Counterfeiting of goods is a widespread epidemic that is affecting the world economy. The conventional labeling techniques are proving inadequate to thwart determined counterfeiters equipped with sophisticated technologies. There is a growing need of a secure labeling that is easy to manufacture and analyze but extremely difficult to copy. Programmable metallization cell technology operates on a principle of controllable reduction of a metal ions to an electrodeposit in a solid electrolyte by application of bias. The nature of metallic electrodeposit is unique for each instance of growth, moreover it has a treelike, bifurcating fractal structure with high information capacity. These qualities of the electrodeposit can be exploited to use it as a physical unclonable function. The secure labels made from the electrodeposits grown in radial structure can provide enhanced authentication and protection from counterfeiting and tampering.

So far only microscale radial structures and electrodeposits have been fabricated which limits their use to labeling only high value items due to high cost associated with their fabrication and analysis. Therefore, there is a need for a simple recipe for fabrication of macroscale structure that does not need sophisticated lithography tools and cleanroom environment. Moreover, the growth kinetics and material characteristics of such macroscale electrodeposits need to be investigated. In this thesis, a recipe for fabrication of centimeter scale radial structure for growing Ag electrodeposits using simple fabrication techniques was proposed. Fractal analysis of an electrodeposit suggested information capacity of 1.27 x 1019. The kinetics of growth were investigated by electrical characterization of the full cell and only solid electrolyte at different temperatures. It was found that mass transport of ions is the rate limiting process in the growth. Materials and optical characterization techniques revealed that the subtle relief like structure and consequently distinct optical response of the electrodeposit provides an added layer of security. Thus, the enormous information capacity, ease of fabrication and simplicity of analysis make macroscale fractal electrodeposits grown in radial programmable metallization cells excellent candidates for application as physical unclonable functions.

The coexistence of superconductivity and ferromagnetic orders has been the subject of study for many years. It well known that these materials possess two competing order parameters; however the two order parameters can coexist under special circumstances inducing interesting physical phenomena. In recent years the demand of ultra-low-power, high density cryogenic memories has brought considerable interest to integrate superconducting and magnetic thin films in one structure to produce novel memory elements. The operation of the device depends on the unusual electronic properties associated with the Superconductor (S) /Ferromagnetic (F) proximity effect.

Niobium (Nb) based Josephson junction devices were fabricated with barriers containing two ferromagnetic layers separated by a normal metal space layer. In device operation, electrons in the superconductor are injected into the ferromagnets, causing the superconductor wavefunction to shift its phase and decay in amplitude. Such devices have two different states that depend on the relative magnetization of their ferromagnetic barrier layers, parallel or antiparallel. In these different states, the junctions have different phase shifts and critical currents. Superconducting circuits containing these devices can be designed to operate as memory cells using either one of these outputs.

To quantify the shift in phase and amplitude decay of the wavefunction through a common ferromagnet, permalloy, a series of Nb/permalloy/Nb Josephson junctions with varying ferromagnetic layer thicknesses were fabricated. Data have shown that the optimal thickness of a fixed layer composed of permalloy is 2.4 nm, as it shifts the wavefunction phase to π/2, its “pivot point.” If set to precisely this value, the free layer in SFNF'S junctions will switch the junction into either the 0 or π state depending on its magnetic orientation. To minimize the free-layer switching energy dilute Cu-permalloy alloy [Cu0.7(Ni80Fe20)0.3] with a low magnetic saturation (Ms of ~80 emu/cm3) was used as the free layer. These devices exhibit switching energies at small magnetic fields, demonstrating their potential use for low power non-volatile memory for superconductor circuits.

Lastly, to study the proximity effect using other potentially-useful ferromagnetic layers, measurements were performed on Nb/F bilayers and Nb/F/AlOx/Al tunnel junctions with ferromagnets Ni8Fe19, Ni65Fe15Co20, and Pd1-xNix. The dependence of the critical temperature of the bilayers and density of states that propagated through the ferromagnetic layer were studied as a function of thickness. From this study, crucial magnetic and electrical parameters like magnetic coherence lengths (ξF), exchange energy (Eex), and the rate of shift in the wavefunction’s phase and amplitude as a function of thickness were determined.

The use of nanoparticle-in-matrix composites is a common motif among a broad range of nanoscience applications and is of particular interest to the thermal sciences community. To explore this morphological theme, crystalline inorganic composites were synthesized by mixing colloidal CdSe nanocrystals and In2Se3 metal chalcogenide complex (MCC) precursor in hydrazine solvent and then thermally transform the MCC precursor into a crystalline In2Se3 matrix. The volume fraction of CdSe nanocrystals was varied from 0 to ~100% .Rich structural and chemical interactions between the CdSe nanocrystals and the In2Se3 matrix were observed. The average thermal conductivities of the 100% In2Se3 and ~100% CdSe composites are 0.32 and 0.53 W/m-K, respectively, which are remarkably low for inorganic crystalline materials. With the exception of the ~100% CdSe samples, the thermal conductivities of these nanocomposites are insensitive to CdSe volume fraction.This insensitivity is attributed to competing effects rise from structural morphology changes during composite formation.

Next, thermoelectric properties of metal chalcogenide thin films deposited from precursors using thiol-amine solvent mixtures were first reported. Cu2-xSeyS1-y and Ag-doped Cu2-xSeyS1-y thin films were synthesized, and the interrelationship between structure, composition, and room temperature thermoelectric properties was studied. The precursor annealing temperature affects the metal:chalcogen ratio, and leads to charge carrier concentration changes that affect Seebeck coefficient and electrical conductivity. Incorporating Ag into the Cu2-xSeyS1-y film leads to appreciable improvements in thermoelectric performance. Overall, the room temperature thermoelectric properties of these solution-processed materials are comparable to measurements on Cu2-xSe alloys made via conventional thermoelectric material processing methods.

Finally, a new route to make soluble metal chalcogenide precursors by reacting organic dichalcogenides with metal in different solvents was reported. By this method, SnSe, PbSe, SnTe and PbSexTe1-x precursors were successfully synthesized, and phase-pure and impurity-free metal chalcogenides were recovered after precursor decomposition. Compared to the hydrazine and diamine-dithiol route, the new approach uses safe solvent, and avoids introducing unwanted sulfur into the precursor. SnSe and PbSexTe1-x thin films, both of which are interesting thermoelectric materials, were also successfully made by solution deposition. The thermoelectric property measurements on those thin films show a great potential for future improvements.

Measurements of the geometrical magnetoresistance of a conventional semiconductor, gallium arsenide (GaAs), and a more recently developed semiconductor, iron pyrite (FeS2) were measured in the Corbino disc geometry as a function of magnetic field to determine the carrier mobility (μm). These results were compared with measurements of the Hall mobility (μH) made in the Van der Pauw configuration. The scattering coefficient (ξ), defined as the ratio between magnetoresistance and Hall mobility (μm/μH), was determined experimentally for GaAs and natural pyrite from 300 K to 4.2 K. The effect of contact resistance and heating on the measurement accuracy is discussed.

Pyrite is a 0.95 eV bandgap semiconductor which is purported to have great potential in widespread, low–cost photovoltaic cells. A thorough material selection process was used in the design of a pyrite sequential vapor deposition chamber aimed at reducing and possibly eliminating contamination during thin film growth. The design process focused on identifying materials that do not produce volatile components when exposed to high temperatures and high sulfur pressures. Once the materials were identified and design was completed, the ultra–high vacuum growth system was constructed and tested.

Pyrite thin films were deposited using the upgraded sequential vapor deposition chamber by varying the substrate temperature from 250°C to 420°C during deposition, keeping sulfur pressure constant at 1 Torr. Secondary Ion Mass Spectrometry (SIMS) results showed that all contaminants in the films were reduced in concentration by orders of magnitude from those grown with the previous system. Characterization techniques of Rutherford Back–scattering Spectrometry (RBS), X–Ray Diffraction (XRD), Raman Spectroscopy, Optical Profilometry and UV/Vis/Near–IR Spectroscopy were performed on the deposited thin films. The results indicate that stoichiometric ratio of S:Fe, structural–quality (epitaxy), optical roughness and percentage of pyrite in the deposited thin films improve with increase in deposition temperature. A Tauc plot of the optical measurements indicates that the pyrite thin films have a bandgap of 0.94 eV.

Microwave properties of low-loss commercial dielectric materials are optimized by adding transition-metal dopants or alloying agents (i.e. Ni, Co, Mn) to tune the temperature coefficient of resonant frequency (τf) to zero. This occurs as a result of the temperature dependence of dielectric constant offsetting the thermal expansion. At cryogenic temperatures, the microwave loss in these dielectric materials is dominated by electron paramagnetic resonance (EPR) loss, which results from the spin-excitations of d-shell electron spins in exchange-coupled clusters. We show that the origin of the observed magnetically-induced shifts in the dielectric resonator frequency originates from the same mechanism, as described by the Kramers-Kronig relations. The temperature coefficient of resonator frequency, τf, is related to three material parameters according to the equation, τf = - (½ τε + ½ τµ + αL), where τε, τµ, and αL are the temperature coefficient of dielectric constant, magnetic permeability, and lattice constant, respectively. Each of these parameters for dielectric materials of interest are measured experimentally. These results, in combination with density functional simulations, developed a much improved understanding of the fundamental mechanisms responsible for τf. The same experimental methods have been used to characterize in-situ the physical nature and concentration of performance-degrading point defects in the dielectrics of superconducting planar microwave resonators.

A series of pyrite thin films were synthesized using a novel sequential evaporation

technique to study the effects of substrate temperature on deposition rate and micro-structure of

the deposited material. Pyrite was deposited in a monolayer-by-monolayer fashion using

sequential evaporation of Fe under high vacuum, followed by sulfidation at high S pressures

(typically > 1 mTorr to 1 Torr). Thin films were synthesized using two different growth processes; a

one-step process in which a constant growth temperature is maintained throughout growth, and a

three-step process in which an initial low temperature seed layer is deposited, followed by a high

temperature layer, and then finished with a low temperature capping layer. Analysis methods to

analyze the properties of the films included Glancing Angle X-Ray Diffraction (GAXRD),

Rutherford Back-scattering Spectroscopy (RBS), Transmission Electron Microscopy (TEM),

Secondary Ion Mass Spectroscopy (SIMS), 2-point IV measurements, and Hall effect

measurements. Our results show that crystallinity of the pyrite thin film improves and grain size

increases with increasing substrate temperature. The sticking coefficient of Fe was found to

increase with increasing growth temperature, indicating that the Fe incorporation into the growing

film is a thermally activated process.

A series of Molybdenum-Copper bilayers were studied for use in 120mK superconducting transition edge sensors for spectrometer applications. The Transition temperature (T_C) was tuned to the desired temperature using the proximity effect, by adjusting the thickness of a normal copper layer in direct contact with the superconducting molybdenum layer in a proximitized bilayer structure. The bilayers have a fixed normal metal thickness d_Cu=1250 Å, on top of a variable superconductor thickness 650 Å ≤ d_Mo ≤ 1000 Å. Material characterization techniques including X-ray Diffraction (XRD), Rutherford Backscattering Spectroscopy (RBS), Atomic Force Microscopy (AFM), and 4-point electrical characterization are used to characterize the films. Film TC are compared with the results of the Usadel proximity theory. The results of RBS analysis demonstrated that some Argon-contamination is observed at the Mo film-substrate interface, which correlates with bilayer surface roughness (as observed with AFM), reduced crystalline quality (via XRD Rocking Curve), and a deviation from the theoretical expected TC for a bilayer. The Argon contamination is presumably the cause of interface roughness, reducing the interface transmission coefficient in the Usadel model, and producing the discrepancy from the expected TC.

In this research, our goal was to fabricate Josephson junctions that can be stably processed at 300°C or higher. With the purpose of integrating Josephson junction fabrication with the current semiconductor circuit fabrication process, back-end process temperatures (>350 °C) will be a key for producing large scale junction circuits reliably, which requires the junctions to be more thermally stable than current Nb/Al-AlOx/Nb junctions. Based on thermodynamics, Hf was chosen to produce thermally stable Nb/Hf-HfOx/Nb superconductor tunnel Josephson junctions that can be grown or processed at elevated temperatures. Also elevated synthesis temperatures improve the structural and electrical properties of Nb electrode layers that could potentially improve junction device performance. The refractory nature of Hf, HfO2 and Nb allow for the formation of flat, abrupt and thermally-stable interfaces. But the current Al-based barrier will have problems when using with high-temperature grown and high-quality Nb. So our work is aimed at using Nb grown at elevated temperatures to fabricate thermally stable Josephson tunnel junctions. As a junction barrier metal, Hf was studied and compared with the traditional Al-barrier material. We have proved that Hf-HfOx is a good barrier candidate for high-temperature synthesized Josephson junction. Hf deposited at 500 °C on Nb forms flat and chemically abrupt interfaces. Nb/Hf-HfOx/Nb Josephson junctions were synthesized, fabricated and characterized with different oxidizing conditions. The results of materials characterization and junction electrical measurements are reported and analyzed. We have improved the annealing stability of Nb junctions and also used high-quality Nb grown at 500 °C as the bottom electrode successfully. Adding a buffer layer or multiple oxidation steps improves the annealing stability of Josephson junctions. We also have attempted to use the Atomic Layer Deposition (ALD) method for the growth of Hf oxide as the junction barrier and got tunneling results.

I studied the properties of novel Co2FeAl0.5Si0.5 (CFAS), ZnGeAs2, and FeS2 (pyrite) thin films for microelectronic applications ranging from spintronic to photovoltaic. CFAS is a half metal with theoretical spin polarization of 100%. I investigated its potential as a spin injector, for spintronic applications, by studying the critical steps involved in the injection of spin polarized electron populations from tunnel junctions containing CFAS electrodes. Epitaxial CFAS thin films with L21 structure and saturation magnetizations of over 1200 emu/cm3 were produced by optimization of the sputtering growth conditions. Point contact Andreev reflection measurements show that the spin polarization at the CFAS electrode surface exceeds 70%. Analyses of the electrical properties of tunnel junctions with a superconducting Pb counter-electrode indicate that transport through native Al oxide barriers is mostly from direct tunneling, while that through the native CFAS oxide barriers is not. ZnGeAs2 is a semiconductor comprised of only inexpensive and earth-abundant elements. The electronic structure and defect properties are similar in many ways to GaAs. Thus, in theory, efficient solar cells could be made with ZnGeAs2 if similar quality material to that of GaAs could be produced. To understand the thermochemistry and determine the rate limiting steps of ZnGeAs2 thin-film synthesis, the (a) thermal decomposition rate and (b) elemental composition and deposition rate of films were measured. It is concluded that the ZnGeAs2 thin film synthesis is a metastable process with an activation energy of 1.08±0.05 eV for the kinetically-limited decomposition rate and an evaporation coefficient of ~10-3. The thermochemical analysis presented here can be used to predict optimal conditions of ZnGeAs2 physical vapor deposition and thermal processing. Pyrite (FeS2) is another semiconductor that has tremendous potential for use in photovoltaic applications if high quality materials could be made. Here, I present the layer-by-layer growth of single-phase pyrite thin-films on heated substrates using sequential evaporation of Fe under high-vacuum followed by sulfidation at S pressures between 1 mTorr and 1 Torr. High-resolution transmission electron microscopy reveals high-quality, defect-free pyrite grains were produces by this method. It is demonstrated that epitaxial pyrite layer was produced on natural pyrite substrates with this method.