Thesis (M. Phil.)--University of Hong Kong.

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published_or_final_version / Electrical Engineering / Master / Master of Philosophy

Among the newly discovered iron-based superconductor, FeSe with the simplest structure and a transition temperature (T_c) around 8 K arouses much research interest. Although its Tc is much lower than that of the cuprates, iron chalcogenide has low anisotropy, slow decrease of the critical current density (J_c) with increasing magnetic field and high upper critical field H_c2 as well as easy composition control, which makes it a promising candidate to substitute NbSn/NbTi for high field applications. Compared with its bulk counterpart, iron-based superconductor thin film has a great potential in developing the ordered quasi-2D structure and is suitable for coating technology which has already been applied in YBa_2Cu_3O_7-x coated conductors. In this thesis, we first optimized pure FeSe thin films by different growth conditions using pulsed laser deposition (PLD) and post-annealing procedures. The microstructure properties of the films including the epitaxial quality, interface structure and secondary phase have been studied and correlated with the superconducting properties. Second, we reported our initial attempt on introducing the flux pinning centers into FeSe_0.5Te_0.5 thin films either under a controlled oxygen atmosphere or with a thin CeO_2 interlayer. The microstructure of the FeSe_0.5Te_0.5 films including the epitaxial quality, the interface structure and the secondary phase have been studied and correlated with the in-field performance of the superconducting thin films to explore the pinning properties of these nanoscale defects. Very recently, ion beam assisted deposition (IBAD) substrates have been used to grow high quality FeSe_0.5Te_0.5 tape with excellent in-field performance. The film on IBAD substrate involves multiple steps of seed layer and buffer layer deposition to establish the epitaxial growth template. Therefore a simplified and cost effective iron-based coated conductor is more desirable. Towards the practical application, we demonstrated the growth of superconducting FeSe_0.5Te_0.5 film on amorphous glass substrates for the first time. The film is highly textured with excellent superconducting properties, e.g., T_c of 10 K and J_c under self-field as high as 1.2×10^4 A/cm^2 at 4 K. Further optimization of the film growth with various nanoscale interlayers has been carried out. In addition the Te rich iron chalcogenide thin film with composition close to the composition with antiferromagnetic (AFM) transition has been demonstrated. Compared to the FeSe_0.5Te_0.5 which claimed to be the optimum composition from the literature report, the FeSe_0.1Te_0.9 is even more promising for the high field application with its coexistence of super high upper critical field and high critical current density.

Calcium lanthanum sulfide (CLS) has been identified as a candidate material for various optical applications due to its wide transmission range, high refractive index, desirable thermo-optic properties, and refractory behavior. Implementation of CLS in optical systems has remained unrealized due to various difficulties in the synthesis and bulk fabrication of this material. The key challenge facing the development of CLS is the incorporation of oxygen and the presence of unwanted secondary phases related to the lack of control of stoichiometric variations across the ternary phase diagram. Though these difficulties have been previously discussed in the processing of CLS, the exact form, mechanisms of formation and impact of these attributes have not been systematically evaluated. Each of these problems must be meticulously elaborated upon to understand what processing conditions are needed to avoid these common pitfalls which have been shown to degrade the ultimate optical quality of the resulting ceramic. This thesis investigated the role of oxygen in CLS ceramics as it applies to the resulting optical quality of the processed ceramic. The research done specifically examined ceramic materials with high La- content, prepared by hot pressing and hot isostatic pressing. The materials chosen for this work displayed varying levels of optical quality and phase purity. Determination of the desired cubic crystal structure as the main phase present was confirmed using x-ray diffraction and transmission electron microscopy. Through the correlation of data from multiple material metrology tools, the concentration and bond environment of oxygen in the ceramics and starting powders has been determined. It has been shown that the role of oxygen does not necessarily induce local phase transformation in the crystalline material, but rather can be dissolved into the CLS crystal lattice in low levels. Raman spectroscopy has been identified as a simple, useful tool that can be used to aid future synthesis routes due to its ability to differentiate the different types of O present. This thesis demonstrates how low levels of oxygen impurities can be incorporated into the CLS lattice utilizing simple IR and Raman spectroscopy techniques.

Chalcogenide glass based Phase Change Memories (PCMs) are being considered recently as promising alternatives to conventional non-volatile Random Access Memories (NVRAMs). PCMs offer high performance & low power consumption, in addition to other advantages, such as high scalability, high endurance and compatibility with complementary metal oxide semiconductors (CMOS) technologies. Basically PCM is a resistance variable non-volatile memory in which the memory bit state is defined by the resistance of the material. In this case, the initial ‘OFF’ state (logic zero) corresponds to the high resistance amorphous state and the logic 1 or ‘ON’ state corresponds to low resistance crystalline state. The present thesis work deals with electrical, thermal, mechanical and optical characterization of certain tellurium based chalcogenide glasses in bulk and thin film form for phase change memory applications. A comparative study has been done on the electrical switching behavior of Ge-Te-Se & Ge-Te-Si amorphous thin film samples with their bulk counterparts. Further, electrical switching and thermal studies have been undertaken on bulk Ge-Te-Bi and Ge-Te-Sn series of samples. The composition dependence of switching voltages of bulk and thin film samples studied has been explained on the basis of different factors responsible for electrical switching. The thesis contains ten chapters: Chapter 1 deals with a brief introduction on chalcogenides and their applicability in phase change memories. The glass transition phenomenon, synthesis of chalcogenide alloys, different structural models of amorphous semiconductors and electrical switching behavior are also discussed in detail in this chapter. Further, a brief description of optical and mechanical properties along with the principles of few characterization techniques used is discussed. Also, a brief overview on PCM application of chalcogenides is presented. The second chapter provides the details of various experimental techniques used to measure electrical, thermal, optical and mechanical properties of few tellurium based chalcogenide glassy systems. In the third chapter, the electrical switching behavior of amorphous Al23Te77 thin film devices, deposited in co-planar geometry, has been discussed. It is found that these samples exhibit memory type electrical switching. Scanning Electron Microscopic studies show the formation of a crystalline filament in the electrode region which is responsible for switching of the device from high resistance OFF state to low resistance ON state. The switching behavior of thin film Al-Te samples is found to be similar to that of bulk samples, with the threshold fields of bulk samples being higher. This has been understood on the basis of higher thermal conductance in bulk, which reduces the Joule heating and temperature rise in the electrode region. Electrical switching and thermal behavior of bulk; melt quenched Ge18Te82-xBix glasses (1 ≤ x ≤ 4) are presented in chapter 4. Ge-Te-Bi glasses have been found to exhibit memory type electrical switching behavior, which is in agreement with the lower thermal diffusivity values of these samples. A linear variation in switching voltages (also known as threshold voltages) (Vt) has been found with increase in thickness. The switching voltages have been found to decrease with an increase in temperature which is due to the decrease in the activation energy for crystallization at higher temperatures. Further, Vt of Ge18Te82-xBix glasses have been found to decrease with the increase in Bi content, indicating that in the Ge-Te-Bi system, the resistivity of the additive has a stronger role to play in the composition dependence of Vt, in comparison with the network connectivity and rigidity factors. In addition, the composition dependence of crystallization activation energy has been found to show a decrease with an increase in Bi content. X-ray diffraction studies on thermally crystallized samples reveal the presence of hexagonal Te, GeTe and Bi2Te3 phases. The fifth chapter deals with the electrical switching studies and optical band gap measurements on GexSe35-xTe65 (17 ≤ x ≤ 23) amorphous thin film samples. These thin film samples coated with sandwich geometry are found to switch with very low voltages as compared to bulk samples of the same chalcogenide glasses. The switching voltages and optical band gap are found to increase with the addition of Ge at the expense of Se. High structural cross linking with progressive addition of 4-fold coordinated Ge atoms could be the one of the reasons of increasing switching voltage and stronger Ge-Se bond strength could be the reason of increasing band gap for these chalcogenide glasses. In chapter 6, electrical switching studies on amorphous Ge15Te85-xSix (1 ≤ x ≤ 6) thin film samples have been described and the results are compared with their bulk counterparts. Similar trend has been found for both bulk and film samples when the threshold field is varied with composition. Optical band gap has been measured as a function of composition for these films, which also shows a behavior similar to that of switching voltages. The increasing trend in the variation with composition of electrical switching voltages and optical band gap are due to the increase in network connectivity and rigidity as Si atoms are incorporated into the Ge-Te system. Chapter 7 summarizes the electrical switching and glass forming ability of the Ge-Te-Sn glasses of two different composition tie-lines, namely Ge15Te85-xSnx and Ge17Te83-xSnx. Glasses belonging to both the series have been found to exhibit memory type of electrical switching behavior. The thickness dependence of threshold voltages is also found to support the memory switching behavior of the system. Further, ADSC studies are undertaken to explore the thermal behavior of these glasses which indicates that the crystallization tendency increases as Sn concentration is increased in the Ge-Te network. XRD studies done on two samples from both the series, reveal the fact that Sn atoms do not take part actively to enhance the network connectivity and rigidity. The composition dependence of crystallization temperature, metallicity factor and results of XRD studies are put together to explain the variation with composition of threshold voltages for both the series of samples. In chapter 8, investigations on the electrical switching behavior of Ge15Te85-xSnx (1 ≤ x ≤ 5) and Ge17Te83-xSnx (1 ≤ x ≤ 4) amorphous thin films have been discussed. Both the series of samples have been found to exhibit memory type of electrical switching behavior. The composition dependence of threshold voltage shows a decreasing trend, which has been explained on the basis of the Chemically Ordered Network (CON) model, bond strength and the metallicity factor. The optical band gap variation of both the series also exhibits a similar decreasing trend with composition. The observed behavior has been understood on the basis of higher atomic radius of Sn atom than Ge atom, which makes the energy difference between bonding and anti bonding state less at band edge. Chapter 9 deals with the nano-indentation studies on Ge15Te85-xSix (0 ≤ x ≤ 9) bulk glasses. The composition dependence of young’s modulus and hardness is studied systematically in this glassy system. The density of the samples of different compositions has also been measured, which strongly supports the variation of Young’s Modulus and hardness with composition. The composition dependence of mechanical properties of Ge-Te-Si samples has been understood on the basis of the presence of an intermediate phase and a thermally reversing window in this glassy system. A summary of the significant results obtained in the present thesis work is presented in the last chapter along with the scope for future work.

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A chalcogenide glass (arsenic-trisulfide, As2S3) optical waveguide is vertically integrated onto titanium-diffused lithium-niobate (Ti:LiNbO3) waveguides to add optical feedback paths and to create more compact optical circuits. Lithium-niobate waveguides are commonly used as building blocks for phase and amplitude modulators in high speed fiber communication networks due to its high electrooptic coefficient and low mode coupling loss to single-mode optical fibers. Although it can easily be modulated using an RF signal to create optical modulators, it lacks the intrinsic trait to create optical feedback loops due to its low core-to-cladding index contrast. Ring resonators are main building blocks of many chip-scale optical filters that require these feedback loops and are already demonstrated with other material systems. We have, for the first time, incorporated As2S3 as a guiding material on Ti:LiNbO3 and fabricated s-bends and ring resonators. We have examined As2S3-on-Ti:LiNbO3 waveguides at simulation, microfabrication, and optical characterization levels.

Te2As3Se5 (TAS) fibers are often used in bio-sensing applications requiring direct contact between the fiber and live cells. However, the toxicity and stability of chalcogenide glasses typically used in such bio-sensing applications are not well known. The stability and toxicity of TAS glass fibers were therefore examined. The surface of TAS fibers stored for up to three years in air were analyzed using X-ray photoelectron spectroscopy (XPS), inductively coupled plasma mass spectrometry (ICP-MS), and atomic force microscopy (AFM). It is shown that an oxide layer develops on the surface of TAS fibers stored in air. This oxide layer is highly soluble in water and therefore easily removed. Additional studies using cyclic voltammetry show that the fresh TAS glass surface is insoluble in water for at least a few days, and attenuation measurements show that oxidation does not affect the transmission properties of the glass fibers. It was also determined that old, oxidized fibers pose a toxic threat to cells, while washed and new fibers show no toxic effect. Therefore, it is concluded that a soluble oxide layer forms on the surface of TAS fibers stored in air and that this layer has a toxic effect on cells in an aqueous environment. However, through etching, the oxide layer and the toxicity can be easily removed.In other applications of telluride glasses, such as the search for possible signs of life on exoplanets, a glass transmitting further into the IR is required in order to detect molecules, such as CO2. A new family of Tellurium based glasses from the Ge-Te-I ternary system has therefore been investigated for use in space and bio-sensing applications. A systematic series of compositions has been synthesized in order to explore the ternary phase diagram in an attempt to optimize the glass composition for the fiber drawing and molding process. The resulting glass transition temperature range lies between 139°C and 174°C, with deltaT values between 64°C and 124°C. The most stable glass composition was found to be Ge20Te73I7. The Ge-Te-I glasses were found to have an effective transmission window between 2-20 microns, encompassing the region of interest for the identification of biologically relevant species such as carbon dioxide. Furthermore, the successful fibering and molding of the composition Ge20Te73I7 are shown. Lastly, an investigation into glass conductivity was completed resulting in a maximum conductivity value on the order of 10^-4 Ohm-1 cm-1 for the composition Ge20Te73I7.In an attempt to take advantage of the high conductivity of telluride glasses, a new approach to virus detection in an aqueous environment has been developed using the electrophoretic deposition of protein and viruses on the charged glass surface for in situ infrared characterization and identification. A proof of concept experiment has been completed using a germanium ATR plate and an indium tin oxide (ITO) plate as the experimental electrodes. Charged proteins and viruses were driven to the surface of the oppositely charged germanium ATR crystal, once a potential was applied to the system. FTIR/ATR spectroscopy was used before and throughout electro-deposition to enable the in situ observation of the deposition with time. This technique resulted in the successful deposition and removal of the protein Bovine Serum Albumin (BSA), and deposition of the virus MS2, a bacteriophage that infects only bacteria, with an applied voltage of only 1.1V. Furthermore, based on analysis of the ATR spectra, distinct spectral features were identified for the protein and virus showing the potential for identification and characterization of biological molecules in an aqueous environment. A Ge20Te73I7 ATR plate was synthesized but unsuccessfully applied as an electrode in these experiments, likely due to an inconsistent conductivity along the plate. A glass from the Ge-As-Te system with a lower but more consistent conductivity was thereafter synthesized and successfully used as an electrode and sensing element in the electro-deposition experiment.

The environmental challenges are increasing, and so is the need for renewable energy. For photovoltaic applications, thin film Cu(In,Ga)(S,Se)2 (CIGS) and CuIn(S,Se)2 (CIS) solar cells are attractive with conversion efficiencies of more than 20%. However, the high-efficiency cells are fabricated using vacuum technologies such as sputtering or thermal co-evaporation, which are very costly and unfeasible at industrial level. The fabrication involves the uses of highly toxic gases such as H2Se, adding complexity to the fabrication process. The work described here focused on non-vacuum deposition methods such as printing. Special attention has been given to printing designed in a moving Roll-to-Roll (R2R) fashion. The results show potential of such technology to replace the vacuum processes. Conversion efficiencies for such non-vacuum deposition of Cu(In,Ga)(S,Se)2 solar cells have exceeded 15% using hazardous chemicals such as hydrazine, which is unsuitable for industrial scale up. In an effort to simplify the process, non-toxic suspensions of Cu(In,Ga)S2 molecular-based precursors achieved efficiencies of ~7-15%. Attempts to further simplify the selenization step, deposition of CuIn(S,Se)2 particulate solutions without the Ga doping and non-toxic suspensions of Cu(In,Ga)Se2 quaternary precursors achieved efficiencies (~1-8%). The contribution of this research was to provide a new method to monitor printed structures through spectral-domain optical coherence tomography SD-OCT in a moving fashion simulating R2R process design at speeds up to 1.05 m/min. The research clarified morphological and compositional impacts of Nd:YAG laser heat-treatment on Cu(In,Ga)Se2 absorber layer to simplify the annealing step in non-vacuum environment compatible to R2R. Finally, the research further simplified development methods for CIGS solar cells based on suspensions of quaternary Cu(In,Ga)Se2 precursors and ternary CuInS2 precursors. The methods consisted of post deposition reactive annealing for performance enhancement up to 2.0% solar cell conversion efficiency. Chemical treatment using metal salt solutions and Na2Se4 for Na and Se incorporation provided efficiencies up to 1.1%.