Henk Vrielinck

Investigation of defects by admittance spectroscopy measurements in poly (3-hexylthiophene):(6,6)-phenyl C61-butyric acid methyl ester organic solar cells degraded under air exposure

Electrical transport properties of poly (3-hexylthiophene) (P3HT) (6,6)-phenyl C61-butyric acid methyl ester (PCBM) solar cells, with and without encapsulation, have been investigated and analyzed using admittance spectroscopy and capacitance voltage measurements at different temperatures. The admittance spectroscopy clearly reveals two defect states with activation energies of 53 and 100 meV, and a concentration ten times higher in the unencapsulated sample. These defects seem to have a strong effect on the charge transport and the solar cell performance when they are present with a high concentration, since they lead to a decrease of the mobility and also the short-circuit current and the efficiency. The origin of these defects has been assigned to reaction of the blend with O2 which is also known to induce p-type doping in pure P3HT. In an attempt to understand the effect of these defects on the organic solar cell performance, modeling and simulation were carried out using the effective medium layer mo...

Differences in the chemical composition of organic-walled dinoflagellate resting cysts from phototrophic and heterotrophic dinoflagellates

Dinoflagellates constitute a large proportion of the planktonic biomass from marine to freshwater environments. Some species produce a preservable organic‐walled resting cyst (dinocyst) during the sexual phase of their life cycle that is an important link between the organisms, the environment in which their parent motile theca grew, and the sedimentary record. Despite their abundance and widespread usage as proxy indicators for environmental conditions, there is a lack of knowledge regarding the dinocyst wall chemical composition. It is likely that numerous factors, including phylogeny and life strategy, determine the cyst wall chemistry. However, the extent to which this composition varies based on inherent (phylogenetic) or variable (ecological) factors has not been studied. To address this, we used micro‐Fourier transform infrared spectroscopy to analyze nine cyst species produced by either phototrophic or heterotrophic dinoflagellates from the extant orders Gonyaulacales, Gymnodiniales, and Peridiniales. Based on the presence of characteristic functional groups, two significantly different cyst wall compositions are observed that correspond to the dinoflagellates nutritional strategy. The dinocyst wall compositions analyzed appeared carbohydrate‐based, but the cyst wall produced by phototrophic dinoflagellates suggested a cellulose‐like glucan, while heterotrophic forms produced a nitrogen‐rich glycan. This constitutes the first empirical evidence nutritional strategy is related to different dinocyst wall chemistries. Our results indicated phylogeny was less important for predicting composition than the nutritional strategy of the dinoflagellate, suggesting potential for cyst wall chemistry to infer past nutritional strategies of extinct taxa preserved in the sedimentary record.

Identification and conformational study of stable radiation-induced defects in sucrose single crystals using density functional theory calculations of electron magnetic resonance parameters.

One of the major stable radiation-induced radicals in sucrose single crystals (radical T2) has been identified by means of density functional theory (DFT) calculations of electron magnetic resonance parameters. The radical is formed by a net glycosidic bond cleavage, giving rise to a glucose-centered radical with the major part of the spin density residing at the C 1 carbon atom. A concerted formation of a carbonyl group at the C 2 carbon accounts for the relatively small spin density at C 1 and the enhanced g factor anisotropy of the radical, both well-known properties of this radical from several previous experimental investigations. The experimentally determined and DFT calculated proton hyperfine coupling tensors agree very well on all accounts. The influence of the exact geometrical configuration of the radical and its environment on the tensors is explored in an attempt to explain the occurrence and characteristics of radical T3, another major species that is most likely another conformation of T2. No definitive conclusions with regard to the actual structure of T3 could be arrived at from this study. However, the results indicate that, most likely, T3 is identical in chemical structure to T2 and that changes in the orientation of neighboring hydroxy groups or changes in the configuration of the neighboring fructose ring can probably not account for the type and size of the discrepancies between T2 and T3.

Schonland ambiguity in the electron nuclear double resonance analysis of hyperfine interactions: principles and practice.

For the analysis of the angular dependence of electron paramagnetic resonance (EPR) spectra of low-symmetry centres with S=1/2 in three independent planes, it is well-established-but often overlooked-that an ambiguity may arise in the best-fit g<--> tensor result. We investigate here whether a corresponding ambiguity also arises when determining the hyperfine coupling (HFC) A<--> tensor for nuclei with I=1/2 from angular dependent electron nuclear double resonance (ENDOR) measurements. It is shown via a perturbation treatment that for each set of M(S) ENDOR branches two best-fit A<--> tensors can be derived, but in general only one unique solution simultaneously fits both. The ambiguity thus only arises when experimental data of only one M(S) multiplet are used in analysis or in certain limiting cases. It is important to realise that the ambiguity occurs in the ENDOR frequencies and therefore the other best-fit result for an ENDOR determined A<--> tensor depends on various details of the ENDOR experiment: the M(S) state of the fitted transitions, the microwave frequency (or static magnetic field) in the ENDOR measurements and the rotation planes in which data have been collected. The results are of particular importance in the identification of radicals based on comparison of theoretical predictions of HFCs with published literature data. A procedure for obtaining the other best-fit result for an ENDOR determined A<--> tensor is outlined.

Signature of a back contact barrier in DLTS spectra

The DLTS signal induced by a back contact barrier is studied both theoretically and through experiments on model circuits. A nonideal back contact is modeled either by a resistor and a capacitor, or by a germanium diode inversely polarized with respect to the junction diode. Depending on the back contact properties, this may result in a positive or negative capacitance transient. For these model circuits the capacitance transient time constants and amplitudes are studied as a function of voltage pulse height and compared with signals originating from emission and slow capture from a defect level. These two origins of DLTS signals present very different properties, which opens possibilities to distinguish between them.

The Growth of Co:ZnO/ZnO Core/Shell Colloidal Quantum Dots: Changes in Nanocrystal Size, Concentration and Dopant Coordination

We report a synthesis route for the growth of Co:ZnO/ZnO core/shell quantum dots. This procedure consists of successive steps, comprising the addition of diluted precursor salt solutions, and heat treatment at 50 degrees C. By deriving a relation between the extinction coefficient at 250 nm and the nanocrystal diameter, we are able to monitor changes in quantum dot concentration during shell growth. We found that a mechanism based on the nucleation of new particles after salt addition and subsequent Ostwald ripening during the heat treatment is responsible for the shell growth. Based on ligand-field absorption spectroscopy, we demonstrate that the Co(2+) ions adsorbed at the surface of Co:ZnO quantum dots are incorporated inside the ZnO shells. Finally, EPR spectroscopy indicates that the surface-adsorbed Co(2+) ions can be incorporated as substitutional as well as interstitial Co(2+) ions.

Electron spin resonance of rhodium-vacancy complexes in solution-grown NaCl crystals

Three different paramagnetic [RhCl6]4− complexes were detected in x-ray irradiated solution-grown NaCl single crystals: RhCl64−⋅nVac, n=2, 1, 0. These complexes all have a 4d7 ground state, with the unpaired electron spin mainly in a 4dz2 orbital and differ only by the presence of two, one, or none next-nearest cation vacancy (Vac). The RhCl64−⋅2Vac is formed at 77 K and partially converts into RhCl64−⋅1Vac at about 190 K. At room temperature the RhCl64−⋅0Vac is dominant, but traces of the RhCl64−⋅1Vac and RhCl64−⋅2Vac centers remain. A thermally induced reorientation motion of the 4dz2 molecular orbital is used to explain the temperature dependence of the RhCl64−⋅1Vac electron spin resonance spectrum.

Electron nuclear double resonance of stable Rh centers in solution-grown NaCl single crystals

Unlike the photographically important silver halides, large NaCl single crystals can be grown from solution. In such NaCl crystals, with doping comparable to practical AgCl and AgBr microcrystals, three stable Rh centers were detected and studied by electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR). The primary center was identified as a nonlocally compensated [RhCl6]4− complex, at variance with earlier reported EPR work. By lack of sufficient EPR and/or ENDOR evidence, the identity of the two other Rh related centers with orthorhombic and isotropic symmetry respectively, remains rather speculative.

Combined electron magnetic resonance and density functional theory study of 10 K X-irradiated beta-D-fructose single crystals.

Primary free radical formations in fructose single crystals X-irradiated at 10 K were investigated at the same temperature using X-band Electron Paramagnetic Resonance (EPR), Electron Nuclear Double Resonance (ENDOR) and ENDOR induced EPR (EIE) techniques. ENDOR angular variations in the three principal crystallographic planes and a fourth skewed plane allowed the unambiguous determination of five proton hyperfine coupling tensors. From the EIE studies, these hyperfine interactions were assigned to three different radicals, labeled T1, T1* and T2. For the T1 and T1* radicals, the close similarity in hyperfine coupling tensors suggests that they are due to the same type of radical stabilized in two slightly different geometrical conformations. Periodic density functional theory calculations were used to aid the identification of the structure of the radiation-induced radicals. For the T1/T1* radicals a C3 centered hydroxyalkyl radical model formed by a net H abstraction is proposed. The T2 radical is proposed to be a C5 centered hydroxyalkyl radical, formed by a net hydrogen abstraction. For both radicals, a very good agreement between calculated and experimental hyperfine coupling tensors was obtained.

Magnetic resonance study of Rh complexes in AgCl microcrystals

X-ray or UV irradiation at room temperature of Rh3+ doped AgCl emulsion powders leads to the production of three paramagnetic Rh2+ related centres, labeled R4, R5 and R6. A combined X and Q band electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) study allowed the determination of a nearly complete structural model for these centres. In the X band ENDOR spectra of R4 and R5 interactions of the unpaired electron with nearby protons have been identified, indicating that for these centres Cl- ligands have been exchanged by H2O or OH-. The R6 centre, identified as a (RhCl6)4- complex, has been found to be fundamentally different from the dominant centre in large Rh2+ doped AgCl single crystals grown from the melt. The results are compared with recent work by other researchers in the same field.