Influence of Cs doping in spray deposited SnO2 thin films for LPG sensors

Detection of low concentrations of petroleum gas was achieved using transparent conducting SnO₂ thin films doped with 0–4 wt.% caesium (Cs), deposited by spray pyrolysis technique. The electrical resistance change of the films was evaluated in the presence of LPG upon doping with different concentrations of Cs at different working temperatures in the range 250–400 °C. The investigations showed that the tin oxide thin film doped with 2% Cs with a mean grain size of 18 nm at a deposition temperature of 325 °C showed the maximum sensor response (93.4%). At a deposition temperature of 285 °C, the film doped with 3% Cs with a mean grain size of 20 nm showed a high response of 90.0% consistently. The structural properties of Cs-doped SnO₂ were studied by means of X-ray diffraction (XRD); the preferential orientation of the thin films was found to be along the (3 0 1) directions. The crystallite sizes of the films determined from XRD are found to vary between 15 and 60 nm. The electrical investigations revealed that Cs-doped SnO₂ thin film conductivity in a petroleum gas ambience and subsequently the sensor response depended on the dopant concentration and the deposition temperature of the film. The sensors showed a rapid response at an operating temperature of 345 °C. The long-term stability of the sensors is also reported.     

Sensor properties and surface characterization of the metal-deposited SPR optical fiber sensors with Au,Ag, Cu,and Al

Metal-deposited optical fiber sensors with Cu and Al with a film thickness of 45 nm based on surface plasmon resonance (SPR) were fabricated for the first time. The response curves and the properties of these sensors were investigated with a comparison of those of the sensors with Au and Ag. The reflection properties of thin films of Au, Ag, Cu, and Al due to the SPR phenomenon were also measured and considered. The metal-deposited SPR optical fiber sensors with Au, Ag, and Cu have high sensitivities and good responses. Though the sensor with Al shows a lower sensitivity, it has a wider response range in the refractivity. The response curve of the sensor with Au calculated from SPR theoretical equations agreed well with that obtained by the experiment. However, the response curves of the sensors with Ag, Cu, and Al have the effects of the surface oxide layers. The surface characterization of these metal films by X-ray photoelectron spectroscopy (XPS) showed the presence of oxide layers on the films of Ag, Cu, and Al. A very thin (about 0.3 nm) oxide layer is present on Ag, while thick (about 2 nm) oxide layers are present on Cu and Al.     

Mesoporous nanoparticle TiO2 thin films for conductometric gas sensing on microhotplate platforms

Mesoporous TiO₂ nanoparticle thin films were prepared on MEMS microhotplate (μHP) platforms and evaluated as high-sensitivity conductometric gas sensor materials. The nanoparticle films were deposited onto selected microhotplates in a multi-element array via microcapillary pipette and were sintered using the microhotplate. The films were characterized by optical and scanning electron microscopies and by conductometric measurements. The thin films were evaluated as conductometric gas sensors based on the critical performance elements of sensitivity, stability, speed and selectivity. The nanoparticle films were compared with compact TiO₂ films deposited via chemical vapor deposition (CVD) and the nanoparticle films were found to demonstrate higher sensitivity to target analytes. The nanoparticle films were also stable with regard to both baseline conductance and signal response over 60 h of continuous operation at high temperatures (up to 475 °C). Sensor response times were evaluated and the TiO₂ nanoparticle films showed fast responses to the presence of analyte (≈5 s) and a response-time dependence on the analyte concentration. Control of the sensor operating temperature, an inherent benefit of the microhotplate platform, was employed to demonstrate the selectivity of the nanoparticle films.     

Moisture sensor at glass/polymer interface for monitoring of photovoltaic module encapsulants

A sensor developed for measurement of water concentration inside glass/polymer encapsulation structures with a particular application area in accelerated aging of photovoltaic module encapsulants is described. An approximately 5 μm thick porous TiO₂ film applied to a glass substrate with a conductive coating acts as the moisture-sensitive component. The response is calibrated with weather chamber experiments for sensors open to the environment and with diffusion experiments for sensors laminated under an encapsulant. For the interpretation of diffusion experiment results, a transport model describing the diffusion of water across the polymer/TiO₂ interface is developed. The logarithm of AC resistance shows a linear dependence on water concentration in both open and encapsulated calibration. The first measurable response from an encapsulated 3.5 mm × 8 mm size sensor is obtained when approximately 10 μg of water has entered the film. Implications of the calibration results for sensor usage in accelerated aging tests are discussed.     

Fabrication of micro sensors on a flexible substrate

Flexible micro temperature and humidity sensors on parylene thin films were designed and fabricated using a micro-electro-mechanical-systems (MEMS) process. Based on the principles of the thermistor and the ability of a polymer to absorb moisture, the sensing device comprised gold wire and polyimide film. The flexible micro sensors were patterned between two pieces of parylene thin film that had been etched using O₂ plasma to open the contact pads. The sacrificial Cr spacer layer was removed from the Cr etchant to release the flexible temperature and humidity sensors from the silicon substrate. Au was used to form the sensing electrode of the sensors while Ti formed the adhesion layer between the parylene and Au. The thickness of the device was 7 ± 1 μm, so the sensors attached easily to highly curved surfaces. The sensitivities of the temperature and humidity sensor were 4.81 × 10⁻³ °C⁻¹ and 0.03 pF/%RH, respectively. This work demonstrates the feasibility and compatibility of thin film sensor applications based on flexible parylene. The sensor can be applied to fuel cells or components that must be compressed.     

Flexible vapour sensors using single walled carbon nanotubes

Thin, strongly adhering films of single-walled carbon nanotube bundles (SWNT) on flexible substrates such as poly(ethyleneterephthalate) (PET) were used for vapour sensing (hexane, toluene, acetone, chloroform, acetonitrile, methanol, water, etc.). These sensors are extremely easy to fabricate using the line patterning method. For example, ‘4-probe’ sensor patterns are drawn on a computer and then printed on overhead transparency (PET) sheets. These PET patterns were coated with films of electronically conductive SWNT bundles (1–2 μm thick) by dip-coating in aqueous surfactant-supported dispersions and mounted in glass chambers equipped for vapour sensing. Experiments conducted under saturated vapour conditions in air showed sensor responses that correlated well with solvent polarity [E_T(30) scale]. Similar results were obtained under controlled vapour conditions (no air) at 10,000 ppm. Control experiments using films of carbon black on PET (Aquadag-E^®), also prepared by the line patterning method, showed very little response to vapours under identical experimental conditions. The sensors are very flexible, e.g., they can be bent to diameters as small as 10 mm without significantly compromising sensor function.     

Evaluation of response characteristics of resistive oxygen sensors based on porous cerium oxide thick film using pressure modulation method

In order to reduce the response time of resistive oxygen sensors using porous cerium oxide thick film, it is important to ascertain the factors controlling response. Pressure modulation method (PMM) was used to find the rate-limiting step of sensor response. This useful method measures the amplitude of sensor output (H(f)) for the sine wave modulation of oxygen partial pressure at constant frequency (f). In PMM, “break” response time, which is minimum period in which the sensor responds precisely, can be measured. Three points were examined: (1) simulated calculations of PMM were carried out using a model of porous thick film in which spherical particles are connected in a three-dimensional network; (2) sensor response speed was experimentally measured using PMM; and (3) the diffusion coefficient and surface reaction coefficient were estimated by comparison between experiment and calculation. The plot of log f versus log H(f) in the high f region was found to have a slope of approximately −0.5 for both porous thick film and non-porous thin film, when the rate-limiting step was diffusion. Calculations showed the response time of porous thick film was 1/20 that of non-porous thin film when the grain diameter of the porous thick film was the same as the thickness of non-porous thin film. At 973 K, “break” response time (t_b) of the resistive oxygen sensor was found by experiment to be 109 ms. It was concluded that the response of the resistive oxygen sensor prepared in this study was strongly controlled by diffusion at 923–1023 K, since the experiment revealed that the slope of plot of log f versus log H(f) in the high f region was approximately −0.5. At 923–1023 K, the diffusion coefficient of oxygen vacancy in porous ceria (D_V) was expressed as follows: D_V (m²s⁻¹) = 5.78 × 10⁻⁴ exp(−1.94 eV/kT). At 1023 K, the surface reaction coefficient (K) was found to exceed 10⁻⁴ m/s.     

Bulk property of 1/f noise for piezoresistive Ni/Cr thin films in pressure sensors on flexible substrate

In the current paper, we report the 1/f noise measurement of nichrome Ni/Cr (80/20 %) thin films for two types of pressure sensors: relative pressure sensors and absolute pressure sensors. The normalized Hooge coefficient for nichrome thin film was found to be 1.89 × 10^?10 for the relative pressure sensors and 4.64 × 10^?11 for the absolute pressure sensors. We demonstrated that the normalized Hooge coefficient multiplied by the volume of the thin film become constant regardless of the sensor types and discuss the complexities arise for the miniaturization of MEMS sensors due to the bulk noise properties of piezoresistive thin films.     

Using a PEDOT:PSS modified electrode for detecting nitric oxide gas

PEDOT:PSS thick films, prepared by the drop-coated method, were used in this study for sensing nitric oxide (NO) gas. The thickness of PEDOT-PSS film was controlled by dropping different volumes of PEDOT-PSS solution to improve the response of PEDOT-PSS film. Due to its porous structure, the thicker the PEDOT-PSS film is, the higher the noticeable surface area. Thus, a larger response is found. However, since the concentration of NO gas used was low (10 ppm), the effect of the surface area was not noticeable when the thickness of the film was greater than 5 μm. In the range of 2.5–10 ppm NO, the relationship between the response of the PEDOT-PSS film and the NO concentration was linear. The limit of detection (S/N = 3), response time (t₉₅), and recovery time (t₉₅) were about 350 ppb, 527 s, and 1780 s, respectively. The response of PEDOT-PSS film to 10 ppm NO gas was dramatically affected by the presence of either O₂ or CO. The standard deviation, with respect to the sensitivity of the NO gas sensor based on PEDOT:PSS film, was 2.2%. The sensitivity of the sensor remained at about 74.5% that of a fresh one.     

Gas sensing behavior of polyvinylpyrrolidone-modified ZnO nanoparticles for trimethylamine

Gas sensors based on polyvinylpyrrolidone (PVP)-modified ZnO nanoparticles with different molar ratios of Zn²⁺: PVP were prepared by a sol–gel method. Morphology of the sensors was characterized by field emission-scanning electron microscopy (FE-SEM), which indicated that the sensor with a molar ratio of Zn²⁺: PVP = 5:5 showed uniform morphology. Moreover, the sensor exhibited fairly excellent sensitivity and selectivity to trimethylamine (TMA). The response and recovery time of the sensor were 10 and 150 s, respectively. Finally, the mechanism for the improvement in the gas sensing properties was discussed.     

Fabrication and flow-sensor application of flexible thermal MEMS device based on Cu on polyimide substrate

A Cu on polyimide (COP) substrate was proposed as a MEMS material, and the fabrication process for a flexible thermal MEMS sensor was developed. The COP substrate application to MEMS devices has the advantage that typical MEMS structures fabricated in a SOI wafer in the past—such as a diaphragm, a beam, a heater formed on a diaphragm—can also be easily produced in the COP substrate in the flexible fashion. These structures can be used as the sensing element in various physical sensors, such as flow, acceleration, and shear stress sensors. A flexible thermal MEMS sensor was produced by using a lift-off process and sacrificial etching of a copper layer on the COP substrate. A metal film working as a flow sensing element was formed on a thin polyimide membrane produced by the sacrificial etching. The fabricated flexible thermal MEMS sensor was used as a flow sensor, and its characteristics were evaluated. The obtained sensor output versus the flow rate curve closely matched the approximate curve derived using King’s law. The rising and falling response times obtained were 0.50 and 0.67 s, respectively.

     

A wet-chemical process to form palladium oxide sensitiser layer on thin film zinc oxide based LPG sensor

The liquid petroleum gas (LPG) sensitivity characteristics of zinc oxide (ZnO) films have been studied for an optimised level of Pd loading. The sensor element comprises of a layer of chemically deposited ZnO on which an overlayer of palladium (Pd) sensitiser was formed by a chemical dipping technique. The room temperature resistance of the film was found to be a sensitive function of the quantity of palladium loading, which could be optimised for stable and reproducible sensor properties. The sensor characteristics that are dependent also on the operating temperature could be optimised at around 250 °C. A sensitivity of 88% was observed in presence of 1.6 vol.% LPG in air at this optimum temperature with reasonably fast response and recovery times.     

Fabrication of wireless sensors on flexible film using screen printing and via filling

Wireless sensors are fabricated on flexible plastic films by means of screen printing and via-hole filling. The wireless sensors are battery free with data and power transmission functions. The sensors, fabricated on polyethylene terephtalate films, are designed based on RFID technology. Using an additive patterning process known as screen printing, metallization on polymer films is created. Both sides of a polymer film are printed with metallic patterns and connected with micro vias filled with conductive paste. One side of the film consists of printed electrical traces for discrete components like resistors and transistors that would be mounted onto it; the other side consists of a printed inductive coil used for wireless data and power transmission. The micro vias, which have a diameter of 120 μm, are formed by mechanical punching and filled with conductive silver paste. The size of one sensor unit is approximately 2 cm × 1.5 cm; an array of 4 × 7 sensor units are printed over an area of 15 cm × 15 cm on a PET film. Details of manufacturing processes, component assembly and functionality test are presented in this paper.     

Necked ZnO nanoparticle-based NO2 sensors with high and fast response

The NO₂ gas sensing characteristics of semiconductor type gas sensors with channels composed of necked ZnO nanoparticles (NPs) were investigated in this study. The heat treatment of the NPs at 400 °C led to their necking and coarsening. The response of the necked-NP-based sensors was as high as 100 when exposed to 0.2 ppm of NO₂ at 200 °C. As the concentration of NO₂ increased to 5 ppm, their response was enhanced to approximately 400. During the repeated injection of NO₂ gas with a concentration of 0.4 ppm, the sensors exhibited stable response characteristics. Furthermore, the 90% response and recovery times of the gas sensor were as fast as 13 and 10 s, respectively. These observations indicate that the non-agglomerated necking of the NPs induced by the heat treatment significantly enhances the gas sensing characteristics of the NP-based gas sensors.     

One-step fabrication of a polyaniline nanofiber vapor sensor

A single-step, bottom-up technique has been used to fabricate sensors, based on conducting polymer nanofibers. A small amount of an aqueous solution containing aniline, a dopant, and an oxidant was placed on an interdigitated electrode array. Ultraviolet (UV)-irradiation of the solutions affected polymerization, yielding a highly porous film of polyaniline nanofibers with a mean diameter of around 100 nm and a length on the order of 1 μm. Solutions that were not irradiated formed bulk-like polyaniline (PANI) films. Nanofibers and bulk polyaniline sensors were exposed to chloroform, a weak proton donor; to toluene, a vapor that causes polymer swelling; and to triethylamine, which alters the doping level. Because of their higher surface areas, the response times of the fiber sensors were about a factor of 2 faster, with the current variations up to 4 times larger than those of the bulk polyaniline sensors. These results suggest methods for the advancement of simple and environment-friendly production of organic nanofiber-based sensors and electronic devices.     

Gas sensors based on anodic tungsten oxide

Nanostructured porous tungsten oxide materials were synthesized by the means of electrochemical etching (anodization) of tungsten foils in aqueous NaF electrolyte. Formation of the sub-micrometer size mesoporous particles has been achieved by infiltrating the pores with water. The obtained colloidal anodic tungsten oxide dispersions have been used to fabricate resistive WO₃ gas sensors by drop casting the sub-micrometer size mesoporous particles between Pt electrodes on Si/SiO₂ substrate followed by calcination at 400 °C in air for 2 h. The synthesized WO₃ films show slightly nonlinear current-voltage characteristics with strong thermally activated carrier transport behavior measured at temperatures between −20 °C and 280 °C. Gas response measurements carried out in CO, H₂, NO and O₂ analytes (concentration from 1 to 640 ppm) in air as well as in Ar buffers (O₂ only in Ar) exhibited a rapid change of sensor conductance for each gas and showed pronounced response towards H₂ and NO in Ar and air, respectively. The response of the sensors was dependent on temperature and yielded highest values between 170 °C and 220 °C.     

High-performance liquefied petroleum gas sensing based on nanostructures of zinc oxide and zinc stannate

Toxic and combustible gas detection plays a major role in environmental air quality monitoring. Real-time monitoring of hazardous gases and signal of accidental leakages is of great importance owing to the concern for safety requirements in industries and household applications. A simple and economical method for the fabrication of highly sensitive zinc oxide (ZnO) nanorods based gas sensors for detecting low concentrations of Liquefied Petroleum Gas (LPG) was studied in this work. Platinum (Pt) nanoparticles were deposited on the sensing medium which acts as catalysts to improve the sensor performance. The change in electrical resistance of the metal oxide semiconductor for varying concentrations of LPG was measured. Maximum response of 59% was achieved for 9000 ppm LPG at 250 °C. Further to improve the sensing performance of the sensor towards LPG, surface modification of ZnO nanorods using zinc stannate (Zn₂SnO₄) microcubes was performed. High response of 63% was observed for 3000 ppm LPG at 250 °C. Significant improvement in response of the sensor with Zn₂SnO₄ microcubes on ZnO nanorods was observed when compared to sensor with ZnO nanorods.     

Sensing properties of organised films based on a bithiophene derivative

Highly reproducible optic and electrochemical sensors have been developed using organised films from a polar bithiophene derivative, the 5-(dimethylamino)-5′-nitro-2,2′-bithiophene (Me₂N–T₂–NO₂). The strength of the molecular dipole moment of this push–pull end-capped bithiophene has permitted to obtain highly ordered, homogeneous and reproducible films by using both the Langmuir–Blodgett and the casting techniques. The organisation of the molecules in LB films and cast films has been established by means of UV–vis, infrared and Raman spectroscopy and by AFM.Me₂N–T₂–NO₂ thin films possess appealing optical and electrochemical sensing capabilities. UV–vis spectra can be modified in the presence of a variety of volatile organic compounds and the sensitivity is related to the polarity of the gas analysed. Films can also be used as electrochemical sensors because the characteristics of the current/potential curves are sensitive to the nature of the electrolytic solution. The spectral changes accompanying the applied voltage could be used to produce ionochromic sensor electrodes.The structure of the films has an important impact in the sensing properties of the films and in their stability. The optical and electrochemical sensing properties of Langmuir–Blodgett films are more reproducible than those observed in cast films. This makes films prepared using the LB technique to be preferred as sensing devices. However the casting technique provides a fast method to obtain cheap and highly ordered sensors.     

Design and optimization of heating plate for metal oxide semiconductor gas sensor

A thin film was coated onto the top of the heating electrodes to reduce the power consumption and improve the uniformity of temperature distribution. Finite element simulation software COMSOL was used to simulate the effect of coating materials and dependence of thicknesses of the coating film on the power consumption of the heating plate. On the basis of simulation, the temperature distribution of different heating plates was measured using infrared thermography. Experiments have showed that the power consumption of the heating plate can be significantly reduced and the temperature uniformity is promoted with adding the coating film on the top of the heating electrodes. The response of the gas sensor based on PdO-WO₃ nanoparticles was characterized with analyte of acetone. It was found that the addition of the coating film could enhance the response to acetone. In addition, the response speed of sensors was investigated with coating films and the results indicated that with the coating film sensor response speed became faster.

     

Thin polymer film based rapid surface acoustic wave humidity sensors

Polyvinyl alcohol (PVA) and polyvinyl pyrrolidone (PVP) thin films, deposited on the surface of glass slides, were studied using transmission FTIR spectroscopy upon varying relative humidity (RH) from 2 to 70%. The obtained data revealed fast dynamics of water vapor adsorption-desorption with responses on the order of several seconds. Based on the fast FTIR signal intensity changes versus RH, it was proposed that a similar rapid response can be achieved for PVA and PVP coated SAW devices due to changes in mass-loading and film viscoelastic properties upon absorption of water vapor in the films. Sub-micron thickness films were spin-coated onto the surface of LiNbO₃ SAW substrates. Both PVA and PVP based humidity sensors revealed prompt reversible response to variations in humidity, although PVP-based device demonstrated better sensor parameters with total insertion loss variation of about 50 dB over the studied RH range and response time 1.5 s for the humidity step 5-95% (recovery time - 2.5 s), representing one of the fastest SAW-based humidity sensors reported to date.