Prospects of sprayed CZTS thin film solar cells from the perspective of material characterization and device performance

This thesis is devoted to the development of a relatively new, rapidly developing quaternary semiconducting material (viz., Cu2ZnSnS4) used for photovoltaic applications. This semiconductor, commonly known as CZTS, is closely related to a family of materials that have been used for solar cell applications. It is a compound semiconductor made of copper, zinc, tin and sulfur, which are sufficiently abundant elements; none of them is harmful to the environment even at large scale usage. Aim of this study is to fabricate CZTS solar cells through chemical spray pyrolysis (CSP) technique. At first the influence of various spray parameters like substrate temperature, spray rate, precursor ratio etc. on the opto-electronic properties of CZTS films will be studied in detail. Then the fabrication of CZTS/In2S3 hetero junctions and various ways to improve the performance parameters will be tried

Development of p-type transparent semiconducting oxides for thin film transistor applications

Semiconductor physics has developed significantly in the field of re- search and industry in the past few decades due to it’s numerous practical applications. One of the relevant fields of current interest in material science is the fundamental aspects and applications of semi- conducting transparent thin films. Transparent conductors show the properties of transparency and conductivity simultaneously. As far as the band structure is concerned, the combination of the these two properties in the same material is contradictory. Generally a trans- parent material is an insulator having completely filled valence and empty conduction bands. Metallic conductivity come out when the Fermi level lies within a band with a large density of states to provide high carrier concentration. Effective transparent conductors must nec- essarily represent a compromise between a better transmission within the visible spectral range and a controlled but useful electrical con- ductivity [1–6]. Generally oxides like In2O3, SnO2, ZnO, CdO etc, show such a combination. These materials without any doping are insulators with optical band gap of about 3 eV. To become a trans- parent conductor, these materials must be degenerately doped to lift the Fermi level up into the conduction band. Degenerate doping pro- vides high mobility of extra carriers and low optical absorption. The increase in conductivity involves an increase in either carrier concen- tration or mobility. Increase in carrier concentration will enhance the absorption in the visible region while increase in mobility has no re- verse effect on optical properties. Therefore the focus of research for new transparent conducting oxide (TCO) materials is on developing materials with higher carrier mobilities.

Properties of DLC films deposited by an oxyacetylene flame

Diamond-like carbon (DLC) films were obtained by spinning a tungsten carbide substrate at a high speed using an oxyacetylene flame. The films deposited at a typical experimental condition of substrate temperature of 810 degrees C, rotation of 600 rpm and 3 h deposition time, exhibited an uniform, very smooth, hard and glassy surface covering the entire exposed face of the substrate. These films were identified as DLC by their characteristic broad Raman spectra centered at 1554 cm(-1) and micro-Vicker's hardness > 3400 kg mm(-2). For substrate temperatures < 800 degrees C the film started losing the uniform glassy surface and the hardness deteriorated. For temperatures > 950 degrees C the film was still hard and shiny, but black in color. DLC films were also obtained in a wide range of speeds of rotation (300-750 rpm), as long as the temperature remained close to 850 degrees C. (C) 1999 Elsevier B.V. S.A. All rights reserved.

Photoelectrocatalytic treatment of p-nitrophenol using Ti/TiO2 thin-film electrode

The photoelectrochemical degradation of p-nitrophenol (PNP) was investigated using titanium dioxide thin-film photoelectrode. The effects of different supporting electrolytes, pH, applied potential and PNP concentration were examined and discussed. Complete photodegradation was obtained in perchlorate medium at pH 2 when the photoanode was biased at +1.0 V (versus SCE) during a 3-h experiment. Under these conditions, carbon removal of approximately 60% was achieved. (C) 2005 Elsevier B.V. All rights reserved.

Nanoporous of W/WO3 Thin Film Electrode Grown by Electrochemical Anodization Applied in the Photoelectrocatalytic Oxidation of the Basic Red 51 used in Hair Dye

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Ferroelectric and optical properties of Ba0.8Sr0.2TiO3 thin film

Barium strontium titanate (Ba0.8Sr0.2TiO3) thin films have been prepared on Pt/Ti/SiO2/Si substrates using a soft solution processing. X-ray diffraction and also micro-Raman spectroscopy showed that the Ba0.8Sr0.2TiO3 thin films exhibited a tetragonal structure at room temperature. The presence of Raman active modes was clearly shown at the 299 and 725 cm(-1) peaks. The tetragonal-to-cubic phase transition in the Ba0.8Sr0.2TiO3 thin films is broadened, and suppressed at about 35 degreesC, with a maximum dielectric constant of 948 (100 kHz). Electrical measurements for the prepared Ba0.8Sr0.2TiO3 thin films showed a remnant polarization (P-r) of 6.5 muC/cm(2), a coercive field (E-c) of 41 kV/cm, and good insulating properties. The dispersion of the refractive index is interpreted in terms of a single electronic oscillator at 6.97 eV. The direct band gap energy (E-g) and the refractive index (n) are estimated to be 3.3 eV and n = 2.27-2.10, respectively. (C) 2002 American Institute of Physics.

Effects of post-annealing on the dielectric properties of Au/BaTiO3/Pt thin film capacitors

Barium titanate thin films were prepared by the polymeric precursor method and deposited onto Pt/Ti/SiO2/Si substrates. X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FT-IR) and micro-Raman spectroscopy were used to investigate the formation of the BaTiO3 perovskite phase. Afterwards, the films were submitted to post-annealing treatments in oxygen and nitrogen atmospheres at 300 degreesC for 2 h, and had their dielectric properties measured. It was observed that the electric properties of the thin films are very sensitive to the nature of the post-annealing atmosphere. This study demonstrates that post-annealing in an oxygen atmosphere increases the dielectric relaxation phenomenon and that post-annealing in a nitrogen atmosphere produces a slight dielectric relaxation. (C) 2004 Elsevier B.V All rights reserved.

HMDSO plasma polymerization and thin film optical properties

Thin films were deposited from hexamethyldisiloxane (HMDSO) in a glow discharge supplied with radiofrequency (rf) power. Actino-metric optical emission spectroscopy was used to follow trends in the plasma concentrations of the species SiH (414.2 nm), CH (431.4 nm), CO (520.0 nm), and H (656.3 nm) as a function of the applied rf power (range 5 to 35 W). Transmission infrared spectroscopy (IRS) was employed to characterize the molecular structure of the polymer, showing the presence of Si-H, Si-O-Si, Si-O-C and C-H groups. The deposition rate, determined by optical interferometry, ranged from 60 to 130 nm/min. Optical properties were determined from transmission ultra violet-visible spectroscopy (UVS) data. The absorption coefficient α, the refractive index n, and the optical gap E04 of the polymer films were calculated as a function of the applied power. The refractive index at a photon energy of 1 eV varied from 1.45 to 1.55, depending on the rf power used for the deposition. The absorption coefficient showed an absorption edge similar to other non-crystalline materials, amorphous hydrogenated carbon, and semiconductors. For our samples, we define as an optical gap, the photon energy E04 corresponding to the energy at an absorption of 104 cm-1. The values of E04 decreased from 5.3 to 4.6 as the rf power was increased from 5 to 35 W. © 1995.

One-dimensional analytical model for oxide thin film growth on Ti metal layers during laser heating in air

This paper presents the theoretical and experimental results for oxide thin film growth on titanium films previously deposited over glass substrate. Ti films of thickness 0.1 μm were heated by Nd:YAG laser pulses in air. The oxide tracks were created by moving the samples with a constant speed of 2 mm/s, under the laser action. The micro-topographic analysis of the tracks was performed by a microprofiler. The results taken along a straight line perpendicular to the track axis revealed a Gaussian profile that closely matches the laser's spatial mode profile, indicating the effectiveness of the surface temperature gradient on the film's growth process. The sample's micro-Raman spectra showed two strong bands at 447 and 612 cm -1 associated with the TiO 2 structure. This is a strong indication that thermo-oxidation reactions took place at the Ti film surface that reached an estimated temperature of 1160 K just due to the action of the first pulse. The results obtained from the numerical integration of the analytical equation which describes the oxidation rate (Wagner equation) are in agreement with the experimental data for film thickness in the high laser intensity region. This shows the partial accuracy of the one-dimensional model adopted for describing the film growth rate. © 2001 Elsevier Science B.V.

Composite Thin Film Obtained Using Tetraethoxysilane and Aimed at VOCs Detection

The aim of this work was production of tetraethoxysilane (TEOS) plasma polymerized thin films and optimization of their physical-chemical characteristic for sensor development. The films were analyzed using several techniques. It was possible to produce composites (graphite clusters imbibed by silicon oxide film) made from only one reactant (TEOS). Deposition rate can vary significantly, reaching a maximum of 30 nm/min; cluster formation and their size widely depending on deposition parameters. The film surface was hydrophobic but can be wetted by organic compounds, probably due to carbon radicals. These films are good candidates for sensor development.

Efeito in vivo da deposição de filmes de DLC com e sem nanopartículas de prata sobre liga de titânio para utilização em próteses articulares

Pós-graduação em Biopatologia Bucal - ICT

Optimising thin-film solar cells by computer simulations

CIGS-Dünnschichtsolarzellen verbinden hohe Effizienz mit niedrigen Kosten und sind damit eine aussichtsreiche Photovoltaik-Technologie. Das Verständnis des Absorbermaterials CIGS ist allerdings noch lückenhaft und benötigt weitere Forschung. In dieser Dissertation werden Computersimulationen vorgestellt, die erheblich zum besseren Verständnis von CIGS beitragen. Es wurden die beiden Systeme Cu(In,Ga)Se2 und (Cu,In,Vac)Se betrachtet. Die Gesamtenergie der Systeme wurde in Clusterentwicklungen ausgedrückt, die auf der Basis von ab initio Dichtefunktionalrechnungen erstellt wurden. Damit war es möglich Monte Carlo (MC)-Simulationen durchzuführen. Kanonische MC-Simulationen von Cu(In,Ga)Se2 zeigen das temperaturabhängige Verhalten der In-Ga-Verteilung. In der Nähe der Raumtemperatur findet ein Übergang von einer geordneten zu einer ungeordneten Phase statt. Unterhalb separiert das System in CuInSe2 und CuGaSe2. Oberhalb existiert eine gemischte Phase mit inhomogen verteilten In- und Ga-Clustern. Mit steigender Temperatur verkleinern sich die Cluster und die Homogenität nimmt zu. Bei allen Temperaturen, bis hin zur Produktionstemperatur der Solarzellen (¼ 870 K), ist In-reiches CIGS homogener als Ga-reiches CIGS. Das (Cu,In,Vac)Se-System wurde mit kanonischen und großkanonischen MC-Simulationen untersucht. Hier findet sich für das CuIn5Se8-Teilsystem ein Übergang von einer geordneten zu einer ungeordneten Phase bei T0 = 279 K. Großkanonische Simulationen mit vorgegebenen Werten für die chemischen Potentiale von Cu und In wurden verwendet, um die Konzentrations- Landschaft und damit die sich ergebenden Stöchiometrien zu bestimmen. Stabilitätsbereiche wurden für stöchiometrisches CuInSe2 und für die Defektphasen CuIn5Se8 und CuIn3Se5 bei einer Temperatur von 174 K identifiziert. Die Bereiche für die Defektphasen sind bei T = 696 K verschwunden. Die Konzentrations-Landschaft reproduziert auch die leicht Cu-armen Stöchiometrien, die bei Solarzellen mit guten Effizienzen experimentell beobachtet werden. Die Simulationsergebnisse können verwendet werden, um den industriellen CIGS-Produktionspr

Ultra high frequency thin film saw devices

Durante los últimos años el flujo de datos en la transmisión que tiene lugar en los sistemas de comunicación ha aumentado considerablemente de forma que día a día se requieren más aplicaciones trabajando en un rango de frecuencias muy alto (3-30 GHz). Muchos de estos sistemas de comunicación incluyen dispositivos de onda acústica superficial (SAW) y por tanto se hace necesario el aumento de frecuencia a la que éstos trabajan. Pero este incremento de frecuencia de los dispositivos SAW no sólo es utilizado en los sistemas de comunicación, varios tipos de sensores, por ejemplo, aumentan su sensibilidad cuando la frecuencia a la que trabajan también lo hace. Tradicionalmente los dispositivos SAW se han fabricado sobre cuarzo, LiNbO3 y LiTaO3 principalmente. Sin embargo la principal limitación de estos materiales es su velocidad SAW. Además, debido a la alta temperatura a la que se depositan no pueden ser integrados en la tecnología de fabricación CMOS. El uso de la tecnología de capa delgada, en la que un material piezoeléctrico es depositado sobre un substrato, se está utilizando en las últimas décadas para incrementar la velocidad SAW de la estructura y poder obtener dispositivos trabajando en el rango de frecuencias requerido en la actualidad. Por otra parte, esta tecnología podría ser integrada en el proceso de fabricación CMOS. Durante esta tesis nos hemos centrado en la fabricación de dispositivos SAW trabajando a muy alta frecuencia. Para ello, utilizando la tecnología de capa delgada, hemos utilizado la estructura nitruro de aluminio (AlN) sobre diamante que permite conseguir velocidades SAW del sustrato que no se pueden alcanzar con otros materiales. El depósito de AlN se realizó mediante sputtering reactivo. Durante esta tesis se han realizado diferentes experimentos para optimizar dicho depósito de forma que se han obtenido los parámetros óptimos para los cuales se pueden obtener capas de AlN de alta calidad sobre cualquier tipo de sustrato. Además todo el proceso se realizó a baja temperatura para que el procesado de estos dispositivos pueda ser compatible con la tecnología CMOS. Una vez optimizada la estructura AlN/diamante, mediante litografía por haz de electrones se fabricaron resonadores SAW de tamaño nanométrico que sumado a la alta velocidad resultante de la combinación AlN/diamante nos ha permitido obtener dispositivos trabajando en el rango de 10-28 GHz con un alto factor de calidad y rechazo fuera de la banda. Estás frecuencias y prestaciones no han sido alcanzadas por el momento en resonadores de este tipo. Por otra parte, se han utilizado estos dispositivos para fabricar sensores de presión de alta sensibilidad. Estos dispositivos son afectados altamente por los cambios de temperatura. Se realizó también un exhaustivo estudio de cómo se comportan en temperatura estos resonadores, entre -250ºC y 250ºC (rango de temperaturas no estudiado hasta el momento) diferenciándose dos regiones una a muy baja temperatura en la que el dispositivo muestra un coeficiente de retraso en frecuencia (TCF) relativamente bajo y otra a partir de los -100ºC en la que el TCF es similar al observado en la bibliografía. Por tanto, durante esta tesis se ha optimizado el depósito de AlN sobre diamante para que sea compatible con la tecnología CMOS y permita el procesado de dispositivos trabajando a muy alta frecuencia con altas prestaciones para comunicaciones y sensores. ABSTRACT The increasing volume of information in data transmission systems results in a growing demand of applications working in the super-high-frequency band (3–30 GHz). Most of these systems work with surface acoustic wave (SAW) devices and thus there is a necessity of increasing their resonance frequency. Moreover, sensor application includes this kind of devices. The sensitivity of them is proportional with its frequency. Traditionally, quartz, LiNbO3 and LiTaO3 have been used in the fabrication of SAW devices. These materials suffer from a variety of limitations and in particular they have low SAW velocity as well as being incompatible with the CMOS technology. In order to overcome these problems, thin film technology, where a piezoelectric material is deposited on top of a substrate, has been used during the last decades. The piezoelectric/substrate structure allows to reach the frequencies required nowadays and could be compatible with the mass electronic production CMOS technology. This thesis work focuses on the fabrication of SAW devices working in the super-high-frequency range. Thin film technology has been used in order to get it, especially aluminum nitride (AlN) deposited by reactive sputtering on diamond has been used to increase the SAW velocity. Different experiments were carried out to optimize the parameters for the deposit of high quality AlN on any kind of substrates. In addition, the system was optimized under low temperature and thus this process is CMOS compatible. Once the AlN/diamond was optimized, thanks to the used e-beam lithography, nanometric SAW resonators were fabricated. The combination of the structure and the size of the devices allow the fabrication of devices working in the range of 10-28 GHz with a high quality factor and out of band rejection. These high performances and frequencies have not been reached so far for this kind of devices. Moreover, these devices have been used as high sensitivity pressure sensors. They are affected by temperature changes and thus a wide temperature range (-250ºC to 250ºC) study was done. From this study two regions were observed. At very low temperature, the temperature coefficient of frequency (TCF) is low. From -100ºC upwards the TCF is similar to the one appearing in the literature. Therefore, during this thesis work, the sputtering of AlN on diamond substrates was optimized for the CMOS compatible fabrication of high frequency and high performance SAW devices for communication and sensor application.

Tuning the functional properties of Silicon Carbide Thin Film and Nanowires

The present thesis has been devoted to the synthesis and investigation of functional properties of silicon carbide thin films and nanowires. The work took profit from the experience of the research group in the synthesis of 3C-SiC from vapour phase. 3C-SiC thin films Thin films heteroepitaxy on silicon substrates was carried out in a vapour phase epitaxy reactor. The initial efforts were committed to the process development in order to enhance the crystal quality of the epi-layer. The carbonization process and a buffer layer procedure were optimized in order to obtain good quality monocrystalline 3C-SiC layers. The films characterization was used not only to improve the entire process, but also to assess the crystalline quality and to identify the defects. Methyltrichlorosilane (MTS) was introduced during the synthesis to increase the growth rate and enhance crystalline quality. The effect of synthesis parameters such as MTS flow and process temperature was studied in order to promote defect density reduction and the release of the strain due to lattice mismatch between 3C-SiC and silicon substrate. In-growth n-type doping was implemented using a nitrogen gas line and the effect of different synthesis parameters on doping level was studied. Raman measurements allowed a contactless characterization and evaluation of electrically active dopant. The effect of MTS on nitrogen incorporation was investigated and a promotion of dopant concentration together with a higher growth rate were demonstrated. This result allows to obtain higher doping concentrations without deteriorating crystal quality in 3C-SiC and, to the best of our knowledge, it has never been demonstrated before. 3C-SiC nanowires Core-shell SiC-SiO2 nanowires were synthesized using a chemical vapour deposition technique in an open tube configuration reactor on silicon substrates. Metal catalyst were used to promote a uniaxial growth and a dense bundle of nanowires 100 µm long and 60 nm thick was obtained. Substrate preparation was found to be fundamental in order to obtain a uniform nanowire density. Morphological characterization was carried out using scanning electron microscopy and the analysis of structural, compositional, optical properties is reported.

TILTED COLUMNAR THIN FILM COATINGS WITH ANISOTROPIC LIGHT SCATTERING PROPERTIES FOR SOLAR ENERGY APPLICATIONS

The main goal of this thesis is to show the versatility of glancing angle deposition (GLAD) thin films in applications. This research is first focused on studying the effect of select deposition variables in GLAD thin films and secondly, to demonstrate the flexibility of GLAD films to be incorporated in two different applications: (1) as a reflective coating in low-level concentration photovoltaic systems, and (2) as an anode structure in dye-sensitized solar cells (DSSC). A particular type of microstructure composed of tilted micro-columns of titanium is fabricated by GLAD. The microstructures form elongated and fan-like tilted micro-columns that demonstrate anisotropic scattering. The thin films texture changes from fiber texture to tilted fiber texture by increasing the vapor incidence angle. At very large deposition angles, biaxial texture forms. The morphology of the thin films deposited under extreme shadowing condition and at high temperature (below recrystallization zone) shows a porous and inclined micro-columnar morphology, resulting from the dominance of shadowing over adatom surface diffusion. The anisotropic scattering behavior of the tilted Ti thin film coatings is quantified by bidirectional reflectance distribution function (BRDF) measurements and is found to be consistent with reflectance from the microstructure acting as an array of inclined micro-mirrors that redirect the incident light in a non-specular reflection. A silver-coating of the surface of the tilted-Ti micro-columns is performed to enhance the total reflectance of the Ti-thin films while keeping the anisotropic scattering behavior. By using such coating is as a booster reflector in a laboratory-scale low-level concentration photovoltaic system, the short-circuit current of the reference silicon solar cell by 25%. Finally, based on the scattering properties of the tilted microcolumnar microstructure, its scattering effect is studied as a part of titanium dioxide microstructure for the anode in DSSCs. GLAD-fabricated TiO2 microstructures for the anode in a DSSC, consisting of vertical micro-columns, and combined vertical topped with tilted micro-columns are compared. The solar cell with the two-part microstructure shows the highest monochromatic incident photon to current efficiency with 20% improvement compared to the vertical microstructure, and the efficiency of the cell increases from 1.5% to 2% due to employing the scattering layer.