm, all Er3+ doped chlorides exhibited infrared emissions at ~2750, ~3500, and ~4500 nm at room temperature. The mid-infrared emission at 4500 nm originating from the 4I9/2 → 4I11/2 transition showed long emission lifetime values of ~7.8 ms and ~11.6 ms for Er3+ doped Cs2HfCl6 and CsCdCl3 crystals, respectively. In comparison, Er3+ doped KPb2Cl5 and CsPbCl3 demonstrated shorter lifetimes of ~3 ms and ~1.8 ms, respectively. The temperature dependence of the 4I9/2 decay times was performed for Er3+ doped CsPbCl3 and CsCdCl3 crystals. We observed that the fluorescence lifetimes were nearly independent of the temperature, indicating a negligibly small non-radiative decay rate through multiphonon relaxation, as predicted by the energy gap law for low phonon energy hosts. The room temperature stimulated emission cross-sections for the 4I9/2 → 4I11/2 transition were determined to be in a range of ~0.14-0.54 x 10-20 cm2 for the studied Er doped chloride crystals.
In the pursuit of new mid-IR laser gain materials, dysprosium-doped barium fluoride was evaluated for its potential laser emission in the 3-μm spectral region. Comprehensive spectroscopic characterization was performed, including absorption, fluorescence, and decay-time measurements. Efforts to determine the discrete Stark splittings of various Dy3+ manifolds in this host material were hampered by apparent multisite behavior of the RE dopant. Laser-relevant parameters such as absorption and stimulated-emission cross sections, quantum-efficiencies, and radiative lifetimes were determined for room temperature (300 K) and cryogenic temperature (77 K). The gain cross sections, which predict overall laser performance, were also calculated. Room-temperature laser operation of the 3-μm transition would suffer from low quantum efficiency and would require a high population inversion of approximately 40%. The parameters at 77 K show improvement across the board with multiple-times-higher cross-section intensities, nearly 4× higher quantum efficiency, and a positive gain cross section requiring less than 20% population inversion.
The development of new solid-state laser materials for mid-infrared (mid-IR) laser sources continues to be interest for potential applications in remote sensing of bio-chemical agents, IR countermeasures, and IR spectroscopy. Fluorescent materials based on Ho3+ doped crystals and glasses with narrow phonon spectra cover a wide wavelength range between ~1-4 µm. In this work, spectroscopic characterization on infrared emission properties of trivalent holmium (Ho3+) doped potassium lanthanum chloride (K2LaCl5) were explored. K2LaCl5 is slightly hygroscopic but possesses a maximum phonon energy of 235 cm-1. The low maximum phonon energy of K2LaCl5 leads to low non-radiative decay rates and efficient IR fluorescence. The studied Ho3+ doped K2LaCl5 material was grown by Bridgman technique. Using ~900 nm excitation, IR emissions centered at ~1.66, ~1.995, and ~3.90 µm were observed from Ho:K2LaCl5 corresponding to the 5I5-->5I7, 5I7-->5I8, and 5I5-->5I6 transitions of Ho3+ ions. Spectroscopic results and data modeling including the Stark level energies, Judd-Ofelt analysis, transitions cross-sections, and fluorescence dynamics will be presented at the conference.
Recently, a mercury-cadmium-telluride (MCT) linear array detection system that is capable of rapidly capturing (~1-5 second) a broad spectrum of atomic and molecular laser-induced breakdown spectroscopy (LIBS) emissions in the longwave infrarμed region (LWIR, ~5.6 to 10 μm) has been developed. Similar to the conventional Ultraviolet (UV)-Visible (Vis) LIBS, a broad band emission spectrum of condensed phase samples covering the entire 5.6 to 10 μm region can be acquired from just a single laser-induced micro-plasma or averaging a few single laser-induced micro-plasmas. This setup has enabled probing samples “as is” without the need for extensive sample preparation and also offers the possibility of a simultaneous UV-Vis and LWIR LIBS measurement. A Martian regolith simulant (JSC Mars-1A) was studied with this novel Vis + LWIR LIBS array system. A broad SiO2 vibrational emission feature around 9.5 μm and multiple strong emission features between 6.5 to 8 μm can be clearly identified. The 6.5 to 8 μm features are possibly from biological impurities of the simulant. JSC Mars-1A samples with organic methyl salicylate (MeS, wintergreen oil) and Dimethyl methyl-phosphonate (DMMP) residues were also probed using the LWIR LIBS array system. Both molecular spectral signature around 6.5 μm and 9.5 μm of Martian regolith simulant and MeS and DMMP molecular signature emissions, such as Aromatic CC stretching band at 7.5 μm, C-CH3O asymmetric deformation at 7.6 μm, and P=O stretching band at 7.9 μm, are clearly observed from the LIBS emission spectra in the LWIR region.
Laser-induced breakdown spectroscopy is a powerful diagnostic tool for detection of trace elements by monitoring the atomic and ionic emission from laser-induced plasmas. Besides elemental emissions from conventional UV-Vis LIBS, molecular LIBS emission signatures of the target compounds were observed in the long-wave infrared (LWIR) region in recent studies. Most current LIBS studies employ the fundamental Nd:YAG laser output at 1.064 μm, which has extremely low eye-damage threshold. In this work, comparative LWIR-LIBS emissions studies using traditional 1.064 μm pumping and eye-safe laser wavelength at 1.574 μm were performed on several energetic materials for applications in chemical, biological, and explosive (CBE) sensing. A Q-switched Nd: YAG laser operating at 1.064 μm and the 1.574 μm output of a pulsed Nd:YAG pumped Optical Parametric Oscillator were employed as the excitation sources. The investigated energetic materials were studied for the appearance of LWIR-LIBS emissions (4-12 μm) that are directly indicative of oxygenated breakdown products as well as partially dissociated and recombination molecular species. The observed molecular IR LIBS emission bands showed strong correlation with FTIR absorption spectra of the studied materials for 1.064 μm and 1.574 μm pump wavelengths.
Conventional laser induced breakdown spectroscopy (LIBS) mostly uses silicon-based detectors and measures the atomic emission in the UV-Vis-NIR (UVN) region of the spectrum. It can be used to detect the elements in the sample under test, such as the presence of lead in the solder for electronics during RoHS compliance verification. This wavelength region, however, does not provide sufficient information on the bonding between the elements, because the molecular vibration modes emit at longer wavelength region. Measuring long-wave infrared spectrum (LWIR) in a LIBS setup can instead reveal molecular composition of the sample, which is the information sought in applications including chemical and explosive detection and identification. This paper will present the work and results from the collaboration of several institutions to develop the methods of LWIR LIBS for chemical/explosive/pharmaceutical material detection/identification, such as DMMP and RDX, as fast as using a single excitation laser pulse. In our latest LIBS setup, both UVN and LWIR spectra can be collected at the same time, allowing more accurate detection and identification of materials.
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.
The luminescent properties of rare-earth doped solids have been under intense exploration for a wide range of applications ranging from displays and lasers to scintillators. In this work, the material purification, crystal growth, and spectroscopic properties of Ce3+-, and Eu3+- doped KPb2Cl5 as well as Pr3+ doped KPb2Cl5 and KPb2Br5 were investigated for possible applications in infrared lasers and radiation detectors. The studied materials were synthesized through careful purification of starting materials including multi-pass zone-refinement and halogination. The growth of the purified materials was then carried out through vertical or horizontal Bridgman technique. The trivalent praseodymium ion (Pr3+) offers a large number of laser transitions in the visible and infrared (IR) spectral regions. Using ~1.45 μm and 1.9 μm pumping, IR emissions at ~1.6, ~2.4, and ~4.6 μm were observed from Pr: KPb2Cl5 and Pr: KPb2Br5 corresponding to the 4f-4f transitions of 3F4/3F3→3H4, 3F2/3H6→3H4, and 3H5→3H4, respectively. Large emission cross-sections in the range of (4.8-6.1) x 10-20 cm2 (near-IR, ~1.6 μm) and (5.5-6.0) x 10-20 cm2 (mid-IR, ~4.6 μm) were observed for both crystals. Emission characteristics of the ~1.6 μm Pr3+ transition including IR to visible upconversion emission studies were also discussed. Under Xenon lamp excitation, preliminary spectroscopic results showed allowed 5d-4f Ce3+ emission centered at ~375 nm in Ce3+ doped KPb2Cl5. In addition, commercial Ce:YAG and Ce:YAP crystals are included in this study for comparison. Pr3+ and Eu2+ 5d-4f emissions were not observed from Pr3+/Eu2+ doped KPb2Cl5 crystals.
The infrared (IR) absorption and emission properties of Ho:KPC, Ho:KPB, and Ho:YAG were compared for possible applications in 2 µm laser cooling. Ho:KPC and Ho:KPB crystals were grown by vertical Bridgman technique using purified starting materials. A commercial Ho:YAG crystal was included in this study for comparison. Under resonant pumping at ~1.907 µm, the Ho-doped KPC/KPB crystals exhibited broad IR emission centered at ~2 µm based on the Ho3+ intra-4f transition 5I7 → 5I8. Under similar experimental conditions, Ho:YAG showed a narrow-structured emission band reflective of individual Stark levels. The average emission wavelength for Ho:YAG was determined to be ~2.03 µm. Initial heat loading/cooling experiments under ambient air were performed using a fiber laser operating at ~2.036 µm with an output power of 2 W. The Ho:KPC/KPB crystals exhibited small temperature increases of ~1.0 ºC. A significantly larger temperature increase of ~5 ºC was observed for Ho:YAG. IR transmission studies revealed the existence of OH impurities in the Ho-doped halides, which possibly lead to non-radiative decay channels.
Spectroscopic properties of the 2 μm infrared (IR) emission (5I7 → 5I8) from trivalent holmium (Ho3+) doped potassium lead bromide (KPb2Br5) are presented. The investigated Ho3+ doped KPb2Br5 (KPB) material was synthesized through purification of starting materials including multi-pass zone-refinement, bromination, and subsequently grown using horizontal Bridgman technique. The bromination process was critical for removing oxidic impurities and enhancing the quality of the crystal. Judd-Ofelt intensity parameters, radiative rates, branching ratios, and emission lifetimes were calculated and compared with results reported for Ho3+ doped KPb2Cl5 (KPC). Under resonant pumping (~1.907 μm), Ho: KPB showed a broad IR emission centered at ~2 μm with an exponential decay time of 7.1 ms at room temperature. The nearly temperature independent emission lifetime is consistent with a negligibly small non-radiative decay rate for the 5I7 excited state of Ho3+, as predicted by the multiphonon energy gap law. The optical absorption, emission and gain cross-sections of Ho: KPB were determined for the 2 μm transition. The Ho: KPB crystal was also evaluated as a potential solid-state material for laser cooling applications.
The 1.6 μm emission properties originating from the 3F3, 3F4 → 3H4 transition of Pr3+ ions in Pr-doped PbCl2 crystals were investigated for possible application in resonantly-pumped, eye-safe laser development. Pr: PbCl2 was synthesized and purified through a combination of zone-refinement and chlorination of the melt before growing crystals by Bridgman technique. Under optical pumping using a ~1.48 μm laser diode, an IR emission band centered at ~1.65 μm with a full width at half maximum of 75 nm was observed at room temperature. The decay transient of the thermally coupled 3F3 and 3F4 excited states was single exponential with a value of 170 μs at room temperature. The lifetime increased to 350 μs at 77 K suggesting the existence of some non-radiative decay through multi-phonon relaxation. Emission cross-section spectra were determined using the principle of reciprocity and Ladenburg-Fuchtbauer method and yielded peak values of 3.8x10-20 cm2 and 5.7x10-20 cm2 at room-temperature and 77 K, respectively. The effective gain cross-section spectra of Pr: PbCl2 will be discussed for possible lasing in the 1.6-1.7 μm region.
Tm3+ doped solids have shown promising results for laser cooling applications at IR wavelengths of ~2 μm. The extended IR fluorescence of the involved Tm3+ transition (3H6 → 3F4), however, requires low-phonon energy hosts reducing the detrimental effect of non-radiative decay through multiphonon relaxation. In this work the temperature dependent absorption and emission properties of Tm doped KPC (hνmax<200 cm-1) and KPB (hνmax<140 cm-1) crystals were evaluated for applications in laser cooling. Under laser pumping both crystals exhibited broad IR fluorescence at room temperature with a mean fluorescence wavelength of 1.82 μm and bandwidth of 0.14 μm (FWHM). Initial experiments on laser-induced heating and cooling were performed using a combined IR imaging and fluorescence thermometry setup. Employing a continuous-wave laser operating at 1.907 μm, Tm: KPC and Tm: KPB crystals revealed a very small heat load resulting in a temperature increase of ~0.3 (±0.1) °C compared to undoped reference samples. Further work on material improvement will be necessary to identify possible non-radiative loss mechanisms and to improve the crystal quality.
Laser-induced breakdown spectroscopy (LIBS) is a powerful analytical technique to detect the elemental composition of solids, liquids, and gases in real time. For example, recent advances in UV-VIS LIBS have shown great promise for applications in chemical, biological, and explosive sensing. The extension of conventional UVVIS LIBS to the near-IR (NIR), mid-IR (MIR) and long wave infrared (LWIR) regions (~1-12 μm) offers the potential to provide additional information due to IR atomic and molecular signatures. In this work, a Q-switched Nd: YAG laser operating at 1064 nm was employed as the excitation source and focused onto several chlorate and nitrate compounds including KClO3, NaClO3, KNO3, and NaNO3 to produce intense plasma at the target surface. IR LIBS studies on background air, KCl , and NaCl were also included for comparison. All potassium and sodium containing samples revealed narrow-band, atomic-like emissions assigned to transitions of neutral alkali-metal atoms in accordance with the NIST atomic spectra database. In addition, first evidence of broad-band molecular LIBS signatures from chlorate and nitrate compounds were observed at ~10 μm and ~7.3 μm, respectively. The observed molecular emissions showed strong correlation with FTIR absorption spectra of the investigated materials.
In this study, cw and pulsed 1532 laser excitation of the 4I13/2 band of Er3+ was explored in the low phonon-energy hosts KPb2Cl5and KPb2Br5. Crystal growth along with upconversion and eye-safe emission (~ 1550 nm) studies were conducted on both samplesunder 140 mW of cw laser excitation. Excitation spectra and emission decay transients of the infrared (4I9/2 →4I15/2) and green upconversion (2H11/2 + 4S3/2 →4I15/2) revealed that energy transfer upconversion (ETU) is the origin of the infrared and the green upconversion under 1532 nm excitation. Spectral emission measurements indicate that the infrared upconversion is dominant relative to the green upconversion in both Er: KPb2Cl5and Er: KPb2Br5 crystals.
We report on the spectroscopic characteristics and upconversion emission in Er3+ doped Yttria (Y2O3) transparent ceramics prepared by a modified two-step sintering method. The near-infrared (1.5 μm) emission properties were evaluated as a function of Er3+ concentration. Judd-Ofelt intensity parameters, radiative rates, branching ratios, and emission lifetimes were calculated and compared with results reported for Er3+ doped Y2O3 single crystal and nanocrystals. Following pumping at 1.532 μm, weak blue (~0.41 μm, 2H9/2→4I15/2), strong green (~0.56 μm, 2H11/2, 4S3/2→4I15/2) and red (~0.67 μm, 4F9/2→4I15/2) emission bands were observed as well as weak near-infrared emissions at 0.8 μm (4I9/2→4I15/2) and 0.85 μm (4S3/2→4I13/2) at room temperature. The upconversion emission properties under ~1.5 μm pumping were further investigated through pump power dependence and decay time studies. Sequential two-photon absorption leads to the 4I9/2 upconversion emission while energy transfer upconversion is responsible for the emission from the higher excited states 2H9/2, 2H11/2, 4S3/2, and 4F9/2. The enhanced red emission with increasing Er3+ concentration most likely occurred via the cross-relaxation process between (4F7/2 → 4F9/2) and (4I11/2 → 4F9/2) transitions, which increased the population of the 4F9/2 level.
Laser-induced breakdown spectroscopy (LIBS) has shown great promise for applications in chemical,
biological, and explosives (CBE) sensing and has significant potential for real time standoff detection and
analysis. We have studied LIBS emissions in the mid-infrared (MIR) spectral region for potential
applications in CBE sensing. Detailed MIR-LIBS studies were performed for several energetic materials
for the first time. In this study, the IR signature spectral region between 4 - 12 um was mined for the
appearance of MIR-LIBS emissions that are directly indicative of oxygenated breakdown products as well
as partially dissociated and recombination molecular species.
We report on the 5 μm emission characteristics and energy transfer properties of Tb3+ doped KPb2Br5 and Nd3+ doped
KPb2Br5 sensitized by Tm3+ ions. A series of co-doped samples of Tm,Tb: KPb2Br5 and Tm,Nd: KPb2Br5 samples were
prepared from purified starting materials of PbBr2, KBr, and rare earth halides. Resonant excitation into the 3H6 → 3F4
absorption transition of Tm3+ at ~1760 nm resulted in an enhanced 5 μm emission from Tb3+ and Nd3+ ions in Tm,Tb:
KPb2Br5 and Tm,Nd: KPb2Br5, respectively. The existence of energy transfer between Tm → Tb and Tm → Nd was
further evidenced by the quenching of the emission decay times of the 3F4 → 3H6 transition of Tm3+ in doubly doped
Tm,Tb: KPb2Br5 and Tm,Nd: KPb2Br5 compared to singly doped Tm: KPb2Br5.
Solid-state lasers operating in the mid-infrared (MIR) wavelength region (3-5 μm) are of significant current interest for laser remote sensing of chemical and biological agents as well as for military countermeasures. The development of MIR solid-state lasers based on oxide and fluoride laser hosts is limited by non-radiative decay through multi-phonon relaxations. Rare earth doped crystals with low maximum phonon energies can exhibit efficient MIR emission at room temperature. In this paper, we present results of the material synthesis and optical properties of rare earth (Pr, Nd, Dy, Er) doped KPb2Br5, which has a maximum phonon energy of only ~140 cm-1.
In this work we present a detailed analysis of the room temperature infrared to visible upconversion in Nd3+-doped KPb2Br5 crystal by using both steady-state and time-resolved luminescence spectroscopy. The study includes one photon absorption and emission spectroscopy and lifetime measurements for the visible and infrared fluorescence, and infrared to, blue, green, orange, and red upconversion processes. The possible upconversion mechanisms are discussed in terms of excitation spectra, excitation power dependence, and lifetimes of the upconversion emissions.
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