Low Excitation Densities Research Articles

Comparative studies of optoelectrical properties of prominent PV materials: Halide perovskite, CdTe, and GaAs

We compare three representative high performance PV materials: halide perovskite MAPbI3, CdTe, and GaAs, in terms of photoluminescence (PL) efficiency, PL lineshape, carrier diffusion, and surface recombination and passivation, over multiple orders of photo-excitation density or carrier density appropriate for different applications. An analytic model is used to describe the excitation density dependence of PL intensity and extract the internal PL efficiency and multiple pertinent recombination parameters. A PL imaging technique is used to obtain carrier diffusion length without using a PL quencher, thus, free of unintended influence beyond pure diffusion. Our results show that perovskite samples tend to exhibit lower Shockley–Read–Hall (SRH) recombination rate in both bulk and surface, thus higher PL efficiency than the inorganic counterparts, particularly under low excitation density, even with no or preliminary surface passivation. PL lineshape and diffusion analysis indicate that there is considerable structural disordering in the perovskite materials, and thus photo-generated carriers are not in global thermal equilibrium, which in turn suppresses the nonradiative recombination. This study suggests that relatively low point-defect density, less detrimental surface recombination, and moderate structural disordering contribute to the high PV efficiency in the perovskite. This comparative photovoltaics study provides more insights into the fundamental material science and the search for optimal device designs by learning from different technologies.

Precharging Photon Upconversion: Interfacial Interactions in Solution-Processed Perovskite Upconversion Devices.

Recent advances in perovskite-sensitized photon upconversion via triplet-triplet annihilation (TTA) in rubrene have yielded several unanswered questions about the underlying mechanism and processes occurring at the interface. In particular, the near-infrared perovskite emission is not significantly quenched and a rapid reversible "photobleach" of the upconverted emission can be observed under fairly low excitation densities of 3.2 mW/cm2. In this contribution, we investigate the perovskite/rubrene interface in more detail and conclude that noncovalent interactions between the organic layer and the perovskite result in surface trap passivation. In addition, band bending results in a space charge region at the perovskite/rubrene interface, which "precharges" the rubrene with holes. Upon initial illumination, electrons can rapidly transfer to the excited triplet state of rubrene, followed by efficient TTA upconversion. As the device is continuously illuminated, the existing holes are consumed and a new equilibrium is reached, resulting in the previously investigated steady-state upconversion efficiency.

Dry Mechanochemical Synthesis of Highly Luminescent, Blue and Green Hybrid Perovskite Solids

AbstractA simple method to obtain bright photoluminescent wide bandgap mixed‐halide 3D perovskites is reported. The materials are prepared by dry mechanochemical synthesis (ball‐milling) starting from neat binary precursors, and show enhanced photoluminescence upon the addition of an adamantane derivative in the precursors' mixture. The structural characterization suggests that the additive does not participate in the crystal structure of the perovskite, which remains unvaried even with high loading of amantadine hydrochloride. By simple stoichiometric control of the halide precursors, the photoluminescence can be finely tuned from the UV to the green part of the visible spectrum. Photoluminescence quantum yields as high as 29% and 5% have been obtained for green‐ and blue‐emitting perovskite solids, even at very low excitation densities.

Spectra stable blue perovskite light-emitting diodes

Device performance and in particular device stability for blue perovskite light-emitting diodes (PeLEDs) remain considerable challenges for the whole community. In this manuscript, we conceive an approach by tuning the ‘A-site’ cation composition of perovskites to develop blue-emitters. We herein report a Rubidium-Cesium alloyed, quasi-two-dimensional perovskite and demonstrate its great potential for pure-blue PeLED applications. Composition engineering and in-situ passivation are conducted to further improve the material’s emission property and stabilities. Consequently, we get a prominent film photoluminescence quantum yield of around 82% under low excitation density. Encouraged by these findings, we finally achieve a spectra-stable blue PeLED with the peak external quantum efficiency of 1.35% and a half-lifetime of 14.5 min, representing the most efficient and stable pure-blue PeLEDs reported so far. The strategy is also demonstrated to be able to generate efficient perovskite blue emitters and PeLEDs in the whole blue spectral region (from 454 to 492 nm).

Terahertz Luminescence Induced by Intra‐Exciton Radiative Transitions in Silicon

This article reports the results of experimental investigations of a new type of terahertz emission from semiconductors. This emission is due to radiative transitions between energy levels of free excitons. The intra‐exciton radiative transitions arise during the binding of nonequilibrium electrons and holes into exciton states. The experiments were carried out on high‐purity Si crystals at helium temperatures in the conditions of interband photoexcitation. The excitation densities were in the range of 0.1 to 140 W cm−2. Terahertz luminescence spectra demonstrate narrow lines of optical transitions between the energy levels of free excitons. The intra‐exciton optical transitions dominate the emission spectrum under conditions of both low excitation densities and at excitation densities well above the electron–hole liquid formation threshold. The intra‐exciton terahertz emission intensity becomes superlinear as a function of the excitation density at a high level of the photoexcitation and temperatures above 20–25 K. This experimental observation could be explained by stimulated optical transitions between the energy levels of free excitons, which presumably appear under intense interband pumping.

High-Detectivity Perovskite Light Detectors Printed in Air from Benign Solvents

Summary Here, we propose a simple and low-temperature approach for the synthesis of methylammonium lead halide perovskite inks based on sub-micrometer-sized particles with tunable band gap. The particles allow the formulation of inks in benign solvents, such as propan-2-ol, and the printing of the photoactive layers of planar photoconductors with scalable, large-area coating techniques under ambient conditions. When surface traps are passivated with [6,6]-phenyl-C61-butyric acid methyl ester fullerene (PCBM), a high photoconductive gain (exceeding 200 in the blue) and reduced noise produce record-high specific detectivities exceeding 7 × 1013 cmHz0.5/W and gain-bandwidth product values of 7.5 × 106 Hz. Given the extreme simplicity of the presented device architecture and the straightforward processing, yielding printable light detectors rivalling established technologies, the present work promises a short-term deployment of printed perovskite detectors in a multitude of opto-electronic applications.

Fluorescence Spectrum and Thermalization in a Driven Coupled Cavity Array.

We calculate the fluorescence spectra of a driven lattice of coupled cavities. To do this, we extend methods of evaluating two-time correlations in infinite lattices to open quantum systems; this allows access to momentum-resolved fluorescence spectrum. We illustrate this for a driven-dissipative transverse-field anisotropic XY model. By studying the fluctuation-dissipation theorem, we find the emergence of a quasithermalized steady state with a temperature dependent on system parameters; for blue-detuned driving, we show this effective temperature is negative. In the low excitation density limit, we compare these numerical results to analytical spin-wave theory, providing an understanding of the form of the distribution function and the origin of quasithermalization.

Exciton-phonon and exciton-exciton interactions in GaAs by time-resolved optical reflectivity

Abstract We present the study of the ultrafast carrier dynamics in bulk GaAs at 6 K, by time-resolved optical reflectivity in a wide range of excitation densities. We observe an exciton-phonon interaction at low excitation densities, in terms of a mono-exponential relaxation. Further increase of excitation density above a critical value n c , stimulates a bi-exponential relaxation in which the fast one is added owing to an exciton-exciton scattering channel. Our results reveal n c ∼ 2 × 10 24 photons / m 3 , about an order of magnitude higher than the Mott density previously determined by photoluminescence and terahertz spectroscopy measurements and theoretical calculations.

Effects of saturation of nonradiative recombination centers on internal quantum efficiency in InGaN light-emitting diodes

The internal quantum efficiency (IQE) of InGaN near-UV light-emitting diodes with different threading dislocation densities (TDDs) was studied by using excitation power density and temperature-dependent photoluminescence spectroscopy. The IQE was evaluated as functions of excitation density and temperature under band-to-band and selective excitation of the InGaN active layers. The IQE curves under weak excitation densities were analyzed with a rate equation model of radiative and nonradiative recombination of excitons, in which the exciton localization and the filling of nonradiative recombination centers (NRCs) were considered. Based on the analysis, we discussed the effects of filling NRCs on the IQE as functions of TDD and temperature and we clarified that the increase in the IQE at lower excitation densities was caused by filling NRCs. The analysis also indicated whether the maximum IQE value reached 100% at low temperatures.

Efficient generation of neutral and charged biexcitons in encapsulated WSe2 monolayers

Higher-order correlated excitonic states arise from the mutual interactions of excitons, which generally requires a significant exciton density and therefore high excitation levels. Here, we report the emergence of two biexcitons species, one neutral and one charged, in monolayer tungsten diselenide under moderate continuous-wave excitation. The efficient formation of biexcitons is facilitated by the long lifetime of the dark exciton state associated with a spin-forbidden transition, as well as improved sample quality from encapsulation between hexagonal boron nitride layers. From studies of the polarization and magnetic field dependence of the neutral biexciton, we conclude that this species is composed of a bright and a dark excitons residing in opposite valleys in momentum space. Our observations demonstrate that the distinctive features associated with biexciton states can be accessed at low light intensities and excitation densities.

Ultrafast Dynamics of Photoexcited Charge Carriers in In0.53Ga0.47As/In0.52Al0.48As Superlattices under Femtosecond Laser Excitation

The results of experimental studies of the time dynamics of photoexcited charge carriers in In0.53Ga0.47As/In0.52Al0.48As superlattices grown by molecular-beam epitaxy on a GaAs substrate with a metamorphic buffer are reported. On the basis of the results of the numerical simulation of band diagrams, the optimal thickness of the In0.52Al0.48As barrier layer (4 nm) is chosen. At this thickness, the electron wave functions in In0.53Ga0.47As substantially overlap the In0.52Al0.48As barriers. This makes it possible to attain a short lifetime of photoexcited charge carriers (τ ~ 3.4 ps) at the wavelength λ = 800 nm and the pumping power 50 mW without doping of the In0.53Ga0.47As layer with beryllium. It is shown that an increase in the wavelength to λ = 930 nm (at the same pumping power) yields a decrease in the lifetime of photoexcited charge carriers to τ ~ 2 ps. This effect is attributed to an increase in the capture cross section of trapping states for electrons with lower energies and to a decrease in the occupancy of traps at lower excitation densities.

Quantum beats of a multiexciton state in rubrene single crystals

We observe quantum beats in the nanosecond-scale photoluminescence decay of rubrene single crystals after photoexcitation with short laser pulses in a magnetic field in the range of 0.1 to 0.3 T. The relative amplitude of the quantum beats is of the order of 5%. Their frequency is 1.3 GHz when the magnetic field is oriented parallel to the twofold rotation axis of the rubrene molecules and decreases to 0.6 GHz when the magnetic field is rotated to the crystal's molecular stacking direction. The amplitude of the quantum beats decays alongside the non-oscillatory photoluminescence background, which at low excitation densities has an exponential decay time of 4.0 ± 0.2 ns. We interpret this as the effective lifetime of a multiexciton state that originates from singlet-fission and can undergo geminate recombination back to the singlet state.

Intrinsic optical sectioning with upconverting nanoparticles.

Multiphoton microscopy is a powerful technique for imaging due to its deep penetration, low scattering and sectioning power, allowing control on all three axes for both imaging and molecular actuation, but involves expensive femtosecond lasers. We show that lanthanide-based Upconverting Nanoparticles offer an under $1000 solution with the main advantages of multiphoton imaging, including direct optical sectioning in complex 3D samples.

Исследование временной динамики фотовозбужденных носителей заряда в сверхрешетках In-=SUB=-0.53-=/SUB=-Ga-=SUB=-0.47-=/SUB=-As/In-=SUB=-0.52-=/SUB=-Al-=SUB=-0.48-=/SUB=-As при воздействии фемтосекундными лазерными импульсами

AbstractThe results of experimental studies of the time dynamics of photoexcited charge carriers in In_0.53Ga_0.47As/In_0.52Al_0.48As superlattices grown by molecular-beam epitaxy on a GaAs substrate with a metamorphic buffer are reported. On the basis of the results of the numerical simulation of band diagrams, the optimal thickness of the In_0.52Al_0.48As barrier layer (4 nm) is chosen. At this thickness, the electron wave functions in In_0.53Ga_0.47As substantially overlap the In_0.52Al_0.48As barriers. This makes it possible to attain a short lifetime of photoexcited charge carriers (τ ~ 3.4 ps) at the wavelength λ = 800 nm and the pumping power 50 mW without doping of the In_0.53Ga_0.47As layer with beryllium. It is shown that an increase in the wavelength to λ = 930 nm (at the same pumping power) yields a decrease in the lifetime of photoexcited charge carriers to τ ~ 2 ps. This effect is attributed to an increase in the capture cross section of trapping states for electrons with lower energies and to a decrease in the occupancy of traps at lower excitation densities.

Ultrashort Radiation of Biexcitonic Superfluorescence from High-Density Assembly of Semiconductor Quantum Dots

High-density semiconductor quantum dot (QD) assembly is a promising system to generate ultrashort radiation of superfluorescence (SF) which is a cooperative emission of many coherent excited particles induced by an interaction with a resonant radiation field. In this paper, we report the superfluorescent spectra and time profiles of biexcitons in CuCl QDs where a complete population inversion between the biexciton and exciton states was achieved by resonant two-photon excitation of biexcitons. A spontaneous emission at low excitation density changed to SF by increasing the excitation density. For a high excitation density, superfluorescent characteristics, i.e., narrowing of the pulse width and shortening of the delay time, were observed. Furthermore, broadening of the spectral width was observed, resulting from the enhancement of radiative rate of QD assembly. On the other hand, the SF at low temperature changed to an amplified spontaneous emission with the increase in temperature due to the increase in ...

Dynamic Optical Tuning of Interlayer Interactions in the Transition Metal Dichalcogenides.

Modulation of weak interlayer interactions between quasi-two-dimensional atomic planes in the transition metal dichalcogenides (TMDCs) provides avenues for tuning their functional properties. Here we show that above-gap optical excitation in the TMDCs leads to an unexpected large-amplitude, ultrafast compressive force between the two-dimensional layers, as probed by in situ measurements of the atomic layer spacing at femtosecond time resolution. We show that this compressive response arises from a dynamic modulation of the interlayer van der Waals interaction and that this represents the dominant light-induced stress at low excitation densities. A simple analytic model predicts the magnitude and carrier density dependence of the measured strains. This work establishes a new method for dynamic, nonequilibrium tuning of correlation-driven dispersive interactions and of the optomechanical functionality of TMDC quasi-two-dimensional materials.

Incoherent population mixing contributions to phase-modulation two-dimensional coherent excitation spectra.

We present theoretical and experimental results showing the effects of incoherent population mixing on two-dimensional (2D) coherent excitation spectra that are measured via a time-integrated population and phase-sensitive detection. The technique uses four collinear ultrashort pulses and phase modulation to acquire two-dimensional spectra by isolating specific nonlinear contributions to the photoluminescence or photocurrent excitation signal. We demonstrate that an incoherent contribution to the measured line shape, arising from nonlinear population dynamics over the entire photoexcitation lifetime, generates a similar line shape to the expected 2D coherent spectra in condensed-phase systems. In those systems, photoexcitations are mobile such that inter-particle interactions are important on any time scale, including those long compared with the 2D coherent experiment. Measurements on a semicrystalline polymeric semiconductor film at low temperatures show that, in some conditions in which multi-exciton interactions are suppressed, the technique predominantly detects coherent signals and can be used, in our example, to extract homogeneous line widths. The same method used on a lead-halide perovskite photovoltaic cell shows that incoherent population mixing of mobile photocarriers can dominate the measured signal since carrier-carrier bimolecular scattering is active even at low excitation densities, which hides the coherent contribution to the spectral line shape. In this example, the intensity dependence of the signal matches the theoretical predictions over more than two orders of magnitude, confirming the incoherent nature of the signal. While these effects are typically not significant in dilute solution environments, we demonstrate the necessity to characterize, in condensed-phase materials systems, the extent of nonlinear population dynamics of photoexcitations (excitons, charge carriers, etc.) in the execution of this powerful population-detected coherent spectroscopy technique.

STAR FORMATION LAWS IN BOTH GALACTIC MASSIVE CLUMPS AND EXTERNAL GALAXIES: EXTENSIVE STUDY WITH DUST CONINUUM, HCN (4-3), AND CS (7-6)

ABSTRACT We observed 146 Galactic clumps in HCN (4-3) and CS (7-6) with the Atacama Submillimeter Telescope Experiment 10 m telescope. A tight linear relationship between star formation rate and gas mass traced by dust continuum emission was found for both Galactic clumps and the high redshift (z > 1) star forming galaxies (SFGs), indicating a constant gas depletion time of ∼100 Myr for molecular gas in both Galactic clumps and high z SFGs. However, low z galaxies do not follow this relation and seem to have a longer global gas depletion time. The correlations between total infrared luminosities (L TIR) and molecular line luminosities of HCN (4-3) and CS (7-6) are tight and sublinear extending down to clumps with L TIR ∼ 103 L ☉. These correlations become linear when extended to external galaxies. A bimodal behavior in the L TIR– correlations was found for clumps with different dust temperature, luminosity-to-mass ratio, and σ line/σ vir. Such bimodal behavior may be due to evolutionary effects. The slopes of L TIR–L′mol correlations become more shallow as clumps evolve. We compared our results with lower J transition lines in Wu et al. (2010). The correlations between clump masses and line luminosities are close to linear for low effective excitation density tracers but become sublinear for high effective excitation density tracers for clumps with L TIR larger than L TIR ∼ 104.5 L ☉. High effective excitation density tracers cannot linearly trace the total clump masses, leading to a sublinear correlations for both M clump–L′mol and L TIR–L′mol relations.

Sub-Picosecond Auger-Mediated Hole-Trapping Dynamics in Colloidal CdSe/CdS Core/Shell Nanoplatelets.

Quasi-two-dimensional colloidal nanoplatelets (NPLs) have recently emerged as a class of semiconductor nanomaterials whose atomically precise monodisperse thicknesses give rise to narrow absorption and emission spectra. However, the sub-picosecond carrier dynamics of NPLs at the band edge remain largely unknown, despite their importance in determining the optoelectronic properties of these materials. Here, we use a combination of femtosecond transient absorption spectroscopy and nonadiabatic molecular dynamics simulations to investigate the early time carrier dynamics of CdSe/CdS core/shell NPLs. Band-selective probing reveals sub-picosecond Auger-mediated trapping of holes with an effective second-order rate constant of 3.5 ± 1.0 cm2/s. Concomitant spectral blue shifts that are indicative of Auger hole heating are found to occur on the same time scale as the sub-picosecond trapping dynamics, whereas spectral red shifts that emerge at low excitation densities furnish an electron-cooling time scale of 0.84 ± 0.09 ps. Finally, nonadiabatic molecular dynamics simulations relate the observed sub-picosecond Auger-mediated hole-trapping dynamics to a shallow trap state that originates from the incomplete passivation of dangling bonds on the NPL surface.

Onset of exciton-exciton annihilation in single-layer black phosphorus

The exciton dynamics in monolayer black phosphorus is investigated over a very wide range of photoexcited exciton densities using time resolved photoluminescence. At low excitation densities, the exciton dynamics is successfully described in terms of a double exponential decay. With increasing exciton population, a fast, nonexponential component develops as exciton-exciton annihilation takes over as the dominant recombination mechanism under high excitation conditions. Our results identify an upper limit for the injection density, after which exciton-exciton annihilation reduces the quantum yield, which will significantly impact the performance of light emitting devices based on single-layer black phosphorus.