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Materials Growth and Characterization of Thermoelectric and Resistive Switching Devices

Abstract

In the 74 years since diode rectifier based radar technology helped the allied forces win WWII, semiconductors have transformed the world we live in. From our smart phones to semiconductor-based energy conversion, semiconductors touch every aspect of our lives. With this thesis I hope to expand human knowledge of semiconductor thermoelectric devices and resistive switching devices through experimentation with materials growth and subsequent materials characterization. Metal organic chemical vapor deposition (MOCVD) was the primary method of materials growth utilized in these studies. Additionally, plasma enhanced chemical vapor deposition (PECVD), atomic layer deposition (ALD),ion beam sputter deposition, reactive sputter deposition and electron-beam (e-beam) evaporation were also used in this research for device fabrication. Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), and Electron energy loss spectroscopy (EELS) were the primary characterization methods utilized for this research. Additional device and materials characterization techniques employed include: current-voltage measurements, thermoelectric measurements, x-ray diffraction (XRD), reflection absorption infra-red spectroscopy (RAIRS), atomic force microscopy (AFM), photoluminescence (PL), and raman spectroscopy.

As society has become more aware of its impact on the planet and its limited resources, there has been a push toward developing technologies to sustainably produce the energy we need. Thermoelectric devices convert heat directly into electricity. Thermoelectric devices have the potential to save huge amounts of energy that we currently waste as heat, if we can make them cost-effective. Semiconducting thin films and nanowires appear to be promising avenues of research to attain this goal. Specifically, in this work we will explore the use of ErSb thin films as well as Si and InP nanowire networks for thermoelectric applications. First we will discuss the growth of erbium monoantimonide (ErSb) thin films with thermal conductivities close to or slightly smaller than the alloy limit of the two ternary alloy hosts. Second we consider an ex-situ monitoring technique based on glancing-angle infrared-absorption used to determine small amounts of erbium antimonide (ErSb) deposited on an indium antimonide (InSb) layer, a concept for thermoelectric devices to scatter phonons. Thirdly we begin our discussion of nanowires with the selective area growth (SAG) of single crystalline indium phosphide (InP) nanopillars on an array of template segments composed of a stack of gold and amorphous silicon. Our approach enables flexible and scalable nanofabrication using industrially proven tools and a wide range of semiconductors on various non-semiconductor substrates. Then we examine the use of graphene to promote the growth of nanowire networks on flexible copper foil leading to the testing of nanowire network devices for thermoelectric applications and the concept of multi-stage devices. We present the ability to tailor current-voltage characteristics to fit a desired application of thermoelectric devices by using nanowire networks as building blocks that can be stacked vertically or laterally. Furthermore, in the study of our flexible nanowire network multi-stage devices, we discovered the presence of nonlinear current-voltage characteristics and discuss how this feature could be utilized to increase efficiency for thermoelectric devices. This work indicates that with sufficient volume and optimized doping, flexible nanowire networks could be a low cost semiconductor solution to our wasted heat challenge.

Resistive switching devices are two terminal electrical resistance switches that retain a state of internal resistance based on the history of applied voltage and current. The occurrence of reversible resistance switching has been widely studied in a variety of material systems for applications including nonvolatile memory, logic circuits, and neuromorphic computing. To this end we next we studied devices in each resistance state of a TaOx switch, which has previously shown high endurance and desirable switching behavior, to better understand the system in nanoscale devices. Finally, we will discuss a self-aligned NbO2 nano-cap demonstrated atop a TaO2.2 switching layer. The goal of this device is to create a nanoscale RRAM and selector device in a single stack. These results indicate that ternary resistive switching devices may be a beneficial method of combining behaviors of different material systems and that with proper engineering a self-aligned selector is possible.

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