Organic compounds containing luminous rare-earth ions are of interest for numerous nanophotonic and plasmonic applications, including nanoscale lasers, biosensors, and optical magnetism studies. Optical studies of Eu3+complexes revealed that ultra-thin LB monolayers are highly luminescent even when deposited directly on plasmonic metal, which makes these materials very promising for plasmonic applications and studies, including control and enhancement of magnetic dipole emission with a plasmonic environment. In this work, we synthesize amphiphilic complexes with various rare-earth ions Nd3+, Yb3+, and DPT ligands and show that they all are suitable for monolayer or multilayer deposition with the Langmuir–Blodgett (LB) technique.
Amphiphilic complexes with luminescent rare earth metal ions suitable for Lanmuir-Blodgett (LB) deposition have been synthesized. LB monolayers with closely packed Eu complexes deposited directly on silver demonstrate significant far-field emission in contrast to the theoretical predictions of full quenching. Angular radiation and polarization patterns of the electric and magnetic dipole emission of Eu3+point to a high excitation efficiency of surface plasmon polaritons. Different luminescent behavior of closely packed emitters in comparison to diluted systems is tentatively attributed to the collective state of emitters in LB layers formed via near-field coupling with surface plasmons.
more » « less- PAR ID:
- 10468814
- Publisher / Repository:
- Optical Society of America
- Date Published:
- Journal Name:
- Optics Continuum
- Volume:
- 2
- Issue:
- 10
- ISSN:
- 2770-0208
- Format(s):
- Medium: X Size: Article No. 2200
- Size(s):
- Article No. 2200
- Sponsoring Org:
- National Science Foundation
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We explore a possibility to control magnetic dipole emission with plasmonic cavities, placing Eu3+emitters inside profile-modulated metal-dielectric-metal structures. Significant variations in the branching ratio of the magnetic and electric dipole transitions are observed as the function of the thickness of the intermediate layer. The experimental results are confirmed with numerical simulations which account for cavity and gap plasmon resonances and predict modifications in the spontaneous emission spectrum as the function of the gap size and a strong directionality of the emission for small thicknesses of the intermediate layer. The implications of having a competition between electric and magnetic dipole relaxation channels in Eu3+are discussed.
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Four groups of rare-earth complexes, comprising 11 new compounds, with fluorinated O-donor ligands ([K(THF)6][Ln(OC4F9)4(THF)2] (1-Ln; Ln = Ce, Nd), [K](THF)x[Ln(OC4F9)4(THF)y] (2-Ln; Ln = Eu, Gd, Dy), [K(THF)2][Ln(pinF)2(THF)3] (3-Ln; Ln = Ce, Nd), and [K(THF)2][Ln(pinF)2(THF)2] (4-Ln; Ln = Eu, Gd, Dy, Y) have been synthesized and characterized. Single-crystal X-ray diffraction data were collected for all compounds except 2-Ln. Species 1-Ln, 3-Ln, and 4-Ln are uncommon examples of six-coordinate (Eu, Gd, Dy, and Y) and seven-coordinate (Ce and Nd) LnIII centers in all-O-donor environments. Species 1-Ln, 2-Ln, 3-Ln, and 4-Ln are all luminescent (except where Ln = Gd and Y), with the solid-state emission of 1-Ce being exceptionally blue-shifted for a Ce complex. The emission spectra of the six Nd, Eu, and Dy complexes do not show large differences based on the ligand and are generally consistent with the well-known free-ion spectra. Time-dependent density functional theory results show that 1-Ce and 3-Ce undergo allowed 5f → 4d excitations, consistent with luminescence lifetime measurements in the nanosecond range. Eu-containing 2-Eu and 4-Eu, however, were found to have luminescence lifetimes in the millisecond range, indicating phosphorescence rather than fluorescence. The performance of a pair of multireference models for prediction of the Ln = Nd, Eu, and Dy absorption spectra was assessed. It was found that spectroscopy-oriented configuration interaction as applied to a simplified model in which the free-ion lanthanide was embedded in ligand-centered Löwdin point charges performed as well (Nd) or better (Eu and Dy) than canonical NEVPT2 calculations, when the ligand orbitals were included in the treatment.more » « less
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Abstract Sunspot light bridges (LBs) exhibit a wide range of short-lived phenomena in the chromosphere and transition region. In contrast, we use here data from the Multi-Application Solar Telescope (MAST), the Interface Region Imaging Spectrograph (IRIS), Hinode, the Atmospheric Imaging Assembly (AIA), and the Helioseismic and Magnetic Imager (HMI) to analyze the sustained heating over days in an LB in a regular sunspot. Chromospheric temperatures were retrieved from the MAST Ca
ii and IRIS Mgii lines by nonlocal thermodynamic equilibrium inversions. Line widths, Doppler shifts, and intensities were derived from the IRIS lines using Gaussian fits. Coronal temperatures were estimated through the differential emission measure, while the coronal magnetic field was obtained from an extrapolation of the HMI vector field. At the photosphere, the LB exhibits a granular morphology with field strengths of about 400 G and no significant electric currents. The sunspot does not fragment, and the LB remains stable for several days. The chromospheric temperature, IRIS line intensities and widths, and AIA 171 and 211 Å intensities are all enhanced in the LB with temperatures from 8000 K to 2.5 MK. Photospheric plasma motions remain small, while the chromosphere and transition region indicate predominantly redshifts of 5–20 km s−1with occasional supersonic downflows exceeding 100 km s−1. The excess thermal energy over the LB is about 3.2 × 1026erg and matches the radiative losses. It could be supplied by magnetic flux loss of the sunspot (7.5 × 1027erg), kinetic energy from the increase in the LB width (4 × 1028erg), or freefall of mass along the coronal loops (6.3 × 1026erg). -
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