Picosecond time-resolved dynamics of energy transfer between GaN and the various excited states of Eu3+ ions

To elucidate the energy transfer and reexcitation processes in Eu-doped GaN layers that are used in recently developed, highly efficient red light-emitting diodes, a systematic series of photoluminescence and time-resolved photoluminescence (TR-PL) measurements was performed. Critical insights on how “slow” Eu processes (∼µs) can compete against fast semiconductor processes (∼ps) are revealed using TR-PL with a high temporal resolution, as it is found that the initial energy transfer from GaN to the Eu3+ ions takes place rapidly, on a timescale of \u3c100 ps. Below band-gap resonant excitation was used to identify the states into which the energy transfer occurs. For the most efficient Eu defect complexes, this transfer dominantly occurs directly into the 5 D0 state of Eu3+. Less efficient complexes also exhibit transfer into the 5 D2 state, the emission of which can be detected using photoluminescence at low temperature, indicating the importance of the excitation pathway on device efficiency. Under high excitation intensity, reexcitation can also occur, leading to a redistribution of population into the 5 D2, 5 D1, or 5 D0 states

Temporally modulated energy shuffling in highly interconnected nanosystems

Advances in lighting and quantum computing will require new degrees of control over the emission of photons, where localized defects and the quantum confinement of carriers can be utilized. In this contribution, recent developments in the controlled redistribution of energy in rare earth (RE)–doped nanosystems, such as quantum dots or within bulk insulating and semiconducting hosts, will be reviewed. In their trivalent form, RE ions are particularly useful dopants because they retain much of their atomic nature regardless of their environment; however, in systems such as GaN and Si, the electronic states of the RE ions couple strongly to those of the host material by forming nanocomplexes. This coupling facilities fast energy transfer (ET) (<100 ps) and a carrier-mediate energy exchange between the host and the various states of the RE ions, which is mediated by the presence of carriers. A model has been developed using a set of rate equations, which takes into consideration the various ET pathways and the lifetimes of each state within the nanocomplex, which can be used to predict the nature of the emitted photons given an excitation condition. This model will be used to elucidate recent experimental observations in Eu-doped GaN

Modeling defect mediated color-tunability in LEDs with Eu-doped GaN-based active layers

Color tunability from red to orange to yellow has been demonstrated in GaN-based LED devices with Eu-doped GaN layers as the active region. Under current injection, this is achieved by varying the current density and the pulse conditions. The underlying mechanism behind this color tunability is a redistribution of energy among the D-5(J) states of a Eu3+ ion. This energy shuffling is facilitated by a local defect that has been neglected in previous modeling work. Including this defect allows for a quantitative prediction of the relative time-averaged populations of the Eu3+ ion\u27s D-5(0) and D-5(1) states. Extracting, from experimental results, the red and yellow/green emission spectra due to radiative transitions from the respective levels and mixing them allows the overall chromaticity of the emission to be determined for varied excitation conditions. In addition, the model allows us to determine the optimal injection conditions to maximize the gamut of color tunability while minimizing power consumption. These simulations pave the way for practical, systematic color tuning from a single-contact pixel

An efficiently excited Eu3+ luminescent site formed in Eu,O-codoped GaN

For the development of III-nitride-semiconductor-based monolithic micro-light-emitting diode (LED) displays, Eu,O-codoped GaN (GaN:Eu,O) is a promising material candidate for the red LEDs. The luminescence efficiency of Eu-related emission strongly depends on the local atomic structure of Eu ions. Our previous research has revealed that post-growth thermal annealing is an effective method for reconfiguring luminescent sites, leading to a significant increase in light output. We observed the preferential formation of a site with a peak at ∼2.004 eV by the annealing process. In this study, we demonstrate that it is a previously unidentified independent site (OMVPE-X) using combined excitation–emission spectroscopy and time-resolved photoluminescence measurements. In addition, we perform excitation power-dependent photoluminescence measurements and show that this OMVPE-X site dominates the emission at a low excitation power region despite its small relative abundance, suggesting a high excitation efficiency. Most importantly, applying our annealing technique to an LED exhibits a reasonably increased electroluminescence intensity associated with OMVPE-X, confirming that this site has a high excitation efficiency also under current injection. These results demonstrate the importance of OMVPE-X as a notable luminescent site for brighter and more efficient GaN:Eu,O-based LEDs

Repairing Nanoparticle Surface Defects

Solar devices based on semiconductor nanoparticles require the use of conductive ligands; however, replacing the native, insulating ligands with conductive metal chalcogenide complexes introduces structural defects within the crystalline nanostructure that act as traps for charge carriers. We utilized atomically thin semiconductor nanoplatelets as a convenient platform for studying, both microscopically and spectroscopically, the development of defects during ligand exchange with the conductive ligands Na4SnS4 and (NH4)4Sn2S6. These defects can be repaired via mild chemical or thermal routes, through the addition of L-type ligands or wet annealing, respectively. This results in a higher-quality, conductive, colloidally stable nanomaterial that may be used as the active film in optoelectronic devices

Room temperature synthesis and characterization of novel lead-free double perovskite nanocrystals with a stable and broadband emission

Ajuts: we are grateful for the Dutch Technology Foundation STW, The Netherlands Organization for Scientific Research (NWO), and the Joint Solar Program (JSP III, 680-91-011) of The NWO for financial support. We acknowledge Arnon Lesage and Dido Van der Gon for their kind help. V. S. acknowledges the LMA-INA for offering access to their instruments and expertise.Low-dimensional and lead-free halide perovskites are of great interest for their wide application potential for optoelectronic applications. We report on the successful synthesis of novel lead-free colloidal Cs3BiBr6 nanocrystals (NCs) with an ultra-small size of ∼1.5-3 nm by a room temperature antisolvent process. From crystallographic characterization we show that it is critical to precisely control the ratio of precursors to obtain the pure 3-1-6 phase. The synthesis process is facile and repeatable and results in Cs3BiBr6 NCs that display stable blue emission around 438 nm with a relatively broad linewidth of 92.1 nm. Low-temperature photoluminescence (PL) measurements displayed a red-shift of bandgap with decreasing temperature, which might be attributed to the thermal expansion of the lattice. In addition, the NCs demonstrate high stability at ambient conditions

Electronic Coupling of Highly Ordered Perovskite Nanocrystals in Supercrystals

Assembled perovskite nanocrystals (NCs), known as supercrystals (SCs), can have many exotic optical and electronic properties different from the individual NCs due to energy transfer and electronic coupling in the dense superstructures. We investigate the optical properties and ultrafast carrier dynamics of highly ordered SCs and the dispersed NCs by absorption, photoluminescence (PL), and femtosecond transient absorption (TA) spectroscopy to determine the influence of the assembly on the excitonic properties. Next to a red shift of absorption and PL peak with respect to the individual NCs, we identify signatures of the collective band-like states in the SCs. A smaller Stokes shift, decreased biexciton binding energy, and increased carrier cooling rates support the formation of delocalized states as a result of the coupling between the individual NC states. These results open perspectives for assembled perovskite NCs for application in optoelectronic devices, with design opportunities exceeding the level of NCs and bulk materials.ChemE/Opto-electronic Material