Novel NO2 gas sensor based on cuprous oxide thin films

In this paper we present the results concerning the characterization of cuprous oxide thin films fabricated by chemical deposition and rapid photothermal processing (RPP) method. The growth kinetic effects and influence of the RPP temperature on the chemical deposited cuprous oxide thin films microstructures were investigated by scanning electron microscopy and energy dispersive X-ray spectrometry. The effect of the electrical resistivity change of Cu₂O thin film layer in the presence of NO₂ is used for gas sensing measurements. Cuprous oxide layers are used as NO₂ gas sensitive material in a novel gas sensor element. It can be shown from experimental results that chemical bath deposition and rapid photothermal processing not only allows green materials preparation but also improves the performance and reliability over conventional methods of the production of sensors for continuous environmental monitoring.     

Highly sensitive SnO2 thin film with low operating temperature prepared by sol–gel technique

Sol–gel dip coating technique was employed to prepare Cu-doped SnO₂ thin films, which were able to detect H₂S gas at room temperature with high sensitivity and revealed fast response characteristics. The highest sensor response (the ratio of resistance in air versus in H₂S) was 3648 under H₂S concentration of 68.5 ppm at room temperature. Recoverability of the thin films appeared when the temperature raised to 50 °C. The films were analyzed by means of XRD and the dried gel powder was studied by TG-DTA test. Influences of sintering temperature and doping level on the H₂S response are discussed. The average grain size of the SnO₂ was about 25 nm.     

Temperature dependent H2S and Cl2 sensing selectivity of Cr2O3 thin films

The conductometric gas sensing characteristics of Cr₂O₃ thin films - prepared by electron-beam deposition of Cr films on quartz substrate followed by oxygen annealing - have been investigated for a host of gases (CH₄, CO, NO₂, Cl₂, NH₃ and H₂S) as a function of operating temperature (between 30 and 300 °C) and gas concentration (1-30 ppm). We demonstrate that these films are highly selective to H₂S at an operating temperature of 100 °C, while at 220 °C the films become selective to Cl₂. This result has been explained on the basis of depletion of chemisorbed oxygen from the surface of films due to temperature and/or interaction with Cl₂/H₂S, which is supported experimentally by carrying out the work function measurements using Kelvin probe method. The temperature dependent selectivity of Cr₂O₃ thin films provides a flexibility to use same film for the sensing of Cl₂ as well as H₂S.     

Surface acoustic wave based sensors employing ionic liquid for hydrogen sulfide gas detection

This paper describes a new type hydrogen sulfide (H₂S) gas sensor using ionic liquid (IL). In this sensor, a reservoir for the IL was integrated on a surface acoustic wave (SAW) resonator. The IL serves as an absorber for H₂S gas. Mass change due to this absorption is detected as shift in the resonant frequency. In this study, we fabricated and demonstrated the sensor using the lithium niobate (LiNbO₃) SAW resonator with the resonant frequency of 38 MHz. The integrated reservoir was filled by the IL 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim]-[PF₆]). As an experimental result, we observed the linear correlation between the frequency-shift and the exposure time of the sensor to the H₂S gas.     

Properties and cathodoluminescence of Y2O2S:Eu thin films

Abstract— Europium‐activated yttrium oxysulfide thin films were fabricated by electron‐beam deposition of Y₂O₂S:Eu with consequent annealing in an H₂S/Ar gas mixture. Transformations in film composition and surface morphology as well as corresponding changes in the optical, photoluminescent, and cathodoluminescent properties were studied and will be discussed. It is shown that 248‐nm laser irradiation of heat‐treated films improves cathodoluminescence by as much as 30%, supposedly due to annealing. The developed phosphor films have a luminance comparable to that of annealed europium‐activated yttrium oxide films and improved color properties (CIE color coordinates: x = 0.624, y = 0.329), and are suitable for display and optoelectronics applications.     

A patterning technique of lead zirconate titanate thin film by ultraviolet-light

The patterning technique of Pb(Zr, Ti)O₃ (PZT) thin film is an essential process in device fabrication processes for application in microsensors and microactuators. In this paper, a novel pattern technique is proposed for PZT thin film by UV photolysis processes. PZT thin films were first spin coated on the substrate and exposed by UV light for photolysis step. The UV photolysis step defined exposed and unexposed area by mask, and the pattern will be transferred to PZT thin film. After photolysis, PZT films were placed in non-ionic surfactant to remove unexposed area. Finally, PZT films were sintered at 650 °C in the furnace for crystallization. Experimental results showed that remnant polarization of patterned PZT film by UV photolysis was 21.4 μc cm^?2, which was compared to 17.24 μc cm^?2 by hot plate prolysis. Coercive fields were 45 and 104 kV cm^?1 by UV photolysis and hot plate prolysis, respectively. Dielectric loss was 0.027 by UV photolysis which was much smaller than 0.043 by hot plate prolysis. PZT thin films patterned by UV photolysis showed satisfactory geometries.     

Sensing characteristics of dc reactive sputtered WO3 thin films as an NOx gas sensor

In order to apply WO₃ thin films to the NO_x gas sensor, WO₃ thin films (3000 Å) were fabricated by using dc reactive sputtering method on alumina substrate and assembled as a unit of an NO_x gas sensor by adopting a patterned heater on the back side of substrate. The deposition temperatures of WO₃ thin film were changed from 200°C to 500°C, and then post-annealed for the crystallization for 4 h at 600°C. There were no WO₃ phases at the substrate temperature of 200°C, but the crystalline phases of WO₃ thin film were appeared with the increase of substrate temperature from 200°C to 500°C. The post-annealing of as-deposited WO₃ thin films at 600°C resulted in the enhancements of crystallinity, but it was observed that the quality of the final phases severely depends on the initial formation of phase during deposition. From the SEM images, crack free morphologies were found, which was different from the room temperature growth films. The sensitivity (R_gas/R_air) of as-deposited thin films was ranged from 4 to 10 for the 5 ppm NO test gas at the measuring temperature of 200°C. However, after post-annealing process at the temperature of 600°C, the sensitivities were increased around the values of 70–180 at the same test condition. These results show the WO₃ thin films need to be processed at least at the temperature of 600°C for the well-improved sensitivity against NO_x gas. It was also observed that the recovery rate of a sensing signal after measuring sensitivity was faster in the in-situ sputtered films than in the evaporated films or room temperature sputtered films.     

Spatial–temporal dynamics of gross primary productivity,evapotranspiration, and water-use efficiency in the terrestrial ecosystems of the Yangtze River Delta region and their relations to climatic variables

Moderate Resolution Imaging Spectroradiometer (MODIS) products and climate data collected from meteorological stations were used to characterize the spatial–temporal dynamics of gross primary productivity (GPP), evapotranspiration (ET), and water-use efficiency (WUE) in the Yangtze River Delta (YRD) region and the response of these three variables to meteorological factors. The seasonal patterns of GPP and WUE showed a bimodal distribution, with their peak values occurring in May and August, and April and October, respectively. By contrast, the seasonal variation of ET presented a unimodal pattern with its maximum in July or August. The spatial distribution of ET and GPP was similar to higher values occurring in the south. From 2001 to 2012, GPP in the eastern YRD decreased, while GPP in the western part increased. In comparison, over the 12 years, ET in the northern part of YRD decreased, while ET in the southern part increased. The spatial distribution and spatial variation of WUE were both similar to those of GPP. This implies that the changes in WUE are primarily controlled by the variations in GPP. The annual average WUE over vegetation types followed the order of: evergreen broadleaf forest (1.95 g C kg^?1 H₂O) > deciduous broadleaf forest (1.87 g C kg^?1 H₂O) > evergreen needle leaf forest (1.70 g C kg^?1 H₂O) > deciduous needle leaf forest (1.68 g C kg^?1 H₂O) > grassland (1.66 g C kg^?1 H₂O) > cropland (1.61 g C kg^?1 H₂O). Both GPP and ET increased with increasing annual mean temperature (T_a) and annual mean precipitation across all of the plant function types. WUE decreased as vapour pressure deficit (VPD) increased in all of the biomes. Interestingly, the relationship between WUE and VPD was the most significant in broadleaf forest. Whether this phenomenon is universal should be investigated in future studies.     

Development of local ambient gas control technologies for atmospheric MEMS process

This paper reports a local ambient gas control technology for atmospheric MEMS processes, especially plasma processes, using a new local ambient gas control head. First, the local ambient gas control with this head was investigated by a computational fluid dynamics code. After confirmation of the safe evacuation and the feasible cleanness level, which is comparable to the impurity level in semiconductor grade gas (below 10 ppm), a prototype apparatus was fabricated based on the simulation results. Measuring gas distribution by a gas analyzer, a O₂ meter and a dew point meter, the local ambient gas control was confirmed experimentally. Next, H₂ plasma generation was achieved in open air with H₂ concentrations of 0–100 % even above the explosive limit in air (4.1 %) safely. In addition, Cu reduction and SiO₂ etching by H₂ plasma were demonstrated in open air. These results show high potential of our local ambient gas control technology for atmospheric MEMS processes.     

Enhanced H2S sensing characteristics of SnO2 nanowires functionalized with CuO

The CuO-functionalized SnO₂ nanowire (NW) sensors were fabricated by depositing a slurry containing SnO₂ NWs on a polydimethylsiloxane (PDMS)-guided substrate and subsequently dropping Cu nitrate aqueous solution. The CuO coating increased the gas responses to 20 ppm H₂S up to 74-fold. The R_a/R_g value of the CuO-doped SnO₂ NWs to 20 ppm H₂S was as high as 809 at 300 °C, while the cross-gas responses to 5 ppm NO₂, 100 ppm CO, 200 ppm C₂H₅OH, and 100 ppm C₃H₈ were negligibly low (1.5–4.0). Moreover, the 90% response times to H₂S were as short as 1–2 s at 300–400 °C. The selective detection of H₂S and enhancement of the gas response were attributed to the uniform distribution of the sensitizer (CuO) on the surface of the less agglomerated network of the SnO₂ NWs.     

Gas sensing properties of ZnO thin films prepared by microcontact printing

In situ patterned zinc oxide (ZnO) thin films were prepared by precipitation of Zn(NO₃)₂/urea aqueous solution and by microcontact printing of self-assembled monolayers (SAMs) on Al/SiO₂/Si substrates. The visible precipitation of Zn(OH)₂ from the urea containing Zn(NO₃)₂ solution was enhanced by increasing the reaction temperature and the amount of urea. The optimized condition for the ZnO thin films was found to be the Zn(NO₃)₂/urea ratio of 1/8, the precipitation temperature of 80 °C, the precipitation time of 1 h and the annealing temperature of 600 °C, respectively. SAMs are formed by exposing Al/SiO₂/Si to solutions comprising of hydrophobic octadecylphosphonic acid (OPA) in tetrahydrofuran and hydrophilic 2-carboxylethylphosphonic acid (CPA) in ethanol. The ZnO thin film was then patterned with the heat treatment of Zn(OH)₂ precipitated on the surface of hydrophilic CPA. The ZnO gas sensor was exposed to different concentrations of C₃H₈ (5000 ppm), CO (250 ppm) and NO (1000 ppm) at elevated temperatures to evaluate the gas sensitivity of ZnO sensors. The optimum operating temperatures of C₃H₈, CO and NO gases showing the highest gas sensitivity were determined to be 350, 400 and 200 °C, respectively.     

Improved crystalline structure and H2S sensing performance of CuO-Au-SnO2 thin film using SiO2 additive concentration

In situ SiO₂-doped SnO₂ thin films were successfully prepared by liquid phase deposition. The influence of SiO₂ additive as an inhibitor on the surface morphology and the grain size for the thin film has been investigated. These results show that the morphology of SnO₂ film changes significantly by increasing the concentration of H₂SiF₆ solution which decreases the grain size of SnO₂. The stoichiometric analysis of Si content in the SnO₂ film prepared from various Si/Sn molar ratios has also been estimated. For the sensing performance of H₂S gas, the SiO₂-doped Cu-Au-SnO₂ sensor presents better sensitivity to H₂S gas compared with Cu-Au-SnO₂ sensor due to the fact that the distribution of SiO₂ particles in grain boundaries of nano-crystallines SnO₂ inhibited the grain growth (<6 nm) and formed a porous film. By increasing the Si/Sn molar ratio, the SiO₂-doped Cu-Au-SnO₂ gas sensors (Si/Sn = 0.5) exhibit a good sensitivity (S = 67), a short response time (t_90% < 3 s) and a good gas concentration characteristic (α = 0.6074). Consequently, the improvement of the nano-crystalline structures and high sensitivity for sensing films can be achieved by introducing SiO₂ additive into the SnO₂ film prepared by LPD method.     

Effect of aluminium doping on structural and gas sensing properties of zinc oxide thin films deposited by spray pyrolysis

A facile spray pyrolysis route is used to deposit aluminium doped ZnO (AZO) thin films on to the glass substrates. It is observed that on aluminium doping the particle size of ZnO reduces significantly; moreover, uniformity of particle also gets enhanced. Their XRD study reveals that intensity ratio of crystal planes depend on the aluminium doping concentration. The gas response studies of; ∼800 nm thick Al-doped ZnO films at different operating temperatures show that 5 at% Al-doped ZnO thin film exhibits highest response towards H₂S gas at 200 °C. The results suggest that the gas response strongly depends on the particle size and aluminium doping in the ZnO.     

Flexible H2 sensor fabricated by layer-by-layer self-assembly of thin films of polypyrrole and modified in situ with Pt nanoparticles

A novel flexible H₂ gas sensor was fabricated by the layer-by-layer (LBL) self-assembly of a polypyrrole (PPy) thin film on a polyester (PET) substrate. A Pt-based complex was self-assembled in situ on the as-prepared PPy thin film, which was reduced to form a Pt-PPy thin film. Microstructural observations revealed that Pt nanoparticles formed on the surface of the PPy film. The sensitivity of the PPy thin film was improved by the Pt nanoparticles, providing catalytically active sites for H₂ gas molecules. The interfering gas NH₃ affected the limit of detection (LOD) of a targeted H₂ gas in a real-world binary gas mixture. A plausible H₂ gas sensing mechanism involves catalytic effects of Pt particles and the formation of charge carriers in the PPy thin film. The flexible H₂ gas sensor exhibited a strong sensitivity that was greater than that of sensors that were made of Pd-MWCNTs at room temperature.     

Room-temperature H2S gas sensing at ppb level by single crystal In2O3 whiskers

In₂O₃ whiskers and bipyramidal nano-crystals were prepared by a carbothermal method. These were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray analysis (EDX), photoluminescence and Raman spectroscopy. These were studied for application to sensing of H₂S gas. The single crystal whiskers were found to be sensitive to as low as 200 ppb of H₂S gas at room temperature and showed saturation in response at 10 ppm. On the other hand, the films made of bipyramids were less sensitive to H₂S gas and the response was found to be a nearly linear function of concentration in a concentration range of 10–80 ppm.     

H<Subscript>2</Subscript>S nano-jetting through a p–n junction-like graphene/Au nano-injector: a molecular dynamics study

This paper uses fully atomistic molecular dynamics to outline the dynamics of H₂S nano-jetting through a p–n junction-like graphene/Au nano-injector. We examined the effects of nano-injector diameter (d), system temperature (T), and the extrusion velocity (v) of a graphite piston plate on the formation of H₂S nano-jets, system pressure, and the number of molecules (N _m) in the outflow. The combined effects of high critical pressure and small orifice resulted in a larger jet angle, which increased the number of H₂S molecules stuck to the graphene surface at the outlet. Moving the graphite piston plate toward the orifice of the nano-injector increased in the change in momentum and interactive forces between H₂S molecules, resulting in three phases of pressure establishment in the nano-injector: incubation (phase I), steep pressure increase (phase II), and high pressure (phase III). When operated at T ≥ 300 K and v < 27.912 m/s, the proposed nano-jet device is able to produce a well-dispersed spray of H₂S without H₂S molecules sticking to the graphene surface at the outlet. The p–n junction-like Au-doped graphene surface provides an additional energy barrier preventing the transport of electrons from H₂S molecule to the graphene. This inhibits the accumulation of H₂S molecules and subsequent blockages at the exit of the nano-injector. Simulation results demonstrate the potential of using chemiresistive sensing to monitor H₂S flow patterns during nano-jetting. The findings presented in this study could be transformative to the design of nano-injectors for other gases commonly used as biomarkers.     

Effect of Mg doping on the hydrogen-sensing characteristics of ZnO thin films

Undoped ZnO and Mg_0.1Zn_0.9O films, both with good crystalline quality and smooth surface, were grown on c-cut sapphire by pulsed laser deposition (PLD) technique. Hydrogen-sensing measurements indicated that the MZO film showed much higher H₂ sensing performance than the undoped ZnO film did. The sensor response is 2.9 for undoped ZnO film to 5000 ppm H₂ at 300 °C. The gas response increased to about 50 for the MZO film measured under the same condition. To understand the enhancement of the sensing performances of the MZO film, the gas sensing mechanism of the films was proposed and discussed.     

Fabrication and characterization of PECVD silicon nitride for RF MEMS applications

The structural, optical and electrical properties of plasma enhanced chemical vapor deposited silicon nitride layers are investigated, which have been used as a dielectric layer during RF MEMS fabrication. During growth, the gas ratio (SiH₄/NH₃) is varied between 0.33 and 0.5 and pressure is varied between 400 and 700 mTorr while deposition time is kept constant. The results in the films show differing properties. The thicknesses of the resultant films are between 150 to 220 nm with different gas flow ratios and pressures whereas the deposition time was kept constant. A Bruggeman effective medium approximation is utilized to model the refractive index of the films. Reflectance measurements were carried out in the range of 210–250 nm. The refractive indexes of the films varied between 1.79 and 2.03, with a dielectric constant varying from 6.66 to 7.22. Capacitance voltage measurements yield a fixed dielectric charge value in the low ?10¹² cm^?2 while a breakdown voltage of 915 V μm^?1 is achieved for films grown at the lowest gas ratio and pressure. The quality of Si/Si_xN_y interface is also considered.     

Temperature dependant dielectric breakdown of sputter-deposited AlN thin films using a time-zero approach

In MEMS (micro electromechanical system) devices, piezoelectric aluminum nitride (AlN) thin films are commonly used as functional material for sensing and actuating purposes. Additionally, AlN features excellent dielectric properties as well as a high chemical and thermal stability, making it also a good choice for passivation purposes for microelectronic devices. With those aspects and current trends towards minimization in mind, the dielectric reliability of thin AlN films is of utmost importance for the realization of advanced device concepts. In this study, we present results on the transversal dielectric strength of 100 nm AlN thin films deposited by dc magnetron sputtering. The dielectric strength is measured using a time-zero approach, using a fast voltage ramp to stress the film up to the point of breakdown. The measurements are performed at different device temperatures. In order to achieve statistical significance, at least 12 measurements are performed for each environment parameter set and the results are analyzed using the Weibull approach. Basically, lower breakdown fields are observed with increasing temperatures up to 300 °C with a characteristic breakdown field strength E ₀ following the relationship $\sqrt {E_{0} } \propto T$ as reported in literature for similar measurements performed at silicon nitride thin films. From the intersection of this linear behavior, the Poole–Frenkel (PF) barrier height ? _B is determined to 0.54 eV, which is reasonable for AlN thin films. The slope of this relation is similar to values reported for silicon nitride thin films. This allows an estimation of the breakdown field at higher temperatures by extrapolation. Leakage current measurements show a dominant PF type conduction mechanism, verifying the applicability of $\sqrt {E_{0} } \propto T$ . No breakdown occurs in negative field direction, which is attributed to the metal–insulator–semiconductor configuration of the sample and hence, the presence of a depletion layer forming in the n-doped silicon and dominating the leakage current behavior.     

Accurate design of compact forward-coupled microstrip filters using an integral-equation field solver

In this article, we present forward-coupled microstrip filters designed using an integral-equation-based field solver, and fabricated in high-temperature superconducting (HTS) thin films. Two designs were studied, one a nine-pole bandpass filter at 900 MHz with 25-MHz bandwidth, and the other a five-pole bandpass filter at 2 GHz with 24-MHz bandwidth and 10-Ω resonator characteristic impedance. Both designs were fabricated using YBa₂Cu₃O₇ (YBCO) HTS thin films. Measurements showed excellent agreements with the simulation predictions. For the nine-pole filter design, a measured insertion loss of 0.3 dB, and a measured return loss of 16 dB were achieved in the YBCO filter at 77 K. © 1995 John Wiley & Sons, Inc.