Pablo F. Siles

Characterization of Metal Oxide-Based Gas Nanosensors and Microsensors Fabricated via Local Anodic Oxidation Using Atomic Force Microscopy

This work reports on nanoscale and microscale metal oxide gas sensors, consisting of metal-semiconductor-metal barriers designed via scanning probe microscopy. Two distinct metal oxides, molybdenum and titanium oxides, were tested at different temperatures using CO2 and H2 as test gases. Sensitivities down to ppm levels are demonstrated, and the influence of dry and humid working atmospheres on these metal oxide conductivities was studied. Furthermore, the activation energy was evaluated and analyzed within working sensor temperature range. Finally, full morphological, chemical, and structural analyses of the oxides composites are provided allowing their identification as MoO3 and Ti.

Forming-Free Resistive Switching in Multiferroic BiFeO3 thin Films with Enhanced Nanoscale Shunts

A controlled shunting of polycrystalline oxide thin films on the nanometer length scale opens the door to significantly modify their transport properties. In this paper, the low energy Ar(+) irradiation induced shunting effect of forming-free, non-volatile resistive switching in polycrystalline BiFeO3 thin film capacitor-like structures with macroscopic bottom and top contacts was investigated. Oxygen atoms at the BiFeO3 surface are preferentially sputtered by Ar(+) ion irradiation and oxygen vacancies and a metallic Bi phase are formed at the surface of the BiFeO3 thin film before deposition of the top contacts. A phenomenological model is that of nanoscale shunt resistors formed in parallel to the actual BiFeO3 thin film capacitor-like structure. This model fits the noticeable increase of the retention stability and current density after irradiation. The formation of stable and conductive shunts is further evidenced by conductive atomic force microscopy measurements.

Fully Integrated Organic Nanocrystal Diode as High Performance Room Temperature NO2 Sensor

Organic diodes consisting of molecular nano-pyramid structures sandwiched between metal and strained nano-membrane electrodes are created. The robust and smooth contacts provided by self-curled metal layers render the molecular nano-pyramids efficent channels for detecting nitrogen dioxide airflow.

Tuning resistive switching on single-pulse doped multilayer memristors

Short-period multilayers containing ultrathin atomic layers of Al embedded in titanium dioxide (TiO(2)) film-here called single-pulse doped multilayers-are fabricated by atomic layer deposition (ALD) growth methods. The approach explored here is to use Al atoms through single-pulsed deposition to locally modify the chemical environment of TiO(2) films, establishing a chemical control over the resistive switching properties of metal/oxide/metal devices. We show that this simple methodology can be employed to produce well-defined and controlled electrical characteristics on oxide thin films without compound segregation. The increase in volume of the embedded Al(2)O(3) plays a crucial role in tuning the conductance of devices, as well as the switching bias. The stacking of these oxide compounds and their use in electrical devices is investigated with respect to possible crystalline phases and local compound formation via chemical recombination. It is shown that our method can be used to produce compounds that cannot be synthesized a priori by direct ALD growth procedures but are of interest due to specific properties such as thermal or chemical stability, electrical resistivity or electric field polarization possibilities. The monolayer doping discussed here impacts considerably on the broadening of the spectrum of performance and technological applications of ALD-based memristors, allowing for additional degrees of freedom in the engineering of oxide devices.

Tuning the magneto-optical response of TbPc2 single molecule magnets by the choice of the substrate

In this work, we investigated the magneto-optical response of thin films of TbPc2 on substrates which are relevant for (spin) organic field effect transistors (SiO2) or vertical spin valves (Co) in order to explore the possibility of implementing TbPc2 in magneto-electronic devices, the functionality of which includes optical reading. The optical and magneto-optical properties of TbPc2 thin films prepared by organic molecular beam deposition (OMBD) on silicon substrates covered with native oxide were investigated by variable angle spectroscopic ellipsometry (VASE) and magneto-optical Kerr effect (MOKE) spectroscopy at room temperature. The magneto-optical activity of the TbPc2 films can be significantly enhanced by one to two orders of magnitude upon changing the molecular orientation (from nearly standing molecules on SiO2/Si substrates to nearly lying molecules on perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) templated SiO2/Si substrates) or by using metallic ferromagnetic substrates (Co).

Optical properties and electrical transport of thin films of terbium(III) bis(phthalocyanine) on cobalt

Summary The optical and electrical properties of terbium(III) bis(phthalocyanine) (TbPc2) films on cobalt substrates were studied using variable angle spectroscopic ellipsometry (VASE) and current sensing atomic force microscopy (cs-AFM). Thin films of TbPc2 with a thickness between 18 nm and 87 nm were prepared by organic molecular beam deposition onto a cobalt layer grown by electron beam evaporation. The molecular orientation of the molecules on the metallic film was estimated from the analysis of the spectroscopic ellipsometry data. A detailed analysis of the AFM topography shows that the TbPc2 films consist of islands which increase in size with the thickness of the organic film. Furthermore, the cs-AFM technique allows local variations of the organic film topography to be correlated with electrical transport properties. Local current mapping as well as local I–V spectroscopy shows that despite the granular structure of the films, the electrical transport is uniform through the organic films on the microscale. The AFM-based electrical measurements allow the local charge carrier mobility of the TbPc2 thin films to be quantified with nanoscale resolution.

High-performance organic nanomembrane based sensors for rapid in situ acid detection.

Here, we demonstrate the fabrication, characterization, and tailoring of porous organic nanomembranes and their direct integration on inorganic substrates for sensing applications. The chemically prepared nanomembranes can be integrated on both conducting and insulating substrates by either transfer or direct synthesis. We also successfully demonstrate their use for the detection of commonly used acids including HCl, H(2)SO(4), or H(3)PO(4) and their respective counterions, chlorides, sulfates, and phosphates. Impressively, the in situ acid detection is achieved down to 5 nmol·L(-1), while the quantification is feasible between 5 μmol·L(-1) and 10 mmol·L(-1). These values are among the lowest values reported so far in literature. Furthermore, the organic nanomembrane based sensor covers a wide concentration range of almost 8 orders of magnitude including the environmental limits currently adopted.

Chemisorption of Exchange‐Coupled [Ni2L(dppba)]+ Complexes on Gold by Using Ambidentate 4‐(Diphenylphosphino)benzoate Co‐Ligands

A new strategy for the fixation of redox-active dinickel(II) complexes with high-spin ground states to gold surfaces was developed. The dinickel(II) complex [Ni2L(Cl)]ClO4 (1ClO4), in which L(2-) represents a 24-membered macrocyclic hexaaza-dithiophenolate ligand, reacts with ambidentate 4-(diphenylphosphino)benzoate (dppba) to form the carboxylato-bridged complex [Ni2L(dppba)](+), which can be isolated as an air-stable perchlorate [Ni2L(dppba)]ClO4 (2ClO4) or tetraphenylborate [Ni2L(dppba)]BPh4 (2BPh4) salt. The auration of 2ClO4 was probed on a molecular level, by reaction with AuCl, which leads to the monoaurated Ni(II)2Au(I) complex [Ni(II)2L(dppba)Au(I)Cl]ClO4 (3ClO4). Metathesis of 3ClO4 with NaBPh4 produces [Ni(II)2L(dppba)Au(I)Ph]BPh4 (4BPh4), in which the Cl(-) is replaced by a Ph(-) group. The complexes were fully characterized by ESI mass spectrometry, IR and UV/Vis spectroscopy, X-ray crystallography (2BPh4 and 4BPh4), cyclic voltammetry, SQUID magnetometry and HF-ESR spectroscopy. Temperature-dependent magnetic susceptibility measurements reveal a ferromagnetic coupling J = +15.9 and +17.9 cm(-1) between the two Ni(II) ions in 2ClO4 and 4BPh4 (H = -2 JS1S2). HF-ESR measurements yield a negative axial magnetic anisotropy (D<0), which implies a bistable (easy axis) magnetic ground state. The binding of the [Ni2L(dppba)]ClO4 complex to gold was ascertained by four complementary surface analytical methods: contact angle measurements, atomic-force microscopy, X-ray photoelectron spectroscopy, and spectroscopic ellipsometry. The results indicate that the complexes are attached to the Au surface through coordinative Au-P bonds in a monolayer.

Ultra-dense planar metallic nanowire arrays with extremely large anisotropic optical and magnetic properties

A nanofabrication method for the production of ultra-dense planar metallic nanowire arrays scalable to wafer-size is presented. The method is based on an efficient template deposition process to grow diverse metallic nanowire arrays with extreme regularity in only two steps. First, III–V semiconductor substrates are irradiated by a low-energy ion beam at an elevated temperature, forming a highly ordered nanogroove pattern by a “reverse epitaxy” process due to self-assembly of surface vacancies. Second, diverse metallic nanowire arrays (Au, Fe, Ni, Co, FeAl alloy) are fabricated on these III–V templates by deposition at a glancing incidence angle. This method allows for the fabrication of metallic nanowire arrays with periodicities down to 45 nm scaled up to wafer-size fabrication. As typical noble and magnetic metals, the Au and Fe nanowire arrays produced here exhibited large anisotropic optical and magnetic properties, respectively. The excitation of localized surface plasmon resonances (LSPRs) of the Au nanowire arrays resulted in a high electric field enhancement, which was used to detect phthalocyanine (CoPc) in surface-enhanced Raman scattering (SERS). Furthermore, the Fe nanowire arrays showed a very high in-plane magnetic anisotropy of approximately 412 mT, which may be the largest in-plane magnetic anisotropy field yet reported that is solely induced via shape anisotropy within the plane of a thin film.

Charge transport in organic nanocrystal diodes based on rolled-up robust nanomembrane contacts

The investigation of charge transport in organic nanocrystals is essential to understand nanoscale physical properties of organic systems and the development of novel organic nanodevices. In this work, we fabricate organic nanocrystal diodes contacted by rolled-up robust nanomembranes. The organic nanocrystals consist of vanadyl phthalocyanine and copper hexadecafluorophthalocyanine heterojunctions. The temperature dependent charge transport through organic nanocrystals was investigated to reveal the transport properties of ohmic and space-charge-limited current under different conditions, for instance, temperature and bias.