Dual effect to improve the electrical properties of SZO films grown by nitrogen pneumatic spray pyrolysis.

The principal aim of this study is to reduce considerably, via Sn doping, the resistivity of ZnO thin films prepared by simple, flexible, and cost-effective nitrogen pneumatic spray pyrolysis (NPSP) method on glass substrates at a temperature of 400°C. Different Sn content was tested (Sn/Zn = 0, 1, 3, 5 wt%) in an attempt to reduce the concentration of excessive oxygen atoms and create more free electrons. The microstructural, optical, morphological, and electrical properties of the films have been studied. The x-ray diffraction analysis demonstrated that tin-doped SZO films exhibited polycrystalline nature with a preferential orientation along (002) plane with the appearance of a new orientation (101) with the increase of Sn concentration leading then to bidirectional growth. The deposited SZO films showed an average optical transmittance of about 80% in the UV-visible region (200-800 nm) with optical band gap values at around 3.27 eV. Photoluminescence emissions of SZO samples presented three main peaks: near band edge emission, violet emission, and the blue-green emission. The surface morphology of the films obtained by scanning electron microscope (SEM) exhibited the change in morphology with increasing the Sn content. A minimum electrical resistivity value of about 17·10-3 Ω·cm was obtained for 3% SZO films. SZO films prepared by the NPSP method can be used as transparent window layer and electrodes in solar cells. RESEARCH HIGHLIGHTS: Highly oriented, conducting, and transparent Sn-doped ZnO films are successfully synthesized. The film growth orientation changed from mono-directional (002) axis to bi-directional (002) and (101) axis according to Sn doping. Ultraviolet and green emissions are noted by photoluminescence investigation. A minimum resistivity is observed for 3 wt% SZO film. The dual positive effect of the carrier gas used (N2) and Sn doping is confirmed.

New method for Raman investigation of the orientation of collagen fibrils and crystallites in the Haversian system of bone.

Knowledge of the organization of the components of bone is of primary importance in understanding how this tissue responds to stresses and provides a starting point for the design and development of biomaterials. Bone structure has been the subject of numerous studies. The mineralized fiber arrangement in cortical bone is either a twisted or orthogonal plywood structure. Both mineral models coexist in compact bone. Raman polarized spectroscopy offers definite advantages in the study of biological samples, enabling the simultaneous analysis of mineral and organic components and the determination of molecular orientation through the polarization properties of the Raman scattering. In this study, we used the Raman polarization approach to simultaneously investigate the orientation of collagen fibrils and apatite crystals in human cortical bone. Raman bands ratios were monitored as a function of sample orientation. Specific ratios were chosen--such as nu(3) PO(4)/nu(1) PO(4), amide III (1271 cm(-1))/amide III (1243 cm(-1)), and amide I/amide III (1243 cm(-1))--due to their sensitivity to apatite-crystal and collagen-fibril orientation. Based on this original approach, spatial changes were monitored as a function of distance from the Haversian canal. The results revealed simultaneous tilting in intra-lamellar collagen-fibril and mineral crystal orientations. These results are consistent with a twisted plywood organization in the Haversian bone structure at the lamellar level. But at molecular level, the co-alignment of the collagen fibrils and the apatite crystal is observed in the innermost lamellae and becomes gradually less ordered as the distance from the Haversian canal increases. This work highlights the interest of Raman spectroscopy for the multiscale investigation of bone structure.

Raman microspectrometry of laser-reshaped rabbit auricular cartilage: preliminary study on laser-induced cartilage mineralization.

Laser-assisted cartilage reshaping (LACR) is a relatively novel technique designed to noninvasively and permanently restructure cartilaginous tissue. It is believed that heat-induced stress relaxation, in which a temperature-mediated disruption of H2O binding is associated with conformational alterations in the proteoglycan and collagen-rich matrix, constitutes the underlying mechanism of LACR. Several reports have suggested that laser-mediated cartilage mineralization may contribute to the permanent shape change of laser-reshaped cartilage. In an effort to validate these results in the context of Er:glass LACR, we performed a preliminary Raman microspectrometric study to characterize the crystal deposits in laser-irradiated chondrocytes and extracellular matrix. For the first time, we identified intracellular calcium sulfate deposits and extracellular calcium phosphate (apatite) crystals in laser-reshaped rabbit auricular cartilage. Calcium carbonate deposits are localized in both irradiated and nonirradiated samples, suggesting that this mineral plays no role in conformational retention. In our discussion, we elaborate on the possible molecular and cellular mechanisms responsible for intra- and extracellular crystallization, and propose a novel hypothesis on the formation of apatite, inasmuch as the biological function of this mineral (providing structure and rigidity in bones and dental enamel) may be extrapolated to the permanent shape change of laser-irradiated cartilage.