Organic semiconductors with increased dielectric constants:properties and perspectives

Organic semiconductors are a versatile class of materials whose functionality can be tuned extensively with the use of synthetic organic chemistry techniques. Over the years, this has led to the development of organic light emitting diodes, organic solar cells, organic thermoelectric generators and organic field effect transistors, amongst other organic electronic devices. For organic photovoltaic (OPV) devices, a key challenge to developing high performance solar cells has been overcoming the exciton binding energy. The exciton binding energy keeps the photogenerated electrons (negative charge) and holes (positive charge) attracted to one another and hinders the generation of electrical current from the OPV device. Previous research has suggested that one way to tune the exciton binding energy in organic materials could be to change the dielectric constant. The dielectric constant is a material property that describes the ability of a material to screen charges from one another; in theory if the dielectric constant is increased, the exciton binding energy will decrease. At the University of Groningen, various synthetic approaches have been employed to increase the dielectric constant of organic semiconductors. Of these approaches, the incorporation of polar ethylene glycol (EG) chains into the structure of known organic materials has shown particular promise. This thesis builds on this previous work with a focus on the fundamental aspects of how the EG chains affect the optoelectronic properties. In this way, the aim is to provide insight to the interplay between the dielectric constant and the functionality of organic semiconductors

In Operando Modulation of Rectification in Molecular Tunneling Junctions Comprising Reconfigurable Molecular Self-Assemblies

The reconfiguration of molecular tunneling junctions during operation via the self-assembly of bilayers of glycol ethers is described. Well-established functional groups are used to modulate the magnitude and direction of rectification in assembled tunneling junctions by exposing them to solutions containing different glycol ethers. Variable-temperature measurements confirm that rectification occurs by the expected bias-dependent tunneling-hopping mechanism for these functional groups and that glycol ethers, besides being an unusually efficient tunneling medium, behave similarly to alkanes. Memory bits are fabricated from crossbar junctions prepared by injecting eutectic Ga-In (EGaIn) into microfluidic channels. The states of two 8-bit registers were set by trains of droplets such that they are able to perform logical AND operations on bit strings encoded into chemical packets that alter the composition of the crossbar junctions through self-assembly to effect memristor-like properties. This proof-of-concept work demonstrates the potential for fieldable devices based on molecular tunneling junctions comprising self-assembled monolayers and bilayers

Graphene oxide decorated with gold enables efficient biophotovolatic cells incorporating photosystem I

This paper describes the use of reduced graphene oxide decorated with gold nanoparticles as an efficient electron transfer layer for solid-state biophotovoltic cells containing photosystem I as the sole photo-active component. Together with polytyrosine–polyaniline as a hole transfer layer, this device architecture results in an open-circuit voltage of 0.3 V, a fill factor of 38% and a short-circuit current density of 5.6 mA cm(−2) demonstrating good coupling between photosystem I and the electrodes. The best-performing device reached an external power conversion efficiency of 0.64%, the highest for any solid-state photosystem I-based photovoltaic device that has been reported to date. Our results demonstrate that the functionality of photosystem I in the non-natural environment of solid-state biophotovoltaic cells can be improved through the modification of electrodes with efficient charge-transfer layers. The combination of reduced graphene oxide with gold nanoparticles caused tailoring of the electronic structure and alignment of the energy levels while also increasing electrical conductivity. The decoration of graphene electrodes with gold nanoparticles is a generalizable approach for enhancing charge-transfer across interfaces, particularly when adjusting the levels of the active layer is not feasible, as is the case for photosystem I and other biological molecules

Reaching a Double-Digit Dielectric Constant with Fullerene Derivatives

The dielectric constant (ϵr) of organic semiconductors is a key material parameter for improving device performance in the field of organic electronics. However, the effect of the dielectric constant on the electronic and optoelectronic properties of materials remains unclear due to the scarcity of known organic semiconductors with an ϵr value higher than 6. Herein, the optical and electronic properties of a homologous series of fullerene derivatives with high ϵr are studied. The low frequency (<106 Hz) ϵr is extracted from the capacitance measured using impedance spectroscopy, and the effect of length (n) and geometrical arrangement of the polar ethylene glycol (EG) side chains is investigated. The ϵr is found to correlate with length for the symmetrical Bingel adducts, whereas for the unsymmetrical branched-EG chain adducts there is no significant difference between the two EG chain lengths. For BTrEG-2, the ϵr reaches 10, which is an unprecedented value in monoadduct fullerene derivatives. These materials open up new possibilities of studying the effect of ϵr in organic electronic devices such as organic photovoltaics, organic thermoelectrics, and organic field-effect transistors

Conjugated Polyions Enable Organic Photovoltaics Processed from Green Solvents

This paper describes the design, synthesis, and optical and electronic properties of two conjugated polymers CPIZ-B and CPIZ-T that incorporate closed-shell cations into their conjugated backbones, balanced by anionic pendant groups. The zwitterionic nature of the polymers renders them soluble in and processable from polar, protic solvents to form semiconducting films that are not doped. These unique properties are confirmed by absorption and electron paramagnetic resonance spectroscopy. The energies of the unoccupied states respond to the tritylium moieties in the conjugated backbone, while the occupied states respond to the electron-donating ability of the uncharged, aromatic units in the backbone. Films cast from 80:20 HCOOH/H2O by volume show good electron mobilities, enabling a photovoltaic effect in proof-of-concept, bilayer solar cells

N-type organic thermoelectrics : demonstration of ZT > 0.3

The 'phonon-glass electron-crystal' concept has triggered most of the progress that has been achieved in inorganic thermoelectrics in the past two decades. Organic thermoelectric materials, unlike their inorganic counterparts, exhibit molecular diversity, flexible mechanical properties and easy fabrication, and are mostly 'phonon glasses'. However, the thermoelectric performances of these organic materials are largely limited by low molecular order and they are therefore far from being 'electron crystals'. Here, we report a molecularly n-doped fullerene derivative with meticulous design of the side chain that approaches an organic 'PGEC' thermoelectric material. This thermoelectric material exhibits an excellent electrical conductivity of >10Scm(-1) and an ultralow thermal conductivity of 0.3 for organic thermoelectrics

Increasing the Dielectric Constant of Organic Materials for Photovoltaics

This book covers the recent advances in photovoltaics materials and their innovative applications. Many materials science problems are encountered in understanding existing solar cells and the development of more efficient, less costly, and more stable cells. This important and timely book provides a historical overview, but concentrates primarily on the exciting developments in the last decade. It includes organic and perovskite solar cells, photovoltaics in ferroelectric materials, organic-inorganic hybrid perovskite, materials with improved photovoltaic efficiencies as well as the full range of semiconductor materials for solar-to-electricity conversion, from crystalline silicon and amorphous silicon to cadmium telluride, copper indium gallium sulfide selenides, dye sensitized solar cells, organic solar cells, and environmentally-friendly copper zinc tin sulfide selenides

Stochastic Computing via In Operando Modulation of Rectification in Molecular Tunneling Junctions

This paper describes the reconfiguration of molecular tunneling junctions during operation via the self-assembly of bilayers of glycol ethers. We use well-established functional groups to modulate the magnitude and direction of rectification in assembled tunneling junctions by exposing them to solutions containing different glycol ethers. Variable-temperature measurements establish that rectification occurs by a bias-dependent tunneling-hopping mechanism and that glycol ethers, beside being an unusually efficient tunneling medium, behave identically to alkanes. We fabricated memory bits from crossbar junctions prepared by injecting eutectic Ga-In into microfluidic channels. Two 8-bit registers were able to perform logical AND operations on bit strings encoded into chemical packets as microfluidic droplets that alter the composition of the crossbar junctions through self-assembly to effect memristor-like properties. This proof of concept work demonstrates the potential for fieldable molecular-electronic devices based on tunneling junctions of self-assembled monolayers and bilayers