Organic-based interfaces can possess a range of surprising electronic properties that are of intense interest from both the basic science and the applied research points of view. In this issue of MRS Bulletin, we provide state-of-the-art overviews of selected topics involving three complementary aspects of the electronic properties of organic-based interfaces: the nascent electronics technologies that would gain from improved understanding and control of such interfaces; the novel properties that organic-based interfaces may possess; and the experimental and theoretical challenges afforded by such studies.

Organic and hybrid (organic/inorganic) solar cells are an attractive alternative to traditional silicon-based photovoltaics due to low-temperature, solution-based processing and the potential for rapid, easily scalable manufacturing. Using oxide semiconductors, instead of fullerenes, as the electron acceptor and transporter in hybrid solar cells has the added advantages of better environmental stability, higher electron mobility, and the ability to engineer interfacial band offsets and hence the photovoltage. Further improvements to this structure can be made by using metal oxide nanostructures to increase heterojunction areas, similar to bulk heterojunction organic photovoltaics. However, compared to all-organic solar cells, these hybrid devices produce far lower photocurrent, making improvement of the photocurrent the highest priority. This points to a less than optimized polymer/metal oxide interface for carrier separation. In this article, we summarize recent work on examining the polymer structure, electron transfer, and recombination at the polythiophene-ZnO interface in hybrid solar cells. Additionally, the impact of chemical modification at the donor-acceptor interface on the device characteristics is reviewed.

Self-assembled monolayers (SAMs) of organic dipolar molecules have new electronic and magnetic properties that result from their organization, despite the relatively weak interaction among the molecules themselves. Here we review the origin of this cooperative effect and summarize work performed on spin selective electron transmission through SAMs. The spin selectivity observed, in some cases, is consistent with a model in which a SAM containing chiral dipolar molecules behaves like a magnetic layer. The magnetic properties result in the SAMs behaving as spin filters, even without applying an external magnetic field to the layer.

Van der Waals (vdW) interactions play a prominent role in the structure and function of organic/organic and organic/inorganic interfaces. Their accurate determination from first principles, however, is a notoriously difficult task. Recently, a surge of interest in modeling vdW interactions has led to promising theoretical developments. This article reviews the state-of-the-art of describing vdW interactions by density-functional theory with respect to accuracy and practicability. The performance of the different methods is demonstrated for simple systems, such as rare-gas dimers and small organic molecules. The nature of binding at organic/inorganic interfaces is then exemplified for the perylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride (PTCDA) molecule at surfaces of coinage metals. This fundamental system is the best-characterized organic molecule/metal interface in experiment and theory. We emphasize the crucial importance of a balanced description of both geometry and electronic structure in order to understand and model the properties of such systems. Finally, the relevance of vdW interactions to the function of actual devices based on interfaces is discussed.

We present our understanding of the electronic energy landscape and dynamics of charge separation at organic donor/acceptor interfaces. The organic/organic interface serves as a valuable point of reference and plays an important role in emerging electronic and optoelectronic applications, particularly organic photovoltaics (OPVs). The key issue on electronic structure at organic donor/acceptor interfaces is the difference in the lowest unoccupied molecular orbitals or that in the highest occupied molecular orbitals. This difference represents an energy gain needed to overcome the exciton binding energy in a charge-separation process in OPV. A sufficiently large energy gain favors the formation of charge transfer (CT) states that are energetically close to the charge-separation state. At an organic donor/acceptor interface in an OPV device, these high-energy CT states, also called hot CT excitons, are necessary intermediates in a successful charge-separation process.

The emergence of organic electronics represents one of the most dramatic technological developments of the past two decades. Perhaps the most important frontier of this field involves the interface with biology. The “soft” nature of organics offers better mechanical compatibility with tissue than traditional electronic materials, while their natural compatibility with mechanically flexible substrates suits the nonplanar form factors often required for implants. More importantly, the ability of organics to conduct ions in addition to electrons and holes opens up a new communication channel with biology. In this article, we consider a few examples that illustrate the coupling between organic electronics and biology and highlight new directions of research.

David Turnbull's experiments and theoretical insights paved the way for much of our modern understanding of phase transitions in materials. In recognition of his contributions, this lecture will concentrate on phase transitions in a material system not considered by Turnbull, thin diblock copolymer films. Well-ordered block copolymer films are attracting increasing interest as we attempt to extend photolithography to smaller dimensions. In the case of diblock copolymer spheres, an ordered monolayer is hexagonal, but the ordered bulk is body-centered cubic (bcc). There is no hexagonal plane in the bcc structure, so a phase transition must occur as n, the number of layers of spheres in the film, increases. How this phase transition occurs with nand how it can be manipulated is the subject of the first part of my presentation. In the second part of the talk, I show that monolayers of diblock copolymer spheres and cylinders undergo order-to-disorder transitions that differ greatly from those of the bulk. These ordered 2D monolayers are susceptible to phonon-generated disorder as well as to thermal generation of defects, such as dislocations, which, while they are line defects in 3D, are point defects in 2D. The results are compared to the theories of melting of 2D crystals (spheres) and of 2D smectic liquid crystals (cylinders), a comparison that will allow us to understand most, but not all, of the features of these order-disorder transitions that occur as the temperature is increased.