Mesoporous TiO2 thin film has been considered as a benchmark material in the applications of dye sensitised solar cells (DSSCs) due to a combination of the physical properties that are inherent to the metal oxide and its particular structuring, in addition to its chemical stability and commercial availability. For DSSCs, a more important functionality of mesoporous TiO2 thin films is their extremely high surface and internal surface areas, resulting in high adsorption of dye molecules. However, a major drawback of fabrication of mesoporous TiO2 thin films is its high-temperature furnace sintering at 450à ̄‚°C-500à ̄‚°C for 30 min. The high-temperature process prevents the possibility of integrating different electro-optical devices on the same substrate, and the sintering time required would be a hurdle for potentially rapid manufacturing of mesoporous metal oxide thin films for DSSCs. This thesis demonstrates for the first time the use of a fibre laser with a wavelength of 1070 nm and a pulse width of milliseconds for generation of 1) mesoporous nanocrystalline (nc) TiO2 thin films on ITO coated glass, and 2) compact TiO2 layer and mesoporous TiO2 film on ITO coated glass. The first one was achieved by complete vaporisation of organic binder and inter-connection of TiO2 nanoparticles; and the second one was achieved by full crystallisation of TiO2 precursor to form the compact TiO2 layer and the same sintering process described above. Both processes were one-step, and achieved by stationary laser beam irradiation of 1 minute, compared with 30 min for furnace-sintering to form a mesoporous TiO2 film, and 2 h for two-step furnace treatment to form compact layer and mesoporous film on ITO glass. No thermally damaging of the ITO layers and the glass substrates was observed. The DSSC with the laser-sintered TiO2 photoanode at the optimised laser processing condition of 85 W/cm2 and 100 ms/50 ms pulse mode reached higher power conversion efficiency (PCE) of 3.20% for the TiO2 film thickness of 6 à ̄­m compared with 2.99% for the furnace-sintered; the DSSC with the laser-treated compact TiO2 layer and mesoporous TiO2 film on ITO glass at the optimised laser treatment condition of 85 W/cm2 and 125 ms/25 ms, reached 5.76% compared to 4.83% with the furnace-treated. Electrochemical impedance spectroscopy (EIS) studies revealed that the laser sintering effectively decreased charge transfer resistance and increased electron lifetime of the TiO2 thin films. It is believed that the use of the fibre laser with over 40% wall-plug efficiency offers an economically-feasible, industrial viable solution to the major challenge of rapid fabrication of large scale, mass production of mesoporous metal oxide thin film based solar energy systems, potentially for perovskite and monolithic tandem solar cells, in the future. Another part of the thesis presents a detailed investigation on the improvement of photovoltaic performance of furnace-sintered TiO2 films on ITO-coated glass using an excimer laser with a wavelength of 248 nm and possesses a rectangular beam profile and has a full width at half maximum (FWHM) pulse duration of 13-20 ns. This was achieved by modifying the surface of the furnace-sintered TiO2 films to increase the roughness, which led to increased optical absorbance via light-trapping. The laser process was carried out with variation of laser fluence and number of pulses per unit area. Under the optimised laser fluence of 34 mJ/cm2 and number of pulses of 50, the DSSC with the laser-modified TiO2 photoanode showed a high power conversion efficiency of 2.99% than 2.10% without the laser treatment. EIS studies showed that the films modified under the optimised laser parameter effectively decreased charge transfer resistance and increased electron lifetime of the TiO2 thin films.

The aim of this study is to test the limits of photocatalytic reduction of CO2 over Pt and light harvesting dye promoted TiO2 films under UV and visible light. Thick and thin TiO2 film catalysts are coated onto 1 cm long glass beads via a common sol-gel procedure and dip coating technique. TiO2 thin films were promoted by Pt and three different light harvesting molecules: RuBpy (Tris (2,2&rsquo / &ndash / bipyridyl) ruthenium (II) chloride hexahydrate) , BrGly (1,7-dibromo-N,N&rsquo / -(t-butoxycarbonyl-methyl)-3,4:9,10-perylene-diimide) and BrAsp (1,7-dibromo-N,N&rsquo / -(S-(1-t-butoxy-carbonyl-2-t-butoxycarbonyl-methyl)-ethyl)- 3,4:9,10-perylenediimide). Their SEM, XRD, UV-Vis spectroscopy and hydrogen chemisorption characterizations are performed. Reaction tests are performed for the catalysts under UV and visible light. The only quantifiable reaction product was methane. With RuBpy containing catalysts hydrogen production was observed under UV light, but not quantified. The results indicated that Pt addition resulted in higher yields in UV experiments. The presence of light harvesting molecules resulted in increase in photocatalytic activity for thin films, whereas it resulted in no change or decrease for the thick films. The latter case may occur due to the UV filtering effect of these dyes. Use of dyes (with visible range absorption bands) as promoters made visible light excitation possible. This resulted in photocatalytic activity under visible light, which was not observed with unpromoted and Pt promoted TiO2 thin film catalysts. Under visible light methane was the only quantified photoreduction product. CO evolution was also observed, but not quantified. The photocatalytic activities of the dye promoted TiO2 were in the order of RuBpy~BrAsp&gt / BrGly. The methane yields of visible light experiments were one order of magnitude lower than the ones under UV light.

Les travaux précédents du laboratoire Hubert Curien ont permis d’élaborer des films photosensibles Ag : TiO2 sur verre, support de marquage de motifs actualisables ou permanents. Une adaptation de ces travaux aux supports plastiques et papiers est ici proposée afin d’élargir les domaines d’application potentiels au marquage sécurité des produits par exemple. Des techniques d’élaboration de films Ag : TiO2 compatibles avec les substrats considérés ont donc été développées. Deux voies ont été envisagées. La première utilise la chimie du Sol-Gel combinée à la méthode EISA et des procédés de dépôt tel le spin-coating, le jet d’encre ou la flexographie pour former un film mésoporeux de TiO2 sur les supports. Des traitements basés sur une extraction par solvant ou un recuit infrarouge ont été imaginés afin de libérer la porosité du film sans dégradation du support. Pour réaliser les films sur papier, un sel d’argent est ajouté au Sol avant son dépôt. Dans les cas des films élaborés sur plastique, l’argent est incorporé par imprégnation du matériau dans une solution de sel d’argent. La deuxième voie d’élaboration propose de formuler une encre aqueuse jet d’encre de nanoparticules de TiO2 et d’ions argent, en adaptant la composition d’une suspension commerciale de TiO2 aux exigences du jet d’encre. Après dépôt, l’encre est séchée par recuit infrarouge. Le comportement photochromique sous expositions lumineuses UV et visible des différents films permet leur coloration et décoloration de façon réversible. Les films Sol-Gel déposés sur plastique peuvent également être support de photo-inscriptions permanentes générées par irradiation par une lumière visible d’une certaine intensité / Previous research conducted at laboratory Hubert Curien led to the development of photosensitive Ag: TiO2 films on glass as support for updatable or permanent patterns. An adaptation of this work to plastic and paper substrates is proposed here to broaden the possible application areas such as goods secure labeling, for example. Fabrication techniques of Ag: TiO2 films compatible with flexible substrates have been developed, using two different paths. The first uses the combination of Sol-Gel chemistry with the EISA method. Deposition processes such as spin coating, inkjet or flexographic printing are used to form a mesoporous film of TiO2 on substrates. Treatments based on solvent extraction or infrared annealing have been devised to release the porosity of the film without damaging the supports. Silver salt is either introduced into the titania pores by soaking the films into a silver salt solution or added to the sol before its coating. The second developed option proposes formulating an aqueous ink jet ink made of TiO2 nanoparticles and silver ions by adapting the composition of a commercial suspension of TiO2 with the requirements of the ink jet process. After printing, the ink is dried by infrared annealing. The photochromic behavior under UV and visible light exposures of fabricated films allows to get coloring and bleaching reversibly. Sol-Gel films coated on plastic can also be a support for permanent colored patterns realized by irradiation with a visible light of certain intensity

Thesis (MScEng)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: The purpose of this study was to develop modi ed tract-etched membranes using nanocomposite TiO2 for advanced water treatment processes. Photocatalytic oxidation and reduction reactions take place on TiO2 surfaces under UV light irradiation, therefore sunlight and even normal indoor lighting could be utilised to achieve this effect. In membrane ltration, caking is a major problem, by enhancing the anti-fouling properties of photocatalysts to mineralise organic compounds the membrane life and e ciency can be improved upon. In this study the rst approach in nanocomposite membrane development was to directly modify the surface of polyethylenetherephthalate (PET) track-etched membranes (TMs) with titanium dioxide (TiO2) using inverted cylindrical magnetron sputtering (ICMS) for TiO2 thin lm deposition. The second approach was rst to thermally evaporate silver (Ag) over the entire TM surface, followed by sputtering TiO2 over the silver-coated TM. As a result a noble metal-titania nanocomposite thin lm layer is produced on top of the TM surface with both self-cleaning and superhydrophilic properties. Reactive inverted cylindrical magnetron sputtering is a physical vapour deposition method, where material is separated from a target using high energy ions and then re-assimilated on a substrate to grow thin lms. Argon gas is introduced simultaneously into the deposition chamber along with O2 (the reactive gas) to form TiO2. The photocatalytic activity and other lm properties, such as crystallinity can be in uenced by changing the sputtering power, chamber pressure, target-to-substrate distance, substrate temperature, sputtering gas composition and ow rate. These characteristics make sputtering the perfect tool for the preparation of di erent kinds of TiO2 lms and nanostructures for photocatalysis. In this work, the utilisation of ICMS to prepare photocatalytic TiO2 thin lms deposited on track-etched membranes was studied in detail with emphasis on bandgap reduction and TM surface regeneration. Nanostructured TiO2 photocatalysts were prepared through template directed deposition on track-etched membrane substrates by exploiting the good qualities of ICMS. The TiO2-TM as well as Ag-TiO2-TM thin lms were thoroughly characterised. ICMS prepared TiO2 lms were shown to exhibit good photocatalytic activities. However, the nanocomposite Ag-TiO2 thin lms were identi ed to be a much better choice than TiO2 thin lms on their own. Finally a clear enhancement in the photocatalytic activity was achieved by forming the Ag-TiO2 nanocomposite TMs. This was evident from the band-gap improvement from 3.05 eV of the TiO2 thin lms to the 2.76 eV of the Ag-TiO2 thin lms as well as the superior surface regenerative properties of the Ag-TiO2-TMs. / AFRIKAANSE OPSOMMING: Die doel van hierdie studie was om verbeterde baan-ge etste membrane (BMe) met behulp van nano-saamgestelde titaandioksied (TiO2) vir gevorderde water behandeling prosesse te ontwikkel. Fotokatalitiese oksidasie- en reduksie reaksies vind plaas op die TiO2 oppervlaktes onder UV-lig bestraling, en dus kan sonlig en selfs gewone binnenshuise beligting gebruik word om die gewenste uitwerking te verkry. In membraan ltrasie is die aanpaksel van onsuiwerhede 'n groot probleem, maar die verbetering van die self-reinigende eienskappe van fotokatalisators deur organiese verbindings te mineraliseer, kan die membraan se leeftyd en doeltre endheid verbeter word. In hierdie studie was die eerste benadering om nano-saamgestelde membraan ontwikkeling direk te verander deur die oppervlak van polyethylenetherephthalate (PET) BMe met 'n dun lagie TiO2 te bedek, met behulp van reaktiewe omgekeerde silindriese magnetron verstuiwing (OSMV).Die tweede benadering was eers om silwer (Ag) termies te verdamp oor die hele BM oppervlak, gevolg deur TiO2 verstuiwing bo-oor die silwer bedekte BM. As gevolg hiervan is 'n edelmetaal-titanium nano-saamgestelde dun lm laag gevorm bo-op die oppervlak van die BM, met beide self-reinigende en verhoogde hidro liese eienskappe. OSMV is 'n siese damp neerslag metode, waar materiaal van 'n teiken, met behulp van ho e-energie-ione, geskei word, en dan weer opgeneem word op 'n substraat om dun lms te vorm. Argon gas word gelyktydig in die neerslag kamer, saam met O2 (die reaktiewe gas), vrygestel om TiO2 te vorm. Die fotokatalitiese aktiwiteit en ander lm eienskappe, soos kristalliniteit, kan be nvloed word deur die verandering van byvoorbeeld die verstuiwingskrag, die druk in die reaksiekamer, teiken-tot-substraat afstand, substraattemperatuur, verstuiwing gassamestelling en vloeitempo. Hierdie eienskappe maak verstuiwing die ideale hulpmiddel vir die voorbereiding van die verskillende soorte TiO2 lms en nanostrukture vir fotokatalisasie. In hierdie tesis word OSMV gebruik ter voorbereiding van fotokatalitiese TiO2 dun lms, wat gedeponeer is op BMe. Hierdie lms word dan in diepte bestudeer, met die klem op bandgaping vermindering en BM oppervlak hergenerasie. Nanogestruktureerde TiO2 fotokataliste is voorberei deur middel van sjabloongerigte neerslag op BM substrate deur die ontginning van die goeie eienskappe van OSMV. Die TiO2-BM dun lms, sowel as Ag-TiO2-BM dun lms, is deeglik gekarakteriseer. OSMV voorbereide TiO2 dun lms toon goeie fotokatalitiese aktiwiteite. Nano-saamgestelde Ag-TiO2 dun lms is egter ge denti seer as 'n veel beter keuse as TiO2 dun lms. Ten slotte is 'n duidelike verbetering in die fotokatalitiese aktiwiteit bereik deur die vorming van die Ag-TiO2 nano-saamgestelde BMe. Dit was duidelik uit die bandgapingverbetering van 3,05 eV van TiO2 dun lms in vergelyking met die 2,76 eV van Ag-TiO2 dun lms. 'n Duidelike verbetering is behaal in die fotokatalitiese aktiwiteit deur die vorming van die Ag-TiO2 nano-saamgestelde TMs.

The continuous downscaling has enforced the device size and oxide thickness to few nanometers. After serving for several decades as an excellent gate oxide layer in complementary metal oxide semiconductor (CMOS) devices, the thickness of SiO2 layer has reached to its theoretical limits. Ultra-thin films of SiO2 can result in severe leakage currents due to direct tunneling as well as maintaining the homogeneity of the layers becomes an additional challenge. The use of a high- (HK) layer can solve these twin concerns of the semiconductor industry, which can also enhance the capacitance due to superior dielectric permittivity and reduce the leakage current by being thicker than the silicon dioxide. This thesis is concerned about the development of solution route fabricated high-k (TiO2, ZrO2 and HfO2) gate dielectrics and the investigation of high-/silicon interfaces by highly sensitive DLTS technique in MOS structures. The solution processing reduce the industrial fabrication cost and the DLTS method has the advantage to accurately measure the interface related defects parameters; such as interface trap density (Dit), capture cross-section (), activation energy (ET) and also distinguish between bulk and interface traps. In this thesis, HK films have been deposited by solution route, the material and electrical properties of the film and the HK/Si interface have been extensively evaluated. IN CHAPTER 1, we have summarized the history and evolution of transistor and it provides the background for the work presented in this thesis. IN CHAPTER 2, we have described the experimental method /technique used for the fabrication and characterization. The advantages and working principals of spin-coating and DLTS techniques are summarized. IN CHAPTER 3, we have presented the preparation and optimization of TiO2 based HK layer. Structural, surface morphology, optical electrical and dielectric properties are discussed in details. A high- 34 value is achieved for the 36 nm TiO2 films. IN CHAPTER 4, we presented the technologically relevant Si/TiO2 interface study by DLTS technique. The DLTS analysis reveals a small capture cross-section of the interface with acceptable interface state density. IN CHAPTER 5, we have focused on the fabrication of amorphous ZrO2 films on p-Si substrate. The advantage of amorphous dielectric layer is summarized as first dielectric reported SiO2 is used in its amorphous phase. The moderate-15 with low leakage current density is achieved. IN CHAPTER 6, the HfO2 films are prepared using hafnium isopropoxide and a high value of dielectric constant 23 is optimized with low leakage current density. The current conduction mechanisms are discussed in details. IN CHAPTER 7, we have probed the oxygen vacancy related sub-band-gap states in HfO2 by DLTS technique. IN CHAPTER 8, we have presented the summary of the dissertation and the prospect research directions are suggested. In summary, we have studied the group IVB transition metal elemental oxides (TMEO); TiO2, ZrO2 and HfO2 thin films in the MOS structure, as a possible replacement of SiO2 gate dielectric. For the TMEO films deposition a low-cost and simple method spin-coating was utilized. The film thicknesses are in the range of 35 – 39 nm, which was measured by ellipsometry and confirmed with the cross-sectional SEM. A rough surface of gate dielectric layer can trap the charge carrier and may cause the Fermi level pinning, which can cause the threshold voltage instabilities. Hence, surface roughness of oxide layer play an important role in CMOS device operation. We have achieved quite good flat surfaces (RMS surface roughness’s are 0.2 – 2.43 nm) for the films deposited in this work. The TiO2 based MOS gate stack shows an optimized high dielectric constant ( 34) with low leakage current density (3.710-7 A.cm-2 at 1 V). A moderate dielectric constant ( 15) with low leakage current density (4.710-9 A.cm-2 at 1 V) has been observed for the amorphous ZrO2 thin films. While, HfO2 based MOS gate stack shows reasonably high dielectric constant ( 23) with low leakage current density (1.410-8 A.cm-2 at 1 V). We have investigated the dominating current conduction mechanism and found that the current is mainly governed by space charge limited conduction (SCLC) mechanism for the high bias voltages, while low and intermediate bias voltages show the (Poole – Frenkel) PF and (Fowler – Nordheim) FN tunneling, respectively. For the HfO2 MOS device band alignment is drawn from the UPS and J-V measurements. The band gap and electron affinity of HfO2 films are estimated 5.9 eV and 3 eV, respectively, which gives a reasonable conduction band offset (1.05 eV) with respect to Si. A TMEO film suffers from a large number of intrinsic defects, which are mostly oxygen vacancies. These defects can create deep levels below the conduction band of high- dielectric material, which can act like a hole and electron traps. In addition to that, interface between Si and high- is an additional concern. These defect states in the band gap of high- or at the Si/ high- interface might lead to the threshold voltage shifts, lower carrier mobility in transistor channel, Fermi level pinning and various other reliability issues. Hence, we also studied bulk and interfacial defects present in the high- films on Si and their interface with Si by a very sensitive DLTS technique. The capture cross-sections are measured by insufficient filling DLTS (IF – DLTS). The defects present at the interface are Si dandling bond and defect in the bulk are mostly oxygen vacancies related defects present in various charge states. The interface states (Dit) are in the range of 2×1011 to 9×1011 eV-1cm-2, which are higher than the Al/SiO2/Si MOS devices (Dit in Al/SiO2/Si is the benchmark and in the order of 1010 eV-1cm-2). Still this is an acceptable value for Si/high-k (non-native oxide) MOS devices and consistent with other deposition methods. The capture cross-sections are found to be quite low in the order of 10-18 to 10-19 cm2, which indicate a minor impact on the device operation. The small value of capture cross-sections are attributed to the involvement of tunneling, to and from the bulk traps to the interface. In conclusion, the low cost solution processed high- thin films obtained are of high quality and find their importance as a potential dielectric layer. DLTS study will be helpful to reveal various interesting facts observed in high- such as resistive switching, magnetism and leakage current problems mediated by oxygen vacancy related defects