Thesis (M. S.)--Materials Science and Engineering, Georgia Institute of Technology, 2005. / Ready, Jud, Committee Co-Chair ; Carter, Brent, Committee Co-Chair ; Snyder, Bob, Committee Member ; Wang, Zhong Lin, Committee Member. Includes bibliographical references.

Thesis (Ph. D.)--Civil and Environmental Engineering, Georgia Institute of Technology, 2006. / Yiacoumi, Sotira, Committee Chair ; Tsouris, Costas, Committee Co-Chair ; Pavlostathis, Spyros, Committee Member ; Tannenbaum, Rina, Committee Member ; Sherrill, David, Committee Member.

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京都大学 / 新制・課程博士 / 博士(工学) / 甲第23913号 / 工博第5000号 / 新制||工||1780(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 作花 哲夫, 教授 安部 武志, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Biosensors are used for the detection of a range of analytes for applications in healthcare, food production, environmental monitoring and biodefence. However, many biosensing platforms are large, expensive, require skilled operators or necessitate the analyte to be labelled. Direct electrochemical detection methods present a particularly attractive platform due to the simplified instrumentation when compared to other techniques such as fluorescence-based biosensors. With modern integrated circuit capabilities electrochemical biosensors offer greater suitability for monolithic integration with any necessary signal processing circuitry. This thesis explores micro- and nanogap devices for both redox cycling and dielectric spectroscopy sensing mechanisms. By using two electrodes with interelectrode separation down to distances in the micro- and nanometre scale, several benefits can be realised. Firstly the close proximity of the two electrodes significantly reduces the interdiffusion time. This allows an electroactive species to be rapidly shuttled across the gap and switched between reduced and oxidised states. The result is feedback amplification of the amperometric response, increasing the signal. The second benefit is that the screening effect caused by electric double layers at the electrode–electrolyte interface is reduced due to the electric double layers occupying a larger fraction of the sensing volume. This significantly improves the sensor suitability for dielectric spectroscopy by increasing the potential drop across the biolayer. These two sensing mechanisms are demonstrated using a large area dual-plate microgap device for the detection of two different analytes. Utilising the first mode, detection of cysteine–cystine, an important redox couple involved in the signalling mechanism for the regulation of protein function, interaction and localisation is shown. The microgap device is then used for dielectric spectroscopy sensing of a mannose-specific uropathogenic Escherichia coli strain whilst also demonstrating the effect of ionic concentration on the capacitive response. The response of these devices is highly dependent on the interelectrode separation as well as the surface area of the electrodes. However, fabrication of large-area nanogap devices presents a significant challenge. This meant that careful optimisation and the development of novel techniques was necessary. This work reports the design, fabrication and characterisation of both a vertical and a horizontal coplanar large area nanogap device. The vertical nanogap device is fabricated using an inductively-coupled plasma reactive ion etching process to create a channel in a silicon substrate. A lower electrode is then optically patterned in the channel before anodically bonding a second identical electrode patterned on glass directly above. The horizontal nanogap device uses a different approach, utilising a state-of-the-art electron-beam lithography system to create a long serpentine nanogap with passivation to reduce fringing effects. The design allows the electron-beam lithography step to be substituted with nanoimprint lithography to reduce cost and improve throughput. Both of these devices have integrated microfluidic channels and provide a capacity for relatively high-throughput production.

Porous carbon derived from an inorganic silicon carbide (SiC) precursor, termed SiC-derived carbon, is an attractive material for electrochemical energy storage applications, including electrodes for electrical double layer capacitors (EDLCs). The objective of this thesis is to investigate the effects that the carbide-derived carbon (CDC) microstructure and pore structure have on the energy and power characteristics of the EDLC electrodes. Conventional SiC CDC is produced from non-porous crystalline SiC powder at temperatures above 800 °C. Here we studied the performance of SiC CDCs produced by chlorination at 700-900 °C of an ordered mesoporous SiC precursor, which was synthesized via a 1000 °C pyrolysis of polycarbosilane infiltrated into an SBA-15 silica template having ordered mesopores. The SiC CDC was purified from chlorine impurities by annealing in ammonia. The surface area and pore size of the purified SiC CDC was characterized via N2 and CO2 sorption using density functional theory (DFT) and Brunnauer, Emmet, and Teller (BET) theory. The specific capacitance, power and energy densities were characterized via electrochemical measurements of the SiC CDC electrodes in 1 M tetraethylammonium tetrafluoroborate (TEABF4) acetonitrile solution. The SiC CDC exhibited a specific surface area (SSA) in excess of 2400 m2/g and gravimetric capacitance values of up to ~ 150 F/g, among the highest ever reported for any electrodes in this electrolyte. The ordered mesopores allowed for fast ion transport within each particle, resulting in excellent capacity retention under high current rates and ultra-fast frequency response, thus allowing for extremely high power and energy densities. The best overall performance was achieved in SiC CDC samples chlorinated at the lowest temperature of 700 °C.

The growing market of mobile electronic devices, renewable off-grid energy sources and electric vehicles requires high-performance energy storage devices. Rechargeable batteries are usually the first choice due to their high energy density. However, supercapacitors have a higher power density and longer life-time compared to batteries. For some applications supercapacitors are more suitable than batteries. They can also be used to complement batteries in order to extend a battery's life-time. The use of supercapacitors is, however, still limited due to their high costs. Most commercially available supercapacitors contain expensive electrolytes and costly electrode materials. In this thesis I will present the concept of cost efficient, paper-based supercapacitors. The idea is to produce supercapacitors with low-cost, green materials and inexpensive production processes. We show that supercapacitor electrodes can be produced by coating graphite on paper. Roll-to-roll techniques known from the paper industry can be employed to facilitate an economic large-scale production. We investigated the influence of paper on the supercapacitor's performance and discussed its role as passive component. Furthermore, we used chemically reduced graphite oxide (CRGO) and a CRGO-gold nanoparticle composite to produce electrodes for supercapacitors. The highest specific capacitance was achieved with the CRGO-gold nanoparticle electrodes. However, materials produced by chemical synthesis and intercalation of nanoparticles are too costly for a large-scale production of inexpensive supercapacitor electrodes. Therefore, we introduced the idea of producing graphene and similar nano-sized materials in a high-pressure homogenizer. Layered materials like graphite can be exfoliated when subjected to high shear forces. In order to form mechanical stable electrodes, binders need to be added. Nanofibrillated cellulose (NFC) can be used as binder to improve the mechanical stability of the porous electrodes. Furthermore, NFC can be prepared in a high-pressure homogenizer and we aim to produce both NFC and graphene simultaneously to obtain a NFC-graphene composite. The addition of 10% NFC in ratio to the amount of graphite, increased the supercapacitor's capacitance, enhanced the dispersion stability of homogenized graphite and improved the mechanical stability of graphite electrodes in both dry and wet conditions. Scanning electron microscope images of the electrode's cross section revealed that NFC changed the internal structure of graphite electrodes depending on the type of graphite used. Thus, we discussed the influence of NFC and the electrode structure on the capacitance of supercapacitors.

Environmental separation processes such as removal of heavy metals from aqueous solutions, electrosorption in groundwater remediation, and capacitive desalination, as well as energy storage in supercapacitors, are based on the electrical double layer (EDL) formation within nanoporous carbon materials. This research is focused on the nano-scale phenomena of EDL formation inside the confined space of nanopores. The electrosorption behavior of nanoporous carbon materials was characterized by measuring the double-layer capacitance using cyclic voltammetry. The presence of micropores results in the occurrence of EDL overlapping, corresponding to a considerable loss of the double-layer capacitance. Hence, pore size distribution plays an important role in determining the double-layer capacitance. EDL formation has significant influence on ion transport and sorption inside nanopores. The data obtained by simple diffusion and electrochemically-aided diffusion experiments demonstrated the size-exclusion effects on pore accessibility by ions. A larger ion-exclusion volume prevents larger ions from penetrating inside the pores. Batch equilibrium electrosorption experiments using nanoporous carbon materials showed that selective electrosorption, imposed by the difference in the size of hydrated ions, occurs in a competitive environment. Molecular modeling based on Monte Carlo methods was developed to simulate the EDL formation in a slit-type nanopore. Simulation results indicated that the competition in asymmetries of ion charge and size not only determines the screening of surface charge but also affects the electrolyte distribution within charged pores. In a mixture of electrolytes, the charge/size competitive effects can dominate pore accessibility. Multivalent counterions with large size have the energetic advantage of screening surface charge. On the other hand, small monovalent counterions present a ¡§size affinity¡¨ to access the pores. Therefore, electrosorption selectivity of counterions with different properties is a result of a counterbalance between minimization of potential energy and size-exclusion effects. Manipulation of electrosorption selectivity to separate ions could in principle be achieved via tuning the EDL formation inside the pores. The findings of the thesis have several significant implications for the development of advanced techniques for selective separation of ions in environmental systems and energy storage.

Investigations performed in order to understand the electronic and optoelectronic properties of field effect transistors based on few layers of 2D Copper Indium Selenide (CuIn7Se11) are reported. In general, field effect transistors (FETs), electric double layer field effect transistors (EDL-FETs), and photodetectors are crucial part of several electronics based applications such as tele-communication, bio-sensing, and opto-electronic industry. After the discovery of graphene, several 2D semiconductor materials like TMDs (MoS2, WS2, and MoSe2 etc.), group III-VI materials (InSe, GaSe, and SnS2 etc.) are being studied rigorously in order to develop them as components in next generation FETs. Traditionally, thin films of ternary system of Copper Indium Selenide have been extensively studied and used in optoelectronics industry as photoactive component in solar cells. Thus, it is expected that atomically thin 2D layered structure of Copper Indium Selenide can have optical properties that could potentially be more advantageous than its thin film counterpart and could find use for developing next generation nano devices with utility in opto/nano electronics. Field effect transistors were fabricated using few-layers of CuIn7Se11 flakes, which were mechanically exfoliated from bulk crystals grown using chemical vapor transport technique. Our FET transport characterization measurements indicate n-type behavior with electron field effect mobility µFE ≈ 36 cm^2 V^-1 s^-1 at room temperature when Silicon dioxide (SiO2) is used as a back gate. We found that in such back gated field effect transistor an on/off ratio of ~ 10^4 and a subthreshold swing ≈ 1 V/dec can be obtained. Our investigations further indicate that Electronic performance of these materials can be increased significantly when gated from top using an ionic liquid electrolyte [1-Butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6)]. We found that electron field effect mobility µFE can be increased from ~ 3 cm^2 V^-1 s^-1 in SiO2 back gated device to ~ 18 cm^2 V^-1 s^-1 in top gated electrolyte devices. Similarly, subthreshold swing can be improved from ~ 30 V/dec to 0.2 V/dec and on/off ratio can be increased from 10^2 to 10^3 by using an electrolyte as a top gate. These FETs were also tested as phototransistors. Our photo-response characterization indicate photo-responsivity ~ 32 A/W with external quantum efficiency exceeding 10^3 % when excited with a 658 nm wavelength laser at room temperature. Our phototransistor also exhibit response times ~ tens of µs with specific detectivity (D*) values reaching ~ 10^12 Jones. The CuIn7Se11 phototransistor properties can be further tuned & enhanced by applying a back gate voltage along with increased source drain bias. For example, photo-responsivity can gain substantial improvement up to ~ 320 A/W upon application of a gate voltage (Vg = 30 V) and/or increased source-drain bias. The photo-responsivity exhibited by these photo detectors are at least an order of magnitude better than commercially available conventional Si based photo detectors coupled with response times that are orders of magnitude better than several other family of layered materials investigated so far. Further photocurrent generation mechanisms, effect of traps is discussed in detail.

Today’s society is currently performing an exit from fossilfuel energy sources. The change to sustainable alternativesrequires inexpensive and environmentally friendly energy storagedevices. However, most current devices contain expensive,rare or toxic materials. These materials must be replaced bylow-cost, abundant, nontoxic components.In this thesis, I suggest the production of paper-based electricdouble-layer capacitors (EDLCs) to meet the demand oflow-cost energy storage devices that provide high power density.To fulfill the requirements of sustainable and environmentallyfriendly devices, production of EDLCs that consist of paper,graphite and saltwater is proposed. Paper can be used as aseparator between the electrodes and as a substrate for theelectrodes. Graphite is suited for use as an active material in theelectrodes, and saltwater can be employed as an electrolyte.Westudied and developed different methods for the productionof nanographite and graphene from graphite. Composites containingthese materials and similar advanced carbon materialshave been tested as electrode materials in EDLCs. I suggest theuse of cellulose nanofibers (CNFs) or microfibrillated cellulose(MFC) as a binder in the electrodes. In addition to improvedmechanical stability, the nanocellulose improved the stabilityof graphite dispersions and the electrical performance of theelectrodes. The influence of the cellulose quality on the electricalproperties of the electrodes and EDLCs was investigated.The results showed that the finest nanocellulose quality is notthe best choice for EDLC electrodes; MFC is recommended forthis application instead. The results also demonstrated thatthe capacitance of EDLCs can be increased if the electrodemasses are adjusted according to the size of the electrolyte ions.Moreover, we investigated the issue of high contact resistancesat the interface between porous carbon electrodes and metalcurrent collectors. To reduce the contact resistance, graphitefoil can be used as a current collector instead of metal foils.Using the suggested low-cost materials, production methodsand conceptual improvements, it is possible to reduce the material costs by more than 90% in comparison with commercialunits. This confirms that paper-based EDLCs are apromising alternative to conventional EDLCs. Our findings andadditional research can be expected to substantially supportthe design and commercialization of sustainable EDLCs andother green energy technologies. / I dagens samhälle pågår en omställning från användning avfossila energikällor till förnybara alternativ. Denna förändringkräver miljövänliga och kostnadseffektiva elektriska energilagringsenheterför att möjliggöra en kontinuerlig energileverans.Dagens energilagringsenheter innehåller ofta dyra, sällsyntaeller giftiga material som behöver bytas ut för att nå hållbaralösningar.I denna avhandling föreslås att tillverka pappersbaseradesuperkondensatorer som möter kraven för kostnadseffektivaelektriska energilagrare med hög effekttäthet. För att nå kravenpå miljömässigt hållbara enheter föreslås användning avendast papper, grafit och saltvatten. Papper kan användas somseparator mellan elektroder likväl som substrat vid elektrodbestrykning.Grafit kan användas som aktivt elektrodmaterialoch saltvatten fungerar som elektrolyt. Olika metoder har härutvecklats för att producera nanografit och grafen från grafit.Dessa material har tillsammans med liknande, kommersiellt tillgängliga,avancerade kolmaterial testats i elektrodkompositerför superkondensatorer. Som bindemedel i dessa kompositerföreslås nanofibrillerad eller mikrofibrillerad cellulosa. Jaghar demonstrerat att nanocellulosa ökar dispersionsstabilitetensamt förbättrar den mekaniska stabiliteten och dom elektriskaegenskaperna i elektroderna. Hur cellulosans kvalitet påverkarelektroderna har undersökts och visar att den finaste kvaliteteninte är det bästa valet för superkondensatorer, istället rekommenderasmikrofibrillerad cellulosa. Utöver detta demonstrerasmöjligheten att öka superkondensatorernas kapacitans genomatt balansera elektrodernas massa med hänsyn till jonernasstorlek i elektrolyten. I avhandlingen diskuteras även svårigheternamed hög kontaktresistans i gränssnittet mellan porösakolstrukturer och metallfolie och hur detta kan undvikas omgrafitfolie används som kontakt.Genom att använda de material, produktionstekniker ochkonceptförbättringar som föreslås i avhandlingen är det möjligtatt reducera materialkostnaderna med mer än 90% i jämförelsemed kommersiella superkondensatorer. Detta bekräftar att pappersbaserade superkondensatorer är ett lovande alternativoch våra resultat tillsammans med vidare utveckling harstor potential att stödja övergången till miljömässigt hållbarasuperkondensatorer och annan grön energiteknik. / <p>Vid tidpunkten för disputationen var följande delarbeten opublicerade: delarbete 6 inskickat.</p><p>At the time of the doctoral defence the following papers were unpublished: paper 6 submitted.</p>