Doctoral theses at Solid-State Electronics

Abstract

Radio Frequency (RF) power sources are extensively applied in various fields. Radioisotope production, i.e., the production of short-lived radioactive isotopes, for positron emission tomography (PET) is one of the most important applications in the medical and healthcare domains. Full-time operation and substantial maintenance of such systems lead to high operating expenses. Hence, the development of more efficient and reliable RF power amplifiers, which are the main contributors to the energy consumption and maintenance costs of the RF power sources, is a high priority. Solid-state technology has emerged as a viable alternative to conventional vacuum tube based high-power RF/microwave systems, offering advanced control, reliability, and ease of use. Power amplifiers based on solid-state technology enable dynamic adjustment of power to optimize the transmitted energy. Furthermore, solid-state power amplifiers (SSPA) technology shows a longer lifetime leading to increased uptime and lower maintenance costs. Concisely, with the introduction of solid-state technology in high-power RF sources, RF energy can be generated more efficiently and more controllable in a smaller form factor, allowing for more compact systems with less downtime and less maintenance. This thesis is one step further toward demonstrating the feasibility of such systems.

The thesis first introduces the RF measurement setup. It implements automation for quick measurements and supports the evaluation of the high-power RF performance of the developed SSPA modules. Moreover, a novel thru-only de-embedding approach is developed to address the calibration difficulties under multi-port excitation conditions. The second part of the thesis deals with the development and analysis of efficient kilowatt SSPA modules. A multimode SSPA with quasi-static supply control for power regulation is implemented. It achieves more than 90% efficiency over a 5 dB output power back-off range. Another compact and efficient SSPA, implemented in push-pull architecture, adopts harmonic load-pull integrated with the same quasi-static supply modulation which also achieves 90% efficiency over a 5 dB output power back-off range. The implemented SSPAs improve the state-of-the-art in these frequency bands and power ranges.

This thesis broadens RF SSPA theoretical research to the kilowatt power range and provides a new understanding of high-power SSPAs from circuits, design methodologies, and analytical approaches. And it leads to new methods and tools to improve the energy efficiency of high-power RF sources. The knowledge gained and technology developed is not limited to RF power sources in radioisotope production applications, it can also be applied in the communication industry, such as radar systems, and other RF energy systems in industrial, scientific, and medical (ISM) fields, such as particle accelerators, welding, drying, heating, and many more.

Abstract

A biosensor based on streaming current is a new and relatively unexplored subject with significant potential. This thesis attempts to gain a deeper understanding of the governing principles, and then exploit them to further improve its performance as well as develop novel applications. To this end, the underlying theoretical frameworks were examined and two critical parameters of the target: its size and electric charge, influencing the sensor’s sensitivity were identified. This was followed by experimental evaluation of the parameters, using a set of tailor-made proteins, aiming to understand the nature and extent of their influence on the sensor response in relation to simulation performed following an established model.

The dependence of the sensor response on the charge of an analyte, or specifically the charge contrast between the sensor surface and an analyte, opens a new avenue to improve the sensitivity and also to develop novel functionality. First, this aspect was exploited to improve the sensitivity by optimizing the surface functionalization strategy. Three such methods were compared in terms of the resulting zeta potential of the surface. The sensitivity was the highest when the charge contrast was maximum. The optimal functionalization strategy was then used for highly sensitive detection of extracellular vesicles (EVs), where an improvement in the limit of detection by two orders of magnitude over the previously reported results was demonstrated. Two applications of the improved method were then demonstrated: monitoring the effectiveness of targeted cancer medicines and analysis of liquid biopsy of cancer patients via sensitive profiling of EV-membrane proteins.

Improvement in the detection specificity is a critical aspect of biosensing. This was achieved by implementing a sandwich immunoassay and demonstrating the proof of concept using trastuzumab as the target and Z-domain as both the capture and detection probes. Although the improved selectivity came at the cost of a lower sensitivity, this could be mitigated via DNA-conjugation with the detection probes, a novel electrostatic labelling strategy that allows for improvement of the sensitivity by exploiting the electrostatic influence. An application of this method was then demonstrated by detecting the target from a complex medium of E. coli cell lysate. Continuing the prospect of charge engineering of antibodies, a set of positively and negatively charged antibodies were synthesized by conjugating poly-lysine and DNA oligonucleotides, respectively. This enabled stepwise, multiplexed membrane protein analysis of EVs using the alternating charge-labelled antibodies. The method was then applied to investigate EV-heterogeneity.

Abstract

Graphene is widely touted as the thinnest and the most versatile material available. As an atomically thin layer of carbon atoms arranged in a hexagonal configuration, graphene has a combination of technologically important properties, such as thermal and electrical conductivity, mechanical strength, and impermeability to gases. From an industrial perspective on applications, water as a dispersing media for graphene offers safer handling and environmental benefits compared with conventional organic solvents. However, the high surface tension of water and the attractive forces between graphene surfaces drive the sheets to aggregation. Although surfactants have been an important stepping stone in the advancement of aqueous graphene dispersions, these surface-active molecules are often needed in excess and have adverse effects on coatings during film formation. These challenges limit the industrial relevance of graphene as an effective barrier in composites. In general, gas barriers against both oxygen and water vapour, made from a single coating formulation, is seemingly a holy grail for the packaging industry. In this thesis work, the aim was to gain a fundamental understanding of aqueous graphene dispersions for gas barriers used in paper packaging. Biobased materials were systematically investigated as dispersing agents for graphene based on dispersing conditions and functional barrier performance. Flavin mononucleotide (FMN), a food additive, dispersed graphene using a relatively low amount of FMN and showed intriguing spectroscopic signatures of π-π interactions with graphene. Starch nanoparticles (SNPs) realised concentrated and stable aqueous graphene dispersions for composite films. The SNP-stabilized graphene sheets in starch films lowered the gas permeability of both oxygen and water vapour simultaneously by over 70% under all the conditions tested. In general, a combined gas barrier performance is unusual for both bioplastics and common petrochemical-based plastics used in the packaging industry. Motivated by the graphene network leading to the extraordinary barrier performance, the aqueous SNP-graphene dispersion was modified for inkjet printing. The printed patterns were flexible and electrically conductive in the order of 10⁴ S m^-1 that is on par with the highest reported values in the literature. These surfactant-free aqueous SNP-graphene dispersions have the potential and versatility for paper-based gas barriers with integrated electronics. Multifunctional composite films made from these dispersions, when optimized, could become competitive with commercial plastics, and meet the current and future demands of the packaging industry.

Abstract

Silicon nanowire (SiNW) based electronic devices fabricated with a complementary metal-oxide-semiconductor (CMOS) compatible process have wide-range and promising applications in sensing area. These SiNW sensors own high sensitivity, low-cost mass production possibility, and high integration density. In this thesis, we design and fabricate SiNW electronic devices with the CMOS-compatible process on silicon-on-insulator (SOI) substrates and explore their applications for ion sensing and quantum sensing. 

The thesis starts with ion sensing using SiNW field-effect transistors (SiNWFETs). The specific interaction between a sensing layer and analyte generates a change of local charge density and electrical potential, which can effectively modulate the conductance of SiNW channel. Multiplexed detection of molecular (MB⁺) and elemental (Na⁺) ions is demonstrated using a SiNWFET array, which is functionalized with ionophore-incorporated mixed-matrix membranes (MMMs). As a follow-up, polyethylene glycol (PEG) doping strategy is explored to suppress interference from the hydrophobic molecular ion and expand the multiplexed detection range. Then, the SiNW is downscaled to sub-10 nm with a gate-oxide-free configuration for single charge detection in liquid. We directly observe the capture and emission of a single H⁺ ion with individually activated Si dangling bonds (DBs) on the SiNW surface. This work demonstrates the unprecedented ability of the sub-10 nm SiNWFET for investigating the physics of the solid/liquid interface at single charge level.

Apart from ion sensing, the SiNWFET can be suspended and act as a nanoelectromechanical resonator aiming for electrically detecting potential quantized mechanical vibration at low temperature. A suspended SiNW based single-hole transistor (SHT) is explored as a nanoelectromechanical resonator at 20 mK. Mechanical vibration is transduced to electrical readout by the SHT, and the transduction mechanism is dominated by piezoresistive effect. A giant effective piezoresistive gauge factor (~6000) with a strong correlation to the single-hole tunneling is also estimated. This hybrid device is demonstrated as a promising system to investigate macroscopic quantum behaviors of vibration phonon modes.

Noise, including intrinsic device noise and environmental interference, is a serious concern for sensing applications of SiNW electronic devices. A H₂ annealing process is explored to repair the SiNW surface defects and thus reduce the intrinsic noise by one order of magnitude. To suppress the external interference, lateral bipolar junction transistors (LBJTs) are fabricated on SOI substrate for local signal amplification of the SiNW sensors. Current gain and overall signal-to-noise ratio of the LBJTs are also optimized with an appropriate substrate voltage.

Abstract

Nanopores have emerged as a special class of single-molecule analytical tool that offers immense potential for sensing and characterizing biomolecules such as nucleic acids and proteins. As an alternative to biological nanopores, solid-state nanopores present remarkable versatility due to their wide-range tunability in pore geometry and dimension as well as their excellent mechanical robustness and stability. However, being intrinsically incompatible with biomolecules, surfaces of inorganic solids need be modified to provide desired functionalities for real-life sensing purposes. In this thesis, we presented an exploration of various surface engineering strategies and an examination of several surface associated phenomena pertaining specifically to solid-state nanopores. Based on the parallel sensing concept using arrayed pores, optical readout is mainly employed throughout the whole study.

For the surface engineering aspect, a list of approaches was explored. A versatile surface patterning strategy for immobilization of biomolecules was developed based on selective poly(vinylphosphonic acid) passivation and electron beam induced deposition technique. This scheme was then implemented on nanopore arrays for nanoparticle localization. In addition, vesicle rupture-based lipid bilayer coating was adapted to truncated-pyramidal nanopores, which was shown to be effective for the minimizing DNA-pore interaction. Further, HfO₂ coating by means of atomic layer deposition was employed to prevent the erosion of Si-based pores and to shrink the pore diameter, which enabled reliable investigations of DNA clogging and DNA polymerase docking.

For the surface associated phenomena, several findings were made. The lipid bilayer formation on truncated pyramidal nanopores via instantaneous rupture of individual vesicles was quantified based on combined ionic current monitoring and optical observation.  The probability of pore clogging appeared to linearly increase with the length of DNA strands and applied bias voltage, which could be attributed a higher probability of knotting and/or folding of longer DNA strands and more frequent translocation events at higher voltage. A free-energy based analytical model was proposed to evaluate the DNA-pore interaction and to interpret observed clogging behavior. Finally, docking of DNA polymerase on nanopore arrays was demonstrated using label-free optical method based on Ca²⁺ indicator dyes, which may open the avenue to sequencing-by-synthesis enabled by the docked polymerase.

Abstract

The demand for wireless data communications is rapidly increasing due to several factors including increased internet access, increasingly growing number of mobile users and services, implementation of the Internet of Things (IoT), high-definition (HD) video streaming and video calling. To meet the bandwidth requirement of new and emerging applications, it is necessary to move from the existing microwave bands towards millimeter-wave bands. 

This thesis presents different antenna arrays at 60 GHz and 28 GHz that are integrated with the front-end RFIC to steer the beam in ≈ ±50° in the azimuth plane. The 5G antenna arrays at 28 GHz are designed to provide broadband high data rate services to the end users. In order to transport this high-volume data to the core network, a fixed wireless access (FWA) link demands the implementation of a broadband, high gain and steerable narrow-beam array. The 60 GHz antenna arrays, presented in this thesis, are good candidates for both FWA as well as backhaul communications. The two proposed arrays at 60 GHz (57-66 GHz) are i) a stacked patches array and ii) a connected slots array feeding a high gain lens antenna. The 2×16 stacked patches antenna array shows more than 20 dBi realized gain. The array is integrated with the front-end RFIC and the resulting module shows > 40 dBm measured effective isotropic radiated power (EIRP). The other 60 GHz antenna array is designed as linear connected slots with sixteen equidistant feeding points. The latest is then used as a feeder of a high gain dielectric lens. Peak measured gain of 25.4 dBi is achieved with this antenna.  Moreover, instead of experiencing scan loss, the lens is designed to get higher gain when the beam is steered away from the broadside direction.

Furthermore, two compact antenna arrays are designed at 28 GHz (24.25 - 29.50 GHz). A linear polarized (LP) and a circular polarized (CP) array are realized in the fan-out embedded wafer level ball-grid-array (eWLB) package. In comparison with the PCB arrays, this antenna in package (AiP) solution is not only cost-effective but it also reduces the integration losses because of shorter feed lines and no geometrical discontinuity.  The LP array is realized as a dipole antenna array feeding a novel horn-shaped heatsink.  The RF module gives 34 dBm peak EIRP with beam-steering in ±35°. Besides, the CP antenna array is realized with the help of crossed dipoles and the RF module provides 31 dBm peak EIRP with beam-steering in ±50°.

The data demands are not limited to the telecom industry as the upgradation of accelerators and experiments at the large hadron collider (LHC) at CERN will result in increased event rate thus demanding higher data rate front-end readout systems. This work thus investigates the feasibility of 60 GHz wireless links for the data readout at CERN. For this purpose, the 60 GHz wireless chips are irradiated with 17 MeV protons [dose 7.4 Mrad (RX) & 4.2 Mrad (TX)] and 200 MeV electrons [dose 270 Mrad (RX) & 314 Mrad (TX)] in different episodes. The chips have been found operational in the post-irradiation investigations with some performance degradation. The encouraging results motivate to move forward and investigate the realization of wireless links in such a complex environment.

Abstract

Nanopores are of great interest in study of DNA sequencing, protein profiling and power generation. Among them, solid-state nanopores show obvious advantages over their biological counterparts in terms of high chemical stability and reusability as well as compatibility with the existing CMOS fabrication techniques. Nanopore sensing is most frequently based on measuring ionic current through a nanopore while applying a voltage across it. When an analyte passes through the pore, the ionic current temporarily changes, providing information of the analyte such as its size, shape and surface charge. Although many magnificent reports on using solid-state nanopores have appeared in the literature, several challenges still remain for their wider applications, which include improvement of fabrication reproducibility for mass production of ultra-small nanopores and minimization of measurement instability as well as control of translocation speed and reduction of background noise. This thesis work explores different techniques to achieve robust and high throughput fabrication of sub-10 nm nanopores for different applications.

The thesis starts with presenting various fabrication techniques explored during my PhD studies. Focused ion beam method was firstly employed to drill nanopores in free-standing SiN_x membranes. Sub-10 nm nanopores could be obtained with a focused helium ion beam. But the fabrication throughput was limited with this technique. A new fabrication process combing electron beam lithography (EBL) with reactive ion etching/ion beam etching, which is compatible with the existing CMOS fabrication technology, was developed to realize a high throughput, mass production of nanopores in free-standing SiN_x membranes. However, the smallest size that could be controllably achieved with this process was around 40 nm, which is still far from sub-10 nm in size required for, e.g., DNA sequencing. Finally, by using anisotropic etching of single-crystal silicon in KOH solution, sub-5 nm truncated pyramidal nanopores were mass produced with good process controllability in a silicon-on-insulator (SOI) substrate. In addition, nanopore arrays were also successfully fabricated using a modified EBL based fabrication process.

Then, several sensing application examples using either single nanopores or nanopore arrays were investigated. Translocation of nanoparticles, DNA and proteins were demonstrated using the fabricated single nanopores or nanopore arrays in a single freestanding membrane. Moreover, the kinetics and mechanism of the lipid bilayer formation in nanopore array, aiming to prevent non-specific adsorption, were studied using ionic current measurements. In addition, individual addressability of a solid-state nanopore array on separated freestanding membranes was realized by integrating microfluidics and a customized multiplexer.

Abstract

Gold based label-free electrochemical DNA sensors have been widely studied for biomarker diagnostics. The sensitivity and reproducibility of these sensors are determined by the sensing interface: the DNA modified gold surfaces. This thesis systematically studies the preparation processes of the DNA sensor interfaces as well as their effects on the sensor performance. First, three pretreatment methods to clean the gold electrode surface and their influence on the subsequent binding of thiolated molecules were carefully investigated. As we found that the surface pretreatment method involving cyclic voltammetry (CV) in H₂SO₄ may induce structural changes to the gold surface, thus greatly impacting the thiolated molecule binding, the factors influencing this pretreatment method were studied. Practical guidelines were summarized for preparing a clean and reproducible gold surface prior to functionalization. Afterwards, the effects of the surface coverage density of probe DNA and the salt concentration on the probe-target DNA hybridization on a gold sensing surface were systematically investigated using surface plasmon resonance (SPR) analysis. Based on the SPR results, the maximum potentiometric signal that could be generated by the DNA hybridization on the surface, and the detection limits, were estimated for different experimental conditions. These estimations were further compared with experimental results obtained using silicon nanowire field effect transistors (SiNW FET) with DNA modified gold on the gate oxide. Practical limitations for the potentiometric DNA sensor were analysed and discussed. Finally, the stability and reproducibility issues on the electrochemical impedance spectroscopy (EIS) analyses of DNA hybridization were also studied on the aptamer/mercaptohexanol (MCH)-modified gold surface. The root cause for the drift problems in this type of sensor and the temperature effects on the aptamer/MCH modified surface were identified. This thesis could serve as a practical reference for the preparation and understanding of the sensing interface of gold-based electrochemical DNA sensors.

Abstract

The rise of Big Science projects brings issues related to the energy consumption and the associated environmental impacts of such large-scale facilities. Therefore, environmentally-sustainable developments are undertaken towards the adoption of energy savings and improved energy-efficient approaches. The advent of the superconducting (SC) radio frequency (RF) accelerating cavity is bringing answers to these issues. Such superconducting RF (SRF) cavity is made of niobium that allows much higher accelerating gradients with a minimization of the energy consumption. The SC RF technology is increasingly used in many modern particle accelerators, including: the European Spallation Source (ESS), the X-ray Free Electron Laser (XFEL), the Linac Coherent Light Source (LCLS)-II and the proposed International Linear Collider (ILC).

The innovation of solid state PA technology pushes limits regarding packaging, efficiency, frequency capability, thermal stability, making them more attractive than other well-established alternative technologies, such as vacuum tube technology in mid-range power applications. Through the investigations of designs and techniques, this research goal of the thesis allows to improve solid-state based power generation systems from module to the overall system design. This thesis introduces the single-ended PA design approach in planar technology and at kilowatt level. The design solution unlocks different possibilities including: improved integration, layout flexibility for tuning, and suitably for mass productions that are demanded in future high peak power generation systems. The novel amplifier design is followed by time domain characterization to fully evaluate the pulse profiles of such amplifiers when delivering kilowatt output power level for operation in conjunction with SRF accelerating cavities. Amplitude and phase stability of those amplifiers are also investigated in time-domain. The extracted data can then be used as measurement-based model for predicting factors which could degrade the overall stability of the associated PA.

Future RF power generation systems built around solid state PAs need also efficient combining strategies. Two engineering design solutions are investigated in this thesis aiming for mid- and high- range power combination. One solution is based on a combination of the Gysel structure using suspended strip-line technology for improved power handling capability. Another solution is implementing a radial combiner, which uses re-entrant cavity resonator at 352 MHz and door-nob geometry for coupling at inputs and at the output. These solutions facilitate the scaling up 400 kW for powering ESS spoke cavities while maintaining a high degree of efficiency in RF power generation. This thesis gives insights of system integration and tuning procedures with a demonstration of combining 8 modules, delivering a total of 10 kW output power. Along with the proposed combining solutions at higher power levels, the nominal power block of 10 kW is used as an elementary block to propose scaling up in power till the 400 kW nominal power required by ESS.

Finally, this thesis focuses on implementing an optimal charging scheme for SRF cavities, which helps reducing the wasted energy and improves the overall efficiency operation at future accelerating facilities. Therefore, these results contribute further to the larger adoption of solid state technologies in the future power generation systems for particle accelerators.

Abstract

In the last two decades, a significant development in the field of medical technology occurred worldwide. This development is characterized by the materialization of various body implants and worn devices, that is devices attached to the body. These devices assist doctors and paramedical staff in effectively monitoring the patient’s health and helping increase patients’ average life expectancy. Furthermore, the various implants inside the human body serve different purposes according to the humans’ needs. As this situation became more prominent, the development of protocols and of reliable transmission media is becomes essential to improve the efficiency of inter-device communications. Positive prospects of the use of human tissue for intra-body communication were proven in recent studies. Fat tissues, for example, which also work as energy banks for human beings, can be potentially used in intra-body communications as transmission media. In this thesis, the fat (adipose) tissue’s function as an intra-body communication channel was investigated. Therefore, various simulations and experimentations were performed in order to characterize the reliability of the fat tissue in terms of communication, considering, for example, the effect that the variability in the thickness of adipose and muscular tissues could have on the communication performance, and the possible effect that the variability in the transmitted signal power could have on the data packet reception. Fat tissue displays superior performance in comparison to muscle tissue in the context of a low loss communication channel. For example, at 2.45 GHz, the path losses of ~0.7 dB/cm and ~1.9 dB/cm were observed for phantom and ex-vivo measurements, respectively. At a higher frequency of 5.8 GHz, the ex-vivo path loss was around 1.4 dB/cm. It was concluded from the results that the adipose tissue could function as a reliable medium supporting intra-body communication even under low power transmitted signals. Moreover, although the presence of thick blood vessels could degrade the signal strength, the results show that communication is possible even under the presence of perturbant tissues. Overall, the results of this thesis would provide a foundation in this area and assist researchers in developing innovative and solutions for intra-body communication.

Abstract

In recent years, the use of microwave techniques for medical diagnostics has experienced impressive developments. It has demonstrated excellent competencies in various modalities such as using non-ionizing electromagnetic waves, providing non-invasive diagnoses, and having the ability to penetrate human tissues within the GHz range. However, due to anatomical, physiological, and biological variations in the human body, certain obstacles are present. Moreover, there are accuracy problems such as the absence of numerical models and experimental data, difficulty in conducting tests due to safety issues with human subjects, and also practical restrictions in clinical implementation. With the presence of these issues, a better understanding of the microwave technique is essential to further improve its medical application and to introduce alternative diagnostic methods that can detect and monitor various medical conditions in real time.

The first part of this thesis focuses on measurement systems for the microwave technique in terms of sensor design and development, numerical analysis, permittivity measurement, and phantom fabrication. The aim is to investigate the feasibility of flexible systems with different fields of application including a microwave sensor system for measuring the healing progression of bone defects present in lower extremity trauma, bone regeneration in craniotomy for craniosynostosis treatments, and dielectric variation for burn injuries. The microwave sensor which utilizes the contrast in dielectric constant between various tissues was used as the primary sensor for the proposed application. This involved detailed optimization of the sensor for greater sensitivity. The experimental work carried out in the lab environment showed that the microwave sensor was able to detect the contrast in dielectric properties so that it can give an indication of the healing status for actual clinical scenarios.

The second part of the thesis is making a significant step towards its practical implementation by establishing a system that can detect and monitor the rate of healing progression with fast data acquisition speed of microseconds, and developing an efficient user interface to convert raw microwave data into legible clinical information in terms of bone healing and burn injuries. As an extension to this thesis, clinical studies were conducted and ethical approval for conducting tests on human subjects was obtained for the development of a microwave medical system. The results showed a clear difference in healing progressions due to high detection capability in terms of dielectric properties of different human tissues. All of these contributions enable a portable system to complement existing medical applications with the aim of providing more advanced healthcare systems.

Abstract

The material supply to build renewable energy conversion systems needs to be considered from both a cost and an energy security perspective. For Cu(In,Ga)Se₂ (CIGS) thin film solar cells the use of indium in the absorber layer is most problematic. The material input per service unit can be reduced, if the absorber layers are thinned down without a loss in power conversion efficiency.

Thinning down absorber layers can increase the conversion efficiency. However, for real CIGS solar cells absorption losses and recombination rates at the rear surface between the CIGS absorber and the Mo rear contact as well as shunt-like behavior increase. Thus, both rear surface passivation and optical management are essential for maintaining high power conversion efficiencies.

In this work, thin oxide layers, so-called passivation layers, are introduced between the CIGS absorber layer and the Mo contact. They can passivate the CIGS surface, if the CIGS-oxide interface has a lower defect density than the CIGS-Mo interface and/or if they contain a negative fixed oxide charge, which increases the hole concentration and reduces the electron concentration in the CIGS in the vicinity of the oxide.

As these oxides are insulators, electrical conduction through the passivation layer has to be ensured. In this work, nanopoint contacts were etched into ALD-Al₂O₃ passivation layers in CIGS solar cells. These solar cells had 0.5 -1.5 µm thin absorber layers with a low In content and a high band gap. Ga grading was not used. Although absorber layers with a high Ga content have a short minority carrier diffusion length, a passivation effect could be discerned with the help of external quantum efficiency measurements and current-voltage measurements under varying temperatures in combination with optical and electrical modeling with a two-diode model. Moreover, the possibility of leaving out the additional fabrication step has been explored for ALD-Al₂O₃ and HfO₂ as passivation layers. The results suggest that the passivation layer does not necessarily need to be opened for electrical conduction in an additional fabrication step, if sodium fluoride (NaF) is deposited onto Al₂O₃ layers prior to CIGS evaporation. In this case solar cells with 215 nm absorber layers and 6 nm thin passivation layers have a power conversion efficiency of 8.6 %, which is 3 % (absolute) higher than the conversion efficiency on a reference. Shunt-like behavior is additionally reduced. For the HfO₂ layers photoluminescence data indicate a good passivation effect, but the layers need to be opened up to ensure conduction.

Abstract

Three-dimensional integrated circuits have great potential for further increasing the number of transistors per area by stacking several device tiers on top of each other and without the need to continue the evermore complicated and expensive down-scaling of transistor dimensions. Among the different approaches towards the realization of such circuits, the monolithic approach, i.e. the tier-by-tier fabrication on a single substrate, is the most promising one in terms of integration density. Germanium is chosen as a substrate material instead of silicon in order to take advantage of its low fabrication temperatures as well as its high carrier mobilities. In this thesis, the work on two key components for the realization of such germanium-based three-dimensional integrated circuits is presented:the source/drain contacts to germanium the interconnects.

As a potential source/drain contact material, nickel germanide is investigated.In particular, the process temperature windows for the fabrication of morphologically stable nickel germanide layers formed from initial nickel layers below 10 nm are identified and the reaction between nickel and germanium is further studied by means of in-situ x-ray diffraction. The agglomeration temperature of nickel germanide is increased by 100 °C by the addition of tantalum and tungsten interlayers and capping layers. In an effort to more thoroughly characterize the contacts, a method to reliably extract the specific contact resistivity is implemented on germanium.

As a potential interconnect material cobalt is investigated. In a first step, highly conductive cobalt thin films are demonstrated by means of high-power impulse magnetron sputtering. The high conductivity of the cobalt films is owing to big grains, high density, high purity, and smooth interfaces. In a second step, the potential of high-power impulse magnetron sputtering for the metallization of nanostructures is further explored.

Abstract

Nanopore based sensing technology has been widely studied for a broad range of applications including DNA sequencing, protein profiling, metabolite molecules, and ions detection. The nanopore technology offers an unprecedented technological solution to meeting the demands of precision medicine on rapid, in-field, and low-cost biomolecule analysis. In general, nanopores are categorized in two families: solid-state nanopore (SSNP) and biological nanopore. The former is formed in a solid-state membrane made of SiN_x, SiO₂, silicon, graphene, MoS₂, etc., while the latter represents natural protein ion-channels in cell membranes. Compared to biological pores, SSNPs are mechanically robust and their fabrication is compatible with traditional semiconductor processes, which may pave the way to their large-scale fabrication and high-density integration with standard control electronics. However, challenges remain for SSNPs, including poor stability, low repeatability, and relatively high background noise level. This thesis explores SSNPs from basic physical mechanisms to versatile applications, by entailing a balance between theory and experiment.

The thesis starts with theoretical models of nanopores. First, resistance of the open pore state is studied based on the distribution of electric field. An important concept, effective transport length, is introduced to quantify the extent of the high field region. Based on this conductance model, the nanopores size of various geometrical shapes can be extracted from a simple resistance measurement. Second, the physical causality of ionic current rectification of geometrically asymmetrical nanopores is unveiled. Third, the origin of low-frequency noise is identified. The contribution of each noise component at different conditions is compared. Forth, a simple nano-disk model is used to describe the blockage of ionic current caused by DNA translocation. The signal and noise properties are analyzed at system level.

Then, nanopore sensing experiments are implemented on cylinder SiN_x nanopores and truncated-pyramid silicon nanopores (TPP). Prior to a systematic study, a low noise electrical characterization platform for nanopore devices is established. Signal acquisition guidelines and data processing flow are standardized. The effects of electroosmotic vortex in TPP on protein translocation dynamics are excavated. The autogenic translocation of DNA and proteins driven by the pW-level power generated by an electrolyte concentration gradient is demonstrated. Furthermore, by extending to a multiple pore system, the group translocation behavior of nanoparticles is studied. Various application scenarios, different analyte categories and divergent device structures accompanying with flexible configurations clearly point to the tremendous potential of SSNPs as a versatile sensor.

Abstract

This thesis work explores electrical conductors based on few-layer graphene flakes as an enabler for low-cost, mechanically flexible, and high-conductivity conductors in large area flexible and printed electronic devices. The flakes are deposited from aqueous solutions and processed at low temperature.

Graphene is selected for its excellent properties in mechanical, optical, electronic, and electrical aspects. However, thin films of pristine few-layer graphene flakes deposited from dispersions normally exhibit inferior electrical conductivity. One cause responsible for this problem is the loose stacking and random orientation of graphene flakes in a graphene deposition. We have solved this problem by implementing a simple post-deposition treatment leading to dramatically densified and planarized thin films. Significantly increased electrical conductivity by ~20 times is obtained. The 1-pyrenebutyric acid tetrabutylammonium salt as an exfoliation enhancer and dispersant in water yields ~110 S/m in conductivity when the graphene based thin films are processed at 90 °C. In order to achieve higher conductivity, a room-temperature method for site-selective copper electroless deposition has been developed. This method is of particular interest for the self-aligned copper deposition to the predefined graphene films. The resultant two-layer graphene/copper structure is characterized by an overall conductivity of ~7.9 × 10⁵ S/m, an increase by ~7000 times from the template graphene films. Several electronic circuits based on the graphene/copper bilayer interconnect have been subsequently fabricated on plastic foils as proof-of-concept demonstrators. Alternatively, highly conductive composites featuring graphene flakes coated with silver nanoparticles with electrical conductivity beyond 10⁶ S/m can be readily obtained at 100 ^oC. Moreover, a highly conductive reduced-graphene-oxide/copper hybrid hydrogel has been achieved by mixing aqueous graphene oxide solution and copper-containing Fehling's solution. The corresponding aerogel of high porosity exhibits an apparent electrical conductivity of ~430 S/m and delivers a specific capacity of ~453 mAh g⁻¹ at current density of 1 A/g. The experimental results presented in this thesis show that the solution-phase, low-temperature fabrication of highly conductive graphene-based materials holds promises for flexible electronics and energy storage applications. 

Abstract

In the past decades, silicon nanowire field-effect transistors (SiNWFETs) have been explored for label-free, highly sensitive, and real-time detections of chemical and biological species. The SiNWFETs are anticipated for sensing analyte at ultralow concentrations, even at single-molecule level, owing to their significantly improved charge sensitivity over large-area FETs. In a SiNWFET sensor, a change in electrical potential associated with biomolecular interactions in close proximity to the SiNW gate terminal can effectively control the underlying channel and modulate the drain-to-source current (I_DS) of the SiNWFET. A readout signal is therefore generated. This signal is primarily determined by the surface properties of the sensing layer on the gate terminal, with sensitivity close up to the Nernstian limit widely demonstrated. To achieve a high signal-to-noise ratio (SNR), it is essential for the SiNWFETs to possess low noise of which intrinsic device noise is one of the major components. In metal-oxide-semiconductor (MOS)-type FETs, the intrinsic noise mainly results from carrier trapping/detrapping at the gate oxide/semiconductor interface and it is inversely proportional to the device area.

This thesis presents a comprehensive study on design, fabrication, and noise reduction of SiNWFET-based sensors on silicon-on-oxide (SOI) substrate. A novel Schottky junction gated SiNWFET (SJGFET) is designed and experimentally demonstrated for low noise applications. Firstly, a robust process employing photo- and electron-beam mixed-lithography was developed to reliably produce sub-10 nm SiNW structures for SiNWFET fabrication. For a proof-of-concept demonstration, MOS-type SiNWFET sensors were fabricated and applied for multiplexed ion detection using ionophore-doped mixed-matrix membranes as sensing layers. To address the fundamental noise issue of the MOS-type SiNWFETs, SJGFETs were fabricated with a Schottky (PtSi/silicon) junction gate on the top surface of the SiNW channel, replacing the noisy gate oxide/silicon interface in the MOS-type SiNWFETs. The resultant SJGFETs exhibited a close-to-ideal gate coupling efficiency (60 mV/dec) and significantly reduced device noise compared to reference MOS-type SiNWFETs. Further optimization was performed by implementing a three-dimensional Schottky junction gate wrapping both top surface and two sidewalls of the SiNW channel. The tri-gate SJGFETs with optimized geometry exhibited significantly enhanced electrostatic control over the channel, thereby confined I_DS in the SiNW bulk, which greatly improved the device noise immunity to the traps at bottom buried oxide/silicon interface. Finally, a lateral bipolar junction transistor (LBJT) was also designed and fabricated on a SOI substrate aiming for immediate sensor current amplification. Integrating SJGFETs with LBJTs is expected to significantly suppress environmental interference and improve the overall SNR especially under low sensor current situations.

Abstract

The outstanding properties of graphene make it attractive ink filler for conductive inks which plays an important role in printed electronics. This thesis focuses on the ink formulation based on graphene and graphene oxide (GO).

Liquid phase exfoliation of graphite is employed to prepare graphene dispersions, i.e., shear- and electrochemical exfoliation. High concentration graphene dispersions with small size, few-layer graphene platelets are obtained by both methods. With the addition of ethyl cellulose stabilizer, shear-exfoliated graphene platelets in NMP were successfully inkjet printed on different substrates. The printed graphene film with electrical conductivity of ~3^10⁴ S/m was obtained after annealing at 350 °C for one hour. Alternatively, the electrochemically exfoliated graphene nano-platelets were collected and redispersed in DMF to form inks. The printed film of conductivity ~2.5^10³ S/m was obtained after annealing at 300 °C for one hour.

Water based GO/Ag hybrid inks were developed for screen printing. When high concentration GO aqueous dispersion was mixed with reactive silver ink, the viscosity of the mixture increased instantly to above 1000 cP as a result of reactions between oxygen functional groups (OFGs) on GO sheets and ingredients in the reactive silver ink. When the screen printed lines with different GO:Ag ratios were annealed in air, the conductivity of the resultant reduced graphene oxide/silver nanoparticles (RGO/AgNP_X) composites decreased as silver content increased. As oxygen enriched compounds in RGO/AgNP_X composites were detected, we proposed that AgOx compounds were generated on the AgNPs surface, which raised the contact resistance between AgNPs and RGO flakes. To solve this problem, the printed patterns were instead annealed in reducing gas (Ar/H₂ 5%). The electrical conductivity ~2.0^10⁴ S/m was then achieved.

Furthermore, the reduction of GO using ammonium formate as reducing reagent was investigated. When applying a hydrothermal method, ammonium formate shows excellent reduction ability, surpassing the widely used reducing agent, L-ascorbic acid, under same condition. Elemental analysis shows the C/O ratio of RGO as high as ~11 and most OFGs were removed in the reduction process. Meanwhile, incorporated nitrogen atoms introduced active sites in resultant RGO, making it a promising electrocatalyst for oxygen reduction reaction.

Abstract

The aim of this thesis is to understand the influence of the deposition process and resulting film properties on Cu₂ZnSnS₄ (CZTS) thin film solar cells. Two main aspects are studied, namely formation of absorber precursors by sputtering, and alternative Cd-free buffer materials with improved band alignment.

Reactive sputtering is used to grow dense and homogeneous precursor films containing all elements needed for CZTS absorbers. The addition of H₂S gas to the inert Ar sputter atmosphere leads to a drastic decrease of Zn-deposition rate due to the sulfurization of the target. Sulfurization also leads to instabilities for targets made of CuSn, Cu and Cu₂S, while sputtering from CuS gave acceptable process stability.

The H₂S/Ar-ratio also affects film morphology and composition. Precursors with sulfur content close to stoichiometric CZTS have a columnar, crystalline structure. Materials analysis suggests a non-equilibrium phase with a cubic structure, where each S atom is randomly surrounded by 2:1:1 Cu:Zn:Sn-atoms, respectively. Substrate heating during sputtering is shown to be important to avoid cracks in the annealed films while stress in the precursor films is not observed to affect the absorber or solar cell quality.

Sputtering from compound targets in Ar-atmosphere yields precursor properties similar to those from reactive sputtering at high H₂S/Ar-ratios and both types can be processed into well-performing solar cells.

Additionally, a low temperature treatment of CZTS absorbers in inert atmosphere prior to buffer layer growth is shown to affect the device properties, which indicates that the thermal history of the CZTS absorber is important.

The alternative buffer system ZnO_1-xS_x is found to yield lower efficiencies than expected, possibly due to inferior interface or buffer quality. The Zn_1-xSn_xO_y (ZTO) buffers instead give better performance than their CdS references. For optimized parameters, the activation energy for recombination coincides with the energy of the photoluminescence peak of the absorber. This can be interpreted as a shift of dominant recombination path from the interface to the CZTS bulk. A well-performing CZTS-ZTO device with antireflective coating yielded an efficiency of 9.0 %, which at the time of publication was the highest value published for a Cd-free pure-sulfide CZTS solar cell.

Abstract

The CIS solar cell family features both a high stability and world-class performances. They can be deposited on a wide variety of substrates and absorb the entire solar spectrum only using a thickness of a few micrometers. These particularities allow them to feature the most positive Energy returned on energy invested (EROI) values and the shortest Energy payback times (EPBT) of all the main photovoltaic solar cells. Using mainly electron microscopy characterization techniques, this thesis has explored the questions related to the interface control in thin-film photovoltaic solar cells based on CuInSe₂ (CIS) absorber materials. Indeed, a better understanding of the interfaces is essential to further improve the solar cell conversion efficiency (currently around 23%), but also to introduce alternative substrates, to implement various alloying (Ga-CIS (CIGS), Ag-CIGS (ACIGS)…) or even to assess alternative buffer layers.

The thread of this work is the understanding and the improvement of the interface control. To do so, the passivation potential of Al₂O₃ interlayers has been studied in one part of the thesis. While positive changes were generally measured, a subsequent analysis has revealed that a detrimental interaction could occur between the NaF precursor layer and the rear Al₂O₃ passivation layer. Still within the passivation research field, incorporation of various alkali-metals to the CIS absorber layer has been developed and analyzed. Large beneficial effects were ordinarily reported. However, similar KF-post deposition treatments were shown to be potentially detrimental for the silver-alloyed CIGS absorber layer. Finally, part of this work dealt with the limitations of the thin-barrier layers usually employed when using steel substrates instead of soda-lime glass ones. The defects and their origin could have been related to the steel manufacturing process, which offered solutions to erase them.

Electron microscopy, especially Transmission electron microscopy (TEM), was essential to scrutinize the local changes occurring at the different interfaces within a few nanometers. The composition variation was measured with both Electron energy loss spectroscopy (EELS) and Energy dispersive X-ray spectroscopy (EDS) techniques. Finally, efforts have been invested in controlling and improving the FIB sample preparation, which was required for the TEM observations in our case.

Abstract

Thin film chalcogenide solar cells are promising photovoltaic technologies. Cu(In,Ga)Se₂ (CIGS)-based devices are already produced at industrial scale and record laboratory efficiency surpasses 22 %. Cu₂ZnSn(S,Se)₄ (CZTS) is an alternative material that is based on earth-abundant elements. CZTS device efficiency above 12 % has been obtained, indicating a high potential for improvement.

In this thesis, in-line vacuum, sputtering-based processes for the fabrication of complete thin film chalcogenide solar cells on stainless steel substrates are studied. CIGS absorbers are deposited in a one-step high-temperature process using compound targets. CZTS precursors are first deposited by room temperature sputtering and absorbers are then formed by high temperature crystallization in a controlled atmosphere. In both cases, strategies for absorber layer improvement are identified and implemented.

The impact of CZTS annealing temperature is studied and it is observed that the absorber grain size increases with annealing temperature up to 550 °C. While performance also improves from 420 to 510 °C, a drop in all solar cell parameters is observed for higher temperature. This loss is caused by blisters forming in the absorber during annealing. Blister formation is found to originate from gas entrapment during precursor sputtering. Increase in substrate temperature or sputtering pressure leads to drastic reduction of gas entrapment and hence alleviate blister formation resulting in improved solar cell parameters, including efficiency.

An investigation of bandgap grading in industrial CIGS devices is conducted through one-dimensional simulations and experimental verification. It is found that a single gradient in the conduction band edge extending throughout the absorber combined with a steeper back-grading leads to improved solar cell performance, mainly due to charge carrier collection enhancement.

The uniformity of both CIGS and CZTS 6-inch solar cells is assessed. For CZTS, the device uniformity is mainly limited by the in-line annealing process. Uneven heat and gas distribution resulting from natural convection phenomenon leads to significant lateral variation in material properties and device performance. CIGS solar cell uniformity is studied through laterally-resolved material and device characterization combined with SPICE network modeling. The absorber material is found to be laterally homogeneous. Moderate variations observed at the device level are discussed in the context of large area sample characterization.

Power conversion efficiency values above 15 % for 225 cm² CIGS cells and up to 5.1 % for 1 cm² CZTS solar cells are obtained.

Abstract

Ion sensing represents a grand research challenge. It finds a vast variety of applications in, e.g., gas sensing for domestic gases and ion detection in electrolytes for chemical-biological-medical monitoring. Semiconductor genome sequencing exemplifies a revolutionary application of the latter. For such sensing applications, the signal mostly spans in the low frequency regime. Therefore, low-frequency noise (LFN) present in the same frequency domain places a limit on the minimum detectable variation of the sensing signal and constitutes a major research and development objective of ion sensing devices. This thesis focuses on understanding LFN in ion sensing based on both experimental and theoretical studies.

The thesis starts with demonstrating a novel device concept, i.e., ion-gated bipolar amplifier (IGBA), aiming at boosting the signal for mitigating the interference by external noise. An IGBA device consists of a modified ion-sensitive field-effect transistors (ISFET) intimately integrated with a bipolar junction transistor as the internal current amplifier with an achieved internal amplification of 70. The efficacy of IGBA in suppressing the external interference is clearly demonstrated by comparing its noise performance to that of the ISFET counterpart.

Among the various noise sources of an ISFET, the solid/liquid interfacial noise is poorly studied. A differential microelectrode cell is developed for characterizing this noise component by employing potentiometry and electrochemical impedance spectroscopy. With the cell, the measured noise of the TiN/electrolyte interface is found to be of thermal nature. The interfacial noise is further found to be comparable or larger than that of the state-of-the-art MOSFETs. Therefore, its influence cannot be overlooked for design of future ion sensors.

To understand the solid/liquid interfacial noise, an electrochemical impedance model is developed based on the dynamic site-binding reactions of surface hydrogen ions with surface OH groups. The model incorporates both thermodynamic and kinetic properties of the binding reactions. By considering the distributed nature of the reaction energy barriers, the model can interpret the interfacial impedance with a constant-phase-element behavior. Since the model directly correlates the interfacial noise to the properties of the sensing surface, the dependencies of noise on the reaction rate constants and binding site density are systematically investigated.

Abstract

In this thesis, modeling and electrical characterization have been performed on Cu(In,Ga)Se₂ (CIGS) and Cu₂ZnSnS₄ (CZTS) thin film solar cells, with the aim to investigate potential improvements to power conversion efficiency for respective technology. The modeling was primarily done in SCAPS, and current-voltage (J-V), quantum efficiency (QE) and capacitance-voltage (C-V) were the primary characterization methods. In CIGS, models of a 19.2 % efficient reference device were created by fitting simulations of J-V and QE to corresponding experimental data. Within the models, single and double GGI = Ga/(Ga+In) gradients through the absorber layer were optimized yielding up to 2 % absolute increase in efficiency, compared to the reference models. For CIGS solar cells of this performance level, electron diffusion length (L_n) is comparable to absorber thickness. Thus, increasing GGI towards the back contact acts as passivation and constitutes largest part of the efficiency increase. For further efficiency increase, majority bottlenecks to improve are optical losses and electron lifetime in the CIGS. In a CZTS model of a 6.7 % reference device, bandgap (E_g) fluctuations and interface recombination were shown to be the majority limit to open circuit voltage (V_oc), and Shockley-Read-Hall (SRH) recombination limiting L_n and thus being the majority limit to short-circuit current and fill-factor. Combined, E_g fluctuations and interface recombination cause about 10 % absolute loss in efficiency, and SRH recombination about 9 % loss, compared to an ideal system. Part of the V_oc-deficit originates from a cliff-type conduction band offset (CBO) between CZTS and the standard CdS buffer layer, and the energy of the dominant recombination path (E_A) is around 1 eV, well below E_g for CZTS. However, it was shown that the CBO could be adjusted and improved with Zn_1-xSn_­xO_y buffer layers. Best results gave E_A = 1.36 eV, close to E_g = 1.3-1.35 eV for CZTS as given by photoluminescence, and the V_oc-deficit decreased almost 100 mV. Experimentally by varying the absorber layer thickness in CZTS devices, the efficiency saturated at <1 μm, due to short L_n, expected to be 250-500 nm, and narrow depletion width, commonly of the order 100 nm in in-house CZTS. Doping concentration (N_A) determines depletion width, but is critical to device performance in general. To better estimate N_A with C-V, ZnS and CZTS sandwich structures were created, and in conjunction with simulations it was seen that the capacitance extracted from CZTS is heavily frequency dependent. Moreover, it was shown that C-V characterization of full solar cells may underestimate N_A greatly, meaning that the simple sandwich structure might be preferable in this type of analysis. Finally, a model of the Cu₂ZnSn(S,Se)₄ was created to study the effect of S/(S+Se) gradients, in a similar manner to the GGI gradients in CIGS. With lower E_g and higher mobility for pure selenides, compared to pure sulfides, it was seen that increasing S/(S+Se) towards the back contact improves efficiency with about 1 % absolute, compared to the best ungraded model where S/(S+Se) = 0.25. Minimizing E_g fluctuation in CZTS in conjunction with suitable buffer layers, and improving L_n in all sulfo-selenides, are needed to bring these technologies into the commercial realm.

Abstract

In Cu(In,Ga)Se₂ (CIGS) solar cells the CIGS layer serves as the light absorber, growing naturally p-type. Together with an n-type buffer layer they form a p-n heterojunction. Typically, CdS is used as a buffer, although other, less toxic materials are investigated as alternatives. The intrinsic p-type doping of CIGS layers is the result of complex defect physics. Defect formation energies in CIGS are very low or even negative, which results in extremely high defect concentrations. This leads to many unusual electrical phenomena that can be observed in CIGS devices. This thesis mostly focuses on three of these phenomena: light-soaking, light-on-bias, and light-enhanced reverse breakdown.

Light-soaking is a treatment that involves illuminating the investigated device for an extended period of time. In most CIGS solar cells it results in an improvement of open-circuit voltage, fill factor, and efficiency that can persist for hours, if not days. The interplay between light-soaking and the remaining two phenomena was studied. It was found that light-soaking has a strong effect on light-on-bias behavior, while the results for light-enhanced breakdown were inconclusive, suggesting little to no impact.

Light-on-bias is a treatment which combines simultaneous illumination and application of reverse bias to the studied sample. Illuminating CdS-based samples with red light while applying a reverse bias results in a significant increase in capacitance due to filling of traps. In many cases, this is accompanied by a decrease in device performance under red illumination. Complete recovery is possible by illuminating the treated sample with blue light, which causes hole injection from the CdS buffer. In samples with alternative buffer layers, there is little distinction between red and blue illumination, and the increase in capacitance is milder. At the same time, there is little effect on device performance.

Reverse breakdown can occur when a sufficiently large reverse bias is applied to a p-n junction, causing a large reverse current to flow through the device. In CIGS solar cells, the voltage at which breakdown occurs in darkness decreases in the presence of blue illumination. A model explaining the breakdown in darkness was proposed as a part of this thesis. The model assumes that all voltage drops on the buffer layer in darkness and on the CIGS layer under blue illumination. The high electric field in the buffer facilitates Poole-Frenkel conduction and Fowler-Nordheim tunneling between the absorber and the buffer.

Abstract

Biosensors are devices that detect biological elements and then transmit a readable signal. Biosensors can automatize diagnostics that would otherwise have to be performed by a physician or perhaps not be possible to perform at all. Current biosensors are however either limited to particular diseases or prohibitively expensive. In order to further the field, sensors capable of many parallel measurements at a lower cost need to be developed. Field effect transistor (FET) based sensors are possible candidates for delivering this, mainly by allowing miniaturization. Smaller sensors could be cheaper, and enable parallel measurements.

Graphene is an interesting material to use as the channel of FET-sensors. The low electrochemical reactivity of its plane makes it possible to have graphene in direct contact with the sample liquid, which enhances the signal from impedance changes. Graphene-FET based impedance sensors should be able to sense almost all possible analytes and allow for scaling without losing sensitivity.

In this work the steps needed to make graphene based biosensors are presented. An improved graphene transfer is described which by using low pressure to dry the graphene removes most contamination. A method to measure the contamination of graphene by surface enhanced Raman scattering is presented. Methods to produce double gated and electrolyte gated graphene transistors on a large scale in an entirely photolithographic process are detailed. The deposition of 1-pyrenebutyric acid (PBA) on graphene is studied. It is shown that at high surface concentrations the PBA stands up on graphene and forms a dense self-assembled monolayer. A new process of using Raman spectroscopy data to quantify adsorbents was developed in order to quantify the molecule adsorption. Biosensing has been performed in two different ways. Graphene FETs have been used to read the signal generated by a streaming potential setup. Using FETs in this context enables a more sensitive readout than what would be possible without them. Graphene FETs have been used to directly sense antibodies in high ionic strength. This sensing was done by measuring the impedance of the interface between the FET and the electrolyte.

Abstract

Kesterite Cu₂ZnSnS₄ (CZTS) is interesting as a sustainable photovoltaic technology due to its earth-abundant elements and suitable semiconducting properties. To date, a record efficiency of 12.6% has been achieved but further improvements are required to reach high efficiency for industrial implementation. Among the limiting issues is the understanding of the annealing process, which is crucial in promoting high material quality. In particular, the knowledge of the effects of segregated secondary compounds on solar cell performance is lacking.

In contrast to formation of ZnS particles throughout CZTS film, it is notable that SnS forms and usually segregates on the CZTS top and rear surfaces. The influence of SnS on CZTS solar cells was studied by electron beam induced current measurements. It is found that SnS presence on the CZTS surfacecan introduce “dead area”, whereas it seems beneficial for solar cell current when accumulates on the CZTS rear. For SnS passivation and from investigation of the passivation effect from an Al₂O₃ thin layer at the CZTS rear, improvement in overall device performance could not be demonstrated, due to either poor CZTS bulk or non-optimal device structure. The limitation in CZTS bulk quality was shown from a thickness study where carrier collection saturated already about 700-1000 nm CZTS thickness.

Formation of SnS alongside CZTS implies the anneal is limited by a deficient sulfur partial pressure (P_S2). By looking into Sn-S phase transformations in SnS₂ films after annealing, we find that P_S2 drops rapidly over the annealing time, which could be well-correlated to a series of changes in CZTS material quality including secondary phase formations and defect modifications. It is shown that annealing CZTS under sufficiently high P_S2 is critical for CZTS solar cells with high open circuit voltage (upto 783mV was reached), possibly due to the defect modification.

Besides SnS, it is observed that Na_xS compounds are also readily formed on CZTS surfaces, due to Na diffusion from the glass substrate during annealing. Na_xS negatively affects the formation of the CdS/CZTS interface during chemical bath deposition. It can be removed by an oxidation process or wet chemical etching.

Abstract

High-temperature electrical- and morphological-stability of interconnect is critical for electronic systems based on wide band gap (WBG) semiconductors. In this context, the thermal stability of both Ag and Cu films with Ta and TaN films as diffusion barriers and/or surface-capping layers at high temperatures up to 800 ^oC is investigated in this thesis.

The investigation of un-capped Ag films with either Ta or TaN diffusion barrier layers shows electrical stability upon annealing up to 600 °C. Degradation occurs above 600 °C mainly as a result of void formation and Ag agglomeration. Sandwiching Ag films between Ta and/or TaN layers is found to electrically and morphologically stabilize the Ag metallization up to 800 °C. The barrier layer plays a key role; the β-to-α phase transition in the underlying Ta barrier layer is identified as the major cause for the morphological instability of the film above 600 °C. This phase transition can be avoided using a stacked Ta/TaN barrier. Furthermore, no observable Ta diffusion in Ag films is found.

Copper films with a Ta diffusion barrier show clearly different behaviors. In the Cu/Ta sample, Ta starts to diffuse up to the surface via fast-diffusing grain boundaries (GBs) after annealing at 500 °C. The activation energy for the GB diffusion is 1.0+0.3 eV. Un-capped Cu is electrically stable up to 800 °C. An appreciable increase in sheet resistance occurs above 600 °C for the asymmetric combinations Ta/Cu/TaN and TaN/Cu/Ta. This degradation is closely related to a substantial diffusion of Ta across the Cu film and on to the TaN layer, where Ta_1+xN forms. The symmetrical combinations Ta/Cu/Ta and TaN/Cu/TaN show only small changes in sheet resistance even after annealing at 800 °C. No Ta diffusion can be found in the Ta/Cu/Ta and TaN/Cu/TaN stacks.

Finally, the influence of barrier and cap, their interfaces to Cu and Ta diffusion and segregation in the Cu GBs on electromigration is studied. Our preliminary results with the TaN/Cu/Ta and TaN/Cu/TaN structures report a 2-fold higher activation energy and a 10-fold longer lifetime for the former, thus confirming an important role of the interface between Cu and the cap and/or barrier.

Abstract

Graphene, with its two-dimensional nature and unique properties, has for over a decade captured enormous interests in both industry and academia. This work tries to answer the question of what would happen to graphene when it is subjected to various processing conditions and how this would affect the graphene functionality. The focus is placed on its ability to withstand different thin-film deposition environments with regard to the implementation of graphene in two application areas: as a diffusion barrier and in electronic devices.

With single-layer graphene films grown in-house by means of chemical vapor deposition (CVD), four techniques among the well-established thin-film deposition methods are studied in detail: atomic layer deposition (ALD), evaporation, sputter-deposition and spray-deposition. And in this order, these methods span a large range of kinetic impact energies from low to high. Graphene is known to have a threshold displacement energy of 22 eV above which carbon atoms are ejected from the lattice. Thus, ALD and evaporation work with energies below this threshold, while sputtering and spraying may involve energies above. The quality of the graphene films undergone the various depositions is mainly evaluated using Raman spectroscopy.

Spray deposition of liquid alloy Ga-In-Sn is shown to require a stack of at least 4 layers of graphene in order to act as an effective barrier to the Ga diffusion after the harsh spray-processing. Sputter-deposition is found to benefit from low substrate temperature and high chamber pressure (thereby low kinetic impact energy) so as to avoid damaging the graphene. Reactive sputtering should be avoided. Evaporation is non-invasiveness with low kinetic impact energy and graphene can be subjected to repeated evaporation and removal steps without losing its integrity. With ALD, the effects on graphene are of different nature and they are investigated in the field-effect-transistor (FET) configuration. The ALD process for deposition of Al₂O₃ films is found to remove undesired dopants from the prior processing and the Al₂O₃ films are shown to protect the graphene channel from doping by oxygen. When the substrate is turned hydrophobic by chemical treatment prior to graphene transfer-deposition, a unipolar transistor behavior is obtained.

Abstract

Soft matter, here, liquids and polymers, have adaptability to a surrounding geometry. They intrinsically have advantageous characteristics from a mechanical perspective, such as flowing and wetting on surrounding surfaces, giving compliant, conformal and deformable behavior. From the behavior of soft matter for heterogeneous surfaces, compliant structures can be engineered as embedded liquid microstructures or patterned liquid microsystems for emerging compliant microsystems.

Recently, skin electronics and soft robotics have been initiated as potential applications that can provide soft interfaces and interactions for a human-machine interface. To meet the design parameters, developing soft material engineering aimed at tuning material properties and smart processing techniques proper to them are to be highly encouraged. As promising candidates, Ga-based liquid alloys and silicone-based elastomers have been widely applied to proof-of-concept compliant structures.

In this thesis, the liquid alloy was employed as a soft and stretchable electrical and thermal conductor (resistor), interconnect and filler in an elastomer structure. Printing-based liquid alloy patterning techniques have been developed with a batch-type, parallel processing scheme. As a simple solution, tape transfer masking was combined with a liquid alloy spraying technique, which provides robust processability. Silicone elastomers could be tunable for multi-functional building blocks by liquid or liquid-like soft solid inclusions. The liquid alloy and a polymer additive were introduced to the silicone elastomer by a simple mixing process. Heterogeneous material microstructures in elastomer networks successfully changed mechanical, thermal and surface properties.

To realize a compliant microsystem, these ideas have in practice been useful in designing and fabricating soft and stretchable systems. Many different designs of the microsystems have been fabricated with the developed techniques and materials, and successfully evaluated under dynamic conditions. The compliant microsystems work as basic components to build up a whole system with soft materials and a processing technology for our emerging society.

Abstract

The aim of this thesis is to provide an in-depth investigation of zinc tin oxide, Zn_1-xSn_xO_y or ZTO, grown by atomic layer deposition (ALD) as a buffer layer in Cu(In,Ga)Se₂ (CIGS) solar cells. The thesis analyzes how changes in the ALD process influence the material properties of ZTO, and how these in turn affect the performance of CIGS solar cells.

It is shown that ZTO grows uniformly and conformably on CIGS and that the interface between ZTO and CIGS is sharp with little or no interdiffusion between the layers. The band gap and conduction band energy level of ZTO are dependent both on the [Sn]/([Zn]+[Sn]) composition and on the deposition temperature. The influence by changes in composition is non-trivial, and the highest band gap and conduction band energy level are obtained at a [Sn]/([Zn]+[Sn]) composition of 0.2 at 120  °C. An increase in optical band gap is observed at decreasing deposition temperatures and is associated with quantum confinement effects caused by a decrease in crystallite size. The ability to change the conduction band energy level of ZTO enables the formation of suitable conduction band offsets between ZTO and CIGS with varying Ga-content.

It is found that 15 nm thin ZTO buffer layers are sufficient to fabricate CIGS solar cells with conversion efficiencies up to 18.2 %. The J_SC is in general 2 mA/cm² higher, and the V_OC 30 mV lower, for cells with the ZTO buffer layer as compared to cells with the traditional CdS buffer layer. In the end comparable efficiencies are obtained for the two different buffer layers. The gain in J_SC for the ZTO buffer layer is associated with lower parasitic absorption in the UV-blue region of the solar spectrum and it is shown that the J_SC can be increased further by making changes to the other layers in the traditional CdS/i-ZnO/ZnO:Al window layer structure. The ZTO is highly resistive, and it is found that the shunt preventing i-ZnO layer can be omitted, which further increases the J_SC. Moreover, an additional increase in J_SC is obtained by replacing the sputtered ZnO:Al front contact with In₂O₃ deposited by ALD. The large gain in J_SC for the ZTO/In₂O₃ window layer stack compensates for the lower V_OC related to the ZTO buffer layer, and it is demonstrated that the ZTO/In₂O₃ window layer structure yields 0.6 % (absolute) higher conversion efficiency than the CdS/i-ZnO/ZnO:Al window layer structure. 

Abstract

This thesis presents solutions and studies related to the design of reconfigurable and wideband receiver circuits for system-on-chip (SoC) radiometer front-ends within the millimetre-wave (mm-wave) range. Whereas many of today’s mm-wave front-ends are bulky and costly due to having discrete RF components, single-chip receiver modules could potentially result in a wider use for emerging applications such as wireless communication, short range radar and passive imaging security sensors if realised with adequate performances and at a lower cost. Three main topics are considered in this thesis, monolithic integration of low-loss RF-MEMS (Dicke) switch networks and switched LNAs in MMIC/RFIC foundry processes, designs of SiGe wideband (IF) amplifier and broadband power detectors up to W-band (75-110 GHz).

Low-loss and high isolation GaAs and SiGe RF-MEMS switch networks were designed and characterised for the 30-110 GHz range. A GaAs MEMS Dicke switch network has a measured minimum loss of 1 dB and maximum isolation of 19 dB at 70-96 GHz, respectively, making it a potential candidate in Dicke switched radiometer receivers. Furthermore, single-chip 30 GHz and W-band MEMS Dicke switched LNA designs have been realised for the first time in SiGe BiCMOS and GaAs mHEMT processes, respectively.

For a targeted 94 GHz passive imaging application two different receiver topologies have been investigated based on direct-detection and direct-conversion (heterodyne) architectures. An optimised detector design fabricated in a 0.13 μm SiGe process achieves a more wideband input matching than earlier silicon W-band detectors and is competitive with reported III-V W-band detectors in terms of a higher responsivity and similar NEP.

A SiGe 2-37 GHz high-gain differential (IF) amplifier design achieves a more wideband matching and an order of magnitude higher linearity than a recent single-ended SiGe LNA. The SiGe IF amplifier was integrated on-chip with a power detector in a 5-35 GHz IF section. Their broadband properties compared with other IF amplifier/detector RFICs, make them suitable for W-band down-conversion receivers with a larger pre-detection bandwidth and improved sensitivity. The experimental results successfully demonstrate the feasibility of the SiGe 5-35 GHz IF section for high performance SoC W-band radiometers using a more wideband heterodyne receiver architecture.

 

Abstract

The main focus of the work presented in this thesis concerns the development and improvement of Wireless Sensor Networks (WSNs) as well as Wireless Body Area Networks (WBANs). WSN consist of interlinked, wireless devices (nodes) capable of relaying data wirelessly between the nodes. The applications of WSNs are very broad and cover both wireless fitness monitoring systems such as pulse watches or wireless temperature monitoring of buildings, among others.

The topics investigated in the work presented within this thesis covers antenna design, wireless propagation environment evaluation and modeling, adaptive antenna control and wireless nodes system design and evaluation. In order to provide an end-user suitable solution for wireless nodes the devices require both small form factor and good performance in order to be competitive on the marked and thus the main part of this thesis focuses on techniques developed and data collected to help achieve these goals. 

Several different prototype systems have been developed which have been used to measure data by the Swedish Defence Research Agency (FOI), GKN Aerospace Sweden AB, the Swedish Transport Administration. The system developed with GKN Aerospace was used to do real-time test measurements inside a running RM12 jet engine and required a substantial amount of measurements, environmental modeling and system validation in order to properly design a wireless system suitable for the harsh and fast fading environment inside a jet engine. For FOI improvements were made on a wearable wireless body area network initially developed during the authors master thesis work. Refinements included work on new generation wireless nodes, antenna packaging and node-supported diversity techniques.

Work and papers regarding the design of different types of antennas suitable for wireless nodes are presented. The primary constraints on the presented antennas are the limited electrical size. The types of antennas developed include electrically small helix antennas manufactured both on stretchable substrates consisting of a PDMS substrate with Galinstan as the liquid metal conductors, screen printed silver ink for helix antennas and conformal dual patch antennas for wireless sensor nodes. Other standard type antennas are included on the wireless sensors as well.

Abstract

The thin film technology is of great importance in modern society and is a key technology in wide spread applications from electronics and solar cells to hard protective coatings on cutting tools and diffusion barriers in food packaging. This thesis deals with various aspects of thin film processing and the aim of the work is twofold; firstly, to obtain a fundamental understanding of the sputter deposition and the reactive sputter deposition processes, and secondly, to evaluate sputter deposition of specific material systems with low friction properties and to improve their performance.From studies of the reactive sputtering process, two new methods of eliminating the problematic and undesirable hysteresis effect were found. In the first method it was demonstrated that an increased process pressure caused a reduction and, in some cases, even elimination of the hysteresis. In the second method it was shown that sufficiently high oxide content in the target will eliminate the hysteresis.

Further studies of non-reactive magnetron sputtering of multi-element targets at different pressures resulted in huge pressure dependent compositional gradients over the chamber due to different gas phase scattering of the elements. This has been qualitatively known for a long time but the results presented here now enable a quantitative estimation of such effects. For example, by taking gas phase scattering into consideration during sputtering from a WS₂ target it was possible to deposit WS_x films with a sulphur content going from sub-stoichiometric to over-stoichiometric composition depending on the substrate position relative the target.

By alloying tungsten disulphide (WS₂) with carbon and titanium (W-S-C-Ti) its hardness was significantly increased due to the formation of a new titanium carbide phase (TiC_xS_y). The best sample increased its hardness to 18 GPa (compared to 4 GPa for the corresponding W-S-C coating) while still maintaining a low friction (µ=0.02) due to the formation of easily sheared WS₂ planes in the wear track. 

Abstract

The requirements of the consumer market on high frequency devices have been more and more demanding over the last decades. Thus, a continuing enhancement of the devices’ performance is required in order to meet these demands. In a macro view, changing the design of the device can result in an improvement of its performance. In a micro view, the physical properties of the device materials have a strong influence on its final performance. In the case of high frequency devices based on piezoelectric materials, a natural way to improve their performance is through the improvement of the properties of the piezoelectric layer. The piezoelectric material studied in this work is AlN, which is an outstanding material among other piezoelectric materials due to its unique combination of material properties.

This thesis presents results from experimental studies on the synthesis of AlN thin films in view of telecom, microelectronic and sensor applications. The main objective of the thesis is to custom design the functional properties of AlN to best suit these for the specific application in mind. This is achieved through careful control of the crystallographic structure and texture as well as film composition.

The piezoelectric properties of AlN films were enhanced by doping with Sc. Films with different Sc concentrations were fabricated and analyzed, and the coupling coefficient (k_t²) was enhanced a factor of two by adding 15% of Sc to the AlN films. The enhancement of k_t² is of interest since it can contribute to a more relaxed design of high frequency devices. Further, in order to obtain better deposition control of c-axis tilted AlN films, a new experimental setup were proposed. When this novel setup was used, films with well-defined thicknesses and tilt uniformity were achieved. Films with such characteristics are very favorable to use in sensors based on electroacoustic devices operating in viscous media. Studies were also performed in order to obtain c-axis oriented AlN films deposited directly on Si substrates at reduced temperatures. The deposition technique used was HiPIMS, and the results indicated significant improvements in the film texture when comparing to the conventional Pulsed DC deposition process.

Abstract

In this thesis, we are making a new approach to fabricate silicon on insulator (SOI). By replacing the buried silicon dioxide and the silicon handling wafer with silicon carbide through hydrophilic wafer bonding, we have achieved silicon on crystalline silicon carbide for the first time and silicon on polycrystalline silicon carbide substrates at 150 mm wafer size. The conditions for the wafer bonding are studied and the surface and bond interface are characterized. Stress free and interfacial defect free hybrid wafer bonding has been achieved.

The thermally unfavourable interfacial oxide that originates from the hydrophilic treatment has been removed through high temperature annealing, denoted as Ox-away. Based on the experimental observations, a model to explain the dynamics of this process has been proposed. Ox-away together with spheroidization are found to be the responsible theories for the behaviour. The activation energy for this process is estimated as 6.4 eV.

Wafer bonding of Si and polycrystalline SiC has been realised by an intermediate layer of amorphous Si. This layer recrystallizes to some extent during heat treatment.

Electronic and thermal testing structures have been fabricated on the 150 mm silicon on polycrystalline silicon carbide hybrid substrate and on the SOI reference substrate. It is shown that our hybrid substrates have similar or improved electrical performance and 2.5 times better thermal conductivity than their SOI counterpart. 2D simulations together with the experimental measurements have been carried out to extract the thermal conductivity of polycrystalline silicon carbide as κpSiC = 2.7 WK-1cm-1.

The realised Si-on-SiC hybrid wafer has been shown to be thermally and electrically superior to conventional SOI and opens up for hybrid integration of silicon and wide band gap material as SiC and GaN.

Abstract

Wireless sensor network (WSN) has become a hot topic lately. By using WSN things that previously were difficult or impossible to measure has now become available. One of the main reasons using WSN for monitoring is to save money by cost optimization and/or increase safety by letting the user knowing the physical status of the monitored structure. This thesis considers four main topics, empirical testing of WSN in harsh environments, antenna designs, antenna measurements and radio environment emulation.

The WSN has been tested in train environment for monitoring of ball bearings and inside jet engines to monitor strain of blades and temperatures. In total, two investigations have been performed aboard the train wagon and one in the jet engine. The trials have been successful and provide knowledge of the difficulties with practical WSN applications. The key issues for WSN are robust communication, energy management (including scavenging) and physical robustness.

For the applications of WSN in harsh environments antennas has to be designed. In the thesis, two antennas has been designed, one for train environment and one for the receiver in the jet engine. In the train environment, a more isotropic radiation pattern is preferable; hence a small dual layered patch antenna is designed. The antenna is at the limit of being electrically small; hence slightly lower radiation efficiency is measured. For the WSN in the jet engine, a directive patch array is designed on an ultra-thin and flexible substrate. The thin substrate of the antenna causes rather lower radiation efficiency. But the antenna fulfils the requirements of being conformal and directive.

In reverberation chambers are used to measure antennas, but there are difficulties to provide a realistic radio environment, for example outdoor or on-body. In this thesis, a large reverberation chamber is designed and verified. It enables measurement between 400 MHz and 3 GHz. Also, a sample selection method is designed to provide a post processing possibilities to emulate the radio environment inside the chamber. The method is to select samples from a data set that corresponds to a desired probability density function. The method presented in this thesis is extremely fast but the implementation of the method is left for future research.

Abstract

With increasing amount of user data and applications in wireless communication technology, demands are growing on performance and fabrication costs. One way to decrease cost is to integrate the building blocks in an RF system where digital blocks and high power amplifiers then are combined on one chip. This thesis presents LDMOS transistors integrated in a 65 nm CMOS process without adding extra process steps or masks. High power performance of the LDMOS is demonstrated for an integrated WLAN-PA design at 2.45 GHz with 32.8 dBm output power and measurements also showed that high output power is achievable at 5.8 GHz. For the first time, this kind of device is moreover demonstrated at X-band with over 300 mW/mm output power, targeting communication and radar systems at 8 GHz. As SOI is increasing in popularity due to better device performance and RF benefits, the buried oxide can cause thermal problems, especially for high power devices. To deal with self-heating effects and decrease the RF substrate losses further, this thesis presents a hybrid substrate consisting of silicon on top of polycrystalline silicon carbide (Si-on-poly-SiC). This hybrid substrate utilizes the high thermal conductivity of poly-SiC to reduce device self-heating and the semi-insulating properties to reduce RF losses. Hybrid substrates were successfully fabricated for the first time in 150 mm wafer size by wafer bonding and evaluation was performed in terms of both electrical and thermal measurements and compared to a SOI reference. Successful LDMOS transistors were fabricated for the first time on this type of hybrid substrate where no degradation in electrical performance was seen comparing the LDMOS to identical transistors on the SOI reference. Measurements on calibrated resistors showed that the thermal conductivity was 2.5 times better for the hybrid substrate compared to the SOI substrate. Moreover, RF performance of the hybrid substrate was investigated and the semi-insulating property of poly-SiC showed to be beneficial in achieving a high equivalent substrate parallel resistance and thereby low substrate losses. In a transistor this would be equal to better efficiency and output power. In terms of integration, the hybrid substrate also opens up the possibility of heterogeneous integration where silicon devices and GaN devices can be fabricated on the same chip.

Abstract

The sun provides us with a surplus of energy convertible to electricity using solar cells. This thesis focuses on solar cells based on chalcopyrite (CIGSe) as well as kesterite (CZTS(e)) absorber layers. These materials yield record efficiencies of 20.4 % and 11.1 %, respectively. Especially for CZTS(e), the absorber layers often do not consist of one single desired phase but can exhibit areas with deviating material properties, referred to as secondary phases. Furthermore, several material layers are required for a working solar cell, each exhibiting interfaces. Even though secondary phases and interfaces represent a very small fraction of the solar cell they can have a profound influence on the over-all electrical solar cell characteristics. As such, it is crucial to understand how secondary phases and interfaces influence the local electrical characteristics.

Characterising secondary phases and interfaces is challenging due to their small sample volume and relatively small differences in composition amongst others. This is where electronmicroscopy, especially transmission electron microscopy, offers valuable insight to material properties on the microscopic scale. The main challenge is, however, to link these material properties to the corresponding electrical characteristics of a solar cell.

This thesis uses electron beam induced current imaging and introduces a new method for JV characterisation of solar cells on the micron scale. Combining microscopic structural and electrical characterisation techniques allowed identifying and characterising local defects found in the absorber layer of CIGS solar cells after thermal treatment. Furthermore, CZTSe solar cells in this thesis exhibited a low photo-current density which is traced to the formation of a current blocking ZnSe secondary phase at the front contact interface. The electron microscopy work has contributed to an understanding of the chemical stability of CZTS and has shown the need for an optimised back contact interface in order to avoid chemical decomposition reactions and formation of detrimental secondary phases. With this additional knowledge, a comprehensive picture of the material properties from the macroscopic down to the microscopic level can be attained throughout all required material layers.

Abstract

Emerging macro- and flexible electronic applications such as foldable displays, artificial skins, and smart textiles grow rapidly into the market. Solution-processed thin-film transistors (TFTs) based on single-walled carbon nanotubes (SWCNTs) as the semiconductor channel can offer high performance, low cost and versatility for macro- and flexible electronics. Major challenges to the development of SWCNT-based TFTs include: (i) hysteresis in their transfer characteristics (TCs), (ii) difficulties in simultaneous achievements of high on-state current I_on and large on/off current ratio I_on/I_off, and (iii) poor uniformity and scalability resulting from the poor solution processability. This thesis aims at developing reliable and simple process techniques for fabrication of the SWCNT-based TFTs that possess the afore-stated characteristics. It presents a systematic investigation to not only explore the fundamental device physics, but also develop novel fabrication methods for enhancement of device performance.

First, issues related to the measurement of gate capacitance (C_g), the determination of current scalability, and the hysteresis in randomly networked SWCNTs are properly addressed. This leads to the establishment of a comprehensive methodology for extraction of carrier mobility (μ) for the SWCNT-based TFTs. In detail, the large hysteresis is effectively suppressed by adopting a pulsed drain current-gate voltage (I_d-V_g) method in which the polarity of the gate pulse was alternating during the measurement. Different from most reported methods in the literature, C_g is accurately determined in our case by performing direct capacitance-voltage measurement on the TFTs.

Second, with the employment of functional composites comprising SWCNTs embedded in a semiconducting polymer, poly-9,9 dioctyl-fluorene-cobithiophene (F8T2), as the semiconducting channel via facile solution processes under ambient conditions, the fabricated TFTs exhibit outstanding electrical performance with: (i) negligible hysteresis, (ii) high μ, (iii) high I_on and large I_on/I_off, (iv) excellent uniformity and dimensional scalability, and (v) good stability. These highly desired performance parameters are achieved owing to an ideal composite structure with metallic SWCNTs being selectively removed and the remaining semiconducting SWCNTs being well wrapped by the polymer matrix.

Finally, the developed TFTs basing on the SWCNT/F8T2 composite are used as the building block to construct some logic circuits. The resultant inverters, NANDs, and NORs are found to retain the small-hysteresis characteristics, with a cut-off frequency reaching 100 kHz. The results presented in this thesis advance the state-of-art SWCNT-based macroelectronics.

Abstract

Point-of-care (POC) diagnostics presents a giant market opportunity with profound societal impact. In particular, specific detection of DNA and protein markers can be essential for early diagnosis of e.g. cancer, cardiovascular disease, infections or allergies. Today, identification of these markers often requires extensive laboratory work and hence is expensive and time consuming. Current methods for recognition and detection of specific biomolecules are mostly optics based and thus impose severe limitations as to convenience, specificity, sensitivity, parallel processing and cost reduction.

Electronic sensors based on silicon nanowire field-effect transistors have been reported to be able to detect biomolecules with concentrations down to femtomolar (fM) level with high specificity. Although the reported capability needs further confirmation, the CMOS-compatible fabrication process of such sensors allows for low cost production and high density integration, which are favorable for POC applications. This thesis mainly focuses on the development of a multiplex detection platform based on silicon nanowire field-effect sensors integrated with a microfluidic system for liquid sample delivery. Extensive work was dedicated to developing a top-down fabrication process of the sensors as well as an effective passivation scheme. The operation mechanism and coupling efficiencies of different gate configurations were studied experimentally with the assistance of numerical simulation and equivalent circuits. Using pH sensing as a model system, large effort was devoted to identifying sources for false responses resulting from the instability of the inert-metal gate electrode. In addition, the drift mechanism of the sensor operating in electrolyte was addressed and a calibration model was proposed. Furthermore, protein detection experiments were performed using small-sized Affibody molecules as receptors on the gate insulator to tackle the Debye screening issue. Preliminary results showed that the directionality of the current changes in the sensors was in good agreement with the charge polarities of the proteins. Finally, a graphene-based capacitor was examined as an alternative to the nanowire device for field-effect ion sensing. Our initial attempts showed some attractive features of the capacitor sensor.

Abstract

The recent development of the commercially viable thin film electro-acoustic technology has triggered a growing interest in the research of plate guided wave or Lamb wave components owing to their unique characteristics. In the present thesis i) an experimental study of the thin film plate resonators (FPAR) performance operating on the lowest symmetrical Lamb wave (S0) propagating in highly textured AlN membranes versus a variety of design parameters has been performed. The S0 mode is excited through an Interdigital Transducer and confined within the structure by means of reflection from metal strip gratings. Devices operating in the vicinity of the stop-band center exhibiting a Q-value of up to 3000 at a frequency around 900MHz have been demonstrated. Temperature compensation of this type of devices has been studied theoretically and successfully realized experimentally for the first time. Further, integrated circuit-compatible S0 Lamb based two-port FPAR stabilized oscillators exhibiting phase noise of -92 dBc/Hz at 1 kHz frequency offset with feasible thermal noise floor below -180 dBc/Hz have been tested under high power for a couple of weeks. More specifically, the FPARs under test have been running without any performance degradation at up to 27 dBm loop power. Further, the S0 mode was experimentally demonstrated to be highly mass and pressure sensitive as well as suitable for in-liquid operation, which together with low phase noise and high Q makes it very suitable for sensor applications; ii) research in view of FPARs operating on other types of Lamb waves as well as novel operation principles has been initiated. In this work, first results on the design, fabrication and characterization of two novel type resonators: The Zero Group Velocity Resonators (ZGVR) and The Intermode-Coupled Thin Film Plate Acoustic Resonators (IC-FPAR), exploiting new principles of operation have been successfully demonstrated. The former exploits the intrinsic zero group velocity feature of the S1 Lamb mode for certain combination of design parameters while the latter takes advantage of the intermode interaction (involving scattering) between S0 and A1 Lamb modes through specially designed metal strip gratings (couplers). Thus both type of resonators operate on principles of confining energy under IDT other than reflection.

Abstract

Thin film technology is of great significance for a variety of products, such as electronics, anti-reflective or hard coatings, sensors, solar cells, etc. This thesis concerns the synthesis of thin functional films, reactive magnetron sputter deposition process as such and the physical and functional characterization of the thin films synthesized. Characteristic for reactive sputtering processes is the hysteresis due to the target poisoning. One particular finding in this work is the elimination of the hysteresis by means of a mixed nitrogen/oxygen processing environment for dual sputtering of Alumina-Zirconia thin films. For a constant moderate flow of nitrogen, the hysteresis could be eliminated without significant incorporation of nitrogen in the films. It is concluded that optimum processing conditions for films of a desired composition can readily be estimated by modeling. The work on reactively sputtered SiO₂–TiO₂ thin films provides guidelines as to the choice of process parameters in view of the application in mind, by demonstrating that it is possible to tune the refractive index by using single composite Si_x/TiO₂ targets with the right composition and operating in a suitable oxygen flow range. The influence of the target composition on the sputter yield is studied for reactively sputtered titanium oxide films. It is shown that by using sub-stoichiometric targets with the right composition and operating in the proper oxygen flow range, it is possible to increase the sputter rate and still obtain stoichiometric coatings. Wurtzite aluminum nitride (w-AlN) thin films are of great interest for electro-acoustic applications and their properties have in recent years been extensively studied. One way to tailor material properties is to vary the composition by adding other elements. Within this thesis (Al,B)N films of the wurtzite structure and a strong c-axis texture have been grown by reactive sputter deposition. Nanoindentation experiments show that the films have nanoindentation hardness in excess of 30 GPa, which is as hard as commercially available hard coatings such as TiN. Electrical properties of w-(Al,B)N thin films were investigated. W-(Al,B)N thin films are found to have a dielectric strength of ~3×10⁶ V/cm, a relatively high k-value around 12 and conduction mechanisms similar to those of AlN. These results serve as basis for further research and applications of w-(Al,B)N thin films. An AlN thin film bulk acoustic resonator (FBAR) and a solidly mounted resonator (SMR) together with a microfluidic transport system have been fabricated. The fabrication process is IC compatible and uses reactive sputtering to deposit piezoelectric AlN thin films with a non-zero mean inclination of the c-axis, which allows in-liquid operation through the excitation of the shear mode. The results on IC-compatibility, Q-values, operation frequency and resolution illustrate the potential of this technology for highly sensitive low-cost micro-biosensor systems for applications in, e.g. point-of-care testing.

Abstract

Today’s MEMS technology allows manufacturing of miniaturized, low power sensors that sometimes exceeds the performance of conventional sensors. The pressure sensor market today is dominated by MEMS pressure sensors.

In this thesis two different pressure sensor techniques are studied. The first concerns ways to improve the sensitivity in the most commonly occurring pressure sensor, namely such based on the piezoresistive technique. Since the giant piezoresistive effect was observed in silicon nanowires, it was assumed that a similar effect could be expected in nano-thin silicon films. However, it turned out that the conductivity was extremely sensitive to substrate bias and could therefore be controlled by varying the backside potential. Another important parameter was the resistivity time drift. Long time measurements showed a drastic variation in the resistance. Not even after several hours of measurement was steady state reached. The drift is explained by hole injection into the buried oxide as well as existence of mobile charges. The piezoresistive effect was studied and shown to be of the same magnitude as in bulk silicon. Later research has shown the existence of such an effect where the film thickness has to be less than around 20 nm. 

The second area that has been studied is the pressure sensitivity of in acoustic resonators. Aluminium nitride thin film plate acoustic resonators (FPAR) operating at the lowest-order symmetric (S0), the first-order asymmetric (A1) as well as the first-order symmetric (S1) Lamb modes have been theoretically and experimentally studied in a comparative manner. The S0 Lamb mode is identified as the most pressure sensitive FPAR mode. The theoretical predictions were found to be in good agreement with the experiments. Additionally, the Lamb modes have been tested for their sensitivities to mass loading and their ability to operate in liquids, where the S0 mode showed good results.

Finally, the pressure sensitivity in aluminium nitride thin film bulk wave resonators employing c- and tilted c-axis texture has been studied. The c-axis tilted FBAR demonstrates a substantially higher pressure sensitivity compared to its c-axis oriented counterpart. 

Abstract

The use of solar cells for energy production has indeed a bright future. Reduction of cost for fabrication along with increased efficiency are key features for a market boom, both achieved as a result of increased knowledge of the technology. Especially the thin film solar cell technology with absorbers made of Cu(In,Ga)Se₂ (CIGS) is promising since it has proven high power conversion efficiency in combination with a true potential for low cost fabrication.

In this thesis different recipes for fabrication of the Cu(In,Ga)Se₂ absorber layer have been studied. The deposition technique used has been co-evaporation from elemental sources. For all depositions the substrate has been heated to a constant temperature of 500 ºC in order for the growing absorber to form a chalcopyrite phase, necessary for the photovoltaic functionality. The selenium has been evaporated such to always be in excess during depositions whereas the metal ratio Cu/(In+Ga) has been varied according to different recipes but always to be less than one at the end of the process. In the work emphasis has been on the radiative properties of the CIGS film during growth.

The substrate heater has been temperature controlled to maintain the constant set temperature of the substrate, regardless of varying emitted power caused by changing surface emissivity. Depending on the growth conditions the emissivity of the growing film is changing, leading to a readable variation in the electrical power to the substrate heater.

Since the thermal radiation from the substrate during growth has been of central focus, this has been studied in detail. For this reason the substrate has been treated as an optical stack composed of glass/Mo/Cu(In,Ga)Se₂/Cu_xSe which determine the thermally radiated power by its emissivity. An optical model has been adopted to simulate the emissivity of the stack. In order to use the model, the optical constants for Cu(In,Ga)Se₂ and Cu_xSe have been derived for the wavelength interval 2 μm to 20 μm. The simulation of the emissivity of the stack during CIGS growth agreed well with what has been seen for actual growth. Features of the OP-signal could hereby be explained as a result of film thickness of Cu(In,Ga)Se₂ and Cu_xSe respectively. This is an important knowledge for an efficient fabrication in large scale.

Abstract

A deeper understanding of Cu(In,Ga)Se₂ (CIGS) solar cells is important for the further improvement of these devices. This thesis is focused on the use of electrical modelling as a tool for pursuing this aim. Finished devices and individual layers are characterized and the acquired data are used as input in the simulations. Band gap gradients are accounted for when modelling the devices. The thesis is divided into two main parts. One part that treats the influence of cadmium free buffer layers, mainly atomic layer deposited (Zn,Mg)O, on devices and another part in which the result of CIGS absorber layer modifications is studied. Recombination analysis indicates that interface recombination is limitting the open circuit voltage (V_oc) in cells with ZnO buffer layers. This recombination path becomes less important when magnesium is introduced into the ZnO giving a positive conduction band offset (CBO) towards the CIGS absorber layer. Light induced persistent photoconductivity (PPC) is demonstrated in (Zn,Mg)O thin films. Device modelling shows that the measured PPC, coupled with a high density of acceptors in the buffer-absorber interface region, can explain light induced metastable efficiency improvement in CIGS solar cells with (Zn,Mg)O buffer layers. It is shown that a thin indium rich layer closest to the buffer does not give any significant impact on the performance of devices dominated by recombination in the CIGS layer. In our cells with CdS buffer the diffusion length in the CIGS layer is the main limitting factor. A thinner CIGS layer improves V_oc by reducing recombination. However, for thin enough absorber layers V_oc deteriorates due to recombination at the back contact. Interface recombination is a problem in thin devices with Zn(O,S) buffer layers. This recombination path is overshadowed in cells of standard thickness by recombination in the CIGS bulk. Thin cells with Zn(O,S) buffer layers have a higher efficiency than CdS cells with the same absorber thickness.

Abstract

Solar cells constitute the most direct way of converting solar energy to electricity, and thin-film solar-cell technologies have lately been growing in importance, allowing the fabrication of less expensive modules that nonetheless have good power-conversion efficiencies. This thesis focuses on solar cells based on Cu(In,Ga)Se₂, which is the thin-film technology that has shown the highest conversion efficiency to date, reaching 20.3 % on the laboratory scale. Solar modules still have some way to go to become entirely competitive with existing energy technologies, and there are two possible paths to this goal: Firstly, reducing their manufacturing costs, for instance by minimizing the material usage per module and/or by increasing the throughput of a given factory; and secondly, increasing the power output per module in other words, the module efficiency. The subject matters of this thesis are related to those two approaches.

The first issue investigated is the possibility for reducing the thickness of the Cu(In,Ga)Se₂ layer and compensating for lost absorption by using a ZrN back reflector. ZrN layers are fabricated by reactive sputtering and I present a method for tuning the sputtering parameters so as to obtain a back reflector with good optical, electrical and mechanical properties. The reflector layer cannot be used directly in CIGS devices, but relatively good devices can be achieved with a precursor providing a homogeneous supply of Na, the addition of a very thin sacrificial Mo layer that allows the formation of a film of MoSe₂ passivating the back contact, and optionally a Ga gradient that further keeps electrons away from the back contact.

The second field of study concerns the three-stage CIGS coevaporation process, which is widely used in research labs around the world and has yielded small-area cells with highest efficiencies, but has not yet made it to large scale production. My focus lies on the development and the effect of gradients in the [Ga]/[In+Ga] ratio. On the one hand, I investigate 'intrinsic' gradients (ones that form autonomously during the evaporation), and present a formation model based on the differing diffusivity of Ga and In atoms in CIGS and on the development along the quasi-binary tie line between (In,Ga)₂Se₃ and Cu₂Se. On the other hand, I determine how the process should be designed in order to preserve 'extrinsic' gradients due to interdiffusion. Lastly, I examine the electrical effects of Ga-enhancement at the back and at the front of the absorber and of In-enhancement at the front. Over a wide range, In-rich top layers prove to have no or a weakly beneficial effect, while Ga-rich top regions pose a high risk to have a devastating effect on device performance.

Abstract

Solar irradiation is a vast and plentiful source of energy. The use of photovoltaic (PV) devices to convert solar energy directly to electrical energy is an elegant way of sustainable power generation which can be distributed or in large PV plants based on the need. Solar cells are the small building blocks of photovoltaics and when connected together they form PV modules. Thin film solar cells require significantly less energy and raw materials to be produced, as compared to the dominant Si wafer technologies. CIGS thin film solar cells are considered to be the most promising thin film alternative due to its proven high efficiency.

Most thin film PV modules utilise monolithic integration, whereby thin film patterning steps are included between film deposition steps, to create interconnection of individual cells within the layered structure. The state of the art is that CIGS thin film modules are made using one laser patterning step (P1) and two mechanical patterning steps (P2 and P3). Here we present work which successfully demonstrates the replacement of mechanical patterning by laser patterning methods. The use of laser ablation promises such advantages as increased active cell area and reduced maintenance and downtime required for regular replacement of mechanical tools.

The laser tool can also be used to transform CIGS into a conducting compound along a patterned line. We have shown that this process can be performed after all semiconductor layers are deposited using a technique we call laser micro-welding. By performing patterning at the end of the process flow P2 and P3 patterning could be performed simultaneously. Such solutions will further reduce manufacturing times and may offer increased control of semiconductor interfaces.

While showing promising performance on par with reference processes there are still open questions of importance for these novel techniques, particularly that of long term stability. Thin film modules are inherently sensitive to moisture and require reliable encapsulation. Before the techniques introduced here can be seen industrially they must have achieved proven stability. In this work we present a proof of existence of stable micro-welded interconnections.

Abstract

CdS is conventionally used as a buffer layer in Cu(In,Ga)Se₂, CIGS, solar cells. The aim of this thesis is to substitute CdS with cadmium-free, more transparent and environmentally benign alternative buffer layers and to analyze how the material properties of alternative layers affect the solar cell performance. The alternative buffer layers have been deposited using Atomic Layer Deposition, ALD. A theoretical explanation for the success of CdS is that its conduction band, E_c, forms a small positive offset with that of CIGS.

In one of the studies in this thesis the theory is tested experimentally by changing both the E_c position of the CIGS and of Zn(O,S) buffer layers through changing their gallium and sulfur contents respectively. Surprisingly, the top performing solar cells for all gallium contents have Zn(O,S) buffer layers with the same sulfur content and properties in spite of predicted unfavorable E_c offsets. An explanation is proposed based on observed non-homogenous composition in the buffer layer.

This thesis also shows that the solar cell performance is strongly related to the resistivity of alternative buffer layers made of (Zn,Mg)O. A tentative explanation is that a high resistivity reduces the influence of shunt paths at the buffer layer/absorber interface. For devices in operation however, it seems beneficial to induce persistent photoconductivity, by light soaking, which can reduce the effective E_c barrier at the interface and thereby improve the fill factor of the solar cells.

Zn-Sn-O is introduced as a new buffer layer in this thesis. The initial studies show that solar cells with Zn-Sn-O buffer layers have comparable performance to the CdS reference devices.

While an intrinsic ZnO layer is required for a high reproducibility and performance of solar cells with CdS buffer layers it is shown in this thesis that it can be thinned if Zn(O,S) or omitted if (Zn,Mg)O buffer layers are used instead. As a result, a top conversion efficiency of 18.1 % was achieved with an (Zn,Mg)O buffer layer, a record for a cadmium and sulfur free CIGS solar cell.

Abstract

This thesis presents various integrated antenna solutions for different types of systems and applications, e.g. wireless sensors, broadband handsets, advanced base stations, MEMS-based reconfigurable front-ends, automotive anti-collision radars, and large area electronics.

For wireless sensor applications, a T-matched dipole is proposed and integrated in an electrically small body-worn sensor node. Measurement techniques are developed to characterize the port impedance and radiation properties. Possibilities and limitations of the planar inverted cone antenna (PICA) for small handsets are studied experimentally. Printed slot-type and folded PICAs are demonstrated for UWB handheld terminals.

Both monolithic and hybrid integration are applied for electrically steerable array antennas. Compact phase shifters within a traveling wave array antenna architecture, on single layer substrate, is investigated for the first time. Radio frequency MEMS switches are utilized to improve the performance of reconfigurable antennas at higher frequencies. Using monolithic integration, a 20 GHz switched beam antenna based on MEMS switches is implemented and evaluated. Compared to similar work published previously, complete experimental results are here for the first time reported. Moreover, a hybrid approach is used for a 24 GHz switched beam traveling wave array antenna. A MEMS router is fabricated on silicon substrate for switching two array antennas on a LTCC chip.

A concept of nano-wire based substrate integrated waveguides (SIW) is proposed for millimeter-wave applications. Antenna prototypes based on this concept are successfully demonstrated for automotive radar applications.

W-band body-worn nonlinear harmonic radar reflectors are proposed as a means to improve automotive radar functionality. Passive, semi-passive and active nonlinear reflectors consisting of array antennas and nonlinear circuitry on flex foils are investigated.

A new stretchable RF electronics concept for large area electronics is demonstrated. It incorporates liquid metal into microstructured elastic channels. The prototypes exhibit high stretchability, foldability, and twistability, with maintained electrical properties.

Abstract

Biomolecular interaction analysis to determine the kinetics and affinity between interacting partners is important for the fundamental understanding of biology, as well as for the development of new pharmaceutical substances. A quartz crystal microbalance instrument suitable for kinetics and affinity analyses of interaction events was developed. The functionality of the sensor system was demonstrated by development of an assay for relative affinity determination of lectin-carbohydrate interactions.

Sensor surfaces allowing for effective immobilization of one interacting partner is a key functionality of a biosensor. Here, three different surfaces and immobilization methods were studied. First, optimized preparation conditions for sensor surfaces based on carboxyl-terminated self assembled monolayers were developed and were demonstrated to provide highly functional biosensor surfaces with low non-specific binding. Second, a method allowing for immobilization of very acidic biomolecules based on the use of an electric field was developed and evaluated. The electric field made it possible to immobilize the highly acidic C-peptide on a carboxylated surface. Third, a method for antibody immobilization on a carboxyl surface was optimized and the influence of immobilization pH on the immobilization level and antigen binding capacity was thoroughly assessed. The method showed high reproducibility for a set of antibodies and allowed for antibody immobilization also at low pH.

Three broadly different strategies to increase the sensitivity of electroacoustic sensors were explored. A QCM sensor with small resonator electrodes and reduced flow cell dimensions was demonstrated to improve the mass transport rate to the sensor surface. The use of polymers on QCM sensor surfaces to enhance the sensor response was shown to increase the response of an antibody-antigen model system more than ten-fold. Moreover, the application of high frequency thin film bulk acoustic resonators for biosensing was evaluated with respect to sensing range from the surface. The linear detection range of the thin film resonator was determined to be more than sufficient for biosensor applications involving, for instance, antibody-antigen interactions. Finally, a setup for combined frequency and resistance measurements was developed and was found to provide time resolved data suitable for kinetics determination.

Abstract

In recent years there has been a huge increase in the growth of communication systems such as mobile phones, wireless local area networks (WLAN), satellite navigation and various other forms of wireless data communication that have made analogue frequency control a key issue. The increase in frequency spectrum crowding and the increase of frequency into microwave region, along with the need for minimisation and capacity improvement, has shown the need for the development of high performance, miniature, on-chip filters operating in the low to medium GHz frequency range. This has hastened the need for alternatives to ceramic resonators due to their limits in device size and performance, which in turn, has led to development of the thin film electro-acoustics industry with surface acoustic wave (SAW) and bulk acoustic wave (BAW) filters now fabricated in their millions. Further, this new technology opens the way for integrating the traditionally incompatible integrated circuit (IC) and electro-acoustic (EA) technologies, bringing about substantial economic and performance benefits.

In this thesis the compatibility of aluminium nitride (AlN) to IC fabrication is explored as a means for furthering integration issues. Various issues have been explored where either tailoring thin film bulk acoustic resonator (FBAR) design, such as development of an improved solidly mounted resonator (SMR) technology, and use of IC technology, such as chemical mechanical polishing (CMP) or nickel silicide (NiSi), has made improvements beneficial for resonator fabrication or enabled IC integration. The former has resulted in major improvements to Quality factor, power handling and encapsulation respectively. The later has provided alternative methods to reduce electro- or acoustomigration, reduced device size, for plate waves, supplied novel low acoustic impedance material for high power applications and alternative electrodes for use in high temperature sensors.

Another method to enhance integration by using the piezoelectric material, AlN, in the IC side has also been explored. Here methods for analysing AlN film contamination and stoichiometry have been used for analysis of AlN as a high-k dielectric material. This has even brought benefits in knowledge of film composition for use as a passivation material with SiC substrates, investigated in high power high frequency applications. Lastly AlN has been used as a buried insulator material for new silicon-on-insulator substrates (SOI) for increased heat conduction. These new substrates have been analysed with further development for improved performance indicated.