ELECTRON TRANSPORT IN LOW-DIMENSIONAL NANOSTRUCTURES - THEORETICAL STUDY WITH APPLICATION

Graphene as a carbon monolayer has attracted extensive research interest in recent years. My research work within the frame of density functional theory has suggested that positioning graphene in proximity to h-BN may induce a finite energy gap in graphene, which is important for device applications. For an AB-stacked graphene/BN bilayer, a finite gap is induced at the equilibrium configuration. This induced gap shows a linear relationship with the applied strain. For a graphene/BN/graphene trilayer, a negligible gap is predicted in the ground state due to the overall symmetry of the system. When an electric field is applied, a tunable gap can be obtained for both AAA and ABA stackings. Enhanced tunneling current in the AA-stacked bilayer nanoribbons is predicted compared to either single-layer or AB-stacked bilayer nanoribbons. Interlayer separation between the nanoribbons is shown to have a profound impact on the conducting features. The effect of boron or nitrogen doping on the electronic transport properties of C60 fullerene is studied. The BC59 fullerene exhibits a considerably higher current than the pristine or nitrogen doped fullerenes beyond the applied bias of 1 V, suggesting it can be an effective semiconductor in p-type devices. The interaction between nucleic acid bases - adenine (A), guanine (G), cytosine (C), thymine (T) and uracil (U) - and a hydrogen-passivated silicon nanowire (SiNW) is investigated. The binding energy of the bases with the SiNW shows the order: G > A~C~T~U. This suggests that the interaction strength of a hydrogen passivated SiNW with the nucleic acid bases is nearly the same-G being an exception. The nature of the interaction is suggested to be electrostatic.

Photolithography based patterning of bacteriorhodopsin films

The patterning of photoactive purple membrane (PM) films onto electronic substrates to create a biologically based light detection device was investigated. This research is part of a larger collaborative effort to develop a miniaturized toxin detection platform. This platform will utilize PM films containing the photoactive protein bacteriorhodopsin to convert light energy to electrical energy. Following an effort to pattern PM films using focused ion beam machining, the photolithography based bacteriorhodopsin patterning technique (PBBPT) was developed. This technique utilizes conventional photolithography techniques to pattern oriented PM films onto flat substrates. After the basic patterning process was developed, studies were conducted that confirmed the photoelectric functionality of the PM films after patterning. Several process variables were studied and optimized in order to increase the pattern quality of the PM films. Optical microscopy, scanning electron microscopy, and interferometric microscopy were used to evaluate the PM films produced by the patterning technique. Patterned PM films with lateral dimensions of 15 μm have been demonstrated using this technique. Unlike other patterning techniques, the PBBPT uses standard photolithographic processes that make its integration with conventional semiconductor fabrication feasible. The final effort of this research involved integrating PM films patterned using the PBBPT with PMOS transistors. An indirect integration of PM films with PMOS transistors was successfully demonstrated. This indirect integration used the voltage produced by a patterned PM film under light exposure to modulate the gate of a PMOS transistor, activating the transistor. Following this success, a study investigating how this PM based light detection system responded to variations in light intensity supplied to the PM film. This work provides a successful proof of concept for a portion of the toxin detection platform currently under development.

Charge and spin transport in nanoscale junction from first principles

Recently nanoscale junctions consisting of 0-D nanostructures (single molecule) or 1-D nanostructures (semiconducting nanowire) sandwiched between two metal electrodes are successfully fabricated and characterized. What lacks in the recent developments is the understanding of the mechanism behind the observed phenomena at the level of atoms and electrons. For example, the origin of observed switching effect in a semiconducting nanowire due to the influence of an external gate bias is not yet understood at the electronic structure level. On the same context, different experimental groups have reported different signs in tunneling magneto-resistance for the same organic spin valve structure, which has baffled researchers working in this field. In this thesis, we present the answers to some of these subtle questions by investigating the charge and spin transport in different nanoscale junctions. A parameter-free, single particle Green’s function approach in conjunction with a posteriori density functional theory (DFT) involving a hybrid orbital dependent functional is used to calculate the tunneling current in the coherent transport limit. The effect of spin polarization is explicitly incorporated to investigate spin transport in a nanoscale junction. Through the electron transport studies in PbS nanowire junction, a new orbital controlled mechanism behind the switching of the current is proposed. It can explain the switching behavior, not only in PbS nanowire, but in other lead-chalcogenide nanowires as well. Beside this, the electronic structure properties of this nanowire are studied using periodic DFT. The quantum confinement effect was investigated by calculating the bandgap of PbS nanowires with different diameters. Subsequently, we explain an observed semiconducting to metallic phase transition of this nanowire by calculating the bandgap of the nanowire under uniform radial strain. The compressive radial strain on the nanowire was found to be responsible for the metallic to semiconducting phase transition. Apart from studying one dimensional nanostructure, we also present transport properties in zero dimensional single molecular junctions. We proposed a new codoping approach in a single molecular carborane junction, where a cation and an anion are simultaneously doped to find the role of a single atom in the device. The main purpose was to build a molecular junction where a single atom can dictate the flow of electrons in a circuit. Recent observations of both positive and negative sign in tunneling magnetoresistance (TMR) the using same organic spin-valve structure hasmystified researchers. From our spin dependent transport studies in a prototypical organic molecular tunneling device, we found that a 3% change in metal-molecule interfacial distance can alter the sign of TMR. Changing the interfacial distance by 3%, the number of participating eigenstates as well as their orbital characteristic changes for anti-parallel configuration of the magnetization at the two electrodes, leading to the sign reversal of the TMR. Apart from this, the magnetic proximity effect under applied bias is investigated quantitatively, which can be used to understand the observed unexpectedmagnetismin carbon basedmaterials when they are in close proximity with magnetic substrates.

Controlling electronic and magnetic properties of ultra narrow multilayered nanowires

Interest in the study of magnetic/non-magnetic multilayered structures took a giant leap since Grünberg and his group established that the interlayer exchange coupling (IEC) is a function of the non-magnetic spacer width. This interest was further fuelled by the discovery of the phenomenal Giant Magnetoresistance (GMR) effect. In fact, in 2007 Albert Fert and Peter Grünberg were awarded the Nobel Prize in Physics for their contribution to the discovery of GMR. GMR is the key property that is being used in the read-head of the present day computer hard drive as it requires a high sensitivity in the detection of magnetic field. The recent increase in demand for device miniaturization encouraged researchers to look for GMR in nanoscale multilayered structures. In this context, one dimensional(1-D) multilayerd nanowire structure has shown tremendous promise as a viable candidate for ultra sensitive read head sensors. In fact, the phenomenal giant magnetoresistance(GMR) effect, which is the novel feature of the currently used multilayered thin film, has already been observed in multilayered nanowire systems at ambient temperature. Geometrical confinement of the supper lattice along the 2-dimensions (2-D) to construct the 1-D multilayered nanowire prohibits the minimization of magnetic interaction- offering a rich variety of magnetic properties in nanowire that can be exploited for novel functionality. In addition, introduction of non-magnetic spacer between the magnetic layers presents additional advantage in controlling magnetic properties via tuning the interlayer magnetic interaction. Despite of a large volume of theoretical works devoted towards the understanding of GMR and IEC in super lattice structures, limited theoretical calculations are reported in 1-D multilayered systems. Thus to gauge their potential application in new generation magneto-electronic devices, in this thesis, I have discussed the usage of first principles density functional theory (DFT) in predicting the equilibrium structure, stability as well as electronic and magnetic properties of one dimensional multilayered nanowires. Particularly, I have focused on the electronic and magnetic properties of Fe/Pt multilayered nanowire structures and the role of non-magnetic Pt spacer in modulating the magnetic properties of the wire. It is found that the average magnetic moment per atom in the nanowire increases monotonically with an ~1/(N(Fe)) dependance, where N(Fe) is the number of iron layers in the nanowire. A simple model based upon the interfacial structure is given to explain the 1/(N(Fe)) trend in magnetic moment obtained from the first principle calculations. A new mechanism, based upon spin flip with in the layer and multistep electron transfer between the layers, is proposed to elucidate the enhancement of magnetic moment of Iron atom at the Platinum interface. The calculated IEC in the Fe/Pt multilayered nanowire is found to switch sign as the width of the non-magnetic spacer varies. The competition among short and long range direct exchange and the super exchange has been found to play a key role for the non-monotonous sign in IEC depending upon the width of the Platinum spacer layer. The calculated magnetoresistance from Julliere's model also exhibit similar switching behavior as that of IEC. The universality of the behavior of exchange coupling has also been looked into by introducing different non-magnetic spacers like Palladium, Copper, Silver, and Gold in between magnetic Iron layers. The nature of hybridization between Fe and other non-magnetic spacer is found to dictate the inter layer magnetic interaction. For example, in Fe/Pd nanowire the d-p hybridization in two spacer layer case favors anti-ferromagnetic (AFM) configuration over ferromagnetic (FM) configuration. However, the hybridization between half-filled Fe(d) and filled Cu(p) state in Fe/Cu nanowire favors FM coupling in the 2-spacer system.

Immobilizing bacteriorhodopsin on a single electron transistor

As awareness of potential human and environmental impacts from toxins has increased, so has the development of innovative sensors. Bacteriorhodopsin (bR) is a light activated proton pump contained in the purple membrane (PM) of the bacteria Halobacterium salinarum. Bacteriorhodopsin is a robust protein which can function in both wet and dry states and can withstand extreme environmental conditions. A single electron transistor(SET) is a nano-scale device that exploits the quantum mechanical properties of electrons to switch on and off. SETs have tremendous potential in practical applications due to their size, ultra low power requirements, and electrometer-like sensitivity. The main goal of this research was to create a bionanohybrid device by integrating bR with a SET device. This was achieved by a multidisciplinary approach. The SET devices were created by a combination of sputtering, photolithography, and focused ion beam machining. The bionanomaterial bacteriorhodopsin was created through oxidative fermentation and a series of transmembrane purification processes. The bR was then integrated with the SET by electrophoretic deposition, creating a bionanohybrid device. The bionanohybrid device was then characterized using a semiconductor parametric analyzer. Characterization demonstrated that the bR modulated the operational characteristics of the SET when bR was activated with light within its absorbance spectrum. To effectively integrate bacteriorhodopsin with microelectromechanical systems (MEMS) and nanoelectromechanical systems (NEMS), it is critical to know the electrical properties of the material and to understand how it will affect the functionality of the device. Tests were performed on dried films of bR to determine if there is a relationship between inductance, capacitance, and resistance (LCR) measurements and orientation, light-on/off, frequency, and time. The results indicated that the LCR measurements of the bR depended on the thickness and area of the film, but not on the orientation, as with other biological materials such as muscle. However, there was a transient LCR response for both oriented and unoriented bR which depended on light intensity. From the impedance measurements an empirical model was suggested for the bionanohybrid device. The empirical model is based on the dominant electrical characteristics of the bR which were the parallel capacitance and resistance. The empirical model suggests that it is possible to integrate bR with a SET without influencing its functional characteristics.

Quantum dot / optical protein bio-nano hybrid system biosensing

The integration of novel nanomaterials with highly-functional biological molecules has advanced multiple fields including electronics, sensing, imaging, and energy harvesting. This work focuses on the creation of a new type of bio-nano hybrid substrate for military biosensing applications. Specifically it is shown that the nano-scale interactions of the optical protein bacteriorhodopsin and colloidal semiconductor quantum dots can be utilized as a generic sensing substrate. This work spans from the basic creation of the protein to its application in a novel biosensing system. The functionality of this sensor design originates from the unique interactions between the quantum dot and bacteriorhodopsin molecule when in nanoscale proximity. A direct energy transfer relationship has been established between coreshell quantum dots and the optical protein bacteriorhodopsin that substantially enhances the protein’s native photovoltaic capabilities. This energy transfer phenomena is largely distance dependent, in the sub-10nm realm, and is characterized experimentally at multiple separation distances. Experimental results on the energy transfer efficiency in this hybrid system correlate closely to theoretical predictions. Deposition of the hybrid system with nano-scale control has allowed for the utilization of this energy transfer phenomena as a modulation point for a functional biosensor prototype. This work reveals that quantum dots have the ability to activate the bacteriorhodopsin photocycle through both photonic and non-photonic energy transfer mechanisms. By altering the energy transferred to the bacteriorhodopsin molecule from the quantum dot, the electrical output of the protein can be modulated. A biosensing prototype was created in which the energy transfer relationship is altered upon target binding, demonstrating the applicability of a quantum dot/bacteriorhodopsin hybrid system for sensor applications. The electrical nature of this sensing substrate will allow for its efficient integration into a nanoelectronics array form, potentially leading to a small-low power sensing platform for remote toxin detection applications.

DESIGN AND FABRICATION OF RESONANT GAS SENSOR FOR HIGH SENSITIVITY IN THE PRESENCE OF AIR DAMPING

Gas sensors have been used widely in different important area including industrial control, environmental monitoring, counter-terrorism and chemical production. Micro-fabrication offers a promising way to achieve sensitive and inexpensive gas sensors. Over the years, various MEMS gas sensors have been investigated and fabricated. One significant type of MEMS gas sensors is based on mass change detection and the integration with specific polymer. This dissertation aims to make contributions to the design and fabrication of MEMS resonant mass sensors with capacitance actuation and sensing that lead to improved sensitivity. To accomplish this goal, the research has several objectives: (1) Define an effective measure for evaluating the sensitivity of resonant mass devices; (2) Model the effects of air damping on microcantilevers and validate models using laser measurement system (3) Develop design guidelines for improving sensitivity in the presence of air damping; (4) Characterize the degree of uncertainty in performance arising from fabrication variation for one or more process sequences, and establish design guidelines for improved robustness. Work has been completed toward these objectives. An evaluation measure has been developed and compared to an RMS based measure. Analytic models of air damping for parallel plate that include holes are compared with a COMSOL model. The models have been used to identify cantilever design parameters that maximize sensitivity. Additional designs have been modeled with COMSOL and the development of an analytical model for Fixed-free cantilever geometries with holes has been developed. Two process flows have been implemented and compared. A number of cantilever designs have been fabricated and the uncertainty in process has been investigated. Variability from processing have been evaluated and characterized.

Integration of room temperature single electron transistor with CMOS subsystem

The single electron transistor (SET) is a charge-based device that may complement the dominant metal-oxide-semiconductor field effect transistor (MOSFET) technology. As the cost of scaling MOSFET to smaller dimensions are rising and the the basic functionality of MOSFET is encountering numerous challenges at dimensions smaller than 10nm, the SET has shown the potential to become the next generation device which operates based on the tunneling of electrons. Since the electron transfer mechanism of a SET device is based on the non-dissipative electron tunneling effect, the power consumption of a SET device is extremely low, estimated to be on the order of 10^-18J. The objectives of this research are to demonstrate technologies that would enable the mass produce of SET devices that are operational at room temperature and to integrate these devices on top of an active complementary-MOSFET (CMOS) substrate. To achieve these goals, two fabrication techniques are considered in this work. The Focus Ion Beam (FIB) technique is used to fabricate the islands and the tunnel junctions of the SET device. A Ultra-Violet (UV) light based Nano-Imprint Lithography (NIL) call Step-and-Flash- Imprint Lithography (SFIL) is used to fabricate the interconnections of the SET devices. Combining these two techniques, a full array of SET devices are fabricated on a planar substrate. Test and characterization of the SET devices has shown consistent Coulomb blockade effect, an important single electron characteristic. To realize a room temperature operational SET device that function as a logic device to work along CMOS, it is important to know the device behavior at different temperatures. Based on the theory developed for a single island SET device, a thermal analysis is carried out on the multi-island SET device and the observation of changes in Coulomb blockade effect is presented. The results show that the multi-island SET device operation highly depends on temperature. The important parameters that determine the SET operation is the effective capacitance Ceff and tunneling resistance Rt . These two parameters lead to the tunneling rate of an electron in the SET device, Γ. To obtain an accurate model for SET operation, the effects of the deviation in dimensions, the trap states in the insulation, and the background charge effect have to be taken into consideration. The theoretical and experimental evidence for these non-ideal effects are presented in this work.

Preparation of highly-ordered TiO₂ nanotube arrays and their applications in Dye-sensitized solar cells

Titanium oxide is an important semiconductor, which is widely applied for solar cells. In this research, titanium oxide nanotube arrays were synthesized by anodization of Ti foil in the electrolyte composed of ethylene glycol containing 2 vol % H2O and 0.3 wt % NH4F. The voltages of 40V-50V were employed for the anodizing process. Pore diameters and lengths of the TiO2 nanotubes were evaluated by field emission scanning electron microscope (FESEM). The obtained highly-ordered titanium nanotube arrays were exploited to fabricate photoelectrode for the Dye-sensitized solar cells (DSSCS). The TiO2 nanotubes based DSSCS exhibited an excellent performance with a high short circuit current and open circuit voltage as well as a good power conversion efficiency. Those can be attributed to the high surface area and one dimensional structure of TiO2 nanotubes, which could hold a large amount of dyes to absorb light and help electron percolation process to hinder the recombination during the electrons diffusion in the electrolyte.

MULTISCALE EXAMINATION AND MODELING OF ELECTRON TRANSPORT IN NANOSCALE MATERIALS AND DEVICES

For half a century the integrated circuits (ICs) that make up the heart of electronic devices have been steadily improving by shrinking at an exponential rate. However, as the current crop of ICs get smaller and the insulating layers involved become thinner, electrons leak through due to quantum mechanical tunneling. This is one of several issues which will bring an end to this incredible streak of exponential improvement of this type of transistor device, after which future improvements will have to come from employing fundamentally different transistor architecture rather than fine tuning and miniaturizing the metal-oxide-semiconductor field effect transistors (MOSFETs) in use today. Several new transistor designs, some designed and built here at Michigan Tech, involve electrons tunneling their way through arrays of nanoparticles. We use a multi-scale approach to model these devices and study their behavior. For investigating the tunneling characteristics of the individual junctions, we use a first-principles approach to model conduction between sub-nanometer gold particles. To estimate the change in energy due to the movement of individual electrons, we use the finite element method to calculate electrostatic capacitances. The kinetic Monte Carlo method allows us to use our knowledge of these details to simulate the dynamics of an entire device— sometimes consisting of hundreds of individual particles—and watch as a device ‘turns on’ and starts conducting an electric current. Scanning tunneling microscopy (STM) and the closely related scanning tunneling spectroscopy (STS) are a family of powerful experimental techniques that allow for the probing and imaging of surfaces and molecules at atomic resolution. However, interpretation of the results often requires comparison with theoretical and computational models. We have developed a new method for calculating STM topographs and STS spectra. This method combines an established method for approximating the geometric variation of the electronic density of states, with a modern method for calculating spin-dependent tunneling currents, offering a unique balance between accuracy and accessibility.

NANOSCALE ELECTROCHEMISTRY BY IN-SITU TRANSMISSION ELECTRON MICROSCOPY

Nanoscale research in energy storage has recently focused on investigating the properties of nanostructures in order to increase energy density, power rate, and capacity. To better understand the intrinsic properties of nanomaterials, a new and advanced in situ system was designed that allows atomic scale observation of materials under external fields. A special holder equipped with a scanning tunneling microscopy (STM) probe inside a transmission electron microscopy (TEM) system was used to perform the in situ studies on mechanical, electrical, and electrochemical properties of nanomaterials. The nanostructures of titanium dioxide (TiO2) nanotubes are characterized by electron imaging, diffraction, and chemical analysis techniques inside TEM. TiO2 nanotube is one of the candidates as anode materials for lithium ion batteries. It is necessary to study their morphological, mechanical, electrical, and electrochemical properties at atomic level. The synthesis of TiO2 nanotubes showed that the aspect ratio of TiO2 could be controlled by processing parameters, such as anodization time and voltage. Ammonium hydroxide (NH4OH) treated TiO2 nanotubes showed unexpected instability. Observation revealed the nanotubes were disintegrated into nanoparticles and the tubular morphology was vanished after annealing. The nitrogen compounds incorporated in surface defects weaken the nanotube and result in the collapse of nanotube into nanoparticles during phase transformation. Next, the electrical and mechanical properties of TiO2 nanotubes were studied by in situ TEM system. Phase transformation of anatase TiO2 nanotubes into rutile nanoparticles was studied by in situ Joule heating. The results showed that single anatase TiO2 nanotubes broke into ultrafine small anatase nanoparticles. On further increasing the bias, the nanoclusters of anatase particles became prone to a solid state reaction and were grown into stable large rutile nanoparticles. The relationship between mechanical and electrical properties of TiO2 nanotubes was also investigated. Initially, both anatase and amorphous TiO2 nanotubes were characterized by using I-V test to demonstrate the semiconductor properties. The observation of mechanical bending on TiO2 nanotubes revealed that the conductivity would increase when bending deformation happened. The defects on the nanotubes created by deformation helped electron transportation to increase the conductivity. Lastly, the electrochemical properties of amorphous TiO2 nanotubes were characterized by in situ TEM system. The direct chemical and imaging evidence of lithium-induced atomic ordering in amorphous TiO2 nanotubes was studied. The results indicated that the lithiation started with the valance reduction of Ti4+ to Ti3+ leading to a LixTiO2 intercalation compound. The continued intercalation of Li ions in TiO2 nanotubes triggered an amorphous to crystalline phase transformation. The crystals were formed as nano islands and identified to be Li2Ti2O4 with cubic structure (a = 8.375 Å). This phase transformation is associated with local inhomogeneities in Li distribution. Based on these observations, a new reaction mechanism is proposed to explain the first cycle lithiation behavior in amorphous TiO2 nanotubes.