Interconexión monolítica de módulos fotovoltaicos de silicio amorfo en lámina delgada sobre vidrio mediante ablación láser en régimen de nanosegundos

Esta tesis se centra en el estudio de una secuencia de procesos basados en la tecnología láser y ejecutados en dispositivos fotovoltaicos, que son imprescindibles para el desarrollo en general de las tecnologías fotovoltaicas basadas en lámina delgada y, en particular, de aquellas que utilizan silicio amorfo como absorbente, así como en aplicaciones posteriores de estas tecnologías de alto valor añadido como es la integración arquitectónica de este tipo de dispositivos. En gran parte de las tecnologías FV de lámina delgada, y muy particularmente en la de silicio amorfo, el material se deposita sobre un substrato en un área lo suficientemente grande para que se requiera de un proceso de subdivisión del dispositivo en células de tamaño adecuado, y su posterior conexión en serie para garantizar las figuras eléctricas nominales del dispositivo. Este proceso se ha desarrollado industrialmente hace años, pero no ha habido un esfuerzo científico asociado que permitiera conocer en profundidad los efectos que los procesos en si mismos tiene de forma individualizada sobre los materiales que componen el dispositivo y sus características finales. Este trabajo, desarrollado durante años en el Centro Láser de la UPM, en estrecha colaboración con Centro de Investigaciones Energéticas y Medioambientales (CIEMAT), la Universidad de Barcelona (UB), y la Universidad Politécnica de Cataluña (UPC), se centra justamente en un estudio detallado de dichos procesos, denominados habitualmente P1, P2, P3 y P4 atendiendo al orden en el que se realizan en el dispositivo. Este estudio incluye tanto la parametrización de los procesos, el análisis del efecto que los mismos producen sobre los materiales que componen el dispositivo y su comportamiento fotoeléctrico final, así como la evaluación del potencial uso de fuentes láser de última generación (ultrarrápidas) frente al estándar industrial en la actualidad que es el empleo de fuentes láser convencionales de ancho temporal en el rango de los nanosegundos. En concreto se ha estudiado en detalle las ventajas y limitaciones del uso de sistemas con diferentes rangos espectrales (IR, VIS y UV) y temporales (nanosegundos y picosegundos) para diferentes tipos de configuraciones y disposiciones tecnológicas (entendiendo por estas las habituales configuraciones en substrato y superestrato de este tipo de dispositivos). La caracterización individual de los procesos fue realizada primeramente en células de laboratorio específicamente diseñadas, abriendo nuevos planteamientos y conceptos originales para la mejora de los procesos láser de interconexión y posibilitando el empleo y desarrollo de técnicas y métodos avanzados de caracterización para el estudio de los procesos de ablación en las distintas láminas que conforman la estructura de los dispositivos fotovoltaicos, por lo que se considera que este trabajo ha propuesto una metodología completamente original, y que se ha demostrado efectiva, en este ámbito. Por último el trabajo aborda un tema de particular interés, como es el posible uso de los procesos desarrollados, no para construir los módulos fotovoltaicos en sí, sino para personalizarlos en forma y efectos visuales para potenciar su uso mediante elementos integrables arquitectónicamente, lo que es un ámbito de gran potencial de desarrollo futuro de las tecnologías fotovoltaicas de lámina delgada. En concreto se presentan estudios de fabricación de dispositivos integrables arquitectónicamente y plenamente funcionales no solo en dispositivos de silicio amorfo con efectos de transparencias y generación de formas libres, si no que también se incluye la posibilidad de hacer tales dispositivos con células de silicio cristalino estándar que es la tecnología fotovoltaica de mayor presencia en mercado. Es importante, además, resaltar que la realización de este trabajo ha sido posible gracias a la financiación obtenida con dos proyectos de investigación aplicada, MICROSIL (PSE-120000-2008-1) e INNDISOL (IPT-420000-2019-6), y los correspondientes al Plan Nacional de I+D+I financiados por el ministerio de Ciencia e Innovación y el Ministerio de Economía y Competitividad: CLÁSICO (ENE 2007- 67742-C04-04) y AMIC ENE2010-21384-C04-02. De hecho, y en el marco de estos proyectos, los resultados de este trabajo han ayudado a conseguir algunos de los hitos más importantes de la tecnología fotovoltaica en nuestro país en los últimos años, como fue en el marco de MICROSIL la fabricación del primer módulo de silicio amorfo con tecnología íntegramente española (hecho en colaboración con el CIEMAT), o la fabricación de los dispositivos para integración arquitectónica con geometrías libres que se describen en esta Tesis y que fueron parte de los desarrollos del proyecto INNDISOL. ABSTRACT This thesis focuses on the study of a sequence of laser-based technology and processes executed in photovoltaic devices, which are essential for the overall development of photovoltaic technologies based on thin film and, in particular, those using amorphous silicon as absorbent and subsequent applications of these technologies with high added value such as the architectural integration of such devices. In much of the PV thin film technologies, and particularly in the amorphous silicon material is deposited on a substrate in an area large enough so that it requires a process of subdivision of the device in cells of appropriate size, and subsequent serial connection to ensure nominal device power figures. This process has been industrially developed years ago, but there has been an associate scientific effort that would learn more about the effects that the processes themselves have either individually on the materials that make up the device and its final characteristics. This work, developed over years in the Laser Center of the UPM, in close collaboration with Centre for Energy and Environmental Research (CIEMAT), the University of Barcelona (UB) and the Polytechnic University of Catalonia (UPC)., Focuses precisely in a detailed study of these processes, usually they called P1, P2, P3 and P4 according to the order in which they perform on the device. This study includes both the parameters of the processes, the analysis of the effect they produce on the materials making up the device and its final photoelectric behavior as well as the potential use of EVALUATION of next-generation laser sources (ultrafast) versus standard industry today is the use of conventional laser sources temporal width in the range of nanoseconds. In particular we have studied in detail the advantages and limitations of using systems with different spectral ranges (IR, UV and VIS) and time (nanosecond and picosecond) for different configurations and technological provisions (meaning these typical configurations in substrate and superstrate such devices). Individual characterization of the processes was conducted primarily in laboratory cells specifically designed, opening new approaches and original concepts for improving laser interconnection processes and enabling the use and development of advanced techniques and characterization methods for studying the processes ablation in the different sheets making up the structure of the photovoltaic devices, so it is considered that this work has proposed a completely original methodology, which has proven effective in this area. Finally, the paper addresses a topic of particular interest, as is the possible use of lso developed processes, not to build the photovoltaic modules themselves but to customize fit and visual effects to enhance their use by integrated architectural elements, which is an area of great potential for future development of thin film photovoltaic technologies. Specifically studies manufacture of integrated architecturally and fully functional not only in amorphous silicon devices with transparency effects and generating freeform devices occur, if not also include the ability to make such devices with cells of standard crystalline silicon photovoltaic technology is more visible in the market. It is also important to note that the completion of this work has been possible thanks to the financing obtained with two applied research projects, Microsil (PSE-120000- 2008-1) and INNDISOL (IPT-420000-2019-6), and those for the National R & D funded by the Ministry of Science and Innovation and the Ministry of Economy and Competitiveness: CLASSIC (ENE 2007-67742-C04-04) and AMIC ENE2010-21384-C04- 02. In fact, within the framework of these projects, the results of this work have helped get some of the most important milestones of photovoltaic technology in our country in recent years, as it was under Microsil making the first module Amorphous silicon technology with entirely Spanish (made in collaboration with CIEMAT), or the manufacture of devices for architectural integration with free geometries that are described in this thesis and that were part of the project Inndisol developments.

Optics and Optoelectronics of Two-dimensional Semiconducting Monolayers and Heterostructures

Thesis (Ph.D.)--University of Washington, 2016-06

Controlling PbS nanocrystal aggregation in conducting polymers

PbS nanocrystals were synthesized directly in the conducting polymer, poly (3 -hexylthiophene-2,5-diyl). Transmission electron microscopy shows that the PbS nanocrystals are faceted and relatively uniform in size with a mean size of 10 nm. FFT analysis of the atomic lattice planes observed in TEM and selected area electron diffraction confirm that the nanocrystals have the PbS rock salt structure. The synthesis conditions are explored to show control over the aggregation of PbS nanocrystals in the thiophene conducting polymer.

Lead sulfide nanocrystal: conducting polymer solar cells

In this paper, we report photovoltaic devices fabricated from lead sulfide nanocrystals and the conducting polymer poly(2-methoxy-5-(2'-ethyl-hexyloxy)-p-phenylene vinylene). This composite material was produced via a new single-pot synthesis which solves many of the issues associated with existing methods. Our devices have white light power conversion efficiencies under AM 1.5 illumination of 0.7% and single wavelength conversion efficiencies of 1.1%. Additionally, they exhibit remarkably good ideality factors (n = 1.15). Our measurements show that these composites have significant potential as soft optoelectronic materials.

Block copolymer strategies for solar cell technology

A simple overview of the methods used and the expected benefits of block copolymers in organic photovoltaic devices is given in this review. The description of the photovoltaic process makes it clear how the detailed self-assembly properties of block copolymers can be exploited. Organic photovoltaic technology, an inexpensive, clean and renewable energy source, is an extremely promising option for replacing fossil fuels. It is expected to deliver printable devices processed on flexible substrates using high-volume techniques. Such devices, however, currently lack the long-term stability and efficiency to allow organic photovoltaics to surpass current technologies. Block copolymers are envisaged to help overcome these obstacles because of their long term structural stability and their solid-state morphology being of the appropriate dimensions to efficiently perform charge collection and transfer to electrodes.

Directed phase separation of PFO:PS blends during spin-coating using feedback controlled in situ stroboscopic fluorescence microscopy

Uniform thin-films of polymer blends can be produced through spin-coating, which is used on an industrial scale for the production of light emitting diodes, and more recently organic photovoltaic devices. Here, we present the results of the direct observation, and control, over the phase separation of polystyrene and poly(9,9′-dioctylfluorene) during spin-coating using high speed stroboscopic fluorescence microscopy. This new approach, imaging the fluorescence, from a blend of fluorescent + non-fluorescent polymers allows for intensity to be directly mapped to composition, providing a direct determination of composition fluctuations during the spin-coating process. We have studied the compositional development and corresponding structural development for a range of compositions, which produce a range of different phase separated morphologies. We initially observe domains formed by spinodal decomposition, coarsening via Ostwald Ripening until an interfacial instability causes break-up of the bicontinuous morphology. Ostwald ripening continues, and depending upon composition a bicontinuous morphology is re-established. By observing compositional and morphological development in real-time, we are able to direct and control morphological structure development through control of the spin coating parameters via in situ feedback. © 2013 The Royal Society of Chemistry.

Dispositifs optoélectroniques à base de semi-conducteurs organiques en couches minces

Les petites molécules de type p à bandes interdites étroites sont de plus en plus perçues comme des remplaçantes possibles aux polymères semi-conducteurs actuellement utilisés conjointement avec des dérivés de fullerènes de type n, dans les cellules photovoltaïques organiques (OPV). Par contre, ces petites molécules tendent à cristalliser facilement lors de leur application en couches minces et forment difficilement des films homogènes appropriés. Des dispositifs OPV de type hétérojonction de masse ont été réalisés en ajoutant différentes espèces de polymères semi-conducteurs ou isolants, agissant comme matrices permettant de rectifier les inhomogénéités des films actifs et d’augmenter les performances des cellules photovoltaïques. Des polymères aux masses molaires spécifiques ont été synthétisés par réaction de Wittig en contrôlant précisément les ratios molaires des monomères et de la base utilisée. L’effet de la variation des masses molaires en fonction des morphologies de films minces obtenus et des performances des diodes organiques électroluminescentes reliées, a également été étudié. La microscopie électronique en transmission (MET) ou à balayage (MEB) a été employée en complément de la microscopie à force atomique (AFM) pour suivre l’évolution de la morphologie des films organiques minces. Une nouvelle méthode rapide de préparation des films pour l’imagerie MET sur substrats de silicium est également présentée et comparée à d’autres méthodes d’extraction. Motivé par le prix élevé et la rareté des métaux utilisés dans les substrats d’oxyde d’indium dopé à l’étain (ITO), le développement d’une nouvelle méthode de recyclage eco-responsable des substrats utilisés dans ces études est également présenté.

Diketopyrrolopyrrole derivatives for bulk heterojunction and dye sensitised solar cells

This thesis describes the synthesis and characterisation of a series of molecules for use in bulk heterojunction and dye sensitised solar cells. The target molecules were based on a central diketopyrrolopyrrole subunit. Molecules based on diketopyrrolopyrrole have a conjugated structure, allowing for π-π interaction. Diketopyrrolopyrrole molecules also have relatively low lying HOMO and LUMO levels and high absorption coefficients and exhibit efficient charge transport properties. Furthermore, their electron withdrawing properties have warranted their use as promising organic photovoltaic materials. A number of molecules were successfully synthesised and sent to collaborators for testing in organic photovoltaic devices and development of this series of molecules continues to be of interest within the research group.

Dispositifs optoélectroniques à base de semi-conducteurs organiques en couches minces

Les petites molécules de type p à bandes interdites étroites sont de plus en plus perçues comme des remplaçantes possibles aux polymères semi-conducteurs actuellement utilisés conjointement avec des dérivés de fullerènes de type n, dans les cellules photovoltaïques organiques (OPV). Par contre, ces petites molécules tendent à cristalliser facilement lors de leur application en couches minces et forment difficilement des films homogènes appropriés. Des dispositifs OPV de type hétérojonction de masse ont été réalisés en ajoutant différentes espèces de polymères semi-conducteurs ou isolants, agissant comme matrices permettant de rectifier les inhomogénéités des films actifs et d’augmenter les performances des cellules photovoltaïques. Des polymères aux masses molaires spécifiques ont été synthétisés par réaction de Wittig en contrôlant précisément les ratios molaires des monomères et de la base utilisée. L’effet de la variation des masses molaires en fonction des morphologies de films minces obtenus et des performances des diodes organiques électroluminescentes reliées, a également été étudié. La microscopie électronique en transmission (MET) ou à balayage (MEB) a été employée en complément de la microscopie à force atomique (AFM) pour suivre l’évolution de la morphologie des films organiques minces. Une nouvelle méthode rapide de préparation des films pour l’imagerie MET sur substrats de silicium est également présentée et comparée à d’autres méthodes d’extraction. Motivé par le prix élevé et la rareté des métaux utilisés dans les substrats d’oxyde d’indium dopé à l’étain (ITO), le développement d’une nouvelle méthode de recyclage eco-responsable des substrats utilisés dans ces études est également présenté.

Cálculo de constantes ópticas de películas delgadas de Cu3BiS3 a través del método de Wolfe

Se calculó la obtención de las constantes ópticas usando el método de Wolfe. Dichas contantes: coeficiente de absorción (α), índice de refracción (n) y espesor de una película delgada (d ), son de importancia en el proceso de caracterización óptica del material. Se realizó una comparación del método del Wolfe con el método empleado por R. Swanepoel. Se desarrolló un modelo de programación no lineal con restricciones, de manera que fue posible estimar las constantes ópticas de películas delgadas semiconductoras, a partir únicamente, de datos de transmisión conocidos. Se presentó una solución al modelo de programación no lineal para programación cuadrática. Se demostró la confiabilidad del método propuesto, obteniendo valores de α = 10378.34 cm−1, n = 2.4595, d =989.71 nm y Eg = 1.39 Ev, a través de experimentos numéricos con datos de medidas de transmitancia espectral en películas delgadas de Cu3BiS3.

Hall Effect and transient surface photovoltage (SPV) study of Cu3BiS3 thin films

Se presentan las propiedades eléctricas del compuesto Cu3BiS3 depositado por co-evaporación. Este es un nuevo compuesto que puede tener propiedades adecuadas para ser utilizado como capa absorbente en celdas solares. Las muestras fueron caracterizadas a través de medidas de efecto Hall y fotovoltaje superficial transiente (SPV). A través de medidas de efecto Hall se encontró que la concentración de portadores de carga n es del orden de 1016 cm-3 independiente de la relación de masas de Cu/Bi. También se encontró que la movilidad de este compuesto (μ del orden de 4 cm2V -1s-1) varía de acuerdo con los mecanismos de transporte que la gobiernan en dependencia con la temperatura. A partir de las medidas de SPV se encontró alta densidad de defectos superficiales, defectos que son pasivados al superponer una capa buffer sobre el compuesto Cu3BiS3.

Selective ablation of photovoltaic materials with UV laser sources for monolithic interconnection of devices based on a-Si:H

Lasers are essential tools for cell isolation and monolithic interconnection in thin-film-silicon photovoltaic technologies. Laser ablation of transparent conductive oxides (TCOs), amorphous silicon structures and back contact removal are standard processes in industry for monolithic device interconnection. However, material ablation with minimum debris and small heat affected zone is one of the main difficulty is to achieve, to reduce costs and to improve device efficiency. In this paper we present recent results in laser ablation of photovoltaic materials using excimer and UV wavelengths of diode-pumped solid-state (DPSS) laser sources. We discuss results concerning UV ablation of different TCO and thin-film silicon (a-Si:H and nc-Si:H), focussing our study on ablation threshold measurements and process-quality assessment using advanced optical microscopy techniques. In that way we show the advantages of using UV wavelengths for minimizing the characteristic material thermal affection of laser irradiation in the ns regime at higher wavelengths. Additionally we include preliminary results of selective ablation of film on film structures irradiating from the film side (direct writing configuration) including the problem of selective ablation of ZnO films on a-Si:H layers. In that way we demonstrate the potential use of UV wavelengths of fully commercial laser sources as an alternative to standard backscribing process in device fabrication.

Mesoscale Optoelectronic Design of Wire-Based Photovoltaic and Photoelectrochemical Devices

The overarching theme of this thesis is mesoscale optical and optoelectronic design of photovoltaic and photoelectrochemical devices. In a photovoltaic device, light absorption and charge carrier transport are coupled together on the mesoscale, and in a photoelectrochemical device, light absorption, charge carrier transport, catalysis, and solution species transport are all coupled together on the mesoscale. The work discussed herein demonstrates that simulation-based mesoscale optical and optoelectronic modeling can lead to detailed understanding of the operation and performance of these complex mesostructured devices, serve as a powerful tool for device optimization, and efficiently guide device design and experimental fabrication efforts. In-depth studies of two mesoscale wire-based device designs illustrate these principles—(i) an optoelectronic study of a tandem Si|WO3 microwire photoelectrochemical device, and (ii) an optical study of III-V nanowire arrays.

The study of the monolithic, tandem, Si|WO3 microwire photoelectrochemical device begins with development and validation of an optoelectronic model with experiment. This study capitalizes on synergy between experiment and simulation to demonstrate the model’s predictive power for extractable device voltage and light-limited current density. The developed model is then used to understand the limiting factors of the device and optimize its optoelectronic performance. The results of this work reveal that high fidelity modeling can facilitate unequivocal identification of limiting phenomena, such as parasitic absorption via excitation of a surface plasmon-polariton mode, and quick design optimization, achieving over a 300% enhancement in optoelectronic performance over a nominal design for this device architecture, which would be time-consuming and challenging to do via experiment.

The work on III-V nanowire arrays also starts as a collaboration of experiment and simulation aimed at gaining understanding of unprecedented, experimentally observed absorption enhancements in sparse arrays of vertically-oriented GaAs nanowires. To explain this resonant absorption in periodic arrays of high index semiconductor nanowires, a unified framework that combines a leaky waveguide theory perspective and that of photonic crystals supporting Bloch modes is developed in the context of silicon, using both analytic theory and electromagnetic simulations. This detailed theoretical understanding is then applied to a simulation-based optimization of light absorption in sparse arrays of GaAs nanowires. Near-unity absorption in sparse, 5% fill fraction arrays is demonstrated via tapering of nanowires and multiple wire radii in a single array. Finally, experimental efforts are presented towards fabrication of the optimized array geometries. A hybrid self-catalyzed and selective area MOCVD growth method is used to establish morphology control of GaP nanowire arrays. Similarly, morphology and pattern control of nanowires is demonstrated with ICP-RIE of InP. Optical characterization of the InP nanowire arrays gives proof of principle that tapering and multiple wire radii can lead to near-unity absorption in sparse arrays of InP nanowires.

Perylene Diimide acceptors: Fabrication and characterization of electron-only, hole-only devices and solar cells

The thrust towards energy conservation and reduced environmental footprint has fueled intensive research for alternative low cost sources of renewable energy. Organic photovoltaic cells (OPVs), with their low fabrication costs, easy processing and flexibility, represent a possible viable alternative. Perylene diimides (PDIs) are promising electron-acceptor candidates for bulk heterojunction (BHJ) OPVs, as they combine higher absorption and stability with tunable material properties, such as solubility and position of the lowest unoccupied molecular orbital (LUMO) level. A prerequisite for trap free electron transport is for the LUMO to be located at a level deeper than 3.7 eV since electron trapping in organic semiconductors is universal and dominated by a trap level located at 3.6 eV. Although the mostly used fullerene acceptors in polymer:fullerene solar cells feature trap-free electron transport, low optical absorption of fullerene derivatives limits maximum attainable efficiency. In this thesis, we try to get a better understanding of the electronic properties of PDIs, with a focus on charge carrier transport characteristics and the effect of different processing conditions such as annealing temperature and top contact (cathode) material. We report on a commercially available PDI and three PDI derivatives as acceptor materials, and its blends with MEH-PPV (Poly[2-methoxy 5-(2-ethylhexyloxy)-1,4-phenylenevinylene]) and P3HT (Poly(3-hexylthiophene-2,5-diyl)) donor materials in single carrier devices (electron-only and hole-only) and in solar cells. Space-charge limited current measurements and modelling of temperature dependent J-V characteristics confirmed that the electron transport is essentially trap-free in such materials. Different blend ratios of P3HT:PDI-1 (1:1) and (1:3) show increase in the device performance with increasing PDI-1 ratio. Furthermore, thermal annealing of the devices have a significant effect in the solar cells that decreases open-circuit voltage (Voc) and fill factor FF, but increases short-circuit current (Jsc) and overall device performance. Morphological studies show that over-aggregation in traditional donor:PDI blend systems is still a big problem, which hinders charge carrier transport and performance in solar cells.

Analysis of S-rich CuIn(S,Se)2 layers for photovoltaic applications: Influence of the sulfurization temperature on the crystalline properties of electrodeposited and sulfurized CuInSe2 precursors

This paper reports the microstructural analysis of S-rich CuIn(S,Se)2 layers produced by electrodeposition of CuInSe2 precursors and annealing under sulfurizing conditions as a function of the temperature of sulfurization. The characterization of the layers by Raman scattering, scanning electron microscopy, Auger electron spectroscopy, and XRD techniques has allowed observation of the strong dependence of the crystalline quality of these layers on the sulfurization temperature: Higher sulfurization temperatures lead to films with improved crystallinity, larger average grain size, and lower density of structural defects. However, it also favors the formation of a thicker MoS2 interphase layer between the CuInS2 absorber layer and the Mo back contact. Decreasing the temperature of sulfurization leads to a significant decrease in the thickness of this intermediate layer and is also accompanied by significant changes in the composition of the interface region between the absorber and the MoS2 layer, which becomes Cu rich. The characterization of devices fabricated with these absorbers corroborates the significant impact of all these features on device parameters as the open circuit voltage and fill factor that determine the efficiency of the solar cells.