Crystal structure of polymeric carbon nitride and the determination of its process-temperature-induced modifications.

Based on the arrangement of two-dimensional 'melon', we construct a unit cell for polymeric carbon nitride (PCN) synthesized via thermal polycondensation, whose theoretical diffraction powder pattern includes all major features measured in x-ray diffraction. With the help of this unit cell, we describe the process-temperature-induced crystallographic changes in PCN that occur within a temperature interval between 510 and 610 °C. We also discuss further potential modifications of the unit cell for PCN. It is found that both triazine- and heptazine-based g-C3N4 can only account for minor phases within the investigated synthesis products.

AgGaSe2 thin films grown by chemical close-spaced vapor transport for photovoltaic applications: structural, compositional and optical properties.

Thin films of chalcopyrite AgGaSe(2) have been successfully grown on glass and glass/molybdenum substrates using the technique of chemical close-spaced vapor transport. The high crystallinity of the samples is confirmed by grazing-incidence x-ray diffraction, scanning and transmission electron microscopy, and optical transmission/reflection spectroscopy. Here, two of the three expected direct optical bandgaps are found at 1.77(2) and 1.88(6) eV at 300 K. The lowest bandgap energy at 4 K is estimated to be 1.82(3) eV. Photoluminescence spectroscopy has further revealed the nature of the point defects within the AgGaSe(2), showing evidence for the existence of very shallow acceptor levels of 5(1) and 10(1) meV, and thus suggesting the AgGaSe(2) phase itself to exhibit a p-type conductivity. At the same time, electrical characterization by Hall, Seebeck and four-point-probe measurements indicate properties of a compensated semiconductor. The electrical properties of the investigated thin films are mainly influenced by the presence of Ag(2)Se and Ga(2)O(3) nanometer-scaled surface layers, as well as by Ag(2)Se inclusions in the bulk and Ag clusters at the layers' rear side.

Selective self assembly of glutamate molecules on polyelectrolyte multilayers.

The adsorption behavior of neurotransmitter biomolecule, glutamate, on terminal poly-(allylamine)hydrochloride (PAH) polyelectrolyte multilayer is compared with its adsorption on a terminal poly(styrenesulfonate) (PSS) polyelectrolyte multilayer. Using X-ray and neutron reflectivity experiments, the internal structure of such a supramolecular film has been revealed with high resolution and the volume fraction of the adsorbed glutamate is determined. It has been shown that the glutamate binds only to the terminal PAH multilayer. Multiple attenuated total reflection infrared spectroscopy indicates that glutamate is electrostatically physisorbed on PAH surface in the zwitterionic form. Index matching neutron experiments have been done where the scattering length density of the solvent is varied, by changing the ratio of heavy water and light water, until it completely matches with that of the polyelectrolyte layer. The resulting absorption of the glutamic acid leads to changes in scattering profile which are analyzed and it is seen that the adsorption is restricted only to the surface layers. On the other hand, terminal poly(styrenesulfonate) multilayers show resistance toward glutamate. Such repulsion and adsorption between the neurotransmitter and polyelectrolytes could be potentially used in a variety of medicinal applications.

Tunable optical transition in polymeric carbon nitrides synthesized via bulk thermal condensation.

Polymeric derivatives of dicyandiamide were synthesized via a bulk thermal condensation method, using a range of process temperatures between 400 and 610 °C. The obtained carbon nitride powders exhibit an optical transition in the UV-green range that has been assigned to the direct bandgap of a semiconductor-like material. Within this context, the apparent bandgap is linearly tunable with increasing process temperatures, showing a temperature coefficient of - 1.7(1) meV K(-1) between 2.5 and 3.0 eV. The obtained results show a predominant optical transition within the tri-s-triazine unit of the polymer, with a bathochromic shift originating from a gradually increasing degree of polymerization.

Modeling plasmonic scattering combined with thin-film optics.

Plasmonic scattering from metal nanostructures presents a promising concept for improving the conversion efficiency of solar cells. The determination of optimal nanostructures and their position within the solar cell is crucial to boost the efficiency. Therefore we established a one-dimensional optical model combining plasmonic scattering and thin-film optics to simulate optical properties of thin-film solar cells including metal nanoparticles. Scattering models based on dipole oscillations and Mie theory are presented and their integration in thin-film semi-coherent optical descriptions is explained. A plasmonic layer is introduced in the thin-film structure to simulate scattering properties as well as parasitic absorption in the metal nanoparticles. A proof of modeling concept is given for the case of metal-island grown silver nanoparticles on glass and ZnO:Al/glass substrates. Using simulations a promising application of the nanoparticle integration is shown for the case of CuGaSe(2) solar cells.

Direct evidence for a reduced density of deep level defects at grain boundaries of Cu(In,Ga)Se2 thin films.

The unusual optoelectronic properties of chalcopyrite grain boundaries (GBs) have become the subject of an intense debate in recent years. In this work we investigate the defect density at GBs of Cu(In,Ga)Se2 by scanning tunneling spectroscopy. Contrary to our expectation, our results give evidence for a reduced density of deep level defects and point to an increased density of defect levels in resonance with the lower conduction band at GBs. Our findings imply low recombination activity at GBs, and thus can explain the low impact of GBs on the efficiency of chalcopyrite based solar cells.

The influence of surface topography on Kelvin probe force microscopy.

Long-range electrostatic forces govern the imaging mechanism in electrostatic force microscopy as well as in Kelvin probe force microscopy. To improve the analysis of such images, simulations of the electrostatic field distribution have been performed in the past using a flat surface and a cone-shaped tip. However, the electrostatic field distribution between a tip and a sample depends strongly on the surface topography, which has been neglected in previous studies. It is therefore of general importance to study the influence of sample topography features on Kelvin probe force microscopy images, which we address here by performing finite element simulations. We show how the surface potential measurement is influenced by surface steps and surface grooves, considering potential variations in the form of a potential peak and a potential step. The influence of the topography on the measurement of the surface potential is found to be rather small compared to a typical experimental resolution. Surprisingly, in the case of a coinciding topography and potential step an improvement of the potential profile due to the inclusion of the topography is observed. Finally, based on the obtained results, suggestions for the realization of KPFM measurement are given.

Surface photovoltage spectroscopy in a Kelvin probe force microscope under ultrahigh vacuum.

Surface photovoltage (SPV) spectroscopy is a common method for optoelectronic semiconductor characterization. Kelvin probe force microscopy has developed into a widely used tool for nanoscale characterization of semiconductors, metals, and insulators. We present here a setup for the measurement of local SPV spectra in a Kelvin probe force microscope operated under ultrahigh vacuum conditions. The atomic force microscope tip can be placed to any desired position with nanometer precision and the SPV can then be recorded as a function of the wavelength of the illuminating light. We introduce the realization of the setup and present the SPV spectra on two test systems, an epitaxially grown GaAs/CuGaSe(2) junction and a Zn-doped CuInS(2) polycrystalline thin film.

Surface photovoltage analysis of thin CdS layers on polycrystalline chalcopyrite absorber layers by Kelvin probe force microscopy.

An extensive Kelvin probe force microscopy study in an ultrahigh vacuum has been undertaken to examine the influence of growth modifications of a few nm thick CdS buffer layers in thin film chalcopyrite solar cells. In regions around the grain boundaries of the polycrystalline Cu(In,Ga)Se(2) substrate a lowering of the work function extending to about 200 nm away from this vertical interface was observed. This electrical inhomogeneity depends strongly on the Cu(In,Ga)Se(2) surface condition and is interpreted by a diffusion process along the substrate grain boundaries. Our results contribute to the understanding of the crucial role of the several nm thick CdS layer for improving the photovoltaic performance of chalcopyrite thin film solar cells.

Hybrid flexible vertical nanoscale diodes prepared at low temperature in large area.

Fabrication and operation of hybrid flexible vertical nanoscale diodes are reported. The diodes, formed by n-type ZnO and p-type CuSCN, were embedded in a 6 µm polymer foil, provided with vertical cylindrical openings of about 100 nm, by using a low temperature solution based electrochemical deposition technique. Electrical measurements show diode function with sound device characteristics at operation temperatures up to 67 °C. This heterojunction shows the potential for ZnO based ultraviolet light-emitting diodes.

Spectroscopic investigation of the deeply buried Cu(In,Ga)(S,Se)2/Mo interface in thin-film solar cells.

The Cu(In,Ga)(S,Se)(2)Mo interface in thin-film solar cells has been investigated by surface-sensitive photoelectron spectroscopy, bulk-sensitive x-ray emission spectroscopy, and atomic force microscopy. It is possible to access this deeply buried interface by using a suitable lift-off technique, which allows us to investigate the back side of the absorber layer as well as the front side of the Mo back contact. We find a layer of Mo(S,Se)(2) on the surface of the Mo back contact and a copper-poor stoichiometry at the back side of the Cu(In,Ga)(S,Se)(2) absorber. Furthermore, we observe that the Na content at the Cu(In,Ga)(S,Se)(2)Mo interface as well as at the inner grain boundaries in the back contact region is significantly lower than at the absorber front surface.

Kelvin probe force microscopy study on conjugated polymer/fullerene bulk heterojunction organic solar cells.

We conducted a comprehensive Kelvin probe force microscopy (KPFM) study on a classical organic solar cell system consisting of MDMO-PPV/PCBM blends. The KPFM method yields the information of topography and local work function at the nanometer scale. Experiments were performed either in the dark or under cw laser illumination at 442 nm. We identified distinct differences in the energetics on the surface of chlorobenzene and toluene cast blend films. Together with high-resolution scanning electron microscopy (SEM) experiments we were able to interpret the KPFM results and to draw some conclusions for the electron transport toward the cathode in the solar cell configuration. The results suggest that surfaces of toluene cast films exhibit a morphologically controlled hindrance for electron propagation toward the cathode, which is usually evaporated on top of the films in the solar cell device configuration.