Bert de Boer

Small Bandgap Polymers for Organic Solar Cells (Polymer Material Development in the Last 5 Years)

During the last decade the field of polymer photovoltaics has seen a tremendous improvement in both device efficiency and understanding of the underlying physical processes. One has come to a point in which the prototypical large bandgap material system P3HT:PCBM is nearing optimal device performance. In order to enhance efficiencies even further, research activities for new materials are needed with better aligned energy levels. One interesting approach is by narrowing the donor bandgap to enhance light absorption. Recent developments on small band gap (<2.0 eV) materials for photovoltaic applications are reviewed. First, an introduction is given regarding the processes governing the exciton dissociation, charge transport requirements, energy level engineering of both donor and acceptor materials, and other parameters determining the photovoltaic performance. The focus is on polymeric donor materials, which are subdivided by the type of monomeric units that constitute the backbone. Finally, the synthetic methods and conditions, processing of the devices, and the device performances are summarized.

Towards molecular electronics with large-area molecular junctions

Electronic transport through single molecules has been studied extensively by academic and industrial research groups. Discrete tunnel junctions, or molecular diodes, have been reported using scanning probes, break junctions, metallic crossbars and nanopores. For technological applications, molecular tunnel junctions must be reliable, stable and reproducible. The conductance per molecule, however, typically varies by many orders of magnitude. Self-assembled monolayers (SAMs) may offer a promising route to the fabrication of reliable devices, and charge transport through SAMs of alkanethiols within nanopores is well understood, with non-resonant tunnelling dominating the transport mechanism. Unfortunately, electrical shorts in SAMs are often formed upon vapour deposition of the top electrode, which limits the diameter of the nanopore diodes to about 45 nm. Here we demonstrate a method to manufacture molecular junctions with diameters up to 100 µm with high yields (> 95 per cent). The junctions show excellent stability and reproducibility, and the conductance per unit area is similar to that obtained for benchmark nanopore diodes. Our technique involves processing the molecular junctions in the holes of a lithographically patterned photoresist, and then inserting a conducting polymer interlayer between the SAM and the metal top electrode. This simple approach is potentially low-cost and could pave the way for practical molecular electronics.

Organic Nonvolatile Memory Devices Based on Ferroelectricity

A memory functionality is a prerequisite for many applications of electronic devices. Organic nonvolatile memory devices based on ferroelectricity are a promising approach toward the development of a low-cost memory technology. In this Review Article we discuss the latest developments in this area with a focus on three of the most important device concepts: ferroelectric capacitors, field-effect transistors, and diodes. Integration of these devices into larger memory arrays is also discussed.

Bottom-up organic integrated circuits

Self-assembly—the autonomous organization of components into patterns and structures—is a promising technology for the mass production of organic electronics. Making integrated circuits using a bottom-up approach involving self-assembling molecules was proposed in the 1970s. The basic building block of such an integrated circuit is the self-assembled-monolayer field-effect transistor (SAMFET), where the semiconductor is a monolayer spontaneously formed on the gate dielectric. In the SAMFETs fabricated so far, current modulation has only been observed in submicrometre channels, the lack of efficient charge transport in longer channels being due to defects and the limited intermolecular π–π coupling between the molecules in the self-assembled monolayers. Low field-effect carrier mobility, low yield and poor reproducibility have prohibited the realization of bottom-up integrated circuits. Here we demonstrate SAMFETs with long-range intermolecular π–π coupling in the monolayer. We achieve dense packing by using liquid-crystalline molecules consisting of a π-conjugated mesogenic core separated by a long aliphatic chain from a monofunctionalized anchor group. The resulting SAMFETs exhibit a bulk-like carrier mobility, large current modulation and high reproducibility. As a first step towards functional circuits, we combine the SAMFETs into logic gates as inverters; the small parameter spread then allows us to combine the inverters into ring oscillators. We demonstrate real logic functionality by constructing a 15-bit code generator in which hundreds of SAMFETs are addressed simultaneously. Bridging the gap between discrete monolayer transistors and functional self-assembled integrated circuits puts bottom-up electronics in a new perspective.

Electrical conduction through single molecules and self-assembled monolayers

Although research on molecular electronics has drawn increasingly more attention in the last decade, the large spread in obtained results for the conduction rescaled to a single molecule indicates a strong dependence of the measured data on the experimental testbed used. We subdivided a generalized metal-molecule-metal junction into different components and discuss their influence on electrical transport measurements of a single organic molecule or an assembly of molecules. By relating the advantages and disadvantages of different experimental testbeds to the more general view of a molecular junction, we strive to explain the discrepancies between the obtained results on molecular conduction. The reported results on molecular conduction of molecules with an alkane backbone can be categorized into three groups with different resistance values, depending on the device area of the molecular junction and the nature of the contacts.

Organic non-volatile memories from ferroelectric phase-separated blends

New non-volatile memories are being investigated to keep up with the organic-electronics road map. Ferroelectric polarization is an attractive physical property as the mechanism for non-volatile switching, because the two polarizations can be used as two binary levels. However, in ferroelectric capacitors the read-out of the polarization charge is destructive. The functionality of the targeted memory should be based on resistive switching. In inorganic ferroelectrics conductivity and ferroelectricity cannot be tuned independently. The challenge is to develop a storage medium in which the favourable properties of ferroelectrics such as bistability and non-volatility can be combined with the beneficial properties provided by semiconductors such as conductivity and rectification. Here we present an integrated solution by blending semiconducting and ferroelectric polymers into phase-separated networks. The polarization field of the ferroelectric modulates the injection barrier at the semiconductor-metal contact. The combination of ferroelectric bistability with (semi)conductivity and rectification allows for solution-processed non-volatile memory arrays with a simple cross-bar architecture that can be read out non-destructively. The concept of an electrically tunable injection barrier as presented here is general and can be applied to other electronic devices such as light-emitting diodes with an integrated on/off switch.

Origin of the enhanced performance in poly(3-hexylthiophene): [6,6]-phenyl C61-butyric acid methyl ester solar cells upon slow drying of the active layer

The origin of the enhanced performance of bulk heterojunction solar cells based on slowly dried films of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61-butyric acid methyl ester is investigated, combining charge transport measurements with numerical device simulations. Slow drying leads to a 33-fold enhancement of the hole mobility up to 5.0×10−7m2V−1s−1 in the P3HT phase of the blend, thereby balancing the transport of electrons and holes in the blend. The resulting reduction of space-charge accumulation enables the use of thick films (∼300nm), absorbing most of the incoming photons, without losses in the fill factor and short-circuit current of the device.

Supramolecular self-assembly and opto-electronic properties of semiconducting block copolymers

Abstract With continuous and nanometre-scale interpenetrating phases of electron donor and acceptor components, a novel diblock copolymer, in which one block is poly(p-phenylene vinylene) (PPV) and the other is a C60-functionalized polystyrene, is designed to be an efficient photovoltaic material. The synthesis involves the polymerization of a styrene derivative from a PPV-based macroinitiator via living free radical polymerization, and its subsequent functionalization with C60 via atom transfer radical addition. In selective solvents for the polystyrene block, aggregation is detected by means of optical spectroscopy and small-angle neutron scattering. Solid films exhibit honeycomb-structuring at the micrometre level when cast from CS2. As active layer in a device, the donor–acceptor diblock copolymer shows enhanced photovoltaic response relative to a blend of its constituent polymers.

Electron tunneling through alkanedithiol self-assembled monolayers in large-area molecular junctions

The electrical transport through self-assembled monolayers of alkanedithiols was studied in large-area molecular junctions and described by the Simmons model [Simmons JG (1963) J Appl Phys 34:1793–1803 and 2581–2590] for tunneling through a practical barrier, i.e., a rectangular barrier with the image potential included. The strength of the image potential depends on the value of the dielectric constant. A value of 2.1 was determined from impedance measurements. The large and well defined areas of these molecular junctions allow for a simultaneous study of the capacitance and the tunneling current under operational conditions. Electrical transport for octanedithiol through tetradecanedithiol self-assembled monolayers up to 1 V can simultaneously be described by a single effective mass and a barrier height. There is no need for additional fit constants. The barrier heights are in the order of 4–5 eV and vary systematically with the length of the molecules. Irrespective of the length of the molecules, an effective mass of 0.28 was determined, which is in excellent agreement with theoretical predictions.

Solution-processed organic tandem solar cells with embedded optical spacers

We demonstrate a solution-processed polymer tandem solar cell in which the two photoactive single cells are separated by an optical spacer. The use of an optical spacer allows for an independent optimization of both the electronic and optical properties of the tandem cell. The optical transmission window of the bottom cell is optimized to match the optical absorption of the top cell by varying the layer thickness of the optical spacer. The two bulk heterojunction subcells have complementary absorption maxima at λmax∼850nm for the top cell and λmax∼550nm for the bottom cell. The subcells are electronically coupled in series or in parallel using four electrical contacts. The series configuration leads to an open-circuit voltage of >1V, which is equal to the sum of both subcells. The parallel configuration leads to a high short-circuit current of 92A∕m2, which is equal to the sum of both subcells. The parallel configuration results in a much higher efficiency compared to the series configuration.