Two-photon photocurrent and voltage up-conversion in a quantum dot intermediate band solar cell

It has been proposed that the use of self-assembled quantum dot (QD) arrays can break the Shockley-Queisser efficiency limit by extending the absorption of solar cells into the low-energy photon range while preserving their output voltage. This would be possible if the infrared photons are absorbed in the two sub-bandgap QD transitions simultaneously and the energy of two photons is added up to produce one single electron-hole pair, as described by the intermediate band model. Here, we present an InAs/Al 0.25Ga 0.75As QD solar cell that exhibits such electrical up-conversion of low-energy photons. When the device is monochromatically illuminated with 1.32 eV photons, open-circuit voltages as high as 1.58 V are measured (for a total gap of 1.8 eV). Moreover, the photocurrent produced by illumination with photons exciting the valence band to intermediate band (VB-IB) and the intermediate band to conduction band (IB-CB) transitions can be both spectrally resolved. The first corresponds to the QD inter-band transition and is observable for photons of energy mayor que 1 eV, and the later corresponds to the QD intra-band transition and peaks around 0.5 eV. The voltage up-conversion process reported here for the first time is the key to the use of the low-energy end of the solar spectrum to increase the conversion efficiency, and not only the photocurrent, of single-junction photovoltaic devices. In spite of the low absorption threshold measured in our devices - 0.25 eV - we report open-circuit voltages at room temperature as high as 1.12 V under concentrated broadband illumination.

Preparation and characterization of stable aqueous suspensions of up-converting Er3+/Yb3+-doped LiNbO3 nanocrystals

The preparation of LiNbO3:Er3+/Yb3+ nanocrystals and their up-conversion properties have been studied. It is demonstrated that polyethyleneimine- (PEI) assisted dispersion procedures allow obtaining stable aqueous LiNbO3:Er3+/Yb3+ powder suspensions, with average size particles well below the micron range (100–200 nm) and the isoelectric point of the suspension reaching values well above pH 7. After excitation of Yb3+ ions at a wavelength of 980 nm, the suspensions exhibit efficient, and stable, IR-to-visible (green and red) up-conversion properties, easily observed by the naked eye, very similar to those of the starting crystalline bulk material.

Research on wide-bandgap intermediate band solar cells and development of experimental techniques for their characterization

El trabajo que ha dado lugar a esta Tesis Doctoral se enmarca en la invesitagación en células solares de banda intermedia (IBSCs, por sus siglas en inglés). Se trata de un nuevo concepto de célula solar que ofrece la posibilidad de alcanzar altas eficiencias de conversión fotovoltaica. Hasta ahora, se han demostrado de manera experimental los fundamentos de operación de las IBSCs; sin embargo, esto tan sólo has sido posible en condicines de baja temperatura. El concepto de banda intermedia (IB, por sus siglas en inglés) exige que haya desacoplamiento térmico entre la IB y las bandas de valencia y conducción (VB and CB, respectivamente, por sus siglas en inglés). Los materiales de IB actuales presentan un acoplamiento térmico demasiado fuerte entre la IB y una de las otras dos bandas, lo cual impide el correcto funcionamiento de las IBSCs a temperatura ambiente. En el caso particular de las IBSCs fabricadas con puntos cuánticos (QDs, por sus siglas en inglés) de InAs/GaAs - a día de hoy, la tecnología de IBSC más estudiada - , se produce un rápido intercambio de portadores entre la IB y la CB, por dos motivos: (1) una banda prohibida estrecha (< 0.2 eV) entre la IB y la CB, E^, y (2) la existencia de niveles electrónicos entre ellas. El motivo (1) implica, a su vez, que la máxima eficiencia alcanzable en estos dispositivos es inferior al límite teórico de la IBSC ideal, en la cual E^ = 0.71 eV. En este contexto, nuestro trabajo se centra en el estudio de IBSCs de alto gap (o banda prohibida) fabricadsas con QDs, o lo que es lo mismo, QD-IBSCs de alto gap. Hemos fabricado e investigado experimentalmente los primeros prototipos de QD-IBSC en los que se utiliza AlGaAs o InGaP para albergar QDs de InAs. En ellos demostramos une distribución de gaps mejorada con respecto al caso de InAs/GaAs. En concreto, hemos medido valores de E^ mayores que 0.4 eV. En los prototipos de InAs/AlGaAs, este incremento de E^ viene acompaado de un incremento, en más de 100 meV, de la energía de activación del escape térmico. Además, nuestros dispositivos de InAs/AlGaAs demuestran conversión a la alza de tensión; es decir, la producción de una tensión de circuito abierto mayor que la energía de los fotones (dividida por la carga del electrón) de un haz monocromático incidente, así como la preservación del voltaje a temperaura ambiente bajo iluminación de luz blanca concentrada. Asimismo, analizamos el potencial para detección infrarroja de los materiales de IB. Presentamos un nuevo concepto de fotodetector de infrarrojos, basado en la IB, que hemos llamado: fotodetector de infrarrojos activado ópticamente (OTIP, por sus siglas en inglés). Nuestro novedoso dispositivo se basa en un nuevo pricipio físico que permite que la detección de luz infrarroja sea conmutable (ON y OFF) mediante iluminación externa. Hemos fabricado un OTIP basado en QDs de InAs/AlGaAs con el que demostramos fotodetección, bajo incidencia normal, en el rango 2-6/xm, activada ópticamente por un diodoe emisor de luz de 590 nm. El estudio teórico del mecanismo de detección asistido por la IB en el OTIP nos lleva a poner en cuestión la asunción de quasi-niveles de Fermi planos en la zona de carga del espacio de una célula solar. Apoyados por simuaciones a nivel de dispositivo, demostramos y explicamos por qué esta asunción no es válida en condiciones de corto-circuito e iluminación. También llevamos a cabo estudios experimentales en QD-IBSCs de InAs/AlGaAs con la finalidad de ampliar el conocimiento sobre algunos aspectos de estos dispositivos que no han sido tratados aun. En particular, analizamos el impacto que tiene el uso de capas de disminución de campo (FDLs, por sus siglas en inglés), demostrando su eficiencia para evitar el escape por túnel de portadores desde el QD al material anfitrión. Analizamos la relación existente entre el escape por túnel y la preservación del voltaje, y proponemos las medidas de eficiencia cuántica en función de la tensión como una herramienta útil para evaluar la limitación del voltaje relacionada con el túnel en QD-IBSCs. Además, realizamos medidas de luminiscencia en función de la temperatura en muestras de InAs/GaAs y verificamos que los resltados obtenidos están en coherencia con la separación de los quasi-niveles de Fermi de la IB y la CB a baja temperatura. Con objeto de contribuir a la capacidad de fabricación y caracterización del Instituto de Energía Solar de la Universidad Politécnica de Madrid (IES-UPM), hemos participado en la instalación y puesta en marcha de un reactor de epitaxia de haz molecular (MBE, por sus siglas en inglés) y el desarrollo de un equipo de caracterización de foto y electroluminiscencia. Utilizando dicho reactor MBE, hemos crecido, y posteriormente caracterizado, la primera QD-IBSC enteramente fabricada en el IES-UPM. ABSTRACT The constituent work of this Thesis is framed in the research on intermediate band solar cells (IBSCs). This concept offers the possibility of achieving devices with high photovoltaic-conversion efficiency. Up to now, the fundamentals of operation of IBSCs have been demonstrated experimentally; however, this has only been possible at low temperatures. The intermediate band (IB) concept demands thermal decoupling between the IB and the valence and conduction bands. Stateof- the-art IB materials exhibit a too strong thermal coupling between the IB and one of the other two bands, which prevents the proper operation of IBSCs at room temperature. In the particular case of InAs/GaAs quantum-dot (QD) IBSCs - as of today, the most widely studied IBSC technology - , there exist fast thermal carrier exchange between the IB and the conduction band (CB), for two reasons: (1) a narrow (< 0.2 eV) energy gap between the IB and the CB, EL, and (2) the existence of multiple electronic levels between them. Reason (1) also implies that maximum achievable efficiency is below the theoretical limit for the ideal IBSC, in which EL = 0.71 eV. In this context, our work focuses on the study of wide-bandgap QD-IBSCs. We have fabricated and experimentally investigated the first QD-IBSC prototypes in which AlGaAs or InGaP is the host material for the InAs QDs. We demonstrate an improved bandgap distribution, compared to the InAs/GaAs case, in our wide-bandgap devices. In particular, we have measured values of EL higher than 0.4 eV. In the case of the AlGaAs prototypes, the increase in EL comes with an increase of more than 100 meV of the activation energy of the thermal carrier escape. In addition, in our InAs/AlGaAs devices, we demonstrate voltage up-conversion; i. e., the production of an open-circuit voltage larger than the photon energy (divided by the electron charge) of the incident monochromatic beam, and the achievement of voltage preservation at room temperature under concentrated white-light illumination. We also analyze the potential of an IB material for infrared detection. We present a IB-based new concept of infrared photodetector that we have called the optically triggered infrared photodetector (OTIP). Our novel device is based on a new physical principle that allows the detection of infrared light to be switched ON and OFF by means of an external light. We have fabricated an OTIP based on InAs/AlGaAs QDs with which we demonstrate normal incidence photodetection in the 2-6 /xm range optically triggered by a 590 nm light-emitting diode. The theoretical study of the IB-assisted detection mechanism in the OTIP leads us to questioning the assumption of flat quasi-Fermi levels in the space-charge region of a solar cell. Based on device simulations, we prove and explain why this assumption is not valid under short-circuit and illumination conditions. We perform new experimental studies on InAs/GaAs QD-IBSC prototypes in order to gain knowledge on yet unexplored aspects of the performance of these devices. Specifically, we analyze the impact of the use of field-damping layers, and demonstrate this technique to be efficient for avoiding tunnel carrier escape from the QDs to the host material. We analyze the relationship between tunnel escape and voltage preservation, and propose voltage-dependent quantum efficiency measurements as an useful technique for assessing the tunneling-related limitation to the voltage preservation of QD-IBSC prototypes. Moreover, we perform temperature-dependent luminescence studies on InAs/GaAs samples and verify that the results are consistent with a split of the quasi-Fermi levels for the CB and the IB at low temperature. In order to contribute to the fabrication and characterization capabilities of the Solar Energy Institute of the Universidad Polite´cnica de Madrid (IES-UPM), we have participated in the installation and start-up of an molecular beam epitaxy (MBE) reactor and the development of a photo and electroluminescence characterization set-up. Using the MBE reactor, we have manufactured and characterized the first QD-IBSC fully fabricated at the IES-UPM.

New strategies in laser processing of TCOs for light management improvement in thin-film silicon solar cells

Light confinement strategies play a crucial role in the performance of thin-film (TF) silicon solar cells. One way to reduce the optical losses is the texturing of the transparent conductive oxide (TCO) that acts as the front contact. Other losses arise from the mismatch between the incident light spectrum and the spectral properties of the absorbent material that imply that low energy photons (below the bandgap value) are not absorbed, and therefore can not generate photocurrent. Up-conversion techniques, in which two sub-bandgap photons are combined to give one photon with a better matching with the bandgap, were proposed to overcome this problem. In particular, this work studies two strategies to improve light management in thin film silicon solar cells using laser technology. The first one addresses the problem of TCO surface texturing using fully commercial fast and ultrafast solid state laser sources. Aluminum doped Zinc Oxide (AZO) samples were laser processed and the results were optically evaluated by measuring the haze factor of the treated samples. As a second strategy, laser annealing experiments of TCOs doped with rare earth ions are presented as a potential process to produce layers with up-conversion properties, opening the possibility of its potential use in high efficiency solar cells.

Optimization of InGaAsN(Sb)/GaAs quantum dots for optical emission at 1.55 µm with low optical degradation

Low optical degradation in GaInAsN(Sb)/GaAs quantum dots (QDs) p–i–n structures emitting up to 1.55 μm is presented in this paper. We obtain emission at different energies by means of varying N content from 1 to 4%. The samples show a low photoluminescence (PL) intensity degradation of only 1 order of magnitude when they are compared with pure InGaAs QD structures, even for an emission wavelength as large as 1.55 μm. The optimization studies of these structures for emission at 1.55 μm are reported in this work. High surface density and homogeneity in the QD layers are achieved for 50% In content by rapid decrease in the growth temperature after the formation of the nanostructures. Besides, the effect of N and Sb incorporation in the redshift and PL intensity of the samples is studied by post-growth rapid thermal annealing treatments. As a general conclusion, we observe that the addition of Sb to QD with low N mole fraction is more efficient to reach 1.55 μm and high PL intensity than using high N incorporation in the QD. Also, the growth temperature is determined to be an important parameter to obtain good emission characteristics. Finally, we report room temperature PL emission of InGaAsN(Sb)/GaAs at 1.4 μm.

Clean Coal Technologies Scenario and Evaluation of Present CO2 Dwindling Initiatives to Approach Zero Emission Power Stations By Coal Combustion. Deployment Situation and Evaluation Study

In the present uncertain global context of reaching an equal social stability and steady thriving economy, power demand expected to grow and global electricity generation could nearly double from 2005 to 2030. Fossil fuels will remain a significant contribution on this energy mix up to 2050, with an expected part of around 70% of global and ca. 60% of European electricity generation. Coal will remain a key player. Hence, a direct effect on the considered CO2 emissions business-as-usual scenario is expected, forecasting three times the present CO2 concentration values up to 1,200ppm by the end of this century. Kyoto protocol was the first approach to take global responsibility onto CO2 emissions monitoring and cap targets by 2012 with reference to 1990. Some of principal CO2emitters did not ratify the reduction targets. Although USA and China spur are taking its own actions and parallel reduction measures. More efficient combustion processes comprising less fuel consuming, a significant contribution from the electricity generation sector to a CO2 dwindling concentration levels, might not be sufficient. Carbon Capture and Storage (CCS) technologies have started to gain more importance from the beginning of the decade, with research and funds coming out to drive its come in useful. After first researching projects and initial scale testing, three principal capture processes came out available today with first figures showing up to 90% CO2 removal by its standard applications in coal fired power stations. Regarding last part of CO2 reduction chain, two options could be considered worthy, reusing (EOR & EGR) and storage. The study evaluates the state of the CO2 capture technology development, availability and investment cost of the different technologies, with few operation cost analysis possible at the time. Main findings and the abatement potential for coal applications are presented. DOE, NETL, MIT, European universities and research institutions, key technology enterprises and utilities, and key technology suppliers are the main sources of this study. A vision of the technology deployment is presented.

Super-Resolution in Respiratory Synchronized Positron Emission Tomography

Respiratory motion is a major source of reduced quality in positron emission tomography (PET). In order to minimize its effects, the use of respiratory synchronized acquisitions, leading to gated frames, has been suggested. Such frames, however, are of low signal-to-noise ratio (SNR) as they contain reduced statistics. Super-resolution (SR) techniques make use of the motion in a sequence of images in order to improve their quality. They aim at enhancing a low-resolution image belonging to a sequence of images representing different views of the same scene. In this work, a maximum a posteriori (MAP) super-resolution algorithm has been implemented and applied to respiratory gated PET images for motion compensation. An edge preserving Huber regularization term was used to ensure convergence. Motion fields were recovered using a B-spline based elastic registration algorithm. The performance of the SR algorithm was evaluated through the use of both simulated and clinical datasets by assessing image SNR, as well as the contrast, position and extent of the different lesions. Results were compared to summing the registered synchronized frames on both simulated and clinical datasets. The super-resolution image had higher SNR (by a factor of over 4 on average) and lesion contrast (by a factor of 2) than the single respiratory synchronized frame using the same reconstruction matrix size. In comparison to the motion corrected or the motion free images a similar SNR was obtained, while improvements of up to 20% in the recovered lesion size and contrast were measured. Finally, the recovered lesion locations on the SR images were systematically closer to the true simulated lesion positions. These observations concerning the SNR, lesion contrast and size were confirmed on two clinical datasets included in the study. In conclusion, the use of SR techniques applied to respiratory motion synchronized images lead to motion compensation combined with improved image SNR and contrast, without any increase in the overall acquisition times.

Low-density InAs QDs with subcritical coverage obtained by conversion of In nanocrystals

We report growth of InAs/GaAs quantum dots (QDs) by molecular beam epitaxy with low density of 2 μm−2 by conversion of In nanocrystals deposited at low temperatures. The total amount of InAs used is about one monolayer, which is less than the critical thickness for conventional Stranski–Krastanov QDs. We also demonstrate the importance of the starting surface reconstruction for obtaining uniform QDs. The QD emission wavelength is easily tunable upon post-growth annealing with no wetting layer signal visible for short anneals. Microphotoluminescence measurements reveal well separated and sharp emission lines of individual QDs.

Top-Hat HELLISH-VCSOA for optical amplification and wavelength conversion for 0.85 to 1.3ìm operation

The Top-Hat hot electron light emission and lasing in semiconductor heterostructure (HELLISH)-vertical cavity semiconductor optical amplifier (VCSOA) is a modified version of a HELLISH-VCSOA device. It has a shorter p-channel and longer n-channel. The device studied in this work consists of a simple GaAs p-i-n junction, containing 11 Ga0.35In0.65 N0.02As0.08/GaAs multiple quantum wells in its intrinsic region; the active region is enclosed between six pairs of GaAs/AlAs top distributed Bragg reflector (DBR) mirrors and 20.5 pairs of AlAs/GaAs bottom DBR mirrors. The operation of the device is based on longitudinal current transport parallel to the layers of the GaAs p-n junction. The device is characterised through I-V-L and by spectral photoluminescence, electroluminescence and electro-photoluminescence measurements. An amplification of about 25 dB is observed at applied voltages of around V = 88 V.

Enhanced radon emission in natural CO2 flows in Campo de Calatrava region (central Spain)

Activity of radon gas in natural soils is commonly low (in the order of few thousands of Bq·m-3) due to the fast decay (half-life= 3.8 days in the case of 222Rn) that prevents accumulation in soil pores. Exceptionally, high Rn soil activity (up to 430 KBq·m-3) is found around point sources of deep CO2 fluxes. These fluxes allow the transport of trace gases (including Rn) to long distances in the geosphere leading to a potential hazard as Rn accumulation in buildings. CO2 degassing is common in active or ancient volcanic fields and occurs as free gas fluxes or dissolved in groundwater. In this work, the occurrence of Rnbearing, CO2 fluxes from the Campo de Calatrava region in Central Spain has been studied in order to determine their (1) magnitude, (2) migration paths and (3) potential impact on the environment, and (4) methodologies to best detection and measurement.

A methodology to compute emission projections from road transport (EmiTRANS)

Atmospheric emissions from road transport have increased all around the world during the last decades more rapidly than from other pollution sources. For instance, they contribute to more than 25% of total CO, CO2, NOx, and fine particle emissions in most of the European countries. This situation shows the importance of road transport when complying with emission ceilings and air quality standards applied to these pollutants. This paper presents a modelling system to perform atmospheric emission projections (simultaneously both air quality pollutants and greenhouse gases) from road transport including the development of a tailored software tool (EmiTRANS) as a planning tool. The methodology has been developed with two purposes: 1) to obtain outputs used as inputs to the COPERT4 software to calculate emission projections and 2) to summarize outputs for policy making evaluating the effect of emission abatement measures for a vehicle fleet. This methodology has been applied to the calculation of emission projections in Spain up to 2020 under several scenarios, including a sensitivity analysis useful for a better interpretation and confidence building on the results. This case study demonstrates the EmiTRANS applicability to a country, and points out the need for combining both technical and non-technical measures (such as behavioural changes or demand management) to reduce emissions, indirectly improving air quality and contributing to mitigate climate change.

Road Dust Emission Sources and Assessment of Street Washing Effect

Although previous studies report on the effect of street washing on ambient particulate matter levels, there is a lack of studies investigating the results of street washing on the emission strength of road dust. A sampling campaign was conducted in Madrid urban area during July 2009 where road dust samples were collected in two sites, namely Reference site (where the road surface was not washed) and Pelayo site (where street washing was performed daily during night). Following the chemical characterization of the road dust particles the emission sources were resolved by means of Positive Matrix Factorization, PMF (Multilinear Engine scripting) and the mass contribution of each source was calculated for the two sites. Mineral dust, brake wear, tire wear, carbonaceous emissions and construction dust were the main sources of road dust with mineral and construction dust being the major contributors to inhalable road dust load. To evaluate the effectiveness of street washing on the emission sources, the sources mass contributions between the two sites were compared. Although brake wear and tire wear had lower concentrations at the site where street washing was performed, these mass differences were not statistically significant and the temporal variation did not show the expected build-up after dust removal. It was concluded that the washing activities resulted merely in a road dust moistening, without effective removal and that mobilization of particles took place in a few hours between washing and sampling. The results also indicated that it is worth paying attention to the dust dispersed from the construction sites as they affect the emission strength in nearby streets.

Evaluación de las Consecuencias de la Nueva Regulación de la OMI sobre Combustibles Marinos

El 10 de octubre de 2008 la Organización Marítima Internacional (OMI) firmó una modificación al Anexo VI del convenio MARPOL 73/78, por la que estableció una reducción progresiva de las emisiones de óxidos de azufre (SOx) procedentes de los buques, una reducción adicional de las emisiones de óxidos de nitrógeno (NOx), así como límites en las emisiones de dióxido de Carbono (CO2) procedentes de los motores marinos y causantes de problemas medioambientales como la lluvia ácida y efecto invernadero. Centrándonos en los límites sobre las emisiones de azufre, a partir del 1 de enero de 2015 esta normativa obliga a todos los buques que naveguen por zonas controladas, llamadas Emission Control Area (ECA), a consumir combustibles con un contenido de azufre menor al 0,1%. A partir del 1 de enero del año 2020, o bien del año 2025, si la OMI decide retrasar su inicio, los buques deberán consumir combustibles con un contenido de azufre menor al 0,5%. De igual forma que antes, el contenido deberá ser rebajado al 0,1%S, si navegan por el interior de zonas ECA. Por su parte, la Unión Europea ha ido más allá que la OMI, adelantando al año 2020 la aplicación de los límites más estrictos de la ley MARPOL sobre las aguas de su zona económica exclusiva. Para ello, el 21 de noviembre de 2013 firmó la Directiva 2012 / 33 / EU como adenda a la Directiva de 1999. Tengamos presente que la finalidad de estas nuevas leyes es la mejora de la salud pública y el medioambiente, produciendo beneficios sociales, en forma de reducción de enfermedades, sobre todo de tipo respiratorio, a la vez que se reduce la lluvia ácida y sus nefastas consecuencias. La primera pregunta que surge es ¿cuál es el combustible actual de los buques y cuál será el que tengan que consumir para cumplir con esta Regulación? Pues bien, los grandes buques de navegación internacional consumen hoy en día fuel oil con un nivel de azufre de 3,5%. ¿Existen fueles con un nivel de azufre de 0,5%S? Como hemos concluido en el capítulo 4, para las empresas petroleras, la producción de fuel oil como combustible marino es tratada como un subproducto en su cesta de productos refinados por cada barril de Brent, ya que la demanda de fuel respecto a otros productos está bajando y además, el margen de beneficio que obtienen por la venta de otros productos petrolíferos es mayor que con el fuel. Así, podemos decir que las empresas petroleras no están interesadas en invertir en sus refinerías para producir estos fueles con menor contenido de azufre. Es más, en el caso de que alguna compañía decidiese invertir en producir un fuel de 0,5%S, su precio debería ser muy similar al del gasóleo para poder recuperar las inversiones empleadas. Por lo tanto, el único combustible que actualmente cumple con los nuevos niveles impuestos por la OMI es el gasóleo, con un precio que durante el año 2014 estuvo a una media de 307 USD/ton más alto que el actual fuel oil. Este mayor precio de compra de combustible impactará directamente sobre el coste del trasporte marítimo. La entrada en vigor de las anteriores normativas está suponiendo un reto para todo el sector marítimo. Ante esta realidad, se plantean diferentes alternativas con diferentes implicaciones técnicas, operativas y financieras. En la actualidad, son tres las alternativas con mayor aceptación en el sector. La primera alternativa consiste en “no hacer nada” y simplemente cambiar el tipo de combustible de los grandes buques de fuel oil a gasóleo. Las segunda alternativa es la instalación de un equipo scrubber, que permitiría continuar con el consumo de fuel oil, limpiando sus gases de combustión antes de salir a la atmósfera. Y, por último, la tercera alternativa consiste en el uso de Gas Natural Licuado (GNL) como combustible, con un precio inferior al del gasóleo. Sin embargo, aún existen importantes incertidumbres sobre la evolución futura de precios, operación y mantenimiento de las nuevas tecnologías, inversiones necesarias, disponibilidad de infraestructura portuaria e incluso el desarrollo futuro de la propia normativa internacional. Estas dudas hacen que ninguna de estas tres alternativas sea unánime en el sector. En esta tesis, tras exponer en el capítulo 3 la regulación aplicable al sector, hemos investigado sus consecuencias. Para ello, hemos examinado en el capítulo 4 si existen en la actualidad combustibles marinos que cumplan con los nuevos límites de azufre o en su defecto, cuál sería el precio de los nuevos combustibles. Partimos en el capítulo 5 de la hipótesis de que todos los buques cambian su consumo de fuel oil a gasóleo para cumplir con dicha normativa, calculamos el incremento de demanda de gasóleo que se produciría y analizamos las consecuencias que este hecho tendría sobre la producción de gasóleos en el Mediterráneo. Adicionalmente, calculamos el impacto económico que dicho incremento de coste producirá sobre sector exterior de España. Para ello, empleamos como base de datos el sistema de control de tráfico marítimo Authomatic Identification System (AIS) para luego analizar los datos de todos los buques que han hecho escala en algún puerto español, para así calcular el extra coste anual por el consumo de gasóleo que sufrirá el transporte marítimo para mover todas las importaciones y exportaciones de España. Por último, en el capítulo 6, examinamos y comparamos las otras dos alternativas al consumo de gasóleo -scrubbers y propulsión con GNL como combustible- y, finalmente, analizamos en el capítulo 7, la viabilidad de las inversiones en estas dos tecnologías para cumplir con la regulación. En el capítulo 5 explicamos los numerosos métodos que existen para calcular la demanda de combustible de un buque. La metodología seguida para su cálculo será del tipo bottom-up, que está basada en la agregación de la actividad y las características de cada tipo de buque. El resultado está basado en la potencia instalada de cada buque, porcentaje de carga del motor y su consumo específico. Para ello, analizamos el número de buques que navegan por el Mediterráneo a lo largo de un año mediante el sistema AIS, realizando “fotos” del tráfico marítimo en el Mediterráneo y reportando todos los buques en navegación en días aleatorios a lo largo de todo el año 2014. Por último, y con los datos anteriores, calculamos la demanda potencial de gasóleo en el Mediterráneo. Si no se hace nada y los buques comienzan a consumir gasóleo como combustible principal, en vez del actual fuel oil para cumplir con la regulación, la demanda de gasoil en el Mediterráneo aumentará en 12,12 MTA (Millones de Toneladas Anuales) a partir del año 2020. Esto supone alrededor de 3.720 millones de dólares anuales por el incremento del gasto de combustible tomando como referencia el precio medio de los combustibles marinos durante el año 2014. El anterior incremento de demanda en el Mediterráneo supondría el 43% del total de la demanda de gasóleos en España en el año 2013, incluyendo gasóleos de automoción, biodiesel y gasóleos marinos y el 3,2% del consumo europeo de destilados medios durante el año 2014. ¿Podrá la oferta del mercado europeo asumir este incremento de demanda de gasóleos? Europa siempre ha sido excedentaria en gasolina y deficitaria en destilados medios. En el año 2009, Europa tuvo que importar 4,8 MTA de Norte América y 22,1 MTA de Asia. Por lo que, este aumento de demanda sobre la ya limitada capacidad de refino de destilados medios en Europa incrementará las importaciones y producirá también aumentos en los precios, sobre todo del mercado del gasóleo. El sector sobre el que más impactará el incremento de demanda de gasóleo será el de los cruceros que navegan por el Mediterráneo, pues consumirán un 30,4% de la demanda de combustible de toda flota mundial de cruceros, lo que supone un aumento en su gasto de combustible de 386 millones de USD anuales. En el caso de los RoRos, consumirían un 23,6% de la demanda de la flota mundial de este tipo de buque, con un aumento anual de 171 millones de USD sobre su gasto de combustible anterior. El mayor incremento de coste lo sufrirán los portacontenedores, con 1.168 millones de USD anuales sobre su gasto actual. Sin embargo, su consumo en el Mediterráneo representa sólo el 5,3% del consumo mundial de combustible de este tipo de buques. Estos números plantean la incertidumbre de si semejante aumento de gasto en buques RoRo hará que el transporte marítimo de corta distancia en general pierda competitividad sobre otros medios de transporte alternativos en determinadas rutas. De manera que, parte del volumen de mercancías que actualmente transportan los buques se podría trasladar a la carretera, con los inconvenientes medioambientales y operativos, que esto produciría. En el caso particular de España, el extra coste por el consumo de gasóleo de todos los buques con escala en algún puerto español en el año 2013 se cifra en 1.717 millones de EUR anuales, según demostramos en la última parte del capítulo 5. Para realizar este cálculo hemos analizado con el sistema AIS a todos los buques que han tenido escala en algún puerto español y los hemos clasificado por distancia navegada, tipo de buque y potencia. Este encarecimiento del transporte marítimo será trasladado al sector exterior español, lo cual producirá un aumento del coste de las importaciones y exportaciones por mar en un país muy expuesto, pues el 75,61% del total de las importaciones y el 53,64% del total de las exportaciones se han hecho por vía marítima. Las tres industrias que se verán más afectadas son aquellas cuyo valor de mercancía es inferior respecto a su coste de transporte. Para ellas los aumentos del coste sobre el total del valor de cada mercancía serán de un 2,94% para la madera y corcho, un 2,14% para los productos minerales y un 1,93% para las manufacturas de piedra, cemento, cerámica y vidrio. Las mercancías que entren o salgan por los dos archipiélagos españoles de Canarias y Baleares serán las que se verán más impactadas por el extra coste del transporte marítimo, ya que son los puertos más alejados de otros puertos principales y, por tanto, con más distancia de navegación. Sin embargo, esta no es la única alternativa al cumplimiento de la nueva regulación. De la lectura del capítulo 6 concluimos que las tecnologías de equipos scrubbers y de propulsión con GNL permitirán al buque consumir combustibles más baratos al gasoil, a cambio de una inversión en estas tecnologías. ¿Serán los ahorros producidos por estas nuevas tecnologías suficientes para justificar su inversión? Para contestar la anterior pregunta, en el capítulo 7 hemos comparado las tres alternativas y hemos calculado tanto los costes de inversión como los gastos operativos correspondientes a equipos scrubbers o propulsión con GNL para una selección de 53 categorías de buques. La inversión en equipos scrubbers es más conveniente para buques grandes, con navegación no regular. Sin embargo, para buques de tamaño menor y navegación regular por puertos con buena infraestructura de suministro de GNL, la inversión en una propulsión con GNL como combustible será la más adecuada. En el caso de un tiempo de navegación del 100% dentro de zonas ECA y bajo el escenario de precios visto durante el año 2014, los proyectos con mejor plazo de recuperación de la inversión en equipos scrubbers son para los cruceros de gran tamaño (100.000 tons. GT), para los que se recupera la inversión en 0,62 años, los grandes portacontenedores de más de 8.000 TEUs con 0,64 años de recuperación y entre 5.000-8.000 TEUs con 0,71 años de recuperación y, por último, los grandes petroleros de más de 200.000 tons. de peso muerto donde tenemos un plazo de recuperación de 0,82 años. La inversión en scrubbers para buques pequeños, por el contrario, tarda más tiempo en recuperarse llegando a más de 5 años en petroleros y quimiqueros de menos de 5.000 toneladas de peso muerto. En el caso de una posible inversión en propulsión con GNL, las categorías de buques donde la inversión en GNL es más favorable y recuperable en menor tiempo son las más pequeñas, como ferris, cruceros o RoRos. Tomamos ahora el caso particular de un buque de productos limpios de 38.500 toneladas de peso muerto ya construido y nos planteamos la viabilidad de la inversión en la instalación de un equipo scrubber o bien, el cambio a una propulsión por GNL a partir del año 2015. Se comprueba que las dos variables que más impactan sobre la conveniencia de la inversión son el tiempo de navegación del buque dentro de zonas de emisiones controladas (ECA) y el escenario futuro de precios del MGO, HSFO y GNL. Para realizar este análisis hemos estudiado cada inversión, calculando una batería de condiciones de mérito como el payback, TIR, VAN y la evolución de la tesorería del inversor. Posteriormente, hemos calculado las condiciones de contorno mínimas de este buque en concreto para asegurar una inversión no sólo aceptable, sino además conveniente para el naviero inversor. En el entorno de precios del 2014 -con un diferencial entre fuel y gasóleo de 264,35 USD/ton- si el buque pasa más de un 56% de su tiempo de navegación en zonas ECA, conseguirá una rentabilidad de la inversión para inversores (TIR) en el equipo scrubber que será igual o superior al 9,6%, valor tomado como coste de oportunidad. Para el caso de inversión en GNL, en el entorno de precios del año 2014 -con un diferencial entre GNL y gasóleo de 353,8 USD/ton FOE- si el buque pasa más de un 64,8 % de su tiempo de navegación en zonas ECA, conseguirá una rentabilidad de la inversión para inversores (TIR) que será igual o superior al 9,6%, valor del coste de oportunidad. Para un tiempo en zona ECA estimado de un 60%, la rentabilidad de la inversión (TIR) en scrubbers para los inversores será igual o superior al 9,6%, el coste de oportunidad requerido por el inversor, para valores del diferencial de precio entre los dos combustibles alternativos, gasóleo (MGO) y fuel oil (HSFO) a partir de 244,73 USD/ton. En el caso de una inversión en propulsión GNL se requeriría un diferencial de precio entre MGO y GNL de 382,3 USD/ton FOE o superior. Así, para un buque de productos limpios de 38.500 DWT, la inversión en una reconversión para instalar un equipo scrubber es más conveniente que la de GNL, pues alcanza rentabilidades de la inversión (TIR) para inversores del 12,77%, frente a un 6,81% en el caso de invertir en GNL. Para ambos cálculos se ha tomado un buque que navegue un 60% de su tiempo por zona ECA y un escenario de precios medios del año 2014 para el combustible. Po otro lado, las inversiones en estas tecnologías a partir del año 2025 para nuevas construcciones son en ambos casos convenientes. El naviero deberá prestar especial atención aquí a las características propias de su buque y tipo de navegación, así como a la infraestructura de suministros y vertidos en los puertos donde vaya a operar usualmente. Si bien, no se ha estudiado en profundidad en esta tesis, no olvidemos que el sector marítimo debe cumplir además con las otras dos limitaciones que la regulación de la OMI establece sobre las emisiones de óxidos de Nitrógeno (NOx) y Carbono (CO2) y que sin duda, requerirán adicionales inversiones en diversos equipos. De manera que, si bien las consecuencias del consumo de gasóleo como alternativa al cumplimiento de la Regulación MARPOL son ciertamente preocupantes, existen alternativas al uso del gasóleo, con un aumento sobre el coste del transporte marítimo menor y manteniendo los beneficios sociales que pretende dicha ley. En efecto, como hemos demostrado, las opciones que se plantean como más rentables desde el punto de vista financiero son el consumo de GNL en los buques pequeños y de línea regular (cruceros, ferries, RoRos), y la instalación de scrubbers para el resto de buques de grandes dimensiones. Pero, por desgracia, estas inversiones no llegan a hacerse realidad por el elevado grado de incertidumbre asociado a estos dos mercados, que aumenta el riesgo empresarial, tanto de navieros como de suministradores de estas nuevas tecnologías. Observamos así una gran reticencia del sector privado a decidirse por estas dos alternativas. Este elevado nivel de riesgo sólo puede reducirse fomentando el esfuerzo conjunto del sector público y privado para superar estas barreras de entrada del mercado de scrubbers y GNL, que lograrían reducir las externalidades medioambientales de las emisiones sin restar competitividad al transporte marítimo. Creemos así, que los mismos organismos que aprobaron dicha ley deben ayudar al sector naviero a afrontar las inversiones en dichas tecnologías, así como a impulsar su investigación y promover la creación de una infraestructura portuaria adaptada a suministros de GNL y a descargas de vertidos procedentes de los equipos scrubber. Deberían además, prestar especial atención sobre las ayudas al sector de corta distancia para evitar que pierda competitividad frente a otros medios de transporte por el cumplimiento de esta normativa. Actualmente existen varios programas europeos de incentivos, como TEN-T o Marco Polo, pero no los consideramos suficientes. Por otro lado, la Organización Marítima Internacional debe confirmar cuanto antes si retrasa o no al 2025 la nueva bajada del nivel de azufre en combustibles. De esta manera, se eliminaría la gran incertidumbre temporal que actualmente tienen tanto navieros, como empresas petroleras y puertos para iniciar sus futuras inversiones y poder estudiar la viabilidad de cada alternativa de forma individual. ABSTRACT On 10 October 2008 the International Maritime Organization (IMO) signed an amendment to Annex VI of the MARPOL 73/78 convention establishing a gradual reduction in sulphur oxide (SOx) emissions from ships, and an additional reduction in nitrogen oxide (NOx) emissions and carbon dioxide (CO2) emissions from marine engines which cause environmental problems such as acid rain and the greenhouse effect. According to this regulation, from 1 January 2015, ships travelling in an Emission Control Area (ECA) must use fuels with a sulphur content of less than 0.1%. From 1 January 2020, or alternatively from 2025 if the IMO should decide to delay its introduction, all ships must use fuels with a sulphur content of less than 0.5%. As before, this content will be 0.1%S for voyages within ECAs. Meanwhile, the European Union has gone further than the IMO, and will apply the strictest limits of the MARPOL directives in the waters of its exclusive economic zone from 2020. To this end, Directive 2012/33/EU was issued on 21 November 2013 as an addendum to the 1999 Directive. These laws are intended to improve public health and the environment, benefiting society by reducing disease, particularly respiratory problems. The first question which arises is: what fuel do ships currently use, and what fuel will they have to use to comply with the Convention? Today, large international shipping vessels consume fuel oil with a sulphur level of 3.5%. Do fuel oils exist with a sulphur level of 0.5%S? As we conclude in Chapter 4, oil companies regard marine fuel oil as a by-product of refining Brent to produce their basket of products, as the demand for fuel oil is declining in comparison to other products, and the profit margin on the sale of other petroleum products is higher. Thus, oil companies are not interested in investing in their refineries to produce low-sulphur fuel oils, and if a company should decide to invest in producing a 0.5%S fuel oil, its price would have to be very similar to that of marine gas oil in order to recoup the investment. Therefore, the only fuel which presently complies with the new levels required by the IMO is marine gas oil, which was priced on average 307 USD/tonne higher than current fuel oils during 2014. This higher purchasing price for fuel will have a direct impact on the cost of maritime transport. The entry into force of the above directive presents a challenge for the entire maritime sector. There are various alternative approaches to this situation, with different technical, operational and financial implications. At present three options are the most widespread in the sector. The first option consists of “doing nothing” and simply switching from fuel oil to marine gas oil in large ships. The second option is installing a scrubber system, which would enable ships to continue consuming fuel oil, cleaning the combustion gases before they are released to the atmosphere. And finally, the third option is using Liquefied Natural Gas (LNG), which is priced lower than marine gas oil, as a fuel. However, there is still significant uncertainty on future variations in prices, the operation and maintenance of the new technologies, the investments required, the availability of port infrastructure and even future developments in the international regulations themselves. These uncertainties mean that none of these three alternatives has been unanimously accepted by the sector. In this Thesis, after discussing all the regulations applicable to the sector in Chapter 3, we investigate their consequences. In Chapter 4 we examine whether there are currently any marine fuels on the market which meet the new sulphur limits, and if not, how much new fuels would cost. In Chapter 5, based on the hypothesis that all ships will switch from fuel oil to marine gas oil to comply with the regulations, we calculate the increase in demand for marine gas oil this would lead to, and analyse the consequences this would have on marine gas oil production in the Mediterranean. We also calculate the economic impact such a cost increase would have on Spain's external sector. To do this, we also use the Automatic Identification System (AIS) system to analyse the data of every ship stopping in any Spanish port, in order to calculate the extra cost of using marine gas oil in maritime transport for all Spain's imports and exports. Finally, in Chapter 6, we examine and compare the other two alternatives to marine gas oil, scrubbers and LNG, and in Chapter 7 we analyse the viability of investing in these two technologies in order to comply with the regulations. In Chapter 5 we explain the many existing methods for calculating a ship's fuel consumption. We use a bottom-up calculation method, based on aggregating the activity and characteristics of each type of vessel. The result is based on the installed engine power of each ship, the engine load percentage and its specific consumption. To do this, we analyse the number of ships travelling in the Mediterranean in the course of one year, using the AIS, a marine traffic monitoring system, to take “snapshots” of marine traffic in the Mediterranean and report all ships at sea on random days throughout 2014. Finally, with the above data, we calculate the potential demand for marine gas oil in the Mediterranean. If nothing else is done and ships begin to use marine gas oil instead of fuel oil in order to comply with the regulation, the demand for marine gas oil in the Mediterranean will increase by 12.12 MTA (Millions Tonnes per Annum) from 2020. This means an increase of around 3.72 billion dollars a year in fuel costs, taking as reference the average price of marine fuels in 2014. Such an increase in demand in the Mediterranean would be equivalent to 43% of the total demand for diesel in Spain in 2013, including automotive diesel fuels, biodiesel and marine gas oils, and 3.2% of European consumption of middle distillates in 2014. Would the European market be able to supply enough to meet this greater demand for diesel? Europe has always had a surplus of gasoline and a deficit of middle distillates. In 2009, Europe had to import 4.8 MTA from North America and 22.1 MTA from Asia. Therefore, this increased demand on Europe's already limited capacity for refining middle distillates would lead to increased imports and higher prices, especially in the diesel market. The sector which would suffer the greatest impact of increased demand for marine gas oil would be Mediterranean cruise ships, which represent 30.4% of the fuel demand of the entire world cruise fleet, meaning their fuel costs would rise by 386 million USD per year. ROROs in the Mediterranean, which represent 23.6% of the demand of the world fleet of this type of ship, would see their fuel costs increase by 171 million USD a year. The greatest cost increase would be among container ships, with an increase on current costs of 1.168 billion USD per year. However, their consumption in the Mediterranean represents only 5.3% of worldwide fuel consumption by container ships. These figures raise the question of whether a cost increase of this size for RORO ships would lead to short-distance marine transport in general becoming less competitive compared to other transport options on certain routes. For example, some of the goods that ships now carry could switch to road transport, with the undesirable effects on the environment and on operations that this would produce. In the particular case of Spain, the extra cost of switching to marine gas oil in all ships stopping at any Spanish port in 2013 would be 1.717 billion EUR per year, as we demonstrate in the last part of Chapter 5. For this calculation, we used the AIS system to analyse all ships which stopped at any Spanish port, classifying them by distance travelled, type of ship and engine power. This rising cost of marine transport would be passed on to the Spanish external sector, increasing the cost of imports and exports by sea in a country which relies heavily on maritime transport, which accounts for 75.61% of Spain's total imports and 53.64% of its total exports. The three industries which would be worst affected are those with goods of lower value relative to transport costs. The increased costs over the total value of each good would be 2.94% for wood and cork, 2.14% for mineral products and 1.93% for manufactured stone, cement, ceramic and glass products. Goods entering via the two Spanish archipelagos, the Canary Islands and the Balearic Islands, would suffer the greatest impact from the extra cost of marine transport, as these ports are further away from other major ports and thus the distance travelled is greater. However, this is not the only option for compliance with the new regulations. From our readings in Chapter 6 we conclude that scrubbers and LNG propulsion would enable ships to use cheaper fuels than marine gas oil, in exchange for investing in these technologies. Would the savings gained by these new technologies be enough to justify the investment? To answer this question, in Chapter 7 we compare the three alternatives and calculate both the cost of investment and the operating costs associated with scrubbers or LNG propulsion for a selection of 53 categories of ships. Investing in scrubbers is more advisable for large ships with no fixed runs. However, for smaller ships with regular runs to ports with good LNG supply infrastructure, investing in LNG propulsion would be the best choice. In the case of total transit time within an ECA and the pricing scenario seen in 2014, the best payback periods on investments in scrubbers are for large cruise ships (100,000 gross tonnage), which would recoup their investment in 0.62 years; large container ships, with a 0.64 year payback period for those over 8,000 TEUs and 0.71 years for the 5,000-8,000 TEU category; and finally, large oil tankers over 200,000 deadweight tonnage, which would recoup their investment in 0.82 years. However, investing in scrubbers would have a longer payback period for smaller ships, up to 5 years or more for oil tankers and chemical tankers under 5,000 deadweight tonnage. In the case of LNG propulsion, a possible investment is more favourable and the payback period is shorter for smaller ship classes, such as ferries, cruise ships and ROROs. We now take the case of a ship transporting clean products, already built, with a deadweight tonnage of 38,500, and consider the viability of investing in installing a scrubber or changing to LNG propulsion, starting in 2015. The two variables with the greatest impact on the advisability of the investment are how long the ship is at sea within emission control areas (ECA) and the future price scenario of MGO, HSFO and LNG. For this analysis, we studied each investment, calculating a battery of merit conditions such as the payback period, IRR, NPV and variations in the investors' liquid assets. We then calculated the minimum boundary conditions to ensure the investment was not only acceptable but advisable for the investor shipowner. Thus, for the average price differential of 264.35 USD/tonne between HSFO and MGO during 2014, investors' return on investment (IRR) in scrubbers would be the same as the required opportunity cost of 9.6%, for values of over 56% ship transit time in ECAs. For the case of investing in LNG and the average price differential between MGO and LNG of 353.8 USD/tonne FOE in 2014, the ship must spend 64.8% of its time in ECAs for the investment to be advisable. For an estimated 60% of time in an ECA, the internal rate of return (IRR) for investors equals the required opportunity cost of 9.6%, based on a price difference of 244.73 USD/tonne between the two alternative fuels, marine gas oil (MGO) and fuel oil (HSFO). An investment in LNG propulsion would require a price differential between MGO and LNG of 382.3 USD/tonne FOE. Thus, for a 38,500 DWT ship carrying clean products, investing in retrofitting to install a scrubber is more advisable than converting to LNG, with an internal rate of return (IRR) for investors of 12.77%, compared to 6.81% for investing in LNG. Both calculations were based on a ship which spends 60% of its time at sea in an ECA and a scenario of average 2014 prices. However, for newly-built ships, investments in either of these technologies from 2025 would be advisable. Here, the shipowner must pay particular attention to the specific characteristics of their ship, the type of operation, and the infrastructure for supplying fuel and handling discharges in the ports where it will usually operate. Thus, while the consequences of switching to marine gas oil in order to comply with the MARPOL regulations are certainly alarming, there are alternatives to marine gas oil, with smaller increases in the costs of maritime transport, while maintaining the benefits to society this law is intended to provide. Indeed, as we have demonstrated, the options which appear most favourable from a financial viewpoint are conversion to LNG for small ships and regular runs (cruise ships, ferries, ROROs), and installing scrubbers for large ships. Unfortunately, however, these investments are not being made, due to the high uncertainty associated with these two markets, which increases business risk, both for shipowners and for the providers of these new technologies. This means we are seeing considerable reluctance regarding these two options among the private sector. This high level of risk can be lowered only by encouraging joint efforts by the public and private sectors to overcome these barriers to entry into the market for scrubbers and LNG, which could reduce the environmental externalities of emissions without affecting the competitiveness of marine transport. Our opinion is that the same bodies which approved this law must help the shipping industry invest in these technologies, drive research on them, and promote the creation of a port infrastructure which is adapted to supply LNG and handle the discharges from scrubber systems. At present there are several European incentive programmes, such as TEN-T and Marco Polo, but we do not consider these to be sufficient. For its part, the International Maritime Organization should confirm as soon as possible whether the new lower sulphur levels in fuels will be postponed until 2025. This would eliminate the great uncertainty among shipowners, oil companies and ports regarding the timeline for beginning their future investments and for studying their viability.

A methodology to estimate uncertainty for emission projections through sensitivity analysis

Air pollution abatement policies must be based on quantitative information on current and future emissions of pollutants. As emission projections uncertainties are inevitable and traditional statistical treatments of uncertainty are highly time/resources consuming, a simplified methodology for nonstatistical uncertainty estimation based on sensitivity analysis is presented in this work. The methodology was applied to the “with measures” scenario for Spain, concretely over the 12 highest emitting sectors regarding greenhouse gas and air pollutants emissions. Examples of methodology application for two important sectors (power plants, and agriculture and livestock) are shown and explained in depth. Uncertainty bands were obtained up to 2020 by modifying the driving factors of the 12 selected sectors and the methodology was tested against a recomputed emission trend in a low economic-growth perspective and official figures for 2010, showing a very good performance. Implications: A solid understanding and quantification of uncertainties related to atmospheric emission inventories and projections provide useful information for policy negotiations. However, as many of those uncertainties are irreducible, there is an interest on how they could be managed in order to derive robust policy conclusions. Taking this into account, a method developed to use sensitivity analysis as a source of information to derive nonstatistical uncertainty bands for emission projections is presented and applied to Spain. This method simplifies uncertainty assessment and allows other countries to take advantage of their sensitivity analyses.