The modification of the surface reception properties of nanocrystalline structures is of great interest in environmental, catalysis and energy related applications. For instance, an oxide surface covered with a layer of another oxide opens the possibility of creating the nanosized counterparts of bulk catalytic systems. A relevant example is the TiO2-WO3, which is an active catalysts in a broad range of reactions. The chemical synthesis of the colloidal, nanocrystalline version of such system will first be exposed, by coupling suitable sol-gel chemistry with solvothermal processing. Then, the range of obtained structures will be discussed, ranging from WOx-surface modified TiO2 to TiO2-WO3 heterojunctions. The complex structural evolution of the materials will be discussed, depending on the W concentration. A summary of the acetone sensing properties of these systems will be shown. In particular, the surface activation of the otherwise almost inactive pure TiO2 by surface deposition of WO3-like layers will be highlighted. Addition of the smallest W concentration boosted the sensor response to values comparable to those of pure WO3, ranging over 2-3 orders of magnitude of conductance variation in presence of ethanol or acetone gases. Simple analysis of the sensing data will evidence that the combination of such nanocrystalline oxides results in catalytic activation effects, with exactly opposite trend, with respect to pure TiO2, of the activation energies and best responses.
TiO2 is well known as a low-cost, highly active photocatalyst showing good environmental compatibility. Recently it was found that TiO2 nanotubes promise to enable for high photocatalytic activity (PCA). In our experiments, we studied the PCA and spectroscopic properties of TiO2 nanotube arrays formed by the anodization of Ti. The PCA efficiency related to the decomposition of methylene-blue was measured. To obtain reliable data, the results were calibrated by comparing with standard materials like Pilkington Activ™ which is a commercially available self cleaning glass. The studies included a search strategy for finding optimum conditions for the nanotube formation and the investigation of the relationship between PCA and annealing temperature. TiO2 nanotubes of different shapes and sizes were prepared by an anodization of Ti foil in different electrolytes, at variable applied voltages and concentrations. The photo-dissociation of methylene-blue was detected spectroscopically. For the optimized material, an enhancement factor of 2 in comparison to the standard reference material was found. Furthermore, femtosecond-laser induced photoluminescence and nonlinear absorption of the material were investigated. Possibilities for further enhancements of the PCA are discussed.
The development of an integrated gas chromatographic system using micro and nanotechnologies is presented in this
paper. For this purpose, the different components of the chromatographic system, namely the preconcentrator, the
chromatographic column and the gas sensors are being investigated and developed, and the actual state of this
investigation is presented. The proposed target application comes from the agrofood industry, in particular the
determination of the fish freshness. The structure of the preconcentrator has been fabricated using deep reactive ion
etching (DRIE). The same fabrication technique has been employed for the patterning of the silicon microcolumns,
which have been sealed with Pyrex glass. Inlet and outlets have been connected and initial experiments of
functionalization have been performed. Gas sensors have been obtained by microdeposition of doped WO3 or SnO2
nanomaterials on microhotplates and their responses to the gases of interest have been measured, proving that the target
gas concentrations can be detected.
This work describes the design and implementation of a resonator structure for the fabrication of an electromagnetic inertial microgenerator for energy scavenging from ambient vibrations. This structure is based in the use of a permanent magnet (inertial mass) mounted onto a polymeric membrane. ANSYS simulations are carried out to investigate the influence of the membrane geometry on the resonant frequency. Moreover, generator prototypes have been fabricated with a modular manufacturing process in which the electromagnetic converter and the mechanical resonator are manufactured separately, diced and then assembled. In these prototypes, the influence of the resonator geometry (membrane dimensions) on the generator behaviour has been investigated. The experimental results show the ability of these devices to generate power levels in the range of μW's and output voltages in the range of hundreds of mV. The parasitic damping of the resonator structures is estimated from the fitting of the experimental data, and suggests the existence of an intrinsic limitation of the polymers related to spring stiffening effects at large excitation amplitudes.
Functional metal oxide micro and nanostructures for the detection of gas are a very promising candidate for future gas-sensors.
Due to reduced size and thus an increased surface to volume ratio nanosized sensitive structures offer a high
potential for increasing sensitivity. A top down sputtering approach for gas sensors with nano-sized gas sensitive metal
oxide areas is presented. Oxidised silicon wafer were used as substrates. The silicon dioxide film of 1 &mgr;m thickness was
prepared by thermal oxidation in order to insulate the gas sensing elements from the substrate. At the sensor chips (1.5 x
1.5 mm2) a Ta/Pt film (20/200 nm thickness) was deposited and patterned to act as interdigital electrodes, heater and
temperature sensor. In a second step nano-scaled tin oxide layers (60nm thick, 5 &mgr;m width) were deposited by sputtering
techniques and photolithographical pattering between the platinum micro-electrodes (4 &mgr;m gap). As the last step the
width of the stripes was reduced by using Focused Ion Beam (FIB) technology to obtain the desired size and structure.
This enables the control of the dimensions of the structures down to the resolution limit of the FIB-system which is a
few tens of nm. The structural and electrical characterisation of the sensors and their responses during exposure to
several test gases including O2, CO, NO2 and H2O are presented as well.
KEYWORDS: Sensors, Gas sensors, Reliability, Silicon, Platinum, 3D metrology, Temperature metrology, Digital image correlation, Atomic force microscopy, Scanning probe microscopy
Micromachined microsensors for gas or flow detection based on physical behaviour of a special layer of a membrane have to fulfil high quality and reliability requirements especially in safety or security applications. For the reliability assessment a combination of simulative and experimental methods is usually carried out for the fully understanding of the thermo-mechanical behaviour. Due to the micromachining involved in the production of the sensor components the thermo-mechanical response of the layers are strongly dependent on process parameters. Therefore experimental methods for the 3D deformation detection are essential. In this paper experimental methods such as profilometry and scanning probe microscopy are tested for the evaluation of residual stresses and thermomechanical induced stress/strain fields.
Due to their simple implementation, low cost and good reliability for real-time control systems, semiconductor gas sensors offer good advantages with respect to other gas sensor devices. As gas adsorption is a surface effect, one of the most important parameter to tailor the sensitivity of the sensor material is to increase the surface area. For these propose, mesoporous oxides have been synthesized. Nanostructured mesoporous materials present a large and controllable pore size and high surface are. For the preparation of ordered nanostructure arrays, a hard template method has been used. This method presents some advantages when compared with a soft template method, especially in its specific topological stability, veracity, predictability and controllability. Moreover, with this hard template method we can obtain crystalline mesoporous oxides, with small particle size and high surface area. We have used SBA-15 (two-dimensional hexagonal structure) and KIT-6 (three-dimensional cubic structure) as a template for the synthesis of different crystalline mesoporous WO3 with a particle size about 8-10 nm and high surface area. Low angle XRD spectra show a high order mesoporous structure, without rests of silica template. TEM confirms that the silica host has been completely removed; therefore, the nanowires constitute a self-supported superlattice. HRTEM studies have been focused on the detailed structural characterization of these materials. Electrical characterization of the sensor response in front of NO2 has been performed. Some catalytic additives have been also introduced, in order to increase the sensitivity of the material.
KEYWORDS: Digital image correlation, Ions, Scanning electron microscopy, Microelectromechanical systems, Ion beams, Material characterization, Image resolution, Sensors, Error analysis, Copper
The authors present a new approach, fibDAC, which allows to measure and analyze deformation fields on stressed micro and nano components, which can be utilized for mechanical material characterization. The method bases on digital image correlation (DIC) algorithms applied locally to load state images captured from focused ion beam (FIB) equipment. As a result, deformation fields are determined, which occur due to loading of microsystem structures inside the focused ion beam system. A similar tool, called microDAC/nanoDAC, has been reported earlier and applies DIC techniques to SEM or AFM images. The advantages of the new fibDAC approach occur in the incorporation of specimen preparation like ion milling, ion beam surface polishing and DIC patterning as well as specimen loading by ion milling and DIC deformation measurement in a single equipment. Combining measured fields with finite element simulations or analytical solutions of the corresponding mechanical problem, relevant mechanical material properties can be evaluated. Corresponding object loading is accomplished either externally by testing modules designed for application inside the FIB equipment or by ion milling on the test specimen. As an example ion milling on specimens with residual stresses is demonstrated. Released in this way residual stresses cause object deformations nearby the milling area. Measured deformation fields by fibDAC allow to evaluate very local residual stresses. Some principal experiments illustrate the feasibility of the chosen approach. Features and challenges connected with this new method are discussed in some detail.
The requirements of flow measurement and control in the home-appliances field lead to the need of a measurement system able to monitor the flow and the quality of gas. The integration of a set of sensors with different functionalities on a single chip arises as an advantageous solution. In this paper, the description of the structures and technologies required for the gas, flow and temperature sensor devices is presented prior to the complete description of the process flow for the full on-chip compatibilization. In this sense, semiconductor gas sensors and thermal flow sensors have arisen as the best candidates to address the compatibilization.
The detailed microstructural characterization of CuInS2 (CIS) polycrystalline films is performed by combined in depth MicroRaman scattering/Auger Electron Spectroscopy measurements as a function of the chemical composition and temperature of processing. This has allowed to identify the main secondary phases in the layers as CuIn5S8 for Cu-poor samples and CuS for Cu-rich ones. The presence of such phases is strongly related to the temperature of processing, being secondary phase formation inhibited when the growing temperature decreases from 520°C to 370°C. This is also accompanied by a significant degradation of the structural CIS features, as reflected by the increase in both shift and broadening of the A1 CIS mode in the spectra, and by the decrease of the grain size estimated by cross-section TEM. Besides, Raman spectra measured from samples grown at lower temperatures are characterized by the presence of an additional mode at about 305 cm-1. The presence of this mode in the spectra from Cu-rich samples gives experimental support to its previously proposed structural origin. Finally, MoS2 secondary phase has also been identified at the CIS/Mo interface region, being its occurrence also inhibited at low growing temperatures.
A gas flow sensor has been developed for home-appliances applications. The main requirements were to obtain a low cost single device able to work in the range 0-1slm with high linearity, low power, reliability and robustness. A thermal flow sensor has been designed with the help of thermal and flow FEM simulation for the design of the sensor chip as well as its packaging. The process flow is based on a simple silicon micromachined technology. Chip-on-board solution has been selected to simplify the packaging. Electronics for driving the sensor and for compensation offsets and temperature dependence and for linearising the output signal has been implemented. Final device shows good sensitivity and linearity in different zones of the range of interest.
KEYWORDS: Gas sensors, Temperature metrology, Dielectrics, Finite element methods, 3D modeling, Sensors, Convection, Electronics engineering, Electrodes, Silicon
A laboratory model of a gas sensor substrate produced in microelectronic technology has been experimentally analyzed and simulated by means of a 3D FEM model. This paper discusses its thermal and mechanical behavior under different working temperatures. The thermal expansion mismatch between different materials induces thermal stresses and structure deflection. Simulated and experimental results are proved to be in good agreement. Moreover, the proposed design offers low-power consumption, good thermal uniformity, low thermal inertia and mechanical stability up to 650 degrees Celsius.
Our researches were devoted to the micromechanical elements fabricated by the surface micromachining technology, in order to reduce or to eliminate the internal stress or the stress gradients. We used an analysis based on secondary ion mass spectroscopy and the spreading resistance profiling determinations, correlated with cross-section electron transmission spectroscopy. The stress induced in the polysilicon layers by the technological processes depends on: (i) the conditions of the low pressure chemical vapor deposition process; (ii) the phosphorus doping technique; (iii) the subsequent multi-step annealing processes. In our experiments the LP-CVD conditions were maintained the same, but the condition specified previously as items (ii) was varied by using two different doping techniques: thermal- chemical doping consisting in prediffusion from a POCl3 source in an open furnace tube; ionic implantation with an energy E equals 65KeV and a dose N equals 4.5 X 1015 cm-2. The implantation process was followed by an annealing at 900 degrees C in an oxygen ambient for 30 minutes. The thermal budget was varied after the doping in order to reduce the stress gradient in the polysilicon layers. The results of our analysis allow us to show that: (1) the doping gradients are correlated with the slower phosphorus grains forme by an excess of the oxygen atoms; a concurrent process induced by the silicon self-interstitial injection during the diffusion and oxidation, determines the enhancement of the grain growth and therefore the enhancement of the electrical activation especially near the internal polysilicon interface; (2) the post-doping annealing conditions could be varied in a convenient manner, so that the doping induced stress gradients into the polysilicon layers to be reduced or completely eliminated for suitable micromechanical induced stress gradients into the polysilicon layers to be reduced or completely eliminated for suitable micromechanical applications. The results were used for the process optimization of micromechanical elements. The internal stress was determined by using anew, pull-in voltage method, allowing the comparison of the theory with the experimental data. It was deduced a new form of the equations set useful to extract the mechanical parameters like the internal stress and the Young's module. It was also deduced a simplified approximate formula useful to apply the least square fitting method for the extraction of the mechanical parameters. The results confirms the conclusions of the doping and the structural analysis.
Comparative study of nitrogen implanted a-C:H film has been carried out by micro-Raman and nanoindentation techniques. At high dose nitrogen implantation (1(DOT)1017 cm-2) the structural inhomogeneities are observed in the implanted region. After implantation a significant broadening and energy shift of both G- and D-bands in Raman spectra are observed. On the other hand, film hardness measurements reveal the existence of more dramatic differences between both implanted regions with homogeneous and structural inhomogeneities. The film hardness in the inhomogeneous region more than by 5 times exceed the one in the homogeneous region. The hardness improvement of ion implanted a-C:H film is related to film disordering and ion beam induced phase-structure transformation in the implanted region.
Si and epitaxial SiGe strained and relaxed layers have been implanted with C+ ions to investigate the formation of SiCy and SiGexCy alloys (medium doses) as well as the ion beam synthesis of SiC in SiGe matrices (high doses). These layers have been analyzed by Raman scattering, in correlation with XRD, XPS and TEM. These data show that for implant temperature of 500 degree(s)C (crystalline target), carbon is not incorporated in substitutional sites, and (beta) -SiC precipitates aligned with the implanted matrix are formed. The residual strain and the degree of missorientation of these precipitates depend on the strain, defects and bond length of the implanted matrix. Moreover, precipitation of (beta) -SiC in the implanted region causes an enhanced Ge migration, mainly towards the surface. This determines a Ge enrichment and consequent relaxation of the Si1-xGex matrix. This contrasts with the room temperature implants performed in preamorphized Si layers, where carbon incorporation in substitutional sites (Cs) takes place after thermal annealing. The maximum amount of Cs is found for the implanted dose corresponding to a peak carbon concentration of 1.3%. For higher doses, there is a degradation of the crystal quality of the recrystallized layer.
Thick polysilicon layers (greater than 10 micrometer), grown in an epitaxial reactor, are highly desirable for surface micromachining applications. The mechanical properties of these layers were studied extensively by characterizing the stress and stress gradient. The stress profile and texture were insensitive to variations of deposition parameters both of the polysilicon seed layer and the epitaxial process, and were influenced to a small degree by doping with phosphorous. Annealing in oxygen ambient resulted in compressive stresses up to 80 MPa and stress gradients of -10 MPa/micrometer. Subsequent annealing in nitrogen reduced the stress and stress gradient, but it can be reversed by re-annealing in oxygen. A model based on diffusion of oxygen is presented explaining the influence of the annealing on stress. Oxygen atoms diffuse into polysilicon during an anneal in the oxygen ambient, introducing compressive stress. Upon annealing in the nitrogen ambient, oxygen is released from the polysilicon layers due to the partial pressure of oxygen at the annealing temperature. The diffusion of oxygen atoms out of the layers results in a partial reversal of the mechanical effects. This insight gives the possibility to tailor the stress of thick polysilicon layers within certain limits to the specific needs of the application.
The Raman scattering analysis of damaged and amorphous SiC layers obtained by ion beam processing has been performed as a function of the processing parameters. Two different sets of samples are investigated: (a) 6H-SiC samples implanted with Ge+ ions at different doses, and (b) SiC layers obtained by C+ ion implantation into amorphous Si. In the first case, damage accumulation and amorphization are analyzed as a function of the implanted dose. In the second case, deep in the analysis of the dependence of recrystallization processes on the amorphous structure, the ion beam induced epitaxial crystallization (IBIEC) of amorphous layers obtained by carbon implantation is also studied. The results show the strong ability of Raman scattering for the identification of amorphous phases in the layers, as well as for the evaluation of residual damage after thermal or IBIEC processes. Correlation of these data with IR, RBS and TEM allows us to determine the structural evolution of the samples under thermal or irradiation processes.
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