Mn12-acetate single-molecule magnets (SMMs) are nano-scale magnets showing a strong magnetic anisotropy, slow relaxation and stepwise magnetic hysteresis curves. Possible applications of Mn12-acetate, e.g. for ultra high density magnetic information storage device, quantum computation, and magnetic molecular electronics, have been suggested due to the unusual magnetic behavior. It is an important prerequisite for the applications to develop a reliable technique to organize the molecules on a surface and to detect the magnetic signals of the molecules. A solution evaporation technique combined with conventional lithography is a simple but reliable method to create Mn12-acetate thin film patterns on the micro/nano-scale. The method is demonstrated with a series of analysis. A superconducting quantum interference device (SQUID) shows a non-linear I-V (Current vs. Voltage) characteristic that is modulated by a magnetic flux inside the loop, allowing one to sense and analyze an extremely weak magnetic field. The miniaturized SQUID is appropriate for sensing the magnetic flux from the film structure of the molecular magnets. Theoretical ideas, fabrication, and a measurement technique of the device are presented. A new interesting system, the so-called superconductor/SMM hybrid, results from the experimental configuration. Understanding this new type of hybrid system is important not only because of the expectation of new phenomena affecting the functionality of superconducting devices, but also because the two coupled substances are fundamentally incompatible phases. The first experimental attempt to investigate the interaction between an aluminum superconducting film and Mn12-acetate SMMs will be discussed.

Los imanes unimoleculares presentan un estado fundamental de espín elevado y una marcada anisotropía magnética, dando lugar a una barrera energética para la interconversión del momento magnético. Por consiguiente, presentan una velocidad lenta de relajación de la magnetización que origina la observación de propiedades magnéticas interesantes características de los dominios magnéticos, tales como las curvas de susceptibilidad magnética ac fuera de fase y las curvas de histéresis magnética. Adicionalmente, y debido a tratarse de materiales mesoscópicos, formados por unos cientos de átomos, las curvas de histéresis muestran un aumento en la velocidad de relajación de la magnetización a campos resonantes atribuidos a fenómenos cuánticos de relajación por efecto túnel. El origen de estas propiedades magnéticas se deben a moléculas individuales y no a efectos de largo alcance, tal y como confirman los estudios de relajación de la magnetización y capacidad calorífica. Los imanes unimoleculares son sistemas moleculares monodispersos que presentan un tamaño perfectamente definido a escala nanométrica. Por consiguiente, son perfectos candidatos como sistemas de almacenamiento de alta densidad de información con aplicaciones en el campo computacional cuántico. Sin embargo, para disponer en un futuro de un ordenador cuántico a nivel molecular, es necesario el desarrollo de nuevas técnicas de detección rápida. En comparación con los métodos de medida magnética convencionales, las técnicas espectroscópicas permiten una mayor sensibilidad y rapidez de lectura, tal y como demuestran las medidas magneto-ópticas realizadas por dicroísmo circular magnético (MCD). Además, para generar memoria magnética a nivel molecular, simultáneamente, es preciso desarrollar métodos sistemáticos que permitan depositar de forma controlada en superficie moléculas individuales o bien agregados moleculares para ser utilizados como bits de información magnética. En base a estos estudios, la aplicación de técnicas litográficas blandas ha permitido controlar el tamaño, posición y geometría de los agregados de Mn12 en superficie, tras ser caracterizados mediante técnicas de microscopia de fuerzas atómicas (AFM) y magnéticas (MFM). Un ejemplo a destacar lo constituye la superficie de películas delgadas poliméricas, debido a la combinación de las propiedades magnéticas de los Mn12, como imanes unimoleculares, y las características físicas en las matrices poliméricas tales como la flexibilidad, transparencia y baja densidad, siendo estos sistemas compuestos magnéticos perfectos materiales con aplicaciones magneto-ópticas. / Single-molecule magnets (SMM) have a large-spin ground state with appreciable magnetic anisotropy, resulting in an energy barrier for the spin reversal. As a consequence, the observation of interesting magnetic properties occurs, such as out-of-phase ac magnetic susceptibility signals and stepwise magnetization hysteresis loops. In addition to resonant magnetization tunnelling, during the last few years several other interesting phenomena have also been reported. The origin of the slow magnetization relaxation rates as well as of other phenomena are due to individual molecules rather than to long-range ordering, as confirmed by magnetization relaxation and heat capacity studies. Therefore, SMM represent nanoscale molecular magnets of a sharply defined size with potential use in quantum computing applications and towards the realization of the ultimate high-density information storage devices. However, if a truly molecular computational device based on SMM is to be achieved, the development of new spectroscopic techniques to detect them rapidly, taking advantage of magneto-optical properties, as well as new systematic studies to address them properly on surfaces, are highly required. On the basis of this, patterning with Mn12 aggregates can be attained on surfaces by applying soft lithography techniques, thereby controlling their size, distance and geometry control. Surface characterization of Mn12 patterns have been studied by Atomic Force Microscopy (AFM) and Magnetic Force Microscopy (MFM) imaging. For instance, the surface of polymer thin films results particularly interesting because of the advantageous properties of polymer matrices, such as flexibility, transparency and low density, which make these magnetic materials potentially useful for magneto-optical applications.

Interactions between Mn12–acetate molecular magnets and thin gold films have been explored in light of the theory of weak localization. Low-temperature measurements of the magnetoresistance of gold films of varying thicknesses, with and without the presence of a surface layer of Mn12–acetate, have been performed using a dilution refrigerator. Quantitative fits to the data using the predictions of weak localization theory were performed using a least-squares fit method in order to determine characteristic times for elastic, inelastic, spin-orbit and spin scattering events within the gold. These data indicate that the presence of Mn12–acetate on the surface of the gold film leads to a significant enhancement of the spin scattering within the gold films.

We used self-assembling tunnel junctions (SATJs) to study the electron transport through films of the molecular magnets, Mn12-Acetate. Pulse laser deposition (PLD) was used to deposit two monolayers of Mn12-Acetate on thin Pt wires (diameter 0.001 in). The electron tunneling current was measured with typical bias voltages from -1 to 1 V at liquid helium temperature, 4.2 K. I, dI/dV , and d2I/dV 2 signals were directly acquired with the aid of a current amplifier and two lock-in-amplifiers. Results show that the differential conductance is approximately 10â 6 S for bias voltages 0.04 V < or =| V |< or = V and exhibits a strong voltage dependence. In the region | V |< or = 0.04 V, we find a zero-bias feature (ZBF) in which the differential conductance is suppressed. In some samples, we observe I -V staircases which we attribute to electrons "hopping" between the electrodes and the molecules. The observed hysteresis was attributed to the slow relaxation of molecules re-orienting within the junction. Abrupt conductance jumps at a bias voltage of -0.12 V were also observed and may indicate state transitions in the Mn12-Acetate molecules. Furthermore, we observed that the zero bias feature (ZBF) can switch from an enhancement to a suppression of the differential conductance. A dip and dry (DAD) method was also used to form films of Mn12-Acetate on Al and Pt wires. Although the conductances were similar to those obtained using the PLD method, there were some subtle differences. In particular, we did not observe the I -V staircases and the state jumps were more ambiguous. The differential conductance for the Mn12-Acetate films on Al wires were typically 10- 7 S, which we attributed to the oxide layer on Al surfaces. We have also found substantial changes in the I - V characteristics when the Pt wires coated with the Mn12-Acetate films were stored in 10-2 Torr for 6 months. In particular, we observed many new features such as peaks in the conductance as a function as the bias voltage. We believe that these effects may be caused by the slow oxidation of the Mn12-Acetate molecules.

This dissertation focuses on three separate studies. First, magnetization of the Mn12- acetate was studied by low temperature hysteresis loops and DC magnetization data on magnetically aligned Mn12-acetate micro-crystals. Secondly, Mn12-acetate thin films were fabricated and characterized by AFM and STM. Finally, magnetization of the film material was also studied. Enhanced alignment of Mn12-acetate micro-crystals as compared to prior studies was verified by observation of several sharp steps in low temperature hysteresis loops. It was found that ~ 0.5 T is sufficient to orient the micro-crystals in an organic solvent to a degree comparable to a single crystal. The degree of the alignment was controlled by varying the magnetic field at room temperature and during the cooling process. Subsequently, low temperature hysteresis loops and DC magnetizations were measured for each prepared orientation state of a sample. The high temperature magnetic anisotropy responsible for the alignment could not be measured, possibly due to its small magnitude. Mn12-acetate was deposited onto Si/SiO2 by a solution evaporation method. Atomic force microscopy studies revealed that 2 nm thick films of molecular level smoothness were formed. Mn12-acetate was also deposited onto a Highly Ordered Pyrolytic Graphite (HOPG) surface for scanning tunneling microscopy (STM) studies. A self-assembled triangular lattice was observed in the Mn12-acetate thin films by STM at room temperature under ambient conditions. These STM images show typical center to center intermolecular separations of about 6.3 nm and height corrugation of less than 0.5 nm. Magnetization measurements were not successful in Mn12-acetate thin films due to the small amount of material in the film and the large background signal from the substrate. Therefore, a sample for the magnetization measurements, called “film material”, was made by evaporating a dilute solution of Mn12-acetate powder in acetonitrile. Significant changes in magnetic properties of the film material were observed from magnetization measurements. The blocking temperature of the film material was found to increase to TB > 10 K at low magnetic fields.

Orientador: Kleber Roberto Pirota / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-23T16:30:39Z (GMT). No. of bitstreams: 1 Almeida_PriscilaToderode_M.pdf: 4163268 bytes, checksum: 28aa8c398a21212739c3588c9ce78593 (MD5) Previous issue date: 2013 / Resumo: O principal objetivo desse trabalho consiste em uma nova abordagem para o tunelamento da magnetização do magneto molecular Mn12, embasado em uma ampliação do modelo de Preisach. Introduziremos novos operadores que levam em conta a possibilidade de efeitos quânticos. Implementamos esse novo modelo num programa de simulação que é capaz de simular curvas de histerese e curvas de relaxação magnética sem recorrer a resolução de hamiltonianas de spin. Além disso, este programa utiliza simulação estocástica, apresentando os resultados em poucos minutos. Os resultados obtidos concordam com os experimentos realizados de histerese e relaxação magnética. Apesar de ser um modelo de simulação simples, reproduz adequadamente a fenomenologia, pois introduz os dois ingredientes essenciais de um sistema com inversão da magnetização por efeito túnel termicamente ativado: a ativação térmica, descrita pela ocupação de níveis segundo a distribuição de Boltzmann e a possibilidade do efeito túnel descrita pelo modelo de Landau¿Zenner. A consistência física do modelo é estudada através da variação de parâmetros do modelo de forma sistemática / Abstract: The main objective of this work consists of a new approach concerning the tunneling of the magnetization of the molecular magnet Mn12, based on an extension of the Preisach model. We will introduce new operators that take into account the possibility of quantum effects. Thus, we have implemented this new model in a simulation software that is capable of simulating hysteresis curves and magnetic relaxation curves without utilizing resolution of spin Hamiltonians. Also, this program uses stochastic simulation, presenting the results in only a few minutes. The results obtained agree with the hysteresis and relaxation experiments. Despite being a simple simulation model, it adequately reproduces the phenomenology, because it introduces two key ingredients of a system with inversion of magnetization by thermally activated tunnel effect: the thermal activation, described by the occupation of levels according to the Boltzmann distribution and the possibility of tunnel effect described by the Landau-Zenner model. The physical consistency of the model is studied by systematically varying the model¿s parameters / Mestrado / Física / Mestra em Física

Magnetism of carbon-based materials is a challenging area for both fundamental research and possible applications. We present studies of low-dimensional carbon-based magnetic systems (fullerene-diluted molecular magnets, carbon nanotubes, graphite fluoride, and nanoporous carbon) by means of SQUID magnetometer, X-ray diffraction and vibrational spectroscopy, the latter techniques used as complementary instruments to find a correlation between the magnetic behaviour and the structure of the samples.In the first part of the thesis, characteristic features of the magnetization process in aligned films of carbon nanotubes with low concentration of iron are discussed. It is shown that the magnetism of such structures is influenced by quantum effects, and the anisotropy behaviour is opposite to what is observed in heavily doped nanotubes.In the second part, Mn12-based single molecular magnets with various carboxylic ligands and their 1:1 fullerene-diluted complexes are studied. We prove that magnetic properties of such systems strongly depend on the environment, and, in principle, it is possible to design a magnet with desirable properties. One of the studied compounds demonstrated a record blocking temperature for a single molecular magnet. Both fullerene-diluted complexes demonstrated “magnetization training” effect in alternating magnetic fields and the ability to preserve magnetic moment.The third and the fourth parts of the thesis are dedicated to the analysis of various contributions to the magnetic susceptibility of metal-free carbon-based systems – intercalated compounds of graphite fluorides and nanoporous oxygen-eroded graphite. The magnetic properties of these systems are strongly dependent on structure, and can be delicately tuned by altering the π-electron system of graphite, i. e. by degree of fluorination of intercalated compounds and by introduction of boron impurity to the host matrix of nanoporous graphite. / Magnetism av kolbaserade material är ett utmanande område för både grundforskning och möjliga tillämpningar. Vi presenterar studier med låg-dimensionella kolbaserade magnetiska system (fulleren-utspädda molekylära magneter, kolnanorör, grafit fluorid och nanoporösa kol) med hjälp av SQUID magnetometer, röntgendiffraktion och vibrerande spektroskopi, de senare tekniker som används som komplement instrument för att finna sambandet mellan den magnetiska uppträdande och strukturen hos proven. I den första delen av avhandlingen är egenheter från magnetisering processen i linje filmer av kolnanorör med låg koncentration av järn diskuteras. Det visas att magnetism av sådana strukturer påverkas av kvantmekaniska effekter och anisotropin beteende är motsatsen till vad som observerats i kraftigt dopade nanorör. I den tvåa delen är Mn12-baserade enda-molekyl magneter med olika karboxylsyror ligander och deras 1:1 fulleren-utspädda komplex studeras. Vi visar att magnetiska egenskaperna hos sådana system beror i hög grad på miljön, och i princip är det möjligt att utforma en magnet med önskvärda egenskaper. En av de studerade föreningarna visade en post blockeringstemperaturen för en enda molekylär magnet. Både fulleren-utspädda komplex visade "magnetisering utbildning" effekt i alternerande magnetfält och möjligheten att bevara magnetiskt moment. Den tredje och fjärde delarna av avhandlingen är avsedda för inneboende magnetism av analys av olika bidrag till magnetisk susceptibilitet av metall-fritt kol-baserade system -inskjutna föreningar grafit fluorider och nanoporösa O2-eroderade grafit. Magnetiska egenskaperna hos dessa system är starkt beroende av strukturen, och kan fint avstämmas genom att man ändrar π-elektronsystem av grafit, i. e. med graden av fluorering av inskjutna föreningar och genom införandet av bor föroreningar till värd matris av nanoporösa grafit.

En aquest treball de tesi doctoral es presenta l’estudi del magnetisme de diferents materials de naturalesa metal•lorgànica emmarcats en diferents famílies. Per un cantó, tenim molècules d’alt espí amb anisotropia magnètica uniaxial negativa. Aquesta anisotropia genera una barrera d’energia en aquestes molècules que impedeix al moment magnètic girar lliurement i l’orienta de forma preferent en una direcció de l’espai. El moment magnètic pot canviar el seu sentit d’orientació superant la barrera d’energia de forma clàssica per activació tèrmica o quànticament per efecte túnel. Aquesta propietat es pot utilitzar per aplicacions tecnològiques d’aquestes molècules en el camp de la gravació magnètica d’ultra-alta densitat o en el camp de la computació quàntica, com a qubits magnètics. En la primera part d’aquesta tesi es presenten els estudis de les propietats magnètiques d’algunes d’aquestes molècules pertanyents a la família del Mn12, en diferents entorns (des de monocristalls fins a partícules polimèriques passant per dissolucions), així com noves tècniques de caracterització magnètica d’aquestes molècules com és el dicroisme circular magnètic. Aquest mètode ens permet per primera vegada mesurar alguns fenòmens de física fonamental en aquestes molècules mitjançant caracterització magneto-òptica, com és ara l’efecte túnel del moment magnètic macroscòpic. En el segon bloc d’aquesta tesis es presenta l’estudi del magnetisme d’una nova família de materials nanoporosos altament innovadors, sintetitzats a partir de radicals trifenilmetílics perclorats (PTM), funcionalitzats amb diferents grups carboxílics. L’ús d’aquests radicals ens ha portat a l’obtenció no només de materials nanoporosos amb un alt grau de porositat i unes propietats magnètiques destacables. La cristal•lització d’aquests radicals ha permès la obtenció del primer ferromagnet nanoporós purament orgànic, amb una temperatura de transició del ordre de 125 mK. La cristal•lització de combinacions d’aquests radicals amb ions de metalls de transició en la aproximació metal-orgànica ha donat lloc a varis sistemes notables. La combinació de ions de Cu(III) amb radicals PTM ens permet obtenir la primera esponja magnètica, material nanoporós amb uns 3 nm de diàmetre i amb propietats de pèrdua i reabsorció de solvents reversibles i detectables a través de les seves propietats magnètiques, convertint-se per tant en un sensor magnètic selectiu a certs dissolvents. Per altra banda, la combinació de ions de Co(II) amb els radicals PTM ens porta a la primera estructura nanoporosa magnètica formada per sistemes helicoïdals no inter penetrats i que presenta uns fenòmens de relaxació lenta molt inusuals: aquesta relaxació presenta una forta dependència amb el camp magnètic aplicat y pot ser descrita mitjançant el model de Davidson-Cole. Així doncs, en aquesta tesi es presenten l’estudi de les propietats magnètiques de diversos materials diferents les propietats dels quals poden ser aprofitades sens dubte per aplicacions d’alt nivell tecnològic que van des de la computació quàntica a sensors magnètics de baixa temperatura, passant per la gravació magnètica d’alta densitat. Els resultats presentats han donat lloc a una sèrie de publicacions en revistes científiques d’alt nivell que es detallen a continuació: 1. Gerbier Ph., et al., Synthesis and Characterization of a [Mn12O12(O2CR)16(H2O)4] Complex Bearing Paramagnetic Carboxylate Ligands. Use of a Modified Acid Replacement Synthetic Approach, Monatshefte für Chemie 134 (2003) 265-276 2. Maspoch D.,et al., A nanoporous molecular magnet with a reversible solvent-induced mechanical and magnètic properties, Nature Materials, 2 (2003) 190-195 3. Ruiz-Molina D.,et al., Isolated Single-Molecule Magnets on the Surface of a Polymeric Thin Film, Advanced Materials, 15 (2003) 42-45 4. Domingo N., et al., Synthesis and Characterization of a new chiral nanomagnet, Polyhedron, 22 (2003) 2355-2358 5. Domingo N., et al., Magnetism of Isolated Mn12 Single-molecule Magnets Detected by Magnetic Circular Dichroism: Observation of Spin Tunneling with a Magneto-optical Technique, Physical Review B 69 (2004) 052405 6. Maspoch D., et al., Self-assembly of a Dicarboxylic Radical: a New Pure Organic Robust Paramagnetic Nanoporous Molecular Material, Journal of the American Chemical Society, 126 (2004) 730-731 7. Maspoch D., et al., A New Robust Nanoporous Pure Organic Magnet, Angewandte Chemie Int. Ed. 43 (2004) 1828-1832 8. Gerbier Ph., et al., Chiral, single-molecule nanomagnets: synthesis, magnètic characterization and natural and magnètic circular dichroism, Journal of Materials Chemistry 14 (2004) 2455-2460 9. Maspoch D., et al.,Open-shell nanoporous salts formed by the supramolecular assembly of a polycarboxylate perchlorinated triphenylmethyl radical and a Co(bpy)3]2+ cation, Crystal Engineering Communications, 6 (2004) 573 - 578 10. Maspoch D., et al., Carboxylic-substituted Polychlorotriphenylmethyl Radicals, New Organic Building-Blocks to Design Nanoporous Magnetic Molecular Materials, Comptes Rendus Chemie 8 (2005) 1213-1225 / This work shows the study of magnetism of different metal-organic materials from different families. On one side, there are the high spin molecules with negative uniaxial magnetic anisotropy. This anisotropy is the origin of an energy barrier in this type of molecules that blocks the orientation of magnetic moment in a single direction of the space. The magnetic moment can change the sense of its orientation in two ways: classically, by thermal activation over the energy barrier, or in a quantic manner, by quantic tunneling effect of the macroscopic magnetic moment through the energy barrier. This property allows thinking about applications of these type of molecules for ultra-high density magnetic recording and quantum computing, as magnetic qubits. The first part of this thesis is devoted to the study of the magnetic properties of some of this molecules of the Mn12 family, in different environments (from monocrystals to polymeric thin films and dissolutions), as well as new characterization techniques for the magnetic characterization of these molecules such as magnetic circular dichroism. This technique, allowed for the first time the measurement of some fundamental physics phenomena in this molecules through magneto-optical characterization, such as the quantum tunneling of the macroscopic magnetic moment. The second part of this thesis is devoted to the study of the magnetic properties of a new family of nanoporous metal-organic and pure organic materials, synthesized on the basis of perclorated triphenylmethyl radicals (PTM), functionalized with different carboxylic groups. The use of this radicals lead to nanoporous materials with a very high degree of porosity combined with interesting magnetic properties. For example, it is shown the first pure organic nanoporous ferromagnet, with a transition temperature of the order of 125 mK. The combination of these radicals with transition metal ions in the metal-organic approximation, also lead to interesting systems. The combination with Cu(III) ions with PTM radicals lead to the first nanoporous magnetic sponge, with reversible properties of solvent absorption-desorption that can be monitorized through its magnetic properties, thus becoming a low temperature magnetic sensor with solvent selectivity. Finally, the combination of Co(II) ions with PTM radicals lead to the firms nanoporous magnetic structure with non-interpenetrated helical networks that show an unusual slow relaxation of the magnetization; this relaxation shows a strong dependence with the magnetic field and can be described with the Davidson-Cole model.