El óxido de zinc: crecimiento cristalino mediante transporte en fase gaseosa y caracterización de propiedades físicas.

RESUMEN Esta tesis está centrada en el estudio del crecimiento cristalino y propiedades físicas del óxido de zinc (ZnO). Este material puede ser considerado como un semiconductor antiguo, cuyo interés en la investigación se ha mantenido vivo durante varias décadas debido a su aplicación en diferentes áreas científicas e industriales, como son los dispositivos acusto-ópticos, los varistores, los sensores de gas, los electrodos transparentes conductores o su uso como ventana óptica en células solares. Además, en los últimos años ha surgido un interés especial debido a que sus propiedades físicas le convierten en un serio candidato para la fabricación de dispositivos optoelectrónicos en el rango del ultravioleta. La alta temperatura de fusión del ZnO hace que sea difícil abordar el crecimiento de cristales masivos de este material a partir de la fase liquida. Por tanto, el método hidrotermal y los métodos de transporte en fase gaseosa han sido los habitualmente utilizados para abordar el crecimiento de cristales de ZnO. Los cristales obtenidos mediante el método hidrotermal presentan una buena calidad estructural. Sin embargo, estos cristales contienen impurezas de litio y/o potasio, procedentes de los disolventes utilizados, que pueden afectar a las propiedades ópticas del ZnO. El crecimiento mediante métodos de transporte en fase gaseosa aparece como una alternativa atractiva para mejorar este punto. En el caso de los métodos de transporte en fase gaseosa es bien conocido que la velocidad de crecimiento del ZnO en sistemas cerrados, en el rango de temperaturas próximas a 1000 ºC y gradientes térmicos habituales, es muy baja si el proceso tiene lugar en ausencia de especies adicionales. El uso de ciertas especies adicionales permite obtener velocidades de crecimiento mayores. En esta tesis hemos profundizado en la comprensión de los procesos involucrados en el crecimiento cristalino de ZnO mediante estos métodos, tanto en los mecanismos de generación de vapor como en los relacionados con el transporte de éste. El entendimiento de estos procesos ha sido muy útil para la optimización de la velocidad de crecimiento y para el control de la composición de la mezcla gaseosa existente dentro de la ampolla de crecimiento. Este hecho ha permitido actuar sobre la estequiometria de los cristales de ZnO y, por tanto, sobre sus propiedades físicas. Además, se han analizado diferentes estrategias para localizar y controlar el proceso de nucleación inicial. De esta forma se ha conseguido actuar sobre las propiedades estructurales de los cristales de ZnO. En este sentido, también se han sometido algunos de los cristales obtenidos a diferentes tratamientos térmicos posteriores al crecimiento. Estos se han llevado a cabo en le rango de temperaturas comprendido entre 900 y 1200 ºC tanto en vacío, como en atmósferas de oxígeno o zinc. Estos procesos térmicos han mejorado la calidad estructural de los cristales y, además, han aportado información sobre la naturaleza química y la concentración de defectos intrísencos puntuales presentes en los cristales de ZnO obtenidos. Para ello se han analizado la variación de sus propiedades estructurales, ópticas y eléctricas mediante diferentes técnicas de caracterización (difracción de rayos X de alta resolución, espectroscopia Raman, medidas de transmisión óptica y efecto may). Adicionalmente, en la última parte de esta tesis, se ha abordado el crecimiento de dos heerostructuras basadas en capas de ZnO con morfología nano-estructurada y su posible aplicabilidad como células solares. Las curvas tensión-voltaje (iV) obtenidas para la heterostructura ZnO/CdSe/CuSCN la convierten en una opción interesante para el desarrollo de una nueva tecnología en la producción de células solares. Este hecho pone de manifiesto la multifuncionalidad del ZnO. ____________________________________________________________________________________________________Due to its high melting point (~2000ºC), is difficult to grow ZnO from the liquid phase. That is why hydrothermal and vapour transport methods have been mainly implemented so far for the growth of bulk ZnO crystals. Crystal growth from the vapour phase appears as an attractive alternative. Nevertheless, it has been well established that the growth rate of ZnO in closed ampoules at moderate temperatures (~1000ºC) and temperature gradients is very low if the process takes place in absence of any additional species. Higher growth rates are obtained if some particular additional species are introduced in the ampoule In this work, we will try to gain a further insight into the vapour generation and transport mechanisms involved in the ZnO growth using some additional species. The knowledge of these mechanisms can be very useful to optimise the growth rate and it could allow to control the gas composition inside the growth ampoule. This fact would allow to act on the off-stoichiometry degree of the ZnO crystals and, therefore, on their physical properties. Besides, we will analyse some ways to localise and control the onset of nucleation that can improve the structural properties and the crystal size. On the other hand, some of the grown ZnO crystals will be annealed at temperatures in the range 900-1200 ºC in vacuum, as well as in oxygen and zinc atmospheres. These annealing processes improve the structural quality and will be used as a tool to obtain some information about the initial intrinsic defects present in as-grown crystals. Different fundamental characterisation techniques as X-ray diffraction, Raman spectroscopy, optical transmission and Hall effect measurements will be used to study the physical properties of the as-grown and annealed ZnO crystals. In addition, we will study the application of two p-i-n heterostructures based on a ZnO electrodeposited layer, which shows nanocolumnar morphology, as eta (extremely thin absorber)-solar cells. The ZnO and the successively built up layers will be analysed by scanning electron microscopy, X-ray diffraction and optical transmission and reflectance. Finally, the i-V curves and the energy conversion efficiency of the device will be measured

All-in-One Gel-Based Electrochromic Devices: Strengths and Recent Developments

Electrochromic devices (ECDs) have aroused great interest because of their potential applicability in displays and smart systems, including windows, rearview mirrors, and helmet visors. In the last decades, different device structures and materials have been proposed to meet the requirements of commercial applications to boost market entry. To this end, employing simple device architectures and achieving a competitive electrolyte are crucial to accomplish easily implementable, high-performance ECDs. The present review outlines devices comprising gel electrolytes as a single electroactive layer (“all-in-one”) ECD architecture, highlighting some advantages and opportunities they offer over other electrochromic systems. In this context, gel electrolytes not only overcome the drawbacks of liquid and solid electrolytes, such as liquid’s low chemical stability and risk of leaking and soil’s slow switching and lack of transparency, but also exhibit further strengths. These include easier processability, suitability for flexible substrates, and improved stabilization of the chemical species involved in redox processes, leading to better cyclability and opening wide possibilities to extend the electrochromic color palette, as discussed herein. Finally, conclusions and outlook are provided.This work has been partially supported by the European Union’s Horizon 2020 research and innovation program under the INNPAPER project (grant agreement No. 760876)

Spray-Pyrolyzed ZnO as Electron Selective Contact for Long-Term Stable Planar CH3NH3PbI3 Perovskite Solar Cells

Electron selective contacts (ESCs) play an important role in the performance of perovskite solar cells (PSCs). ZnO has attracted important attention as a good material for ESCs because of its matched energy levels with those of perovskite, its high transmittance in the visible region, and its high electron mobility. Here we reported the use of ZnO thin layers prepared by spray pyrolysis as ESC for PSCs. Our ZnO based planar CH3NH3PbI3 (MAPbI3) devices not only were stable in a humidity of 35% but also improved the performance even after more than 1 month of preparation, due to an increase of charge transfer at the ZnO interface as it has been characterized by impedance spectroscopy. The formation of ZnO depends on preparation conditions such as gas flow, zinc acetate solution concentrations, and substrate temperatures, all of which have an effect on the performance of stability of MAPbI3 solar cells. Also, the low hysteresis reported for these samples was discussed in this study. We have also observed that long-term structural evolution of perovskite film also depends on the ZnO substrate and its deposition method

ZnO growth by MOCVD: numerical study

EnIII−V compound device fabrication is facing today challenging issues typically related to high volume manufacturing such as process reliability, process consistency, cost−reduction. Each step of the overall device manufacturing process must be carefully analysed and replicated to obtain reproducible device structures. Purifiers are commonly used in MOVPE processes and are becoming standard equipment in both research and production environments. In most cases implementation of gas purification strategies is enabling to achieve ultimate product purity and process reproducibility by defect and contamination control. In addition, an appropriate gas purification strategy is effective in high value component/chemicals protection (e.g. high purity MO sources), and as an assurance against line contamination due to human error or component failure. Purifier operating conditions can vary noticeably and a knowledge of which parameters can affect ultimate gas purity should be of interest to MOVPE operators to master gas distribution line contamination issues. Expertise on such parameters and their effect is essential to obtain a reliable product and sub−ppb contamination control throughout the purifier's lifetime and not only in spot demonstrations

Electrodeposited NiO anode interlayers: Enhancement of the charge carrier selectivity in organic solar cells

Nickel oxide (NiO) thin films prepared by cathodic electrodeposition exhibit superior electrical performace than PEDOT:PSS when used as anode interlayers of bulk-heterojunction solar cells. Devices incorporating 30 nm-thick NiO films firstly annealed at 320 °C in air and posteriorly treated with UV-O3 reach power conversion efficiencies comparable to that obtained for PEDOT:PSS-based cells. NiO interlayers enhance contact selectivity by simulataneously increasing shunt resistance (lower leakage current related to electron-blocking ability), and reducing hole-extraction resistance. Carrier selectivity is quantified from the resistance components associated with the impedance response of the anode contacts. The versatile electrodeposition technique of NiO interlayers permits avoiding PEDOT:PSS use as it presents disadvantages related to its acid character and hygroscopic nature

Electrodeposition and impedance spectroscopy characterization of ZnO nanowire arrays

An overview of the electrodeposition of ZnO nanowire arrays from the reduction of dissolved molecular oxygen in zinc chloride solutions was reported. In spite of the internal structure of ZnO which favours the anisotropic growth along the [0001] direction, the change in the local composition of the electrolyte around the nanowire during the electrodeposition was proposed as a major parameter to affect the nanowire growth mechanism. The influence of the ratio between the O2 reduction rate and the diffusion of Zn2+ to the cathode was emphasized. Due to the particular morphology of the nanowire arrays, no lateral growth was observed when the reduction of O2 was relatively fast, while the corresponding deposition efficiency was very low. The decrease of the O2 reduction rate resulted in an enhancement of the deposition efficiency. The highest efficiencies (40–55%) were attained by using high chloride concentrations ([KCl] = 3.4 M) resulting not only in an enhancement of the longitudinal growth, but also in a considerable lateral growth. The influence of the electrodeposition conditions on the donor density of ZnO nanowires was investigated by using electrochemical impedance spectroscopy. Donor densities from 5 × 1019 cm–3 to 3 × 1020 cm–3 were obtained for as deposited samples. They decreased to values in the range of 1017–1018 cm–3 after annealing in air (1 hour at 450 °C). (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim

Positron annihilation lifetime spectroscopy of ZnO bulk samples

In order to gain a further insight into the knowledge of point defects of ZnO, positron annihilation lifetime spectroscopy was performed on bulk samples annealed under different atmospheres. The samples were characterized at temperatures ranging from 10 to 500 K. Due to difficulties in the conventional fitting of the lifetime spectra caused by the low intensity of the defect signals, we have used an alternative method as a solution to overcome these difficulties and resolve all the lifetime components present in the spectra. Two different vacancy-type defects are identified in the samples: Zn vacancy complexes (VZn−X) and vacancy clusters consisting of up to five missing Zn-O pairs. In addition to the vacancies, we observe negative-ion-type defects, which are tentatively attributed to intrinsic defects in the Zn sublattice. The effect of the annealing on the observed defects is discussed. The concentrations of the VZn−X complexes and negative-ion-type defects are in the 0.2–2 ppm range, while the cluster concentrations are 1–2 orders of magnitude lower.Peer reviewe

Anharmonic effects in ZnO optical phonons probed by Raman spectroscopy

We report Raman spectroscopy measurements on ZnO crystals grown by the vapor transport method and annealed. Vacuum annealing is found to yield single crystals with ultra low density of defects. We focus on the optical E2 phonon linewidth temperature dependence in the 10?500 K range. The linewidth decrease at low temperature is analyzed and discussed in the light of anharmonic up- and down-conversion processes, unveiling strongly different behaviors for the two E2 phonons

Positron annihilation lifetime spectroscopy of ZnO bulk samples

In order to gain a further insight into the knowledge of point defects of ZnO, positron annihilation lifetime spectroscopy was performed on bulk samples annealed under different atmospheres. The samples were characterized at temperatures ranging from 10 to 500 K. Due to difficulties in the conventional fitting of the lifetime spectra caused by the low intensity of the defect signals, we have used an alternative method as a solution to overcome these difficulties and resolve all the lifetime components present in the spectra. Two different vacancy-type defects are identified in the samples: Zn vacancy complexes (VZn−X) and vacancy clusters consisting of up to five missing Zn-O pairs. In addition to the vacancies, we observe negative-ion-type defects, which are tentatively attributed to intrinsic defects in the Zn sublattice. The effect of the annealing on the observed defects is discussed. The concentrations of the VZn−X complexes and negative-ion-type defects are in the 0.2–2 ppm range, while the cluster concentrations are 1–2 orders of magnitude lower.Peer reviewe

Ultrafast characterization of the electron injection from CdSe quantum dots and dye N719 co-sensitizers into TiO2 using sulfide based ionic liquid for enhanced long term stability

Combination of inorganic quantum dots (QDs) and organic/metallorganic dyes as supracollectors nanocomposites could have an important role on the development of efficient photovoltaic devices based on the synergistic action of the hybrid-sensitizers. Here we have analyzed the combination of CdSe QDs and polypyridil N719 ruthenium dye. By ultrafast transient grating measurements we show that the cascading structure (type II) of this system takes full advantage to augment electron injection and hole regeneration efficiencies. Co-sensitized TiO2 electrodes lead to an improvement in charge separation, increasing the number of injected electrons from the CdSe QDs to the TiO2 as a consequence of the suppression of back reaction, by fast regeneration of holes by the dye action. The potentiality of this supracollector system has been verified in a complete cell configuration. Sulfide/polysulfide based ionic liquid in which both sensitizers (QD and dye) are stable has been employed as hole conducting media. In spite of the limited efficiencies of the analyzed cells, the higher photocurrents measured for CdSe/N719 co-sensitization compared to the cells sensitized using a single sensitizer constitutes a valid proof of the concept. Impedance spectroscopy unveiled the recombination limitation of the analyzed cells. On the other hand, ionic liquid exhibits an enhanced cell stability maintaining cell efficiency after one week and keeping it at 80% after 21 days. The reported results highlight a huge potential of the synergetic combination of QD and dyes for improving solar cell performance and of novel sulfide/polysulfide ionic liquid-based electrolytes for enhancing long term stability and sustainability of QD sensitizers