Nanotechnology is a rising field and nanomaterials can now be found in a vast variety of products with different chemical compositions, sizes and shapes. New nanostructures combining different nanomaterials are being developed due to their enhancing characteristics when compared to nanomaterials alone. In the present study, the toxicity of a nanostructure composed by a ZnO nanomaterial with Ag nanomaterials on its surface (designated as ZnO/Ag nanostructure) was assessed using the model-organism Daphnia magna and its toxicity predicted based on the toxicity of the single components (Zn and Ag). For that ZnO and Ag nanomaterials as single components, along with its mixture prepared in the laboratory, were compared in terms of toxicity to ZnO/Ag nanostructures. Toxicity was assessed by immobilization and reproduction tests. A mixture toxicity approach was carried out using as starting point the conceptual model of Concentration Addition. The laboratory mixture of both nanomaterials showed that toxicity was dependent on the doses of ZnO and Ag used (immobilization) or presented a synergistic pattern (reproduction). The ZnO/Ag nanostructure toxicity prediction, based on the percentage of individual components, showed an increase in toxicity when compared to the expected (immobilization) and dependent on the concentration used (reproduction). This study demonstrates that the toxicity of the prepared mixture of ZnO and Ag and of the ZnO/Ag nanostructure cannot be predicted based on the toxicity of their components, highlighting the importance of taking into account the interaction between nanomaterials when assessing hazard and risk.
The nanocarbon allotropes constitute valid alternatives when designing control and actuation devices for electrically assisted tissue regeneration purposes, gathering among them important characteristics such as chemical inertness, biocompatibility, extreme mechanical properties, and, importantly, low and tailorable electrical resistivity. In this work, coatings of thin (100 nm) vertically aligned nanoplatelets composed of diamond (5 nm) and graphite were produced via a microwave plasma chemical vapor deposition (MPCVD) technique and used as substrates for electrical stimulation of MC3T3-E1 preosteoblasts. Increasing the amount of N2 up to 14.5 vol % during growth lowers the coatings' electrical resistivity by over 1 order of magnitude, triggers the nanoplatelet vertical growth, and leads to the higher crystalline quality of the nanographite phase. When preosteoblasts were cultured on these substrates and subjected to two consecutive daily cycles of 3 μA direct current stimulation, enhanced cell proliferation and metabolism were observed accompanied by high cell viability. Furthermore, in the absence of DC stimulation, alkaline phosphatase (ALP) activity is increased significantly, denoting an up-regulating effect of preosteoblastic maturation intrinsically exerted by the nanoplatelet substrates.
Grazing incidence and grazing emission X-ray fluorescence spectroscopy (GI/GE-XRF) are techniques that enable non-destructive, quantitative analysis of elemental depth profiles with a resolution in the nanometer regime. A laboratory setup for soft X-ray GEXRF measurements is presented. Reasonable measurement times could be achieved by combining a highly brilliant laser produced plasma (LPP) source with a scanning-free GEXRF setup, providing a large solid angle of detection. The detector, a pnCCD, was operated in a single photon counting mode in order to utilize its energy dispersive properties. GEXRF profiles of the Ni-L-alpha,L-beta line of a nickel-carbon multilayer sample, which displays a lateral (bi)layer thickness gradient, were recorded at several positions. Simulations of theoretical profiles predicted a prominent intensity minimum at grazing emission angles between 5 degrees and 12 degrees, depending strongly on the bilayer thickness of the sample. This information was used to retrieve the bilayer thickness gradient. The results are in good agreement with values obtained by X-ray reflectometry, conventional X-ray fluorescence and transmission electron microscopy measurements and serve as proof-of-principle for the realized GEXRF setup. The presented work demonstrates the potential of nanometer resolved elemental depth profiling in the soft X-ray range with a laboratory source, opening, for example, the possibility of in-line or even in situ process control in semiconductor industry.
Pulsed laser ablation in water was validated as an effective method to produced erbium-doped ZrO2nanoparticles with intense up-conversion luminescence.
Wide band gap oxides, such as ZnO, SnO2 and ZrO2, are functional materials with a wide range of applications in several important technological areas such as those including lighting, transparent electronics, sensors, catalysis and biolabeling. Recently, doping and co-doping of oxides with lanthanides have attracted a strong interest for lighting purposes, especially among them nanophosphors for bioassays. Tailoring the crystalline materials physical properties for such applications often requires a well-controlled incorporation of dopants in the material lattice and a comprehensive understanding of their role in the oxides matrices. These undoped or intentionally doped oxides have band gap energies exceeding 3.3 eV at room temperature and are known to exhibit optically active centers that span from the ultraviolet to the near infrared region. Typically, by using photon energy excitation above the materials band gap, high quality undoped materials display narrow emission lines near the band edge due to free and bound-exciton recombination, as well as shallow donor-acceptor recombination pairs. Additionally, broad emission bands are often observed in these wide band gap hosts, hampering some of the desired physical properties for further applications. Recognizing and understanding the role of the dopant-related defects when deliberately introduced in the oxide hosts, as well as their influence on the samples luminescence properties, constitutes a matter of exploitation by the scientific community worldwide.In this work, we investigate the luminescence properties of undoped and lanthanide doped oxide materials grown by laser assisted techniques. Laser assisted flow deposition (LAFD) and pulse laser ablation in liquids (PLAL) were used for the growth of ZnO, SnO2 and yttria stabilized ZrO2 (YSZ) micro and nanocrystals with different morphologies, respectively. Regarding the YSZ host, trivalent lanthanide ions were optically activated by in-situ doping and co-doping. The influence of the defect energy states on the optical properties of the different undoped and doped metal oxide hosts is investigated under ultraviolet and infrared excitation by means of photoluminescence and photoluminescence excitation.
An innovation is reported in the synthesis of a hybrid carbon structure resulting from the simultaneous growth of graphene and nanocrystalline diamond (NCD) by the microwave plasma chemical vapor deposition technique. This strategy allows to take advantage of the complementary electronic behavior of each carbon allotrope, a key feature in new nanostructured materials for electronics under the graphene/insulator all-carbon approach. The graphene-diamond hybrid structures were grown on copper and transferred to a glass substrate to be further characterized. Raman analysis puts in evidence the signature of both phases and the high crystallinity of the graphene layer, based on band intensity and width measurements. Raman mapping and SEM observations show a uniform distribution of the NCD clusters, confirmed by AFM/EFM measurements. Additionally, HRTEM analysis permitted to detail the diamond nanocrystalline structure, revealing a close link to the graphene layer on the basis of which a diamond on graphene nucleation mechanism is proposed.
Transparent conductive tin oxide materials have been a research topic extensively studied in recent years due to the great interest for many applications. However, in most of them, the pure form is rarely used, being usually modified by the incorporation of dopants. Selecting the most appropriate technique to develop nanocrystals of doped tin oxide and understanding the influence of dopant on the optical properties are the challenges that need to be addressed when envisaging devices. To fulfill this objective, the recently developed laser assisted flow deposition (LAFD) method is explored to grow SnO2 and SnO2:Eu nanocrystals. The morphology of these nanocrystals was investigated by scanning electron microscopy and well defined prismatic nanocrystals with sizes of ∼60 nm were identified. The crystalline quality assessed by X-ray diffraction measurements and Raman spectroscopy indicates that the produced nanocrystals are monophasic and crystallize in the tetragonal rutile structure. Steady state luminescence studies provide the information on the optical active centres in the SnO2 and SnO2:Eu nanocrystals. For the undoped samples only broad emission bands were observed by pumping the samples in the ultraviolet region. The broad emission was found to be an overlap of green and red optical centres as identified by temperature and excitation intensity dependent luminescence. The latter was found to exhibit an excitonic-related behaviour and the green emission was found to be of utmost importance to discuss the intraionic luminescence in the doped samples. For the SnO2:Eu nanocrystals the luminescence is dominated by the magnetic allowed (5)D0 → (7)F1 transition with the ions in almost undistorted centrosymmetric sites. The ion luminescence integrated intensity is found to increase with increasing temperatures being well accounted for a thermal population provided by the thermal quenching of the green band.
Diamond-based microelectromechanical resonators have the potential of enhanced performance due to the chemical inertness of the diamond structural layer and its high Young's modulus, high wear resistance, low thermal expansion coefficient, and very high thermal conductivity. In this work, the resonance frequency and quality factor of MEMS resonators based on nanocrystalline diamond films are characterized under different air pressures. The dynamic behavior of 50-300 mu m long linear bridges and double ended tuning forks, with resonance frequencies between 0.5 and 15 MHz and quality factors as high as 50 000 are described as a function of measurement pressure from high vacuum(similar to 10 mTorr) up to atmospheric conditions. The resonance frequencies and quality factors in vacuum show good agreement with the theoretical models including anchor and thermoelastic dissipation (TED). The Young's moduli for nanocrystalline diamond films extrapolated from experimental data are between 840-920 GPa. The critical pressure values, at which the quality factor starts decreasing due to dissipation in air, are dependent on the resonator length. Longer structures, with quality factors limited by TED and lower resonance frequencies, have low critical pressures, of the order of 1-10 Torr and go from an intrinsic dissipation, to a molecular dissipation regime and finally to a region of viscous dissipation. Shorter resonators, with higher resonance frequencies and quality factors limited by anchor losses, have higher critical pressures, some higher than atmospheric pressure, and enter directly into the viscous dissipation regime from the intrinsic region.
ZnO microrods were grown by laser assisted flow deposition technique in order to study their luminescence behaviour in the near band edge spectral region. Transmission electron microscopy analysis put in evidence the high crystallinity degree and microrod's compositional homogeneity. Photoluminescence revealed a dominant 3.31 eV emission. The correlation between this emission and the presence of surface states was investigated by performing plasma treatments with hydrogen and nitrogen. The significant modifications in photoluminescence spectra after the plasma treatments suggest a connexion between the 3.31 eV luminescence and the surface related electronic levels.
In this work the MPCVD (microwave plasma chemical vapour deposition) conditions for the growth of nanocarbon hybrids were studied. Using a single run MPCVD procedure, nanocrystalline diamond (NCD) and carbon nanotubes (CNTs) hybrids were obtained using a continuous delivery of catalytic Fe particles. The grown films were characterized by Scanning Electron Microscopy (SEM) and μ-Raman spectroscopy, proving the coexistence of sp2 and sp3 bonded phases, either in a dense multi-layer arrangement or in a porous 3-D like morphology. Without the addition of a catalyst, NCD/carbon nanowalls (CNWs) hybrids were also synthesized. High quality and well intercalated hybrid carbon forms were successfully obtained in a simultaneous growth procedure.
Crystalline carbon-based materials are intrinsically chemically inert and good heat conductors, allowing their applications in a great variety of devices. A technological step forward in heat dissipators production can be given by tailoring the carbon phase microstructure, tuning the CVD synthesis conditions. In this work, a rapid bottom-up synthesis of vertically aligned hybrid material comprising diamond thin platelets covered by a crystalline graphite layer was developed. A single run was designed in order to produce a high aspect ratio nanostructured carbon material favoring the thermal dissipation under convection-governed conditions. The produced material was characterized by multiwavelength Raman spectroscopy and electron microscopy (scanning and transmission), and the macroscopic heat flux was evaluated. The results obtained confirm the enhancement of heat dissipation rate in the developed hybrid structures, when compared to smooth nanocrystalline diamond films.
Given the specific properties of each carbon allotrope such as high electrical/thermal conductivity of multiwall carbon nanotubes (MWCNT) and extreme hardness and high inertness of nanocrystalline diamond (NCD), the integration of both carbon phases is highly desirable. Therefore, in the present work, buckypapers were produced from MWCNT suspensions and were used as free-standing substrates to be coated with NCD by microwave plasma chemical vapor deposition (MPCVD). The integration of both allotropes was successfully achieved, the CNTs being preserved after diamond growth as confirmed by μ-Raman spectroscopy and scanning electron microscopy (SEM). Additionally, a good linkage was observed, the CNTs remaining embedded within the NCD matrix, thus reinforcing the interface of the resulting hybrid structure. This was corroborated by bending tests in a modified nanohardness tester. The increase of the Young's modulus from 0.3 to 300 GPa after NCD growth enables the use of this material in a wide range of applications including microelectromechanical systems (MEMS). Additionally, a highly anisotropic electrical resistivity behavior was confirmed: low in-plane values were found for the CNT layer (1.39 × 10(-2) Ω.cm), while high transverse ones were measured for both the NCD coated and uncoated CNT buckypapers (8.13 × 10(5) and 6.18 × 10(2) Ω.cm, respectively).
Laser assisted flow deposition (LAFD) is a very high yield method based on a vapor-solid mechanism, allowing the production of ZnO crystals in a very short time. The LAFD was used in the growth of different morphologies (nanoparticles, tetrapods and microrods) of ZnO micro/nanocrystals and their microstructural characterization confirms the excellent crystallinity of the wurtzite structure. The optical properties of the as-grown ZnO crystals investigated by low temperature photoluminescence (PL) evidence a well-structured near band edge emission (NBE) due to the recombination of free (FX), surface (SX) and donor bound (D0X) excitons. Among the most representative emission lines, the 3.31 eV transition was found to occur in the stacking faults-free microrods. The luminescence behavior observed in H passivated samples suggests a closer relationship between this optical center and the presence of surface states. Besides the unintentionally doped micro/nanocrystals, ZnO/Ag and ZnO/carbon nanotubes (CNT) hybrid structures were processed by LAFD. The former aims at the incorporation of silver as a p-type dopant and the latter envisaging photovoltaic applications. Silver-related spherical particles were found to be inhomogeneously distributed at the microrods surface, accumulating at the rods tips and promoting the ZnO nanorods re-nucleation. Despite the fact that energy dispersive X-ray measurements suggest that a fraction of the silver could be incorporated in the ZnO rods, no new related luminescence lines or bands were observed when compared with the as-grown samples. For the case of the ZnO/CNT composites two main approaches were adopted: i) a direct deposition of ZnO particles on the surface of vertically aligned multi-walled carbon nanotubes (VACNTs) forests without employing any additional catalyst and ii) new ZnO/CNT hybrids were developed as buckypaper nanocomposites. The use of the LAFD technique in the first approach preserves the CNTs structure and alignment and avoids the collapse of the VACNTs array, which is a major advantage of this method. On the other hand, LAFD grown ZnO nanoparticles and tetrapods were used to produce ZnO/CNT buckypaper nanocomposites. When compared with the as-grown samples the PL spectra of the composites structures behave differently. For the case of the ZnO/VACNTs no changes on the peak position and spectral shape were observed. Only an enhancement of the overall luminescence was found to occur. On contrary, for the buckypaper nanocomposites notable changes on the spectral shape and peak position were observed, likely due to distinct surface band bending effects for the ZnO nanoparticles and tetrapods embedded in the CNTs.
The main advantage of Bragg reflection from a multilayer mirror as a monochromator for hard X-rays, is the higher photon flux density because of the larger spectral bandpass compared with crystal lattice reflection. The main disadvantage lies in the strong modulations of the reflected beam profile. This is a major issue for micro-imaging applications, where multilayer-based monochromators are frequently employed to deliver high photon flux density. A subject of particular interest is the origin of the beam profile modifications, namely the irregular stripe patterns, induced by the reflection on a multilayer. For multilayer coatings in general it is known that the substrate and its surface quality significantly influence the performance of mirrors, as the coating reproduces to a certain degree the roughness and shape of the substrate. This proceedings article reviews recent experiments that indicate potential options for producing wave front-preserving multilayer mirrors, as well as new details on the particular mirrors our group has extensively studied in the past.
The use of multilayer mirrors is an interesting alternative for reflective X-ray monochromatization with respect to reflection from crystal optics. The increased photon flux density due to the multilayers' larger bandwidth is of crucial importance for, e.g, full-field X-ray imaging applications. Drawbacks are the introduced modifications of the reflected beam profile as well as a certain loss of coherence, summarized as wavefront degradation. Our recent work has shown that the modification of the beam profile can vary with, e.g., the material composition of the coating applied. In order to verify our findings, a beamline round-robin has been initiated, comparing the wavefront profiles after reflection by selected multilayers at beamlines 32-ID (Advanced Photon Source) and ID19 (European Synchrotron Radiation Facility) with our initial results acquired at BM05 (ESRF) [1].
The European Integrated Activity of Excellence and Networking for nanoand Micro-Electronics Analysis (ANNA), www.ANNA-i3.net, has addressed the further development and assessment of methodologies for the detection of low concentration inorganic contaminants on and in silicon as well as for novel materials. The comparison of various analytical techniques available to the ANNA partners helped to identify the degree of comparableness of results revealed at different installations. The assessment of improved methodologies as well as the reliability of quantification and calibration procedures of specific analytical techniques such as Total-Reflection X-ray Fluorescence (TXRF) analysis has been of particular interest.
The field of single and multilayer based optics has seen significant improvements and new applications in recent years. In this paper, we give an overview of the numerous types of single and multilayer optics that have been developed. The fabrication possibilities of well-known regular periodic multilayers have been driven close to the theoretical limit, providing high resolution or high flux optics for a wide range of photon energies. In addition to that, multilayers with a lateral gradient have been developed to be adapted to curved substrates (for example for focusing purposes) or varying incidence angles on long, flat substrates. Depth-graded multilayers with arbitrarily selectable layer thicknesses over the entire layer stack have been simulated and manufactured, mainly as broadband mirrors with immense bandwidths. Finally, new applications of high precision deposition are reference sample for XRF (having several elements in low concentrations of few ng/mm(2)) and TXRF (with mass deposition in the range of 10(11) atoms/cm(2)) pay tribute to the low detection limits achievable in modern instruments for these techniques.