Carlos Monton

Magnetism of Metal Phthalocyanines

Metal-phthalocyanine (MPc) are uniquely suited for the exploration of the intrinsic mechanisms which gives rise to molecular magnetism. In this chap- ter, we review the structural and magnetic properties of bulk crystal, thin film and single MPcs molecules adsorbed on different substrates. Traditional magnetic mea- surements and new techniques like x-ray magnetic circular dichroism show that the magnetic behavior of MPc molecules is strongly related with the electronic ground state of the central metal atom hybridized with the ligand states (intra-molecular in- teraction). In bulk and thin films, with stacked molecules, intermolecular exchange interactions between magnetic M atoms regulates their magnetic properties. More- over experimental results show that the magnetic properties of single molecules are strongly affected by the electronic coupling to the supporting substrate.

Electronic Structure Differences Between H2-, Fe-, Co-, and Cu-Phthalocyanine Highly Oriented Thin Films Observed Using NEXAFS Spectroscopy

Phthalocyanines, a class of macrocyclic, square planar molecules, are extensively studied as semiconductor materials for chemical sensors, dye-sensitized solar cells, and other applications. In this study, we use angular dependent near-edge x-ray absorption fine structure (NEXAFS) spectroscopy as a quantitative probe of the orientation and electronic structure of H2-, Fe-, Co-, and Cu-phthalocyanine molecular thin films. NEXAFS measurements at both the carbon and nitrogen K-edges reveal that phthalocyanine films deposited on sapphire have upright molecular orientations, while films up to 50 nm thick deposited on gold substrates contain prostrate molecules. Although great similarity is observed in the carbon and nitrogen K-edge NEXAFS spectra recorded for the films composed of prostrate molecules, the H2-phthalocyanine exhibits the cleanest angular dependence due to its purely out-of-plane π* resonances at the absorption onset. In contrast, organometallic-phthalocyanine nitrogen K-edges have a small in-plane resonance superimposed on this π* region that is due to a transition into molecular orbitals interacting with the 3dx(2)-y(2) empty state. NEXAFS spectra recorded at the metal L-edges for the prostrate films reveal dramatic variations in the angular dependence of specific resonances for the Cu-phthalocyanines compared with the Fe-, and Co-phthalocyanines. The Cu L3,2 edge exhibits a strong in-plane resonance, attributed to its b1g empty state with dx(2)-y(2) character at the Cu center. Conversely, the Fe- and Co- phthalocyanine L3,2 edges have strong out-of-plane resonances; these are attributed to transitions into not only b1g (dz(2)) but also eg states with dxz and dyz character at the metal center.

Effect of photodiode angular response on surface plasmon resonance measurements in the Kretschmann-Raether configuration.

We study the effect of photodiode angular response on the measurement of surface plasmon resonance (SPR) in metallic thin films using the Kretschmann-Raether configuration. The photodiode signal depends not only on the light intensity but also on the incidence angle. This implies that the photodiode sensitivity changes along the SPR curve. Consequently, the measured SPR spectrum is distorted, thus affecting fits and numerical analyses of SPR curves. We analyze the magnitude of this change, determine when it is significant, and develop a calibration method of the experimental setup which corrects for this type of spectral shape distortions.

The role of micro-shorts and electrode-film interface in the electrical transport of ultra-thin metallophthalocyanine capacitive devices

The transport properties of metallophthalocyanine thin films are important ingredients in many technological applications. Ohmic conductance of thin film (15 nm to 90 nm) Co-phthalocyanine (CoPc) capacitive devices has been investigated in the temperature range of 40 K to 300 K. For Pd and V electrodes, the electrode-film (E-F) interface and metallic micro-shorts contribute substantially to the conductance with decrease in CoPc layer thickness. A quantitative model which describes E-F interface, CoPc roughness, micro-shorts, and the exponential temperature and thickness dependence of conductance was developed. Parameters obtained from this model are in good quantitative agreement with independent measurements. The model predicts a 15-20 nm lower limit for capacitive device thickness, below which the conduction is mainly controlled by shorts. In this regime, small changes in mean CoPc thickness result in drastic variation in device conductance.

Microscopy image segmentation tool: Robust image data analysis

We present a software package called Microscopy Image Segmentation Tool (MIST). MIST is designed for analysis of microscopy images which contain large collections of small regions of interest (ROIs). Originally developed for analysis of porous anodic alumina scanning electron images, MIST capabilities have been expanded to allow use in a large variety of problems including analysis of biological tissue, inorganic and organic film grain structure, as well as nano- and meso-scopic structures. MIST provides a robust segmentation algorithm for the ROIs, includes many useful analysis capabilities, and is highly flexible allowing incorporation of specialized user developed analysis. We describe the unique advantages MIST has over existing analysis software. In addition, we present a number of diverse applications to scanning electron microscopy, atomic force microscopy, magnetic force microscopy, scanning tunneling microscopy, and fluorescent confocal laser scanning microscopy.

Study of Co-phthalocyanine films by surface plasmon resonance spectroscopy

We present a Surface Plasmon Resonance spectroscopy study of Co-Phthalocyanine (CoPc) thin films grown on Au layers at different substrate temperatures. We demonstrate that for quantitative analysis, fitting of the resonance angle alone is insufficient and Whole Curve Analysis (WCA) needs to be performed. This is because CoPc thin film dielectric constant and thickness are strongly affected by substrate temperature, even when the total deposited mass remains fixed. Using WCA, we are able to uniquely fit both the dielectric constants and the thicknesses of the films without making a priori assumptions.

Simultaneous surface plasmon resonance and x-ray absorption spectroscopy

We present an experimental setup for the simultaneous measurement of surface plasmon resonance (SPR) and x-ray absorption spectroscopy (XAS) on metallic thin films at a synchrotron beamline. The system allows measuring in situ and in real time the effect of x-ray irradiation on the SPR curves to explore the interaction of x-rays with matter. It is also possible to record XAS spectra while exciting SPR in order to study changes in the films induced by the excitation of surface plasmons. Combined experiments recording simultaneously SPR and XAS curves while scanning different parameters can be also carried out. The relative variations in the SPR and XAS spectra that can be detected with this setup range from 10(-3) to 10(-5), depending on the particular experiment.

Template-assisted electrodeposition of Ni and Ni/Au nanowires on planar and curved substrates

We present a variant of the template-assisted electrodeposition method that enables the synthesis of large arrays of nanowires (NWs) on flat and curved substrates. This method uses ultra-thin (50 nm-10 μm) anodic aluminum oxide membranes as a template. We have developed a procedure that uses a two-polymer protective layer to transfer these templates onto almost any surface. We have applied this technique to the fabrication of large arrays of Ni and segmented composition Ni/Au NWs on silicon wafers, Cu tapes, and thin (0.2 mm) Cu wires. In all cases, a complete coverage with NWs is achieved. The magnetic properties of these samples show an accentuated in-plane anisotropy which is affected by the form of the substrate (flat or curve) and the length of the NWs. Unlike current lithography techniques, the fabrication method proposed here allows the integration of complex nanostructures into devices, which can be fabricated on unconventional surfaces.

Superconducting heterostructures: from antipinning to pinning potentials

We study vortex lattice dynamics in a heterostructure that combines two type-II superconductors: a niobium film and a dense triangular array of submicrometric vanadium (V) pillars. Magnetic ac susceptibility measurements reveal a sudden increase in ac penetration, related to an increase in vortex mobility above a magnetic field, , that decreases linearly with temperature. Additionally, temperature independent matching effects that occur when the number of vortices in the sample is an integer of the number of V pillars, strongly reduce vortex mobility, and were observed for the first and second matching fields, and . The angular dependence of , and shows that matching is determined by the normal applied field component, while is independent of the applied field orientation. This important result identifies with the critical field boundary for the normal to superconducting transition of V pillars. Below , superconducting V pillars repel vortices, and the array becomes an ?antipinning? landscape that is more effective in reducing vortex mobility than the ?pinning? landscape of the normal V sites above . Matching effects are observed both below and above , implying the presence of ordered vortex configurations for ?antipinning? or ?pinning? arrays.

Charge injection across a metal-organic interface suppressed by thermal diffusion

We find that the ohmic conductance of Co-phthalocyanine (CoPc) vertical capacitive devices is irreversibly suppressed by orders of magnitude when they are heated above 340 K. Detailed structural and transport studies imply that the changes in the conductance are due to diffusion of the top Pd electrode into the CoPc layer. This leads to a decrease in Pd electrode effective work function, which increases the potential barrier for hole injection.