J. D’Haen

Disclosure of the nanostructure of MDMO-PPV:PCBM bulk hetero-junction organic solar cells by a combination of SPM and TEM

Abstract The microstructure of MDMO-PPV:PCBM blends as used in bulk hetero-junction organic solar cells is studied by atomic force microscopy (AFM) to image the surface morphology and by means of transmission electron microscopy (TEM) to disclose the bulk nanostructure of the film. Typical thin films, as used for state-of-the-art organic bulk hetero-junction solar cells consist of a 1:4 ratio by weight of MDMO-PPV as electron donating polymer and PCBM, a soluble electron accepting C 60 derivative. For these films it is found, using both TEM an AFM, that phase separation occurs. A two-phase system is observed that consists of PCBM-rich domains that are embedded in a matrix consisting of a mixture of MDMO-PPV and PCBM. By combining planar and cross-sectional views, three-dimensional information is obtained on the phase separated PCBM-rich regions, formed during spincoating. Changing the solvent is found to influence the size of the phase separated PCBM-rich domains. But not only the dimensions of the phase separated regions are affected by changing the solvent. Also the composition of the matrix is found to be determined by the choice of solvent. This was studied by changing the ratio of PCBM compared to MDMO-PPV. Since it is commonly believed that the morphology of the active layer influences electrical properties and photovoltaic performance, the nanostructural information obtained with the presented analytical techniques will attribute to a better understanding and improvement of present organic photovoltaic devices.

Synthesis of ZnO nanopowder via an aqueous acetate–citrate gelation method

The synthesis of nanoparticulate ZnO via an aqueous carboxylate gelation route is presented. Starting from a solution of zinc acetate with citric acid as a complexing agent, a solid glassy gel is obtained after drying that is converted into a fine powder by calcination. It is found that a very homogeneous precursor is indispensable when preparing very fine particles with a narrow size distribution. Cryo-transmission electron microscopy (Cryo-TEM) investigation is used as a feedback tool to prevent early precipitation during gelation. Study of the thermal decomposition of the gel shows that ZnO is formed before the final decomposition step takes place. After removing the organic backbone, very small oxide particles are found. The influence of the thermal treatment parameters on the particle size is investigated and a particle growth process is found. By a proper adjustment of the final calcination temperature in dry air, the mean particle size can be controlled between ∼11 and 175 nm. It was also seen that even in inert atmosphere, ZnO is formed and that particle morphology is greatly influenced by the calcination atmosphere.

Surface acoustic wave propagation in aluminum nitride-unpolished freestanding diamond structures

High-quality surface acoustic wave (SAW) filters based on aluminum nitride (AlN)/diamond layered structures were prepared using the nucleation side of polycrystalline chemical vapor deposition (CVD) diamond, removed from a silicon substrate by wet etching. Highly oriented AlN thin films with optimized piezoelectric properties and with various thicknesses were sputtered onto the nucleation side of freestanding diamond. The effect of AlN thickness on the SAW phase velocity, the coupling coefficient, and the device characteristics were investigated. Experimental results show that the Rayleigh wave and the higher modes are generated. These results agree well with calculated dispersion curves and demonstrate that a high electromechanical coupling coefficient together with a high phase velocity can be obtained by using the nucleation side of freestanding CVD diamond layer.

Electrical activity of intragrain defects in polycrystalline silicon layers obtained by aluminum-induced crystallization and epitaxy

Defect etching revealed a very large density (∼109cm−2) of intragrain defects in polycrystalline silicon (pc-Si) layers obtained through aluminum-induced crystallization of amorphous Si and epitaxy. Electron-beam-induced current measurements showed a strong recombination activity at these defects. Cathodoluminescence measurements showed the presence of two deep-level radiative transitions (0.85 and 0.93eV) with a relative intensity varying from grain to grain. These results indicate that the unexpected quasi-independence on the grain size of the open-circuit voltage of these pc-Si solar cells is due to the presence of numerous electrically active intragrain defects.

Structural and optical properties of DNA layers covalently attached to diamond surfaces

Label-free detection of DNA molecules on chemically vapor-deposited diamond surfaces is achieved with spectroscopic ellipsometry in the infrared and vacuum ultraviolet range. This nondestructive method has the potential to yield information on the average orientation of single as well as double-stranded DNA molecules, without restricting the strand length to the persistence length. The orientational analysis based on electronic excitations in combination with information from layer thicknesses provides a deeper understanding of biological layers on diamond. The pi-pi* transition dipole moments, corresponding to a transition at 4.74 eV, originate from the individual bases. They are in a plane perpendicular to the DNA backbone with an associated n-pi* transition at 4.47 eV. For 8-36 bases of single- and double-stranded DNA covalently attached to ultra-nanocrystalline diamond, the ratio between in- and out-of-plane components in the best fit simulations to the ellipsometric spectra yields an average tilt angle of the DNA backbone with respect to the surface plane ranging from 45 degrees to 52 degrees . We comment on the physical meaning of the calculated tilt angles. Additional information is gathered from atomic force microscopy, fluorescence imaging, and wetting experiments. The results reported here are of value in understanding and optimizing the performance of the electronic readout of a diamond-based label-free DNA hybridization sensor.

Toward bulk heterojunction polymer solar cells with thermally stable active layer morphology

Abstract. When state-of-the-art bulk heterojunction organic solar cells with ideal morphology are exposed to prolonged storage or operation at elevated temperatures, a thermally induced disruption of the active layer blend can occur, in the form of a separation of donor and acceptor domains, leading to diminished photovoltaic performance. Toward the long-term use of organic solar cells in real-life conditions, an important challenge is, therefore, the development of devices with a thermally stable active layer morphology. Several routes are being explored, ranging from the use of high glass transition temperature, cross-linkable and/or side-chain functionalized donor and acceptor materials, to light-induced dimerization of the fullerene acceptor. A better fundamental understanding of the nature and underlying mechanisms of the phase separation and stabilization effects has been obtained through a variety of analytical, thermal analysis, and electro-optical techniques. Accelerated aging systems have been used to study the degradation kinetics of bulk heterojunction solar cells in situ at various temperatures to obtain aging models predicting solar cell lifetime. The following contribution gives an overview of the current insights regarding the intrinsic thermally induced aging effects and the proposed solutions, illustrated by examples of our own research groups.

Hydrothermal synthesis of ZnO nanorods: a statistical determination of the significant parameters in view of reducing the diameter

In this paper a 2(8-4) fractional factorial design of experiments is applied to identify the important parameters that affect the average diameter of ZnO rods, synthesized by means of a hydrothermal procedure. A water-based Zn(2+) precursor is used for the formation of one-dimensional ZnO particles, without the presence of an organic additive. Results indicate that, at the investigated levels, four of the parameters have a significant effect on the mean diameter. These are the temperature, the heating rate, stirring and an ultrasonic pre-treatment of the precursor solution. Experiments carried out with zinc acetate and zinc chloride do not show a significant difference in rod diameter. Other parameters that do not show a significant effect are the concentration of Zn(2+), the molar ratio between the hydroxyl and the zinc ions, and the reaction time. Interactions are observed between stirring and an ultrasonic pre-treatment and between the zinc concentration and the OH:Zn ratio. By fixing the significant factors at their optimal value it is possible to decrease the mean diameter. The particles are characterized by means of x-ray diffraction (XRD) and transmission electron microscopy (TEM).

Contrasting colonization and plant growth promoting capacity between wild type and a gfp-derative of the endophyte Pseudomonas putida W619 in hybrid poplar:

This study aims to investigate the colonization of poplar by the endophyte Pseudomonas putida W619 and its capacity to promote plant growth. Poplar cuttings were inoculated with P. putida W619 (wild-type or gfp-labelled). The colonization of both strains was investigated and morphological, physiological and biochemical parameters were analyzed to evaluate plant growth promotion. Inoculation with P. putida W619 (wild-type) resulted in remarkable growth promotion, decreased activities of antioxidative defence related enzymes, and reduced stomatal resistance, all indicative of improved plant health and growth in comparison with the non-inoculated cuttings. In contrast, inoculation with gfp-labelled P. putida W619 did not promote growth; it even had a negative effect on plant health and growth. Furthermore, compared to the wildtype strain, colonization by the gfp-labelled P. putida W619::gfp1 was much lower; it only colonized the rhizosphere and root cortex while the wild-type strain also colonized the root xylem vessels. Despite the strong plant growth promoting capacity of P. putida W619 (wild-type), after gfp labelling its growth promoting characteristics disappeared and its colonization capacity was strongly influenced; for these reasons gfp labelling should be applied with sufficient caution.

Exploring the rhizospheric and endophytic bacterial communities of Acer pseudoplatanus growing on a TNT-contaminated soil: towards the development of a rhizocompetent TNT-detoxifying plant growth promoting consortium

Background and aimsNumerous microorganisms have been isolated from trinitrotoluene (TNT)-contaminated soils, however TNT tends to persist, indicating that the microbial biomass or activity is insufficient for degradation. Deep-rooting trees at military sites have been found to take-up contaminants from groundwater, and the extensive root and endosphere provide ideal niches for microbial TNT-transformations.MethodsWe characterised the rhizosphere, root endosphere and endo-phyllosphere bacteria of Acer pseudoplatanus growing at a historically TNT-contaminated location, using 16S rRNA gene fingerprinting, bacteria isolation, oxidoreductase gene-cloning, in planta growth-promotion (PGP) tests, inoculation, plant physiology measurements and microscopy.ResultsBased on terminal-restriction-fragment-length-polymorphism analysis, bulk soil and rhizosphere samples were highly clustered. Proteo- and Actinobacteria dominated the rhizosphere and root endosphere, whereas Alphaproteobacteria were more abundant in shoots and Actinobacteria in leaves. We isolated multiple PGP-bacteria and cloned 5 flavin-oxidoreductases belonging to the Old Yellow Enzyme family involved in TNT-reduction from 3 Pseudomonas spp., the leaf symbiont Stenotrophomonas chelatiphaga and the root endophyte Variovorax ginsengisola.ConclusionsThe inoculation with a selection of these strains, consortium CAP9, which combines efficient TNT-transformation capabilities with beneficial PGP-properties, has the ability to detoxify TNT in the bent grass (Agrostis capillaris) rhizosphere, stimulate plant growth and improve plant health under TNT stress.

Ground-state charge-transfer complex formation in hybrid poly(3-hexyl thiophene):titanium dioxide solar cells

The existence of a ground-state charge-transfer (CT) complex in a conjugated polymer:metal oxide nanoparticle bulk heterojunction photovoltaic cell is demonstrated by Fourier-transform photocurrent spectroscopy (FTPS). The CT complex between poly(3-hexylthiophene) (P3HT) and titanium dioxide (TiO2) is characterized by a weak additional photocurrent band (onset 1eV) in the FTPS spectra, situated below the conjugated polymer bandgap of 2eV. The presence of CT interaction between P3HT and TiO2 in relation to frontier orbital alignment is discussed, as well as the contribution of a sub-bandgap interfacial CT state to the electron transfer process in P3HT:TiO2 solar cells.