Extended X-ray absorption fine structure (EXAFS) of FAPbI_(3) for understanding local structure-stability relation in perovskite solar cells

Perovskite solar cells (PSCs) employing formamidinium lead iodide (FAPbI_(3)) have shown high efficiency.However,operational stability has been issued due to phase instability of α phase FAPbI_(3) at ambient temperature.Excess precursors in the perovskite precursor solution has been proposed to improve not only power conversion efficiency (PCE) but also device stability.Nevertheless,there is a controversial issue on the beneficial effect on PCE and/or stability between excess FAI and excess PbI_(2).We report here extended X-ray absorption fine structure (EXAFS) of FAPbI_(3) to study local structural change and explain the effect of excess precursors on photovoltaic performance and stability.Perovskite films prepared from the precursor solution with excess PbI_(2)shows better stability than those from the one with excess FAI,despite similar PCE.A rapid phase transition from α phase to non-perovskite δ phase is observed from the perovskite film formed by excess FAI.Furthermore,the (Pb-I) bond distance evaluated by the Pb L_(III)-edge EXAFS study is increased by excess FAI,which is responsible for the phase transition and poor device stability.This work can provide important insight into local structure-stability relation in the FAPbI_(3)-based PSCs.

Data-collection system for high-throughput X-ray absorption fine structure measurements

A new X-ray absorption fine structure(XAFS)data-collection system based on the Experimental Physics and Industrial Control System software environment has been established at the BL14W1 beamline of the Shanghai Synchrotron Radiation Facility. The system provides for automatic sequential analysis of multiple samples for continuous high-throughput(HT) measurements. Specifically, 8 sample pellets are loaded into an alumina holder,and a high-precision two-dimensional translation stage is programmed to switch these samples automatically for collecting the XAFS spectrum of each sample in sequence.Experimenters implement HT measurements via a graphical user interface developed with Control System Studio.Finally, the successful operation of the HT XAFS system is demonstrated by running experiments on two groups of copper–ceria catalysts, each of which contains 8 different powder samples.

Interpretation of the pre-edge X-ray absorption fine structures in MnO

The weak pre-edge features in the Mn K-edge X-ray absorption near-edge structure (XANES) spectrumof manganese monoxide (MnO) were investigated by comparing experimental data with dipolar and quadrupolarcross-section calculations in the framework of multiple-scattering theory. We assign the first pre-edge feature to a di-rect quadrupolar transition from Is core state to 3d molecular orbitals of the central atom, e.g., the lowest in energy,due to the more effective attraction of the core hole. The second peak in this region arises unambiguously from thehybridization between p-orbitals of the central atom with higher-shell metal octahedral orbitals.

Oxidation of antimony (Ⅲ) in soil by manganese (Ⅳ) oxide using X-ray absorption fine structure

The oxidation of antimony （Ⅲ） in soils was studied using X-ray absorption fine structure （XAFS） spectra. An andosol soft sample and artificial soil samples （SiO2 blended with iron （Ⅲ） hydroxide and manganese （Ⅳ） oxide） were used herein. After adding antimony （Ⅲ） oxide to all soil samples, the oxidation process was observed by recording the XAFS spectra of Sb K-edge, Fe Kedge, and Mn K-edge. The results indicated that manganese （Ⅳ） oxide played an important role in the oxidation of Sb（Ⅲ）; however iron （Ⅲ） hydroxide was not directly related to the reaction. During a 2-hr continuous Sb K-edge X-ray absorption near edge structure （XANES） measurement with an interval of I rain of one of the artificial soil samples （SiO2 ＋ MnO2 ＋ Sb2O3）, a pseudo-first-order reaction was determined with an average estimated rate of 0.52 ±0.04 hr-1. Compared to the lower oxidation rate of andosol, it is suggested that because of the low concentration of Mn（Ⅳ） in natural soils, the oxidation process of Sb（Ⅲ） might be relatively slow and require more time to convert Sb（Ⅲ） to Sb（V）.

Synthesis, characterization and extended X-ray absorption fine structure of novel polynuclear copper complexes with new eighteen-membered macrocycle ligands

Macrocycle compounds have great importance in host-guest chemistry and moleculeidentifications. 4-acetyl-bispyrazolones are a new type of polydentate ligands. Whenthey react with diamine compounds, new compounds or complexes containing C=O andC=N groups can be obtained. These compounds can be used to study the relationship ofcoordination structure and its properties, energy transferring processes between metal

INVESTIGATION OF BONDING IN NANO-SiO_(2) BY Si L_(2,3) X-RAY ABSORPTION NEAR-EDGE STRUCTURE SPECTROSCOPY

The Si L2,3 X-ray absorption near-edge structure (XANES) can be used to probe thelocal structure around Si and derive electronic information of the unoccupied s- andd-like partial density of states in nano-size SiO2. We present Si L2,3-edge for threedifferent size silicates acquired by total electron yield (TEY) at the photoemission sta-tion of Beijing Synchrotron Radiation Facility (BSRF). The Si L2,3-edge spectra areinterpreted based on ab initio full multiple-scattering (MS) calculation. The Si L2.3-edge of nano-size materials has XANES similar to that of a-quartz. The similaritiesbetween the Si L2.3-edge shapes attest to a common molecular-orbital picture of theirSi-O bonding and the same coordination state. However, a considerable broadeningof Si L2,3-edge XANES spectra as decrease of particle size is also an indicative ofpolyhedral distortions.

X-ray absorption near the edge structure and x-ray photoelectron spectroscopy studies on pyrite prepared by thermally sulfurizing iron films

This paper reports how pyrite films were prepared by thermal sulfurization of magnetron sputtered iron films and characterized by X-ray absorption near edge structure spectra and X-ray photoelectron spectroscopy on a 4B9B beam line at the Beijing Synchrotron Radiation Facility. The band gap of the pyrite agrees well with the optical band gap obtained by a spectrophotometer. The octahedral symmetry of pyrite leads to the splitting of the d orbit into t2g and eg levels. The high spin and low spin states were analysed through the difference of electron exchange interaction and the orbital crystal field. Only when the crystal field splitting is higher than 1.5 eV, the two weak peaks above the white lines can appear, and this was approved by experiments in the present work.

X-ray absorption near-edge structure study on the configuration of Cu2＋/histidine complexes at different pH values

The local configurations around metal ions in metalloproteins are of great significance for understanding their biolog- ical functions. Cu2＋/histidine （His） is a typical complex existing in many metalloproteins and plays an important role in lots of physiological functions. The three-dimensional （3D） structural configurations of Cu2＋/His complexes at different pH values （2.5, 6.5, and 8.5） are quantitatively determined by x-ray absorption near-edge structure （XANES）. Generally Cu2＋/His complex keeps an octahedral configuration consisting of oxygen atoms from water molecules and oxygen or nitrogen atoms from histidine molecules coordinated around Cu2＋. It is proved in this work that the oxygen atoms from water molecules, when increasing the pH value from acid to basic value, are gradually substituted by the Ocarboxy1, Nam, and Nim from hisitidine molecules. Furthermore, the symmetries of Cu2＋/His complexes at pH 6.5 and pH 8.5 are found to be lower than at pH 2.5.

Landscape of s-triazine molecule on Si(100) by a theoretical x-ray photoelectron spectroscopy and x-ray absorption near-edge structure spectra study

The chemisorbed structure for an aromatic molecule on a silicon surface plays an important part in promoting the development of organic semiconductor material science. The carbon K-shell x-ray photoelectron spectroscopy（XPS） and the x-ray absorption near-edge structure（XANES） spectra of the interfacial structure of an s-triazine molecule adsorbed on Si（100） surface have been performed by the first principles, and the landscape of the s-triazine molecule on Si（100） surface has been described in detail. Both the XPS and XANES spectra have shown their dependence on different structures for the pristine s-triazine molecule and its several possible adsorbed configurations. By comparison with the XPS spectra, the XANES spectra display the strongest structural dependency of all of the studied systems and thus could be well applied to identify the chemisorbed s-triazine derivatives. The exploration of spectral components originated from non-equivalent carbons in disparate local environments has also been implemented for both the XPS and XANES spectra of s-triazine adsorbed configurations.

Local Structure Analysis of Lead Zinc Niobate-Barium Titanate Ceramic by X-Ray Absorption Spectroscopy and Density Functional Calculation

The local structure of an alternative Pb（Zn1/3Nb2/3）O3-based perovskite ceramic is investigated. The 0.07BaTiO33-0.93Pb（Zn1/3Nb2/3）O3 ceramic is synthesized using a combination of Zn3Nb2O8 B-site precursor and BaTiO33 perovskite phase stabilizer. Then, x-ray absorption spectroscopy and density functional theory are employed to calculate the local structure configuration and formation energy of the prepared samples. Ba2＋ is found to replace Pb2＋ in AA-site with Zn2＋ occupying BB-site in Pb（Zn1/3Nb2/3）O3, while in the neighboring structure, Ti4＋4＋ replaces Nb5＋5＋ in BB-site with Pb2＋2＋ occupying AA-site. With the substitution of BaTiO33 in Pb（Zn1/3Nb2/3）O3, the bond length between Zn2＋ and Pb2＋ is longer than that of the typical perovskite phase of Pb（Zn1/3Nb2/3）O3. This indicates the key role of BaTiO33 in decreasing the steric hindrance of Pb2＋ lone pair, and the mutual interactions between Pb2＋ lone pair and Zn2＋ and the formation energy is seen to decrease. This finding of the formation energy and local structure configuration relationship can further extend a fundamental understanding of the role of BaTiO33 in stabilizing the perovskite phase in PbZn13Nb23O3-based materials, which in turn will lead to an improved preparation technique for desired electrical properties.

STRUCTURAL DETERMINATION OF TITANIUM-OXIDE NANOPARTICLES BY X-RAY ABSORPTION SPECTROSCOPY

As a potential application of titanium-oxide nanoparticles, it is extremely important to investigate a detailed picture of the surface and interior structural properties of nanocrystalline materials, such as rutile and anatase with diameters 7.0 and 4.5nm, respectively. X-ray absorption spectroscopy has been used to identify the local Ti environment and related electronic structure. We combine the experimental results at the Ti edge in both bulk and nano-crystals to determine the lattice distortion in terms of differently characteristic preedge features and the variation in the multiple-scattering region of X-ray absorption near-edge structure (XANES) spectra. The relationship between the transition peaks and the surface-to volume ratio is also discussed.

Theoretical characterization of the adsorption configuration of pyrrole on Si(100)surface by x-ray spectroscopy

The possible configurations of pyrrole absorbed on a Si(100)surface have been investigated by x-ray photoelectron spectroscopy(XPS)and near-edge x-ray absorption fine structure(NEXAFS)spectra.The C-1s XPS and NEXAFS spectra of these adsorption configurations have been calculated by using the density functional theory(DFT)method and fullcore hole(FCH)approximation to investigate the relationship between the adsorption configurations and the spectra.The result shows that the XPS and NEXAFS spectra are structurally dependent on the configurations of pyrrole absorbed on the Si(100)surface.Compared with the XPS,the NEXAFS spectra are relatively sensitive to the adsorption configurations and can accurately identify them.The NEXAFS decomposition spectra produced by non-equivalent carbon atoms have also been calculated and show that the spectral features vary with the diverse types of carbon atoms and their structural environments.

FINE STRUCTURE ANALYSIS OF DEFORMED STEEL 1Cr18Ni9

X-ray diffraction profiles of various deformed steel 1Cr18Ni9 through stepped scanning were obtained.By profile analysis,some structure parameters such as effective domain size D_(eff), dislocation density in domain,distribution parameterand bulk stored energy densiy (E/V),etc.,were obtained.The results were compared with those of TEM observation.The true domain sizes D_e are comparable,but the minimum and characteristics of width of stack- ing fault are different.This may be resulted from the large fluctuation in width of stacking fault.

Structure and chemical valence study of Sr_(n+1)Ru_nO_(3n+1)(n= 1, 2, ∞) series

Effect of structure parameter n and its coupling with the connection mode among RuO6 octahedra of Srn＋1RUnO3n＋1 （n = 1, 2, ∞） are investigated. The gradually enhanced rotation and tilting effect with increasing n are observed in Srn＋1RUnO3n＋1. Besides, the chemical valence of Ru is not changed, while the one of Sr gradually varies with increasing n, which highlights the great contribution of connection mode to the chemical environment. Our results show a strong n dependence on the connection mode between octahedra in Srn＋1RUnO3n＋1 （n = 1, 2, ∞）.

Analysis of Local Structures around Ni Atoms Doped in ZnO-Based Diluted Magnetic Semiconductors by Fluorescence EXAFS

Zn1 终止 NixO (x = 0-001， 0.01， 0,02， 0.05 和 0.20 ) 粉末被准备 bysol 胶化方法。为阿里·凯切斯的一种扩大 X 光吸收罚款结构技术(EXAFS ) 采用了在荧光模式在 ZnO 粉末做的 Ni 原子附近探查本地结构。样品的近的边 EXAFS 不从 x = 0.001to 在 Ni 集中的范围变化 0.05，它与样品的 X 光衍射的结果一致。第一个壳 EXAFS 信号的模拟结果显示阿里原子在 Zn 地点被代替。

Relating atomic local structures and Curie temperature of NdFeB permanent magnets:an X-ray absorption spectroscopic study

Relationship between atomic local structures and Curie temperature of NdFeB permanent magnets was investigated semi-quantitatively using synchrotron radiation technique. Fe K-edge X-ray absorption spectroscopy(XAS) was employed to study the local structure of Fe atoms for samples before and after doping Dy, Tb or Gd. It is found that the bond lengths and coordination numbers are changed. Thus, the exchange interaction between Fe atoms increases with Dy, Tb or Gd doping, resulting in the improvement of Curie temperature of NdFeB permanent magnets. The doping effect is proven by experimental measurement of the magnetic properties. Microstructural characterization using scanning electron microscopy(SEM) was also used to further analyze the effect of different rare earth elements doping on Curie temperature of NdFeB permanent magnets.

SHORT-RANGE ORDER STRUCTURES OF Fe-Ge AMORPHOUS THIN FILMS

The short-range order structures of Fe_xGe_(1-x) amorphous thin films,(x=8.7,19.1 and 28.5%)have been studied by means of X-ray absorption spectrum.The nearest neighbors around a Ge or an Fe atom are constituted by two coordinate sub-shells with a very short dis- tance,In two films with lower Fe content,structural parameters of the nearest neighbors around a Ge atom are very near to that in amorphous germanium,and the positions of Fe at- oms are randomly substitutional.But when x=28.5%,some great changes occur on the short-range order structure of a-Fe_xGe_(1-x) film:its structure deviates from continuous ran- dora network and tends toward dense random packing of atoms.Meanwhile,there is a strong- er interaction between near neighboring Fe-Ge atoms in a-Fe_xGe_(1-x) films.

MULTIPLE-SCATTERING STUDIES OF ADSORPTION STRUCTURE OF C_2D_2/Si(111)7×7

The multiple scattering cluster (MSC) method has been employed to perform a theoretical analysis on carbon is near edge X-ray absorption fine structure of the deuteron acetylene (C2 D2) adsorbed on Si(111)7× 7 at room temperature. From the MSC study. it is confirmed that the (22D2 molecule is bonded to a pair of adjacent Si adatom and Si restatom with C-Si bond length about 0.18nm. The carbon-deuteron bond is bent away front the surface and the CCD bond angle is about 120°. The molecule plane tilt slightly away from the surface normal. Compared with C2D2 in gas phase, the C-C bond and C-D bond are elongated by about 0.03nm and 0.02nm respectively when acetylene was adsorbed on the subtrate. Keyowrds: adsorption of deuteron acetylene on Si(111)7×7. near edge X- ray absorption fine structure. multiple scattering cluster method

Structural distortions and magnetisms in Fe-doped LaMn_(1-x) Fe_x O_3(0

X-ray absorption spectra （XAS） at Mn K-edge and Fe K-edge in LaMnl-xFexO3 show that with the increase of Fe substitution the chemical valence of Mn4＋ decreases, while the chemical valence of Fe3＋ remains unchanged. Structural distortions, such as the rotating and tilting for oxygen octahedron in the unit cell vary with iron content. A phase transition occurs at the Fe content values of 0.2~0.3. The evolutions of rotation and tilting angle of FeO6/MnO6 octahedral may be the vital factors to the structure and magnetism. We believe that the spin configuration of Fe3＋ may vary from the intermediate spin t2g4eg1 （S = 3/2） to the higher spin t2g3eg2 （S = 5/2） near the phase transition.

Research Article Local structure and magnetic properties of a nanocrystalline Mnrich Cantor alloy thin film down to the atomic scale

The huge atomic heterogeneity of high-entropy materials along with a possibility to unravel the behavior of individual components at the atomic scale suggests a great promise in designing new compositionally complex systems with the desired multifunctionality.Herein,we apply multi-edge X-ray absorption spectroscopy(extended X-ray absorption fine structure(EXAFS),Xray absorption near edge structure(XANES),and X-ray magnetic circular dichroism(XMCD))to probe the structural,electronic,and magnetic properties of all individual constituents in the single-phase face-centered cubic(fcc)-structured nanocrystalline thin film of Cr_(20)Mn_(26)Fe_(18)Co_(19)Ni_(17)(at.%)high-entropy alloy on the local scale.The local crystallographic ordering and componentdependent lattice displacements were explored within the reverse Monte Carlo approach applied to EXAFS spectra collected at the K absorption edges of several constituents at room temperature.A homogeneous short-range fcc atomic environment around the absorbers of each type with very similar statistically averaged interatomic distances(2.54-2.55Å)to their nearest-neighbors and enlarged structural relaxations of Cr atoms were revealed.XANES and XMCD spectra collected at the L2,3 absorption edges of all principal components at low temperature from the oxidized and in situ cleaned surfaces were used to probe the oxidation states,the changes in the electronic structure,and magnetic behavior of all constituents at the surface and in the sub-surface volume of the film.The spin and orbital magnetic moments of Fe,Co,and Ni components were quantitatively evaluated.The presence of magnetic phase transitions and the co-existence of different magnetic phases were uncovered by conventional magnetometry in a broad temperature range.