Mid-infrared photodetectors based on GaAsSb-capped InAs quantum dots

Quantum dot infrared photodetectors (QDIPs) are very attractive for many applications such as infrared imaging, remote sensing and gas sensing, thanks to its promising features such as high temperature operation, normal incidence response and low dark current [1]. However, the key issue is to obtain a high-quality active region which requires an optimization of the nanostructure. By using GaAsSb capping layer, InAs QDs have improved their optical emission in the range between 1.15 and 1.3 m (at Sb composition of 14 %), due to a reduction of a compressive strain in QD and an increment of a QD height [2]. In this work, we have demonstrated strong and narrow intraband photoresponses at ~ 5 m from GaAsSb-capped InAs/GaAs QDIPs under normal light-incidence.

Photoconductivity and Electro-Optical Properties of Wide Band Gap Metal Oxides

The PhD activity described in this Thesis was focused on the study of metal-oxide wide-bandgap materials, aiming at fabricating new optoelectronic devices such as solar-blind UV photodetectors, high power electronics, and gas sensors. Photocurrent spectroscopy and DC photocurrent time evolution were used to investigate the performance of prototypes under different atmospheres, temperatures and excitation wavelengths (or dark conditions). Cathodoluminescence, absorption spectroscopy, XRD and SEM were used to assess structural, morphologic, electrical and optical properties of materials. This thesis is divided into two main sections, each describing the work done on a different metal-oxide semiconductor. 1) MOVPE-grown Ga2O3 thin films for UV solar-blind photodetectors and high power devices The semiconducting oxides, among them Ga2O3, have been employed for several decades as transparent conducting oxide (TCO) electrodes for fabrication of solar cells, displays, electronic, and opto-electronic devices. The interest was mainly confined to such applications, as these materials tend to grow intrinsically n-type, and attempts to get an effective p-type doping has consistently failed. The key requirements of TCO electrodes are indeed high electrical conductivity and good transparency, while crystallographic perfection is a minor issue. Furthermore, for a long period no high-quality substrates and epi-layers were available, which in turn impeded the development of a truly full-oxide electronics. Recently, Ga2O3 has attracted renewed interest, as large single crystals and high-quality homo- and hetero-epitaxial layers became available, which paved the way to novel application areas. Our research group spent the last two years in developing a low temperature (500-700°C) MOVPE growth procedure to obtain thin films of Ga2O3 on different substrates (Dept. of Physics and IMEM-CNR at UNIPR). We obtained a significant result growing on oriented sapphire epitaxial films of high crystalline, undoped, pure phase -Ga2O3 (hexagonal). The crystallographic properties of this phase were investigated by XRD, in order to clarify the lattice parameters of the hexagonal cell. First design and development of solar blind UV photodetectors based on -phase was carried out and the optoelectronic performance is evaluated by means of photocurrent spectroscopy. The UV-response is adequately fast and reliable to render this unusual phase a subject of great interest for future applications. The availability of a hexagonal phase of Ga2O3 stable up to 700°C, belonging to the same space group of gallium nitride, with high crystallinity and tunable electrical properties, is intriguing in view of the development of nitride-based devices, by taking advantage of the more favorable symmetry and epitaxial relationships with respect to the monoclinic β-phase. In addition, annealing at temperatures higher than 700°C demonstrate that the hexagonal phase converts totally in the monoclinic one. 2) ZnO nano-tetrapods: charge transport mechanisms and time-response in optoelectronic devices and sensors Size and morphology of ZnO at the nanometer scale play a key role in tailoring its physical and chemical properties. Thanks to the possibility of growing zinc oxide in a variety of different nanostructures, there is a great variety of applications, among which gas sensors, light emitting diodes, transparent conducting oxides, solar cells. Even if the operation of ZnO nanostructure-based devices has been recently demonstrated, the mechanisms of charge transport in these assembly is still under debate. The candidate performed an accurate investigation by photocurrent spectroscopy and DC-photocurrent time evolution of electrical response of both single-tetrapod and tetrapod-assembly devices. During the research done for this thesis, a thermal activation energy enables the performance of samples at high temperatures (above about 300°C). The energy barrier is related to the leg-to-leg interconnection in the assembly of nanotetrapods. Percolation mechanisms are responsible for both the very slow photo-response (minutes to hours or days) and the significant persistent photocurrent. Below the bandgap energy, electronic states were investigated but their contribution to the photocurrent are two-three order of magnitude lower than the band edge. Such devices are suitable for employ in photodetectors as well as in gas sensors, provided that the mechanism by which the photo-current is generated and gas adsorption on the surface modify the conductivity of the material are known.

3190-3275 nm tuneable, room temperature, external cavity InAs/AlSb Quantum Cascade Laser

We demonstrated a room temperature, tuneable, external cavity Quantum Cascade Laser for the use in compact spectroscopic gas sensing system. Wavelength tuning of 85 nm between 3190 nm and 3275 nm was achieved at room temperature.

Graphene-based D-shaped polymer FBG for highly sensitive erythrocyte detection

Graphene-based silica fiber-optic sensors, with high sensitivity, fast response, and low cost, have shown great promise for gas sensing applications. In this letter, by covering a monolayer of p-doped graphene on a D-shaped microstructured polymer fiber Bragg grating (FBG), we propose and demonstrate a novel biochemical probe sensor, the graphene-based D-shaped polymer FBG (GDPFBG). Due to the graphene-based surface evanescent field enhancement, this sensor shows high sensitivity to detect surrounding biochemical parameters. By monitoring the Bragg peak locations of the GDPFBG online, human erythrocyte (red blood cell) solutions with different cellular concentrations ranging from 0 to 104 ppm were detected precisely, with the maximum resolution of sub-ppm. Such a sensor is structurally compact, is clinically acceptable, and provides good recoverability, offering a state-of-the-art polymer-fiber-based sensing platform for highly sensitive in situ and in vivo cell detection applications.

Localized surface plasmon fiber device coated with carbon nanotubes for the specific detection of CO2

We explored the potential of a carbon nanotube (CNT) coating working in conjunction with a recently developed localized surface plasmon (LSP) device (based upon a nanostructured thin film consisting of of nano-wires of platinum) with ultra-high sensitivity to changes in the surrounding index. The uncoated LSP sensor’s transmission resonances exhibited a refractive index sensitivity of Δλ/Δn ~ -6200nm/RIU and ΔΙ/Δn ~5900dB/RIU, which is the highest reported spectral sensitivity of a fiber optic sensor to bulk index changes within the gas regime. The complete device provides the first demonstration of the chemically specific gas sensing capabilities of CNTs utilizing their optical characteristics. This is proven by investigating the spectral response of the sensor before and after the adhesion of CNTs to alkane gases along with carbon dioxide. The device shows a distinctive spectral response in the presence of gaseous CO2 over and above what is expected from general changes in the bulk refractive index. This fiber device yielded a limit of detection of 150ppm for CO2 at a pressure of one atmosphere. Additionally the adhered CNTs actually reduce sensitivity of the device to changes in bulk refractive index of the surrounding medium. The polarization properties of the LSP sensor resonances are also investigated and it is shown that there is a reduction in the overall azimuthal polarization after the CNTs are applied. These optical devices offer a way of exploiting optically the chemical selectivity of carbon nanotubes, thus providing the potential for real-world applications in gas sensing in many inflammable and explosive environments. © (2015) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE). Downloading of the abstract is permitted for personal use only.

Engineering thin films of magnetic alloys and semiconductor oxides at the nanoscale

The thesis aims to exploit properties of thin films for applications such as spintronics, UV detection and gas sensing. Nanoscale thin films devices have myriad advantages and compatibility with Si-based integrated circuits processes. Two distinct classes of material systems are investigated, namely ferromagnetic thin films and semiconductor oxides. To aid the designing of devices, the surface properties of the thin films were investigated by using electron and photon characterization techniques including Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), grazing incidence X-ray diffraction (GIXRD), and energy-dispersive X-ray spectroscopy (EDS). These are complemented by nanometer resolved local proximal probes such as atomic force microscopy (AFM), magnetic force microscopy (MFM), electric force microscopy (EFM), and scanning tunneling microscopy to elucidate the interplay between stoichiometry, morphology, chemical states, crystallization, magnetism, optical transparency, and electronic properties. Specifically, I studied the effect of annealing on the surface stoichiometry of the CoFeB/Cu system by in-situ AES and discovered that magnetic nanoparticles with controllable areal density can be produced. This is a good alternative for producing nanoparticles using a maskless process. Additionally, I studied the behavior of magnetic domain walls of the low coercivity alloy CoFeB patterned nanowires. MFM measurement with the in-plane magnetic field showed that, compared to their permalloy counterparts, CoFeB nanowires require a much smaller magnetization switching field , making them promising for low-power-consumption domain wall motion based devices. With oxides, I studied CuO nanoparticles on SnO2 based UV photodetectors (PDs), and discovered that they promote the responsivity by facilitating charge transfer with the formed nanoheterojunctions. I also demonstrated UV PDs with spectrally tunable photoresponse with the bandgap engineered ZnMgO. The bandgap of the alloyed ZnMgO thin films was tailored by varying the Mg contents and AES was demonstrated as a surface scientific approach to assess the alloying of ZnMgO. With gas sensors, I discovered the rf-sputtered anatase-TiO2 thin films for a selective and sensitive NO2 detection at room temperature, under UV illumination. The implementation of UV enhances the responsivity, response and recovery rate of the TiO2 sensor towards NO2 significantly. Evident from the high resolution XPS and AFM studies, the surface contamination and morphology of the thin films degrade the gas sensing response. I also demonstrated that surface additive metal nanoparticles on thin films can improve the response and the selectivity of oxide based sensors. I employed nanometer-scale scanning probe microscopy to study a novel gas senor scheme consisting of gallium nitride (GaN) nanowires with functionalizing oxides layer. The results suggested that AFM together with EFM is capable of discriminating low-conductive materials at the nanoscale, providing a nondestructive method to quantitatively relate sensing response to the surface morphology.

A novel gas flow sensing application using piezoelectric ZnO thin films deposited on Phynox alloy

We report on the novel flow sensing application of piezoelectric ZnO thin film deposited on Phynox alloy sensing element. Characterization of piezoelectric ZnO films deposited on Phynox (Elgiloy) substrate at different RF powers is discussed. ZnO films deposited at RF power of 100W were found to have fine c-axis orientation, possesses excellent surface morphology with lower rms surface roughness of 1.87 nm and maximum d(31) coefficient value 4.7 pm V-1. The thin cantilever strip of Phynox alloy with ZnO film as a sensing layer for flow sensing has been tested for flow rates ranging from 2 to 18 L min(-1). A detailed theoretical analysis of the experimental set-up showing the relationship between output voltage and force at a particular flow rate has been discussed. The sensitivity of now sensing element is similar to 18 mV/(L min(-1)) and typical response time is of the order of 20 m s. The sensing element is calibrated using in-house developed testing set-up. (C) 2012 Elsevier B.V. All rights reserved.

Study on sensing properties of tin oxide CO gas sensor with low power consumption

In this paper, the fabrication method of a new type of carbon monoxide gas sensor based on SnOx with low power consumption and its sensing characteristics have been reported. The electric conductance of this type of sensor evolves oscillation form regularly when the sensor is exposed to low level of CO gas. The oscillation amplitude is directly proportional to the concentration of CO gas over a wide range. The effects of relevant factors. such as. humidity, temperature and interference gases on the sensor properties were examined. The sensing oscillation response mechanism was also discussed.

Reduced graphene oxide multilayers for gas and liquid phases chemical sensing

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Gas monitoring methodology and application to CCS projects as defined by atmospheric and remote sensing survey in the natural analogue of Campo de Calatrava

CO2 capture and storage (CCS) projects are presently developed to reduce the emission of anthropogenic CO2 into the atmosphere. CCS technologies are expected to account for the 20% of the CO2 reduction by 2050. Geophysical, ground deformation and geochemical monitoring have been carried out to detect potential leakage, and, in the event that this occurs, identify and quantify it. This monitoring needs to be developed prior, during and after the injection stage. For a correct interpretation and quantification of the leakage, it is essential to establish a pre-injection characterization (baseline) of the area affected by the CO2 storage at reservoir level as well as at shallow depth, surface and atmosphere, via soil gas measurements. Therefore, the methodological approach is important because it can affect the spatial and temporal variability of this flux and even jeopardize the total value of CO2 in a given area. In this sense, measurements of CO2 flux were done using portable infrared analyzers (i.e., accumulation chambers) adapted to monitoring the geological storage of CO2, and other measurements of trace gases, e.g. radon isotopes and remote sensing imagery were tested in the natural analogue of Campo de Calatrava (Ciudad Real, Spain) with the aim to apply in CO2 leakage detection; thus, observing a high correlation between CO2 and radon (r=0,858) and detecting some vegetation indices that may be successfully applied for the leakage detection.

Optical fibre sensors with applications in gas and biological sensing

This thesis describes the study of various grating based optical fibre sensors for applications in refractive index sensing. The sensitivity of these sensors has been studied and in some cases enhanced using novel techniques. The major areas of development are as follows. The sensitivity of long period gratings (LPGs) to surrounding medium refractive index (SRI) for various periods was investigated. The most sensitive period of LPG was found to be around 160 µm and this was due to the core mode coupling to a single cladding mode but phase matching at two wavelength locations, creating two attenuation peaks, close to the waveguide dispersion turning point. Large angle tilted fibre gratings (TFGs) have similar behaviour to LPGs, in that they couple to the co-propagating cladding modes. The tilted structure of the index modulation within the core of the fibre gives rise to a polarisation dependency, differing the large angle TFG from a LPG. Since the large angle TFG couple to the cladding mode they are SRI sensitive, the sensitivity to SRI can be further increased through cladding etching using HF acid. The thinning of the cladding layer caused a reordering of the cladding modes and shifted to more SRI sensitive cladding modes as the investigation discovered. In a SRI range of 1.36 to 1.40 a sensitivity of 506.9 nm/URI was achieved for the etched large angle TFG, which is greater than the dual resonance LPG. UV inscribed LPGs were coated with sol-gel materials with high RIs. The high RI of the coating caused an increase in cladding mode effective index which in turn caused an increase in the LPG sensitivity to SRI. LPGs of various periods of LPG were coated with sol-gel TiO2 and the optimal thickness was found to vary for each period. By coating of the already highly SRI sensitive 160µm period LPG (which is a dual resonance) with a sol-gel TiO2, the SRI sensitivity was further increased with a peak value of 1458 nm/URI, which was an almost 3 fold increase compared to the uncoated LPG. LPGs were also inscribed using a femtosecond laser which produced a highly focused index change which was no uniform throughout the core of the optical fibre. The inscription technique gave rise to a large polarisation sensitivity and the ability to couple to multiple azimuthal cladding mode sets, not seen with uniform UV inscribed gratings. Through coupling of the core mode to multiple sets of cladding modes, attenuation peaks with opposite wavelength shifts for increasing SRI was observed. Through combining this opposite wavelength shifts, a SRI sensitivity was achieved greater than any single observed attenuations peak. The maximum SRI achieved was 1680 nm/URI for a femtosecond inscribed LPG of period 400 µm. Three different types of surface plasmon resonance (SPR) sensors with a multilayer metal top coating were investigated in D shape optical fibre. The sensors could be separated into two types, utilized a pre UV inscribed tilted Bragg grating and the other employed a post UV exposure to generate surface relief grating structure. This surface perturbation aided the out coupling of light from the core but also changed the sensing mechanism from SPR to localised surface plasmon resonance (LSPR). This greatly increased the SRI sensitivity, compared to the SPR sensors; with the gold coated top layer surface relief sensor producing the largest SRI sensitivity of 2111.5nm/URI was achieved. While, the platinum and silver coated top layer surface relief sensors also gave high SRI sensitivities but also the ability to produce resonances in air (not previously seen with the SPR sensors). These properties were employed in two applications. The silver and platinum surface relief devices were used as gas sensors and were shown to be capable of detecting the minute RI change of different gases. The calculated maximum sensitivities produced were 1882.1dB/URI and 1493.5nm/URI for silver and platinum, respectively. Using a DFB laser and power meter a cheap alternative approach was investigated which showed the ability of the sensors to distinguish between different gases and flow rates of those gases. The gold surface relief sensor was coated in a with a bio compound called an aptamer and it was able to detect various concentrations of a biological compound called Thrombin, ranging from 1mM to as low as 10fM. A solution of 2M NaCl was found to give the best stripping results for Thrombin from the aptamer and showed the reusability of the sensor. The association and disassociation constants were calculated to be 1.0638×106Ms-1 and 0.2482s-1, respectively, showing the high affinity of the Aptamer to thrombin. This supports existing working stating that aptamers could be alternative to enzymes for chemical detection and also helps to explain the low detection limit of the gold surface relief sensor.

Evaluation of remote sensing for the detection of landfill gas and leachate in an urban environment

The technique of remote sensing provides a unique view of the earth's surface and considerable areas can be surveyed in a short amount of time. The aim of this project was to evaluate whether remote sensing, particularly using the Airborne Thematic Mapper (ATM) with its wide spectral range, was capable of monitoring landfill sites within an urban environment with the aid of image processing and Geographical Information Systems (GIS) methods. The regions under study were in the West Midlands conurbation and consisted of a large area in what is locally known as the Black Country containing heavy industry intermingled with residential areas, and a large single active landfill in north Birmingham. When waste is collected in large volumes it decays and gives off pollutants. These pollutants, landfill gas and leachate (a liquid effluent), are known to be injurious to vegetation and can cause stress and death. Vegetation under stress can exhibit a physiological change, detectable by the remote sensing systems used. The chemical and biological reactions that create the pollutants are exothermic and the gas and leachate, if they leave the waste, can be warmer than their surroundings. Thermal imagery from the ATM (daylight and dawn) and thermal video were obtained and used to find thermal anomalies on the area under study. The results showed that vegetation stress is not a reliable indicator of landfill gas migration, as sites within an urban environment have a cover too complex for the effects to be identified. Gas emissions from two sites were successfully detected by all the thermal imagery with the thermal ATM being the best. Although the results were somewhat disappointing, recent technical advancements in the remote sensing systems used in this project would allow geo-registration of ATM imagery taken on different occasions and the elimination of the effects of solar insolation.

The investigation of vegetation change using remote sensing to detect and monitor migration of landfill gas

Decomposition of domestic wastes in an anaerobic environment results in the production of landfill gas. Public concern about landfill disposal and particularly the production of landfill gas has been heightened over the past decade. This has been due in large to the increased quantities of gas being generated as a result of modern disposal techniques, and also to their increasing effect on modern urban developments. In order to avert diasters, effective means of preventing gas migration are required. This, in turn requires accurate detection and monitoring of gas in the subsurface. Point sampling techniques have many drawbacks, and accurate measurement of gas is difficult. Some of the disadvantages of these techniques could be overcome by assessing the impact of gas on biological systems. This research explores the effects of landfill gas on plants, and hence on the spectral response of vegetation canopies. Examination of the landfill gas/vegetation relationship is covered, both by review of the literature and statistical analysis of field data. The work showed that, although vegetation health was related to landfill gas, it was not possible to define a simple correlation. In the landfill environment, contribution from other variables, such as soil characteristics, frequently confused the relationship. Two sites are investigated in detail, the sites contrasting in terms of the data available, site conditions, and the degree of damage to vegetation. Gas migration at the Panshanger site was dominantly upwards, affecting crops being grown on the landfill cap. The injury was expressed as an overall decline in plant health. Discriminant analysis was used to account for the variations in plant health, and hence the differences in spectral response of the crop canopy, using a combination of soil and gas variables. Damage to both woodland and crops at the Ware site was severe, and could be easily related to the presence of gas. Air photographs, aerial video, and airborne thematic mapper data were used to identify damage to vegetation, and relate this to soil type. The utility of different sensors for this type of application is assessed, and possible improvements that could lead to more widespread use are identified. The situations in which remote sensing data could be combined with ground survey are identified. In addition, a possible methodology for integrating the two approaches is suggested.

Reversed bias Pt/nanostructured ZnO Schottky diode with enhanced electric field for hydrogen sensing

In this paper, the effect of electric field enhancement on Pt/nanostructured ZnO Schottky diode based hydrogen sensors under reverse bias condition has been investigated. Current-voltage characteristics of these diodes have been studied at temperatures from 25 to 620 °C and their free carrier density concentration was estimated by exposing the sensors to hydrogen gas. The experimental results show a significantly lower breakdown voltage in reversed bias current-voltage characteristics than the conventional Schottky diodes and also greater lateral voltage shift in reverse bias operation than the forward bias. This can be ascribed to the increased localized electric fields emanating from the sharp edges and corners of the nanostructured morphologies. At 620 °C, voltage shifts of 114 and 325 mV for 0.06% and 1% hydrogen have been recorded from dynamic response under the reverse bias condition. © 2010 Elsevier B.V. All rights reserved.