Dissertations / Theses on the topic 'Semiconductors Surface chemistry. Electrical engineering'

Molecular doping of organic semiconductors is becoming exceedingly important and has led to significant commercial developments in organic electronics, since it allows to overcome performance deficiencies and material limitations.

Increasing attention has recently been placed on using very low concentrations of dopants to eliminate the effect of gap states in organic semiconductors, in order to improve carrier mobility, adjust the energy level alignment at interfaces, and achieve overall better device performance. However, direct spectroscopic observations and quantitative analyses have not been done yet to study the impact of dopants on the density of states of organic semiconductors. Here, by using a combination of electron spectroscopy and carrier transport measurements, we investigate the distribution of valence and gap states in copper phthalocyanine (CuPc) upon the introduction of minute amounts of the p-dopant molybdenum tris[1,2-bis-(trifluoromethyl)ethane-1,2-dithiolene] (Mo(tfd)3). We observe the progressive filling (and deactivation) of the deepest tail states accompanied by a decrease of the hopping transport activation energy by charges introduced by the dopants, as well as a significant broadening of the CuPc density of states. Simulations relate this broadening to the electrostatic and structural disorder induced by the dopant in the CuPc matrix.

Another challenge in this field is n-type doping. Although a variety of stable molecular p-dopants have been developed and successfully deployed in devices, air-stable molecular n-dopants suitable for materials with low electron affinity, which are exceedingly important in a range of applications, are essentially non-existent. We demonstrate a major advance to n-dope very low electron affinity organic semiconductors using cleavable air-stable dimeric dopants. Although the reduction potentials of these host materials are beyond the thermodynamic reach of the dimer's effective reducing strength, photo-activation of the doped system can result in kinetically stable and efficient n-doping. High-efficiency organic light-emitting diodes are fabricated by using electron-transport layers doped in this manner. Our strategy thus enables a new paradigm for using air-stable molecular dopants to improve conductivity in organic semiconductors with very low electron affinity and provide ohmic contacts to these materials regardless of the electrode work function, giving more freedom to device design and optimization.

Ultrathin organized films of organic electronic materials, such as phthalocyanines (Pc), are promising for both fundamental and applied studies due to their special optical, electronic and photoconductive properties. The studies presented in this dissertation include fabrication of ultrathin molecular assemblies by molecular beam epitaxy and Langmuir-Blodgett techniques. The degree of molecular order, extent of charge transfer and the morphology within these films, assessed by methodologies, such as photoelectrochemistry, electrochemistry, surface analysis and optical spectroscopy were discussed and characterized. Under high vacuum condition, a wide range of ordered structures of some trivalent metal phthalocyanines, such as GaPc-Cl, InPc-Cl and AlPc-F, can be fabricated. These materials exhibit "layer-by-layer" growth on the single crystal SnS₂ surface when deposited by molecular beam epitaxy (MBE). The MBE technique allows for closer packing of these highly ordered phthalocyanines than in self-assembled (SA) or Langmuir-Blodgett (LB) thin films, due to the lack of hydrocarbon side chains which are necessary for control of molecular architecture during SA or LB depositions. Several new solution processable substituted phthalocyanines are introduced, which due to their strong self-assembled tendency, may be suitable for the formation of well organized thin films by SA and LB techniques. It is found that the types of the substituents attached to the Pc rings play a significant role in determining both the aggregation tendency and the electrochemical properties of Pcs. Surface pressure-area isotherms of these substituted phthalocyanines show that there can be one or two stable phase transition regimes for monomolecular film at the air/water interface. On-trough spectroscopic studies of benzylalkoxy substituted phthalocyanines show that in the pressure-area region prior to the formation of the first stable phase extensive aggregation has occurred. Electrochemical studies of fully compressed films of substituted phthalocyanines on certain substrates show the presence of multiple electroactive domains, controlling the oxidation or reduction process of the Pc rings. Spectroelectrochemical studies of LB films of CuPcOC₂OBz suggest that the presence of both monomer and aggregates leads to the two separate oxidation processes.

Continuous scaling down of the dimensions of electronic devices has made present day computers more powerful. In the front end of line, the minimum lateral dimensions in a transistor have shrunk from 45 nm in 2007 to 22 nm currently, and the gate oxide film thickness is two to three monolayers. This reduction in dimensions makes surface preparation an increasingly important part of the device fabrication process. The atoms or molecules that terminate surfaces function as passivation layers, diffusion barriers, and nucleation layers. In the back end of line, metal layers are deposited to connect transistors. We demonstrate a reproducible process that deposits a monolayer of aminopropyltrimethoxysilane molecules less than one nanometer thick on a silicon dioxide surface. The monolayer contains a high density of amine groups that can be used to deposit Pd and Ni and subsequently Co and Cu to serve as the nucleation layer in an electroless metal deposition process. Because of the shrinking device dimensions, there is a need to find new transistor channel materials that have high electron mobilities along with narrow band gaps to reduce power consumption. Compound III--V channel materials are candidates to enable increased performance and reduced power consumption at the current scaled geometries. But many challenges remain for such high mobility materials to be realized in high volume manufacturing. For instance, low defect density (1E7 /cm²) III--V and Ge on Si is the most fundamental issue to overcome before high mobility materials become practical. Unlike Si, dry etching of III-V semiconductor surfaces is believed to be difficult and uncontrollable. Therefore, new wet etching chemistries are needed. Si has been known to passivate by etching in hydrofluoric acid, but similar treatments on III--Vs are known to temporarily hydrogen passivate the surfaces. However, any subsequent exposure to the ambient reoxidizes the surface, resulting in a chemically unstable and high defect density interface. This work compares old and new wet etching chemistries and investigates new methods of passivating the III--V semiconductors.

This thesis reports the investigation of Bismuth oxybromide (BiOBr) semiconductor material as an efficient photocatalyst for the sunlight harvesting as well as environmental cleanup. I have utilised different synthetic methodologies to obtain BiOBr and its derivatives, such as co-precipitation, ultrasonification, and photo-deposition; and have studied their structural and optical properties by X-ray diffraction and surface analysis techniques. I report the synthesis and characterisation of two new p-n heterojunction systems, AgBr-BiOBr and BiOBr-ZnFe₂O₄, and have performed initial studies on photocatalytic reaction and their catalytic decomposition mechanisms. I have also reported the surface modification method including the deposition of noble metal on BiOBr to investigate the role played by the noble metal and the interactions between semiconductor and metal using various characterisation measurements. Furthermore, a continuous series of BiOBr-BiOI solid solutions were synthesised, characterised and the photocatalytic degradation was performed on the as-obtained semiconductors, to study the band structure properties of the solid solutions.

Infectious diseases continue to kill millions of people every year and are a significant burden on the socio-economic development of developing countries. After many years of international policy aimed at containing diseases, it has recently become an explicit aim to move towards elimination of infectious diseases. However, if this is to occur, it will be necessary to have highly eficacious diagnostic tools to ensure infected individuals are identified and treated. However, the diagnosis of infectious diseases in the developed and developing world requires the full integration of complex assays in easy-to-use platforms with robust analytical performances at low cost. Many relevant bioanalytical technologies have been developed for use in laboratories and clinics, including the current gold standard for the diagnosis of tuberculosis and malaria. The miniaturization and integration of complex functions into lab-on-a-chip (LOC)technologies using microfluidics have only had limited success in translating diagnosis assays out of a centralized laboratory to point-of-care (POC) settings, because they still remain constrained due to chip interconnection and they are either not likely to go out of research laboratories or are not appropriate for low resource settings. In this thesis, a new microfluidic platform was developed that reduced the dependency of the diagnostic procedure on large laboratory instruments providing simplicity of use, enabling the patient sample to be processed and diagnosed on a low cost, disposable biochip. Surface acoustic wave (SAW) devices, which are commonly used in mobile phone technologies, were adapted to provide controlled microfluidic functions by shaping the SAW using particular designs of electrodes and phononic structures. The control of lateral positioning of the SAW was demonstrated using a slanted finger interdigitated transducer (IDT) in a frequency tuneable manner allowing microfluidic functions such as mixing, moving and merging, sequentially performed using a single IDT both on the substrate and on a disposable chip. Alternatively, phononic bandgaps were designed to break the symmetry of the SAW in a tuneable manner and gradient index phononic crystals (GRIN-PC) lenses were designed to focus the SAW and successfully increased the amplitude of the wave by a factor 3 while the focal position could be tuned with the frequency. The potential of these techniques was demonstrated by controlling the amplitude and direction of water jet towers by the use of a phononic horn structure that allowed the enhancement of energy at defined positions and by propelling and directing a macrometer scale object in water using a slanted IDT. As proof of concepts of diagnostic devices for the developing world, an immunoassay for tuberculosis using only mobile phone technologies (SAW, light-emitting diode(LED) and complementary metaloxidesemiconductor (CMOS) camera) was demonstrated with a limit of detection of 1 pM, which is the limit required in an interferon-release assay. This limit of detection was only achievable because of the ability of SAW to increase the mixing and to reduce the non-specific binding. Furthermore, a method to enrich malaria infected cells, based on SAW and isopycnic gradient, was also demonstrated and showed an enrichment up to 100x in the equivalent of a fingerprick of blood in 3 seconds. This technique will allow to reduce the limit of detection of the current gold standard. This platform not only opens a clear road toward POC diagnostics due to its size, cost, versatility and ease in integration, but has also the potential to provide useful tools in laboratory settings for large scale, high throughput technologies.

Organic semiconductors (OSCs) present an electron mobility lower by several orders of magnitude than the hole mobility, giving rise to an electron-hole charge imbalance in organic devices such as organic light-emitting diodes (OLEDs) and organic light-emitting transistors (OLETs). In this thesis project, I tried to achieve an efficient electron transport and injection properties in opto-electronic devices, using inorganic n-type metal oxides (MOs) instead of organic n-type materials and a polyethyleneimine ethoxylated (PEIE) thin layer as electron transport (ETLs) and injection layers (EILs), respectively. In the first part of this thesis, inverted OLEDs were fabricated in order to study the effect of the PEIE layer in-between ZnO and two different emissive layers (EMLs): poly(9,9-dioctylfluorene-alt-benzothiadiazole) polymer (F8BT) and tris(8-hydroxyquinolinato) aluminum small molecule (Alq3), based on a solution and thermal evaporation processes, respectively. Different concentrations (0.80 %, 0.40 %) of PEIE layers were used to further study electron injection capability in OLEDs. After a series of optimizations in the fabrication process, the opto-electrical characterization showed high-performance of devices. The inverted OLEDs reported a maximum luminance over 104 cd m-2 and a maximum external quantum efficiency (EQE) around 1.11 %. The results were attributed to the additional PEIE layer which provided a good electron injection from MOs into EMLs. In the last part of the thesis, OLETs were fabricated and discussed by directly transferring the energy modification layer from OLEDs to OLETs. As metal oxide layer, ZnO:N was employed for OLETs since ZnO:N-based thin film transistors (TFTs) showed better performance than ZnO-based TFTs. Finally, due to their short life-time, OLETs were characterized electrically but not optically.

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.

Nanomaterials have attracted great interest due to the unique physical properties and great potential in the applications of nanoscale devices. Two dimensional atomic crystals, which are atomic thickness, especially graphene, have triggered the gold rush recently due to the fascinating high mobility at room temperature for future electronics. The crystal structure of nanomaterials will have great influence on their physical properties. Thus, this thesis is focused on developing the methods to control the crystal structure of nanomaterials, namely quantum dots as semiconductor, boron nitride (BN) as insulator, graphene as semimetal, with low cost for their applications in photonics, structural support and electronics. In this thesis, firstly, Mn doped ZnSe quantum dots have been synthesized using colloidal synthesis. The shape control of Mn doped ZnSe quantum dots has been achieved from branched to spherical by switching the injection temperature from kinetics to thermodynamics region. Injection rates have been found to have effect on controlling the crystal phase from zinc blende to wurtzite. The structural-property relationship has been investigated. It is found that the spherical wurtzite Mn doped ZnSe quantum dots have the highest quantum yield comparing with other shape or crystal phase of the dots. Then, the Mn doped ZnSe quantum dots were deposited onto the BN sheets, which were micron-sized and fabricated by chemical exfoliation, for high resolution imaging. It is the first demonstration of utilizing ultrathin carbon free 2D atomic crystal as support for high resolution imaging. Phase contrast images reveal moiré interference patterns between nanocrystals and BN substrate that are used to determine the relative orientation of the nanocrystals with respect to the BN sheets and interference lattice planes using a newly developed equation method. Double diffraction is observed and has been analyzed using a vector method. As only a few microns sized 2D atomic crystal, like BN, can be fabricated by the chemical exfoliation. Chemical vapour deposition (CVD) is as used as an alternative to fabricate large area graphene. The mechanism and growth dynamics of graphene domains have been investigated using Cu catalyzed atmospheric pressure CVD. Rectangular few layer graphene domains were synthesized for the first time. It only grows on the Cu grains with (111) orientation due to the interplay between atomic structure of Cu lattice and graphene domains. Hexagonal graphene domains can form on nearly all non-(111) Cu surfaces. The few layer hexagonal single crystal graphene domains were aligned in their crystallographic orientation over millimetre scale. In order to improve the alignment and reduce the layer of graphene domains, a novel method is invented to perform the CVD reaction above the melting point of copper (1090 ºC) and using molybdenum or tungsten to prevent the balling of the copper from dewetting. By controlling the amount of hydrogen during the growth, individual single crystal domains of monolayer over 200 µm are produced determined by electron diffraction mapping. Raman mapping shows the monolayer nature of graphene grown by this method. This graphene exhibits a linear dispersion relationship and no sign of doping. The large scale alignment of monolayer hexagonal graphene domains with epitaxial relationship on Cu is the key to get wafer-sized single crystal monolayer graphene films. This paves the way for industry scale production of 2D single crystal graphene.

We focused on a non-cooling room temperature microbolometer infrared imaging array device which includes a sensing layer of p-type a-Si:H component layers doped with boron. Boron incorporation and bonding configuration were investigated for a-Si:H films grown by plasma enhanced chemical deposition (PECVD) at varying substrate temperatures, hydrogen dilution of the silane precursor, and dopant to silane ratio using multiple internal reflection infrared spectroscopy (MIR-IR). This study was then confirmed from collaborators via Raman spectroscopy. MIR-IR analyses reveal an interesting counter-balance relationship between boron-doping and hydrogen-dilution growth parameters in PECVD-grown a-Si:H. Specifically, an increase in the hydrogen dilution ratio (H2/SiH4) or substrate temperature was found to increase organization of the silicon lattice in the amorphous films. It resulted in the decrease of the most stable SiH bonding configuration and thus decrease the organization of the film. The new chemical bonding information of a-Si:H thin film was correlated with the various boron doping mechanisms proposed by theoretical calculations. The study revealed the corrosion morphology progression on aluminum alloy (Al, 0.5% Cu) under acidic chloride solution. This is due to defects and a higher copper content at the grain boundary. Direct galvanic current measurement, linear sweep voltammetry (LSV), and Tafel plots are used to measure corrosion current and potential. Hydrogen gas evolution was also observed (for the first time) in Cu/Al bimetallic interface in areas of active corrosion. Mechanistic insight that leads to effective prevention of aluminum bond pad corrosion is explored and discussed. (Chapter 4) Aluminum bond pad corrosion activity and mechanistic insight at a Cu/Al bimetallic interface typically used in microelectronic packages for automotive applications were investigated by means of optical and scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and electrochemistry. Screening of corrosion variables (temperature, moisture, chloride ion concentration, pH) have been investigated to find their effect on corrosion rate and to better understand the Al/Cu bimetallic corrosion mechanism. The study revealed the corrosion morphology progression on aluminum alloy (Al, 0.5% Cu) under acidic chloride solution. The corrosion starts as surface roughening which evolves into a dendrite structure and later continues to grow into a mud-crack type corrosion. SEM showed the early stage of corrosion with dendritic formation usually occurs at the grain boundary. This is due to defects and a higher copper content at the grain boundary. The impact of copper bimetallic contact on aluminum corrosion was explored by sputtering copper microdots on aluminum substrate. Copper micropattern screening revealed that the corrosion is activated on the Al/Cu interface area and driven by the large potential difference; it was also seen to proceed at much higher rates than those observed with bare aluminum. Direct galvanic current measurement, linear sweep voltammetry (LSV), and Tafel plots are used to measure corrosion current and potential. Hydrogen gas evolution was also observed (for the first time) in Cu/Al bimetallic interface in areas of active corrosion. Mechanistic insight that leads to effective prevention of aluminum bond pad corrosion is explored and discussed. Micropattern corrosion screening identified hydrogen evolution and bimetallic interface as the root cause of Al pad corrosion that leads to Cu ball lift-off, a fatal defect, in Cu wire bonded device. Complete corrosion inhibition can be achieved by strategically disabling the mutually coupled cathodic and anodic reaction cycles.

abstract: Optoelectronic and microelectronic applications of germanium-based materials have received considerable research interest in recent years. A novel method for Ge on Si heteroepitaxy required for such applications was developed via molecular epitaxy of Ge5H12. Next, As(GeH3)3, As(SiH3)3, SbD3, S(GeH3)2 and S(SiH3)2 molecular sources were utilized in degenerate n-type doping of Ge. The epitaxial Ge films produced in this work incorporate donor atoms at concentrations above the thermodynamic equilibrium limits. The donors are nearly fully activated, and led to films with lowest resistivity values thus far reported. Band engineering of Ge was achieved by alloying with Sn. Epitaxy of the alloy layers was conducted on virtual Ge substrates, and made use of the germanium hydrides Ge2H6 and Ge3H8, and the Sn source SnD4. These films exhibit stronger emission than equivalent material deposited directly on Si, and the contributions from the direct and indirect edges can be separated. The indirect-direct crossover composition for Ge1-ySny alloys was determined by photoluminescence (PL). By n-type doping of the Ge1-ySny alloys via P(GeH3)3, P(SiH3)3 and As(SiH3)3, it was possible to enhance photoexcited emission by more than an order-of-magnitude. The above techniques for deposition of direct gap Ge1-ySny alloys and doping of Ge were combined with p-type doping methods for Ge1-ySny using B2H6 to fabricate pin heterostructure diodes with active layer compositions up to y=0.137. These represent the first direct gap light emitting diodes made from group IV materials. The effect of the single defected n-i¬ interface in a n-Ge/i-Ge1-ySny/p-Ge1-zSnz architecture on electroluminescence (EL) was studied. This led to lattice engineering of the n-type contact layer to produce diodes of n-Ge1-xSnx/i-Ge1-ySny/p-Ge1-zSnz architecture which are devoid of interface defects and therefore exhibit more efficient EL than the previous design. Finally, n-Ge1-ySny/p-Ge1-zSnz pn junction devices were synthesized with varying composition and doping parameters to investigate the effect of these properties on EL.
Dissertation/Thesis
Doctoral Dissertation Chemistry 2016

The research presented in this dissertation focuses on the design and synthesis of novel hybrid conjugated polymer materials using two different approaches: (1) inorganic/organic hybrid semiconductors through the incorporation of carboranes into the polymer structure and (2) the modification of surfaces with conjugated polymers via grafting approaches. Hybrid conjugated polymeric materials, which are materials or systems in which conjugated polymers are chemically integrated with non-traditional structures or surfaces, have the potential to harness useful properties from both components of the material to help overcome hurdles in their practical realization in polymer-based devices. This work is centered around the synthetic challenges of creating new hybrid conjugated systems and their potential for advancing the field of polymer-based electronics through both greater understanding of the behavior of hybrid systems, and access to improved performance and new applications. Chapter 1 highlights the potential applications and advantages for these hybrid systems, and provides some historical perspective, along with relevant background materials, to illustrate the rationale behind this work. Chapter 2 explores the synthesis of poly(fluorene)s with pendant carborane cages. The Ni(0) dehalogenative polymerization of a dibromofluorene with pendant carborane cages tethered to the bridging 9-position produced hybrid polymers produced polymers which combined the useful emissive characteristics of poly(fluorene) with the thermal and chemical stability of carborane cages. The materials were found to display increased glass transition temperatures and showed improved emission color stability after annealing at high temperatures relative to the non-hybrid polymer. The design and synthesis of a poly(fluorene)-based hybrid material with carborane cages in the backbone, rather than as pendant groups, begins in chapter 3. Poly(fluorene) with p-carborane in the backbone is synthesized and characterized, and the material is found to be a high MW, soluble blue emitter which shows a higher glass transition temperature and greater stability than a non-hybrid polymer. UV absorbance and fluorescence spectroscopy indicated some electronic interaction between the conjugated polymer and the cages, but they did not appear to be fully conjugated in the traditional sense. Chapter 4 describes the design, synthesis, and characterization of poly(fluorene) with o-carborane in the backbone. Profound changes in the behavior of the polymer, from its polymerization behavior to its emission characteristics, were observed and their origins are discussed. Experiments to explore the nature of the cage/polymer interactions were performed and possible applications which take advantage of the unique nature of the o-carborane hybrid polymer are explored and discussed. Hybrid conjugated polymer materials via grafting approaches to surfaces and surface modification are discussed starting in chapter 5. The synthesis of a dibromofluorene-based silane coupling agent for the surface functionalization of oxide surfaces is presented, and the surface directed Ni(0) dehalogenative polymerization of poly(dihexylfluorene) is explored. Chapter 6 focuses on the exploration of conjugated polymer/cellulose hybrid materials. Surface medication of cellulose materials with monomer-like anchor points is discussed. Grafting of the modified cellulose with conjugated polymers was explored and the grafting of three different repeat structures based on fluorene-, fluorenevinylene-, and fluoreneethynylene motifs were optimized to provide a general route to cellulose/conjugated polymer hybrid materials. Characterization and possible applications of such hybrid materials are discussed. Finally, chapter 7 is devoted to the simultaneous surface patterning and functionalization of poly(2-hydroxyethylmethacrylate) thin films using a silane infusion-based wrinkling technique. While not a conjugated polymer system, the spontaneous patterning and functionalization methods explored in this chapter produce hybrid organic/inorganic polymer thin films which have applications that range from optics, to adhesion, to polymer-based electronics, and the research compliments the other chapters. The spontaneous generation of complex patterns, of a small scale approaching 100nm feature size, over a large area with simultaneous control over surface chemistry is explored. Examples of complex, hierarchically patterned films which integrate lithographic processes such as nanoimprint lithography and electron beam lithography with spontaneous patterning via wrinkling are presented.

Through the history of mankind, novel materials have played a key role in techno- logical progress. As we approach the limits of scaling it becomes difficult to squeeze out any more extensions to Moore’s law by just reducing device feature sizes. It is important to look for an alternate semiconductor to silicon in order to continue making the progress predicted by Moore’s law. Among the various semiconductor options being explored world-wide, the III-nitride semiconductor material system has certain unique characteristics that make it one of the leading contenders. We explore the III-nitride semiconductor material system for the unique advantages that it offers over the other alternatives available to us. This thesis studies the device applications of epitaxial III-nitride films and nanos- tructures grown using plasma assisted molecular beam epitaxy (PAMBE) The material characterisation of the PAMBE grown epitaxial III-nitrides was car- ried out using techniques like high resolution X-ray diffraction (HR-XRD), field emis- sion scanning electron microscopy (FESEM), room temperature photoluminescence (PL) and transmission electron microscopy (TEM). The epitaxial III-nitrides were then further processed to fabricate devices like Schottky diodes, photodetectors and surface acoustic wave (SAW) devices. The electrical charcterisation of the fabricated devices was carried out using techniques like Hall measurement, IV and CV measure- ments on a DC probe station and S-parameter measurements on a vector network analyser connected to an RF probe station. We begin our work on Schottky diodes by explaining the motivation for adding an interfacial layer in a metal-semiconductor Schottky contact and how high-k di- electrics like HfO2 have been relatively unexplored in this application. We report the work carried out on the Pt/n-GaN metal-semiconductor (MS) Schottky and the Pt/HfO2/n-GaN metal-insulator-semiconductor (MIS) Schottky diode. We report an improvement in the diode parameters like barrier height (0.52 eV to 0.63 eV), ideality factor (2.1 to 1.3) and rectification ratio (35.9 to 98.9 @2V bias) after the introduction of 5 nm of HfO2 as the interfacial layer. Temperature dependent I-V measurements were done to gain a further understanding of the interface. We observe that the barrier height and ideality factor exhibit a temperature dependence. This was attributed to inhomogeneities at the interface and by assuming a Gaussian distribution of barrier heights. UV and IR photodetectors using III-nitrides are then studied. Our work on UV photodetectors describes the growth of epitaxial GaN films. Au nanoparticles were fabricated on these films using thermal evaporation and annealing. Al nanostruc- tures were fabricated using nanosphere lithography. Plasmonic enhancement using these metallic nanostructures was explored by fabricating metal-semiconductor-metal (MSM) photodetectors. We observed plasmonic enhancement of photocurrent in both cases. To obtain greater improvement, we etched down on the GaN film using reac tive ion etching (RIE). This resulted in further increase in photocurrent along with a reduction in dark current which was attributed to creation of new trap states. IR photodetectors studied in this thesis are InN quantum dots whose density can be controlled by varying the indium flux during growth. We observe that increase in InN quantum dot density results in increase in photocurrent and decrease in dark current in the fabricated IR photodetectors. We then explore the advantages that InGaN offers as a material that supports surface acoustic waves and fabricate InGaN based surface acoustic wave devices. We describe the growth of epitaxial In0.23 Ga0.77 N films on GaN template using molecular beam epitaxy. Material characterisation was carried out using HR-XRD, FESEM, PL and TEM. The composition was determined from HR-XRD and PL measurements and both results matched each other. This was followed by the fabrication of interdigited electrodes with finger spacing of 10 µm. S-parameter results showed a transmission peak at 104 MHz with an insertion loss of 19 dB. To the best of our knowledge, this is the first demonstration of an InGaN based SAW device. In summary, this thesis demonstrates the practical advantages of epitaxially grown film and nanostructured III-nitride materials such as GaN, InN and InGaN using plasma assisted molecular beam epitaxy for Schottky diodes, UV and IR photodetec- tors and surface acoustic wave devices.

This work considers the transport and attachment of nanoscale particles to surfaces and the associated phenomena that dictate particle-surface interactions. A consideration of the deposition of nano-scale particles on surfaces is a natural outgrowth of more than a century of research in the area of colloid science, and has taken on new pertinence in the context of understanding the fate and transport of engineered nanoparticles in aqueous environments. More specifically, the goal of this work is to better understand the effects of particle size, surface polymer coatings, and aggregation state on the kinetics of nanoparticle deposition. Theoretical tools such as those developed by Derjaguin-Landau-Verwey-Overbeek (DLVO) and Flory-Krigbaum , as well as the soft particle theory and surface element integration scaling methods are employed to address certain problems that were not considered with the existing theoretical frameworks for the conventional colloidal problems. Consequences of theoretical predictions are evaluated experimentally using column experiments or the quartz crystal microbalance techniques to monitor deposition kinetics. One of the key findings of this work is the observation that polymer coatings may stabilize nanoparticles against deposition or increase deposition, depending on whether the polymer coatings exist on both of the interacting surfaces and the interaction between the polymer and the collector surface. Both steric and bridging mechanisms are possible depending on whether contact between the polymer and collector surface can result in successful attachment. In addition, limitations in the use of conventional, equilibrium-based DLVO theory to describe the deposition of nano-scale particles at very low ionic strength are also identified and discussed. Moreover, it is demonstrated that the interaction between the aggregated nano-scale particles and environmental surfaces is controlled by the characteristic size of the primary particles rather than that of the aggregates. Thus despite an increase in hydrodynamic diameter, aggregation is predicted to reduce deposition only from the hydrodynamic aspects, but not from the colloidal interaction aspect. The affinity between aggregated nanoparticles and a surface may be increased at the initial stage of deposition while being unaffected by aggregation state during later stages of deposition. The results of this study lead to better understandings, at least on a qualitative level, of the factors that controlling the kinetics of deposition and, in a broader sense, the fate and transport of nanoscale particles in the aqueous environment.

Dissertation

abstract: Obtaining local electrochemical (EC) information is extremely important for understanding basic surface reactions, and for many applications. Scanning electrochemical microscopy (SECM) can obtain local EC information by scanning a microelectrode across the surface. Although powerful, SECM is slow, the scanning microelectrode may perturb reaction and the measured signal decreases with the size of microelectrode. This thesis demonstrates a new imaging technique based on a principle that is completely different from the conventional EC detection technologies. The technique, referred to as plasmonic-based electrochemical imaging (PECI), images local EC current (both faradaic and non-faradaic) without using a scanning microelectrode. Because PECI response is an optical signal originated from surface plasmon resonance (SPR), PECI is fast and non-invasive and its signal is proportional to incident light intensity, thus does not decrease with the area of interest. A complete theory is developed in this thesis work to describe the relationship between EC current and PECI signal. EC current imaging at various fixed potentials and local cyclic voltammetry methods are developed and demonstrated with real samples. Fast imaging rate (up to 100,000 frames per second) with 0.2×3µm spatial resolution and 0.3 pA detection limit have been achieved. Several PECI applications have been developed to demonstrate the unique strengths of the new imaging technology. For example, trace particles in fingerprint is detected by PECI, a capability that cannot be achieved with the conventional EC technologies. Another example is PECI imaging of EC reaction and interfacial impedance of graphene of different thicknesses. In addition, local square wave voltammetry capability is demonstrated and applied to study local catalytic current of platinum nanoparticle microarray. This thesis also describes a related but different research project that develops a new method to measure surface charge densities of SPR sensor chips, and micro- and nano-particles. A third project of this thesis is to develop a method to expand the conventional SPR detection and imaging technology by including a waveguide mode. This innovation creates a sensitive detection of bulk index of refraction, which overcomes the limitation that the conventional SPR can probe only changes near the sensor surface within ~200 nm.
Dissertation/Thesis
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Ph.D. Electrical Engineering 2011