Processing and adsorption control in ZnO single nanowire photodetectors

ZnO single nanowire photodetectors have been measured in different ambient conditions in order to understand and control adsorption processes on the surface. A decrease in the conductivity has been observed as a function of time when the nanowires are exposed to air, due to adsorbed O2/H2O species at the nanowire surface. In order to have a device with stable characteristics in time, thermal desorption has been used to recover the original conductivity followed by PMMA coating of the exposed nanowire surface.

Oxygen photo-adsorption related quenching of photoluminescence in group-III nitride nanocolumns

GaN and InGaN nanocolumns of various compositions are studied by room-temperature photoluminescence (PL) under different ambient conditions. GaN nanocolumns exhibit a reversible quenching upon exposure to air under constant UV excitation, following a t−1/2 time dependence and resulting in a total reduction of intensity by 85–90%, as compared to PL measured in vacuum, with no spectral change. This effect is not observed when exposing the samples to pure nitrogen. We attribute this effect to photoabsorption and photodesorption of oxygen that modifies the surface potential bending. InGaN nanocolumns, under the same experimental conditions do not show the same quenching features: The high-energy part of the broad PL line is not modified by exposure to air, whereas a lower-energy part, which does quench by 80–90%, can now be distinguished. We discuss the different behaviors in terms of carrier localization and possible composition or strain gradients in the InGaN nanocolumns.

Application of photoreflectance to advanced multilayer structures for photovoltaics

Photoreflectance (PR) is a convenient characterization tool able to reveal optoelectronic properties of semiconductor materials and structures. It is a simple non-destructive and contactless technique which can be used in air at room temperature. We will present experimental results of the characterization carried out by means of PR on different types of advanced photovoltaic (PV) structures, including quantum-dot-based prototypes of intermediate band solar cells, quantum-well structures, highly mismatched alloys, and III?V-based multi-junction devices, thereby demonstrating the suitability of PR as a powerful diagnostic tool. Examples will be given to illustrate the value of this spectroscopic technique for PV including (i) the analysis of the PR spectra in search of critical points associated to absorption onsets; (ii) distinguishing signatures related to quantum confinement from those originating from delocalized band states; (iii) determining the intensity of the electric field related to built-in potentials at interfaces according to the Franz?Keldysh (FK) theory; and (v) determining the nature of different oscillatory PR signals among those ascribed to FK-oscillations, interferometric and photorefractive effects. The aim is to attract the interest of researchers in the field of PV to modulation spectroscopies, as they can be helpful in the analysis of their devices.

Open-atmosphere structural depth profiling of multilayer samples of photovoltaic interest using laser-induced plasma spectrometry

The present work aims to assess Laser-Induced Plasma Spectrometry (LIPS) as a tool for the characterization of photovoltaic materials. Despite being a well-established technique with applications to many scientific and industrial fields, so far LIPS is little known to the photovoltaic scientific community. The technique allows the rapid characterization of layered samples without sample preparation, in open atmosphere and in real time. In this paper, we assess LIPS ability for the determination of elements that are difficult to analyze by other broadly used techniques, or for producing analytical information from very low-concentration elements. The results of the LIPS characterization of two different samples are presented: 1) a 90 nm, Al-doped ZnO layer deposited on a Si substrate by RF sputtering and 2) a Te-doped GaInP layer grown on GaAs by Metalorganic Vapor Phase Epitaxy. For both cases, the depth profile of the constituent and dopant elements is reported along with details of the experimental setup and the optimization of key parameters. It is remarkable that the longest time of analysis was ∼10 s, what, in conjunction with the other characteristics mentioned, makes of LIPS an appealing technique for rapid screening or quality control whether at the lab or at the production line.

Carbon dioxide adsorption in chemically activated carbon from sewage sludge

In this work, sewage sludge was used as precursor in the production of activated carbon by means of chemical activation with KOH and NaOH. The sludge-based activated carbons were investigated for their gaseous adsorption characteristics using CO2 as adsorbate. Although both chemicals were effective in the development of the adsorption capacity, the best results were obtained with solid NaOH (SBAT16). Adsorption results were modeled according to the Langmuir and Freundlich models, with resulting CO2 adsorption capacities about 56 mg/g. The SBAT16 was characterized for its surface and pore characteristics using continuous volumetric nitrogen gas adsorption and mercury porosimetry. The results informed about the mesoporous character of the SBAT16 (average pore diameter of 56.5 Å). The Brunauer-Emmett-Teller (BET) surface area of the SBAT16 was low (179 m2/g) in comparison with a commercial activated carbon (Airpel 10; 1020 m2/g) and was mainly composed of mesopores and macropores. On the other hand, the SBAT16 adsorption capacity was higher than that of Airpel 10, which can be explained by the formation of basic surface sites in the SBAT16 where CO2 experienced chemisorption. According to these results, it can be concluded that the use of sewage-sludge-based activated carbons is a promising option for the capture of CO2. Implications: Adsorption methods are one of the current ways to reduce CO2 emissions. Taking this into account, sewage-sludge-based activated carbons were produced to study their CO2 adsorption capacity. Specifically, chemical activation with KOH and NaOH of previously pyrolyzed sewage sludge was carried out. The results obtained show that even with a low BET surface area, the adsorption capacity of these materials was comparable to that of a commercial activated carbon. As a consequence, the use of sewage-sludge-based activated carbons is a promising option for the capture of CO2 and an interesting application for this waste.

Proceso metodológico para optimizar la toma de decisiones en el proyecto de envolventes arquitectónicas multicapa = Methodological process for the optimization of the decision making in multilayer building envelope projects

La presente tesis doctoral se enmarca dentro del concepto de la sistematización del conocimiento en arquitectura, más concretamente en el campo de las construcciones arquitectónicas y la toma de decisiones en la fase de proyecto de envolventes arquitectónicas multicapa. Por tanto, el objetivo principal es el establecimiento de las bases para una toma de decisiones informadas durante el proyecto de una envolvente multicapa con el fin de colaborar en su optimización. Del mismo modo que la historia de la arquitectura está relacionada con la historia de la innovación en construcción, la construcción está sujeta a cambios como respuesta a los fracasos anteriores. En base a esto, se identifica la toma de decisiones en la fase de proyecto como el estadio inicial para establecer un punto estratégico de reflexión y de control sobre los procesos constructivos. La presente investigación, conceptualmente, define los parámetros intervinientes en el proyecto de envolventes arquitectónicas multicapa a partir de una clasificación y sistematización de todos los componentes (elementos, unidades y sistemas constructivos) utilizados en las fachadas multicapa. Dicha sistematización se materializa en una hoja matriz de datos en la que, dentro de una organización a modo de árbol, se puede acceder a la consulta de cada componente y de su caracterización. Dicha matriz permite la incorporación futura de cualquier componente o sistema nuevo que aparezca en el mercado, relacionándolo con aquellos con los que comparta ubicación, tipo de material, etc. Con base en esa matriz de datos, se diseña la sistematización de la toma de decisiones en la fase de proyecto de una envolvente arquitectónica, en concreto, en el caso de una fachada. Operativamente, el resultado se presenta como una herramienta que permite al arquitecto o proyectista reflexionar y seleccionar el sistema constructivo más adecuado, al enfrentarse con las distintas decisiones o elecciones posibles. La herramienta se basa en las elecciones iniciales tomadas por el proyectista y se estructura, a continuación y sucesivamente, en distintas aproximaciones, criterios, subcriterios y posibilidades que responden a los distintos avances en la definición del sistema constructivo. Se proponen una serie de fichas operativas de comprobación que informan sobre el estadio de decisión y de definición de proyecto alcanzados en cada caso. Asimismo, el sistema permite la conexión con otros sistemas de revisión de proyectos para fomentar la reflexión sobre la normalización de los riesgos asociados tanto al proprio sistema como a su proceso constructivo y comportamiento futuros. La herramienta proporciona un sistema de ayuda para ser utilizado en el proceso de toma de decisiones en la fase de diseño de una fachada multicapa, minimizando la arbitrariedad y ofreciendo una cualificación previa a la cuantificación que supondrá la elaboración del detalle constructivo y de su medición en las sucesivas fases del proyecto. Al mismo tiempo, la sistematización de dicha toma de decisiones en la fase del proyecto puede constituirse como un sistema de comprobación en las diferentes fases del proceso de decisión proyectual y de definición de la envolvente de un edificio. ABSTRACT The central issue of this doctoral Thesis is founded on the framework of the concept of the systematization of knowledge in architecture, in particular, in respect of the field of building construction and the decision making in the design stage of multilayer building envelope projects. Therefore, the main objective is to establish the bases for knowledgeable decision making during a multilayer building envelope design process, in order to collaborate with its optimization. Just as the history of architecture is connected to the history of innovation in construction, construction itself is subject to changes as a response to previous failures. On this basis, the decisions made during the project design phase are identified as the initial state to establish an strategic point for reflection and control, referred to the constructive processes. Conceptually, this research defines the parameters involving the multilayer building envelope projects, on the basis of a classification and systematization for all the components (elements, constructive units and constructive systems) used in multilayer façades. The mentioned systematization is materialized into a data matrix sheet in which, following a tree‐like organization, the access to every single component and its characterization is possible. The above data matrix allows the future inclusion of any new component or system that may appear in the construction market. That new component or system can be put into a relationship with another, which it shares location, type of material,… with. Based on the data matrix, the systematization of the decision making process for a building envelope design stage is designed, more particularly in the case of a façade. Putting this into practice, it is represented as a tool which allows the architect or the designer, to reflect and to select the appropriate building system when facing the different elections or the different options. The tool is based on the initial elections taken by the designer. Then and successively, it is shaped on the form of different operative steps, criteria, sub‐criteria and possibilities which respond to a different progress in the definition of the building construction system. In order to inform about the stage of the decision and the definition reached by the project in every particular case, a range of operative sheets are proposed. Additionally, the system allows the connection with other reviewing methods for building projects. The aim of this last possibility is to encourage the reflection on standardization of the associated risks to the building system itself and its future performance. The tool provides a helping system to be used during the decision making process for a multilayer façade design. It minimizes the arbitrariness and offers a qualification previous to the quantification that will be done with the development of the construction details and their bill of quantities, that in subsequent project stages will be executed. At the same time, the systematization of the mentioned decision making during the design phase, can be found as a checking system in the different stages of the decision making design process and in the different stages of the building envelope definition.

Structural changes in hemoglobin during adsorption to solid surfaces: Effects of pH, ionic strength, and ligand binding

We have studied the adsorption of two structurally similar forms of hemoglobin (met-Hb and HbCO) to a hydrophobic self-assembled methyl-terminated thiol monolayer on a gold surface, by using a Quartz Crystal Microbalance (QCM) technique. This technique allows time-resolved simultaneous measurements of changes in frequency (f) (c.f. mass) and energy dissipation (D) (c.f. rigidity/viscoelastic properties) of the QCM during the adsorption process, which makes it possible to investigate the viscoelastic properties of the different protein layers during the adsorption process. Below the isoelectric points of both met-Hb and HbCO, the ΔD vs. Δf graphs displayed two phases with significantly different slopes, which indicates two states of the adsorbed proteins with different visco-elastic properties. The slope of the first phase was smaller than that of the second phase, which indicates that the first phase was associated with binding of a more rigidly attached, presumably denatured protein layer, whereas the second phase was associated with formation of a second layer of more loosely bound proteins. This second layer desorbed, e.g., upon reduction of Fe3+ of adsorbed met-Hb and subsequent binding of carbon monoxide (CO) forming HbCO. Thus, the results suggest that the adsorbed proteins in the second layer were in a native-like state. This information could only be obtained from simultaneous, time-resolved measurements of changes in both D and f, demonstrating that the QCM technique provides unique information about the mechanisms of protein adsorption to solid surfaces.

Peptide interfacial adsorption is kinetically limited by the thermodynamic stability of self association

We present a study of the adsorption of two peptides at the octane–water interface. The first peptide, Lac21, exists in mixed monomer–tetramer equilibrium in bulk solution with an appreciable monomer concentration. The second peptide, Lac28, exists as a tetramer in solution, with minimal exposed hydrophobic surface. A kinetic limitation to interfacial adsorption exists for Lac28 at moderate to high surface coverage that is not observed for Lac21. We estimate the potential energy barrier for Lac28 adsorption to be 42 kJ/mol and show that this is comparable to the expected free energy barrier for tetramer dissociation. This finding suggests that, at moderate to high surface coverage, adsorption is kinetically limited by the availability of interfacially active monomeric “domains” in the subinterfacial region. We also show how the commonly used empirical equation for protein adsorption dynamics can be used to estimate the potential energy barrier for adsorption. Such an approach is shown to be consistent with a formal description of diffusion–adsorption, provided a large potential energy barrier exists. This work demonstrates that the dynamics of interfacial adsorption depend on protein thermodynamic stability, and hence structure, in a quantifiable way.

Adsorption from a one-dimensional lattice gas and the Brunauer–Emmett–Teller equation

An exact treatment of adsorption from a one-dimensional lattice gas is used to eliminate and correct a well-known inconsistency in the Brunauer–Emmett–Teller (B.E.T.) equation—namely, Gibbs excess adsorption is not taken into account and the Gibbs integral diverges at the transition point. However, neither model should be considered realistic for experimental adsorption systems.

Selective adsorption of l- and d-amino acids on calcite: Implications for biochemical homochirality

The emergence of biochemical homochirality was a key step in the origin of life, yet prebiotic mechanisms for chiral separation are not well constrained. Here we demonstrate a geochemically plausible scenario for chiral separation of amino acids by adsorption on mineral surfaces. Crystals of the common rock-forming mineral calcite (CaCO3), when immersed in a racemic aspartic acid solution, display significant adsorption and chiral selectivity of d- and l-enantiomers on pairs of mirror-related crystal-growth surfaces. This selective adsorption is greater on crystals with terraced surface textures, which indicates that d- and l-aspartic acid concentrate along step-like linear growth features. Thus, selective adsorption of linear arrays of d- and l-amino acids on calcite, with subsequent condensation polymerization, represents a plausible geochemical mechanism for the production of homochiral polypeptides on the prebiotic Earth.

Photo-induced inactivation of viruses: adsorption of methylene blue, thionine, and thiopyronine on Qbeta bacteriophage.

The adsorption of cationic organic dyes (methylene blue, thionine, and thiopyronine) on Qbeta bacteriophage was studied by UV-visible and fluorescence spectroscopy. The dyes have shown a strong affinity to the virus and some have been used as sensitizers for photo-induced inactivation of virus. In the methylene blue concentration range of 0.1-5 microM and at high ratios of dye to virus (greater than 1000 dye molecules per virion), the dyes bind as aggregates on the virus. Aggregation lowers the efficiency of photoinactivation because of self-quenching of the dye. At lower ratios of dye to virus (lower than 500 dye molecules per virion), the dye binds to the virus as a monomer. Fluorescence polarization and time-resolved studies of the fluorescence support the conclusions based on fluorescence quenching. Increasing the ionic strength (adding NaCl) dissociates bound dye aggregates on the virus and releases monomeric dye into the bulk solution.

Dressed polyions, counterion condensation, and adsorption excess in polyelectrolyte solutions.

The phenomenon of Manning-Oosawa counterion condensation is given an explicit statistical mechanical and qualitative basis via a dressed polyelectrolyte formalism in connection with the topology of the electrostatic free-energy surface and is derived explicitly in terms of the adsorption excess of ions about the polyion via the nonlinear Poisson-Boltzmann equation. The approach is closely analogous to the theory of ion binding in micelles. Our results not only elucidate a Poisson-Boltzmann analysis, which shows that a fraction of the counterions lie within a finite volume around the polyion even if the volume of the system tends towards infinity, but also provide a direct link between Manning's theta-the number of condensed counterions for each polyion site-and a statistical thermodynamic quantity, namely, the adsorption excess per monomer.

Drug delivery: piercing vesicles by their adsorption onto a porous medium.

Experimental evidence is presented that supports the possibility of building a "molecular drill." By the adsorption of a vesicle onto a porous substrate (specifically, a lycopode grain), it was possible to increase the permeability of the vesicle by locally stretching its membrane. Molecules contained within the vesicle, which could not cross the membrane, were delivered to the porous substrate upon adsorption. This general process could provide another method for drug delivery and targeting.

The Adsorption of Polyatomic Molecules on Carbon Surfaces

Carbon nanotubes exhibit the structure and chemical properties that make them apt substrates for many adsorption applications. Of particular interest are carbon nanotube bundles, whose unique geometry is conducive to the formation of pseudo-one-dimensional phases of matter, and graphite, whose simple planar structure allows ordered phases to form in the absence of surface effects. Although both of these structures have been the focus of many research studies, knowledge gaps still remain. Much of the work with carbon nanotubes has used simple adsorbates1-43, and there is little kinetic data available. On the other hand, there are many studies of complex molecules adsorbing on graphite; however, there is almost no kinetic data reported for this substrate. We seek to close these knowledge gaps by performing a kinetic study of linear molecules of increasing length adsorbing on carbon nanotube bundles and on graphite. We elucidated the process of adsorption of complex admolecules on carbon nanotube bundles, while at the same time producing some of the first equilibrium results of the films formed by large adsorbates on these structures. We also extended the current knowledge of adsorption on graphite to include the kinetics of adsorption. The kinetic data that we have produced enables a more complete understanding of the process of adsorption of large admolecules on carbon nanotube bundles and graphite. We studied the adsorption of particles on carbon nanotube bundles and graphite using analytical and computational techniques. By employing these methods separately but in parallel, we were able to constantly compare and verify our results. We calculated and simulated the behavior of a given system throughout its evolution and then analyzed our results to determine which system parameters have the greatest effect on the kinetics of adsorption. Our analytical and computational results show good agreement with each other and with the experimental isotherm data provided by our collaborators. As a result of this project, we have gained a better understanding of the kinetics of adsorption. We have learned about the equilibration process of dimers on carbon nanotube bundles, identifying the “filling effect”, which increases the rate of total uptake, and explaining the cause of the transient “overshoot” in the coverage of the surface. We also measured the kinetic effect of particle-particle interactions between neighboring adsorbates on the lattice. For our simulations of monomers adsorbing on graphite, we succeeded in developing an analytical equation to predict the characteristic time as a function of chemical potential and of the adsorption and interaction energies of the system. We were able to further explore the processes of adsorption of dimers and trimers on graphite (again observing the filling effect and the overshoot). Finally, we were able to show that the kinetic behaviors of monomers, dimers, and trimers that have been reported in experimental results also arise organically from our model and simulations.

Assessment of CO2 adsorption capacity on activated carbons by a combination of batch and dynamic tests

In this work, batch and dynamic adsorption tests are coupled for an accurate evaluation of CO2 adsorption performance for three different activated carbons obtained from olives stones by chemical activation followed by physical activation with CO2 at varying times, i.e. 20, 40 and 60 h. Kinetic and thermodynamic CO2 adsorption tests from simulated flue-gas at different temperature and CO2 pressure are carried out both in batch (a manometric equipment operating with pure CO2) and dynamic (a lab-scale fixed-bed column operating with CO2/N2 mixture) conditions. The textural characterization of the activated carbon samples shows a direct dependence of both micropore and ultramicropore volume on the activation time, hence AC60 has the higher contribution. The adsorption tests conducted at 273 and 293 K showed that, when CO2 pressure is lower than 0.3 bar, the lower the activation time the higher CO2 adsorption capacity and a ranking ωeq(AC20)>ωeq(AC40)>ωeq(AC60) can be exactly defined when T= 293 K. This result can be likely ascribed to a narrower pore size distribution of the AC20 sample, whose smaller pores are more effective for CO2 capture at higher temperature and lower CO2 pressure, the latter representing operating conditions of major interest for decarbonation of a flue-gas effluent. Moreover, the experimental results obtained from dynamic tests confirm the results derived from the batch tests in terms of CO2 adsorption capacity. It is important to highlight that the adsorption of N2 on the synthesized AC samples can be considered negligible. Finally, the importance of a proper analysis of characterization data and adsorption experimental results is highlighted for a correct assessment of CO2 removal performances of activated carbons at different CO2 pressure and operating temperature.