Doping in MARCA (1975-1990)

En el estudio histórico del dopaje en España, conocer el papel de los medios de comunicación escritos, como el diario deportivo Marca, resulta ser de gran relevancia. La función que el periódico más vendido en España ha desempeñado a lo largo de los años con relación al deportista sospechoso, permite conocer de qué manera el discurso social se ha estructurado basándose precisamente en cómo sus cronistas han narrado el caso de dopaje.

Optimizing phosphorus diffusion for photovoltaic applications: peak doping, inactive phosphorus,gettering, and contact formation

The phosphosilicate glass (PSG), fabricated by tube furnace diffusion using a POCl3 source, is widely used as a dopant source in the manufacturing of crystalline silicon solar cells. Although it has been a widely addressed research topic for a long time, there is still lack of a comprehensive understanding of aspects such as the growth, the chemical composition, possible phosphorus depletion, the resulting in-diffused phosphorus profiles, the gettering behavior in silicon, and finally the metal-contact formation. This paper addresses these different aspects simultaneously to further optimize process conditions for photovoltaic applications. To do so, a wide range of experimental data is used and combined with device and process simulations, leading to a more comprehensive interpretation. The results show that slight changes in the PSG process conditions can produce high-quality emitters. It is predicted that PSG processes at 860 °C for 60 min in combination with an etch-back and laser doping from PSG layer results in high-quality emitters with a peak dopant density Npeak = 8.0 × 1018 cm−3 and a junction depth dj = 0.4 μm, resulting in a sheet resistivityρsh = 380 Ω/sq and a saturation current-density J0 below 10 fA/cm2. With these properties, the POCl3 process can compete with ion implantation or doped oxide approaches.

InN/GaN heterojunction electrical behavior

Indium nitride (InN) has been the subject of intense research in recent years. Some of its most attractive features are its excellent transport properties such as its small band edge electron effective mass, high electron mobilities and peak drift velocities, and high frequency transient drift velocity oscillations [1]. These suggest enormous potential applications for InN in high frequency electronic devices. But to date the high unintentional bulk electron concentration (n~1018 cm-3) of undoped InN samples and the surface electron accumulation layer make it a hard task to create a reliable metalsemiconductor Schottky barrier. Some attempts have been made to overcome this problem by means of material oxidation [2] or deposition of insulators [3]. In this work we present a way to obtain an electrical rectification behaviour by means of heterojunction growth. Due to the big band gap differences among nitride semiconductors, it’s possible to create a structure with high band offsets. In InN/GaN heterojunctions, depending on the GaN doping, the magnitude of conduction and valence band offset are critical parameters which allow distinguishing among different electrical behaviours. The earliest estimate of the valence band offset at an InN–GaN heterojunction in a wurtzite structure was measured to be ~0.85 eV [4], while the Schottky barrier heights were determined to be ~ 1,4 eV [5].We grew In-face InN layer with varying thickness (between 150 nm and 1 mm) by plasma assisted molecular beam epitaxy (PA-MBE) on GaNntemplates (GaN/Al2O3), with temperatures ranging between 300°C and 450°C. The different doping in GaN template (Si doping, Fe doping and Mg doping) results in differences in band alignments of the two semiconductors changing electrical barriers for carriers and consequently electrical conduction behaviour. The processing of the devices includes metallization of the ohmic contacts on InN and GaN, for which we used Ti/Al/Ni/Au. Whereas an ohmic contact on InN is straightforward, the main issue was the fabrication of the contact on GaN due to the very low decomposition temperature of InN. A standard ohmic contact on GaN is generally obtained by high temperature rapid thermal annealing (RTA), typically done between 500ºC and 900ºC[6]. In this case, the limitation due to the presence of In-face InN imposes an upper limit on the temperature for the thermal annealing process and ohmic contact formation of about 450°C. We will present results on the morphology of the InN layers by X-Ray diffraction and SEM, and electrical measurements, in particular current-voltage and capacitance-voltage characteristics.

Individualization and Electrical Characterization of SiGe Nanowires

SiGe nanowires of different Ge atomic fractions up to 15% were grown and ex-situ n-type doped by diffusion from a solid source in contact with the sample. The phenomenon of dielectrophoresis was used to locate single nanowires between pairs of electrodes in order to carry out electrical measurements. The measured resistance of the as-grown nanowires is very high, but it decreases more than three orders of magnitude upon doping, indicating that the doping procedure used has been effective

Diffusion of Zn into GaAs and AlGaAs from isothermal Liquid-phase epitaxy solutions

In this work we present results of zinc diffusion in GaAs using the liquid phase epitaxy technique from liquid solutions of Ga‐As‐Zn and Ga‐As‐Al‐Zn. Using silicon‐doped n‐GaAs substrates, working at a diffusion temperature of 850 °C, and introducing a dopant concentration ranging 1018–1019 cm−3, the most important findings regarding the diffusion properties are as follows: (a) zinc concentration in the solid depends on the square root of zinc atomic fraction in the liquid; (b) the diffusion is dominated by the interstitial‐substitutional process; (c) the diffusivity D varies as about C3 in the form D=2.9×10−67C3.05; (d) aluminum plays the role of the catalyst of the diffusion process, if it is introduced in the liquid solution, since it is found that D varies as (γAsXlAs)−1; (e) the zinc interstitial is mainly doubly ionized (Zn++i); (f) the zinc diffusion coefficient in Al0.85 Ga0.15 As is about four times greater than in GaAs; (g) by means of all these results, it is possible to control zinc diffusion processes in order to obtain optimized depth junctions and doping levels in semiconductor device fabrication.

Microprocesos láser para la mejora de dispositivos fotovoltaicos basados en silicio cristalino

En los últimos años la tecnología láser se ha convertido en una herramienta imprescindible en la fabricación de dispositivos fotovoltaicos, ayudando a la consecución de dos objetivos claves para que esta opción energética se convierta en una alternativa viable: reducción de costes de fabricación y aumento de eficiencia de dispositivo. Dentro de las tecnologías fotovoltaicas, las basadas en silicio cristalino (c-Si) siguen siendo las dominantes en el mercado, y en la actualidad los esfuerzos científicos en este campo se encaminan fundamentalmente a conseguir células de mayor eficiencia a un menor coste encontrándose, como se comentaba anteriormente, que gran parte de las soluciones pueden venir de la mano de una mayor utilización de tecnología láser en la fabricación de los mismos. En este contexto, esta Tesis hace un estudio completo y desarrolla, hasta su aplicación en dispositivo final, tres procesos láser específicos para la optimización de dispositivos fotovoltaicos de alta eficiencia basados en silicio. Dichos procesos tienen como finalidad la mejora de los contactos frontal y posterior de células fotovoltaicas basadas en c-Si con vistas a mejorar su eficiencia eléctrica y reducir el coste de producción de las mismas. En concreto, para el contacto frontal se han desarrollado soluciones innovadoras basadas en el empleo de tecnología láser en la metalización y en la fabricación de emisores selectivos puntuales basados en técnicas de dopado con láser, mientras que para el contacto posterior se ha trabajado en el desarrollo de procesos de contacto puntual con láser para la mejora de la pasivación del dispositivo. La consecución de dichos objetivos ha llevado aparejado el alcanzar una serie de hitos que se resumen continuación: - Entender el impacto de la interacción del láser con los distintos materiales empleados en el dispositivo y su influencia sobre las prestaciones del mismo, identificando los efectos dañinos e intentar mitigarlos en lo posible. - Desarrollar procesos láser que sean compatibles con los dispositivos que admiten poca afectación térmica en el proceso de fabricación (procesos a baja temperatura), como los dispositivos de heterounión. - Desarrollar de forma concreta procesos, completamente parametrizados, de definición de dopado selectivo con láser, contactos puntuales con láser y metalización mediante técnicas de transferencia de material inducida por láser. - Definir tales procesos de forma que reduzcan la complejidad de la fabricación del dispositivo y que sean de fácil integración en una línea de producción. - Mejorar las técnicas de caracterización empleadas para verificar la calidad de los procesos, para lo que ha sido necesario adaptar específicamente técnicas de caracterización de considerable complejidad. - Demostrar su viabilidad en dispositivo final. Como se detalla en el trabajo, la consecución de estos hitos en el marco de desarrollo de esta Tesis ha permitido contribuir a la fabricación de los primeros dispositivos fotovoltaicos en España que incorporan estos conceptos avanzados y, en el caso de la tecnología de dopado con láser, ha permitido hacer avances completamente novedosos a nivel mundial. Asimismo los conceptos propuestos de metalización con láser abren vías, completamente originales, para la mejora de los dispositivos considerados. Por último decir que este trabajo ha sido posible por una colaboración muy estrecha entre el Centro Láser de la UPM, en el que la autora desarrolla su labor, y el Grupo de Investigación en Micro y Nanotecnologías de la Universidad Politécnica de Cataluña, encargado de la preparación y puesta a punto de las muestras y del desarrollo de algunos procesos láser para comparación. También cabe destacar la contribución de del Centro de Investigaciones Energéticas, Medioambientales y Tecnológicas, CIEMAT, en la preparación de experimentos específicos de gran importancia en el desarrollo del trabajo. Dichas colaboraciones se han desarrollado en el marco de varios proyectos, tales como el proyecto singular estratégico PSE-MICROSIL08 (PSE-iv 120000-2006-6), el proyecto INNDISOL (IPT-420000-2010-6), ambos financiados por el Fondo Europeo de Desarrollo Regional FEDER (UE) “Una manera de hacer Europa” y el MICINN, y el proyecto del Plan Nacional AMIC (ENE2010-21384-C04-02), cuya financiación ha permitido en gran parte llevar a término este trabajo. v ABSTRACT. Last years lasers have become a fundamental tool in the photovoltaic (PV) industry, helping this technology to achieve two major goals: cost reduction and efficiency improvement. Among the present PV technologies, crystalline silicon (c-Si) maintains a clear market supremacy and, in this particular field, the technological efforts are focussing into the improvement of the device efficiency using different approaches (reducing for instance the electrical or optical losses in the device) and the cost reduction in the device fabrication (using less silicon in the final device or implementing more cost effective production steps). In both approaches lasers appear ideally suited tools to achieve the desired success. In this context, this work makes a comprehensive study and develops, until their implementation in a final device, three specific laser processes designed for the optimization of high efficiency PV devices based in c-Si. Those processes are intended to improve the front and back contact of the considered solar cells in order to reduce the production costs and to improve the device efficiency. In particular, to improve the front contact, this work has developed innovative solutions using lasers as fundamental processing tools to metalize, using laser induced forward transfer techniques, and to create local selective emitters by means of laser doping techniques. On the other side, and for the back contact, and approached based in the optimization of standard laser fired contact formation has been envisaged. To achieve these fundamental goals, a number of milestones have been reached in the development of this work, namely: - To understand the basics of the laser-matter interaction physics in the considered processes, in order to preserve the functionality of the irradiated materials. - To develop laser processes fully compatible with low temperature device concepts (as it is the case of heterojunction solar cells). - In particular, to parameterize completely processes of laser doping, laser fired contacts and metallization via laser transfer of material. - To define such a processes in such a way that their final industrial implementation could be a real option. - To improve widely used characterization techniques in order to be applied to the study of these particular processes. - To probe their viability in a final PV device. Finally, the achievement of these milestones has brought as a consequence the fabrication of the first devices in Spain incorporating these concepts. In particular, the developments achieved in laser doping, are relevant not only for the Spanish science but in a general international context, with the introduction of really innovative concepts as local selective emitters. Finally, the advances reached in the laser metallization approached presented in this work open the door to future developments, fully innovative, in the field of PV industrial metallization techniques. This work was made possible by a very close collaboration between the Laser Center of the UPM, in which the author develops his work, and the Research Group of Micro y Nanotecnology of the Universidad Politécnica de Cataluña, in charge of the preparation and development of samples and the assessment of some laser processes for comparison. As well is important to remark the collaboration of the Centro de Investigaciones Energéticas, Medioambientales y Tecnológicas, CIEMAT, in the preparation of specific experiments of great importance in the development of the work. These collaborations have been developed within the framework of various projects such as the PSE-MICROSIL08 (PSE-120000-2006-6), the project INNDISOL (IPT-420000-2010-6), both funded by the Fondo Europeo de Desarrollo Regional FEDER (UE) “Una manera de hacer Europa” and the MICINN, and the project AMIC (ENE2010-21384-C04-02), whose funding has largely allowed to complete this work.

Performance analysis of AlGaAs/GaAs tunnel junctions for ultra-high concentration photovoltaics

An n(++)-GaAs/p(++)-AlGaAs tunnel junction with a peak current density of 10 100Acm(-2) is developed. This device is a tunnel junction for multijunction solar cells, grown lattice-matched on standard GaAs or Ge substrates, with the highest peak current density ever reported. The voltage drop for a current density equivalent to the operation of the multijunction solar cell up to 10 000 suns is below 5 mV. Trap-assisted tunnelling is proposed to be behind this performance, which cannot be justified by simple band-to-band tunnelling. The metal-organic vapour-phase epitaxy growth conditions, which are in the limits of the transport-limited regime, and the heavy tellurium doping levels are the proposed origins of the defects enabling trap-assisted tunnelling. The hypothesis of trap-assisted tunnelling is supported by the observed annealing behaviour of the tunnel junctions, which cannot be explained in terms of dopant diffusion or passivation. For the integration of these tunnel junctions into a triple-junction solar cell, AlGaAs barrier layers are introduced to suppress the formation of parasitic junctions, but this is found to significantly degrade the performance of the tunnel junctions. However, the annealed tunnel junctions with barrier layers still exhibit a peak current density higher than 2500Acm(-2) and a voltage drop at 10 000 suns of around 20 mV, which are excellent properties for tunnel junctions and mean they can serve as low-loss interconnections in multijunction solar cells working at ultra-high concentrations.

Electronic, structural, and optical properties of the host and Cr-doped cadmium thioindate

The cadmium thioindate spinel CdIn2S4 semiconductor has potential applications for optoelectronic devices. We present a theoretical study of the structural and optoelectronic properties of the host and of the Cr-doped ternary spinel. For the host spinel, we analyze the direct or indirect character of the energy bandgap, the change of the energy bandgap with the anion displacement parameter and with the site cation distribution, and the optical properties. The main effect of the Cr doping is the creation of an intermediate band within the energy bandgap. The character and the occupation of this band are analyzed for two substitutions: Cr by In and Cr by Cd. This band permits more channels for the photon absorption. The optical properties are obtained and analyzed. The absorption coefficients are decomposed into contributions from the different absorption channels and from the inter-and intra-atomic components.

Electronic property analysis of O-doped Cu3SbS3

The ternary Cu-Sb-S semiconductors are considered to be sustainable and potential alternative absorber materials in thin film photovoltaic applications. In these compounds, several phases may coexist, albeit in different proportions depending on experimental growth conditions. Additionally, the photovoltaic efficiency could be increased with isoelectronic doping. In this work we analyze the electronic properties of O-doped Cu3SbS3 in two structures: the wittichenite and the skinnerite. We use first-principles within the density functional formalism with two different exchange-correlation potentials. In addition, we estimate the potential of these compounds for photovoltaic applications.

Effect of concentration on the performance of quantum dot intermediate-band solar cells

Implementation of a high-efficiency quantum dot intermediate-band solar cell (QD-IBSC) must accompany a sufficient photocurrent generation via IB states. The demonstration of a QD-IBSC is presently undergoing two stages. The first is to develop a technology to fabricate high-density QD stacks or a superlattice of low defect density placed within the active region of a p-i-n SC, and the second is to realize half-filled IB states to maximize the photocurrent generation by two-step absorption of sub-bandgap photons. For this, we have investigated the effect of light concentration on the characteristics of QDSCs comprised of multi-layer stacks of self-organized InAs/GaNAs QDs grown with and without impurity doping in molecular beam epitaxy.

Vanadium-Doped In and Sn Sulphides: Photocatalysts able to use the whole visible light spectrum

Using photocatalysis for energy applications depends, more than for environmental purposes or selective chemical synthesis, on converting as much of the solar spectrum as possible; the best photocatalyst, titania, is far from this. Many efforts are pursued to use better that spectrum in photocatalysis, by doping titania or using other materials (mainly oxides, nitrides and sulphides) to obtain a lower bandgap, even if this means decreasing the chemical potential of the electron-hole pairs. Here we introduce an alternative scheme, using an idea recently proposed for photovoltaics: the intermediate band (IB) materials. It consists in introducing in the gap of a semiconductor an intermediate level which, acting like a stepstone, allows an electron jumping from the valence band to the conduction band in two steps, each one absorbing one sub-bandgap photon. For this the IB must be partially filled, to allow both sub-bandgap transitions to proceed at comparable rates; must be made of delocalized states to minimize nonradiative recombination; and should not communicate electronically with the outer world. For photovoltaic use the optimum efficiency so achievable, over 1.5 times that given by a normal semiconductor, is obtained with an overall bandgap around 2.0 eV (which would be near-optimal also for water phtosplitting). Note that this scheme differs from the doping principle usually considered in photocatalysis, which just tries to decrease the bandgap; its aim is to keep the full bandgap chemical potential but using also lower energy photons. In the past we have proposed several IB materials based on extensively doping known semiconductors with light transition metals, checking first of all with quantum calculations that the desired IB structure results. Subsequently we have synthesized in powder form two of them: the thiospinel In2S3 and the layered compound SnS2 (having bandgaps of 2.0 and 2.2 eV respectively) where the octahedral cation is substituted at a â?10% level with vanadium, and we have verified that this substitution introduces in the absorption spectrum the sub-bandgap features predicted by the calculations. With these materials we have verified, using a simple reaction (formic acid oxidation), that the photocatalytic spectral response is indeed extended to longer wavelengths, being able to use even 700 nm photons, without largely degrading the response for above-bandgap photons (i.e. strong recombination is not induced) [3b, 4]. These materials are thus promising for efficient photoevolution of hydrogen from water; work on this is being pursued, the results of which will be presented.

New Intermediate band sulphide nanoparticles acting in the full visible light range spectra as an active photocatalyst

Nowadays one of the challenges of materials science is to find new technologies that will be able to make the most of renewable energies. An example of new proposals in this field are the intermediate-band (IB) materials, which promise higher efficiencies in photovoltaic applications (through the intermediate band solar cells), or in heterogeneous photocatalysis (using nanoparticles of them, for the light-induced degradation of pollutants or for the efficient photoevolution of hydrogen from water). An IB material consists in a semiconductor in which gap a new level is introduced [1], the intermediate band (IB), which should be partially filled by electrons and completely separated of the valence band (VB) and of the conduction band (CB). This scheme (figure 1) allows an electron from the VB to be promoted to the IB, and from the latter to the CB, upon absorption of photons with energy below the band gap Eg, so that energy can be absorbed in a wider range of the solar spectrum and a higher current can be obtained without sacrificing the photovoltage (or the chemical driving force) corresponding to the full bandgap Eg, thus increasing the overall efficiency. This concept, applied to photocatalysis, would allow using photons of a wider visible range while keeping the same redox capacity. It is important to note that this concept differs from the classic photocatalyst doping principle, which essentially tries just to decrease the bandgap. This new type of materials would keep the full bandgap potential but would use also lower energy photons. In our group several IB materials have been proposed, mainly for the photovoltaic application, based on extensively doping known semiconductors with transition metals [2], examining with DFT calculations their electronic structures. Here we refer to In2S3 and SnS2, which contain octahedral cations; when doped with Ti or V an IB is formed according to quantum calculations (see e.g. figure 2). We have used a solvotermal synthesis method to prepare in nanocrystalline form the In2S3 thiospinel and the layered compound SnS2 (which when undoped have bandgaps of 2.0 and 2.2 eV respectively) where the cation is substituted by vanadium at a ?10% level. This substitution has been studied, characterizing the materials by different physical and chemical techniques (TXRF, XRD, HR-TEM/EDS) (see e.g. figure 3) and verifying with UV spectrometry that this substitution introduces in the spectrum the sub-bandgap features predicted by the calculations (figure 4). For both sulphide type nanoparticles (doped and undoped) the photocatalytic activity was studied by following at room temperature the oxidation of formic acid in aqueous suspension, a simple reaction which is easily monitored by UV-Vis spectroscopy. The spectral response of the process is measured using a collection of band pass filters that allow only some wavelengths into the reaction system. Thanks to this method the spectral range in which the materials are active in the photodecomposition (which coincides with the band gap for the undoped samples) can be checked, proving that for the vanadium substituted samples this range is increased, making possible to cover all the visible light range. Furthermore it is checked that these new materials are more photocorrosion resistant than the toxic CdS witch is a well know compound frequently used in tests of visible light photocatalysis. These materials are thus promising not only for degradation of pollutants (or for photovoltaic cells) but also for efficient photoevolution of hydrogen from water; work in this direction is now being pursued.

New laser-based approaches to improve the passivation and rear contact quality in high effiency crystalline silicon solar cells

Laser processing has been the tool of choice last years to develop improved concepts in contact formation for high efficiency crystalline silicon (c-Si) solar cells. New concepts based on standard laser fired contacts (LFC) or advanced laser doping (LD) techniques are optimal solutions for both the front and back contacts of a number of structures with growing interest in the c-Si PV industry. Nowadays, substantial efforts are underway to optimize these processes in order to be applied industrially in high efficiency concepts. However a critical issue in these devices is that, most of them, demand a very low thermal input during the fabrication sequence and a minimal damage of the structure during the laser irradiation process. Keeping these two objectives in mind, in this work we discuss the possibility of using laser-based processes to contact the rear side of silicon heterojunction (SHJ) solar cells in an approach fully compatible with the low temperature processing associated to these devices. First we discuss the possibility of using standard LFC techniques in the fabrication of SHJ cells on p-type substrates, studying in detail the effect of the laser wavelength on the contact quality. Secondly, we present an alternative strategy bearing in mind that a real challenge in the rear contact formation is to reduce the damage induced by the laser irradiation. This new approach is based on local laser doping techniques previously developed by our groups, to contact the rear side of p-type c-Si solar cells by means of laser processing before rear metallization of dielectric stacks containing Al2O3. In this work we demonstrate the possibility of using this new approach in SHJ cells with a distinct advantage over other standard LFC techniques.

Synthetic strategy of porous ZnO and CdS nanostructures doped ferroelectric liquid crystal and its optical behavior

A simple and scalable chemical approach has been proposed for the generation of 1-dimensional nanostructures of two most important inorganic materials such as zinc oxide and cadmium sulfide. By controlling the growth habit of the nanostructures with manipulated reaction conditions, the diameter and uniformity of the nanowires/nanorods were tailored. We studied extensively optical behavior and structural growth of CdS NWs and ZnO NRs doped ferroelectric liquid crystal Felix-017/100. Due to doping band gap has been changed and several blue shifts occurred in photoluminescence spectra because of nanoconfinement effect and mobility of charges.

Laser Processes for Contact Optimization in c-Si Solar Cells

Solid State Lasers (SSL) have been used in microelectronic and photovoltaic (PV) industry for decades but, currently, laser technology appears as a key enabling technology to improve efficiency and to reduce production costs in high efficiency solar cells fabrication. Moreover, the fact that the interaction between the laser radiation and the device is normally localized and restricted to a controlled volume makes SSL a tool of choice for the implementation of low temperature concepts in PV industry. Specifically, SSL are ideally suited to improve the electrical performance of the contacts further improving the efficiency of these devices. Advanced concepts based on standard laser firing or advanced laser doping techniques are optimal solutions for the back contact of a significant number of structures of growing interest in the c-Si PV industry, and a number of solutions has been proposed as well for emitter formation, to reduce the metallization optical losses or even to remove completely the contacts from the front part of the cell. In this work we present our more recent results of SSL applications for contact optimization in c-Si solar cell technology, including applications on low temperature processes demanding devices, like heterojunction solar cells.