In this study, we used UV-ozone Ar sputtering, X-ray photoelectron and ultra-violet photoelectron spectroscopies and sputtering based depositions of RuO2 and Se nano-layers on indium tin oxides (ITOs). We elucidated the effect of Ar sputtering on the composition and chemistry of Sn rich ITO surface. We demonstrated that while a combination of UV-ozone radiation and Ar sputtering removes most of the hydrocarbons responsible for degrading the work function of ITO, it also removes significant amount of the segregated SN at the ITO surface that's responsible for its reasonable work function of 4.7eV. We also demonstrated for the first time that sputtering cleaning ITO surface leads to the reduction of the charge state of Sn from Sn4+ to Sn2+ that adds to the degradation of the work function. For the nano-layers coverage of ITO studies, we evaluated both RuO2 and Se. For RuO2 coated ITO, XPS showed the formation of a Ru-Sn-O ternary oxide. The RuO2 nano-layer reduced the oxidation state of Sn in the Sn-rich surface of ITO from +4 to +2. The best work function obtained for this system is 4.98eV, raising the effective work function of ITO by more than 0.5 eV. For the Se coated ITO studies, a systematic study of the dependence of the effective work function on the thickness of Se overage and its chemistry at the Se/ITO interface was undertaken. XPS showed that Se reacts with Sn at the Sn-rich surface of ITO determined the presence of both negative and positive oxidation state of Se at the Se/ITO interface. The Se also reduced the oxidation state of Sn from Sn4+ to Sn2+ in the Sn-rich ITO surface. The highest effective work function obtained for this system is 5.06eV. A combination of RuO2/Se nanoscale coating of optimally cleaned ITO would be a good alternative for device applications that would provide work function tuning in addition to their potential ability to act as interface stabilizers and a barrier to reaction and inter-diffusion at ITO/active layers interfaces responsible for long term stability of devices and especially organic solar cells and organic light emitting diodes.

No description available.

Ce travail de thèse porte sur la modélisation, la fabrication et la caractérisation de Lasers à Cavité Verticale Emettant par la Surface (VCSEL) de grandes dimensions pour la manipulation de solitons de cavité, pour lesquels ces lasers permettraient une manipulation électrique plus souple de ces ondes stationnaires. Pour cela, il est nécessaire de disposer de structures à large zone d'émission uniforme (~100µm). Or, l'injection par électrode annulaire dans les VCSEL émettant par la surface entraîne une inhomogénéité rédhibitoire. Cette étude vise donc à proposer et évaluer des solutions technologiques innovantes pour atteindre une uniformité optimale dans ces dispositifs. Après une introduction dressant un état de l'art des solutions rapportées dans la littérature, nous présentons les travaux que nous avons menés sur la modélisation électrique des lasers pour évaluer les approches génériques de complexité croissante suivantes : l'ajout d'une couche d'étalement du courant en surface (électrode transparente en ITO) ; l'association de cette dernière à une barrière de potentiel (diode Zener) et la discrétisation de l'injection par création de zones localisées de conduction. L'optimisation des électrodes en ITO déposées sur GaAs, l'évaluation de l'apport d'une diode Zener ainsi que la mesure du contraste d'injection obtenu par gravure localisée en surface du composant sont ensuite détaillées. Suite à cette mise au point technologique, l'insertion des solutions que nous avons finalement retenues (gravures localisées et ITO) pour la réalisation de VCSEL est ensuite décrite. Enfin, les caractérisations électro-optiques des composants réalisés sont présentées; elles ont déjà permis d'obtenir des dispositifs de forme allongée émettant 50mW en continu à l'ambiante. Ces premiers résultats prometteurs ont cependant mis en évidence la nécessité d'améliorer encore les propriétés de l'interface ITO/GaAs. Ces solutions pourront alors être mises à profit pour l'application visée mai s également pour la génération de puissance ou encore la réalisation de VCSEL à cavité externe (VECSEL).

In order to truly understand the process-property behavior of polymer systems it is essential to identify the three dimensional structure of the materials fabricated. For heterogeneous polymer systems such as nanoparticle filled systems, determination of the three dimensional optical properties are particularly difficult. Such information is essential, however, if the behavior of these systems are to be understood and formalized. The purpose of the present research was to develop methods for measuring the optical characteristics of heterogeneous polymer systems nondestructively, in order to characterize their three dimensional behavior. The thesis contains three parts: Part A: Study of an Oriented Uniformly Distributed System: Stretched Isotactic Polypropylene- nano Carbon Black Films (IPP-CB). Three nondestructive optical methods: optical waveguide coupling, Fourier Transform Infrared (FTIR) spectroscopy and x-ray diffraction, were used to investigate the effect of the carbon black on the phase behavior and orientation of the films. It was found that the carbon black has little effect on the crystal form and crystallinity, but has a significant effect on the three dimensional orientation behavior of the polypropylene in the IPP-CB systems. Part B: Study of a non-Uniformly Distributed System: Compression Molded Poly (Methyl Methacrylate) with Nano Indium Tin Oxide (PMMA-ITO) The PMMA-ITO sample is an un-oriented and non-uniformly mixed system which has a grain structure. A unique Break Point Waveguide Method was developed to deal with this problem. It was found that both the refractive index and the extinction coefficient increased with ITO concentration and the samples were three dimensionally random. Part C: Development of Computational Improvements in System Operations Four methods were developed to improve the accuracy of the waveguide methods. They are the Bootstrap Method, the Two-Line Method, the Big Area Method and the Modified Knee method. In conclusion, the three dimensional optical characteristics of two different kinds of heterogeneous polymer systems, oriented uniformly distributed IPP-CB films and non-uniformly distributed PMMA-ITO composites, are obtained and their structures evaluated. Further, several new methods were developed to improve the accuracy of the current optical waveguide methods.

This thesis focuses on the use of surface modifiers to tune the properties of both metals and metal oxides. Particular attention is given to examine the modification of transparent conducting oxides (TCOs) including indium tin oxide and zinc oxide both through the use of phosphonic acids as well as organic and metal-organic dopants. In this thesis a variety of known and new phosphonic acids are synthesized. A subset of these molecules are then used to probe the relationship between the ability of a phosphonic acid to tune the work function of ITO and how that interrelates with the coverage and molecular orientation of the modifier on the surface. Experimental techniques including XPS, UPS, and NEXAFS are coupled with theoretical DFT calculations in order to more closely examine this relationship. Literature surrounding the modification of zinc oxide with phosphonic acids is not as prevalent as that found for the modification of ITO. Thus, effort is placed on attempting to determine optimal modification conditions for phosphonic acids on zinc oxide. As zinc oxide is already a low work function metal oxide, modifiers were synthesized in an attempt to further decrease the work function of this substrate in an effort to minimize the barrier to carrier collection/injection. Etching of the substrate by phosphonic acids is also examined. In a related technique, n- and p-dopants are used to modify the surfaces of ITO, zinc oxide, and gold and it was found that the work function can be drastically altered, to approximately 3.3 – 3.6 eV for all three of the substrates examined. Surface reactions are straightforward to conduct typically taking only 60 s to achieve this change in work function.

This dissertation has focused on i) optimizing charge transfer rates at indium-tinoxide (ITO) electrodes, and ii) characterization of the supramolecular structure and properties of ultra thin surface modifier films on modified electrodes for various device applications. Commercial ITO surfaces were modified using conducting polymer thin film architectures with and without various chemical activation procedures. Ferrocene derivatives were used as redox probes, which showed dramatic changes in electron transfer rate as the SA-PANI/PAA layers were added to the ITO surface. Highest rates of electron transfer were observed for DMFc, whose oxidation potential coincides with the potential region where these SA-PANI/PAA films reach their optimal electroactivity. Apparent heterogeneous electron transfer rate constants, kS, measured voltammetrically, were ca.10 x higher for SA-PANI/PAA films on ITO, versus clean ITO substrates. These films also showed linear potentiometric responses with retention of the ITO transparency with the capability to create smoothest films using an aqueous deposition protocol, which proved important in other applications. ITO electrodes were also modified via chemisorption of carboxy functionalized EDOTCA and electropolymerization of PEDOTCA/PEDOT copolymers, when properly optimized for thickness and structure, enhance voltammetrically determined electron transfer rates (kS) to solution probe molecules, such as dimethylferrocene (DMFc). Values of kS ≥ 0.4 cm•sec⁻¹, were determined, approaching rates seen on clean gold surfaces. ITO activation combined with formation of these co-polymer films has the effect of enhancing the electroactive fraction of electrode surface, versus a non-activated, unmodified ITO electrode, which acts as a “blocked” electrode. The electroactivity and spectroelectrochemistry of these films helped to resolve the electron transfer rate mechanism and enabled the construction of models in combination with AFM, XPS, UPS and RAIRS studies. The surface topography, structure, composition, work function and contact angle, also revealed other desirable properties for molecular electronic devices. The carboxylic functionality of the EDOTCA molecule adds more desirable properties compared to normal PEDOT films, such as favoring the deposition of smooth films, increasing the optical contrast, participating in hydrogen-bonding, chemisorption to oxide surface, self-doping and providing a linker for incorporation of different functional groups, new molecules, or nanoparticles. Periodic sub-micron electrode arrays can be created using micro-contact printing and electropolymerization. The sinusoidal modulation of the refractive index of such confined conducting polymer nanostructures or nanoparticle stripes allows efficient visible light diffraction. The modulation of the diffraction efficiency at PANI and PEDOT gratings in the presence of an analytical stimulus such as pH or potential demonstrate the sensing capability at these surfaces. The template stripped gold surfaces that are being developed in our lab demonstrate several advantages over commercially available evaporated gold films especially for nanoscale surface modification.

Transparent electrodes (TEs) have become important components of displays, touch screens, and solar photovoltaic (PV) energy conversion devices. As electrodes, they must be electrically conductive while being transparent. Transparent materials are normally poor conductors and materials with high electrical conductivity, such as metals, are typically not transparent. From the few candidate materials, indium tin oxide (ITO) is currently the best available, but indium is an expensive material and ITO cost has risen with increasing demand. Therefore, alternative materials or methods are sought to encourage production needs of applications and help in reducing their price. This thesis presents and discusses results of experimental work for a method, field-directed chaining, to produce a TE device which is nanowire-based, with a figure of merit FoM= 2.39 x10E-4 Ohm E-1, comparable to ITO but with potential for far lower cost. Using electric field-directed chaining, multiple parallel long chains of metal nanowires are assembled on inexpensive transparent materials such as glass by field directed nanowire chaining, using methods first demonstrated in our laboratory. In this work, we have improved the fraction of functional chains, by tuning the field/voltage, a key step in increasing the FoM and lowering the cost. The effect of operating parameters on TE optical and electrical properties has been studied and identified as well. From experiments with twenty seven substrates, each with a range of electric field and nanowire concentration, the highest light transmission achieved is 78% and the lowest sheet resistance achieved is 100 Ohm/sq. Among all the operating parameters, the electric field has the most significant influence on the fraction of nanowire chains that are functional. In the operating range of electric field strength available to us, we observed a monotonic increase in the fraction of functional nanowire chains. We found a counter-intuitive change in TE properties in a sub-range of nanowire concentration, associated with a change in the structure of chained patterns. / Graduate

ITO is widely regarded as the optimal TCO for serving as front window layer in PSK/c-Si tandem solar cells. It is known to effectively mitigate several stability issues present in perovskite solar cells while demonstrating excellent lateral conductivities and optical transparency across the entire solar spectrum. However, due to the damaging effects of traditional magnetron sputtering methods on the underlying cell precursor and the limited range of annealing temperatures viable for maintaining the stability of Perovskite Solar cells, realizing the full capability of ITO layer is constrained. This investigation focuses on developing and optimizing the front Indium Tin Oxide (ITO) layer properties for high-efficiency monolithic Perovskite/PERC tandem solarcells. The study employs two widely employed industrial techniques, Magnetron Sputtering and Screen Printing for the deposition of ITO thin-films and subsequent metallization of Ag front contacts. The sputtering process parameters, namely the carrier speed, O2 : Ar ratio, and the sputter power were varied to obtain an optimized ITO layer, which exhibited a thickness of 53nm, Rsheet of 107 ohm/□, mobility of 37 cm2/V s, and 90 % average optical transparency between 400−1200nm. A low contact resistivity of 5.4mΩ·cm2 was achieved between the ITO and metal contacts which is the lowest reported value for ITO annealed at low temperature (140 °C). Champion cells, featuring Perovskite on Ohmic substrate and 2T perovskite/PERC tandem cells, exhibited high VOC values of 1.116 V and 1.75 V on 0.97 cm2 cell aperture areas and cell efficiencies of 17.2 % and 23.85 %. Additionally, a large area (158.7 cm2) tandem cell was also fabricated which demonstrated an excellent VOC of 1.75 V . The results of this investigation demonstrates the versatility of ITO layer properties achievable at low-temperatures through Magnetron sputtering and underscores the potential of existing commercialized technologies for the fabrication of high-efficiency tandem solar cells. / ITO anses allmänt vara den optimala TCO för användning som frontfönsterskikt i PSK/c-Si tandemsolceller. Den är känd för att effektivt mildra flera stabilitetsproblem som finns i perovskitsolceller samtidigt som den uppvisar utmärkt lateral konduktivitet och optisk transparens över hela solspektrumet. På grund av de skadliga effekterna av traditionella magnetronförstoftningsmetoder på den underliggande cellprekursorn och det begränsade intervallet av glödgningstemperaturer som är användbara för att upprätthålla stabiliteten hos perovskitsolceller, begränsas dock ITO-skiktens fulla kapacitet. Denna undersökning fokuserar på att utveckla och optimera egenskaperna hos det främre Indium Tin Oxide (ITO)-skiktet för högeffektiva monolitiska Perovskite/PERC tandemsolceller. I studien används två allmänt använda industriella tekniker, magnetronförstoftning och screentryckning, fördeponering av ITO-tunnfilmer och efterföljande metallisering av Ag-frontkontakter. Parametrarna för sputteringsprocessen, nämligen bärarhastigheten, förhållandet O2 : Ar och sputterkraften varierades för att få ett optimerat ITO-lager, som uppvisade en tjocklek på 53nm, Rsheet på 107 ohm/□, rörlighet på 37 cm2/V s och 90 % genomsnittlig optisk transparens mellan 400 − 1200 nm. En låg kontaktresistivitet på 5.4mΩ.cm2 uppnåddes mellan ITO och metallkontakterna, vilket är de lägstarapporterade värdena för ITO glödgat vid låg temperatur (140 °C). Champion-cellerna, med perovskit på ohmskt substrat och 2T perovskit/PERC tandemkonfigurationer, uppvisade höga VOC-värden på 1.116 V och 1.75 V på 0.97 cm2 cellaperturområden och cellverkningsgrader på 17.2 % och 23.85 %. Dessutom tillverkades en tandemcell med stor area (158.7 cm2) som uppvisade en utmärkt VOC på 1.75 V . Resultaten av denna undersökning visar mångsidigheten hos ITO-skiktets egenskaper som kan uppnås vid låga temperaturer genom magnetronförstoftning och understryker potentialen hos befintliga kommersialiserade tekniker för tillverkning av högeffektiva tandemsolceller.

The increasing energy demand, combined with the use of harmful non-renewable energy sources calls for the search of alternative methods to cover our energy need.Renewable energy can be harvested in different ways, through the movement of wind and water, biomass, or directly from the rays of the sun, as in the case of photovoltaic (PV) devices. Whilst crystalline silicon (c-Si) is the most common absorber used for solar cells, other technologies are emerging. Solar cells with copper indium gallium diselenide (CIGS) as an absorber have the possibility of being flexible, which is an advantage due to the many more application possibilities that appear compared to the rigid and heavy c-Si solar cells. CIGS solar cells have some long-term stability issues, especially regarding ingression of atmospheric species through the front contact layer. This calls for further research in the front contact of the CIGS solar cell, exploring alternative materials to prevent degradation. The front contact of a solar cell must be both optically transparent and conduct electricity. Transparent conductive oxides (TCO) are materials characterized by the ability to conduct electricity, while also possessing a certain degree of optical transparency. The combination of conductivity and transparency makes TCOs ideal as front contacts in solar cells. A very common TCO for front contacts in CIGS solar cells is aluminum-doped zinc oxide (AZO) due to its low cost, good electrical conductivity and optical transparency. Because of its low resistance to degradation in humid environments more robust TCO alternatives, such as indium-doped tin oxide (ITO), are being investigated. Indium-doped tin oxide possesses similar electrical and optical properties as AZO, but better stability in humid environments.The ITO was deposited through RF magnetron sputtering, on a glass substrate to be able to measure optical properties. Initially, experiments focusing on oxygen content in the deposition atmosphere were done, together with a reproducibility experiment. This gave useful information about sputtering parameters and stability of the deposition. Thereon, an experiment was done varying three parameters: oxygen content in deposition atmosphere, sputtering power and temperature of substrate. A statistical software was used to analyze the data, identifying the effects of the changing parameters. The best performing samples were made with an oxygen content of 0,4-0,6 vol%. A high sensibility for oxygen in the system was also observed, as a result of the initial reproducibility experiments. This led to the introduction of a sacrificial deposition step after the machine had been shut down. Optimal substrate temperature was around 150°Cand it was not possible to go higher due to sensibility of the underlying solar cell layers.A lower threshold for the film thickness, located somewhere between 125 and 175 nm, was observed. Films with thickness below this threshold experienced a large resistivityincrease. Further depositions with higher oxygen content are advised to see if the properties of the films further improve.

No description available.