An experimental study of the transport properties of a low‐bandgap conjugated polymer giving high photovoltaic quantum efficiencies in the near infrared spectral region (Eg‐opt ∼ 1.35 eV) is presented. Using a organic thin film transistor geometry, we demonstrate a relatively high in‐plane hole mobility, up to 1.5 · × 10−2 cm2 V−1 s−1 and quantify the electron mobility at 3 × · 10−5 cm2 V−1 s−1 on a SiO2 dielectric. In addition, singular contact behavior results in bipolar quasi‐Ohmic injection both from low and high workfunction metals like LiF/Al and Au. X‐ray investigations revealed a degree of interchain π‐stacking that is probably embedded in a disordered matrix. Disorder also manifests itself in a strong positive field dependence of the hole mobility from the electric field. In blends made with the electron acceptor methanofullerene [6,6]‐phenyl C61 butyric acid methyl ester (PCBM), the transistor characteristics suggest a relatively unfavorable intermixing of the two components for the application to photovoltaic devices. We attribute this to a too fine dispersion of [C60]‐PCBM in the polymer matrix, that is also confirmed by the quenching of the photoluminescence signal measured in PCPDTBT [C60]‐PCBM films with various composition. We show that a higher degree of phase separation can be induced during the film formation by using 1,8‐octanedithiol (ODT), which leads to a more efficient electron percolation in the [C60]‐PCBM. In addition, the experimental results, in combination with those of solar cells seem to support the correlation between the blend morphology and charge recombination. We tentatively propose that the drift length, and similarly the electrical fill factor, can be limited by the recombination of holes with electrons trapped on isolated [C60]‐PCBM clusters. Ionized and isolated [C60]‐PCBM molecules can modify the local electric field in the solar cell by build‐up of a space‐charge. The results also suggest that further improvements of the fill factor may also be limited by a strong electrical‐field dependence of the hole transport.

We report on the metalorganic chemical vapor deposition (MOCVD) of GaN:Fe and (Ga,Fe)N layers on c-sapphire substrates and their thorough characterization via high-resolution x-ray diffraction (HRXRD), transmission electron microscopy (TEM), spatially-resolved energy dispersive X-ray spectroscopy (EDS), secondary-ion mass spectroscopy (SIMS), photoluminescence (PL), Hall-effect, electron-paramagnetic resonance (EPR), and magnetometry employing a superconducting quantum interference device (SQUID). A combination of TEM and EDS reveals the presence of coherent nanocrystals presumably FexN with the composition and lattice parameter imposed by the host. From both TEM and SIMS studies, it is stated that the density of nanocrystals and, thus the Fe concentration increases towards the surface. According to Hall effect measurements, electrons from residual donors are trapped by mid-gap Fe acceptor states in the limit of low iron content x 0.4%, indicating that the concentration of Fe 2+ ions increases at the expense of Fe ions in the 3+ charge state. This effect is witnessed by photoluminescence (PL) measurements as changes in the intensity of the Fe 3+ -related intra-ionic transition, which can be controlled by co-doping with Si donors and Mg acceptors. In this regime, EPR of Fe 3+ ions and Curie-like magnetic susceptibility are observed. As a result of the spin-orbit interaction, Fe 2+ does not produce any EPR response. However, the presence of Fe ions in the 2+ charge state may account for a temperature-independent Van Vleck-type paramagnetic signal that we observe by SQUID magnetometry. Surprisingly, at higher Fe concentrations, the electron density is found to increase substantially with the Fe content. The co-existence of electrons in the conduction band and Fe in the 3+ charge state is linked to the gradient in the Fe concentration. In layers with iron content x 0.4% the presence of ferromagnetic signatures, such as magnetization hysteresis and spontaneous magnetization, have been detected. A set of precautions has been undertaken in order to rule out possible sources of spurious ferromagnetic contributions. Under these conditions, a ferromagnetic-like response is shown to arise from the (Ga,Fe)N epilayers, it increases with the iron concentration, it persists up to room temperature, and it is anisotropic -i.e., the saturation value of the magnetization is higher for in-plane magnetic field. We link the presence of ferromagnetic signatures to the formation of Fe-rich nanocrystals, as evidenced by TEM and EDS studies. This interpretation is supported by magnetization measurements after cooling in-and without an external magnetic field, pointing to superparamagnetic properties of the system. It is argued that the high temperature ferromagnetic response due to spinodal decomposition into regions with small and large concentration of the magnetic component is a generic property of diluted magnetic semiconductors and diluted magnetic oxides showing high apparent Curie temperature.

This review presents the recent progress in computational materials design, experimental realization, and control methods of spinodal nanodecomposition under three-and two-dimensional crystal-growth conditions in spintronic materials, such as magnetically doped semiconductors. The computational description of nanodecomposition, performed by combining first-principles calculations with kinetic Monte Carlo simulations, is discussed together with extensive electron microscopy, synchrotron radiation, scanning probe, and ion beam methods that have been employed to visualize binodal and spinodal nanodecomposition (chemical phase separation) as well as nanoprecipitation (crystallographic phase separation) in a range of semiconductor compounds with a concentration of transition metal (TM) impurities beyond the solubility limit. The role of growth conditions, codoping by shallow impurities, kinetic barriers, and surface reactions in controlling the aggregation of magnetic cations is highlighted. According to theoretical simulations and experimental results the TM-rich regions appear in the form of either nanodots (the dairiseki phase) or nanocolumns (the konbu phase) buried in the host semiconductor. Particular attention is paid to Mn-doped group III arsenides and antimonides, TM-doped group III nitrides, Mn-and Fe-doped Ge, and Cr-doped group II chalcogenides, in which ferromagnetic features persisting up to above room temperature correlate with the presence of nanodecomposition and account for the application-relevant magnetooptical and magnetotransport properties of these compounds. Finally, it is pointed out that spinodal nanodecomposition can be viewed as a new class of bottom-up approach to nanofabrication.

The control on the distribution of magnetic ions into a semiconducting host is crucial for the functionality of magnetically doped semiconductors. Through a structural analysis at the nanoscale, we give experimental evidence that the aggregation of Fe ions in (Ga,Fe)N and consequently the magnetic response of the material are affected by the growth rate and doping with shallow impurities.

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