Infrared Spectroscopic Study of Vibrational Modes across the Orthorhombic Tetragonal Phase Transition in Methylammonium Lead Halide Single Crystals

Single crystals of the methylammonium MA lead halides MAPbI3, MAPbBr3, and MAPbCl3 have been investigated using infrared spectroscopy with the aim of analyzing structural and dynamical aspects of processes that enable the ordering of the MA molecule in the orthorhombic crystal structure of these hybrid perovskites. Our temperature dependent studies were focused on the analysis of the CH NH rocking, C N stretching, and CH NH bending modes of the MA molecule in the 800 1750 cm 1 frequency range. They deliver a direct comparison of the behaviors of the three halides on crossing the orthorhombic tetragonal phase transition in MA lead halide single crystals. Drastic changes of all vibrational modes close to the phase transition were clearly observed. Additional spectral features that were not discussed previously are pointed out. The transformation of the two dimensional orthorhombic hydrogen bond layers into a more three dimensional arrangement in the tetragonal phase seems to be an important feature providing deeper insights into the mechanisms that lead to a free rotating MA molecule in the inorganic host structure. The change of the molecule site symmetry in the tetragonal crystal structure seems to be an important feature of the orthorhombic tetragonal phase transition. For low temperatures, it can be stated that the iodide is stronger influenced by hydrogen bonding than the bromide and the chlorid

Competing Jahn Teller distortions and ferrimagnetic ordering in the geometrically frustrated system Ni1 xCuxCr2O4

Competing Jahn Teller distortions combined with geometrical frustration give rise to a rich phase diagram as a function of x Cu and temperature in the spinel system Ni1 xCuxCr2O4. The Jahn Teller distortion of the end members acts in opposite ways, with an elongation of the NiO4 tetrahedra resulting in a structural transition at TS1 317K in NiCr2O4, but a flattening in the CuO4 tetrahedra at TS1 846K in CuCr2O4. In both cases the symmetry is lowered from cubic Fd 3m to tetragonal I41 amd on cooling. In order to follow the influence of Jahn Teller active Ni2 and Cu2 ions on the structural and magnetic properties of chromium spinels, we have investigated a series of samples of Ni1 xCuxCr2O4 by x ray and neutron powder diffraction. In the critical range 0.10 lt; x Cu lt; 0.20, strong orthorhombic distortions were observed, where competing Jahn Teller activities between the Cu2 and Ni2 ions result in distortions along both the a and c axes. For Ni0.85Cu0.15Cr2O4, the orthorhombic structure Fddd is stabilized up to TS2 368 2 K, close to the first structural phase transition at TS1 374 2 K. A ferrimagnetic spin alignment of the Ni Cu and chromium atoms sets in at much lower temperature TC 95K in this compound. The end members NiCr2O4 and CuCr2O4 undergo this ferrimagnetic transition at TC 74 and 135 K, respectively. These transitions are accompanied by the structural change to the orthorhombic symmetry which relieves the frustration. NiCr2O4 and Ni0.85Cu0.15Cr2O4 undergo a second magnetic transition at TM2 24 and 67K due to a superimposed antiferromagnetic ordering of the Cr moments resulting in a noncollinear magnetic structure. In the system Ni1 xCuxCr2O4, the magnetic transitions TC and TM2 merge with increasing copper content up to x Cu similar to 0.5. For the Ni rich chromites, geometrical frustration causes a strong reduction of the chromium moments, where magnetic long range order coexists with a disordered spin liquid like or a reentrant spin glass like state. This paper provides insight into the interplay between the Jahn Teller effect, geometrical frustration, and long range magnetic order in these complex system

Cu Zn disorder in stoichiometric Cu2ZnSn S1 xSex 4 semiconductors A complementary neutron and anomalous X ray diffraction study

The quaternary compound semiconductor Cu2ZnSn S1 xSex 4 CZTSSe which crystallizes in the kesterite type structure, is a promising material to be used as p type absorber layer in thin film solar cell applications based on earth abundant elements. The absorber band tailing caused by an exceptionally high Cu Zn disorder is believed to be one of the reasons for the limited open circuit voltage in CZTSSe based photovoltaic devices. This work is an experimental study of the Cu Zn disorder in a unique set of single phase, stoichiometric CZTSSe mixed crystals, synthesized by solid state reaction, by means of neutron powder diffraction and anomalous X ray powder diffraction. The existence of Cu Zn disorder was revealed as the only intrinsic point defect in these mixed crystals within the detection limits of our measurements. The order parameter Q was calculated on the basis of the occurring CuZn and ZnCu anti site defects causing the Cu Zn disorder. Variations of the order parameter with anion composition and the effect on the optoelectronic properties of the partial substitution of Se with S in Cu2ZnSn S1 xSex 4 was elaborate

Temperature Dependent Crystallization Mechanisms of Methylammonium Lead Iodide Perovskite From Different Solvents

Hybrid perovskites are a novel type of semiconductors that show great potential for solution processed optoelectronic devices. For all applications, the device performance is determined by the quality of the solution processed perovskite thin films. During solution processing, the interaction of solvent with precursor molecules often leads to the formation of solvate intermediate phases that may diverge the crystallization pathway from simple solvent evaporation to a multi step formation process. We here investigate the crystallization of methylammonium lead iodide MAPbI 3 from a range of commonly utilized solvents, namely dimethyl sulfoxide DMSO , N,N dimethylformamide DMF , N methylpyrrolidone NMP , and gamma butyrolactone GBL at different temperatures ranging from 40 C to gt;100 C by in situ grazing incidence wide angle X ray scattering GIWAXS measurements. For all solvents but GBL, we clearly observe the formation of solvate intermediate phases at moderate processing temperatures. With increasing temperatures, an increasing fraction of the MAPbI 3 perovskite phase is observed to form directly. From the temperature dependence of the phase formation and phase decomposition rates, the activation energy to form the MAPbI 3 perovskite phase from the solvate phases are determined as a quantitative metric for the binding strength of the solvent within the solvate intermediate phases and we observe a trend of DMSO gt; DMF gt; NMP gt; GBL. These results enable prediction of processing temperatures at which solvent molecules can be effectively remove

Quantitative anomalous powder diffraction analysis of cation disorder in kesterite semiconductors

Kesterite type compound semiconductors, containing copper and zinc, have photovoltaic properties depending on cation distribution in the crystal structure. Anomalous diffraction allows discrimination of isoelectronic cations, in principle allowing a straightforward determination of site occupation factors from data collected at multiple energies close to the X ray absorption edges of copper and zinc. However, extremely strong correlation between structural parameters precludes this. We present a recipe based on the direct dependency between refined occupation factors and atomic scattering power, which allows to lift the correlations and to detect issues of individual diffraction patterns or assumptions in the model, thereby allowing for reliable quantitative analysis of the Cu Zn distributio

The influence of deuteration on the crystal structure of hybrid halide perovskites a temperature dependent neutron diffraction study of FAPbBr3

This paper discusses the full structural solution of the hybrid perovskite formamidinium lead tribromide FAPbBr3 and its temperature dependent phase transitions in the range from 3 K to 300 K using neutron powder diffraction and synchrotron X ray diffraction. Special emphasis is put on the influence of deuteration on formamidinium, its position in the unit cell and disordering in comparison to fully hydrogenated FAPbBr3. The temperature dependent measurements show that deuteration critically influences the crystal structures, i.e. results in partially ordered temperature dependent structural modifications in which two symmetry independent molecule positions with additional dislocation of the molecular centre atom and molecular angle inclinations are presen

Annealing effects on the film stress and adhesion of tungsten titanium barrier layers

Tungsten titanium WTi alloys are important barrier materials in microelectronic devices. Thus the adhesion of WTi to silicate glass substrates influences the reliability of these devices. One factor that affects the adhesion of barrier layers are thermal treatments during and after fabrication. To address the impact of annealing, WTi films deposited on silicate glass substrates were subjected to different annealing treatments. The stress development in the WTi film has been monitored with wafer curvature and X ray diffraction. Quantitative measurements of the adhesion energies were performed using scratch testing to induce interface delamination. Imaging with atomic force microscopy provided the dimensions of the buckles to quantify adhesion energies. Focused ion beam crosssections were used to verify the failing interfaces and to inspect any deformation in the film and the substrate caused by scratch testing. It was found that as the annealing duration increased, the residual compressive stresses in the film and the adhesion energy increase

Microstructural influence on the cyclic electro mechanical behaviour of ductile films on polymer substrates

When ductile metal films on compliant polymer substrates are strained in tension catastrophic failure can be suppressed by the substrate, thus allowing for their use in flexible electronics and sensors. However, the charge carrying ductile films must be of an optimum thickness and microstructure for the suppression of cracking to occur. Studies of strained films on polymer substrates tend to have more emphasis on the electrical properties and thickness effects than on the film microstructure or deformation behaviour. To address both the electrical degradation and deformation behaviour of metal films supported by polymer substrates two types of combined electro-mechanical in-situ tests were performed. First, is a combination of in-situ resistance measurements with in-situ confocal scanning laser microscopy imaging of the film surface during cycling. The 4 point probe resistance measurements allow for the examination of the changes in resistance with strain, while the surface imaging permits the visualization of extrusion and crack formation. Second, is the combination of in-situ resistance with in-situ X-ray diffraction measurements of the film stresses during cycling. The combination of electrical measurements, surface imaging, and stress measurements allow for a complete picture of electromechanical behaviour needed for the improvement and future success of flexible electronic devices

Mechanical and optical degradation of flexible optical solar reflectors during simulated low earth orbit thermal cycling

Multilayer thin film systems on flexible polymer substrates are used as flexible optical solar reflectors or thermal insulation of satellites and spacecraft. During one year of operation, a satellite in low earth orbit typically encounters 6000 thermal cycles of ±100 °C. Due to the different coefficients of thermal expansion between the individual layers and the substrate it is important to investigate the thermo-mechanical stability of the multilayers as a function of the cyclic heat load. Scanning electron microscopy and focused ion beam cross-sectioning revealed that Inconel-Ag bilayers on fluorinated ethylene propylene (FEP) substrate severely degrade during thermal cycling of ±150 °C in a gaseous N2 atmosphere. After only 100 cycles through thickness cracks and subsurface voids in the Ag layer form as a result of equi-biaxial thermal stresses caused by the large difference in thermal expansion between film and substrate. Transmission Kikuchi Diffraction (TKD) before and after thermal cycling also revealed grain growth and twin widening in the Ag layer. Cracking and void formation are detrimental to application relevant material properties including corrosion protection (Inconel) and reflectivity (Ag). Reflectance measurements revealed that the amount of reflected energy as well as the reflection mode (specular vs. diffuse) significantly change during the first 100 cycles. Saturation of reflection characteristics was observed after 25 cycles, which correlates to a turning point in the evolution of Ag voids. Results of this study indicate that special focus should be directed towards thermal stress control (Δα) and tailoring of the metal-polymer interface to improve resistance of versatile metal-polymer systems against thermal cycling. © 2020 IA