>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.

The characterization of work functions and field emission stability for molybdenum and iridium oxide coatings was examined. Single emission tips and flat samples of molybdenum and iridium oxide were prepared for characterization. The flat samples were characterized using X-ray Photoelectron Spectroscopy and X-ray diffraction to determine elemental composition, chemical shift, and crystal structure. Flat coatings of iridium oxide were also scanned by Atomic Force Microscopy to examine topography. Work functions were characterized by Ultraviolet Photoelectron Spectroscopy from the flat samples and by Field Emission Electron Distributions from the field emission tips. Field emission characterization was conducted in a custom build analytical chamber capable of measuring Field Emission Electron Distribution and Fowler-Nordheim I-V plots simultaneously to independently evaluate geometric and work function changes. Scanning Electron Microscope pictures were taken of the emission tips before and after field emission characterization to confirm geometric changes. Measurement of emission stability and work functions were the emphasis of this research. In addition, use of iridium oxide coatings to enhance emission stability was evaluated. Molybdenum and iridium oxide, IrO2, were characterized and found to have a work function of 4.6 eV and 4.2 eV by both characterization techniques, with the molybdenum value in agreement with previous research. The analytic chamber used in the field emission analysis demonstrated the ability to independently determine the value and changes in work function and emitter geometry by simultaneous measurement of the Field Emission Energy Distribution and Fowler-Nordheim I-V plots from single emitters. Iridium oxide coating was found to enhance the stability of molybdenum emission tips with a relatively low work function of 4.2 eV and inhibited the formation of high work function molybdenum oxides. However, the method of deposition of iridium and annealing in oxygen to form iridium oxide on molybdenum emitters left rather severe cracking in the protective oxide coating exposing the molybdenum substrate.

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.

No description available.

No description available.

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.

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.

Thesis (PhD (Physics))--University of Stellenbosch, 2002. / Includes bibliography. / ENGLISH ABSTRACT: High temperature superconductivity is an important topic in contemporary solid state physics, and an area of very active research. Due to it’s potential for application in low temperature electronic devices, the material has attracted the attention of researchers in the electronic engineering and material science fields alike. Moreover, from a fundamental point of view, several questions remain unanswered, related to the origin of superconductivity of this class of materials and the nature of quantised magnetic flux present in magnetised samples. In this work, flux creep phenomena in a thin superconducting YBa₂Cu₃O₇ film deposited by pulsed laser deposition, is investigated near the critical temperature 0 ≤ Tc – T ≤ 10 K. Creep activation energy U0 and critical current density jc were determined as a function of temperature close to Tc, providing important data to a problem of high-Tc superconductivity which is still a matter of debate. In particular it is still an open question whether restoring the temperature in a creep freezing experiment in fact restores the film to it's original state before the freezing. The most important novel results concern the regime of critical fluctuations in the vicinity Tc - T < 1 K. We studied the isothermal relaxation of trapped magnetic flux, and determined that the long time decay follows a power law, where the exponent is inversely proportional to the creep activation energy. The temperature dependence of the critical current density jc(T) of the YBa₂Cu₃O₇ film close to Tc was obtained during warming runs. It was determined that jc(T) follows a square root dependence on T to high accuracy in the range 0.2 ≤ Tc – T ≤ 1.5 K. During flux creep experiments an interesting phenomenon called creep freezing related to the strong temperature dependence of the relaxation rate was observed. A pronounced slowing of relaxation with only a small drop in temperature from a starting temperature close to Tc was detected. Experiments were conducted by initiating an isothermal flux decay run. At a certain point the temperature was slightly lowered, and the flux decay stopped within experimental accuracy. When the temperature was restored to the initial value, the flux decay resumed at the previous rate before cooling. An argument based on vortex drift velocity was employed to explain the phenomenon qualitatively. During the course of this investigation, a pulsed laser deposition (PLD) system was designed and built from scratch. PLD involves the interaction of a focussed laser pulse with a multielemental solid target material. Material ablated from the target forms a fast moving plume consisting of atomic and molecular particles, directed away from the target, and towards a usually heated substrate on which the particles condense layer by layer to form a thin film. The substrate temperature and background gas are carefully controlled to be conductive to the growth of a desired phase of the multi-elemental compound. The PLD system proved to be quite versatile in the range of materials that could be deposited. It was used to deposit thin films of different materials, most notable were good quality superconducting YBa₂Cu₃O₇, thermochromic VO2, and magnetoresistive LaxCa1-xMnO3. Metallic Au and Ag layers were also successfully deposited on YBa2Cu3O7 thin films, to serve as protective coatings. The critical temperatures of the best superconducting films were 90 K as determined by resistivity measurement. The optimal deposition conditions to deposit high quality superconducting YBa₂Cu₃O₇ thin films was found to be: deposition temperature 780°C, laser energy density 2-3 J/cm2, oxygen partial pressure 0.2 mbar, and target-substrate distance 35 mm. This yields film with Tc ~ 90 K. It was found that deposition temperature plays the predominant role in determining the quality of YBa₂Cu₃O₇ thin films deposited by PLD. / AFRIKAANSE OPSOMMING: Hoë temperatuur supergeleiding is tans ’n aktuele onderwerp van vastetoestandfisika en dit is ’n gebied van baie aktiewe navorsing. Weens die potensiaal vir toepassings van hoë temperatuur supergeleiers in elektronika, het dié klas materiale die aandag van fisici and elektronici getrek. Verskeie fundamentele vraagstukke bly steeds onbeantwoord, veral met betrekking tot die oorsprong van supergeleiding in hierdie materiale en die gedrag van gekwantiseerde magnetiese vloed (“vortekse”) in gemagnetiseerde monsters. In hierdie werk word diffusie van vortekse in dun supergeleidende YBa₂Cu₃O₇ films ondersoek naby die kritieke temperatuur (0 ≤ Tc - T ≤ 10 K). Die temperatuur afhanklikheid van die diffusie aktiveringsenergie U0 en die kritieke stroomdigtheid jc word bepaal naby Tc. Dit verskaf belangrike inligting tot probleme in hoë temperatuur supergeleiding wat tans nog onbeantwoord bly. In die besonder is dit steeds ’n ope vraag of die herstel van die aanvanklike temperatuur in ’n vloedstollings eksperiment waarlik die film tot die oorspronklike toestand herstel. Die belangrikste nuwe resultate hou verband met die gebied van kritieke fluktuasies van die orde parameter in die omgewing 0 < Tc - T < 1 K. Ons het die isotermiese ontspanning van vortekse verstrik in die kristalstruktuur bestudeer, en bepaal dat die lang tydsverval ’n magsverwantskap handhaaf, waar die eksponent omgekeerd eweredig is aan U0. Die temperatuur afhanklikheid van die kritieke stroomdigtheid jc(T) van die YBa₂Cu₃O₇ film naby Tc is bepaal tydens verhittingslopies. Daar is bevind dat naby Tc, jc ’n vierkantswortel verband met T volg, tot hoë noukeurigheid in die gebied 0.2 ≤ Tc – T ≤ 1.5 K. Gedurende vorteksdiffusie eksperimente is ’n interessante verskynsel naamlik vloedstolling (“flux freezing”) waargeneem. Dit hou verband met die sterk temperatuur afhanklikheid van die vervaltempo van die magnetiese moment van ’n gemagnetiseerde film. ’n Skerp daling van die vervaltempo, weens slegs ’n klein temperatuurdaling vanaf die begin temperatuur naby Tc, is waargeneem. Gedurende eksperimente is daar aanvanklik ’n isotermiese vloedontspanning teweeg gebring. Op ’n sekere tydstip is die temperatuur effens verlaag, waarby die vloedontspanning tot stilstand gekom het binne grense van waarneming. Wanneer die temperatuur weer herstel is na die oorspronklike, het die vloedontspanning voortgegaan teen die tempo voor die temperatuurverlaging. ’n Verklaring wat gebaseer is op vorteks dryfsnelheid was aan die hand gedoen om hierdie gedrag te verklaar. ’n Groot komponent van die projek was om die dun YBa₂Cu₃O₇ films self te vervaardig. Tydens hierdie ondersoek, is ’n gepulseerde laser deposisie (“PLD”) sisteem eiehandig ontwerp en gebou. PLD behels die interaksie van ’n gefokuseerde laser puls met ’n teiken bestaande uit ’n multi-element vastestofverbinding. Materiaal wat verdamp (“ablate”) word, vorm ’n snelbewegende pluim bestaande uit atomiese en molekulêre deeltjies. Dit beweeg vanaf die teiken na ’n verhitte substraat, waarop die deeltjies kondenseer om laag vir laag ’n dun film te vorm. Die substraat temperatuur en agtergrond gas word sorgvuldig beheer om die groei van die verlangde fase van die multi-element verbinding teweeg te bring. Die PLD sisteem is baie veeldoelig ten opsigte van die verskeidenheid materiale wat suksesvol neergeslaan kan word. Dit was aangewend om verskillende materiale neer te slaan, onder andere supergeleidende YBa₂Cu₃O₇, termochromiese VO2, en magnetoresistiewe LaxCa1-xMnO3. Geleidende Au en Ag lagies is ook suksesvol neergeslaan op YBa₂Cu₃O₇ dun films, om te dien as beskermingslagies. Die kritieke temperatuur van die beste supergeleidende films was 90 K soos bepaal deur weerstandsmetings. Die optimale neerslaan toestand vir hoë kwaliteit YBa₂Cu₃O₇ dun films was: substraat temperatuur 780°C, laser energiedigtheid 2 - 3 J/cm2, suurstofdruk 0.2 mbar, en teiken-substraat afstand 35 mm. Daar is bevind dat die substraat temperatuur die deurslaggewende rol speel tydens die neerslaan proses om die kwaliteit van die supergeleidende films te bepaal.

Thesis (MEng (Electrical and Electronic Engineering))--University of Stellenbosch, 2006. / The Josephson effect of high-temperature superconducting nanobridge structures is studied worldwide. Until now, nanobridges are generally fabricated with focused ion beam milling on planar thin films. These nanobridges are employed as weak links in superconducting quantum interference devices (SQUIDs) and used in superconducting flux flow transistors and devices. This project had two main objectives: to improve the sidewall angle of photoresist lines, with the aid of atomic force microscopy (AFM) nanolithography; and to fabricate hightemperature Josephson junctions by constricting superconductive YBCO lines on MgO substrates with AFM nanolithography. The entire fabrication process is explained including photolithography, deposition of the YBCO thin films with pulsed laser deposition (PLD), nanolithography and wet etching. Although the testing of the junctions did not show any Josephson behaviour, it could be demonstrated that nanobridge structures can successfully be created by AFM nanolithography. The entire fabrication process has been demonstrated in detail for the benefit of future research.