High-performance polymer semiconducting heterostructure devices by nitrene-mediated photocrosslinking of alkyl side chains.

Heterostructures are central to the efficient manipulation of charge carriers, excitons and photons for high-performance semiconductor devices. Although these can be formed by stepwise evaporation of molecular semiconductors, they are a considerable challenge for polymers owing to re-dissolution of the underlying layers. Here we demonstrate a simple and versatile photocrosslinking methodology based on sterically hindered bis(fluorophenyl azide)s. The photocrosslinking efficiency is high and dominated by alkyl side-chain insertion reactions, which do not degrade semiconductor properties. We demonstrate two new back-infiltrated and contiguous interpenetrating donor-acceptor heterostructures for photovoltaic applications that inherently overcome internal recombination losses by ensuring path continuity to give high carrier-collection efficiency. This provides the appropriate morphology for high-efficiency polymer-based photovoltaics. We also demonstrate photopatternable polymer-based field-effect transistors and light-emitting diodes, and highly efficient separate-confinement-heterostructure light-emitting diodes. These results open the way to the general development of high-performance polymer semiconductor heterostructures that have not previously been thought possible.

Role of delta-hole-doped interfaces at Ohmic contacts to organic semiconductors.

An electromodulated absorption spectroscopy study of the contact between an organic semiconductor (OSC) poly(2,5-dialkoxy-p-phenylenevinylene) and p-doped poly(3,4-ethylenedioxythiophene) electrodes of different work functions (phivac) reveals direct evidence for the formation of a hole-doped layer at the OSC interface in equilibrium with high-phivac electrodes. When the hole density at this interface exceeds a few 10(11) cm(-2), degenerate "bandlike" polaron states emerge. This appears to be crucial to furnish efficient carrier injection into the bulk of the OSC to achieve Ohmic injection. The gap measured by ultraviolet photoemission between the electrode Fermi level and the OSC transport level (typically pinned at 0.6 eV) does not reflect the true injection barrier.

Direct evidence for the role of the madelung potential in determining the work function of doped organic semiconductors.

The work function of a model degenerately doped organic semiconductor p-doped poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) can be systematically tuned over an eV-wide range by exchanging excess matrix protons with spectator cations, without altering the organic semiconductor doping level or polaron density. Ultraviolet photoelectron spectroscopy reveals this to arise not from an interface dipole, but from a bulk effect due to a shift in the Madelung potential set up by the local counter- and spectator-ion structure at the polaron sites. Electrostatic modeling of this potential is in agreement with the observed shift in carrier energetics. The spectator cations also cause a systematic shift in electron-phonon coupling and carrier delocalization, as revealed by infrared and Raman phonon modes, and charge-modulated absorption, which can be related to disorder in this potential.

Controlled insulator-to-metal transformation in printable polymer composites with nanometal clusters.

Although organic semiconductors have received the most attention, the development of compatible passive elements, such as interconnects and electrodes, is also central to plastic electronics. For this, ligand-protected metal-cluster films have been shown to anneal at low temperatures below 250 degrees C to highly conductive metal films, but they suffer from cracking and inadequate substrate adhesion. Here, we report printable metal-cluster-polymer nanocomposites that anneal to a controlled-percolation nanostructure without complete sintering of the metal clusters. This overcomes the previous challenges while still retaining the desired low transformation temperatures. Highly water- and alcohol-soluble gold clusters (75 mg ml-1) were synthesized and homogeneously dispersed into poly(3,4-ethylenedioxythiophene) to give a material with annealed d.c. conductivity tuneable between 10(-4) and 10(5) S cm-1. These composites can inject holes efficiently into all-printed polymer organic transistors. The insulator-metal transformation can also be electrically induced at 1 MV cm-1, suggesting possible memory applications.

Large damage threshold and small electron escape depth in X-ray absorption spectroscopy of a conjugated polymer thin film.

The information depth of near-edge X-ray absorption fine structure spectroscopy in the total electron yield mode (TEY-NEXAFS) is given by the escape depth of the TEY electrons z(TEY). This is determined by the effective ranges both of the inelastically scattered secondary electrons and of the primary excited electron before they thermalize below the vacuum level. For regioregular poly(3-hexylthiophene) (rreg-P3HT) thin films, we have measured the total electron emission efficiency to be 0.028 +/- 0.005 e/ph at an incident photon energy of 320 eV. The range of the primary electron was computed using optical dielectric-loss theory to be 7.5 nm. The range of the secondary electrons was then found by modeling to be 3.0 nm. This gives z(TEY) to be 2.5 nm, which is considerably less than the often-assumed value of 10 nm in the literature. It is also considerably smaller than the computed electron-electron scattering inelastic mean free path in the material, which suggests the predominance of electron-phonon scattering. Thus, TEY-NEXAFS has sufficient surface sensitivity to probe the frontier molecular layers of these organic conjugated polymers. In a second aspect of this report, the rreg-P3HT films have been characterized by in-situ core and valence photoemission spectroscopies and by ex-situ microattenuated total-reflection vibrational spectroscopy as a function of irradiation dose. No damage was observed in composition, bonding, orientation, and surface morphology under typical TEY-NEXAFS spectral acquisition conditions. For an integrated TEY that exceeds 2 x 10(-3) C cm(-2), however, the material degrades via alkyl side-chain dehydrogenation to unsaturated units, cross linking, ring opening of the backbone, and sulfur extrusion. Given that secondary electrons are the dominant cause of radiation damage, this exposure threshold measured by integrated TEY should also be valid at other X-ray energies.