Björn Bräuer

Solvent additives and their effects on blend morphologies of bulk heterojunctions

Controlling the blend morphology is one of the ways to achieve high power conversion efficiency in organic bulk heterojunction (BHJ) photovoltaic devices. One simple yet effective method is “solvent additive” approach, which involves the addition of a small fraction of high boiling point solvent into the blend of donor/acceptor dissolved in another host solvent. Even though this method has been successfully applied in a number of polymer/fullerene BHJ devices, the selection rule of the choice of additive and the host solvent has yet to be fully established. In this work, we performed a systematic study of the effect of alkyl lengths of alkanedithiol additives on the nanoscale phase separation of P3HT:PC61BM blends and consequently, the power conversion efficiency (PCE) of the devices. The extent of the additive-induced phase separation is related to the additive boiling point and the degree of interaction between the additive and fullerene, as evident from grazing incidence X-ray diffractometry (GIXRD) and scanning transmission X-ray microscopy (STXM) data. We found that both the boiling point and the degree of interaction are correlated and should be considered simultaneously in the selection of the appropriate solvent additives. Lastly, PCE as high as 3.1% can be achieved in an optimally phase-separated blend due to an improvement in the charge dissociation and a decrease in bimolecular recombination.

Speed limit of the insulator–metal transition in magnetite

As the oldest known magnetic material, magnetite (Fe3O4) has fascinated mankind for millennia. As the first oxide in which a relationship between electrical conductivity and fluctuating/localized electronic order was shown, magnetite represents a model system for understanding correlated oxides in general. Nevertheless, the exact mechanism of the insulator-metal, or Verwey, transition has long remained inaccessible. Recently, three-Fe-site lattice distortions called trimerons were identified as the characteristic building blocks of the low-temperature insulating electronically ordered phase. Here we investigate the Verwey transition with pump-probe X-ray diffraction and optical reflectivity techniques, and show how trimerons become mobile across the insulator-metal transition. We find this to be a two-step process. After an initial 300 fs destruction of individual trimerons, phase separation occurs on a 1.5±0.2 ps timescale to yield residual insulating and metallic regions. This work establishes the speed limit for switching in future oxide electronics.

Magneto-Optical Kerr Effect Spectroscopy—A Sensitive Tool for Investigating the Molecular Orientation in Organic Semiconductor Films

The detection and control of the molecular growth mode is a key prerequisite for fabricating opto-electronic devices. In this work we present the magneto-optical Kerr effect (MOKE) spectroscopy to be a highly sensitive method for the detection of the molecular orientation. On the example of metal free phthalocyanine (H(2)Pc) in thin films, it will be shown that also for diamagnetic molecules a strong magneto-optical response can be expected. The growth mode and thus the intensity of the MOKE signal of H2Pc is strongly influenced by a templating effect using ultrathin layers of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA). From the MOKE spectra in the energy range from 1.5 to 5.0 eV and the optical constants, the Voigt constant of thin organic films was determined. From the strong in-plane/out-of-plane anisotropy of the optical constants and the value of the Voigt constant the average molecular tilt angle of H2Pc molecules with respect to the substrate plane can be obtained.

Electronic and Magnetic Properties of Ni Nanoparticles Embedded in Various Organic Semiconductor Matrices

Ni nanoparticles with a size distribution from 2 to 6 nm, embedded in various organic matrices, were fabricated in ultrahigh vacuum. For this purpose metal free and Ni phthalocyanine, fullerene C(60), and pentacene were coevaporated with Ni. When coevaporated, Ni and H(2)Pc react, leading to the formation of NiPc and Ni nanoparticles. The molecular structure of the matrix was found to have negligible effect on the size of the nanoparticles but to influence the magnetic anisotropy of the nanoparticles: Ni nanoparticles formed in the buckyball matrix have a cubic symmetry, while nanoparticles formed in matrices consisting of planar molecules exhibit a uniaxial symmetry. After exposure to atmosphere, photoelectron spectroscopy investigations demonstrate the presence of metallic Ni nanoparticles accompanied by Ni oxide and the existence of a charge transfer from the organic matrix to the particles in all investigated systems. The oxidized Ni nanoparticles exhibit a larger magnetic anisotropy compared to the freshly prepared particles which show superparamagnetic properties above 17 K. Moreover, photoelectron spectroscopy was used to probe the oxidation process of the Ni nanoparticles in different organic matrices. It could thus be shown that a matrix consisting of spherical molecules like C(60) prevent the particles much better from oxidation compared to matrices of flat molecules.

Magnetic and Optical Properties of Cu(II)-Bis(oxamato) Complexes : Combined Quantum Chemical Density Functional Theory and Vibrational Spectroscopy Studies

Vibrational spectroscopies are shown to be highly sensitive to the structural modifications of paramagnetic mono- and trinuclear Cu(II)-bis(oxamato) complexes. The vibrational bands are assigned using density functional theory (DFT) calculations. Moreover, Raman spectroscopy investigations for different temperatures of thin films show that the onset of superexchange interactions at low temperatures does not involve a modification of the structural parameters. The influence of packing effects, however, on the magnetic properties is significant, as demonstrated by means of DFT using the broken symmetry approach.

How Photoelectron Spectroscopy and Quantum Chemical Studies Can Help Understanding the Magnetic Properties of Molecules: An Example from the Class of Cu(II)-Bis(oxamato) Complexes

Nanometer thin films of nonsublimable multinuclear transition metal complexes were deposited on Si by means of spin coating to enable photoelectron spectroscopy studies. In combination with density functional theory calculations, photoelectron spectroscopy is applied to gain insight into the electronic and magnetic properties of the complexes.

Correction: Polymer nanofibers: preserving nanomorphology in ternary blend organic photovoltaics

Correction for ‘Polymer nanofibers: preserving nanomorphology in ternary blend organic photovoltaics’ by Teddy Salim et al., Phys. Chem. Chem. Phys., 2014, 16, 23829–23836.