Energy-Transfer Mechanisms and Emission Quantum Yields In Eu3+-Based Siloxane-Poly(oxyethylene) Nanohybrids

• Published in: Chemistry of materials Vol. 13; no. 9; pp. 2991 - 2998
• Main Authors: Sá Ferreira, R. A, Carlos, L. D, Gonçalves, R. R, Ribeiro, S. J. L, de Zea Bermudez, V
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 17-09-2001
• Subjects: Applied sciences; Composites; Exact sciences and technology; Forms of application and semi-finished materials; Polymer industry, paints, wood; Technology of polymers; Excitation energy transfer; Luminescent material; Experimental study; Quantum yield; Silica; Emission spectrum; Mechanism; Ethylene oxide polymer; Lanthanide ion; Optical properties; Europium III; Doped polymer; Excitation spectrum
• ISSN: 0897-4756; 1520-5002
• DOI: 10.1021/cm010311o

We report the energy-transfer mechanisms and emission quantum yield measurements of sol−gel-derived Eu3+-based nanohybrids. The matrix of these materials, classified as diureasils and termed U(2000) and U(600), includes urea cross-links between a siliceous backbone and polyether-based segments of two molecular weights, 2000 and 600, respectively. These materials are full-color emitters in which the Eu3+ 5D0 → 7F0 - 4 lines merge with the broad green-blue emission of the nanoscopic matrix's backbone. The excitation spectra show the presence of a large broad band (∼27000−29000 cm-1) undoubtedly assigned to a ligand-to-metal charge-transfer state. Emission quantum yields range from 2% to 13.0% depending on the polymer molecular weight and Eu3+ concentration. Energy transfer between the hybrid hosts and the cations arises from two different and independent processes:  the charge-transfer band and energy transfer from the hybrid's emitting centers. The activation of the latter mechanisms induces a decrease in the emission quantum yields (relative to undoped nanohybrids) and permits a fine-tuning of the emission chromaticity across the Comission Internacionalle d'Éclairage diagram, e.g., (x, y) color coordinates from (0.21, 0.24) to (0.39, 0.36). Moreover, that activation depends noticeably on the ion local coordination. For the diureasils with longer polymer chains, energy transfer occurs as the Eu3+ coordination involves the carbonyl-type oxygen atoms of the urea bridges, which are located near the hybrid's host emitting centers. On the contrary, in the U(600)-based diureasils, the Eu3+ ions are coordinated to the polymer chains, and therefore, the distance between the hybrid's emitting centers and the metal ions is large enough to allow efficient energy-transfer mechanisms.