Cette thèse est consacrée au silicium polymorphe hydrogéné (pm-Si:H). Elle porte tout d'abord sur une étude du pm-Si :H puis sur une étude des cellules photovoltaïques fabriquées à partir de ce matériau. Le pm-Si:H est formé de couches minces nanostructurées et peut être déposé par PECVD conventionnelle. Les effets des différents paramètres de dépôt (mélanges gazeux, pression, puissance RF, température du substrat) sur les propriétés du matériau ont été étudiés pour optimiser sa qualité. La caractérisation des couches a été un enjeu primordial. Pour cela, nous avons choisi de combiner une palette très large de méthodes de caractérisation (ellipsomètrie spectroscopique, exodiffusion d'hydrogène, SIMS, FTIR, AFM, etc...). A cause de la contribution des nanoparticules de silicium dans le plasma, la nature du dépôt du pm-Si:H montre la différence contrairement au a-Si:H pour lequel le dépôt se fait par le biais de radicaux ionisés. L'étude des conditions du procédé nous a conduit à fabriquer des cellules solaires d'un rendement initial de 9.22 % avec un facteur de forme élevé (74.1), mais aussi de démontrer des effets de vieillissement inhabituels, tels que i) une dégradation initiale rapide, ii) une dégradation irréversible, et iii) de grands changements structuraux macroscopiques. Nous avons découvert que le principal problème se situe entre le substrat et la couche mince de silicium. L'hydrogène moléculaire diffuse et s'accumule à l'interface entre le substrat et la couche mince, ce qui introduit un délaminage local qui a pour conséquence une dégradation initiale rapide des performances des cellules. Nous avons trouvé que sous éclairement une structure PIN facilite l'accumulation d'hydrogène et le délaminage à l'interface entre le substrat et la couche dopée p. Cependant, l'utilisation d'une structure NIP empêche l'accumulation d'hydrogène et le délaminage. Cela nous a permis de fabriquer des cellules solaires pm-Si:H de structure NIP d'un rendement stable de 8.43 %, mais aussi de démontrer une degradation minimale (10 %) après un vieillissement de 500 heures.

Passivation of the crystalline silicon (c-Si) wafer surface and decreasing the number of interface defects are basic requirements for development of high efficiency a-Si:H/c-Si heterojunction solar cells. Surface passivation is generally achieved by development of detailed silicon wafer cleaning processes and the optimization of PECVD parameters for the deposition of intrinsic hydrogenated amorphous silicon layer. a-Si:H layers are grown in UHV-PECVD system. Solar cells were deposited on the p type Cz-silicon substrates in the structure of Al front contact/a-Si:H(n)/a-Si:H(i)/c-Si(p)/Al back contact. Solar cell parameters were determined under standard test conditions namely, using 1000 W/m2, AM 1.5G illumination at 25 oC. Growth of (i) a-Si:H, films on the clean wafer surface was investigated as a function of substrate temperature, RF power density, gas flow rate, hydrogen dilution ratio and deposition time and was characterized using SEM, HRTEM, AFM, SE, ATR-FTIR and I/V measurements. Structural properties of the films deposited on silicon wafer surface are directly effective on the solar cell efficiency. Morphological characterization of the grown films on the crystalline surface was found to be very complex depending on the deposition parameters and may even change during the deposition time. At 225 oC substrate temperature, at the beginning of the deposition, (i) a-Si:H films was found grown in epitaxial structure, followed by a simultaneous growth of crystalline and amorphous structure, and finally transforming to complete amorphous structure. Despite this complex structure, an efficiency of 9.2% for solar cells with total area of 72 cm2 was achieved. In this cell structure, TCO and back surface passivation do not exist. In the

Nanocrystalline silicon (nc-Si:H) is an attractive material for fabrication of low temperature, large area electronic devices due to superior properties versus the traditional amorphous silicon (a-Si:H) and polycrystalline silicon (polySi). Nanocrystalline silicon possess higher carrier mobility and better stability than a-Si:H and better device uniformity and lower fabrication cost than polySi. This thesis looks at the application of nc-Si:H material in fabricating two different diodes used for rectification and light generation. Optimization of n-type nc-Si:H deposited via plasma enhanced vapor chemical deposition (PECVD) was achieved through adjusting the concentration ratio of phosphine (PH3) dopant source gas versus silane (SiH4). Optimizing for dark conductivity, n+ nc-Si:H material with dark conductivity of 25.3 S/cm was deposited using a [PH3]/[SiH4] ratio of 2%. Using the optimized n+ nc-Si:H film, a p-n junction diode utilizing an undoped and an n+ nc-Si:H layers was fabricated designed for rectification use. The diode achieved a current density of 1 A/cm2, an ON/OFF current ratio of 106 and a non-ideality factor of 1.9. When the 200*200µm2 nc-Si:H diodes were employed in a full-wave bridge rectifier, a 2.6 V direct current voltage could be generated from an input sine wave signal with amplitude 2 VRMS and frequency of 13.56 MHz, thus demonstrating the feasibility of using nc-Si:H to fabricate diodes for using on radio frequency identification (RFID) tags. Nanocrystalline silicon was also applied in fabrication of a light emitting diode (LED), by utilizing the nanocrystals embedded inside nc-Si:H, inside which recombination of carriers could result in radiative recombination. By limiting the deposition time of the nc-Si:H, 10 – 20 nm thick films of nc-Si:H were used to fabrication a p-i-n structure LED with average crystallite size between 7.5 nm to 13.7 nm corresponding to an theoretical emission wavelengths in the near infrared region of 875 nm to 963 nm. Unfortunately, light emission from the nc-Si:H LED were not detected using two different methods. Undetectable emission could have been due to a combination of low recombination efficiency due to carriers recombining in defects in the a-Si:H matrix and majority of current travelling completely through the nc-Si:H films without recombining. A study of the thin intrinsic nc-Si:H films used in the LED was carried out. The thin films were found to be highly defected, with large variation in current-voltage relationship measured and hysteresis observed in the IV characteristic. Annealing the nc-Si:H films were found to cause a drop in conductivity explained through hydrogen effusion from the nc-Si:H film during annealing. Passivation of defects was achieved through the use of hydrogen plasma which resulted in a lowering of activation energy measured in the film. Oxygen plasma was also trialed for passivating the nc-Si:H film but the effect was only a temporary increase in current conduction attributed to oxygen ions chemisorbing temporarily at the film surface.

Nanocrystalline silicon (nc-Si:H) is an attractive material for fabrication of low temperature, large area electronic devices due to superior properties versus the traditional amorphous silicon (a-Si:H) and polycrystalline silicon (polySi). Nanocrystalline silicon possess higher carrier mobility and better stability than a-Si:H and better device uniformity and lower fabrication cost than polySi. This thesis looks at the application of nc-Si:H material in fabricating two different diodes used for rectification and light generation. Optimization of n-type nc-Si:H deposited via plasma enhanced vapor chemical deposition (PECVD) was achieved through adjusting the concentration ratio of phosphine (PH3) dopant source gas versus silane (SiH4). Optimizing for dark conductivity, n+ nc-Si:H material with dark conductivity of 25.3 S/cm was deposited using a [PH3]/[SiH4] ratio of 2%. Using the optimized n+ nc-Si:H film, a p-n junction diode utilizing an undoped and an n+ nc-Si:H layers was fabricated designed for rectification use. The diode achieved a current density of 1 A/cm2, an ON/OFF current ratio of 106 and a non-ideality factor of 1.9. When the 200*200µm2 nc-Si:H diodes were employed in a full-wave bridge rectifier, a 2.6 V direct current voltage could be generated from an input sine wave signal with amplitude 2 VRMS and frequency of 13.56 MHz, thus demonstrating the feasibility of using nc-Si:H to fabricate diodes for using on radio frequency identification (RFID) tags. Nanocrystalline silicon was also applied in fabrication of a light emitting diode (LED), by utilizing the nanocrystals embedded inside nc-Si:H, inside which recombination of carriers could result in radiative recombination. By limiting the deposition time of the nc-Si:H, 10 – 20 nm thick films of nc-Si:H were used to fabrication a p-i-n structure LED with average crystallite size between 7.5 nm to 13.7 nm corresponding to an theoretical emission wavelengths in the near infrared region of 875 nm to 963 nm. Unfortunately, light emission from the nc-Si:H LED were not detected using two different methods. Undetectable emission could have been due to a combination of low recombination efficiency due to carriers recombining in defects in the a-Si:H matrix and majority of current travelling completely through the nc-Si:H films without recombining. A study of the thin intrinsic nc-Si:H films used in the LED was carried out. The thin films were found to be highly defected, with large variation in current-voltage relationship measured and hysteresis observed in the IV characteristic. Annealing the nc-Si:H films were found to cause a drop in conductivity explained through hydrogen effusion from the nc-Si:H film during annealing. Passivation of defects was achieved through the use of hydrogen plasma which resulted in a lowering of activation energy measured in the film. Oxygen plasma was also trialed for passivating the nc-Si:H film but the effect was only a temporary increase in current conduction attributed to oxygen ions chemisorbing temporarily at the film surface.

A series of experiments was carried out to compare the structural and electronic properties of intrinsic nanocrystalline silicon (nc-Si:H) thin films deposited via continuous wave (cw) and pulsed (p)-PECVD at 150°C substrate temperature. Working at this temperature allows for the easy transfer of film recipes from glass to plastic substrates in the future. During the p-PECVD process the pulsing frequency was varied from 0.2 to 50 kHz at 50% duty cycle. Approximately 15% drop in the deposition rate was observed for the samples fabricated in p-PECVD compared to cw-PECVD. The optimum crystallinity and photo (σph) and dark conductivity (σD) were observed at 5 kHz pulsing frequency, with ~10% rise in crystallinity and about twofold rise in the σph and σD compared to cw-PECVD. However, for both the cw and p-PECVD nc-Si:H films, the observed σph and σD were one to two orders and three orders of magnitude higher respectively than those reported in literature. The average activation energy (EA) of 0.16 ∓ 0.01 eV for nc-Si:H films deposited using p-PECVD confirmed the presence of impurities, which led to the observation of the unusually high conductivity values. It was considered that the films were contaminated by the impurity atoms after they were exposed to air. Following the thin film characterization procedure, the optimized nc-Si:H film recipes, from cw and p-PECVD, were used to fabricate the absorber layer of thin film solar cells. The cells were then characterized for J-V and External Quantum Efficiency (EQE) parameters. The cell active layer fabricated from p-PECVD demonstrated higher power conversion efficiency (η) and a maximum EQE of 1.7 ∓ 0.06 % and 54.3% respectively, compared to 1.00 ∓ 0.04 % and 48.6% respectively for cw-PECVD. However, the observed η and EQE of both the cells were lower than a reported nc-Si:H cell fabricated via p-PECVD with similar absorber layer thickness. This was due to the poor Short-circuit Current Density (Jsc), Open-circuit Voltage (Voc), and Fill Factor (FF) of the cw and p-PECVD cells respectively, compared to the reported cell. The low Jsc resulted from the poor photocarrier collection at longer and shorter wavelengths and high series resistance (Rseries). On the other hand, the low Voc stemmed from the low shunt resistance (Rsh). It was inferred that the decrease in the Rsh occurred due to the inadequate electrical isolation of the individual cells and the contact between the n – layer and the front TCO contact at the edge of the p-i-n deposition area. Additionally, the net effect of the high Rseries and the low Rsh led to a decrease in the FF of the cells.

Solar photovoltaic has become one of the potential solutions for current energy needs and for combating greenhouse gas emissions. The photovoltaics (PV) industry is booming, with a yearly growth rate well in excess of 30% over the last decade. This explosive growth has been driven by market development programs to accelerate the deployment of sustainable energy options and rapidly increasing fossil fuel prices. Currently, the PV market is based on silicon wafer solar cells (thick cells of around 150–300 μm made of crystalline silicon). This technology, classified as the first-generation of photovoltaic cells. The second generation of photovoltaic materials is based on the introduction of thin film layers of semiconductor materials. Unfortunately, the conversion efficiency of the current PV systems is low despite the lower manufacturing costs. Nevertheless, to achieve highly efficient silicon solar cell devices, the development of new high quality materials in terms of structure and electrical properties is a must to overcome the issues related to amorphous silicon (a -Si:H) degradation. Meanwhile, to remain competitive with the conventional energy sources, cost must be taken into consideration. Moreover, novel approaches combined with conventional mature silicon solar cell technology can boost the conventional efficiency and break its maximum limits. In our approach, we set to achieve efficient, stable and affordable silicon solar cell devices by focusing on the development of a new device made of epitaxial films. This new device is developed using new epitaxial growth phosphorous and/or boron doped layers at low processing temperature using plasma enhanced chemical vapor deposition (PECVD). The junction between the phosphorous or boron-doped epitaxial film of the device is formed between the film and the p or n-type crystalline silicon (c-Si) substrate, giving rise to (n epi-Si/p c-Si device or p epi-Si/n c-Si device), respectively. Different processing conditions have been fully characterized and deployed for the fabrication of different silicon solar cells architectures. The high quality epitaxial film (up to 400 nm) was used as an emitter for an efficient stable homojunction solar cell. Extensive analysis of the developed fine structure material, using high resolution transmission electron microscope (HRTEM), showed that hydrogen played a crucial role in the epitaxial growth of highly phosphorous doped silicon films. The main processing parameters that influenced the quality of the structure were; radio frequency (RF) power density, the processing chamber pressure, the substrate temperature, the gas flow rate used for deposition of silicon films, and hydrogen dilution. The best result, in terms of structure and electrical properties, was achieved at intermediate hydrogen dilution (HD) regime between 91 and 92% under optimized deposition conditions of the rest of the processing parameters. The conductivity and the carrier mobility values are good indicators of the electrical quality of the silicon (Si) film and can be used to investigate the structural quality indirectly. The electrical conductivity analyses using spreading resistance profile (SRP), through the detection of active carriers inside the developed films, are presented in details for the developed epitaxial film under the optimized processing conditions. Measurements of the active phosphorous dopant revealed that, the film has a very high active carrier concentration of an average of 5.0 x1019 cm-3 with a maximum value of 6.9 x 1019 cm-3 at the interface between substrate and the epitaxial film. The observed higher concentration of electrically active P atoms compared to the total phosphorus concentration indicates that more than half of dopants become incorporated into substitutional positions. Highly doping efficiency ηd of more than 50 % was calculated from both secondary ion mass spectroscopy (SIMS) and SRP analysis. A variety of proposed structures were fabricated and characterized on planar, textured, and under different deposition temperatures. Detailed studies of the photovoltaic properties of the fabricated devices were carried out using epitaxial silicon films. The results of these studies confirmed that the measured open circuit voltage (Voc) of the device ranged between 575 and 580 mV with good fill factor (FF) values in the range of 74-76 %. We applied the rapid thermal process (RTP) for a very short time (60 s) at moderate temperature of 750oC to enhance the photovoltaic properties of the fabricated device. The following results were achieved, the values of Voc, and the short circuit current (Isc) were 598 mV and 27.5 mA respectively, with a fill factor value of up to 76 % leading to an efficiency of 12.5 %. Efficiency enhancement by 13.06 % was achieved over the reference cell which was prepared without using RTP. Another way to increase the efficiency of the fabricated device is to reduce the reflections from its polished substrate. This was achieved by utilizing the light trapping technique that transforms the reflective polished surface into a pyramidical texturing using alkaline solutions. Further enhancements of both Voc and Isc were achieved with values of 612 mV and 31mA respectively, and a fill factor of 76 % leading to an increase in the efficiency by up to 13.8 %. A noticeable efficiency enhancement by ~20 % over the reference cell is reported for the developed devices on the textured surfaces. Moreover, the efficiency of the fabricated epitaxial silicon solar cells can be boosted by the deployment of silicon nanocrystals (Si NCs) on the top surface of the fabricated devices. In the course of this PhD research we found a way to achieve this by depositing a thin layer of Si NCs, embedded in amorphous silicon matrix, on top of the epitaxial film. Structural analysis of the deposited Si NCs was performed. It is shown from the HRTEM analysis that the developed Si NCs, are randomly distributed, have a spherical shape with a radius of approximately 2.5 nm, and are 10-20 nm apart in the amorphous silicon matrix. Based on the size of the developed Si NCs, the optical band gap was found to be in the region of 1.8-2.2 eV. Due to the incorporation of Si NCs layer a noticeable enhancement in the Isc was reported.

Amorphous Silicon alloy thin films were deposited by plasma enhanced chemical vapor deposition technique. In order to make optoelectronic measurements, diode structures were fabricated by depositing transparent metal electrodes. Theoretical background of localized density of states in the mobility gap and photocurrent mechanisms has been revisited. In light of this, time of flight technique, using transient photocurrent, was utilized to determine mobility in extended states and characteristic energy of tail states in the film. The actual density of states (DOS) in the mobility gap of the deposited films was determined by using absorption coefficients obtained via constant photocurrent measurements. Finally, adverse effects of small Oxygen incorporation on mobility and DOS were observed.

Novel electrophoresis devices for protein and DNA separation and identification have been presented and studied. The new device utilizes a contact resistance change detection method to identify protein and DNA in situ. The devices were prepared with a microelectronic micromechanical system (MEMS) fabrication method. Three model proteins and six DNA fragments were separated by polyacrylamide gel microchannel electrophoresis and surface electrophoresis. The detection of the proteins or DNA fragments was accomplished using the contact resistance increase of the detection electrode due to adsorption of the separated biomolecules. Key factors for the success of these devices were the optimization of fabrication process and the enhancement of detection efficiency of the devices. Parameters, such as microchannel configuration, size of electrode, and affinity of protein or polyacrylamide gel to the microchannel sidewall and bottom surface were explored in detail. For DNA analysis, the affinity to the bottom surface of the channel was critical. The surface modification method was used to enhance the efficiency of the microchannel surface electrophoresis device. The adsorption of channel separated protein and DNA on the detection electrode was confirmed with the electron spectroscopy for chemical analysis (ESCA) method. The electrical current (I) from the protein microchannel electrophoresis was usually noisy and fluctuated at the early stage of the electrophoresis process. In order to remove the current perturbation, an amorphous silicon (a-Si:H) thin film transistor (TFT) was connected to the microchannel device. The self-aligned a-Si:H TFT was fabricated with a two-photomask process. The result shows that the attachment of the TFT successfully suppressed the current fluctuation of the microchannel electrophoresis process. In summary, protein and DNA samples were effectively separated and detected with the novel TFT-driven or surface microchannel electrophoresis device.

Die Arbeit beschreibt die Entwicklung von plasmaunterstützten CVD-Prozessen zur Abscheidung ultradünner (≤10 nm) wolframbasierter Diffusionsbarrieren für die Kupfermetallisierung in integrierten Schaltkreisen. Es wird ein PECVD-Prozess mit der Gaschemie WF₆/N₂/H₂/(Ar) vorgestellt, mit dem amorphe und leitfähige WN_x-Schichten abgeschieden werden. Dabei wird der Prozess umfassend charakterisiert (z.B. Rate, Homogentität, Kantenbedeckung) und die Einflüsse von Parameteränderungen (besonders Gasflussvariationen) auf die Schichteigenschaften untersucht. Ausgewählte Schichtzusammensetzungen, welche den Barriereanforderungen hinsichtlich geringen elektrischen Widerstandes und sehr guter Homogenität über den Wafer entsprachen, wurden im für den praktischen Einsatz relevanten Schichtdickenbereich von 10 nm eingehender untersucht. Dies erfolgte einerseits mikrostrukturell mit GI-XRD, GDOES und TEM zu Schichtzusammensetzung, Kristallisationsverhalten und Schichtstabilität unter Wärmebehandlung in verschiedenen Medien in direktem Kontakt zu Kupfer. Zudem erfolgte die Beurteilung der Diffusionswirkung der WN_x-Schichten mit elektrischen Messverfahren (CV, TVS) über MIS-Strukturen. Auf Grundlage des WN_x-Prozesses wird durch Zugabe von Silan zur Prozessgaschemie die Möglichkeit der Abscheidung einer ternären Zusammensetzung WSiN untersucht. Es erfolgt eine ausführliche Auswertung der Literatur zu verschiedenen WSiN-Abscheideprozessen und eine Wertung der beschriebenen ternären Zusammensetzung in Bezug auf geringen elektrischen Widerstand und thermischer Stabilität. Mit den daraus gewonnenen Erkenntnissen kann ein ternärer Zusammensetzungsbereich von Me-Si-N eingegrenzt werden, der sowohl amorphe Mikrostruktur, niedrigen elektrischen Widerstand und hohe thermische Stabilität garantiert. Der entwickelte PECVD-Prozess mit Silan führte zu einer Si-stabilisierten WN_x-Schicht mit nur geringfügig höherer thermischer Stabilität aber deutlich höheren elektrischen Widerstand. Es wird die Frage diskutiert, ob die Entwicklung einer amorphen ternären Verbindung mit höherer thermischer Stabilität aber zu Lasten des elektrischen Widerstandes notwendig ist, wenn für das Stoffsystem schon eine amorphe binäre Zusammensetzung existiert, die die Anforderungen einer Diffusionsbarriere hinsichtlich hoher Leitfähigkeit und ausreichend hoher thermischer Stabilität erfüllt.

Universiẗat, Diss--Bayreuth, 2008.