Abstract: Polycrystalline CuInSe2 semiconductors are efficient light absorber materials for thin film solar cell technology, whereas printing is one of the promising low cost and non-vacuum approaches for the fabrication of thin film solar cells. The printed precursors are transformed into a dense polycrystalline CuInSe2 semiconductor film via thermal treatment in ambient selenium atmosphere (selenization). In this study, the effect of the selenium content in high purity mechanically synthesized CuInSex (x = 2, 1.5, 1 or 0.5) alloy precursors on the recrystallization of the CuInSe2 phase during the selenization process was investigated. The nanostructure and phase variation of CuInSex nanopowders were investigated by different characterization techniques. The recrystallization process of the 12 μm thick CuInSex coatings into the CuInSe2 phase during selenization in selenium vapor was investigated via in-situ high temperature X-ray diffraction. The CuInSex precursors with lower selenium content showed a more pronounced phase conversion into CuInSe2 compared to the higher selenium content CuInSex precursors. Moreover, the CuInSex (x = 0.5 and 1) precursor resulted in a denser polycrystalline CuInSe2 semiconductor film with larger crystals. This could be attributed to a more intensive atomic interdiffusion within the CuInSex precursor system compared to a CuInSe2 phase precursor, and the formation of intermediate CuSe and CuSe2 fluxing phases during selenization.

Abstract: CsTlCl3 and CsTlF3 perovskites have been theoretically predicted to be superconductors when properly hole-doped. Both compounds have been previously prepared as pure compounds: CsTlCl3 in a tetragonal (I4/m) and a cubic (Fm3̅m) perovskite polymorph and CsTlF3 as a cubic perovskite (Fm3̅m). In this work, substitution of Tl in CsTlCl3 with Hg is reported, in an attempt to hole-dope the system and induce superconductivity. The whole series CsTl1xHgxCl3 (x = 0.0, 0.1, 0.2, 0.4, 0.6, and 0.8) was prepared. CsTl0.9Hg0.1Cl3 is tetragonal as the more stable phase of CsTlCl3. However, CsTl0.8Hg0.2Cl3 is already cubic with the space group Fm3̅m and with two different positions for Tl+ and Tl3+. For x = 0.4 and 0.5, solid solutions could not be formed. For x ≥ 0.6, the samples are primitive cubic perovskites with one crystallographic position for Tl+, Tl3+, and Hg2+. All of the samples formed are insulating, and there is no signature of superconductivity. X-ray absorption spectroscopy indicates that all of the samples have a mixed-valence state of Tl+ and Tl3+. Raman spectroscopy shows the presence of the active TlClTl stretching mode over the whole series and the intensity of the TlClHg mode increases with increasing Hg content. First-principle calculations confirmed that the phases are insulators in their ground state and that Hg is not a good dopant in the search for superconductivity in this system.

Abstract: Nanocrystalline ZnO:Al nanoparticles are suitable building blocks for transparent conductive layers. As the concentration of substitutional tetrahedral Al is an important factor for improving conductivity, here we aim to increase the fraction of substitutional Al. To this end, synthesis parameters of a solvothermal reaction yielding ZnO:Al nanorods were varied. A unique set of complementary techniques was combined to reveal the exact position of the aluminium ions in the ZnO lattice and demonstrated its importance in order to evaluate the potential of ZnO:Al nanocrystals as optimal building blocks for solution deposited transparent conductive oxide layers. Both an extension of the solvothermal reaction time and stirring during solvothermal treatment result in a higher total tetrahedral aluminium content in the ZnO lattice. However, only the longer solvothermal treatment effectively results in an increase of the substitutional positions aimed for.

Abstract: For the development of the photovoltaic industry cheap methods for the synthesis of Cu(In,Ga)Se-2 (CIGSe) based solar cells are required. In this work, CIGSe thin films were obtained by a solution-based method using oxygen-bearing derivatives. With the aimof improving the morphology of the printed CIGSe layers, we investigated two different annealing conditions of the precursor layer, consisting of (1) a direct selenization step (reference process), and (2) a pre-treatment thermal step prior to the selenization. We showed that the use of an Air/H2S burn-out step prior to the selenization step increases the CIGSe grain size and reduces the carbon content. However, it leads to the reduction of the solar cell efficiency from 4.5% in the reference sample down to 0.5% in the annealed sample. Detailed transmission electron microscopy analysis, including high angle annular dark field scanning transmission electron microscopy and energy dispersive X-ray mapping, was applied to characterize the microstructure of the film and to determine the relationship between microstructure and the solar cell performance. We demonstrated that the relatively low efficiency of the reference solar cells is related not only to the nanosize of the CIGSe grains and presence of the pores in the CIGSe layer, but also to the high amount of secondary phases, namely, In/Ga oxide (or hydroxide) amorphous matter, residuals of organicmatter (carbon), and copper sulfide that is formed at the CIGSe/MoSe2 interface. The annealing in H2S during the burn-out step leads to the formation of the copper sulfide at all grain boundaries and surfaces in the CIGSe layer, which results in the noticeably efficiency drop. (C) 2015 Elsevier B.V. All rights reserved.

Abstract: New layered structures corresponding to the general formula [PbBiO2]A(n+1)B(n)O(3n-1)Cl(2) Were prepared. Pb5BiFe3O10Cl2 (n = 3) and Pb5Bi2Fe4O13Cl2 (n = 4) are built as a stacking of truncated A(n+1)B(n)O(3n-1) perovskite blocks and alpha-PbO-type [A(2)O(2)](2+) (A = Pb, Bi) blocks combined with chlorine sheets. The alternation of these structural blocks can be represented as an intergrowth between the hematophanite and Sullen-type structural blocks. The crystal and-Magnetic structures of Pb5BiFe3O10Cl2 and Pb5Bi2Fe4O13Cl2 were investigated in the temperature range of 1.5-700 K using X-ray and neutron powder diffraction, transmission electron microscopy and Fe-57 Mossbauer spectroscopy. Both compounds crystallize in the I4/mmm space group with the unit cell parameters a approximate to a(p) approximate to 3.92 angstrom (a unit-cell parameter of the perovskite-structure), c approximate to 43.0 angstrom for the n = 3 member and c approximate to 53.5 angstrom for the n = 4 member. Despite the large separation between the slabs containing the Fe3+ ions (nearly 14 angstrom), long-range antiferromagnetic order sets in below similar to 600 K with the G-type arrangement of the Fe magnetic moments aligned along the c-axis. The possibility of mixing d(0) and d(n) cations at the B sublattice of these structures was also demonstrated by preparing the Ti-substituted n = 4 member Pb6BiFe3TiO13Cl2.

Abstract: The removal of secondary phases from the surface of the kesterite crystals is one of the major challenges to improve the performances of Cu2ZnSn(S,Se)(4) (CZTSSe) thin film solar cells. In this Contribution, the KCN/KOH Chemical etching approach, originally developed for the removal of CuxSe phases in Cu(In,Ga)(S,Se)(2) thin films) is applied to CZTSe absorbers exhibiting various chemical compositions. Two distinct electrical behaviors were observed on CZTSe/CdS solar cells after treatment: (i) the improvement of the fill factor (FF) after 30 s of etching for the CZTSe absorbers showing initially a distortion of the electrical characteristic; (ii) the progressive degradation Of the FF after long treatment time for all Cu-poor CZTSe solar cell samples. The first effect can be attributed to the action of KCN on the absorber, that is found to clean the absorber free surface from most of the secondary phases surrounding the kesterite grains (e.g., Se-0, CuxSe, SnSex, SnO2, Cu2SnSe3 phases, excepting the ZnSe-based phases). The second observation was identified as a consequence of the preferential etching of Se, Sn, and Zn from the CZTSe surface by the KOH solution, combined with the modification of the alkali content of the absorber. The formation of a Cu-rich shell at the absorber/buffer layer interface, leading to the increase of the recombination rate at the interface, and the increase in the doping of the absorber layer after etching are found to be at the origin of the deterioration of the FF of the solar cells.

Abstract: The defect chemistry of the ferroelectric material PbTiO3 after doping with Fe(III) acceptor ions is reported. Using advanced transmission electron microscopy and powder X-ray and neutron diffraction, we demonstrate that even at concentrations as low as circa 1.7% (material composition approximately ABO2.95), the oxygen vacancies are trapped into extended planar defects, specifically crystallographic shear planes. We investigate the evolution of these defects upon doping and unravel their detailed atomic structure using the formalism of superspace crystallography, thus unveiling their role in nonstoichiometry in the Pb-based perovskites.

Abstract: The electrochemical properties and phase transformations during (de)insertion of Li+ in LiFePO4, LiFe0.9Mn0.1PO4 and LiFe0.5Mn0.5PO4 are studied by means of galvanostatic cycling, potential intermittent titration technique (PITT) and in situ X-ray powder diffraction. Different modes of switching between the solid solution and two-phase regimes are revealed which are influenced by the Mn content in Li1-xFe1-yMnyPO4. Additionally, an increase in electrochemical capacity with the Mn content is observed at high rates of galvanostatic cycling (10C, 20C), which is in good agreement with the numerically estimated contribution of the solid solution mechanism determined from PITT data. The observed asymmetric behavior of the phase transformations in Li1-xFe0.5Mn0.5PO4 during charge and discharge is discussed. For the first time, the crystal structures of electrochemically deintercalated Li1-xFe0.5Mn0.5PO4 with different Li content – LiFe0.5Mn0.5PO4, Li0.5Fe0.5Mn0.5PO4 and Li0.1Fe0.5Mn0.5PO4 – are refined, including the occupancy factors of the Li position. This refinement is done using electron diffraction tomography data. The crystallographic analyses of Li1-xFe0.5Mn0.5PO4 reveal that at x = 0.5 and 0.9 the structure retains the Pnma symmetry and the main motif of the pristine x = 0 structure without noticeable short range order effects.

Abstract: The hydrothermal aging stability of 3Y-TZP-xM2O3 (M = La, Nd, Sc) was investigated as a function of 0.02–5 mol% M2O3 dopant content and correlated to the overall phase content, t-ZrO2 lattice parameters, grain size distribution, grain boundary chemistry and ionic conductivity.
The increased aging stability with increasing Sc2O3 content and the optimum content of 0.4–0.6 mol% Nd2O3 or 0.2–0.4 mol% La2O3, resulting in the highest aging resistance, could be directly related to the constituent phases and the lattice parameters of the remaining tetragonal zirconia.
At low M2O3 dopant contents ≤0.4 mol%, the different aging behavior of tetragonal zirconia was attributed to the defect structure of the zirconia grain boundary which was influenced by the dopant cation radius. It was observed that the grain boundary ionic resistivity and the aging resistance followed the same trend: La3+ > Nd3+ > Al3+ > Sc3+, proving that hydrothermal aging is driven by the diffusion of water-derived mobile species through the oxygen vacancies. Accordingly, we elucidated the underlying mechanism by which a larger trivalent cation segregating at the zirconia grain boundary resulted in a higher aging resistance.

Abstract: Co-rich ZnCoO nanoparticles embedded in wurtzite Zn0.7Co0.3O thin films are grown by pulsed laser deposition on a Si substrate. Local superconductivity with an onset Tc at 5.9 K is demonstrated in the hybrid system. The unexpected superconductivity probably results from Co(3+) in the Co-rich ZnCoO nanoparticles or from the interface between the Co-rich nanoparticles and the Zn0.7Co0.3O matrix.

Abstract: Nanocomposites CoOx/SnO2 based on tin oxide powders with different crystallinity have been prepared by wet chemical synthesis and characterized in detail by ICP-MS, XPS, EPR, XRD, HAADF-STEM imaging and EDX-STEM mapping. It was shown that cobalt is distributed differently between the bulk and surface of SnO2 nanocrystals, which depends on the crystallinity of the SnO2 matrix. The measurements of gas sensor properties have been carried out during exposure to CO (10 ppm), and H2S (2 ppm) in dry air. The decrease of sensor signal toward CO was attributed to high catalytic activity of Co3O4 leading to oxidation of carbon monoxide entirely on the surface of catalyst particles. The formation of a p-CoOx/n-SnO2 heterojunction results in high sensitivity of nanocomposites in H2S detection. The conductance significantly changed in the presence of H2S, which was attributed to the formation of metallic cobalt sulfide and removal of the p – n junction.

Abstract: The structural complexity of the antiferromagnetic oxide selenide CaFeSeO is described. The compound contains puckered FeSeO layers composed of FeSe2O2 tetrahedra sharing all their vertexes. Two polymorphs coexist that can be derived from an archetype BaZnSO structure by cooperative tilting of the FeSe2O2 tetrahedra. The polymorphs differ in the relative arrangement of the puckered layers of vertex-linked FeSe2O2 tetrahedra. In a noncentrosymmetric Cmc21 polymorph (a = 3.89684(2) A, b = 13.22054(8) A, c = 5.93625(2) A) the layers are related by the C-centering translation, while in a centrosymmetric Pmcn polymorph, with a similar cell metric (a = 3.89557(6) A, b = 13.2237(6) A, c = 5.9363(3) A), the layers are related by inversion. The compound shows long-range antiferromagnetic order below a Neel temperature of 159(1) K with both polymorphs showing antiferromagnetic coupling via Fe-O-Fe linkages and ferromagnetic coupling via Fe-Se-Fe linkages within the FeSeO layers. The magnetic susceptibility also shows evidence for weak ferromagnetism which is modeled in the refinements of the magnetic structure as arising from an uncompensated spin canting in the noncentrosymmetric polymorph. There is also a spin glass component to the magnetism which likely arises from the disordered regions of the structure evident in the transmission electron microscopy.

Abstract: Layered Li(M,Li)O2 (where M is a transition metal) ordered rock-salt-type structures are used in advanced metal-ion batteries as one of the best hosts for the reversible intercalation of Li ions. Besides the conventional redox reaction involving oxidation/reduction of the M cation upon Li extraction/insertion, creating oxygen-located holes because of the partial oxygen oxidation increases capacity while maintaining the oxidized oxygen species in the lattice through high covalency of the M–O bonding. Typical degradation mechanism of the Li(M,Li)O2 electrodes involves partially irreversible M cation migration toward the Li positions, resulting in gradual capacity/voltage fade. Here, using LiRhO2 as a model system (isostructural and isoelectronic to LiCoO2), for the first time, we demonstrate an intimate coupling between the oxygen redox and M cation migration. A formation of the oxidized oxygen species upon electrochemical Li extraction coincides with transformation of the layered Li1–xRhO2 structure into the γ-MnO2-type rutile–ramsdellite intergrowth LiyRh3O6 structure with rutile-like [1 × 1] channels along with bigger ramsdellite-like [2 × 1] tunnels through massive and concerted Rh migration toward the empty positions in the Li layers. The oxidized oxygen dimers with the O–O distances as short as 2.26 Å are stabilized in this structure via the local Rh–O configuration reminiscent to that in the μ-peroxo-μ-hydroxo Rh complexes. The LiyRh3O6 structure is remarkably stable upon electrochemical cycling illustrating that proper structural implementation of the oxidized oxygen species can open a pathway toward deliberate employment of the anion redox chemistry in high-capacity/high-voltage positive electrodes for metal-ion batteries. Upon chemical or electrochemical oxidation, layered LiRhO2 shows a unique structural transformation that involves both cation migration and oxidation of oxygen resulting in a stable tunnel-like rutile−ramsdellite intergrowth LiyRh3O6 structure. This structure demonstrates excellent performance with the steady and reversible capacity of ∼200 mAh/g. The stability of LiyRh3O6 is rooted in the accommodation of partially oxidized oxygen species through the formation of short O−O distances that are compatible with the connectivity of RhO6 octahedra.

Abstract: The Ca0.85-1.5xGdxEu0.1_0.05-0.5xWO4 (0 < x < 0.567) series of cation-deficient scheelites is investigated to unveil the influence of the cation vacancies on the crystal structure and luminescent properties. The concentration of the vacancies is varied by the heterovalent substitution of Gd3+ for Ca2+, keeping the concentration of the Eu3+ luminescent centers constant in all compounds of the series. The crystal structure of the materials is studied using a combination of transmission electron microscopy and synchrotron X-ray powder diffraction. At low vacancy concentration (x = 0.1, 0.2), cations and cation vacancies are randomly distributed in the structure, and the materials preserve the I41/a symmetry of the parent scheelite structure [x = 0.1: a = 5.25151(1) Å, c = 11.39479(2) Å; x = 0.2: a = 5.25042(1) Å, c = 11.41335(2) Å]. At higher concentration, the cation-vacancy ordering gives rise to incommensurately modulated structures. The x = 0.3 structure has a (3 + 2)D tetragonal symmetry [superspace group I41/a(a,b,0)00(-b,a,0)00, a = 5.24700(1) Å, c = 11.45514(3) Å, q1 = 0.51637(14)a* + 0.80761(13)b*, q2 = -0.80761a* + 0.51637b*]. At x = 0.4, the scheelite basic cell undergoes a monoclinic distortion with the formation of the (3 + 1)D structure [superspace group I2/b(a,b,0)00, a = 5.23757(1) Å, b = 5.25035(1) Å, c = 11.45750(2) Å, g = 90.5120(2) o, q = 0.54206(8)a* + 0.79330(8)b*]. In both structures, the antiphase Ca and (Gd,Eu) occupancy modulations indicate that the ordering between the A cations and vacancies also induces partial Ca/(Gd,Eu) cation ordering. Further increase of the Gd3þ content up to x = 0.567 leads to the formation of a monoclinic phase (space group C2/c) with the Eu2/3WO4-type structure. Despite the difference in the cation-vacancy ordering patterns, all materials in the series demonstrate very similar quantum efficiency and luminescence decay lifetimes. However, the difference in the local coordination environment of the A cation species noticeably affects the line width and the multiplet splitting of the 4f6-4f6 transitions.

Abstract: Barium lanthanum ferrite and four Mn/Ti substituted materials were synthesized by the sol-gel method. The crystal structure of the materials was studied by a combination of X-ray powder diffraction, electron diffraction, scanning transmission electron microscopy and 57Fe Mössbauer spectrometry. BaLaFe2O6-δ has a cubic perovskite structure and Ba0.7La1.3FeMnO6-δ is distorted perovskite with the R-3c symmetry, both from electron diffraction and X-ray powder diffraction. However, according to transmission electron microscopy, the crystals of BaLaFeTiO6-δ, BaLaFeTi0.5Mn0.5O6-δ, and BaLaFe0.5Ti0.5MnO6-δ consist of nanodomains with different symmetries (Pm3m next to R-3c due to octahedral tilts), whereas the bulk X-ray powder diffraction patterns for these compounds correspond to the simple cubic structure. 57Fe Mössbauer spectrometry confirms that all materials contain high spin state Fe3+ ions which are strongly influenced by the chemical disorder
resulting from various cationic environments.