CH3NH3PbI3 perovskite single crystals: surface photophysics and their interaction with the environment

Here we identify structural inhomogeneity on a micrometer scale across the surface of a CH₃NH₃PbI₃ perovskite single crystal. At the crystal edge a local distortion of the crystal lattice is responsible for a widening of the optical bandgap and faster photo-carrier recombination. These effects are inherently present at the edge of the crystal, and further enhanced upon water intercalation, as a preliminary step in the hydration of the perovskite material.     

SOAS: A free program to analyze electrochemical data and other one-dimensional signals

This paper describes an open source program called SOAS, which we developed with the aim of analysing one-dimensional signals. It offers a large set of commands for handling voltammetric and chronoamperometric data, including smoothing signals, differentiation, subtracting baselines, fitting current responses, measuring limiting currents, and searching for peak positions. Although emphasis is on the analysis of electrochemical signals, particularly protein film voltammetry data, SOAS may also prove useful for processing spectra. This free program is available by download from the Internet, and can be installed on computers running any flavor of Unix or Linux, most easily on MacOS X.     

The importance of dye chemistry and TiCl(4) surface treatment in the behavior of Al(2)O(3) recombination barrier layers deposited by atomic layer deposition in solid-state dye-sensitized solar cells

Atomic layer deposition (ALD) was used to fabricate Al(2)O(3) recombination barriers in solid-state dye-sensitized solar cells (ss-DSSCs) employing an organic hole transport material (HTM) for the first time. Al(2)O(3) recombination barriers of varying thickness were incorporated into efficient ss-DSSCs utilizing the Z907 dye adsorbed onto a 2 μm-thick nanoporous TiO(2) active layer and the HTM spiro-OMeTAD. The impact of Al(2)O(3) barriers was also studied in devices employing different dyes, with increased active layer thicknesses, and with substrates that did not undergo the TiCl(4) surface treatment. In all instances, electron lifetimes (as determined by transient photovoltage measurements) increased and dark current was suppressed after Al(2)O(3) deposition. However, only when the TiCl(4) treatment was eliminated did device efficiency increase; in all other instances efficiency decreased due to a drop in short-circuit current. These results are attributed in the former case to the similar effects of Al(2)O(3) ALD and the TiCl(4) surface treatment whereas the insulating properties of Al(2)O(3) hinder charge injection and lead to current loss in TiCl(4)-treated devices. The impact of Al(2)O(3) barrier layers was unaffected by doubling the active layer thickness or using an alternative ruthenium dye, but a metal-free donor-π-acceptor dye exhibited a much smaller decrease in current due to its higher excited state energy. We develop a model employing prior research on Al(2)O(3) growth and dye kinetics that successfully predicts the reduction in device current as a function of ALD cycles and is extendable to different dye-barrier systems.     

On-line solid phase extraction using the Prospekt-2 coupled with a liquid chromatography/tandem mass spectrometer for the determination of dextromethorphan, dextrorphan and guaifenesin in human plasma

An on-line liquid chromatography/tandem mass spectrometry (LC-MS/MS) procedure, using the Prospekt- 2 system, was developed and used for the determination of the levels of the active ingredients of cough/cold medications in human plasma matrix. The experimental configuration allows direct plasma injection by performing on- line solid phase extraction (SPE) on small cartridge columns prior to elution of the analyte(s) onto the analytical column and subsequent MS/MS detection. The quantitative analysis of three analytes with differing polarities, dextromethorphan (DEX), dextrorphan (DET) and guaifenesin (GG) in human plasma presented a significant challenge. Using stable-isotope-labeled internal standards for each analyte, the Prospekt-2 on-line methodology was evaluated for sensitivity, suppression, accuracy, precision, linearity, analyst time, analysis time, cost, carryover and ease of use. The lower limit of quantitation for the on-line SPE procedure for DEX, DET and GG was 0.05, 0.05 and 5.0 ng mL(-1), respectively, using a 0.1 mL sample volume. The linear range for DEX and DET was 0.05-50 ng mL(-1) and was 5-5,000 ng mL(-1) for GG. Accuracy and precision data for five different levels of QC samples were collected over three separate days. Accuracy ranged from 90% to 112% for all three analytes, while the precision, as measured by the %RSD, ranged from 1.5% to 16.0%     

Preparation and polymerization of N-(1,1-dimethyl-3-hydroxybutyl) acrylamide and N-(1,1-dimethyl-3-hydroxybutyl)methacrylamide

The syntheses of N-(1,1-dimethyl-3-hydroxybutyl)acrylamide and the corresponding methacrylamide by reduction of the oxobutyl acrylamides are described. These monomers are colorless liquids which are soluble in water and many organic solvents. They polymerize readily to form homopolymers and copolymers with other vinyl monomers. The preparation of polymers containing these repeating units by reduction of polymers of diacetone acrylamide and diacetone methacrylamide is also described.     

Reversible photo-induced trap formation in mixed-halide hybrid perovskites for photovoltaics

We report on reversible, light-induced transformations in (CH₃NH₃)Pb(Br_xI_1–x)₃. Photoluminescence (PL) spectra of these perovskites develop a new, red-shifted peak at 1.68 eV that grows in intensity under constant, 1-sun illumination in less than a minute. This is accompanied by an increase in sub-bandgap absorption at ∼1.7 eV, indicating the formation of luminescent trap states. Light soaking causes a splitting of X-ray diffraction (XRD) peaks, suggesting segregation into two crystalline phases. Surprisingly, these photo-induced changes are fully reversible; the XRD patterns and the PL and absorption spectra revert to their initial states after the materials are left for a few minutes in the dark. We speculate that photoexcitation may cause halide segregation into iodide-rich minority and bromide-enriched majority domains, the former acting as a recombination center trap. This instability may limit achievable voltages from some mixed-halide perovskite solar cells and could have implications for the photostability of halide perovskites used in optoelectronics.     

Calibration of an optical condensate measurement technique using indirect static headspace gas chromatography.

Researchers in the Department of Mechanical Engineering seek to obtain a means to measure less than 3 mg of H2O that adheres to a metal surface as condensate. The objective is to calibrate optical reflectance measurements of an aluminum surface as a function of the condensate thickness present. Collaboration with the Hazardous Substance Research Center at Michigan State University results in the development of an indirect static headspace gas chromatographic technique capable of measuring H2O in low-milligram quantities. The technique utilizes manual headspace sampling, a megabore capillary column, and a flame ionization detector. A correlation of r2 = 0.999 is obtained for the calibration of the indirect measurement technique. The calibration of the analytical instrument demonstrates adequate precision (< +/- 50 microg at a 95% confidence interval) for such a heterogeneous sample. The calibration samples consist of a strip of aluminum metal, H2O, and pulverized calcium carbide to convert the H2O to acetylene. A scaled calibration technique is used to simplify handling trace water volumes. The surface reflectance measurements are found to correlate well (r2 = 0.935) with measurements of the condensate mass. This result facilitates the development of an optical mass-transfer measurement technique. This study focuses on the analytical method and its relationship with engineering research.     

Beitrag zur Charakterisierung von hochborhältigen Chrom-Nickel-Molybdän-Kupfer-Stählen mit Hilfe der stereometrischen Analyse

Zusammenfassung Eine Serie von Chrom-Nickel-Molybdän-Kupfer-Bor-Stählen mit Borgehalten von 0,5 bis 1,9 Gew.% wurde mit Methoden der stereometrischen Analyse untersucht. Mit verschiedenen Verfahren der Phasenanalyse wurden Informationen über die Verteilung der Elemente und die chemische Zusammensetzung der Phasen dieser Werkstoffe gewonnen. Diese Informationen dienten als Ausgangspunkt für die Strukturanalyse der Boridphase, in deren Rahmen in erster Linie die Frage des Einflusses der chemischen Zusammensetzung auf die Größe der Elementarzelle und damit die Dichte der Boridphase untersucht wurde. Die Werkstoffserie wurde schließlich gefügeanalytisch charakterisiert, wobei die Technik der automatischen Linearanalyse mit der Mikrosonde und die chemische Isolierung der Boride mit lichtoptischer Untersuchung des Isolates angewendet und beispielhaft gegenübergestellt wurden. Die mit den Methoden der Struktur-, Phasen- und Gefügeanalyse gewonnenen Informationen wurden schließlich in einer Bilanz verknüpft.

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On the characterization of Cr-Ni-Mo-Cu-B-alloys by means of stereometric analysis

Summary A series of Chromium-Nickel-Molybdenum-Copper-Boron steel with Boron concentrations in the range from 0,5–1,9 wt.% has been investigated with the methods of stereometric analysis. Different techniques of phase analysis are used to gain information about the distribution of the different elements and the composition of the phases. These informations are the basis for structure analysis of the boride phase. Within this chapter mainly the influence of chemical composition of the boride on the lattice parameters and consequently on the density of the phase are investigated. Furthermore this series of steel is investigated with different methods of quantitative metallography (automatic linear analysis with an electron microprobe and chemical isolation of the boride phase with subsequent light microscopical investigation). The results obtained with the two techniques are compared for one sample. Finally the informations obtained with structure analysis, phase analysis and quantitative metallography are combined to form a balance of stereometric analysis.