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.     

Optical parameters of calix[4]arene films and their response to volatile organic vapors

The Langmuir-Blodgett (LB) technique was employed to produce thin LB films using an amphiphilic calix-4-resorcinarene onto different substrates such as quartz, gold coated glass and quartz crystals. The characteristics of the calix LB films are assessed by UV-visible, quartz crystal microbalance (QCM) and surface plasmon resonance (SPR) measurements. UV-vis and QCM measurements indicated that this material deposited very well onto the solid substrates with a transfer ratio of >0.95. Using SPR data, the thickness and refractive index of this LB film are determined to be 1.14 nm/deposited layer and 1.6 respectively. The sensing application of calixarene LB films towards volatile organic vapors such as chloroform, benzene, toluene and ethanol vapors is studied by the SPR technique. The response of this LB film to saturated chloroform vapor is much larger than for the other vapors. The response is fast and fully recoverable. It can be proposed that this sensing material deposited onto gold coated glass substrates has a good sensitivity and selectivity for chloroform vapor. This material may also find potential applications in the development of room temperature organic vapor sensing devices.     

Flexible sensorial system based on capacitive chemical sensors integrated with readout circuits fully fabricated on ultra thin substrate

In this paper we present the design and fabrication of a fully flexible sensorial system, composed of three different sensor units implemented on an ultrathin polyimide substrate of 8 μm thick. Each unit is composed by a capacitive chemical sensor integrated with readout electronics. The sensors are parallel plate capacitors with the top electrode properly patterned to allow analytes diffusion into the dielectric that acts as chemical interactive material. Three different polymers, poly(tetrafluoroethene) (PTFE), poly(methyl 2-methylpropenoate) (PMMA) and benzocyclobutene (BCB), were used as dielectrics. A ring oscillator circuit, implemented with polysilicon thin film transistors (PS-nTFT), was used to convert the capacitance variations into frequency shifts. The electronic tests show oscillating frequencies of about 211 ± 2 kHz and negligible frequency shifts under different bending radius conditions. Furthermore, system response to some alcohols concentrations (Methanol, ethanol, 1-butanol, and 1-propanol) is reported and data analysis proves that the system is able to discriminate methanol from ethanol.     

Shrink-induced ultrasensitive mercury sensor with graphene and gold nanoparticles self-assembly

Here we report an ultrasensitive trace mercury(II) micro sensor based on heat-shrinkable polymer (polyolefins, PO). The layer-by-layer self-assembly (LBL SA) method was employed to modify mixed gold nanoparticle (Au NPs) and graphene solution on a micro gold electrode with PO substrate. The unique wrinkle structure of the electrode surface and superior properties of modification film enhanced the performance of LBL SA graphene–Au NPs shrink sensor greatly in determination of Hg(II) using anodic stripping voltammetry (ASV): compared with a shrink gold electrode without surface modification, the sensitivity was improved for about 3.7 times from 0.197 to 0.721 μA/ppb; compared with a same-sized sensor without surface modification nor shrink, the sensitivity was improved for over 50 times. This sensor’s detection limit of Hg(II) was achieved as 0.931 ppb with a sensitivity of 0.721 μA/ppb. This simple but highly sensitive sensor can be widely used in applications of on-line environmental monitoring of Hg(II).

     

An Aptameric Microfluidic System for Specific Purification, Enrichment, and Mass Spectrometric Detection of Biomolecules

We present an innovative microfluidic system that accomplishes specific capture, enrichment, and isocratic elution of biomolecular analytes with coupling to label-free mass spectrometric detection. Analytes in a liquid phase are specifically captured and enriched via their affinity binding to aptamers, which are immobilized on microbeads packed inside a microchamber. Exploiting thermally induced reversible disruption of aptamer–analyte binding via on-chip temperature control with an integrated heater and temperature sensor, the captured analytes are released into the liquid phase and then isocratically eluted and transferred via a microfluidic flow gate for detection by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). The utility of the device is demonstrated using adenosine monophosphate (AMP) as a model analyte. Experimental results indicate that the device is capable of purifying and enriching the analyte from a sample mixed with nonspecific analytes and contaminated with salts. In addition, thermally induced analyte release is performed at modest temperatures (45 $^{circ}hbox{C}$), and mass spectra obtained from MALDI-MS demonstrate successful detection of AMP at concentrations as low as 10 nM following enrichment by consecutive infusion of a diluted sample.$hfill$[2009-0176]      

Poly(3-hexylthiophene) and hexafluoro-2-propanol-substituted polysiloxane based OFETs as a sensor for explosive vapor detection

The organic field effect transistors (OFETs) with regioregular poly 3-hexylthiophene (rr-P3HT) and hexafluoro-2-propanol-substituted polysiloxane (SXFA) as an organic layer, have been used for detection of explosive vapors with excellent sensitivity of less than 70 ppt for 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) and less than 100 ppt for 2,4,6-trinitrotoluene (TNT). The sensor response (% change in saturation current) was found to be 125 ± 10% for TNT and 90 ± 10% for RDX. It was also observed that the incorporation of Cu^II tetraphenylporphyrin (CuTPP) into rr-P3HT/SXFA matrix resulted in an improved selectivity for the vapors of nitro based analytes (TNT, RDX and DNB) as compared to the vapors of non explosive oxidizing agents such as nitrobenzene (NB), benzoquinone (BQ) and benzophenone (BP). This is attributed to the increased binding of the vapors containing nitro compound to the thin films due to the presence of CuTTP. Spin coated thin films were further characterized by Atomic Force Microscopy (AFM) and Electrostatic Force Microscopy (EFM).     

Analyte selective response in solution-deposited tetrabenzoporphyrin thin-film field-effect transistor sensors

Organic thin film transistor (OTFT) chemical sensors rely on the specific electronic structure of the organic semiconductor (OSC) film for determining sensor stability and response to analytes. The delocalized electronic structure is influenced not only by the OSC molecular structure, but also the solid state packing and film morphology. Phthalocyanine (H₂Pc) and tetrabenzoporphyrin (H₂TBP) have similar molecular structures but different film microstructures when H₂Pc is vacuum deposited and H₂TBP is solution deposited. The difference in electronic structures is evidenced by the different mobilities of H₂TBP and H₂Pc OTFTs. H₂Pc has a maximum mobility of 8.6 × 10⁻⁴ cm² V⁻¹ s⁻¹ when the substrate is held at 250 °C during deposition and a mobility of 4.8 × 10⁻⁵ cm² V⁻¹ s⁻¹ when the substrate is held at 25 °C during deposition. Solution deposited H₂TBP films have a mobility of 5.3 × 10⁻³ cm² V⁻¹ s⁻¹, which is consistent with better long-range order and intermolecular coupling within the H₂TBP films compared to the H₂Pc films. Solution deposited H₂TBP also exhibits a textured film morphology with large grains and an RMS roughness 3-5 times larger than H₂Pc films with similar thicknesses. Despite these differences, OTFT sensors fabricated from H₂TBP and H₂Pc exhibit nearly identical analyte sensitivity and analyte response kinetics. The results suggest that while the interactions between molecules in the solid state determine conductivity, localized interactions between the analyte and the molecular binding site dominate analyte binding and determine sensor response.     

压电式免疫传感器检测小鼠IgG气溶胶

为优化压电式免疫传感器用于生物大分子气溶胶的检测效果,采用循环伏安法在石英晶体金电极上先聚合一层聚苯胺膜,然后,聚合一层聚间苯三酚膜,构建了双层聚合物膜,用于固定羊抗小鼠IgG抗体。配合超声雾化法产生生物大分子气溶胶,研制了一种直接气相检测小鼠IgG抗体的谐振式免疫传感器。结果表明:该传感器对小鼠IgG的响应快,检测时间为3m in;在0.42~4.8 g.L-1范围内,具有较好的线性关系;稳定性高,经固定的抗体可以保持活性60 d以上。     

A novel multisensing optical approach based on a single phthalocyanine thin films to monitoring volatile organic compounds

This paper reports the use of optical trasduction techniques to characterise solid state chemo-optical sensors prepared by Langmuir–Schäfer technique (LS) in thin film form based onto Cu(II) tris-(2,4-di-t-amylphenoxy)-(12-hydroxy-1,4,7,10-tetraoxadodecyl)-phthalocyanine macromolecules CuPcOH as active layers. The study consists in the UV–vis optical absorption monitoring of the active LS layers in the presence of specific five volatile organic compounds (VOCs) mixed in dry air in controlled atmosphere; in particular tert-butylamine, methanol, ethanol, hexane and ethyl acetate, all analytes of interests in the food quality control. The UV–vis spectra have been monitored by recording the dynamic variation in the integral of the absorbance curves in well defined spectral regions: 300–400 nm, 550–600 nm, 600–640 nm, 640–700 nm, covering the whole spectrum and centred around the typical absorption bands of phthalocyanine thin films. This simultaneous UV–vis four channel monitoring allowed to use only one active layer as sensing element where each selected spectral region generates independent sensors. The dependency of the above mentioned outputs towards the analytes has been discussed. A base optical characterisation of the investigated LS thin films has been performed.     

Design and fabrication of micro-nano fusion gas sensor based on two-beam micro-hotplatform

Micro-nano fusion gas sensors integrating two-beam micro-hotplatform with nanostructured porous film were fabricated in this study. The micro-hotplatform (MHP) was manufactured using standard micro-electro-mechanical systems technology in wafer runs. Based on a colloidal crystal template method, highly ordered porous tin dioxide films were in situ grown on the MHP. The as-fabricated sensors achieved the highest response at 250 °C with power consumption only 24 mW. Due to the low thermal capacity and ordered porous thin films of the sensor, the response time was about 2 s. The sensors are sensitive to ethanol in a large range from 0.1 to 250 ppm. The developed sensor here with high performance is an excellent candidate which can be incorporated into portable devices for alcohol detection such as breath analyzers.

     

Modeling Carbon-Black/Polymer Composite Sensors

Conductive polymer composite sensors have shown great potential in identifying gaseous analytes. To more thoroughly understand the physical and chemical mechanisms of this type of sensor, a mathematical model was developed by combining two sub-models: a conductivity model and a thermodynamic model, which gives a relationship between the vapor concentration of analyte(s) and the change of the sensor signals. In this work, 64 chemiresistors representing eight different carbon concentrations (8-60 vol% carbon) were constructed by depositing thin films of a carbon-black/polyisobutylene composite onto concentric spiral platinum electrodes on a silicon chip. The responses of the sensors were measured in dry air and at various vapor pressures of toluene and trichloroethylene. Three parameters in the conductivity model were determined by fitting the experimental data. It was shown that by applying this model, the sensor responses can be adequately predicted for given vapor pressures; furthermore the analyte vapor concentrations can be estimated based on the sensor responses. This model will guide the improvement of the design and fabrication of conductive polymer composite sensors for detecting and identifying mixtures of organic vapors.     

可鉴别室内有害气体的铟锡氧化物薄膜气敏特性研究

采用无机试剂SnCl2·2H2O及InCl3*4H2O为原料,用溶胶-凝胶提拉法制备了铟锡比不同的氧化铟锡薄膜构成的气敏传感器阵列,并对薄膜的电学性能及气敏性能进行了表征.结果表明,不同铟锡比组成的氧化铟锡薄膜不但载流子浓度不同,而且导电类型也不同,即阵列中每个传感器薄膜的载流子浓度和导电类型是不同的.当气体分子与阵列中的传感器表面接触时,由于载流子种类、载流子浓度、费米能级等的不同,导致电荷转移情况也不同,使得阵列具有很好的选择性.通过对甲醛、苯、甲苯、二甲苯的测试,证明此阵列对四种室内污染气体具有较好的选择性.     

Palladium nanoclusters-coated polyfuran as a novel sensor for catecholamine neurotransmitters and paracetamol

A promising electrochemical biosensor was developed by electrodeposition of palladium nanoclusters on polyfuran film modified platinum electrode. This biosensor electrode was used to determine some catecholamines, namely dopamine, epinephrine and norepinephrine, ascorbic acid and paracetamol. The method of formation of the polymer film and deposition of Pd particles plays a key role in the electroactivity of the resulting hybrid material. This sensor effectively resolved the overlapping anodic peaks of ascorbic acid (AA), dopamine (DA) and paracetamol (ACOP) into three well-defined voltammetric peaks in differential pulse voltammetry analysis. The detection limit of DA in the absence and presence of AA and ACOP are eventually the same which indicates that the oxidation processes of DA, AA and ACOP are independent and that the simultaneous measurements of the three analytes are possible without interference. The electrodeposition of Pd on polyfuran improved exceptionally the detection limit about four decades. Moreover, diffusion coefficient measurements confirmed the fast electron transfer kinetics of the electrochemical oxidation of the analyte molecules at the sensor/solution interface. It is very interesting to note that the electrocatalytic effect of PF/Pd composite has been increased to be sometimes 21 times that of the pristine PF which has been considered for a long time to be of low conductivity and attracted low attention as a result of the difficulty of its formation and poor conductivity.     

LiNbO3棱镜耦合双金属薄膜表面等离子共振传感器

高折射率铌酸锂(LiNbO3)(2.202)为棱镜耦合激发的角度调制型表面等离子共振传感器,利用反射率公式优化单层银膜、金膜和双层银/金膜传感器薄膜的厚度,分别计算了优化厚度的传感器在检测样品折射率为1.330时的共振角、灵敏度、峰值半宽度(FWHM)和品质因数(FOM),理论计算表明:双层金属薄膜,随着金膜厚度的增加,传感器灵敏度增加,但峰值半宽度增加,品质因数下降.综合考虑,选择银/金(41/5)优化组合,传感器品质因数为优化的单层金膜(47 nm)传感器品质因数的2倍以上,另外,与常用的BK7玻璃棱镜耦合相比,LiNbO3棱镜耦合具有较大的样品动态检测范围.优化厚度的传感器实验检测糖水浓度表明:糖水浓度与共振角为线性比例关系.     

Towards the development of a portable device for the monitoring of gaseous toxic industrial chemicals based on a chemical sensor array

The ability of chemical sensor array (CSA) technology to identify multiple gaseous analytes and differentiate between various analyte concentrations has been documented. To date, CSA response was monitored using a flatbed scanner driven by a personal computer. While this system is suitable for use in a laboratory setting it is not suitable for use in the field for environmental monitoring. We describe herein progress made towards the development of a rapid, inexpensive, portable, battery-operated, handheld device based on CSA technology for the detection of toxic industrial compounds (TICs). This prototype successfully differentiates between four TICs at both permissible exposure limit (PEL) and immediately dangerous to life and health (IDLH) concentrations, and three interferent gases, in less than 2 min.     

Composites of carboxylate-capped TiO2 nanoparticles and carbon black as chemiresistive vapor sensors

Titanium (IV) dioxide (TiO₂) nanoparticles (NPs) with a 1-5 nm diameter were synthesized by a sol-gel method, functionalized with carboxylate ligands, and combined with carbon black (CB) to produce chemiresistive chemical vapor sensor films. The TiO₂ acted as an inorganic support phase for the swellable, organic capping groups of the NPs, and the CB imparted electrical conductivity to the film. Such sensor composite films exhibited a reproducible, reversible change in relative differential resistance upon exposure to a series of organic test vapors. The response of such chemiresistive composites was comparable to, but generally somewhat smaller than, that of thiol-capped Au NPs. For a given analyte, the resistance response and signal-to-noise ratio of the capped TiO₂-NP/CB composites varied with the identity of the capping ligand. Hence, an array of TiO₂-NP/CB composites, with each film having a compositionally different carboxylate capping ligand, provided good vapor discrimination and quantification when exposed to a series of organic vapors. Principal components analysis of the relative differential resistance response of the sensor array revealed a clear clustering of the response for each analyte tested. This approach expands the options for composite-based chemiresistive vapor sensing, from use of organic monomeric or polymeric sorbent phases, to use of electrically insulating capped inorganic NPs as the nonconductive phase of chemiresistive composite vapor sensors.     

Characterization of layer-by-layer nano self-assembled carbon nanotube/polymer film sensor for ethanol gas sensing properties

This paper reported a multi-wall carbon nanotubes (MWNTs)/polymer film-based sensor for ethanol gas detection. The film sensor was fabricated using layer-by-layer self-assembly method on the substrate with interdigital electrodes structure. The surface morphology of the self-assembled membranes shows a high strength, dense and random network structures, and the electrical properties of MWNTs/polymer film sensor were investigated. Its ethanol gas-sensing properties with varying gas concentration are characterized at room temperature. The experiment results shown that carboxylic groups attached on the MWNTs surface and the expansion of polyelectrolyte interlayer lead to a prompt response and sensitive resistance change when the sensor exposed to ethanol gas, indicating the unique advantages of layer-by-layer self-assembly of MWNTs/polymer film sensors in prospective application.     

Sol–gel derived polycrystalline Cr1.8Ti0.2O3 thick films for alcohols sensing application

The powder sample of Cr_1.8Ti_0.2O₃ (CTO) was obtained by a sol–gel method. The thick films were developed on identical ceramic tubes of 4 mm length comprising of two Au-electrodes and printing an eight-layer film prepared by mixing CTO with glass powder and -terpinol as an organic vehicle. X-ray powder diffraction (XRD) patterns showed the formation of a single phase. The scanning electron microscope (SEM) images of the ceramic sensor treated at 850 °C revealed that the grain size was larger than 400 nm for the individual isolated grains on the surface, and the agglomerated dense spheroidal platelets had the size of 1–4 μm in diameter. The AC impedance measurement in ambient air showed that the resistance decreased nearly by two orders of magnitude with an increase in temperature in the range of 400–600 °C for both the powder sample and the thick film, and the activation energy E_a derived from the measurement was found to be 0.35 and 0.36 eV for the powder and the film, respectively. The films were exposed to various concentrations of alcohols (0.4–1.2 ppm of methanol and 1.0–5.0 ppm of ethanol), followed by determination of sensor response, sensitivity and reversibility and reproducibility. The origin of the gas response was attributed to the surface reaction of R-OH (R = methyl and ethyl group) with O⁻_(ads) to form adsorbed R-CHO, which was desorbed as a gas at 400 °C after the sensor departing from the gas.     

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.     

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.