Fabrication, Electrical Characterization and Simulation of Thin Film Solar Cells: CdTe and CIGS Materials

CdTe and Cu(In,Ga)Se2 (CIGS) thin film solar cells are fabricated, electrically characterized and modelled in this thesis. We start from the fabrication of CdTe thin film devices where the R.F. magnetron sputtering system is used to deposit the CdS/CdTe based solar cells. The chlorine post-growth treatment is modified in order to uniformly cover the cell surface and reduce the probability of pinholes and shunting pathways creation which, in turn, reduces the series resistance. The deionized water etching is proposed, for the first time, as the simplest solution to optimize the effect of shunt resistance, stability and metal-semiconductor inter-diffusion at the back contact. In continue, oxygen incorporation is proposed while CdTe layer deposition. This technique has been rarely examined through R.F sputtering deposition of such devices. The above experiments are characterized electrically and optically by current-voltage characterization, scanning electron microscopy, x-ray diffraction and optical spectroscopy. Furthermore, for the first time, the degradation rate of CdTe devices over time is numerically simulated through AMPS and SCAPS simulators. It is proposed that the instability of electrical parameters is coupled with the material properties and external stresses (bias, temperature and illumination). Then, CIGS materials are simulated and characterized by several techniques such as surface photovoltage spectroscopy is used (as a novel idea) to extract the band gap of graded band gap CIGS layers, surface or bulk defect states. The surface roughness is scanned by atomic force microscopy on nanometre scale to obtain the surface topography of the film. The modified equivalent circuits are proposed and the band gap graded profiles are simulated by AMPS simulator and several graded profiles are examined in order to optimize their thickness, grading strength and electrical parameters. Furthermore, the transport mechanisms and Auger generation phenomenon are modelled in CIGS devices.

Röntgenabsorptionsspektroskopie und magnetischer Röntgenzirkulardichroismus an dünnen Heusler-Filmen

Verbindungen aus nicht ferromagnetischen Bestandteilen, die ferromagnetische Eigenschaf-ten zeigen, sind seit Anfang des 20. Jahrhunderts bekannt und werden nach ihrem Entdecker als Heusler-Verbindungen bezeichnet. Seitdem haben sie nichts von ihrer Faszination eingebüßt, besitzen sie doch eine Fülle besonderer Eigenschaften mit Anwendungen z.B. in der Spintronik.rnAuf der Suche nach geeigneten Legierungen ist es wünschenswert, zunächst grundlegende Eigenschaften wie das magnetische Moment elementspezifisch bestimmen zu können. Hierfür sind Methoden wie Röntgenabsorptionsspektroskopie und magnetischer Röntgenzirkulardichroismus (XAS/XMCD) prädestiniert.rnIm Rahmen dieser Arbeit wurde eine Apparatur entwickelt, mit deren Hilfe XAS- und XMCD-Messungen an dünnen Heusler-Filmen durchgeführt werden können. Da Grenzflächeneigenschaften von besonderem Interesse sind, wurde der experimentelle Aufbau so gewählt, dass gleichzeitig Volumen und Oberflächeneigenschaften untersucht werden können. Durch Vergleich dieser Messdaten erhält man Zugang zu den Grenzflächeneigenschaften.rnSo konnte mit XAS-Messungen nachgewiesen werden, dass sich die chemischen Eigenschaften an der Grenzfläche mancher Filme von denen im Volumen des Films unterscheiden (Oxidation bzw. Interdiffusion der Abdeckschicht). Auch stöchiometrische Unterschiede zwischen Oberfläche und Volumen konnten so identifiziert werden.rnMit Hilfe von XMCD-Messungen wurden elementspezifische magnetische Momente bestimmt und mit theoretischen Vorhersagen verglichen. Auch hierbei konnten Oberflächen- und Volumenmomente miteinander verglichen werden. So wurde z.B. unter Verwendung einer Schichtserie die Anzahl magnetischer Totlagen an beiden Grenzflächen bestimmt. Diese Informationen sind wichtig, um die Qualität dünner Filme steigern zu können.rnDes Weiteren war es auch möglich, temperaturabhängige Änderungen in der Ni2MnGa Zustandsdichte, die von der Theorie vorhergesagt wurden, in den XAS-Spektren nachzuweisen. Schließlich wurde noch eine Methode entwickelt, die es erlaubt, unter bestimmten Voraussetzungen auf die partielle unbesetzte Zustandsdichte (PDOS) zu schließen. Dies liefert wichtige Hinweise auf Lage und Breite der bisher nur theoretisch vorhergesagten Bandlücke. Es ist mit der hier vorgestellten Methode nicht möglich, die gesamte PDOS für alle Elemente zu vermessen, doch können so relativ leicht vielversprechende Kandidaten für weitere Untersuchungen gefunden werden.rn

Nanocrystalline Silicon Based Films for Renewable Energy Applications

The present thesis is focused on the study of innovative Si-based materials for third generation photovoltaics. In particular, silicon oxi-nitride (SiOxNy) thin films and multilayer of Silicon Rich Carbide (SRC)/Si have been characterized in view of their application in photovoltaics. SiOxNy is a promising material for applications in thin-film solar cells as well as for wafer based silicon solar cells, like silicon heterojunction solar cells. However, many issues relevant to the material properties have not been studied yet, such as the role of the deposition condition and precursor gas concentrations on the optical and electronic properties of the films, the composition and structure of the nanocrystals. The results presented in the thesis aim to clarify the effects of annealing and oxygen incorporation within nc-SiOxNy films on its properties in view of the photovoltaic applications. Silicon nano-crystals (Si NCs) embedded in a dielectric matrix were proposed as absorbers in all-Si multi-junction solar cells due to the quantum confinement capability of Si NCs, that allows a better match to the solar spectrum thanks to the size induced tunability of the band gap. Despite the efficient solar radiation absorption capability of this structure, its charge collection and transport properties has still to be fully demonstrated. The results presented in the thesis aim to the understanding of the transport mechanisms at macroscopic and microscopic scale. Experimental results on SiOxNy thin films and SRC/Si multilayers have been obtained at macroscopical and microscopical level using different characterizations techniques, such as Atomic Force Microscopy, Reflection and Transmission measurements, High Resolution Transmission Electron Microscopy, Energy-Dispersive X-ray spectroscopy and Fourier Transform Infrared Spectroscopy. The deep knowledge and improved understanding of the basic physical properties of these quite complex, multi-phase and multi-component systems, made by nanocrystals and amorphous phases, will contribute to improve the efficiency of Si based solar cells.

Studies of degradation of organic solar cell materials using electrical scanning probe microscopy

Intense research is being done in the field of organic photovoltaics in order to synthesize low band-gap organic molecules. These molecules are electron donors which feature in combination with acceptor molecules, typically fullerene derivarntives, forming an active blend. This active blend has phase separated bicontinuous morphology on a nanometer scale. The highest recorded power conversionrnefficiencies for such cells have been 10.6%. Organic semiconductors differ from inorganic ones due to the presence of tightly bonded excitons (electron-hole pairs)resulting from their low dielectric constant (εr ≈2-4). An additional driving force is required to separate such Frenkel excitons since their binding energy (0.3-1 eV) is too large to be dissociated by an electric field alone. This additional driving force arises from the energy difference between the lowest unoccupied molecular orbital (LUMO) of the donor and the acceptor materials. Moreover, the efficiency of the cells also depends on the difference between the highest occupied molecular orbital (HOMO) of the donor and LUMO of the acceptor. Therefore, a precise control and estimation of these energy levels are required. Furthermore any external influences that change the energy levels will cause a degradation of the power conversion efficiency of organic solar cell materials. In particular, the role of photo-induced degradation on the morphology and electrical performance is a major contribution to degradation and needs to be understood on a nanometer scale. Scanning Probe Microscopy (SPM) offers the resolution to image the nanometer scale bicontinuous morphology. In addition SPM can be operated to measure the local contact potential difference (CPD) of materials from which energy levels in the materials can be derived. Thus SPM is an unique method for the characterization of surface morphology, potential changes and conductivity changes under operating conditions. In the present work, I describe investigations of organic photovoltaic materials upon photo-oxidation which is one of the major causes of degradation of these solar cell materials. SPM, Nuclear Magnetic Resonance (NMR) and UV-Vis spectroscopy studies allowed me to identify the chemical reactions occurring inside the active layer upon photo-oxidation. From the measured data, it was possible to deduce the energy levels and explain the various shifts which gave a better understanding of the physics of the device. In addition, I was able to quantify the degradation by correlating the local changes in the CPD and conductivity to the device characteristics, i.e., open circuit voltage and short circuit current. Furthermore, time-resolved electrostatic force microscopy (tr-EFM) allowed us to probe dynamic processes like the charging rate of the individual donor and acceptor domains within the active blend. Upon photo-oxidation, it was observed, that the acceptor molecules got oxidized first preventing the donor polymer from degrading. Work functions of electrodes can be tailored by modifying the interface with monomolecular thin layers of molecules which are made by a chemical reaction in liquids. These modifications in the work function are particularly attractive for opto-electronic devices whose performance depends on the band alignment between the electrodes and the active material. In order to measure the shift in work function on a nanometer scale, I used KPFM in situ, which means in liquids, to follow changes in the work function of Au upon hexadecanethiol adsorption from decane. All the above investigations give us a better understanding of the photo-degradation processes of the active material at the nanoscale. Also, a method to compare various new materials used for organic solar cells for stability is proposed which eliminates the requirement to make fully functional devices saving time and additional engineering efforts.

HCl gas gettering of 3d transition metals for crystalline silicon solar cell concepts

In order to reduce the costs of crystalline silicon solar cells, low-cost silicon materials like upgraded metallurgical grade (UMG) silicon are investigated for the application in the photovoltaic (PV) industry. Conventional high-purity silicon is made by cost-intensive methods, based on the so-called Siemens process, which uses the reaction to form chlorosilanes and subsequent several distillation steps before the deposition of high-purity silicon on slim high-purity silicon rods. UMG silicon in contrast is gained from metallurgical silicon by a rather inexpensive physicochemical purification (e.g., acid leaching and/or segregation). However, this type of silicon usually contains much higher concentrations of impurities, especially 3d transition metals like Ti, Fe, and Cu. These metals are extremely detrimental in the electrically active part of silicon solar cells, as they form recombination centers for charge carriers in the silicon band gap. This is why simple purification techniques like gettering, which can be applied between or during solar cell process steps, will play an important role for such low-cost silicon materials. Gettering in general describes a process, whereby impurities are moved to a place or turned into a state, where they are less detrimental to the solar cell. Hydrogen chloride (HCl) gas gettering in particular is a promising simple and cheap gettering technique, which is based on the reaction of HCl gas with transition metals to form volatile metal chloride species at high temperatures.rnThe aim of this thesis was to find the optimum process parameters for HCl gas gettering of 3d transition metals in low-cost silicon to improve the cell efficiency of solar cells for two different cell concepts, the standard wafer cell concept and the epitaxial wafer equivalent (EpiWE) cell concept. Whereas the former is based on a wafer which is the electrically active part of the solar cell, the latter uses an electrically inactive low-cost silicon substrate with an active layer of epitaxially grown silicon on top. Low-cost silicon materials with different impurity grades were used for HCl gas gettering experiments with the variation of process parameters like the temperature, the gettering time, and the HCl gas concentration. Subsequently, the multicrystalline silicon neighboring wafers with and without gettering were compared by element analysis techniques like neutron activation analysis (NAA). It was demonstrated that HCl gas gettering is an effective purification technique for silicon wafers, which is able to reduce some 3d transition metal concentrations by over 90%. Solar cells were processed for both concepts which could demonstrate a significant increase of the solar cell efficiency by HCl gas gettering. The efficiency of EpiWE cells could be increased by HCl gas gettering by approximately 25% relative to cells without gettering. First process simulations were performed based on a simple model for HCl gas gettering processes, which could be used to make qualitative predictions.

A new class of bragg stacks and its principle application

This work is focused on the development of high quality nanoporous 1D photonic crystals –so called Bragg stacks – made by spin-coating of approximately 25 nm large SiO2 and TiO2 nanoparticles bearing interparticle voids large enough to infiltrate reactive species. Therefore, the first part of this work describes the synthesis of well-dispersed TiO2 nanoparticles in this size range (the corresponding SiO2 nanoparticles are commercially available). In the second part, a protocol was developed to prepare nanoporous Bragg stacks of up to 12 bilayers with high quality and precision. Tailor-made Bragg stacks were prepared for different applications such as (i) a surface emitting feedback laser with a FWHM of only 6 nm and (ii) an electrochromic device with absorption reversibly switchable by an external electrical bias independently of the Bragg reflection. In the last chapter, the approach to 1D photonic crystals is transferred to 1D phononic crystals. Contrast in the modulus is achieved by spin-coating SiO2 and PMMA as high and low moduli material. This system showed a band gap of fg = 12.6 GHz with a width of Dfg/fg = 4.5 GHz.

Hypersonic phonon propagation in mesoscopic systems by Brillouin spectroscopy

Phononic crystals, capable to block or direct the propagation of elastic/acoustic waves, have attracted increasing interdisciplinary interest across condensed matter physics and materials science. As of today, no generalized full description of elastic wave propagation in phononic structures is available, mainly due to the large number of variables determining the band diagram. Therefore, this thesis aims for a deeper understanding of the fundamental concepts governing wave propagation in mesoscopic structures by investigation of appropriate model systems. The phononic dispersion relation at hypersonic frequencies is directly investigated by the non-destructive technique of high-resolution spontaneous Brillouin light scattering (BLS) combined with computational methods. Due to the vector nature of the elastic wave propagation, we first studied the hypersonic band structure of hybrid superlattices. These 1D phononic crystals composed of alternating layers of hard and soft materials feature large Bragg gaps. BLS spectra are sensitive probes of the moduli, photo-elastic constants and structural parameters of the constituent components. Engineering of the band structure can be realized by introduction of defects. Here, cavity layers are employed to launch additional modes that modify the dispersion of the undisturbed superlattice, with extraordinary implications to the band gap region. Density of states calculations in conjunction with the associated deformation allow for unambiguous identication of surface and cavity modes, as well as their interaction with adjacent defects. Next, the role of local resonances in phononic systems is explored in 3D structures based on colloidal particles. In turbid media BLS records the particle vibration spectrum comprising resonant modes due to the spatial confinement of elastic energy. Here, the frequency and lineshapes of the particle eigenmodes are discussed as function of increased interaction and departure from spherical symmetry. The latter is realized by uniaxial stretching of polystyrene spheres, that can be aligned in an alternating electric field. The resulting spheroidal crystals clearly exhibit anisotropic phononic properties. Establishing reliable predictions of acoustic wave propagation, necessary to advance, e.g., optomechanics and phononic devices is the ultimate aim of this thesis.

Misure di trasmittanza ottica di nanoparticelle di Ti(1-x)V(x)O(2)

Negli ultimi tempi sta assumendo grande importanza la ricerca sulla produzione di idrogeno dall’acqua tramite celle foto-elettrolitiche. In questa tesi vengono descritte le analisi condotte su un materiale che può essere coinvolto in questa applicazione: il TiO2 drogato con atomi di V. In particolare è stato valutato l’effetto del drogaggio sull’energy gap tramite misure di trasmittanza ottica effettuate in laboratorio su campioni con diverse concentrazioni di V e trattati termicamente a varie temperature. Nel primo capitolo vengono descritte le caratteristiche dei semiconduttori legate all’ottica, soffermandosi in particolare sul TiO2. Nel secondo capitolo sono illustrati l’apparato e il metodo sperimentale; viene inoltre fornita una descrizione dettagliata dei campioni analizzati. Nel terzo capitolo vengono esposti i risultati delle analisi dei dati.