Molecular-based Magnetoresistance Devices at Room Temperature
[eng] In this doctoral thesis a series of computational and experimental studies of molecular magnetoresistance devices at room temperature is presented. This sort of devices is included in the molecular electronics framework with the objective of studying molecular systems to build up molecular dev...
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| Tipo de recurso: | tesis doctoral |
| Estado: | Versión publicada |
| Fecha de publicación: | 2021 |
| País: | España |
| Institución: | Universidad de Barcelona |
| Repositorio: | Dipòsit Digital de la UB |
| OAI Identifier: | oai:diposit.ub.edu:2445/180411 |
| Acceso en línea: | https://hdl.handle.net/2445/180411 http://hdl.handle.net/10803/672545 |
| Access Level: | acceso abierto |
| Palabra clave: | Nanociència Electrònica molecular Magnetoresistència Transport d'electrons Teoria del transport Espintrònica Nanoscience Molecular electronics Magnetoresistance Electron transport Transport theory Spintronics |
| Sumario: | [eng] In this doctoral thesis a series of computational and experimental studies of molecular magnetoresistance devices at room temperature is presented. This sort of devices is included in the molecular electronics framework with the objective of studying molecular systems to build up molecular devices. Particularly, molecular systems with unpaired electrons are potential candidates to mimic and miniaturizing nowadays spin valves, widely employed in magnetic memories, besides adding new functionalities through chemical modification. Finding out functional candidates at room temperature is crucial to the posterior application on electronic devices. The first chapter introduces common molecular electronics phenomenology and the most used experimental techniques. Landauer’s formalism is explained in detail along with Green’s function formalism, which permits to describe the electron as a traveling wave from one electrode to the other via an applied bias. Different electronic structure and quantum transport codes employed to perform theoretical calculations are discussed. In the second chapter, a supramolecular landscape of CoII-5,15-diphenylporphyrin (CoDPP) and CoII-Porphyrin (CoP) is proposed to explain the high conductance signatures observed in STM- Break Junction experiments when both gold electrodes are functionalised with pyridine-4-yl- metanthiol (PyrMT) and 4-mercaptopyridine (PyrT). Afterwards, the discussion is expanded to CoII, NiII, CuII and ZnII metallodiphenylporphyrins to explore the magnetoresistance of these systems in the third chapter. Theoretical calculations allow understanding qualitatively the observed magnetoresistance on CoII and CuII metalloporphyrins. The fourth chapter leaves unimolecular devices and tackles, in two collaborations, the computational study of molecular monolayer junctions. The first contribution was in collaboration with Dr. Monakhov’s group (IOM, Leipzig), in which the monolayer junction CuLn(L·SMe)2(OOCMe)2(NO3)] (Ln = Gd, Tb, Dy i Y, x = 0.75-1) is studied employing an eutectic gallium and indium electrode (EGaIn). The experimental current independence of the lanthanide is corroborated in the computational study. A second collaboration with Dr. Nijhuis (NUS, Singapore) and Dr. Harding (Walailak University) studies the first FeIII spin crossover system at room temperature: [FeIII(qsal-I)2]NTf2 (qsal-I = 4-iodo-2-[(8- quinolylimino)methyl]phenolate). In this study an explicit model of EGaIn electrode is included to explain the observed conductance according to the FeIII spin state. The fifth chapter faces, both computational and experimentally, the building of spintronic devices based on Hofmann-type clathrate monolayers {CoII(PyrT)2Pt(CN)4} (PyrT = 4- mercaptopyridine). In the experimental section, the synthesis and characterisation of the monolayer using XPS, ellipsometry, AFM and C-AFM images is explained. Preliminary results about conductance at the molecular level were obtained in blinking STM experiments. The theoretical study permits the understanding of the observed conductance signatures and gives a qualitative explanation to the observed magnetoresistance. The last chapter goes back to unimolecular nanojunctions to study the thermoelectric properties of magnetic complexes. In this chapter, VII, FeII, CoII and NiII metallocenes, GdIII and EuII sandwich compounds and CoII and FeII complexes of the form [MII(SCN)2+x(py)4-x] (x = 0-2, py = pyridine) are theoretically explored to find out common characteristics for potential candidates to future experiments. |
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