Development of gas sensing technology for ground and airborne applications powered by solar energy : methodology and experimental results

Monitoring gases for environmental, industrial and agricultural fields is a demanding task that requires long periods of observation, large quantity of sensors, data management, high temporal and spatial resolution, long term stability, recalibration procedures, computational resources, and energy availability. Wireless Sensor Networks (WSNs) and Unmanned Aerial Vehicles (UAVs) are currently representing the best alternative to monitor large, remote, and difficult access areas, as these technologies have the possibility of carrying specialised gas sensing systems, and offer the possibility of geo-located and time stamp samples. However, these technologies are not fully functional for scientific and commercial applications as their development and availability is limited by a number of factors: the cost of sensors required to cover large areas, their stability over long periods, their power consumption, and the weight of the system to be used on small UAVs. Energy availability is a serious challenge when WSN are deployed in remote areas with difficult access to the grid, while small UAVs are limited by the energy in their reservoir tank or batteries. Another important challenge is the management of data produced by the sensor nodes, requiring large amount of resources to be stored, analysed and displayed after long periods of operation. In response to these challenges, this research proposes the following solutions aiming to improve the availability and development of these technologies for gas sensing monitoring: first, the integration of WSNs and UAVs for environmental gas sensing in order to monitor large volumes at ground and aerial levels with a minimum of sensor nodes for an effective 3D monitoring; second, the use of solar energy as a main power source to allow continuous monitoring; and lastly, the creation of a data management platform to store, analyse and share the information with operators and external users. The principal outcomes of this research are the creation of a gas sensing system suitable for monitoring any kind of gas, which has been installed and tested on CH4 and CO2 in a sensor network (WSN) and on a UAV. The use of the same gas sensing system in a WSN and a UAV reduces significantly the complexity and cost of the application as it allows: a) the standardisation of the signal acquisition and data processing, thereby reducing the required computational resources; b) the standardisation of calibration and operational procedures, reducing systematic errors and complexity; c) the reduction of the weight and energy consumption, leading to an improved power management and weight balance in the case of UAVs; d) the simplification of the sensor node architecture, which is easily replicated in all the nodes. I evaluated two different sensor modules by laboratory, bench, and field tests: a non-dispersive infrared module (NDIR) and a metal-oxide resistive nano-sensor module (MOX nano-sensor). The tests revealed advantages and disadvantages of the two modules when used for static nodes at the ground level and mobile nodes on-board a UAV. Commercial NDIR modules for CO2 have been successfully tested and evaluated in the WSN and on board of the UAV. Their advantage is the precision and stability, but their application is limited to a few gases. The advantages of the MOX nano-sensors are the small size, low weight, low power consumption and their sensitivity to a broad range of gases. However, selectivity is still a concern that needs to be addressed with further studies. An electronic board to interface sensors in a large range of resistivity was successfully designed, created and adapted to operate on ground nodes and on-board UAV. The WSN and UAV created were powered with solar energy in order to facilitate outdoor deployment, data collection and continuous monitoring over large and remote volumes. The gas sensing, solar power, transmission and data management systems of the WSN and UAV were fully evaluated by laboratory, bench and field testing. The methodology created to design, developed, integrate and test these systems was extensively described and experimentally validated. The sampling and transmission capabilities of the WSN and UAV were successfully tested in an emulated mission involving the detection and measurement of CO2 concentrations in a field coming from a contaminant source; the data collected during the mission was transmitted in real time to a central node for data analysis and 3D mapping of the target gas. The major outcome of this research is the accomplishment of the first flight mission, never reported before in the literature, of a solar powered UAV equipped with a CO2 sensing system in conjunction with a network of ground sensor nodes for an effective 3D monitoring of the target gas. A data management platform was created using an external internet server, which manages, stores, and shares the data collected in two web pages, showing statistics and static graph images for internal and external users as requested. The system was bench tested with real data produced by the sensor nodes and the architecture of the platform was widely described and illustrated in order to provide guidance and support on how to replicate the system. In conclusion, the overall results of the project provide guidance on how to create a gas sensing system integrating WSNs and UAVs, how to power the system with solar energy and manage the data produced by the sensor nodes. This system can be used in a wide range of outdoor applications, especially in agriculture, bushfires, mining studies, zoology, and botanical studies opening the way to an ubiquitous low cost environmental monitoring, which may help to decrease our carbon footprint and to improve the health of the planet.

Nanomorphology influence on the light conversion mechanisms in highly efficient diketopyrrolopyrrole based organic solar cells

In this work, diketopyrrolopyrrole-based polymer bulk heterojunction solar cells with inverted and regular architecture have been investigated. The influence of the polymer:fullerene ratio on the photoactive film nanomorphology has been studied in detail. Transmission Electron Microscopy and Atomic Force Microscopy reveal that the resulting film morphology strongly depends on the fullerene ratio. This fact determines the photocurrent generation and governs the transport of free charge carriers. Slight variations on the PCBM ratio respect to the polymer show great differences on the electrical behavior of the solar cell. Once the polymer:fullerene ratio is accurately adjusted, power conversion efficiencies of 4.7% and 4.9% are obtained for inverted and regular architectures respectively. Furthermore, by correlating the optical and morphological characterization of the polymer:fullerene films and the electrical behavior of solar cells, an ad hoc interpretation is proposed to explain the photovoltaic performance as a function of this polymer:blend composition.

Solution processable low bandgap diketopyrrolopyrrole (DPP) based derivatives : novel acceptors for organic solar cells

Novel low bandgap solution processable diketopyrrolopyrrole (DPP) based derivatives functionalized with electron withdrawing end capping groups (trifluoromethylphenyl and trifluorophenyl) were synthesized, and their photophysical, electrochemical and photovoltaic properties were investigated. These compounds showed optical bandgaps ranging from 1.81 to 1.94 eV and intense absorption bands that cover a wide range from 300 to 700 nm, attributed to charge transfer transition between electron rich phenylene-thienylene moieties and the electron withdrawing diketopyrrolopyrrole core. All of the compounds were found to be fluorescent in solution with an emission wavelength ranging from 600 to 800 nm. Cyclic voltammetry indicated reversible oxidation and reduction processes with tuning of HOMO-LUMO energy levels. Bulk heterojunction (BHJ) solar cells using poly(3-hexylthiophene) (P3HT) as the electron donor with these new acceptors were used for fabrication. The best power conversion efficiencies (PCE) using 1:2 donor-acceptor by weight mixture were 1% under simulated AM 1.5 solar irradiation of 100 mW cm-2. These findings suggested that a DPP core functionalized with electron accepting end-capping groups were a promising new class of solution processable low bandgap n-type organic semiconductors for organic solar cell applications.

Water-based nanoparticulate solar cells using a diketopyrrolopyrrole donor polymer

Organic photovoltaic devices with either bulk heterojunction (BHJ) or nanoparticulate (NP) active layers have been prepared from a 1:2 blend of (poly{3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1, 4-dione-alt-naphthalene}) (PDPP-TNT) and the fullerene acceptor, ([6,6]-phenyl C71-butyric acid methyl ester) (PC70BM). Atomic force microscopy (AFM) and scanning electron microscopy (SEM) have been used to investigate the morphology of the active layers of the two approaches. Mild thermal treatment of the NP film is required to promote initial joining of the NPs in order for the devices to function, however the NP structure is retained. Consequently, whereas gross phase segregation of the active layer occurs in the BHJ device spin cast from chloroform, the nanoparticulate approach retains control of the material domain sizes on the length scale of exciton diffusion in the materials. As a result, NP devices are found to generate more than twice the current density of BHJ devices and have a substantially greater overall efficiency. The use of aqueous nanoparticulate dispersions offers a promising approach to control the donor acceptor morphology on the nanoscale with the benefit of environmentally- friendly, solution-based fabrication. © 2014 the Owner Societies.

Nanoscale phase domain structure and associated device performance of organic solar cells based on a diketopyrrolopyrrole polymer

We investigate the blend morphology and performance of bulk heterojunction organic photovoltaic devices comprising the donor polymer, pDPP-TNT (poly{3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1, 4-dione-alt-naphthalene}) and the fullerene acceptor, [70]PCBM ([6,6]-phenyl C71-butyric acid methyl ester). The blend morphology is heavily dependent upon the solvent system used in the fabrication of thin films. Thin films spin-coated from chloroform possess a cobblestone-like morphology, consisting of thick, round-shaped [70]PCBM-rich mounds separated by thin polymer-rich valleys. The size of the [70]PCBM domains is found to depend on the overall film thickness. Thin films spin-coated from a chloroform:dichlorobenzene mixed solvent system are smooth and consist of a network of pDPP-TNT nanofibers embedded in a [70]PCBM-rich matrix. Rinsing the films in hexane selectively removes [70]PCBM and allows for analysis of domain size and purity. It also provides a means for investigating exciton dissociation efficiency through relative photoluminescence yield measurements. Devices fabricated from chloroform solutions show much poorer performance than the devices fabricated from the mixed solvent system; this disparity in performance is seen to be more pronounced with increasing film thickness. The primary cause for the improved performance of devices fabricated from mixed solvents is attributed to the greater donor-acceptor interfacial area and resulting greater capacity for charge carrier generation.

Measurement of contact voltage drop and resistance in organic solar cells

Bulk heterojunction organic solar cells based on poly[4,7-bis(3- dodecylthiophene-2-yl) benzothiadiazole-co-benzothiadiazole] and [6,6]-phenyl C71-butyric acid methyl ester are investigated. A prominent kink is observed in the fourth quadrant of the current density-voltage (J-V) response. Annealing the active layer prior to cathode deposition eliminates the kink. The kink is attributed to an extraction barrier. The J-V response in these devices is well described by a power law. This behavior is attributed to an imbalance in charge carrier mobility. An expected photocurrent for the device displaying a kink in the J-V response is determined by fitting to a power law. The difference between the expected and measured photocurrent allows for the determination of a voltage drop within the device. Under simulated 1 sun irradiance, the peak voltage drop and contact resistance at short circuit are 0.14 V and 90 Ω, respectively. © 2012 American Institute of Physics.

Impact of al passivation and cosputter on the structural property of β-FeSi2 for Al-Doped β-FeSi2/ n -Si(100) based solar cells application

The aluminum (Al) doped polycrystalline p-type β-phase iron disilicide (p-β-FeSi2) is grown by thermal diffusion of Al from Al-passivated n-type Si(100) surface into FeSi2 during crystallization of amorphous FeSi2 to form a p-type β-FeSi 2/n-Si(100) heterostructure solar cell. The structural and photovoltaic properties of p-type β-FeSi2/n-type c-Si structures is then investigated in detail by using X-ray diffraction, Raman spectroscopy, transmission electron microscopy analysis, and electrical characterization. The results are compared with Al-doped p-β-FeSi2 prepared by using cosputtering of Al and FeSi2 layers on Al-passivated n-Si(100) substrates. A significant improvement in the maximum open-circuit voltage (Voc) from 120 to 320 mV is achieved upon the introduction of Al doping through cosputtering of Al and amorphous FeSi2 layer. The improvement in Voc is attributed to better structural quality of Al-doped FeSi2 film through Al doping and to the formation of high quality crystalline interface between Al-doped β-FeSi2 and n-type c-Si. The effects of Al-out diffusion on the performance of heterostructure solar cells have been investigated and discussed in detail.

Hydrothermal synthesis and characterisation of Cu2ZnSnS4 light absorbers for solar cells

This project has extended the knowledge in the hydrothermal synthesis of copper zinc tin sulphide (CZTS) semiconductor material which is regarded as one of the most promising light absorbing material for PV technologies. The investigation of various reaction parameters on the controlled synthesis of CZTS compound has provided important insight into the formation mechanism as well as the crystal growth behaviour of the material. CZTS nanocrystals with different crystal structure and particle size were synthesised throughout this project. The growth mechanism of CZTS crystals through a high temperature annealing treatment was also explored.

High efficiency quantum dot-sensitised solar cells by material science and device architecture

This thesis studied cadmium sulfide and cadmium selenide quantum dots and their performance as light absorbers in quantum dot-sensitised solar cells. This research has made contributions to the understanding of size dependent photodegradation, passivation and particle growth mechanism of cadmium sulfide quantum dots using SILAR method and the role of ZnSe shell coatings on solar cell performance improvement.

A non-fullerene electron acceptor based on fluorene and diketopyrrolopyrrole building blocks for solution-processable organic solar cells with an impressive open-circuit voltage

A novel solution-processable non-fullerene electron acceptor 6,6′-(5,5′-(9,9-dioctyl-9H-fluorene-2,7-diyl)bis(thiophene-5,2-diyl))bis(2,5-bis(2-ethylhexyl)-3-(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione) (DPP1) based on fluorene and diketopyrrolopyrrole conjugated moieties was designed, synthesized and fully characterized. DPP1 exhibited excellent solubility and high thermal stability which are essential for easy processing. Upon using DPP1 as an acceptor with the classical electron donor poly(3-hexylthiophene), solution processable bulk-heterojunction solar cells afforded a power conversion efficiency of 1.2% with a high open-circuit voltage (1.1 V). As per our knowledge, this value of open circuit voltage is one of the highest values reported so far for a bulk-heterojunction device using DPP1 as a non-fullerene acceptor.

Plasmonic effect of annealed gold islands for improving efficiency of organic solar cells

Embedding metallic nanoparticles in organic solar cells can enhance the photoabsorption through light trapping processes. This paper investigates how gold islands obtained by annealing 1–5 nm thick Au layers affect the photoabsorption. Using finite-difference time-domain simulations, the cell efficiency for various island geometries and thicknesses are analyzed and the properties of the islands for maximal photocurrent are discussed. It is shown that a careful choice of size and concentration of gold islands could contribute to enhance the power conversion efficiencies when compared to standard organic solar cell devices. The conclusions are then compared to experimental data for thermally annealed gold islands in bulk heterojunction solar cells. The results of this paper will contribute to the optimization of plasmonic organic solar cell systems and will pave the way for the development of highly efficient organic solar cell devices.

Bias-dependent effects in planar perovskite solar cells based on CH3NH3PbI3−xClx films

A unique bias-dependent phenomenon in CH3NH3PbI3−xClx based planar perovskite solar cells has been demonstrated, in which the photovoltaic parameters derived from the current–voltage (I–V) curves are highly dependent on the initial positive bias of the I–V measurement. In FTO/CH3NH3PbI3−xClx/Au devices, the open-circuit voltage and short-circuit current increased by ca. 337.5% and 281.9% respectively, by simply increasing the initial bias from 0.5 V to 2.5 V.

An efficient hole transport material composite based on poly(3-hexylthiophene) and bamboo-structured carbon nanotubes for high performance perovskite solar cells

In this work, we have developed a new efficient hole transport material (HTM) composite based on poly(3- hexylthiophene) (P3HT) and bamboo-structured carbon nanotubes (BCNs) for CH3NH3PbI3 (MAPbI3) based perovskite solar cells. Compared to pristine P3HT, it is found that the crystallinity of P3HT was significantly improved by addition of BCNs, which led to over one order of magnitude higher conductivity for the composite containing 1–2 wt% BCNs in P3HT. In the meantime, the interfacial charge transfer between the MAPbI3 light absorbing layer and the HTM composite layer based on P3HT/BCNs was two-fold faster than pristine P3HT. More importantly, the HTM film with a superior morphological structure consisting of closely compact large grains was achieved with the composite containing 1 wt% BCNs in P3HT. The study by electrochemical impedance spectroscopy has confirmed that the electron recombination in the solar cells was reduced nearly ten-fold with the addition of 1 wt% carbon nanotubes in the HTM composite. Owing to the superior HTM film morphology and the significantly reduced charge recombination, the energy conversion efficiency of the perovskite solar cells increased from 3.6% for pristine P3HT to 8.3% for P3HT/(1 wt% BCNs) with a significantly enhanced open circuit voltage (Voc) and fill factor (FF). The findings of this work are important for development of new HTM for high performance perovskite solar cells.

Designs and architectures for the next generation of organic solar cells

Organic solar cells show great promise as an economically and environmentally friendly technology to utilize solar energy because of their simple fabrication processes and minimal material usage. However, new innovations and breakthroughs are needed for organic solar cell technology to become competitive in the future. This article reviews research efforts and accomplishments focusing on three issues: power conversion efficiency, device stability and processability for mass production, followed by an outlook for optimizing OSC performance through device engineering and new architecture designs to realize next generation organic solar cells.