Osady kultury przeworskiej w Tomaszach i Magnuszewie Dużym na północnym Mazowszu – wstępna charakterystyka

In den vergangenen 20 Jahren wurden in Polen viele großflächige Rettungsgrabungen im Zusammenhang mit Straßenbaumaßnahmen durchgeführt. Die Quellenlage für die Siedlungen der Przeworsk-Kultur hat sich dadurch wesentlich verbessert. Im vorliegenden Beitrag werden die Siedlungen aus Tomasze, Fdst. 4, und Magnuszew Duży, Fdst. 6 vorgestellt. Das Formenspektrum der Keramik aus diesen Siedlungen unterscheidet sich nicht von jenem, das aus den Gräberfeldern der Przeworsk-Kultur bekannt ist. Im Fundstoff wurden auch Gefäße identifiziert, die ihre deutliche Analogien im Jastorf-Kreis haben. Da geschlossene Fundkomplexe in beiden Siedlungen fehlten, wurde das Material anhand einzelner Gefäßformen bestimmt, deren Datierung auf der Grundlage des Materials aus den Gräberfeldern erfolgte

The Index of Sustainable Economic Welfare revisited for Poland in transition

In the paper, the Index of Sustainable Economic Welfare (ISEW) for Poland was calculated. The research covers the time period between 1990 and 2003. The lowest values of ISEW were observed in 1990, when Poland still experienced the economic crisis. Up to 1992, we can observe a dynamic growth then slowing down and progressing again in succeeding years, which eventually shows back a new and more moderate tendency started in 2000. It seems, that the stagnation effect in ISEW can be attributed, in order of potential, to categories like: losses caused by commuting and road accidents, long-term environmental damage, expenditures on consumer durables, losses due to ozone layer depletion, change in net international position, depletion of non-renewable resources. Moreover, growing welfare inequalities penalize the value of ISEW in recent years much more significantly than before

Speciation of Lanthanide Metal Ion Dopants in Microcrystalline All-Inorganic Halide Perovskite CsPbCl3

Lanthanides are versatile modulators of optoelectronic properties owing to their narrow optical emission spectra across the visible and near-infrared range. Their use in metal halide perovskites (MHPs) has recently gained prominence, although their fate in these materials has not yet been established at the atomic level. We use cesium-133 solid-state NMR to establish the speciation of all nonradioactive lanthanide ions (La3+, Ce3+, Pr3+, Nd3+, Sm3+, Sm2+, Eu3+, Eu2+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+) in microcrystalline CsPbCl3. Our results show that all lanthanides incorporate into the perovskite structure of CsPbCl3 regardless of their oxidation state (+2, +3).</p

Trinuclear Cage-Like ZnII Macrocyclic Complexes: Enantiomeric Recognition and Gas Adsorption Properties

Three zinc(II) ions in combination with two units of enantiopure 3+3 triphenolic Schiff base macrocycles 1, 2, 3 or 4 form cage-like chiral complexes. The formation of these complexes is accompanied by the enantioselective self-recognition of chiral macrocyclic units. The X-ray crystal structures of these trinuclear complexes show hollow metal-organic molecules. In some crystal forms, these barrel-shaped complexes are arranged in a window-to-window fashion which results in formation of 1-D channels and combination of intrinsic porosity with extrinsic porosity. The microporous nature of the [Zn312] complex is reflected in its N2, Ar, H2 and CO2 adsorption properties. The N2 and Ar adsorption isotherms showed pressure gating behaviour which is without precedent for any noncovalent porous material. The comparison of the structures of the [Zn312] and [Zn332] complexes with that of the free macrocycle H31 reveals a striking structural similarity. In the latter compound two macrocyclic units stitched together by hydrogen bonds form a cage very similar to that formed by two macrocyclic units stitched together by Zn(II) ions. This structural similarity is manifested also by the gas adsorption properties of the free H31 macrocycle. Recrystallization of [Zn312] in the presence of racemic 2-butanol results in enantioselective binding of the (S)-2-butanol inside the cage via coordination to one of Zn(II) ions.This work was supported by the NCN (NarodoweCentrumNauki, Poland) (grant 2011/03/B/ST5/01060).D.P.and J.L.thank the FNP Program“Mistrz” for financial support, and D.F.-J. thanks the Royal Society for funding through a University Research Fellowship.This is the author accepted manuscript. The final version is available from Wiley via http://dx.doi.org/10.1002/chem.20150347

Potential and limitations of CsBi3I10 as a photovoltaic material

Herein we demonstrate the dry synthesis of CsBi3I10 both as a free-standing material and in the form of homogeneous thin films, deposited by thermal vacuum deposition. Chemical and optical characterization shows high thermal stability, phase purity, and photoluminescence centered at 700 nm, corresponding to a bandgap of 1.77 eV. These characteristics make CsBi3I10 a promising low-toxicity material for wide bandgap photovoltaics. Nevertheless, the performance of this material as a semiconductor in solar cells remains rather limited, which can be at least partially ascribed to a low charge carrier mobility, as determined from pulsed-radiolysis time-resolved microwave conductivity. Further developments should focus on understanding and overcoming the current limitations in charge mobility, possibly by compositional tuning through doping and/or alloying, as well as optimizing the thin film morphology which may be another limiting factor

Local Structure and Dynamics in Methylammonium, Formamidinium, and Cesium Tin(II) Mixed-Halide Perovskites from 119Sn Solid-State NMR.

Organic-inorganic tin(II) halide perovskites have emerged as promising alternatives to lead halide perovskites in optoelectronic applications. While they suffer from considerably poorer performance and stability in comparison to their lead analogues, their performance improvements have so far largely been driven by trial and error efforts due to a critical lack of methods to probe their atomic-level microstructure. Here, we identify the challenges and devise a 119Sn solid-state NMR protocol for the determination of the local structure of mixed-cation and mixed-halide tin(II) halide perovskites as well as their degradation products and related phases. We establish that the longitudinal relaxation of 119Sn can span 6 orders of magnitude in this class of compounds, which makes judicious choice of experimental NMR parameters essential for the reliable detection of various phases. We show that Cl/Br and I/Br mixed-halide perovskites form solid alloys in any ratio, while only limited mixing is possible for I/Cl compositions. We elucidate the degradation pathways of Cs-, MA-, and FA-based tin(II) halides and show that degradation leads to highly disordered, qualitatively similar products, regardless of the A-site cation and halide. We detect the presence of metallic tin among the degradation products, which we suggest could contribute to the previously reported high conductivities in tin(II) halide perovskites. 119Sn NMR chemical shifts are a sensitive probe of the halide coordination environment as well as of the A-site cation composition. Finally, we use variable-temperature multifield relaxation measurements to quantify ion dynamics in MASnBr3 and establish activation energies for motion and show that this motion leads to spontaneous halide homogenization at room temperature whenever two different pure-halide perovskites are put in physical contact

Cation Dynamics in Mixed-Cation (MA)(x)(FA)(1-x)PbI3 Hybrid Perovskites from Solid-State NMR

Mixed-cation organic lead halide perovskites attract unfaltering attention owing to their excellent photovoltaic properties. Currently, the best performing perovskite materials contain multiple cations and provide power conversion efficiencies up to around 22%. Here, we report the first quantitative, cation-specific data on cation reorientation dynamics in hybrid mixed-cation formamidinium (FA)/methylammonium (MA) lead halide perovskites. We use N-14, H-2, C-13, and H-1 solid-state MAS NMR to elucidate cation reorientation dynamics, microscopic phase composition, and the MA/FA ratio, in (MA)(x)(FA)(1-x)PbI3 between 100 and 330 K. The reorientation rates correlate in a striking manner with the carrier lifetimes previously reported for these materials and provide evidence of the polaronic nature of charge carriers in PV perovskites