Agustín Molina-Ontoria

Benzotrithiophene-Based Hole-Transporting Materials for 18.2% Perovskite Solar Cells

New star-shaped benzotrithiophene (BTT)-based hole-transporting materials (HTM) BTT-1, BTT-2 and BTT-3 have been obtained through a facile synthetic route by crosslinking triarylamine-based donor groups with a benzotrithiophene (BTT) core. The BTT HTMs were tested on solution-processed lead trihalide perovskite-based solar cells. Power conversion efficiencies in the range of 16 % to 18.2 % were achieved under AM 1.5 sun with the three derivatives. These values are comparable to those obtained with todays most commonly used HTM spiro-OMeTAD, which point them out as promising candidates to be used as readily available and cost-effective alternatives in perovskite solar cells (PSCs).

Single-Molecule Junctions with Epitaxial Graphene Nanoelectrodes

On the way to ultraflat single-molecule junctions with transparent electrodes, we present a fabrication scheme based on epitaxial graphene nanoelectrodes. As a suitable molecule, we identified a molecular wire with fullerene anchor groups. With these two components, stable electrical characteristics could be recorded. Electrical measurements show that single-molecule junctions with graphene and with gold electrodes display a striking agreement. This motivated a hypothesis that the differential conductance spectra are rather insensitive to the electrode material. It is further corroborated by the assignment of asymmetries and spectral features to internal molecular degrees of freedom. The demonstrated open-access graphene electrodes and the electrode-insensitive molecules provide a model system that will allow for a thorough investigation of an individual single-molecule contact with additional probes.

Preparation and Characterization of Carbon Nano-Onion/ PEDOT:PSS Composites

Composites of unmodified or oxidized carbon nano-onions (CNOs/ox-CNOs) with poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) are prepared with different compositions. By varying the ratio of PEDOT:PSS relative to CNOs, CNO/PEDOT:PSS composites with various PEDOT:PSS loadings are obtained and the corresponding film properties are studied as a function of the polymer. X-ray photoelectron spectroscopy characterization is performed for pristine and ox-CNO samples. The composites are characterized by scanning and transmission electron microscopy and differential scanning calorimetry studies. The electrochemical properties of the nanocomposites are determined and compared. Doping the composites with carbon nanostructures significantly increases their mechanical and electrochemical stabilities. A comparison of the results shows that CNOs dispersed in the polymer matrices increase the capacitance of the CNO/PEDOT:PSS and ox-CNO/PEDOT:PSS composites.

Synthesis of carbon nano-onion and nickel hydroxide/oxide composites as supercapacitor electrodes

“Small” carbon nano-onions (CNOs) are spherical, ca. 5 nm in diameter, concentric shells of graphitic carbon that can be also described as multi-shelled fullerenes. Given the easy functionalization and high thermal stability of the CNOs produced from nanodiamond, they are the most obvious choice for studying the potential applications of these multi-shelled fullerenes in electrochemical supercapacitors (ES). Since limited accessibility of the carbon surface to electrolyte penetration is observed for carbon nano-onions, performance enhancement was accomplished by modifying the CNO surfaces with pseudocapacitive redox materials: Ni(OH)2 and NiO. These composites were characterized by TEM, SEM, XRD, TGA-DTG-DTA and Raman spectroscopy. The electrochemical properties of these composites were also investigated. Compared with pristine CNOs (30.6 F g−1 at 5 mV s−1), modified CNOs (1225.2 F g−1 for CNOs/Ni(OH)2 and 290.6 F g−1 for CNOs/NiO, both at 5 mV s−1) show improved electrochemical performance, promising for the development of supercapacitors.

Towards enhancing light harvesting-subphthalocyanines as electron acceptors.

One carbon atom is too many. Two subphthalocyanine-extended TTF electron donor-acceptor conjugates were synthesized and characterized. Their photophysical properties prompt the remarkable impact that one extra carbon between the two constitutents exerts on photoinduced processes, that is, charge recombination dynamics in the normal versus inverted region.

Nanoelectrical analysis of single molecules and atomic-scale materials at the solid/liquid interface

Evaluating the built-in functionality of nanomaterials under practical conditions is central for their proposed integration as active components in next-generation electronics. Low-dimensional materials from single atoms to molecules have been consistently resolved and manipulated under ultrahigh vacuum at low temperatures. At room temperature, atomic-scale imaging has also been performed by probing materials at the solid/liquid interface. We exploit this electrical interface to develop a robust electronic decoupling platform that provides precise information on molecular energy levels recorded using in situ scanning tunnelling microscopy/spectroscopy with high spatial and energy resolution in a high-density liquid environment. Our experimental findings, supported by ab initio electronic structure calculations and atomic-scale molecular dynamics simulations, reveal direct mapping of single-molecule structure and resonance states at the solid/liquid interface. We further extend this approach to resolve the electronic structure of graphene monolayers at atomic length scales under standard room-temperature operating conditions.

Isomerism effect on the photovoltaic properties of benzotrithiophene-based hole-transporting materials

Engineering of inorganic–organic lead halide perovskites for photovoltaic applications has experienced significant advances in recent years. However, the use of the relatively expensive spiro-OMeTAD as a hole-transporting material (HTM) poses a challenge due to dopant-induced degradation. Herein we introduce two new three-armed and four-armed HTMs (BTT-4 and BTT-5) based on isomeric forms of benzotrithiophene (BTT). The isomerism impact on the optical, electrochemical and photophysical properties and the photovoltaic performance is systematically investigated. Perovskite solar cells (PSCs) using BTT-4 and BTT-5 as HTMs show remarkable light-to-energy conversion efficiencies of 19.0% and 18.2%, respectively, under standard measurement conditions. These results validate the readily available BTT heteroaromatic structure as a valuable core for the design of highly efficient HTMs for the preparation of PSCs.

Preparation and characterization of soluble carbon nano-onions by covalent functionalization, employing a Na–K alloy

Herein we report the preparation of truly soluble CNOs by covalent functionalization with hexadecyl chains. These compounds are prepared in two steps: first, reduction of CNOs with a Na-K alloy in 1,2-DME under vacuum, followed by nucleophilic substitution employing 1-bromohexadecane.

Determining the Attenuation Factor in Molecular Wires Featuring Covalent and Noncovalent Tectons

Hybrid covalent/supramolecular porphyrin-fullerene structures were synthesized as highly efficient molecular wires with a remarkably low attenuation factor (β=0.07±0.01 Å-1 ). Hydrogen-bonding interactions and p-phenylene oligomers of different lengths are responsible for efficient electron transfer in the molecular wires.

Impact of concentration self-quenching on the charge generation yield of fullerene based donor-bridge-acceptor compounds in the solid state.

A fullerene based Donor-Bridge-Acceptor (DBA) compound, incorporating a π-extended tetrathiafulvalene electron donor, is investigated with respect to its photophysics in solution versus solid state. Solid films of neat DBA are compared with blend films where the DBA compound is diluted in the inert, low dielectric, polymer poly(styrene). It is found that the moderate intermolecular electronic coupling and donor-acceptor separation (22 Å) in this case leads to the generation of more dissociated, intermolecular charges than a mixture of the donor and acceptor reference compounds. However, the increased intermolecular interactions in the solid state lead to the excited state of the fullerene suffering from concentration self-quenching. This is found to severely affect the charge generation yield in solid films. The impact of competing intra and intermolecular interactions in the solid state upon the film photophysics is analysed in terms of a kinetic model which includes both the effects of concentration self-quenching and the impact of film composition upon the dielectric stabilisation of charge separated states. We conclude that both concentration self-quenching and dielectric stabilisation are critical in determining the photophysics of the blend films, and discuss strategies based upon our observations to enhance the charge photogeneration properties of organic films and photovoltaic devices based upon DBA compounds.