Determining Factors to Understand the External Quantum Efficiency Values: Study Carried Out with Copper(I)-I and 1,2-Bis(4-pyridyl)ethane Coordination Polymers as Downshifters in Photovoltaic Modules.

Downshifters refer to compounds with the capacity to absorb UV photons and transform them into visible light. The integration of such downshifters has the potential to improve the efficiency of commercial photovoltaic modules. Initially, costly lanthanide derivatives and organic fluorescent dyes were introduced, resulting in a heightened module efficiency. In a novel research direction guided by the same physicochemical principles, the utilization of copper(I) coordination compounds is proposed. This choice is motivated by its simpler and more economical synthesis, primarily due to copper being a more abundant and less toxic element. Our proposal involves employing 1,2-bis(4-pyridyl) ethane (bpe), an economically viable commercial ligand, in conjunction with CuI to synthesize coordination polymers: [CuI(bpe)]n(1), [Cu3I3(bpe)3]n(2), and [CuI(bpe)0.5]n(3). These polymers exhibit the ability to absorb UV photons and emit light within the green and orange spectra. To conduct external quantum efficiency studies, the compounds are dispersed on glass and then encapsulated with ethylene vinyl acetate through heating to 150 °C. Interestingly, during these procedural steps, the solvents and temperatures employed induce a phase transformation, which has been thoroughly examined through both experimental analysis and theoretical calculations. The outcomes of these studies reveal an enhancement in external quantum efficiency with [Cu3I3(bpe)3]n(2), at a cost significantly lower (between 340 and 350 times) than that associated with lanthanide DS complexes.

Exploring Ln(III)-Ion-Based Luminescent Species as Down-Shifters for Photovoltaic Solar Cells.

In this work, we have compiled our research on lanthanide-based luminescent materials for use as down-shifter layers in photovoltaic (PV) mini-modules. The complexes we have prepared (C1-17), with formulas [Eu2(phen)2(bz)6] (C1), [Eu2(bphen)2(bz)6] (C2), [Eu(tta)3bphen] (C3), [Eu(bta)3pyz-phen] (C4), [Eu(tta)3pyz-phen] (C5), [Eu(bta)3me-phen] (C6), [Er(bta)3me-phen] (C7), [Yb(bta)3me-phen] (C8), [Gd(bta)3me-phen] (C9), [Yb(bta)3pyz-phen] (C10), [Er(tta)3pyz-phen] (C11), [Eu2(bz)4(tta)2(phen)2] (C12), [Gd2(bz)4(tta)2(phen)2] (C13), [EuTb(bz)4(tta)2(phen)2] (C14), [EuGd(bz)4(tta)2(phen)2] (C15), [Eu1.2Gd0.8(bz)4(tta)2(phen)2] (C16), and [Eu1.6Gd0.4(bz)4(tta)2(phen)2] (C17), can be grouped into three families based on their composition: Complexes C1-6 were synthesized using Eu3+ ions and phenanthroline derivatives as the neutral ligands and fluorinated ß-diketonates as the anionic ligands. Complexes C7-11 were prepared with ligands similar to those of complexes C1-6 but were synthesized with Er3+, Yb3+, or Gd3+ ions. Complexes C12-17 have the general formula [M1M2(bz)4(tta)2(phen)2], where M1 and M2 can be Eu3+, Gd3+, or Tb3+ ions, and the ligands were benzoate (bz-), 2-thenoyltrifluoroacetone (tta-), and 1,10-phenanthroline (phen). Most of the complexes were characterized using X-ray techniques, and their photoluminescent properties were studied. We then assessed the impact of complexes in the C1-6 and C12-17 series on the EQE of PV mini-modules and examined the durability of one of the complexes (C6) in a climate chamber when embedded in PMMA and EVA films. This study emphasizes the methodology employed and the key findings, including enhanced mini-module efficiency. Additionally, we present promising results on the application of complex C6 in a bifacial solar cell.

Highly luminescent mixed-ligand bimetallic lanthanoid(III) complexes for photovoltaic applications.

Six new mixed-ligand bimetallic complexes [Eu2(bz)4(tta)2(phen)2] (1), [Gd2(bz)4(tta)2(phen)2] (2), [EuTb(bz)4(tta)2(phen)2] (3), [EuGd(bz)4(tta)2(phen)2] (4), [Eu1,2Gd0,8(bz)4(tta)2(phen)2] (5) and [Eu1,6Gd0,4(bz)4(tta)2(phen)2] (6) have been prepared with the Eu3+, Gd3+ and Tb3+ ions and the benzoate (bz-), 2-thenoyltrifluoroacetonate (tta-) and the 1,10-phenanthroline (phen) ligands. The compounds combine highly efficient antennas to obtain highly luminescent complexes to enhance solar cell efficiency. The benzoate ligand has been chosen to take its advantage as a bridging ligand to end up with bimetallic complexes to study the effect of combining two metal ions in the luminescent molecule. The structure of 1 was obtained by single-crystal X-ray diffraction, and 1-6 were found to be isostructural by powder X-ray diffraction analysis. The photophysical properties were studied by the absorbance and emission spectra and emission lifetimes. The magnetic properties of 2 were studied, and we found intramolecular antiferromagnetic interactions between the Gd3+ ions. We prepared luminescent down-shifting layers (LDSL) with the 1, 3-6 complexes embedded in ethylene-vinyl-acetate and studied their effect in the external quantum efficiency (EQE) and intensity-voltage (I-V) plots of a solar mini-module. We found that LDSL containing the bimetallic complexes 3 and 6 enhance the efficiency of the solar mini-module from 11.26(3)% to 11.76(4)% (+0.52%) and to 11.44(2)% (+0.21%), respectively.

Europium(III)-Doped Gadolinium(III) Complex for High-Sensitivity Temperature Sensing in the Physiological Range.

A new Eu3+-doped Gd3+ complex of formula [Eu0.0135Gd0.9865(pta)3me-phen] was synthesized and structurally characterized (Hpta = benzoyltrifluoroacetone, me-phen = 5-methyl-1,10-phenanthroline). The photoluminescence study revealed that when the compound was excited at RT, under a 457 nm continuous laser, the material exhibited high luminescence due to the antenna effect of the ligands, as well as a good balance between the phosphorescence from the spin-forbidden triplet (from the organic ligands), and the characteristic lanthanide f-f transitions. The ratio between the previous emissions drastically changed when the sample was heated up to 62 °C inside a tubular furnace. This ratio was investigated using the luminescence intensity ratio method, to analyze the capabilities of the sample as a temperature sensor. The relative sensitivity reached a maximum of 11.4 °C-1 %, maintaining a detection limit below 0.15 °C for the whole temperature range.

Visible and NIR emitting Yb(iii) and Er(iii) complexes sensitized by ß-diketonates and phenanthroline derivatives.

Five new complexes namely, [Er(bta)3(me-phen)] (1), [Yb(bta)3(me-phen)] (2), [Gd(bta)3(me-phen)] (3), [Yb(bta)3(pyz-phen)] (4), and [Er(tta)3(pyz-phen)] (5) have been prepared with the fluorinated ß-diketone ligands Hbta and Htta (Hbta = benzoyltrifluoroacetone and Htta = 2-thenoyltrifluoroacetone) combined with the azacyclo phenanthroline-derivatives, 5-methyl-1,10-phenanthroline (me-phen) and pyrazino[2,3-f][1,10]phenanthroline (pyz-phen). The crystal structures of 2, 4 and 5 have been solved by single-crystal X-ray diffraction. PXRD patterns show that 1-3 are isostructural. All the compounds exhibit a molecular structure with the metal atom in an eight-coordination geometry. The photophysical processes involved in the photoluminescence of the complexes are investigated; as a result, the radiative lifetimes (τ Ln), the 4f-4f emission quantum efficiencies (Φ Ln) and the energy-levels diagram are calculated.