Temperature-dependent X-ray Diffraction Research Articles

Room temperature tri-alkynyl benzene based discotic nematic mesophase enabling high-efficiency deep blue OLEDs

In the hunt to develop room-temperature nematic discotic materials, we engineered a molecular structure that employs a tri-alkynyl benzene core incompatible with π-π stacking, providing flexibility to the system. Micro-segregation was prohibited due to the direct attachment of the flexible alkoxy chain to the central benzene ring, leading to a discotic nematic phase. The nematic phase was found stable down to room temperature and, on further cooling, transformed into a glassy state. Detailed analysis of differential scanning calorimetry plots, polarized optical microscopic textures, and temperature-dependent X-ray diffraction patterns confirmed the glassy nematic phase at low temperatures. The tri-alkynyl benzene moiety imparts high solid and solution-state blue emission properties to mesogens 1a and 1b. On stimulating the compounds electrically as a solid-state emitter in organic light-emitting diodes, they showed emission in the deep blue (CIEy < 0.08) region at 100 cd m−2 luminance and pure blue (CIEy < 0.11) region at maximum luminance using CBP host. Amongst all the configurations used, the device based on 0.5 wt% 1a displayed the best performance with a maximum external quantum efficiency of 4.1% with a turn-on voltage of 3.5 V and CIExy coordinates of (0.16,0.07).

Thermal stability of the CuZrSe2

The CuZrSe2 compound was synthesized for the first time by intercalation of Cu into the ZrSe2 lattice at room temperature. Experimental study of the thermal stability of CuZrSe2 has been performed by in-situ temperature-dependent synchrotron radiation X-ray diffraction (SR-XRPD). CuZrSe2 has a layered structure with space group P3‾m1. The copper atoms at room temperature in the interlayer space are octa- and tetrahedrally coordinated by selenium. Heating leads the decomposition of the main layered phase into binary copper chalcogenides and zirconium trichalcogenide as previously shown for CuxZrTe2. With the increase in temperature the octahedral sites in main layered phase become empty, copper atoms occupy the tetrahedral sites only. Thus, the high-temperature form of CuZrSe2 has a delafossite-like structure.

Simple and Scalable Synthesis Method of γ-NaTiOPO4 for Sodium Ion Batteries in Aqueous and Non-Aqueous Electrolytes

Lithium-ion batteries have been considered a suitable battery technology for energy storage systems. However, its scarcity and high cost pose challenges to the availability of lithium for mass adoption in large applications such as energy storage. Due to their natural abundance and economic feasibility, sodium-ion batteries (SIBs) have proven to be a promising alternative for large-scale applications.1 Most anode materials for research on SIBs have focused on carbonaceous materials, oxides and polyanionic compounds of the anode, like that of lithium-ion battery research on anode materials Polyanionic compounds, especially phosphates, are of particular interest due to their structural, thermal properties and, more importantly, for avoiding undesirable sodium plating.2 Contrary to lithium counterparts, SIBs have fewer alternatives for safe anode materials applicable for both non-aqueous and aqueous rechargeable SIBs.3 Various NaTiOPO4 polymorphs have previously been reported, and these materials required a synthesis process that was extremely time-consuming and a highly pressured synthesis atmosphere. However, the methods reported still produced very small amounts of synthesized material.4-8 Due to these limitations, only the β-NaTiOPO4 phase among polymorphs was studied as an anode for SIBs in a non-aqueous electrolyte.7-8 In this study, we first report a simple and scalable solid-state synthesis method for γ-NaTiOPO4, which incorporates a high-temperature quenching process to stabilize metastable γ-NaTiOPO4 with stability. It is a promising anode for SIBs in non-aqueous and aqueous electrolytes, with a capacity of roughly 120mAh/g, voltages of 1.7V and 1.5V vs Na/Na +, and a Coulombic efficiency of up to 99.9% for up to 500 cycles at 0.5C in non-aqueous electrolyte and excellent capacity retention in a full cell of NaMn0.44O2//γ-NaTiOPO4 for up to 175 cycles in aqueous electrolyte.9 El Kharbachi, A.; Zavorotynska, O.; Latroche, M.; Cuevas, F.; Yartys, V.; Fichtner, M., Exploits, advances and challenges benefiting beyond Li-ion battery technologies. Journal of Alloys and Compounds 2020, 817.N. Yabuuchi, K. Kubota, M. Dahbi, S. Komaba, Research development on sodium-ion batteries, Chem. Rev. 114 (23) (2014) 11636–11682. H. Kim, J. Hong, K.Y. Park, H. Kim, S.W. Kim, K. Kang, Aqueous rechargeable Li and Na ion batteries, Chem. Rev. 114 (23) (2014) 11788–11827. Stus, N. V.; Slobodyanik, M. S.; Straitiychuk, D. A.; Lisnyak, V. V., Pressure induced gamma ->alpha-NaTiOPO4 phase transition. J Alloy Compd 2005, 393 (1-2), 66-69.Dahaoui, S.; Hansen, N. K.; Protas, J.; Krane, H.-G.; Fischer, K.; Marnier, G., Electric properties of KTiOPO4 and NaTiOPO4 from temperature-dependent X-ray diffraction. Journal of Applied Crystallography 1999, 32 (1), 1-10.Loiacono, G. M.; Loiacono, D. N.; Stolzenberger, R. A., Growth and properties of crystals in the system KTiOPO4-NaTiOPO4. Journal of Crystal Growth 1994, 144 (3), 223-228.Mu, L. Q.; Ben, L. B.; Hu, Y. S.; Li, H.; Chen, L. Q.; Huang, X. J., Novel 1.5 V anode materials, ATiOPO(4) (A = NH4, K, Na), for room -temperature sodium-ion batteries. Journal Jiang, L. W.; Liu, L. L.; Yue, J. M.; Zhang, Q. Q.; Zhou, A. X.; Borodin, O.; Suo, L. M.; Li, H.; Chen, L. Q.; Xu, K.; Hu, Y. S., High-Voltage Aqueous Na-Ion Battery Enabled by Inert-Cation-Assisted Water-in-Salt Electrolyte. Advanced Materials 2020, 32 (2).Kim, D.; Park, H.; Avdeev, M. ; Kim, M. ; Kang, B. (2022). Newly developed γ – NaTiOPO4 by Simple Solid-State Synthesis for Anode Material of Na-ion Batteries in Both Non-aqueous and Aqueous electrolyte. Journal of Power Sources 2022, 541 (1)

Magnetotransport, spin reorientation, and anomalous ferrimagnetic-to-antiferromagnetic phase transition in epitaxial Mn2Sb alloy thin films

High-quality ferrimagnetic Mn2Sb epitaxial thin films have been successfully grown on SrTiO3 (001) single-crystal substrates via systematically optimizing the growth parameters using molecular beam epitaxy. Magnetotransport and magnetic measurements reveal that a spin reorientation transition occurs in the 260–150 K region where the direction of spins rotates from out-of-plane to in-plane upon cooling, resulting in the ferrimagnetic(II) phase, followed by a giant magnetoresistance associated anomalous ferrimagnetic(II)-to-canted antiferromagnetic (c-AFM) phase transition in the 150–115 K region, resulting in the c-AFM ground state, both of which are completely absent and have yet not been previously observed in Mn2Sb bulk and thin films. Temperature-dependent X-ray diffraction measurements reveal that the low-temperature c-AFM phase originates from the contraction of the out-of-plane lattice constant c, which would increase the exchange interaction between neighbouring magnetic sublattices and thus stabilize the c-AFM phase. DFT calculations reveal that substrate clamping is the cause of the unique c-axis contraction in Mn2Sb films. For the 24-nm films, there is almost no out-of-plane magnetization in the ground state, but exists a weak in-plane remanent magnetization (∼0.4 μB/f.u.) and anomalous Hall effects, implying spin canting within the ab plane. With decreasing film thickness from 64 to 8 nm, the out-of-plane saturation magnetization at 10 K increases by approximately 10 times, and for the 8-nm film, its saturation magnetization (4.8 μB/f.u.) is 2.8 times larger than that of Mn2Sb bulk (∼1.74 μB/f.u.), both of which are attributed to the interfacial strain effect. Our work demonstrates that Mn2Sb films grown on perovskite oxide substrates show anomalous spin-charge-lattice coupling phenomena, which may inspire more study of its basic properties and potential device applications.

Study of the structure, structural transition, interface model, and magnetic moments of CrN grown on MgO(001) by molecular beam epitaxy

Structural phase transition is studied in high quality CrN thin films grown by molecular beam epitaxy on MgO(001) substrates. Cross-sectional transmission electron microscopy and x-ray diffraction reveal that the epitaxial relationship between CrN film and MgO substrate is [100]CrN/[100]MgO, [110]CrN/[110]MgO, and [001]CrN/[001]MgO. The films show tensile strain/compression at the CrN/MgO(001) interface, which relaxes gradually with the film growth. Temperature dependent x-ray diffraction measurements show a first-order structural phase transition. In addition to the experimental measurements, first-principles theoretical calculations have been carried out for finding a stable model for the CrN/MgO interface. These calculations determine two possible models for the interface, where a monolayer of chromium oxide is formed between the CrN and MgO layers.

Temperature-driven structural phase transitions in 0.05(Na0.50Bi0.50)TiO3-0.95NaNbO3 solid solution via amplitude mode analysis

Structural phase transitions in the ABO3-type lead-free eco-friendly piezoelectric (05NBT) have been studied as a function of temperature using dielectric and X-ray diffraction techniques. Below 300 K, we observed dispersion in dielectric permittivity with the frequency, which confirmed relaxor behaviour in 05NBT. Using detailed analysis of temperature-dependent powder X-ray diffraction data of 05NBT, four phase transitions were identified across 600 K, 773 K, 823 K and 923 K. We found that on doping 5% NBT in pure sodium niobate, the low-temperature rhombohedral ferroelectric (N) phase and the high-temperature (S) phase of the sodium niobate get suppressed. To get a better insight about the temperature-driven structural phase transitions, various antiferrodistortive and additional distortive mode as well as the mode amplitude relative to high-symmetry cubic phase were computed and results are discussed.

Leucopterin, the white pigment in butterfly wings: structural analysis by PDF fit, FIDEL fit, Rietveld refinement, solid-state NMR and DFT-D.

Leucopterin (C6H5N5O3) is the white pigment in the wings of Pieris brassicae butterflies, and other butterflies; it can also be found in wasps and other insects. Its crystal structure and its tautomeric form in the solid state were hitherto unknown. Leucopterin turned out to be a variable hydrate, with 0.5 to about 0.1 molecules of water per leucopterin molecule. Under ambient conditions, the preferred state is the hemihydrate. Initially, all attempts to grow single crystals suitable for X-ray diffraction were to no avail. Attempts to determine the crystal structure by powder diffraction using the direct-space method failed, because the trials did not include the correct, but rare, space group P2/c. Attempts were made to solve the crystal structure by a global fit to the pair distribution function (PDF-Global-Fit), as described by Prill and co-workers [Schlesinger et al. (2021). J. Appl. Cryst. 54, 776-786]. The approach worked well, but the correct structure was not found, because again the correct space group was not included. Finally, tiny single crystals of the hemihydrate could be obtained, which allowed at least the determination of the crystal symmetry and the positions of the C, N and O atoms. The tautomeric state of the hemihydrate was assessed by multinuclear solid-state NMR spectroscopy. 15N CPMAS spectra showed the presence of one NH2 and three NH groups, and one unprotonated N atom, which agreed with the 1H MAS and 13C CPMAS spectra. Independently, the tautomeric state was investigated by lattice-energy minimizations with dispersion-corrected density functional theory (DFT-D) on 17 different possible tautomers, which also included the prediction of the corresponding 1H, 13C and 15N chemical shifts in the solid. All methods showed the presence of the 2-amino-3,5,8-H tautomer. The DFT-D calculations also confirmed the crystal structure. Heating of the hemihydrate results in a slow release of water between 130 and 250 °C, as shown by differential thermal analysis and thermogravimetry (DTA-TG). Temperature-dependent powder X-ray diffraction (PXRD) showed an irreversible continuous shift of the reflections upon heating, which reveals that leucopterin is a variable hydrate. This observation was also confirmed by PXRD of samples obtained under various synthetic and drying conditions. The crystal structure of a sample with about 0.2 molecules of water per leucopterin was solved by a fit with deviating lattice parameters (FIDEL), as described by Habermehl et al. [Acta Cryst. (2022), B78, 195-213]. A local fit, starting from the structure of the hemihydrate, as well as a global fit, starting from random structures, were performed, followed by Rietveld refinements. Despite dehydration, the space group remains P2/c. In both structures (hemihydrate and variable hydrate), the leucopterin molecules are connected by 2-4 hydrogen bonds into chains, which are connected by further hydrogen bonds to neighbouring chains. The molecular packing is very efficient. The density of leucopterin hemihydrate is as high as 1.909 kg dm-3, which is one of the highest densities for organic compounds consisting of C, H, N and O only. The high density might explain the good light-scattering and opacity properties of the wings of Pieris brassicae and other butterflies.

Absence of magnetostriction and transition from rapid positive thermal expansion to negative thermal expansion at high temperatures in Sm0.5Y0.5Fe0.58Mn0.42O3 – A synchrotron X-ray diffraction study

X-ray photoemission spectroscopic (XPS) studies and temperature dependent synchrotron X-ray diffraction (SXRD) investigation have been conducted on polycrystalline samples of Sm0.5Y0.5Fe0.58Mn0.42O3 [SYFM (58-42)]. Room temperature XPS measurements revealed the mixed valance of the Fe and Mn ions along with the traces of oxygen vacancies in the material. The room temperature synchrotron X-ray diffraction (SXRD) of specimen shows the monophasic nature of the prepared composition, without the presence of any magnetic or non-magnetic impurity phases. SXRD measurements at variable temperatures between 298 and 873 K, indicates the absence of magnetostriction in the specimen at the magnetic transition temperatures TSR1 ≈ 348 K, TSR2 ≈ 300 K and TN ≈ 361 K. At much higher temperatures above TN, an anisotropic rapid positive thermal expansion (RPTE) to negative thermal expansion (NTE) of the a lattice parameter of the unit cell is further revealed for T > 573 K. The anomalous variation of phonons, are suggested to give rise to anomalous thermal variation in a lattice parameter of the specimen.

Mesomorphism and luminescence in coordination compounds and ionic salts based on pyridine-functionalized β-diketones. Influence of the pyridine nitrogen position

Pyridine-functionalized β-diketones with the pyridine nitrogen atom at 3 or 4 position (L3N and L4N, respectively) have been used as building blocks to obtain two new families of compounds with mesomorphic and luminescent behaviors. The N-pyridine coordination of the β-diketones to zinc(II), palladium(II) and platinum(II) metal centers has allowed to synthesize neutral coordination compounds of the type [MCl2(LZN)2] (M = Zn(II), Pd(II), Pt(II); Z = 3, 4). Particularly, coordination of L4N towards Pt(II) gives rise to the cationic species [Pt(NH3)2(L4N)2]2+. Otherwise, protonation of the pyridine moiety was strategically used to obtain a novel series of pyridinium ionic salts of the type (HLZN)nA (n = 1, A = Cl; n = 2, A = MCl4, M = Zn(II), Pd(II), Pt(II); Z = 3, 4). The neutral or ionic nature of the complexes, as well as the β-diketone ligands and the metal center in both the neutral and anionic complexes, has a great influence on the mesomorphic behavior. Thus, columnar or smectic mesophases can be selectively formed. Single-crystal and temperature-dependent powder X-ray diffraction studies have been performed to analyze the molecular packing in the crystal and the supramolecular ordering in the mesophase. All the aforementioned factors also play a key role on the luminescence properties, the Zn(II) coordination compounds and ionic salts being the best candidates as bifunctional materials.

Simultaneous Thermal Enhancement of Upconversion and Downshifting Luminescence by Negative Thermal Expansion in Nonhygroscopic ZrSc(WO4)2PO4:Yb/Er Phosphors.

Thermal quenching (TQ) is still a critical challenge for lanthanide (Ln3+)-doped luminescent materials. Herein, we report the novel negative thermal expansion nonhygroscopic phosphor ZrSc(WO4)2PO4:Yb3+/Er3+. Upon excitation with a 980 nm laser, a simultaneous thermal enhancement is realized on upconversion (UC) and downshifting (DS) emissions from room temperature to 573 K. In situ temperature-dependent X-ray diffraction and photoluminescence dynamics are used to reveal the luminescence mechanism in detail. The coexistence of the high energy transfer efficiency and the promoted radiative transition probability can be responsible for the thermally enhanced luminescence. On the basis of the luminescence intensity ratio of thermally coupled energy levels 2H11/2 and 4S3/2 at different temperatures, the relative and absolute sensitivities of the targeted samples reach 1.10% K-1 and 1.21% K-1, respectively, and the low-temperature uncertainty is approximately 0.1-0.4 K on the whole temperature with a high repeatability (98%). Our findings highlight a general approach for designing a hygro-stable, thermostable, and highly efficient Ln3+-doped phosphor with UC and DS luminescence.

Control of Thermal Expansion in TaVO5 by Double Chemical Substitution.

The control of thermal expansion is an important and challenging issue. Focusing attention on the class of AMO5 negative thermal expansion (NTE) materials, an approach to control their thermal expansion is still missing. In this work, the thermal expansion of TaVO5 has been controlled from strong negative to zero to positive by double chemical substitution, i.e., Ti and Mo replace Ta and V elements, respectively. A joint study of temperature-dependent X-ray diffraction, X-ray photoelectron spectroscopy, and first-principles calculations has been performed to investigate the thermal expansion mechanism. With the increasing substitution of Ti and Mo atoms, the valence state always remains balanced, and the volume decreases together with a lattice distortion, which leads to the suppression of the NTE. Lattice dynamics calculations confirm that the negative Grüneisen parameters of the low-frequency modes weaken and the thermal vibrations of the polyhedral units diminish after the substitution of Ti and Mo atoms. The present work successfully achieves a tailored thermal expansion in TaVO5 and draws a possible way to control the thermal expansion of other NTE materials.

Negative Thermal Expansion Caused by the Antiferroelectric Phase Transition in Lead-Free Perovskite Ceramics

Due to the structural stability and high adjustability of perovskite, lead-free perovskite ceramics are widely thought to be one of the most promising functional materials. In this work, an abnormal negative thermal expansion behavior with a linear expansion coefficient of −54.95 ppm/K is achieved in the (1-x)NaNbO3-xCaZrO3 system by driving the antiferroelectric phase transition from orthorhombic phase and tetragonal phase. The NTE mechanism is verified by temperature-dependent high-energy synchrotron X-ray diffraction, dielectric spectra, and Raman scattering spectroscopy. The relationship between the antiferroelectric phase transition and negative thermal expansion behavior is systematically revealed by analyzing the evolution of the phase structure with temperature. This novel negative thermal expansion feature caused by the antiferroelectric phase transition provides new guidance for designing more negative thermal expansion materials.

In situ study of the crystallization in GeTe0.26 Se0.74 thick film by synchrotron X-ray diffraction

Crystallization in unencapsulated GeTe0.26Se0.74 amorphous 3 µm-thick films produced by thermal co-evaporation technique was studied by in situ temperature-dependent synchrotron powder X-ray diffraction from room temperature up to 418 °C and back to 30 °C. The experimental results obtained with a continuous heating rate of 2 °C/min under a protective nitrogen atmosphere showed that the crystallization process took place in several steps i) total crystallization of the amorphous phase to an intermediate crystallized phase, (ii) total transformation of the intermediate phase to a second crystallized phase. The intermediate phase corresponds to a solid solution with a metastable α-GeTe-like rhombohedral polar structure (R3m) presenting a uniaxial negative thermal expansion along the c-axis. The onset of crystallization to the polar structure is around 270 °C. The high-temperature phase has a stable hexagonal structure with a P63mc space group. When cooling, until back to room temperature, the hexagonal structure is conserved. The effect of a changing heating rate from 2° to 0.1°C/ min was also investigated. In this context, the crystallization scheme is modified.

Low-temperature synthesis of crystalline vanadium oxide films using oxygen plasmas

Vanadium oxide (VOx) compounds feature various polymorphs, including V2O5 and VO2, with attractive temperature-tunable optical and electrical properties. However, to achieve the desired material property, high-temperature post-deposition annealing of as-grown VOx films is mostly needed, limiting its use for low-temperature compatible substrates and processes. Herein, we report on the low-temperature hollow-cathode plasma-enhanced atomic layer deposition (ALD) of crystalline vanadium oxide thin films using tetrakis(ethylmethylamido)vanadium and oxygen plasma as a precursor and coreactant, respectively. To extract the impact of the type of plasma source, VOx samples were also synthesized in an inductively coupled plasma-enhanced ALD reactor. Moreover, we have incorporated in situ Ar-plasma and ex situ thermal annealing to investigate the tunability of VOx structural properties. Our findings confirm that both plasma-ALD techniques were able to synthesize as-grown polycrystalline V2O5 films at 150 °C. Postdeposition thermal annealing converted the as-grown V2O5 films into different crystalline VOx states: V2O3, V4O9, and VO2. The last one, VO2 is particularly interesting as a phase-change material, and the metal-insulator transition around 70 °C has been confirmed using temperature-dependent x-ray diffraction and resistivity measurements.

Magnetoelastic Coupling and Cryogenic Magnetocaloric Effect in Two-Site Disordered GdSrCoFeO6 Double Perovskite

The development of new magnetic refrigerants demands an effective investigation of materials with a large magnetocaloric effect in a wide temperature range. Herein, we report on the structural, magnetic, and magnetocaloric properties of the two-site disordered double perovskite GdSrCoFeO6 prepared by the modified solid-state synthesis method. Temperature-dependent synchrotron X-ray diffraction analysis revealed that GdSrCoFeO6 crystallizes in the orthorhombic phase (Pnma), with Gd3+/Sr2+ and Co2+/3+/Fe3+/4+ ions randomly distributed on the A- and B-sites, respectively. An observed lattice parameter anomaly around 60 K indicates the occurrence of the magnetoelastic coupling, which coincides with the presence of ferro/ferrimagnetic (FM/FiM) ordering below TC ≈ 65 K from the magnetic measurements. These results match well with our first-principles calculation prediction of low-temperature magnetic (FM/FiM) and electronic (insulating/metal) transitions related to a combined effect of Co and Fe short- and long-range competitions, crossings of spin state at Co ions, and the hybridization degree between Gd-4f and Co-3d states. Additionally, a modified Arrott plot and Kouvel–Fisher analysis were used to establish the nature of the magnetic phase transition in GdSrCoFeO6, yielding the critical exponent β = 1.46(6)/1.45(6), γ = 1.48(5)/1.17(2), and δ = 2.01(3)/1.80(5), respectively. The specific heat analysis reveals two well-defined broad peaks (∼10 and ∼70 K), which match well with a Schottky anomaly (Gd-4f) and the magnetic transition of FM/FiM to paramagnetic order, respectively. The magnetocaloric effect (MCE) analysis reveals a maximum magnetic entropy change ΔSMmax ≈ 13 J kg–1 K–1 (at ∼8 K) under a field of 0–7 T. These results evidence that the Schottky anomaly and the magnetoelastic coupling seem to be key factors for driving further enhancements to the MCE in GdSrCoFeO6, making it a possible candidate for cryogenic applications.

Asymmetric rotations and dimerization driven by normal to modulated phase transition in 4-biphenylcarboxy coupled L-phenylalaninate.

Amongst the derivatives of 4-biphenylcarboxylic acid and amino acid esters, the crystal structure of 4-biphenylcarboxy-(L)-phenylalaninate is unusual owing to its monoclinic symmetry within a pseudo-orthorhombic crystal system. The distortion is described by a disparate rotational property around the chiral centers (ϕchiral ≃ -129° and 58°) of the two molecules in the asymmetric unit. Each of these molecules comprises planar biphenyl moieties (ϕbiphenyl = 0°). Using temperature-dependent single-crystal X-ray diffraction experiments we show that the compound undergoes a phase transition below T ∼ 124 K that is characterized by a commensurate modulation wavevector, q = δ(101), δ = ½. The (3+1)-dimensional modulated structure at T = 100 K suggests that the phase transition drives the biphenyl moieties towards noncoplanar conformations with significant variation of internal torsion angle (ϕmaxbiphenyl ≤ 20°). These intramolecular rotations lead to dimerization of the molecular stacks that are described predominantly by distortions in intermolecular tilts (θmax ≤ 20°) and small variations in intermolecular distances (Δdmax ≃ 0.05 Å) between biphenyl molecules. Atypical of modulated structures and superstructures of biphenyl and other polyphenyls, the rotations of individual molecules are asymmetric (Δϕbiphenyl ≈ 5°) while ϕbiphenyl of one independent molecule is two to four times larger than the other. Crystal-chemical analysis and phase relations in superspace suggest multiple competing factors involving intramolecular steric factors, intermolecular H-C...C-H contacts and weak C-H...O hydrogen bonds that govern the distinctively unequal torsional properties of the molecules.

Structural, magnetic and magnetocaloric properties of hexagonal MnCoGe-based thin films

The characteristic size of the magnetocaloric materials in magnetic refrigerators, thermomagnetic regenerators and energy harvesters is usually down to micrometer and nanometer length scales, which provides the largest possible contact surface area to the heat transfer liquid. Therefore, it is pivotal to investigate the structural, magnetic and magnetocaloric properties of magnetocaloric materials at micrometer and nanometer length scales. In the present study, we have successfully fabricated MnCoGe-based thin films using the pulsed laser deposition (PLD) technique. The as-deposited film shows a dense surface, homogeneous chemical distribution and a preferred orientation along the c-axis of the hexagonal Ni2In-type structure. In-situ temperature-dependent X-ray diffraction measurements on the as-deposited films reveal an irreversible structural degradation above 300 °C due to the considerable evaporation of the Mn atoms, which causes the formation of microscale pores in the films. The thermomagnetic behavior of the film annealed at 250 °C displays a reversible second-order ferromagnetic transition of the hexagonal phase at Curie temperature TC = 275 K, and a first-order hexagonal-orthorhombic structural transition below 200 K. The decoupling of the magnetic and structural transitions brings reversible magnetocaloric effect with the entropy change ΔS values of 2.5 J/(kgK) and the refrigeration capacity reaching 89 J/kg in Δμ0H = 5 T, which are comparable to other reported magnetocaloric thin films. Moreover, antiferromagnetic coupling in the low-temperature orthorhombic phase was observed, which has rarely been reported in the MnCoGe-based bulk alloys. The different magnetic ground states between the thin film and the bulk alloys may be originated from the strain effect imposed by the Al2O3 substrate. Consequently, this work not only provides insights into the structural, magnetic and magnetocaloric properties of the MnCoGe-based alloys at a nanometer length scale, but also offers a new idea for tailoring the multifunctional properties for this material family.

Fabrication and Properties of Epitaxial VO2 Thin Film on m-Al2O3 Substrate

A thin film of thermochromic VO2 was prepared on m-Al2O3 substrate using a radio frequency (RF) magnetron sputtering technique. The epitaxial growth of the monoclinic M1 phase of VO2 on the m-Al2O3 substrate was confirmed through synchrotron X-ray diffraction (XRD) measurements. The transformation of this monoclinic M1 phase into a rutile phase at ~68 °C was reflected in the temperature-dependent XRD measurements of the VO2 thin film. The temperature-dependent electrical resistance measurements of this sample also revealed an abrupt metal-to-insulator transition at ~68 °C, which is reversible in nature. Temperature-dependent X-ray absorption (XAS) measurements at V L-edge and O K-edge were performed to study the electronic structure of the epitaxial VO2/m-Al2O3 thin film during the metal-to-insulator (MIT) transition.

Temperature-Dependent Reversible Optical Properties of Mn-Based Organic–Inorganic Hybrid (C8H20N)2MnCl4 Metal Halides

Organic-inorganic metal halides (OIMHs) have abundant optical properties and potential applications, such as light-emitting diodes, displays, solar cells, and photodetectors. Herein, we report zero-dimensional Mn-based OIMH (C8H20N)2MnCl4 single crystals synthesized by a simple slow evaporation method, which exhibit intense green emission at 520 nm originating from 4T1-6A1 transition of Mn2+ ions. Large organic cations in the crystal structure result in the isolated [MnCl4]2- tetrahedrons, and the closest Mn-Mn distance reaches 9.07 Å, which effectively inhibits the migration of excitation energy between adjacent Mn2+ emission centers, thus achieving a high quantum yield (∼87%) and a long photoluminescence (PL) lifetime (3.42 ms). The different optical and structural properties at low and high temperatures are revealed by temperature-dependent PL and X-ray diffraction spectra. The PL spectra and lifetimes under the heating and cooling processes indicate that the optical property transitions are reversible at 220/240 K. Our work provides a promising strategy for building multifunctional optoelectronic materials and insights into the understanding convertible photophysical properties from isomers of metal halides.

A Melt-Quenched Luminescent Glass of an Organic-Inorganic Manganese Halide as a Large-Area Scintillator for Radiation Detection.

Glass is a group of materials with appealing qualities, including simplicity in fabrication, durability, and high transparency, and they play a crucial role in the optics field. In this paper, a new organic-inorganic metal halide luminescent glass exhibiting >78 % transmittance at 506-800 nm range together with a high photoluminescence quantum yield (PLQY) of 28.5 % is reported through a low-temperature melt-quenching approach of pre-synthesized (HTPP)2 MnBr4 (HTPP=hexyltriphenylphosphonium) single crystal. Temperature-dependent X-ray diffraction, polarizing microscopy, and molecular dynamics simulations were combined to investigate the glass-crystal interconversion process, revealing the disordered nature of the glassy state. Benefiting from the transparent nature, (HTPP)2 MnBr4 glass yields an outstanding spatial resolution of 10 lp mm-1 for X-ray imaging. The superb optical properties and facility of large-scale fabrication distinguish the organic-inorganic metal halide glass as a highly promising class of materials for optical devices.