Extrinsic nature of the broad photoluminescence in lead iodide-based Ruddlesden-Popper perovskites

Two-dimensional metal halide perovskites of Ruddlesden–Popper type have recently moved into the centre of attention of perovskite research due to their potential for light generation and for stabilisation of their 3D counterparts. It has become widespread in the field to attribute broad luminescence with a large Stokes shift to self-trapped excitons, forming due to strong carrier–phonon interactions in these compounds. Contrarily, by investigating the behaviour of two types of lead-iodide based single crystals, we here highlight the extrinsic origin of their broad band emission. As shown by below-gap excitation, in-gap states in the crystal bulk are responsible for the broad emission. With this insight, we further the understanding of the emission properties of low-dimensional perovskites and question the generality of the attribution of broad band emission in metal halide perovskite and related compounds to self-trapped excitons

Elucidating the Structure and Photophysics of Layered Perovskites through Cation Fluorination

Optoelectronic devices based on layered perovskites containing fluorinated cations display a well-documented improved stability and enhanced performance over non-fluorinated cations. The effect of fluorination on the crystal structure and photophysics, however, has received limited attention up until now. Here, 3-fluorophenethylammonium lead iodide ((3-FPEA)(2)PbI4) single crystals are investigated and their properties to the non-fluorinated ((PEA)(2)PbI4) variant are compared. The bulkier 3-FPEA cation increases the distortion of the inorganic layers, resulting in a blue-shifted absorbance and photoluminescence. Temperature-dependent photoluminescence spectroscopy reveals an intricate exciton substructure in both cases. The fluorinated variant shows hot-exciton resonances separated by 12 to 15 meV, values that are much smaller than the 40 to 46 meV found for (PEA)(2)PbI4. In addition, high-resolution spectra show that the emission at lower energies consists of a substructure, previously thought to be a single line. With the analysis on the resolved photoluminescence, a vibronic progression is excluded as the origin of the emission at lower energies. Instead, part of the excitonic substructure is proposed to originate from bound excitons. This work furthers the understanding of the photophysics of layered perovskites that has been heavily debated lately

Photochromism in Ruddlesden-Popper copper-based perovskites:A light-induced change of coordination number at the surface

Ruddlesden-Popper organic-inorganic hybrid copper-based perovskites have been studied for decades owing to a variety of interesting properties, such as thermochromism and piezochromism, and the mechanisms behind these phenomena have been explained. Another possible property of these materials that has seldomly been investigated is photochromism. In this work, the photochromic properties of bis(phenethylammonium) tetrachlorocuprate (also known as phenethylammonium copper chloride) are reported for the first time. This material has attracted scientific interest owing to the fact that it shows both ferroelectric and ferromagnetic behavior. This work highlights the difference in stability between two Ruddlesden-Popper copper-based perovskites - with phenethylammonium (PEA) or methylammonium (MA) as the cations - during external stimuli. Various techniques, such as Raman and X-ray photoelectron spectroscopy, and grazing-incidence wide-angle X-ray scattering, combined with optical studies, were used to investigate the underlying photochemical processes at a molecular level. It is found that for the PEA compound, ultraviolet illumination causes a color change from yellow to brown. This is the result of two independent events, namely a Cu2+ reduction reaction and a transition from an octahedral copper-chloride structure to square-planar CuCl42-. After illumination, the material (brown color) is unstable in air, which is evident from a color change back to yellow. Interestingly, the similar compound bis(methylammonium) tetrachlorocuprate does not display photochromic behavior, which is attributed to the different nature of the two organic cations

Nonlinear magnetotransport in MoTe2

The shape of the Fermi surface influences many physical phenomena in materials and a growing interest in how the spin-dependent properties are related to the fermiology of crystals has surged. Recently, a novel current-dependent nonlinear magnetoresistance effect, known as bilinear magnetoelectric resistance (BMR), has been shown to be not only sensitive to the spin texture in spin-polarized nonmagnetic materials, but also dependent on the convexity of the Fermi surface in topological semimetals. In this paper, we show that the temperature dependence of the BMR signal strongly depends on the crystal axis of the semimetallic MoTe2. For the a axis, the amplitude of the signal remains fairly constant, while for the b axis it reverses sign at about 100K. We calculate the BMR efficiencies at 10K to be χJA=173(3)nm2T-1A-1 and χJB=-364(13)nm2T-1A-1 for the a and b axis, respectively, and we find that they are comparable to the efficiencies measured for WTe2. We use density-functional theory calculations to compute the Fermi surfaces of both phases at different energy levels and we observe a change in convexity of the outermost electron pocket as a function of the Fermi energy. Our results suggest that the BMR signal is mostly dominated by the change in the Fermi-surface convexity.</p

CCDC 2033319: Experimental Crystal Structure Determination

Related Article: Eelco K. Tekelenburg, Simon Kahmann, Machteld E. Kamminga, Graeme R. Blake, Maria A. Loi|2021|Adv.Opt.Mater.||2001647|doi:10.1002/adom.20200164

CCDC 2033318: Experimental Crystal Structure Determination

Related Article: Eelco K. Tekelenburg, Simon Kahmann, Machteld E. Kamminga, Graeme R. Blake, Maria A. Loi|2021|Adv.Opt.Mater.||2001647|doi:10.1002/adom.20200164