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Optical properties and relaxation mechanisms of PbS quantum dots in glass matrix (PbS:Glass) have been systematically investigated by transmission and (steady-state and transient) photoluminescence spectroscopy. Key parameters are determined by combining the data with semiempirical expressions, based on which the recombination mechanisms including spontaneous and stimulated emissions have been discussed as a function of temperature by referring to a multilevel model including intrinsic (or band-to-band transition), bright, dark, and ground states. The results disclose that (i) the existence of a dark exciton state is the main reason for thermal quenching of the emission even at low temperatures due to the strong multiacoustic phonon coupling, (ii) the "intrinsic" spontaneous emission related to the intrinsic state is observed with an approximately nanosecond lifetime, in contrast to the "regular" spontaneous emission from the bright exciton state with an approximately microsecond lifetime, and (iii) stimulated emission, which has a lifetime of 20-40 ps and shows power-dependence of excitation density (or temperature), only appears from the intrinsic state but not the (bright) exciton state when enough accumulation of photogenerated carriers is reached. Furthermore, we find that the thermal conductivity will become crucial for future PbS:Glass related optoelectronic device applications.

The luminescence behavior of PbS-quantum dots in glass matrix (PbS:Glass) is investigated. Steady-state and time-resolved photoluminescence are applied in a wide range of excitation densities up to pulse energies exceeding 50 μJ/cm 2 . While perfect linear recombination is observed across four orders of magnitude, an additional radiative recombination mechanism emerges at an excitation density of 1 μ J/cm 2 per pulse at 390 nm excitation and increases the external quantum efficiency. The time constant of this process is ∼20-40 ps. It is ascribed to stimulated emission. No hint to any non-linear nonradiative processes such as Auger recombination is observed. Thermal effects, however, still set limits. This is encouraging news for PbS:Glass as potential laser material.

Multiple optical transitions from PbS quantum dots (QDs) in glass matrix are observed. Energy separations between them amount up to ∼200 meV. Instead of being due to a size distribution of QDs, they are found to be related to a splitting of the lowest exciton levels. Systematic analysis of the relaxation dynamics reveals the lifetimes of the split states ranging from sub-100-ns to ∼μs. Moreover, we observe excited and "intrinsic" states having a sub-100-ps and ∼ns lifetime, respectively. The behavior of the split structure can be modeled by a phonon-assisted relaxation mechanism. This investigation offers a conclusive interpretation for the wide distribution of experimentally observed nonequilibrium carrier lifetimes in PbS QDs.Lead salt (e.g., PbS) quantum dots (QDs) have been widely investigated for applications in optoelectronic devices [1,2]. The QDs are either colloidal or embedded into a glass matrix. The latter provides substantial advantages in terms of longterm stability [3]. In order to evaluate and improve the properties of materials or devices, the QD size and its distribution as well as the excitonic lifetime are major issues, which should be accurately characterized, e.g., directly by optical methods including steady-state (SS) or transient absorption and photoluminescence (PL) spectroscopy at room temperature [4].However, in rock salt PbS QDs the dimension of the excitonic manifold is theoretically 64 because both the valence-band maximum and the conduction-band minimum originate from the 8-fold (including spin) L valleys in the first Brillouin zone of bulk PbS. The degeneracy of these L valleys becomes lifted due to, e.g., intervalley coupling, interband coupling, and electron-hole Coulomb and exchange interaction [5]. Another mechanism potentially acting into this direction is external forces such as pressure as well as a special chemical surrounding, e.g., in a matrix. The split structure makes the optical transition in QDs complex and affects the characterization of QD features including the lowest excitonic transition energy (for simplicity called E g ) and subsequently the size and distribution of QDs as well as the nonequilibrium carrier recombination mechanism. In spite of the fact that asymmetric-or multi-PL (or absorption) peaks from these kinds of QDs have been observed even at room temperature, no direct reports involve these split states. Typically extrinsic assumptions are made including size distribution (e.g., multimodal QDs) [6], temperature/excitation-induced broadening [7], or defect states [8,9].In this Rapid Communication, PbS QDs embedded in a borosilicate glass matrix are prepared and characterized by SS-or transient-PL spectroscopy at low excitation densities and temperatures. A three-transition structure from the QDs is observed with an energy separation up to 200 meV, in dependence of growth conditions including annealing. The * yue@mbi-berlin.de intrinsic mechanism for this three-transition structure that seems to be sensitive to the host matrix, e.g., with borosilicate b...

Silicate- and borosilicate-based PbS:glass material and borosilicate-glass-based fibers are fabricated and analyzed. Optical properties including absorption and emission are characterized and related to growth and annealing conditions. In silicate glasses PbS volume fractions of exceeding 0.4 percent and almost octave-spanning emission spectra with a halfwidth of 940 nm are achieved. Fiber bundles with a core being surrounded by three PbS:Glass fibers are pulled. A confinement factor of Γ = 0.00406 is determined. Emission properties, in particular emission bandwidth, are subsequently tuned and spectrally widened by annealing fibers in a gradient furnace. The results pave the way towards optically pumped broad-bandwidth light emitters based either on 'bulk' PbS:glass or PbS:glass-based fibers.