Photopatternable di-ureasil-zirconium oxocluster organic-inorganic hybrids as cost effective integrated optical substrates

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dc.contributor.authorOliveira, Daniela C. [UNESP]
dc.contributor.authorMacedo, Andreia G.
dc.contributor.authorSilva, Nuno J. O.
dc.contributor.authorMolina, Celso
dc.contributor.authorFerreira, Rute A. S.
dc.contributor.authorAndre, Paulo S.
dc.contributor.authorDahmouche, Karim
dc.contributor.authorBermudez, Veronica de Zea
dc.contributor.authorMessaddeq, Younes [UNESP]
dc.contributor.authorRibeiro, Sidney José Lima [UNESP]
dc.contributor.authorCarlos, Luis D.
dc.contributor.institutionUniversidade Estadual Paulista (Unesp)
dc.contributor.institutionUniv Aveiro
dc.contributor.institutionUniv Estadual Zona Oeste
dc.contributor.institutionUniv Tras Montes & Alto Douro
dc.date.accessioned2014-05-20T15:30:48Z
dc.date.available2014-05-20T15:30:48Z
dc.date.issued2008-06-10
dc.description.abstractOrganic-inorganic hybrids containing methacrylic acid (McOH, CH(2)= C(CH(3))COOH)) modified zirconium tetrapropoxide, Zr(OPr(n))(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, Si and C 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(OPr(n))(4):McOH (molar ratio 1: 1): d(Si) approximate to 26 +/- 1 angstrom and d(Zr) approximate to 16 +/- 1 angstrom, 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 angstrom and d(Zr) from 14 to 23 angstrom, 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, (29)Si and (13)C 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 % <30) the clusters are well-dispersed within the di-ureasil host, whereas segregation occurs at the 0.1 mu m scale at high Zr-OMc concentration (rel. mol. Zr % = 50). No Zr-O-Si heterocondensation has been discerned. Monomode waveguides, diffractions gratings, and Fabry-Perot cavities have been written through the exposure of the hybrid monoliths to UV light. FT-Raman has shown that the chemical process that takes place under illumination is the polymerization of the methacrylate groups of the Zr-OMc NBBs. The guidance region in patterned channels is a Gaussian section located below the exposed surface with typical dimensions of 320 mu m wide and 88 mu m deep. The effective refractive index is 1.5162 (maximum index contrast on the order of 1 x 10(-4)) and the reflection coeficient of the Fabry-Perot cavity (formed by a grating patterned into a 0.278 cm channel) is 0.042 with a free spectral range value of 35.6 GHz.en
dc.description.affiliationUniv São Paulo, Inst Chem, UNESP, BR-14801970 Araraquara, SP, Brazil
dc.description.affiliationUniv Aveiro, Dept Phys, CICECO, P-3810193 Aveiro, Portugal
dc.description.affiliationUniv Aveiro, Dept Phys, Inst Telecommun, P-3810193 Aveiro, Portugal
dc.description.affiliationUniv Estadual Zona Oeste, BR-23070200 Rio de Janeiro, Brazil
dc.description.affiliationUniv Tras Montes & Alto Douro, Dept Quim, P-5000801 Vila Real, Portugal
dc.description.affiliationUniv Tras Montes & Alto Douro, CQ VR, P-5000801 Vila Real, Portugal
dc.description.affiliationUnespUniv São Paulo, Inst Chem, UNESP, BR-14801970 Araraquara, SP, Brazil
dc.format.extent3696-3705
dc.identifierhttp://dx.doi.org/10.1021/cm7031702
dc.identifier.citationChemistry of Materials. Washington: Amer Chemical Soc, v. 20, n. 11, p. 3696-3705, 2008.
dc.identifier.doi10.1021/cm7031702
dc.identifier.issn0897-4756
dc.identifier.lattes2998503841917815
dc.identifier.lattes6446047463034654
dc.identifier.orcid0000-0003-3286-9440
dc.identifier.urihttp://hdl.handle.net/11449/40105
dc.identifier.wosWOS:000256443900025
dc.language.isoeng
dc.publisherAmer Chemical Soc
dc.relation.ispartofChemistry of Materials
dc.relation.ispartofjcr9.890
dc.relation.ispartofsjr4,675
dc.rights.accessRightsAcesso restrito
dc.sourceWeb of Science
dc.titlePhotopatternable di-ureasil-zirconium oxocluster organic-inorganic hybrids as cost effective integrated optical substratesen
dc.typeArtigo
dcterms.licensehttp://pubs.acs.org/page/copyright/index.html
dcterms.rightsHolderAmer Chemical Soc
unesp.author.lattes2998503841917815
unesp.author.lattes6446047463034654
unesp.author.orcid0000-0003-3286-9440[10]
unesp.campusUniversidade Estadual Paulista (Unesp), Instituto de Química, Araraquarapt

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