Photopatternable Di-ureasil−Zirconium Oxocluster Organic−Inorganic Hybrids As Cost Effective Integrated Optical Substrates

• Published in: Chemistry of materials 2008-06, Vol.20 (11), p.3696-3705
• Main Authors: Oliveira, Daniela C, Macedo, Andreia G, Silva, Nuno J. O, Molina, Celso, Ferreira, Rute A. S, André, Paulo S, Dahmouche, Karim, Bermudez, Verónica De Zea, Messaddeq, Younes, Ribeiro, Sidney J. L, Carlos, Luís D
• Format: Article
• Language: English
• Subjects: Hybrid Inorganic/Organic Materials; Optical Materials (including Non-Linear Optic, Photonic, and Optoelectronic Materials); Patterning of Materials (Micro- and Nanoscale)
• ISSN: 0897-4756; 1520-5002
• DOI: 10.1021/cm7031702

Organic−inorganic hybrids containing methacrylic acid (McOH, CH2C(CH3)COOH)) modified zirconium tetrapropoxide, Zr(OPrn)4, classed as di-ureasil−zirconium oxo-cluster hybrids, have been prepared and structurally characterized by X-ray diffraction (XRD), small-angle X-ray scattering (SAXS), Fourier transform infrared (FT-IR) and Raman (FT-Raman) spectroscopies, 29Si and 13C nuclear magnetic resonance (NMR), and atomic force microscopy (AFM). XRD and SAXS results have pointed out the presence of Si- and Zr-based nanobuilding blocks (NBBs) dispersed into the organic phase. Inter-NBBs correlation distances have been estimated for the pure di-ureasil and a model compound obtained by hydrolysis/condensation of Zr(OPrn)4:McOH (molar ratio 1:1): d Si ≈ 26 ± 1 Å and d Zr ≈ 16 ± 1 Å, respectively. In the case of the di-ureasil−zirconium oxo-cluster hybrids, these distances depend on the Zr relative molar percentage (rel. mol. Zr %) (d Si ranges from 18 to 25 Å and d Zr from 14 to 23 Å, as the rel. mol. Zr % increases from 5 to 75), suggesting that the Si- and Zr-based clusters are interconstrained. Complementary data from FT-IR, FT-Raman, 29Si and 13C NMR, and AFM support to a structural model where McOH-modified Zr-based NBBs (Zr-OMc) are present over the whole range of composition. At low Zr-OMc contents (rel. mol. Zr %