Temperature-dependent X-ray Diffraction Research Articles

Negative Magnetization and Magnetic Ordering of Rare Earth and Transition Metal Sublattices in NdFe0.5Cr0.5O3.

We investigate the effect of alloying at the 3d transition metal site of a rare-earth-transition metal oxide, by considering NdFe0.5Cr0.5O3 mixed perovskite with two equal and random distribution of 3d ions, Cr and Fe, interacting with an early 4f rare earth ion, Nd. Employing temperature- and field- dependent magnetization measurements, temperature-dependent x-ray diffraction, neutron powder diffraction, and Raman spectroscopy, we characterize itsstructural and magnetic properties. Our study reveals bipolar magnetic switching (arising from negative magnetization) and magnetocaloric effect which underline the potential of the studied mixed perovskite in device application. The neutron diffraction study shows the absence of spin reorientation transition over the entire temperature range of 1.5-320 K, although both parent compounds exhibit spin orientation transition. We discuss the microscopic origin of this curious behavior. The neutron diffraction results also reveal the ordering of Nd spins at anunusually high temperature of about 40 K, which is corroborated by Raman measurements.

Mixed Tin Valence in the Tin(II/IV)-Nitridophosphate Sn3P8N16.

Sn3P8N16 combines the structural versatility of nitridophosphates and Sn within one compound. It was synthesized as dark gray powder in a high-pressure high-temperature reaction at 800°C and 6GPa from Sn3N4 and P3N5. The crystal structure was elucidated from single-crystal diffraction data (space group C2/m (no. 12), a=12.9664(4), b=10.7886(4), c=4.8238(2)Å, β=109.624(1)°) and shows a 3D-network of PN4 tetrahedra, incorporating Sn in oxidation states +II and +IV. The Sn cations are located within eight-membered rings of vertex-sharing PN4 tetrahedra, stacked along the [001] direction. A combination of solid-state nuclear magnetic resonance spectroscopy, 119Sn Mössbauer spectroscopy and density functional theory calculations was used to confirm the mixed oxidation of Sn. Temperature-dependent powder X-ray diffraction measurements reveal a low thermal expansion of 3.6ppm/K up to 750°C, beyond which Sn3P8N16 starts to decompose.

Study of the amorphous and crystalline states in Ge(Te1-xSex) thick films (x = 0, 0.50) by in situ temperature-dependent structural analyses

As-deposited and unencapsulated GeTe1-xSex (x = 0, 0.5) 3-μm-thick amorphous films on Si(001) were obtained via the thermal co-evaporation technique. The crystallization and the structure of these phase change materials were examined using in situ temperature-dependent X-ray diffraction (XRD) and grazing-incidence fluorescence X-ray Absorption Near Edge Structure (XANES) in isochronal annealing conditions under nitrogen flow. The results show that the onset temperature of crystallization is highly sensitive to the substitution of the Te atoms by the Se ones and that the rhombohedral structure, with the space group R3m, is the one that crystallized for both samples without Ge or Te rejection. Moreover, the local order around the Ge and Se atoms, probed by Ge and Se K-edge XANES analyses, presents clear modifications from the amorphous state to the crystalline one expecting a Ge four-fold and a Se two-fold coordination in the amorphous state, with an increase of the local disorder with the Se substitution (x = 0.5).

Pressure/temperature-assisted crystallographic engineering–A strategy for developing the infrared phosphors

Light-emitting diodes utilizing the near-infrared (NIR), harnessed through the doping of Cr ion with structural engineering to tune the luminescent properties, provide a compelling avenue for cutting-edge high-tech industries. Overcoming the challenge of altering the local coordination surrounding the activators is crucial for advancing novel NIR phosphors. Here, we propose a pressure-assisted crystallographic engineering strategy to design the new Cr-doped phosphors. Implementing this approach at high temperature and pressure facilitates the phase transition from β-LiGaO2:Cr to α-LiGaO2:Cr, enabling the LiGaO2:Cr material to emit the NIR light, which was initially unattainable. Additionally, we demonstrate the in-situ monitoring of the reverse phase transition from α-LiGaO2:Cr to β-LiGaO2:Cr, validated by in-situ temperature-dependent high-resolution synchrotron X-ray diffraction. Furthermore, α-LiGaO2:Cr and β-LiGaO2:Cr exhibit unexpected optical properties characterized through synchrotron X-ray absorption, photoluminescence, temperature-dependent, and pressure-dependent analyses. Moreover, the α-LiGaO2:Cr shows strong mechanoluminescence and persistent luminescence. This research paves the way for developing novel NIR phosphors and sheds light on the analyses of pressure-assisted research.

Magnetoelastic Coupling Evidence by Anisotropic Crossed Thermal Expansion in Magnetocaloric RSrCoFeO6 (R = Sm, Eu) Double Perovskites.

Double perovskite oxides, characterized by their tunable magnetic properties and robust interconnection between the lattice and magnetic degrees of freedom, present an enticing foundation for advanced magnetic refrigeration materials. Herein, we delve into the influence of rare-earth elements on RSrCoFeO6 (R = Sm, Eu) disordered double perovskites by examining their structural, electronic, magnetic, and magnetocaloric properties. Temperature-dependent synchrotron X-ray diffraction analysis confirmed the stability of the orthorhombic phase (Pnma) across a wide temperature range. X-ray photoemission spectroscopy revealed that both Sm and Eu are in the 3+ state, whereas multiple states for Co2+/3+ and Fe3+/4+ are identified. The magnetic investigation and magnetocaloric effect (MCE) analysis brought to light the presence of a long-range antiferromagnetic (AFM) order with a second-order phase transition (SOPT) in both samples. The maximum magnetic entropy change ΔSMmax was approximately 0.9 J/kg K for both samples at applied field 0-7 T, manifesting prominently above Neel temperatures TN ≈ 93 K (Sm) and 84 K (Eu). Nevertheless, different relative cooling powers (RCP) of 112.6 J/kg (Sm) and 95.5 J/kg (Eu) were observed. A detailed analysis of the temperature-dependent lattice parameters shed light on a distinct magnetocaloric effect across the magnetic transition temperature, unveiling an anisotropic thermal expansion [αV = 1.41 × 10-5 K-1 (Sm) and αV = 1.54 × 10-5 K-1 (Eu)] wherein the thermal expansion axial ratio αbSm/αbEu = 0.61 became lower with increasing temperature, which suggests that the Eu sample experiences a greater thermal expansion in the b-axis direction. At the atomic bonding level, the evidence for magnetoelastic coupling around the magnetic transition temperatures TN was found through the anomalies along the average Co/Fe-O bond distance, formal valence, octahedral distortion, as well as an anisotropic lattice expansion.

Enhanced temperature stability of piezoelectric properties and electrostrain via a diffused phase transition in LaMnO3-doped (K, Na)NbO3-based ceramics

Modern-generation electronic devices face a significant challenge in enhancing the temperature stability of their electrical properties, which are crucial for their practical applications. This study introduces an effective approach to diffused phase engineering, involving doping LaMnO3 to induce diffused phase transition. Consequently, the material achieves temperature-insensitive piezoelectric properties and electrostrain. We combine temperature-dependent X-ray diffraction, first-principle calculations, and other dielectric/piezoelectric properties to elucidate the relationship between dopants, structures, and properties in the (0.96-x)K0.48Na0.52NbO3-0.04Bi0.5Na0.5ZrO3-xLaMnO3 systems. Additionally, LaMnO3 doping in KNN-based ceramics maintains long-range ferroelectric order (LRFO) and enhance ferroelectric relaxor behavior, thereby optimizing the electrical properties (such as the d33*of ∼400 pm/V and the TC of ∼300 °C) of ternary co-doped systems. The normalized unipolar strain (Suni/SRT) exhibits a variation of less than 12.2% over the temperature range of 25–150 °C, while d33 at 200 °C retains 80% of its value at 25°C. Moreover, LaMnO3 doping leads to an increase in both depolarization temperature (Td) and d33. Overall, this study provides an effective paradigm for balancing Td and d33 and designing the composition of temperature-insensitive commercial piezoelectronic devices.

Intertwined crystal structure, magnetic, and charge transport properties in mixed valent A-site ordered manganite NdBaMn2O6

In the present work, we report a correlation between crystal structure, magnetic, and electrical properties in an exotic magnetic compound, NdBaMn2O6 having ∼92% ordering between Nd and Ba, investigated using temperature-dependent synchrotron x-ray diffraction (XRD), dc magnetization and transport measurements. Temperature-dependent XRD data reveals that the compound undergoes various complex crystallographic phase transitions from high-temperature (T > 320 K) P4/mmm phase to intermediate (320 K – 280 K) Cmmm phase to a mixed (Cmmm and P21am) phase (280 K – 220 K) and to low-temperature P21am phase (T < 220 K). It is found that these crystallographic phase compositions play a crucial role in controlling its magnetic and transport properties. Temperature-dependent dc magnetization data show a sharp drop at the onset of mixed phase (Cmmm + P21am) at 280 K followed by a broad hump at ∼ 220 K where mixed phase to P21am transition occurs, thus indicating a correlation between the structural and magnetic properties. The dc magnetization in the mixed phase region is calculated by considering a superposition of the magnetic moments of Cmmm and P21am phases weighted by the fraction of each phase, which exactly follows the experimental magnetization data. Temperature variation of resistivity data shows a jump at ∼260 K, a temperature corresponding to 50–50% phase composition of Cmmm and P21am phases. The compound shows insulating behavior over a whole temperature range as confirmed from the resistivity data. Further, application of magnetic field causes a shift of magnetic and transport transition temperatures which may be due to the magnetic field induced structural transition in the system.

Dynamic Structural Evolution and Dual Emission Behavior in Hybrid Organic Lead Bromide Perovskites.

The optoelectronic properties of organic lead halide perovskites (OLHPs) strongly depend on their underlying crystal symmetry and dynamics. Here, we exploit temperature-dependent synchrotron powder X-ray diffraction and temperature-dependent photoluminescence to investigate how the subtle structural changes happening in the pure and mixed A-site cation MA1-xFAxPbBr3 (x = 0, 0.5, and 1) systems influences their optoelectronic properties. Diffraction investigations reveal a cubic structure at high temperatures and tetragonal and orthorhombic structures with octahedral distortion at low temperatures. Steady state photoluminescence and time correlated single photon counting study reveals that the dual emission behavior of these OLHPs is due to the direct-indirect band formation. In the orthorhombic phase of MAPbBr3, the indirect band is dominated by self-trapped exciton (STE) emission due to the higher-order lattice distortions of PbBr6 octahedra. Our findings provide a comprehensive explanation of the dual emission behavior of OLHPs while also providing a rationale for previous experimental observations.

Origin of linear magnetoresistance in Bi2Te3 topological insulator: Role of surface state and defects

Connection between topological surface states (TSS) and large linear magnetoresistance (LMR) is established in tetradymite Bi2Te3 through tuning of native defects. Thorough analysis of temperature dependent synchrotron X-ray diffraction data quantifies 0-D, 1-D and 2-D defect concentrations. Plausible variation of antisite defects is explained via carrier concentration data. Resistivity data divulge contribution of mixed bulk and surface states in the synthesized samples. High Fermi velocity (∼106 ms−1) and low Fermi energy (∼14 meV) of carriers are obtained. Lower defect concentration sample emerges with high magnetoresistance (MR) and higher mobility. Weak antilocalization (WAL) effect, signature of TSS, is revealed from MR. Large (80%), non-saturating LMR along with ultrahigh mobility (∼1 m2V−1s−1) in Bi2Te3 supports the presence of TSS. Magnetoconductance data are fitted with Hikami-Larkin-Nagaoka equation, obtaining further insight on WAL effect. In addition, extracted parameters like disorder correlation length and coherence length explicate the role of defect density on LMR.

Controlling phase transitions in MnNiGe using thermal quenching and hydrostatic pressure

Abstract The phase transitions in MnNiGe compounds were explored by manipulating the heat treatment conditions and through hydrostatic pressure application. As the quenching temperature increased, both the first-order martensitic structural transition temperatures and magnetic transition temperatures decreased relative to those in the slowly-cooled samples. When the samples were quenched from 1200 ℃, the first-order martensitic structural transition temperature lowered by more than 200 K. The structural transitions also shifted to lower temperature with the application of hydrostatic pressure during measurement. Temperature-dependent X-ray diffraction results reveal&amp;#xD;that the changes of the cell parameters resulting from the structural transitions are nearly identical for all samples regardless of the extensive variation in their structural transition temperatures. In addition, neutron scattering measurements confirm the magnetic structure transition between simple and cycloidal spiral magnetic structures.

Effect of Li on the intrinsic and extrinsic contributions of the piezoelectric response in Lix(Na0.5K0.5)1-xNbO3 piezoelectric ceramics across the polymorphic phase boundary

The temperature-dependent Rayleigh behavior of polycrystalline lead-free Lix(Na0.5K0.5)1-xNbO3 ceramics was characterized to measure the reversible and irreversible piezoelectric response of different compositions with varying Li content. The results revealed that all compositions showed peak values of both reversible and irreversible piezoelectric response near the polymorphic phase boundary. Additionally, depending on the crystal structure, Li content affected the irreversible and reversible contributions. Specifically, at room temperature, there was a notable increase in the irreversible contribution with rising Li content, whereas, within the tetragonal region, the change in Li content predominantly influenced the reversible contributions, resulting in their reduction. These results are discussed in conjunction with temperature-dependent X-ray diffraction and transmission electron microscopy data, which indicated that the lattice distortion and domain structure play an important role in the temperature-dependent variation in the piezoelectric response.

A Novel Ferroelectric Rashba Semiconductor.

Fast, reversible, and low-power manipulation of the spin texture is crucial for next generation spintronic devices like non-volatile bipolar memories, switchable spin current injectors or spin field effect transistors. Ferroelectric Rashba semiconductors (FERSC) are the ideal class of materials for the realization of such devices. Their ferroelectric character enables an electronic control of the Rashba-type spin texture by means of the reversible and switchable polarization. Yet, only very few materials are established to belong to this class of multifunctional materials. Here, Pb1- xGexTe is unraveled as a novel FERSC system down to nanoscale. The ferroelectric phase transition and concomitant lattice distortion are demonstrated by temperature dependent X-ray diffraction, and their effect on electronic properties are measured by angle-resolved photoemission spectroscopy. In few nanometer-thick epitaxial heterostructures, a large Rashba spin-splitting is exhibiting a wide tuning range as a function of temperature and Ge content. This work defines Pb1- xGexTe as a high-potential FERSC system for spintronic applications.

Non-Ambient in-Operando X-Ray Diffraction Study of Li-Ion Batteries on Laboratory Diffractometers

A long outstanding issue when pushing the performance of batteries is the degradation during cycling. Understanding the pertinent mechanisms becomes increasingly significant to tackle them and consequently facilitate the discovery of high-performance batteries that meet the requirements for multiple applications. In operando X-ray diffraction (XRD) is a non-destructive technique which can be used to study the non-equilibrium states of a complete battery cell during cycling by essentially tracing the structure changes. In this talk, we will showcase how high-quality XRD data of Li-ion batteries can be quickly collected and analysed during charge-discharge cycles in transmission geometry on the laboratory diffractometer equipped with an X-ray tube with Ag or Mo anode and an area detector optimized for high energy X-rays. Temperature effects on the performance and life of batteries will be discussed based on the temperature-dependent XRD data collected during the charge-discharge cycling of batteries. Quantification of the structural changes from both cathode and anode materials can be done to essentially understand the structure-property relationship of a complete battery cell.

Insights into the Growth Orientation and Phase Stability of Chemical-Vapor-Deposited Two-Dimensional Hybrid Halide Perovskite Films.

Chemical vapor deposition (CVD) offers a large-area, scalable, and conformal growth of perovskite thin films without the use of solvents. Low-dimensional organic-inorganic halide perovskites, with alternating layers of organic spacer groups and inorganic perovskite layers, are promising for enhancing the stability of optoelectronic devices. Moreover, their multiple quantum-well structures provide a powerful platform for tuning excitonic physics. In this work, we show that the CVD process is conducive to the growth of 2D hybrid halide perovskite films. Using butylammonium (BA) and phenylethylammonium (PEA) cations, the growth parameters of BA2PbI4 and PEA2PbI4 and mixed halide perovskite films were first optimized. These films are characterized by well-defined grain boundaries and display characteristic absorption and emission features of the 2D quantum wells. X-ray diffraction (XRD) and a noninteger dimensionality model of the absorption spectrum provide insights into the orientation of the crystalline planes. Unlike BA2PbI4, temperature-dependent photoluminescence measurements from PEA2PbI4 show a single excitonic peak throughout the temperature range from 20 to 350 K, highlighting the lack of defect states. These results further corroborate the temperature-dependent synchrotron-based XRD results. Furthermore, the nonlinear optical properties of the CVD-grown perovskite films are investigated, and a high third harmonic generation efficiency is observed.

Influence of Ge-doping on the collinear and non-collinear antiferromagnetic phases of Mn[formula omitted]Si[formula omitted] alloy

Effect of Ge-doping at the non-magnetic site (Si-site) of the Mn-based binary alloy Mn5Si3 has been explored through temperature-dependent x-ray diffraction, dc-magnetic, and electrical transport measurements. All the doped alloys show D88 type hexagonal structure with space group P63/mcm at room temperature and undergoes two structural distortions, hexagonal (P63/mcm) → orthorhombic (Ccmm) → orthorhombic (Cc2m), on cooling. The magnetic characters of these orthorhombic (Cc2m), orthorhombic (Ccmm), and hexagonal (P63/mcm) phases are non-collinear antiferromagnetic (AFM1), collinear antiferromagnetic (AFM2), and paramagnetic (PM), respectively. Doping of Ge results in a significant increase in the AFM1 to AFM2 transition temperature (TN1). However, the AFM2 to PM transition point remains unchanged. In addition, a reasonable increase in the critical field values of the AFM1 to AFM2 transition via another non-collinear antiferromagnetic phase (AFM1′) with increasing Ge concentration has been observed, indicating the strengthening of AFM1 and AFM1′ phases over the AFM2 phase. Such behaviors make the observation of unusual magnetic properties of undoped Mn5Si3 alloys, like inverted hysteresis loop (IHL) and thermomagnetic irreversibility (TI), more evident for these Ge-doped alloys. Further, this study unfolds the presence of conventional and inverse magnetocaloric effect and they found to decrease with Ge doping. An interesting interplay for positive and negative magnetoresistance has also been observed in all the studied alloys.

Magnetic structure of the S = ½ staircase kagome lattice PbCu3TeO7

The crystal and magnetic structure characterization of geometrically distorted PbCu3TeO7 with S=1/2 Cu2+ spins forming a staircase kagome lattice was investigated using x-ray and neutron diffraction on a powder sample. The distorted kagome lattice of antiferromagnet PbCu3TeO7 exhibits a quasi-two-dimensional spin network. The x-ray diffraction data show that PbCu3TeO7 crystallizes in the orthorhombic system in the space group Pnma (No. 62). The lattice parameters a = 10.488(1) Å, b = 6.353(1) Å, and c = 8.814(2) Å. Our temperature-dependent x-ray diffraction data show that there is no structure phase transition between 12 and 298 K. From our powder neutron diffraction data at 2 K, we observed two distinct magnetic Bragg peaks at low angles, confirming the magnetic transition to the ordered state at low temperatures. In previous work, the ordering vector for the magnetic structure was determined using simulations to be (0,1/3,0). However, in this work, we found that based on the neutron diffraction data the ordering vector is in fact (0,1/3,1/3). The magnetic structure of PbCu3TeO7 exhibiting an antiferromagnet with noncollinear spin order is proposed.

Stabilization of the VO2(M2) Phase and Change in Lattice Parameters at the Phase Transition Temperature of WXV1-XO2 Thin Films.

Various methods have been used to fabricate vanadium dioxide (VO2) thin films exhibiting polymorph phases and an identical chemical formula suited to different applications. Most fabrication techniques require post-annealing to convert the amorphous VO2 thin film into the VO2 (M1) phase. In this study, we provide a temperature-dependent XRD analysis that confirms the change in lattice parameters responsible for the metal-to-insulator transition as the structure undergoes a monoclinic to the tetragonal phase transition. In our study, we deposited VO2 and W-doped VO2 thin films onto silica substrates using a high repetition rate (10 kHz) fs-PLD deposition without post-annealing. The XRD patterns measured at room temperature revealed stabilization of the monoclinic M2 phase by W6+ doping VO2. We developed an alternative approach to determine the phase transition temperatures using temperature-dependent X-ray diffraction measurements to evaluate the a and b lattice parameters for the monoclinic and rutile phases. The a and b lattice parameters versus temperature revealed phase transition temperature reduction from ∼66 to 38 °C when the W6+ concentration increases. This study provides a novel unorthodox technique to characterize and evaluate the structural phase transitions seen on VO2 thin films.

Pseudogap in BaPb x Bi1‒x O3 (x = 0.7, 0.75 and 1.0)

In this work, we have investigated the crystal and electronic structure of the orthorhombic phase of BaPb x BiO3 (BPBO) for x = 0.7 (BPBO70), 0.75 (BPBO75) and 1.0 (BPO), using temperature dependent x-ray diffraction measurements, photoemission spectroscopy, and electronic structure calculations. Our results show the importance of particle size and strain in governing superconductivity. Interestingly, the temperature evolution of the structural parameters in the case of BPBO70 is similar to that of BPBO75 but the magnitude of the change is diminished. The BPBO75 and BPO compounds exhibit metallic nature, which is corroborated by the core level studies. The electronic structure calculations in conjunction with the core level studies suggest that oxygen vacancies play an important role for metallicity observed in the end compound. The exponent to the spectral line shape close to the Fermi level suggests the origin of pseudogap to be due to other contributions in addition to disorder in the case of BPBO70 and BPO. The core level studies also show that as one goes from x = 0.70 to 1.0, there occurs chemical potential shift towards the valence band suggesting hole doping. Our results open the venue to further study these compounds as a function of particle size, nature of carriers for its transport behaviour, electronic structure below TC , composition at the grain boundaries and microscopic origin of pseudogap in the non-superconducting phase. We believe that our results call for a revision of the temperature-doping phase diagram of BPBO to include the pseudogap phase.

Ultrahigh-performance [001]-oriented porous PZT-5H single crystal grown by the solid state crystal growth method

Porous PZT-5H single crystals are grown by the solid state crystal growth (SSCG) method. The microstructure, phase structure and dielectric/piezoelectric properties are investigated for [001]-oriented porous PZT-5H single crystal. Evolution of phase structure with temperature is researched using in-situ temperature-dependent X-ray diffraction. The effect of pores on performance parameters is simulated using COMSOL Multiphysics® software. Ultrahigh piezoelectric coefficient d33 of up to about 1700 pC/N and effective piezoelectric coefficient d33* of up to about 3700 pm/V at 5 kV/cm are obtained. Moreover, the effective piezoelectric coefficient d33* is stable around 1900 pm/V under 3 kV/cm and 5 kV/cm in the temperature range of 70–160 °C. Importantly, the sample possess an extremely large figure of merit g33*d33 (111 × 10−12 m2/N), which is related to the presence of pores in the single crystal. This work expands the scope of PZT based single crystal and highlights their significant application possibilities in piezoelectric energy harvester, and actuator at high temperature.

Experimental and theoretical (DFT) approaches on novel ternary liquid crystals derived from asymmetric aromatic dicarboxylic acid

Novel ternary liquid crystal (TLC) homologues series was designed and prepared from 4-methoxycinnamic acid (4MCA), homophthalic acid (HPA) and 4-n-alkyloxybenzoic acids (nOBA, where n = 6 to 12). The mesogenic behaviour, phase transition temperature, thermal span width and thermal stability factor of TLC (homologues series) were studied by polarising optical microscopy (POM) and differential scanning calorimetry (DSC) techniques. A noteworthy observation is that, TLC induces smectic A (batonnets texture) along with nematic and smectic F phases whereas, the Sm A is not perceived in the individual compounds while compared with the TLC. Further, the existence of smectic phases (Sm A and Sm F) are identified by temperature dependent X-ray diffraction (XRD) analysis. The same are correlated with DSC observations. Density functional theory (DFT) is used to optimize the molecular geometry of TLC. FMO and MEP study explores the molecular environment and quantum chemical behaviour of TLC. NBO, QTAIM and RDG analysis explicate the charge transfer with stabilization energy and non-covalent interactions. Density functional theory (DFT) calculations confirm the possible conformer of TLC.