>Magister Scientiae - MSc / When the spacecrafts orbit in space, it is subjected to significant thermal cycling variation. Thermal regulation of the spacecraft temperature is required to ensure a good operation of the small crafts such as CubeSats and the on-board equipment while minimizing the weight. Three methods employed for the Smart Radiator Devices (SRD) are (i) mechanical louvers, (ii) electrochromic coatings and (iii) thermochromic coatings (which is of interest in this study). Based on the characteristics of the thermochromic coatings, the passive smart radiator device is by far the most efficient option since there are no mechanical moving components and also no electric energy needed for the craft to operate.

Pulsed lasers are studied as new tools to realize competitive nanomanufacturing. The capabilities of pulsed lasers as promising tools for research, design, manufacturing, and control rely on the flexibility due to the great variety of operation parameters, and the inherent precision in aspects of time, spatial resolution, and energy input. As new tools, the fundamental understanding and technological capabilities of pulsed laser-induced chemical synthesis were explored in this dissertation research. In order to study the capabilities of pulsed laser in controlled synthesis, a thermal model was developed to predict the local temperature change due to the very short period of irradiation by a pulsed laser. And combining with the classical Gibbs free energy theories, a set of guidelines were developed for precision control for pulsed laser-induced chemical synthesis. Zinc oxide crystals were studied as an example case, showing the relationship between the wide range variables of pulsed laser including repetition rate, energy area density, power density, irradiation duration, etc. and the material structures of deposited crystals in aspects of crystal density, size, shape, crystalline properties, surface morphologies, growth rate, etc. Mechanisms from thermodynamic and kinetic aspects were explored. Pulsed laser-induced different heating conditions were found to separate two crystallization processes with different energy barriers, one dominated by a burst of nucleation and the other dominated by crystal growth through particle aggregation. For the study of the fundamental mechanisms in crystallization, pulsed laser initiated and controlled the crystallization in its early stage, and the crystal evolution were observed and analyzed by transmission electron microscopy (TEM). Crystal growth from intermediate monomers was first studied by an electron beam under the condition without precursor solution environment, providing crucial process information of crystal evolution, indicating multistage processes by continuous mass and phase transfer among intermediate monomers. This dissertation shows the capabilities of pulsed laser in realizing precision control for the targeted synthesis in nanomanufacturing, providing unique insight to crystallization mechanisms, and extending prospects to scientific research of other energy beam induced processes.

B-Ga2O3 is one of the emerging semiconductor materials with high breakdown field strength (~ 8 MV/cm) and ultrawide-bandgap (UWBG) 4.9 eV. Therefore, B-Ga2O3 and related compound semiconductors are ideal for power electronics and deep/vacuum ultraviolet-wavelength photodetector applications. High-crystal-quality B-Ga2O3 semiconductor materials epitaxially deposited on the various substrate are prerequisites for realizing any practical application. However, it is still challenging to grow high-crystal-quality V-Ga2O3 layer and to integrate B-Ga2O3 with other semiconductor materials by direct epitaxy. Understanding the epitaxial relationship of the integrated oxide heterostructure and the substrate used helps to shed light on the feasibility of heterojunctions formation for photonic applications, such as the ultraviolet-wavelength photodetectors developed in this thesis. By optimizing pulsed laser deposition (PLD) conditions, such as laser energy, ambient gas, pressure, etc., a single-crystalline oxide heterostructure were successfully integrated into a photonic platform. This included p-NiO/n-B-Ga2O3/a-Al2O3, B-Ga2O3/y-In2O3/a-Al2O3, and B-Ga2O3/TiN/MgO structures. The epitaxial thin film crystallographic and chemical properties were investigated by different characterization techniques. The high-resolution X-ray diffraction (HRXRD) was applied to study the heterostructures’ epitaxial orientation relationship by out-of-plane XRD w-2θ-scan and asymmetric skew ɸ-scan. The lattice-mismatch at the heterostructure interfaces were examined and the crystal quality of the epitaxial thin films were measured by means of full-width at half-maximum (FWHM) fitting. Scanning-TEM energy-dispersive X-ray spectroscopy (STEM-EDX) was applied to qualitatively study the chemical elements’ spatial distribution. Rutherford backscattering spectroscopy (RBS) was applied to study the epitaxial thin film chemical composition, material stoichiometry, and inter-diffusion. The X-ray photoelectron spectroscopy (XPS) was applied to study the conduction and valence band offsets which is essential to determine the types of heterostructures formed. Finally, the p-NiO/n-B-Ga2O3/a-Al2O3 B-Ga2O3/y-In2O3/a-Al2O3, and B-Ga2O3/TiN/MgO epitaxial thin-film were fabricated into ultraviolet-wavelength photodetectors. The wavelength-dependent and power-dependent characterizations were applied to measure the cut-off wavelength and the peak responsivity. The time response characterization was applied to measure the photodetectors’ responses to pulse signals, and the rise and decay times were fitted by a double exponential function.

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Oxide materials display a wide range of physical properties. Recently, doped complex oxides have drawn considerable attention for various applications including thermoelectrics. Doped complex oxide materials have high Seebeck coefficients (S) and electrical conductivities (o) comparable to other doped semiconductors but low thermoelectric figure of merit ZT values due to their poor thermal conductivities. For example, niobium doped strontium titanate (SrNbxTi_1-xO₃ or simply Nb:STO) has a power factor comparable to that of bismuth telluride. Semiconductor nanostructures have demonstrated a decrease in thermal conductivity (κ) resulting in an increase in the thermoelectric figure of merit (ZT). Nanostructures of doped oxides like niobium doped strontium titanate, may also lead to decreased κ and a corresponding increase in ZT. The major impediment to nanostructured oxide thermoelectric materials is the lack of suitable fabrication techniques for testing and eventual use. Electron Beam Lithography (EBL) was used to pattern poly-methyl-methacrylate (PMMA) resists on undoped single crystalline SrTiO₃ (STO) substrates which were then filled with Nb:STO using Pulsed Laser Deposition (PLD) at room temperature. This technique produced nanowires and nanodots with critical dimensions below 100 nm, and a yield of approximately 95%. In addition to scanning electron microscopy and atomic force microscopy morphological studies of the patterned oxide, thin film analogues were used to study composition, crystallinity and electrical conductivity of the material in response to a post deposition heat treatment. Since the thin films were grown under similar experimental parameters as the oxide nanostructres, the patterned oxides are believed to be stoichiometric and highly crystalline. The study found that using a combination of EBL and PLD, it is possible to produce highly crystalline, doped complex oxide nanostructures with excellent control over morphology. Furthermore, the technique is applicable to nearly all materials and provides the capability of patterning doped oxide materials without the requirement of etching or multiple lithography steps makes this approach especially interesting for future fundamental materials research and novel device fabrication. / Master of Science

Layered transition metal dichalcogenides (TMDs) are potentially ideal semiconducting materials due to their in-plane carrier transport and tunable bandgaps, which are favorable properties for electrical and optoelectronic applications. However, the ability to make p-n junctions is the foundation of semiconductor devices, and therefore the ability to achieve reproducible p- and n-type doping in TMD semiconducting materials is critical. In this work, p-type substitutional doping of pulsed laser deposited WS2 films with niobium is reported. The synthesis technique of the PLD target with dopant incorporation which also ensures host material stoichiometry is presented. Hall electrical measurements confirmed stable p-type conductivity of the grown films. Structural characterization revealed that there was no segregation phase of niobium in the fabricated films and x-ray phtoelectron spectroscopy (xps) characterization suggest that the p-type doping is due to Nb4+ which results in p-type behavior. Stable hole concentrations as high as 10E21(cm-3) were achieved. The target fabrication and thin film deposition technique reported here can be used for substitutional doping of other 2D materials to obtain stable doping for device applications.

The present study describes the growth and characterization of pulsed laser ablated Bao.sSro.sTiOs (BST) thin films. Emphasis has been laid on the study of a plausible correlation between structure and property in order to optimize the processing parameters suitably for required application. An attempt has been made to understand the basic properties such as, origin of dielectric response, charge transfer under low and high-applied electric fields across the BST capacitor and finally the dielectric breakdown process. Chapter 1 gives a brief introduction on the application of ferroelectric thin films in microelectronic industry and its growth techniques. It also addresses the present issues involved in the introduction of BST as a capacitor material for high-density dynamic random access memories. Chapter 2 outlines the motivation for the present study and briefly outlines the research work involved. Chapter 3 describes the experimental procedure involved in the growth and characterization of BST thin films using pulsed laser ablation technique. Details include the setup design for PLD growth, material synthesis for the ceramic targets, deposition conditions used for thin film growth and basic characterizations methods used for study of the grown films. Chapter 4 describes the effect of systematic variation of deposition parameters on the physical and electrical properties of the grown BST films. The variation in processing conditions has been found to directly affect the film crystallinity, structure and morphology. The change observed in these physical properties may also be correlated to the observed electrical properties. This chapter summarizes the optimal deposition conditions required for growing BST thin films using a pulsed laser ablation technique. Microstructure of BST films has been categorized into two types: (a) Type I structure, with multi-grains through the film thickness, for amorphous as-grown films after high temperature annealing (exsitu crystallized), and (b) columnar structure (Type II) films, which were as-grown well-crystallized films, deposited at high temperatures. The ac electrical properties have been reviewed in detail in Chapter 5. Type I films showed a relatively lower value of dielectric constant (e ~ 426) than Type II films with dielectric constant around 567. The dissipation factors were around 0.02 and 0.01 for Type I and Type II films respectively. The dispersion in the frequency domain characteristics has been quantitatively explained using Jonscher's theory. Complex impedance spectroscopy employed showed significant grain boundary response in the case of multi-grained Type I films while negligible contribution from grain boundaries has been obtained in the case of columnar grained Type II BST films. The average relaxation time r obtained from the complex impedance plane plots show almost three orders higher values for Type I films. The obtained results suggest that in multi-grained samples, grain boundary play a major role in electrical properties. This has been explained in accordance to a model proposed on the basis of depleted grains in the case of Type I films where the grain sizes are smaller than the grain boundary depletion width. Chapter 6 describes the dc leakage properties of the grown BST thin films and the influence of microstructure on the leakage properties. It was evident from the analysis of the graph of leakage current against measurement temperature, that, the observed leakage behavior in BST films, can not be attributed to a single charge transport mechanism. For Type I films, the Arrhenius plot of the leakage current density with 1000/T exhibits different regions with activation energy values in the range of 0.5 and 2.73 for low fields (2.5kV/cm). The activation energy changes over to 1.28 eV at high fields (170 kV/cm). The obtained values agree well with that obtained from the ac measurements, thus implying a similarity in the origin of the transport process. The activation energy value in the range of 0.5 eV is attributed to the electrode/film Schottky barrier, while the value in the range of 2.73 eV is due to deep trap levels originating from Ti+3 centers. The value in the range of 1.28 eV has been attributed to oxygen vacancy motion. Similar results have been obtained from the Arrhenius plot of the leakage current for Type II films. In this case, only two different activation energy values can be identified in the measured temperature and applied electric field range. At low fields the activation energy value was around 0.38 eV while at high fields the value was around 1.06 eV. These values have been identified to be originating from the electrode/film Schottky barrier and oxygen vacancy motion respectively. Thus a complete picture of the charge transport process in the case of BST thin film may be summarized as comprising of both electronic motion as well as contribution from oxygen vacancy motion. The effect of electrical stress on the capacitance-voltage (C-V) and the leakage current has been analyzed in Chapter 7. From the change in the zero bias capacitance after repeated electron injection through the films the values of the electronic capture cross-section and the total trap density for Type I and II films have been estimated. The results showed higher values for Type I film in comparison to Type II films. The difference has been attributed to the presence of grain boundaries and a different interface in the case of Type I films when compared to Type II films where the absence of grain boundaries is reflected in the columnar microstructure. A study of the time-dependent-dielectric-breakdown (TDDB) characteristics under high fields for Type I and Type II films showed higher endurance for Type I film. On the other hand space-charge-transient characteristics have been observed in the case of Type II films at elevated temperature of measurement. Mobility and activation energy values extracted from the transient characteristics are found to be in the range of 1 x 10~12 cm2 /V-sec and 0.73 eV respectively, suggesting a very slow charge transport process, which has been attributed to the motion of oxygen vacancies. An overall effect of electrical stress suggested that oxygen vacancy motion can be related to the observed resistance degradation and TDDB, which has been further enhanced by the combination of high temperature and high electric fields. Chapter 8 deals with the effect of intentional doping in the BST films. The doping includes Al at the Ti-site, Nb in the Ti-site and La at the Ba/Sr-site. The effect of doping was observed both on the structure and electrical properties of the BST films. Acceptor doping of 0.1 atomic 7c Al was found to decrease the dielectric constant as well as the leakage current. For higher concentration of acceptor-dopant, the leakage current was found to increase while showing space-charge-transient in the TDDB characteristics, again suggesting the effect of increased concentration of oxygen vacancies. Donor doping using 2 atomic % La and Xb significantly improved the leakage as well as the TDDB characteristics by reducing the concentration of oxygen vacancies. A further procedure using graded donor doping in the BST films exhibits even better leakage and TDDB properties. An unconventional, graded doping of donor cations has been carried out to observe the impact on leakage behavior, in particular. The leakage current measured for a graded La-doped BST film show almost six orders of lower leakage current in comparison to undoped BST films, while endurance towards breakdown has been observed to increase many-fold. Chapter 9 highlights the main findings of the work reported in this thesis and lists suggestions for future work, to explore new vistas ahead.

Perovskite based artificial superlattices has recently been extensively investigated due to the immense promise in various device applications. The major applications include non-volatile random access memories, microwave devices, phase shifters voltage tunable capacitor applications etc. In this thesis we have taken up the investigation of two different types of symmetric superlattices, viz. BaZrO3/BaTiO3 and SrTiO3/BaZrO3, with possible applicability to voltage tunable devices. Chapter 1 deals with the introduction to the perovskite based functional oxides. Their various applications and the specific requirements for voltage tunable device applications has also been discussed in detail. The basic properties of BaTiO3 and SrTiO3, which are well documented in the literature, have been reviewed. The fundamental physics of interfacial interactions that influence the properties of superlattices is also discussed using existing models. The reason behind the choice of constructing artificial superlattices of BaZrO3/BaTiO3 and SrTiO3/BaZrO3 and the motivation behind this thesis is outlined. Chapter 2 gives a brief description of the basic characterization techniques that has been employed for studying the thin films. These include pulsed laser deposition of oxide thin films, structural characterization using X-Ray Diffraction and Atomic Force Microscope and electrical characterization of thin film metal-insulator-metal structures. The basic principle behind the techniques has also been included in various sections of this chapter. Chapter 3 introduces the reader to basic properties of the less studied perovskite material BaZrO3, one of the parent components of Ba(Zr,Ti)O3 based ceramics for high frequency applications. BaZrO3 is the common material in both the types of superlattices studied in this thesis. Initially the growth of polycrystalline BaZrO3 on (111)Pt/TiO2/SiO2/Si has been elaborated in this chapter. After characterizing the crystalline quality of the films and optimizing the growth conditions, epitaxial BaZrO3 films has been grown on (001) SrTiO3 substates. Dielectric properties of epitaxial BaZrO3 film have been measured as a function of temperature and frequencies. The electric field tunability of BaZrO3 films has been calculated from capacitance-voltage data for comparison with superlattice structures. Chapter 4 deals with the basic considerations involving growth of artificial superlattices and multilayers using pulsed laser ablation technique. The fundamental differences between formation of multilayers and superlattices have also been discussed, and the basic considerations for optimizing growth parameters are analyzed in this chapter. X-ray θ-2θ and φ-scans have been performed to investigate crystal quality of superlattices. The growth rates calculated from the satellite reflections in X-ray θ-2θ scans indicate fair degree of control over the growth and φ-scans confirms epitaxial cube-on cube growth of both types of superlattices. Atomic Force microscopy has been used to hcaracterize the film quality and surface morphology of superlattice structures and it has been found that the films have a very smooth surface with rms roughness of the order of few nanometres. Chapter5 deals with the detailed electrical characterization of both types of superlattices structures. Dielectric response showed nearly temperature invariance for both types of superlattices. Polarization measurements show that the heterostructures are in paraelectric state. Even for paraelectric/ferroelectric BaZrO3/BaTiO3 superlattices, stress induced stabilization of the paraelectric state is exhibited in low period superlattices. Paraelectric/paraelectric-SrTiO3/BaZrO3 superlattices exhibited a tunability of ~20% at intermediate modulation periods and an extremely stable dissipation factor with respect to temperature which is very attractive for device application point of view. A maximum tunability of ~40% has been observed for lowest period BaZrO3/BaTiO3 superlattice. Relatively high Quality Factors has been observed for both type of superlattices and their dependence on the modulation periods has been analyzed. Dielectric relaxation data showed that Maxwell-Wanger type of behaviour is exhibited but the presence of a conductance component G had to be realized in the equivalent circuit representation, which originates from the observation of a square law dependence of the alternating current on the frequency. Finally DC electrical characteristics were investigated as a function of temperature to determine the type of conduction mechanism that is involoved. The data has been analyzed using existing theories of high field conduction in thin dielectric films and it has been found that at different temperature ranges, the conduction mechanism varied from bulk limited Poole-Frenkel to Space Charge limited conduction. The activation energy calculation indicate that the physical processes responsible for dielectric relaxation and dc conduction are identical.

Thesis (MSc)--Stellenbosch University, 2002. / ENGLISH ABSTRACT: In this investigation the formation of thin film manganites and their electrical characteristics is studied. In order to see the effect of oxidation states on magneto-resistivity, 80% of Mn is replaced by Fe. Pulsed laser deposition (3 J/cm2), carried out in oxygen partial pressures ranging from 0.01 mbar to 1.00 mbar was used to fabricate the thin films from two target compositions, namely La2CaMn2.94Feo.0609 and La2CaMno.6Fe2.409. Films were deposited on Si< 100 >, MgO< 100 >, SrTi03< 100 > and LaAl03< 100 > single crystal substrates. Samples were characterized by RBS, AFM, SEM, and XRD. Electrical measurements were also carried out. One of the main characterization techniques in this investigation is Rutherford Backscattering Spectrometry (RBS). It has been shown that RBS is a very powerful characterization technique when used in conjunction with the RUMP simulation program. The effect of various parameters can be determined beforehand by RUMP simulation of the thin film structures to be investigated. Simulation shows that RBS is an excellent characterization tool for determining film thickness and stoichiometry. The role of oxygen uptake in La2CaMn3_xFexOg was investigated as the oxidation states of elements in manganite materials have a large effect on their magnetoresistive properties. The height of the La signal can be used as a measure of the oxygen content. RBS spectra of films deposited on single crystal silicon substrates at different ambient pressures show that the fit between simulated and measured RBS spectra improves with higher oxygen pressures, thereby indicating better quality manganite material. The RBS spectra also show that the films have good stoichiometry. Atomic force microscopy was used to determine the roughness of the thin films. The annealed film (average roughness 4.5 nm) shows a surface smoother than the non-annealed film (average roughness 5.3 nm). SEM measurements show that in the case of samples having a high Fe content, the crystallite size varies between about 0.04 11m and 0.10 11m, while for samples with high manganese content, the crystallinity varies between 0.03 jJ,m and 0.06jLm. Manganites were analyzed using Bragg-Brentano (28) X-ray diffraction. Measurements show that manganite films cannot be grown epitaxially on Si< 100 > and MgO< 100 > single crystals due to a large lattice mismatch. In the case of SrTi03 and LaAl03 several reflections and sharp peaks from the film can be seen, indicating reasonable epitaxial growth. SEM measurements of the samples however show polycrystallinity. Complete epitaxy has thus not occurred, but many grains have an epitaxial orientation. Resistance versus temperature (the room temperature to about 100 K) in zero magnetic field was measured for a La2CaMno.06Fe2.409 thin film and maximum resistance corresponding to about 108 K was found. At higher temperatures the resistance decreases as temperature increases. The manganite thin film therefore shows semiconductor behaviour. Resistance measurements carried out at different magnetic fields (0 - 1 T) show a small positive magnetoresistance of 0.83 %. Usually the magnetoresistance phenomenon is measured at higher magnetic fields and this could be the reason for our low value as well as the fact that the iron content could be too high. / AFRIKAANSE OPSOMMING: In hierdie ondersoek is die formasie en karakterisering van dunlagie manganiete ondersoek. Om die effek van oksidasie-toestand op magnetoresistiwiteit te bepaal, is 80% van die Mn verplaas deur Fe. Pulseerde laser deposissie(3 J/cm2), is uitgevoer by 'n parsiële suurstof druk tussen 0.10 en 1.00 mbar deur gebruik te maak van La2Ca Mn2.94Feo.o609 en La2CaMno.6Fe2.409 teiken skywe. Dunlagies was gedeponeer op Si<IOO>, MgO<IOO>, SrTi03<100> en LaAl03<100> enkelkristal substrate. Die dunlagies is daarna ge-karakteriseer met behulp van Rutherford terugverstrooing (RBS), atoom krag mikroskopie(AFM), skandeer elektronmikroskopie (SEM) en xstraal diffraksie(XRD). Elektriese metings is ook uitgevoer. Een van die hoof tegnieke wat gebruik is in hierdie ondersoek is Rutherford terugverstrooing (RBS) van 2 Mev alfa-deeltjies. In hierdie navorsing is aangetoon dat RBS saam met spektra simulasie(RUMP), 'n besondere kragtige metode is om die stoichiometrie en dikte van manganiet lagies te bepaal. Die rol van die opname van suurstof in die dunlagies was ondersoek, aangesien die oksidasie toestand van manganiet lagies 'n groot effek het op hulle magnetoresistiwiteit. Die hoogte van die La sein is gebruik as 'n maatstaf van suurstof inhoud. RBS spektra van dunlagies gevorm op enkelkristal silikon substrate by verskillende parsiële suurstof drukke wys dat die passing tussen gemete en gesimuleerde spektra verbeter by hoër suurstof drukke, wat beter kwaliteit manganiet materiaal aandui. Die RBS spektra het ook aangetoon dat die stoichiometrie van die lagies uitstekend is. Atoom krag mikroskopie(AFM) is gebruik om die grofheid van die oppervlaktes van die dunlagies te bepaal. Lagies wat by 750 grade celsius uitgegloei is ( gemiddelde gladheid van 4.5 nm) was gladder as films wat nie na ablasie uitgegloei is nie (gemiddelde gladheid van 5.3 nm). SEM metings toon ook dat dunlagies met 'n hoë Fe inhoud 'n kristalliet deursnit het van 0.04 tot 0.10 mikrometer en die met 'n hoë mangaan inhoud 'n poli-kristalliniteit het van tussen 0.03 en 0.06 mikrometer het. Bragg-Brentano(twee-theta) X-straal diffraksie meting wys dat manganiet films nie epitaksieël op Si<IOO> en MgO<IOO> enkelkristal substrate gevorm kan word nie, weens 'n groot verskil in die kristal-rooster parameters. SEM metings van die monsters wys polikristalliniteit. Algehele epitaksie het dus nie plaasgevind nie, maar verskeie kristalliete het 'n epitaksiële orientasie. Weerstand metings is gemaak by temperature so laag as 100 Kelvin vir La2CaMno.o6Fe2.409dunlagies en 'n maksimum weerstand is by 108 Kelvin gevind. By hoër temperature het die weerstand afgeneem soos die temperatuur toeneem, wat halfgeleier gedrag aandui. Weerstand metings by verskillende magneetvelde (0 tot I Tesla) wys 'n klein magnetoresistiwiteits effek van 0.83%. Gewoonlik word magnetoresistiwiteit gemeet by hoë magneet velde (ongeveer 6 Tesla). Dit, sowel as die hoë Fe samestelling van die monsters kan die rede wees vir die lae magnetoresistiwiteit wat waargeneem word.