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A bit more than a decade after the first report of ferroelectric switching in hafnium dioxide-based ultrathin layers, this family of materials continues to elicit interest. There is ample consensus that the observed switching does not obey the same mechanisms present in most other ferroelectrics, but its exact nature is still under debate. Next to this fundamental relevance, a large research effort is dedicated to optimizing the use of this extraordinary material, which already shows direct integrability in current semiconductor chips and potential for scalability to the smallest node architectures, in smaller and more reliable devices. Here we present a perspective on how, despite our incomplete understanding and remaining device endurance issues, the lessons learned from hafnium dioxide-based ferroelectrics offer interesting avenues beyond ferroelectric random-access memories and field-effect transistors. We hope that research along these other directions will stimulate discoveries that, in turn, will mitigate some of the current issues. Extending the scope of available systems will eventually enable the way to low-power electronics, self-powered devices and energy-efficient information processing.

Over the past few decades, telluride-based chalcogenide multilayers, such as PbSeTe/PbTe, Bi2Te3/Sb2Te3, and Bi2Te3/Bi2Se3, were shown to be promising high-performance thermoelectric films. However, the stability of performance in operating environments, in particular, influenced by intermixing of the sublayers, has been studied rarely. In the present work, the nanostructure, thermal stability, and thermoelectric power factor of Sb2Te3/Ge1+xTe multilayers prepared by pulsed laser deposition are investigated by transmission electron microscopy and Seebeck coefficient/electrical conductivity measurements performed during thermal cycling. Highly textured Sb2Te3 films show p-type semiconducting behavior with superior power factor, while Ge1+xTe films exhibit n-type semiconducting behavior. The elemental mappings indicate that the as-deposited multilayers have well-defined layered structures. Upon heating to 210 °C, these layer structures are unstable against intermixing of sublayers; nanostructural changes occur on initial heating, even though the highest temperature is close to the deposition temperature. Furthermore, the diffusion is more extensive at domain boundaries leading to locally inclined structures there. The Sb2Te3 sublayers gradually dissolve into Ge1+xTe. This dissolution depends markedly on the relative Ge1+xTe film thickness. Rather, full dissolution occurs rapidly at 210 °C when the Ge1+xTe sublayer is substantially thicker than that of Sb2Te3, whereas the dissolution is very limited when the Ge1+xTe sublayer is substantially thinner. The resulting variations of the nanostructure influence the Seebeck coefficient and electrical conductivity and thus the power factor in a systematic manner. Our results shed light on a previously unreported correlation of the power factor with the nanostructural evolution of unstable telluride multilayers.

Given their comparatively narrow band gap, mixed Pb–Sn iodide perovskites are interesting candidates for bottom cells in all-perovskite tandems or single junction solar cells, and their luminescence around 900 nm offers great potential for near-infrared optoelectronics. Here, we investigate mixed FAPb1–xSnxI3 offering the first accurate determination of the crystal structure over a temperature range from 293 to 100 K. We demonstrate that all compositions exhibit a cubic structure at room temperature and undergo at least two transitions to lower symmetry tetragonal phases upon cooling. Using density functional theory (DFT) calculations based on these structures, we subsequently reveal that the main impact on the band gap bowing is the different energy of the s and p orbital levels derived from Pb and Sn. In addition, this energy mismatch results in strongly composition-dependent luminescence characteristics. Whereas neat and Sn-rich compounds exhibit bright and narrow emission with a clean band gap, Sn-poor compounds intrinsically suffer from increased carrier recombination mediated by in-gap states, as evidenced by the appearance of pronounced low-energy photoluminescence upon cooling. This study is the first to link experimentally determined structures of FAPb1–xSnxI3 with the electronic properties, and we demonstrate that optoelectronic applications based on Pb–Sn iodide compounds should employ Sn-rich compositions., ACS Applied Materials & Interfaces, 14 (30), ISSN:1944-8244, ISSN:1944-8252

Magnetic skyrmions, swirling two-dimensional spin textures, are potential candidates for magnetic data storge applications such as racetrack memories, information carriers in spin-logic devices and artificial neurons or synapses in neuromorphic applications. In this thesis various layered materials are investigated for their potential to stabilize magnetic skyrmions by means of magnetic frustration. Theoretical physicists predict that skyrmions by means of magnetic frustration possess even better properties for potential applications than currently known skyrmions. Skyrmions stabilized by way of magnetic frustration are not deflected to one side when moving through a material and can be an order of magnitude smaller. In this thesis structural and magnetic research methods such as single crystal x-ray diffraction and SQUID magnetometry are used to search for magnetic signatures of these type of magnetic skyrmions in various layered materials.

Electronic conduction along individual domain walls (DWs) has been reported in BiFeO$_3$ (BFO) and other nominally insulating ferroelectrics. DWs in these materials separate regions of differently oriented electrical polarization (domains) and are just a few atoms wide, providing self-assembled nanometric conduction paths. In this work, it is shown that electronic transport is possible also from wall to wall through the dense network of as-grown DWs in BFO thin films. Electric field cycling at different points of the network, performed locally by conducting atomic force microscope (cAFM), induces resistive switching selectively at the DWs, both for vertical (single wall) and lateral (wall-to-wall) conduction. These findings are the first step towards investigating DWs as memristive networks for information processing and in-materio computing.

The breaking of inversion symmetry can enhance the multifunctional properties of layered hybrid organic–inorganic perovskites. However, the mechanisms by which inversion symmetry can be broken are not well-understood. Here, we study a series of MnCl4-based 2D perovskites with arylamine cations, namely, (C6H5CxH2xNH3)2MnCl4 (x = 0, 1, 2, 3), for which the x = 0, 1, and 3 members are reported for the first time. The compounds with x = 1, 2, and 3 adopt polar crystal structures to well above room temperature. We argue that the inversion symmetry breaking in these compounds is related to the rotational degree of freedom of the organic cations, which determine the hydrogen bonding pattern that links the organic and inorganic layers. We show that the tilting of MnCl6 octahedra is not the primary mechanism involved in inversion symmetry breaking in these materials. All four compounds show 2D Heisenberg antiferromagnetic behavior. A ferromagnetic component develops in each case below the long-range magnetic ordering temperature of ∼42–46 K due to spin canting., We study a series of MnCl4-based 2D perovskites with arylamine cations: (C6H5CxH2xNH3)2MnCl4 (x = 0, 1, 2, 3). The compounds with x = 1, 2 and 3 adopt polar crystal structures to well above room temperature. The inversion symmetry breaking in these compounds is driven by the rotational degree of freedom of the organic cations, which determine the hydrogen bonding pattern that links the organic and inorganic layers.

While network formation is prevalent in nature, networks are generally not expected in inorganic structures. Exceptions are those cases in which surface states become important, such as nanoparticles. However, even in these cases, the morphology of these networks is difficult to control and they show a large degree of disorder. In this work, we show that highly ordered and interconnected nanoscale networks of functional metal oxides can be fabricated by a combination of polymer imprinting and polymer templating through solution processable methods. We report the fabrication of a number of functional oxide networks (i.e., BiFeO3, SrTiO3, La0.7Ca0.3MnO3, and HfO2) from solution, showing that all the oxide materials tried so far are able to follow the self-assembled network morphology dictated by the polymer structure. These networks were characterized for the overall structure by scanning electron microscopy and atomic force microscopy (AFM). Grazing incidence small angle X-ray scattering showed a good imprint quality on the mm2 scale for the combined networks, which is challenging given that multiple processing steps were involved during the fabrication. The material stoichiometries were investigated by X-ray photoemission spectroscopy and the crystal phases by grazing incidence wide angle X-ray scattering. When electronic functionality is anticipated, the networks behave as expected: conducting AFM on the La0.7Ca0.3MnO3 networks confirmed the conductive character of this composition; and piezoresponse force microscopy of the BiFeO3 network is consistent with the presence of ferroelectric behavior. These nanoscale networks show promise for future applications in adaptable electronics, such as neuromorphic computing or brain-inspired information processing.

Bi2Te3-based alloys are known to have outstanding thermoelectric properties. Although structure-property relations have been studied, still, detailed analysis of the atomic and nano-scale structure of Bi2Te3 thin film in relation to their thermoelectric properties remains poorly explored. Herein, highly-textured (HT) and single-crystal-like (SCL) Bi2Te3 films have been grown using pulsed laser deposition (PLD) on Si wafer covered with (native or thermal) SiOx and mica substrates. All films are highly textured with c-axis out-of-plane, but the in-plane orientation is random for the films grown on oxide and single-crystal-like for the ones grown on mica. The power factor of the film on thermal oxide is about four times higher (56.8 mu W.cm(-1).K-2) than that of the film on mica (12.8 mu W.cm(-1).K-2), which is comparable to the one of the polycrystalline ingot at room temperature (RT). Reduced electron scattering in the textured thin films results in high electrical conductivity, where the SCL film shows the highest conductivity. However, its Seebeck coefficient shows a low value. The measured properties are correlated with the atomic structure details unveiled by scanning transmission electron microscopy. For instance, the high concentration of stacking defects observed in the HT film is considered responsible for the increase of Seebeck coefficient compared to the SCL film. This study demonstrates the influence of nanoscale structural effects on thermoelectric properties, which sheds light on tailoring thermoelectric thin films towards high performance.

So far, a few chemical solution routes for the fabrication of ferroelectric HfO2 films have been reported. Most of them employ precursors, solvents or additives that are considered difficult to handle, unstable, toxic, generally unfriendly with the environment and/or unsuitable for large scale industrial processes. In this work, we present a new effective chemical route for preparation of ferroelectric doped-HfO2 films. The solution is prepared from simple, stable, and available precursors, handled in an open atmosphere and requires no restrictive processing conditions. We used 5 at.% Ca as dopant of HfO2 to induce a maximum remnant polarization of 9.3 and 11.1 µC/cm2 for 54 and 90 nm thick Ca:HfO2 films, respectively. The current-electric field loops show intense and distinctive ferroelectric switching peaks and the corresponding ferroelectric loops show excellent saturation, which speaks of good device quality with low leakage. Crystallization and the wake-up of ferroelectricity in Ca:HfO2 films was attained by means of rapid thermal annealing at different temperatures and times in Ar:O2 atmosphere. In comparison to the thin films, thicker ones exhibited the highest remnant polarization at shorter annealing times, thus evidencing the need for precise control of thermal processing. The Ca:HfO2 films with thickness of 50 nm displayed a good balance between leakage and retention, maintaining the ferroelectric response above 105 cycles at 1 kHz. The developed precursor solution is promising for its use in spray-coating and ink-jet printing techniques.

Efforts to understand metallic behavior have led to important concepts such as those of strange metals, bad metals, or Planckian metals. However, a unified description of metallic resistivity is still missing. An empirical analysis of a large variety of metals shows that the parallel resistor formalism used in the cuprates, which includes T-linear and T-quadratic dependence of the electron scattering rates, can be used to provide a phenomenological description of the electrical resistivity in all metals, where these two contributions are shown to correspond to the first two terms of a Taylor expansion of the resistivity, detached from their physics origin, and thus valid for any metal. Here, we show that the different metallic classes are then determined by the relative magnitude of these two components and the magnitude of the extrapolated residual resistivity. These two parameters allow us to categorize a few systems that are notoriously hard to ascribe to one of the currently accepted metallic classes. This approach also reveals that the T-linear term has a common origin in all cases, strengthening the arguments that propose the universal character of the Planckian dissipation bound., Q.G. acknowledges financial support from a China Scholarship Council (CSC) grant and Q.G. and B.N. acknowledge financial support from CogniGron and the Ubbo Emmius Funds (University of Groningen).

Developing materials that can lead to compact versions of artificial neurons (neuristors) and synapses (memristors) is the main aspiration of the nascent neuromorphic materials research field. Oscillating circuits are interesting as neuristors, as they emulate the firing of action potentials. Here we present room-temperature self-oscillating devices fabricated from epitaxial thin films of semiconducting TbMnO3. We show that the negative differential resistance regime observed in these devices, orginates from transitions across the electronic band gap of the semiconductor. The intrinsic nature of the mechanism governing the oscillations gives rise to a high degree of control and repeatability. Obtaining such properties in an epitaxial perovskite oxide opens the way towards combining self-oscillating properties with those of other piezoelectric, ferroelectric, or magnetic perovskite oxides in order to achieve hybrid neuristor-memristor functionality in compact heterostructures.

Incomplete cancellation of collinear antiparallel spins gives rise to ferrimagnetism. Even if the oppositely polarized spins are owing to the equal number of a single magnetic element having the same valence state, in principle, a ferrimagnetic state can still arise from the crystallographic inequivalence of the host ions. However, experimental identification of such a state as "ferrimagnetic"is not straightforward because of the often tiny magnitude expected for M and the requirement for a sophisticated technique to differentiate similar magnetic sites. We report a synchrotron-based resonant x-ray investigation at the Fe L2,3 edges on an epitaxial film of CaFe2O4, which exhibits two magnetic phases with similar energies. We find that while one phase of CaFe2O4 is antiferromagnetic, the other one is ferrimagnetic with an antiparallel arrangement of an equal number of spins between two distinct crystallographic sites with very similar local coordination environments. Our results further indicate two distinct origins of an overall minute M; one is intrinsic, from distinct Fe3+ sites, and the other one is extrinsic, arising from defective Fe2+ likely forming weakly coupled ferrimagnetic clusters. These two origins are uncorrelated and have very different coercive fields. Hence, this work provides a direct experimental demonstration of ferrimagnetism solely due to crystallographic inequivalence of the Fe3+ as the origin of the weak M of CaFe2O4., The resonant x-ray diffraction experiments were performed at the X11MA beamline in the Swiss Light Source under Proposal No. 20191307 and at the BL17SU in the SPring-8 under Proposal No. 20200012. The x-ray magnetic circular dichroism measurements were performed at the XTreme beamline in the Swiss Light Source during in-house access. H.U. acknowledges the National Centers of Competence in Research in Molecular Ultrafast Science and Technology (NCCR Grant MUST-No. 51NF40-183615) from the Swiss National Science Foundation and from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie Grant Agreement No. 801459–FP-RESOMUS. E.S. is supported by the NCCR Materials’ Revolution: Computational Design and Discovery of Novel Materials (NCCR MARVEL Grant No. 182892) from Swiss National Foundation and the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie Grant Agreement No. 884104 (PSI-FELLOW-III-3i). N.O.H. acknowledges financial support of the Swiss National Science Foundation, Grant No. 200021_169017. M.B. is supported by the Swiss National Science Foundation through Projects No. 200021-196964 and 200021_169698, respectively. Financial support by the Groningen Cognitive Systems and Materials Center (CogniGron) and the Ubbo Emmius Funds of the University of Groningen is also gratefully acknowledged, With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).

Aurivillius phase Bi2LaNb1.5Mn0.5O9, derived from ferroelectric PbBi2Nb2O9 by simultaneous substitution of the A-site and B-site cations, was synthesized using a molten-salt method. Here, we discuss the structure-property relationships in detail. X-ray and neutron diffraction show that Bi2LaNb1.5Mn0.5O9 adopts an A21am orthorhombic crystal structure. Rietveld refinement analysis, supported by Raman spectroscopy, indicates that the Bi3+ ions occupy the bismuth oxide blocks, La3+ ions occupy the perovskite A-site, and Nb5+/Mn3+ ions occupy the perovskite B-site. Ferroelectric ordering takes place at 535 K, which coexists with local ferromagnetic order below 65 K. The cation disorder on the B-site results in relaxor-ferroelectric behavior, and the short-range ferromagnetic order can be attributed to Mn3+/Mn4+ double-exchange. Magnetodielectric coupling measured at 5 K and 100 kHz in a field of 5 T suggests the existence of intrinsic spin-lattice coupling with a magnetodielectric coefficient of 0.20%. These findings will provide significant impetus for further research into potential devices based on the magnetodielectric effect in Aurivillius materials.

CaFe2O4 is a uniaxial antiferromagnet displaying two coexisting magnetic orderings, A and B, characterized by ↑↑↓↓ and ↑↓↑↓ spin modulation, respectively, and the emergence of a net magnetization in a limited temperature range, which is not yet understood. The spin Hall magnetoresistance (SMR) is probed at the interface between Pt and CaFe2O4 and the crystallographic domain structure of thin film samples is exploited to perform single- and multi-domain scale measurements. The SMR response, upon rotating the magnetic field along three orthogonal planes, shows little effect of the strong magnetocrystalline and shape anisotropies. Together with the response to a varying magnetic field strength, the modulations in the SMR signal allow to extract two contributions: one corresponds to the long-range antiferromagnetic ordering, supporting a single ground state scenario; while the second contribution originates from uncompensated, non-interacting spins. These are expected to exist at the antiphase boundaries between antiferromagnetic domains. Here, it is shown that these are also uncoupled from the antiferromagnetic ordering. Nonetheless, the long range correlations that emerge in the proximity of the critical antiferromagnetic transition can give rise to ordering of the uncompensated spins and be responsible for the net magnetization observed in this antiferromagnet.

Metastable single crystals of nonstoichiometric Pb1-xTe are obtained by rapid cooling from the melt. The composition and crystallographic morphology are studied using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and electron backscatter diffraction. Most single crystals have cubic, pyramidal, or hemispherical shapes with sizes ranging from 50 to 400 mu m. All crystals adopt the same face-centered cubic rock salt structure, and the crystal growth direction is . The bulk part of the rapidly cooled material solidifies in the form of a Te-rich polycrystalline material in which grains are separated by the PbTe-Te eutectic phase. The stabilization of nonstoichiometric Pb1-xTe provides further scope for the optimization of lead telluride-based thermoelectric materials.

Germanane (GeH), a germanium analogue of graphane, has recently attracted considerable interest because its remarkable combination of properties makes it an extremely suitable candidate to be used as 2D material for field effect devices, photovoltaics, and photocatalysis. Up to now, the synthesis of GeH has been conducted by substituting Ca by H in a β‐CaGe2 layered Zintl phase through topochemical deintercalation in aqueous HCl. This reaction is generally slow and takes place over 6 to 14 days. The new and facile protocol presented here allows to synthesize GeH at room temperature in a significantly shorter time (a few minutes), which renders this method highly attractive for technological applications. The GeH produced with this method is highly pure and has a band gap (E g) close to 1.4 eV, a lower value than that reported for germanane synthesized using HCl, which is promising for incorporation of GeH in solar cells., Germanane was synthesized by topotatic deintercalation of β‐CaGe2 in aqueous HF solution at room temperature under stirring for 2‐3 minutes. In order to remove the residual CaF2 the material was treated with a saturated aqueous solution of EDTA.

Intensive studies have been carried out over the past decade to identify nanostructured thermoelectric materials that allow the efficient conversion of waste heat to electrical power. However, less attention has been paid to the stability of such materials under operating temperatures, typically 400 degrees C or higher. Conventionally nanostructured ceramics tend to undergo grain growth at high temperature, lowering the density of interfaces and raising the thermal conductivity, which is detrimental to device performance. Therefore it is preferable to identify materials with stable nanostructures, for example systems that undergo spontaneous phase separation. Here we investigate PbTe-GeTe alloys, in which spinodal decomposition occurs on initial cooling from above 580 degrees C, forming complex nanostructures consisting of Ge-rich and Pb-rich domains on different size scales. The resulting dense arrangement of interfaces, combined with mass fluctuation associated with Pb-Ge mixing, enhances phonon scattering and strongly reduces the thermal conductivity. Here we focus on the nominal composition Pb0.49Ge0.51Te and show that by tuning the synthesis procedure, we are able to control the pattern of compositional domains and the density of interfaces between them. This allows low lattice thermal conductivities to be maintained even after thermal cycling over the operating temperature range.

(Formula presented.) single crystals are grown with an optimized chemical vapor transport technique using (Formula presented.) as a transport agent (TA). The optimized growth method allows to selectively produce large high-quality single crystals. The method is shown to consistently produce (Formula presented.) crystals of maximum size 8 × 7 × 4 mm with a transport duration of around three weeks. It is found that this method, with (Formula presented.) as TA, is more efficient and simple compared with the commonly used growth techniques reported in literature with HCl gas as TA. The (Formula presented.) crystals have very high quality and their absolute structures are fully determined by simple single-crystal X-ray diffraction. Enantiomeric crystals with either left- or right-handed chiralities are observed. The magnetization and ferromagnetic resonance data show the same magnetic phase diagram as reported earlier.

To explore the role of Li in establishing room-temperature ferromagnetism in SnO2, the structural, electronic and magnetic properties of Li-doped SnO(2)compounds were studied for different size regimes, from nanoparticles to bulk crystals. Li-doped nanoparticles show ferromagnetic ordering plus a paramagnetic contribution for particle sizes in the range of 16-51 nm, while pure SnO(2)and Li-doped compounds below and above this particular size range are diamagnetic. The magnetic moment is larger for compositions where the Li substitutes for Sn than for compositions where Li prevalently occupies interstitial sites. The observed ferromagnetic ordering in Li-doped SnO(2)nanoparticles is mainly due to the holes created when Li substitutes at a Sn site. Conversely, Li acts as an electron donor and electrons from Li may combine with holes to decrease ferromagnetism when lithium mainly occupies interstitial sites in the SnO(2)lattice.

The double-layer Aurivillius phase Pb0.4Bi2.1La0.5Nb1.7Mn0.3O9 was synthesized by a molten salt method using a K2SO4/Na2SO4 flux. The effect on the crystal structure, morphology, dielectric and magnetic properties of varying the molar ratio of the oxide precursors to salt flux was investigated. Single-phase products with an orthorhombic structure were obtained for oxide to salt ratios of between 1:5 and 1:9, whereas for lower concentrations of salt a pyrochlore impurity phase is found in the products. SEM showed anisotropic plate-like grains, the size of which increases for larger salt ratios. An investigation of the magnetic properties showed the presence of mixed Mn3+ and Mn4+; the unit cell volume of the single-phase products decreases as the proportion of salt increases, which implies a higher proportion of smaller Mn4+ cations. This can be explained by the oxide ion donating properties (oxobasicity) of the molten salt mixture, which produces an oxidizing environment during synthesis. The best dielectric properties are obtained for an oxide to salt ratio of 1:7, exhibiting relaxor ferroelectric behavior. This is also the ratio at which the most pronounced ferromagnetic properties are observed, resulting from double-exchange interactions between Mn3+ and Mn4+ the proportions of which are approximately equal. Pb(0.4)Bi(2.1)La(0.5)Nb(1.7)Mn(0.3)O(9 )synthesized under these conditions thus exhibits optimal multiferroic properties.

$$SiO_2$$SiO2with the$$\alpha$$α-quartz structure is one of the most popular piezoelectrics. It is widely used in crystal oscillators, bulk acoustic wave (BAW) devices, surface acoustic wave (SAW) devices, and so on.$$GeO_2$$GeO2can also be crystallized into the$$\alpha$$α-quartz structure and it has better piezoelectric properties, with higher piezoelectric coefficient and electromechanical coupling coefficients, than$$SiO_2$$SiO2. Experiments on bulk crystals and theoretical studies have shown that these properties can be tuned by varying the Si/Ge ratio in the$$Si_xGe_{1-x}O_2$$SixGe1-xO2solid solution. However, to the best of our knowledge, thin films of$$Si_xGe_{1-x}O_2$$SixGe1-xO2quartz have never been reported. Here we present the successful crystallization of$$Si_xGe_{1-x}O_2$$SixGe1-xO2thin films in the$$\alpha$$α-quartz phase on quartz substrates ($$SiO_2$$SiO2) with x up to 0.75. Generally, the films grow semi-epitaxially, with the same orientation as the substrates. Interestingly, the$$Si_{0.75}Ge_{0.25}O_2$$Si0.75Ge0.25O2composition grows fully strained by the quartz substrates and this leads to the formation of circular quartz domains with an ordered Dauphiné twin structure. These studies represent a first step towards the optimization of piezoelectric quartz thin films for high frequency (> 5 GHz) applications.

We present a comprehensive investigation of the magnetic properties of stage-1 graphite intercalated FeCl$_3$ using a combination of DC and AC magnetic susceptibility, thermoremanent magnetization and field dependent magnetization measurements. This van der Waals system, with a centrosymmetric honeycomb lattice, combines frustration and disorder, due to intercalation, and may be hosting topologically non-trivial magnetic phases. Our study identifies two magnetic phase transitions at $T_{f1} \approx $ 4.2 K and at $T_{f2} \approx $ 2.7 K. We find that the paramagnetic state, for $T > T_{f1}$, is dominated by short-range ferromagnetic correlations. These build up well above $T_{f1}$ and lead to a significant change in magnetic entropy, which reaches $��S_M^{Pk} = $ -5.52 J kg$^{-1}$ K$^{-1}$ at 7 T. Between $T_{f1}$ and $T_{f2}$ we observe slow spin dynamics characteristic of a cluster glass-like state, whereas for $T$ $ < $ $T_{f2}$ our results indicate the onset of a low temperature long range ordered state. The analysis of the experimental results leads to a complex phase diagram, which may serve as a reference for future investigations searching for topological non-trivial phases in this system., 12 pages, 8 figures with attached supplemental information PDF of 2 pages and 2 figures

We report on element-resolved ultrafast magnetization dynamics in multiferroic CoCr2O4 and Co0.975Ge0.025Cr2O4 after optical excitation above the electronic band gap. We observe demagnetization dynamics in the range of several picoseconds, up to two orders of magnitude faster than previously reported demagnetization in other ferrimagnetic insulators. Moreover, we find that the dynamics of the two magnetic ions differ significantly just below the Curie point. The dynamics of the low-temperature multiferroic phase are almost two times slower than those in the ferrimagnetic phase. This suggests that the additional magnetic cycloidal component, which is coupled to electric polarization at low temperatures, might influence the ultrafast magnetization dynamics. ISSN:1098-0121 ISSN:0163-1829 ISSN:1550-235X ISSN:0556-2805 ISSN:2469-9969 ISSN:1095-3795 ISSN:2469-9950

Layered organic-inorganic hybrid perovskites have been the focus of much research regarding their optoelectronic and multiferroic properties. Here, we demonstrate the presence of a large magnetocaloric effect in the ferromagnetic layered perovskite phenylmethylammonium copper chloride ((PMA)2CuCl4) below the Curie temperature of ∼9.5 K. We measure a magnetic entropy change ranging from 0.88 J/kg.K to 2.98 J/kg.K in applied fields of 10 kOe and 70 kOe, respectively. We also study the nature of the magnetic phase transition using critical isotherm analysis. The critical exponents are consistent with the 2D-XY spin model.

Memristive systems emerge as strong candidates for the implementation of resistive random access memories and neuromorphic computing devices, as they can mimic the electrical analog behavior or biological synapses. In addition, complementary functionalities, such as memcapacitance, could significantly improve the performance of bio-inspired devices in key issues, such as energy consumption. However, the physics of mem systems is not fully understood so far, hampering their large-scale implementation in devices. Perovskites that undergo topotactic transitions and redox reactions show improved performance as mem systems, compared to standard perovskites. In this paper, we analyze different strategies to optimize the multi-mem behavior (memristive and memcapacitive) of topotactic redox La1/2Sr1/2Mn1/2Co1/2O3−x (LSMCO) films grown on Nb:SrTiO3. We explored devices with different crystallinities (from amorphous to epitaxial LSMCO), out-of-plane orientation [(001) and (110)], and stimulated either with voltage or current pulses. We found that an optimum memory response is found for epitaxial (110) LSMCO stimulated with current pulses. Under these conditions, the system efficiently exchanges oxygen with the environment minimizing, at the same time, self-heating effects that trigger nanostructural and chemical changes that could affect the device integrity and performance. Our work contributes to pave the way for the integration of multi-mem topotactic redox oxide-based interfaces in multiple device architectures, in order to exploit their memristive and memcapacitive properties for data storage or neuromorphic computation., The authors acknowledge support from the UNCuyo (Grant No. 06/C591), the ANPCyT (Grant Nos. PICT2017-1836, PICT2019-02781, and PICT2019-0654), and the EU-H2020-RISE project “MELON” (Grant No. 872631). This publication is part of the project “Memcapacitive elements for cognitive devices” (Project No. 040.11.735), which is financed by the Dutch Research Council (NWO). The authors acknowledge support from the Ministry of Science and Higher Education of the RF (State Contract No. N13.2251.21.0042). B.N. acknowledges financial support of the CogniGron research center and the Ubbo Emmius Funds (University of Groningen).

The thermoelectric properties of co-doped (Bi0.98In0.02)2Te2.7Se0.3/reduced graphene oxide composites between 10 - 325 K are presented. X-ray diffraction confirms that the composites adopt a rhombohedral structure with space group R3¯m. Field emission scanning electron microscopy reveals an interface structure of reduced graphene oxide (rGO). N-type conducting behaviour is observed for all the samples, as ascertained by Hall effect and Seebeck coefficient measurements, with a carrier concentration of 1025/m3. The thermal conductivity and electrical resistivity of (Bi0.98In0.02)2Te2.7Se0.3/0.02 wt% reduced graphene oxide composite is found to decrease by 1.6 and 10 times respectively in comparison with that of (Bi0.98In0.02)2Te2.7Se0.3. The power factor is enhanced by 7 times for (Bi0.98In0.02)2Te2.7Se0.3/0.01 wt% rGO compared to that of (Bi0.98In0.02)2Te2.7Se0.3.

Organic-inorganic hybrid materials have shown a remarkable and rapid development during the past decade because they can be tailored to obtain new device concepts with controlled physical properties. Here, we report on the electronic and magnetic properties of multilayer organic-inorganic hybrid films. Electrical transport properties arising from the pi electrons in the organic layer are characteristic of a metallic state at high temperature and evolve into a state described by two-dimensional variable range hopping when temperature decreases below 150 K. The intrinsic electronic behavior of the hybrid films was further studied via the optical properties in the IR range. The optical response confirms the metallic character of the hybrid films. In the second part, the magnetic properties are discussed. A long-range ferromagnetic order with an ordering temperature of similar to 1 K is revealed in the Gd-based hybrid film. The Cu-based hybrid film, however, shows more extended ferromagnetic exchange interactions than the Gd-based hybrid LB film.

To obtain crystalline thin films of alpha-Quartz represents a challenge due to the tendency for the material towards spherulitic growth. Thus, understanding the mechanisms that give rise to spherulitic growth can help regulate the growth process. Here the spherulitic type of 2D crystal growth in thin amorphous Quartz films was analyzed by electron back-scatter diffraction (EBSD). EBSD was used to measure the size, orientation, and rotation of crystallographic grains in polycrystalline SiO2 and GeO2 thin films with high spatial resolution. Individual spherulitic Quartz crystal colonies contain primary and secondary single crystal fibers, which grow radially from the colony center towards its edge, and fill a near circular crystalline area completely. During their growth, individual fibers form so-called rotational crystals, when some lattice planes are continuously bent. The directions of the lattice rotation axes in the fibers were determined by an enhanced analysis of EBSD data. A possible mechanism, including the generation of the particular type of dislocation(s), is suggested.

We have investigated a water-stable sol–gel method based on ethylene glycol as a solvent and bridging ligand for the synthesis of ferroelectric lead zirconate titanate in bulk and thin film forms. This method offers lower toxicity of the solvent, higher stability toward atmospheric moisture and a simplified synthetic procedure compared to traditional sol–gel methods. However, the piezoelectric properties of products produced using this method have yet to be systematically studied. We have measured the ferroelectric and piezoelectric properties and compared them to existing literature using different synthesis techniques. Ceramic pellets of Nb-doped lead zirconate titanate (PNZT) in the tetragonal phase were produced with high density and good piezoelectric properties, comparable to those reported in the literature and those found in commercial piezoelectric elements. In addition, a nine-layer thin film stack was fabricated by spin coating onto platinized silicon substrates. The films were crack-free and showed a perovskite grain structure with a weak (111) orientation. Piezoelectric measurements of the film showed a piezoelectric coefficient comparable to literature values and good stability toward fatigue.

Cs2AgBiBr6 is a potential lead-free double perovskite candidate for optoelectronic applications; however, its large and indirect band gap imposes limitations. Here, single crystals of Cs2AgBiBr6 are doped with Cu2+ cations to increase the absorption range from the visible region up to 0.5 eV in the near-infrared region. Inductively coupled plasma spectroscopy confirms the presence of 1.9% of copper in the Cs2AgBiBr6 structure. Structural and optical changes caused by Cu doping were studied by Raman spectroscopy combined with X-ray diffraction, heat capacity measurements, and low-temperature photoluminescence spectroscopy. Along with the 1.9 eV emission typical of the pristine Cs2AgBiBr6 single crystals, we report a novel low-energy emission at 0.9 eV related to deep defects. In the doped crystals, these peaks are quenched, and a new emission band at 1.3 eV is visible. This new emission band appears only above 120 K, showing that thermal energy is necessary to trigger the copper-related emission.

Piezoelectric quartz (SiO2) crystals are widely used in industry as oscillators. As a natural mineral, quartz and its relevant silicates are also of interest in geoscience and mineralogy. However, the nucleation and growth of quartz crystals are difficult to control and not fully understood. Here we report successful solid-state crystallization of thin film of amorphous GeO2 into quartz on various substrates, including Al2O3, MgAl2O4, MgO, LaAlO3 and SrTiO3. At relatively low annealing temperatures, the crystallization process is spherulitic: with fibers growing radially from the nucleation centers and the crystal lattice rotating along the growth direction with a linear dependence between the rotation angle and the distance to the core. For increasingly higher annealing temperatures, quartz crystals begin to form. The edges of the sample play an important role in facilitating nucleation followed by growth sweeping inward until the whole film is crystallized. Control of the growth allows single crystalline quartz to be synthesized, with crystal sizes of hundreds of microns achieved on sapphire substrates, which is promising for further piezoelectric applications. Our study reveals the complexity of the nucleation and growth process of quartz and provides insight for further studies.

We report on the growth of single-crystal potassium birnessite (K0.31MnO2*0.41H2O) and present both the average and local structural characterization of this frustrated magnetic system. Single crystals were obtained employing a flux growth method with a KNO3/B2O3 flux at 700 {\deg}C. Single-crystal X-ray diffraction revealed an average orthorhombic symmetry, with space group Cmcm. A combination of high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) with atomic resolution energy dispersive X-ray spectroscopy (EDS) demonstrated the layered structure of potassium birnessite with manganese-containing planes well separated by layers of potassium atoms. MnO6 octahedra and the K/H2O planes were clearly imaged via integrated differential phase contrast (iDPC) STEM. Furthermore, iDPC-STEM also revealed the existence of local domains with alternating contrast of the manganese oxide planes, most likely originating from charge ordering of Mn3+ and Mn4+ along the c-axis. These charge-ordered domains are clearly correlated with a reduction in the c-lattice parameter compared to the rest of the matrix. The insight gained from this work allows for a better understanding of the correlation between structure and magnetic properties., Comment: A high-resolution version with supplementary information can be found at https://pubs.rsc.org/en/content/articlelanding/2021/TC/D0TC05396A#!divAbstract

The growth of α-quartz-based piezoelectric thin films opens the door to higher-frequency electromechanical devices than those available through top-down approaches. We report on the growth of SiO2/GeO2 thin films by pulsed laser deposition and their subsequent crystallization. By introducing a devitrifying agent uniformly within the film, we are able to obtain the α-quartz phase in the form of platelets with lateral sizes above 100 μm at accessible temperatures. Films containing different amounts of devitrifying agent are investigated, and their crystallinity is ascertained with X-ray diffraction and electron back-scatter diffraction. Our work highlights the difficulty in crystallization when competing phases arise that have markedly different crystalline orientation.

Ruddlesden-Popper perovskite films deposited with different methods show very diverse phase segregation and composition. When DMSO is used as solvent, the conventional method based on spin-coating and annealing produces very poor devices, whereas the vacuum-assisted method proposed here allows obtaining devices with efficiency up to 14.14%. The conventional method gives rise to a three-dimensional (3D)-like phase on the top of the film but dominant n = 2 phase with large domains (∼40 μm) at the bottom of the film. These n = 2 domains are oriented with their inorganic slabs parallel to the substrate and inhibit the charge transport in the vertical direction. Consequently, severe monomolecular and bimolecular charge recombination occurs in the solar cells. Conversely, the vacuum-assisted method yields films with a 3D-like phase dominant throughout their entire thickness and only a small amount of n ≤ 2 domains of limited dimensions (∼3 μm) at the bottom, which facilitate charge transport and reduce charge recombination.

The double-layer Aurivillius phases Pb1-2xBi1.5+2xLa0.5Nb2-xMnxO9 (x = 0, 0.1, 0.3, and 0.5) were synthesized by a molten salt method using a mixture of K2SO4/Na2SO4. The effect of composition on the structure, morphology and dielectric properties was investigated. X-ray diffraction showed that single-phase samples with a non-polar, orthorhombic A21am structure were obtained for x = 0, 0.1 and 0.3. The unit cell becomes more orthorhombic with increasing x as the degree of distortion of the BO6 octahedra in the perovskite layer increases. Raman spectroscopy showed the typical modes of the orthorhombic double-layer Aurivillius structure and indicated that the La3+ ions prefer to occupy the perovskite A-site, Mn3+ occupies the B-site, and the Pb2+ ions are found in the Bi2O2 layer. The morphology of the samples was probed by scanning electron microscopy, which showed anisotropic, plate-like crystallites that increased in size with increasing x. The dielectric constant significantly increased with x, and the ferroelectric properties became more relaxor-like.

Lead chalcogenide quaternary systems have been shown to provide high thermoelectric (TE) efficiency superior to those of binary and ternary lead chalcogenides, arising from both altered electronic band structures and a reduction in lattice thermal conductivity. Here, we have synthesized single-phase samples of the quaternary compound (PbTe)(0.55)(PbS)(0.1)(PbSe)(0.35) doped with Na and characterized their TE properties. We show that the dopant solubility is limited to 1 at. %. A very low lattice thermal conductivity of similar to 0.6 W m(-1) K-1 at 850 K is achieved at all dopant concentrations because of phonon scattering from point defects associated with solute atoms with high contrast atomic mass. As a result, a high TE figure of merit of approximately 1.5 is achieved at 823 K in heavily doped samples. Moreover, the figure of merit is greater than 1 over a wide temperature range above 675 K.

Similar to carbon, germanium exists in various structures such as three-dimensional crystalline germanium and germanene, a two-dimensional germanium atomic layer. Regarding the electronic properties, they are either semiconductors or Dirac semimetals. Here, we report a highly conductive metallic state in thermally annealed germanane (hydrogen-terminated germanene, GeH), which shows a resistivity of similar to 10(-7) Omega.m that is orders of magnitude lower than any other allotrope of germanium. By comparing the resistivity, Raman spectra, and thickness change measured by AFM, we suggest the highly conductive metallic state is associated with the dehydrogenation during heating, which likely transforms germanane thin flakes to multilayer germanene. In addition, weak antilocalization is observed, serving as solid evidence for strong spin-orbit interaction (SOI) in germanane/germanene. Our study opens a possible new route to investigate the electrical transport properties of germanane/germanene, and the large SOI might provide the essential ingredients to access their topological states predicted theoretically.

N,N′-Bis(pyridin-4-ylmethylene)naphthalene-1,5-diamine (L) acts as a bipyridine analogue linker ligand towards {Zn7(μ4-O)2(OAc)10}, {Zn2(NCS)2(OAc)2}, and {Zn(N3)2} nodes and allows construction of three new 1-D coordination polymers, the linear chain [Zn7(μ4-O)2(OAc)10(L)]n (1), [Zn(NCS)(OAc)(L)]n (2) in ladder-type geometry and the zigzag chain [Zn(N3)2(L)]n (3). Structural characterization reveals that in 1 acetate anionic ligands connect seven Zn(II) ions through the bridging coordination modes μ3-η1,η2 and μ2-η1,η1. The resulting heptanuclear node is located on an inversion center and therefore consists of four crystallographically distinct cations; their coordination spheres correspond to distorted octahedra or tetrahedra. The Zn(II) ions in polymer 2 exhibit distorted trigonal bipyramidal {ZnN3O2} coordination; μ2-η1,η1 coordinated acetate and terminal thiocyanate ligands lead to inversion-symmetric [Zn2(NCS)2(OAc)2] secondary building units (SBU), which are further linked by the N,N′-bipyridine analogue L. Terminal coordination of two anionic azide ligands and the bridging bipyridine L result in coordination polymer 3, in which the cations adopt distorted tetrahedral {ZnN4} coordination. In all crystalline solids 1–3, adjacent 1-D chains interact through π–π stacking and non-classical (C − H···O, C − H···π) hydrogen bonds, leading to 3-D supramolecular architectures. Differences in their 3-D arrangement are due to variations in the anionic co-ligands, subtle conformational differences in the semi-rigid linker and the variable coordination sphere about the zinc cations. Thermogravimetric investigations indicate differences in both thermal stability and decomposition mode. Natural bond orbital (NBO) analysis provides a convenient basis for investigating the intramolecular bonding interactions and delocalization effects in these molecular systems. Finally, solids 1–3 exhibit intense luminescence at room temperature.

Samples of PbBi2Nb2O9, PbBi1.5La0.5Nb2O9, and PbBi1.5Nd0.5Nb2O9 have been prepared by the molten salt method. The structure, morphology, and electrical properties were investigated. All samples are single-phase and crystallize in an orthorhombic structure with A21am symmetry. Neutron diffraction data indicate that the Ln3+ cations prefer to occupy the perovskite A-site, whereas Pb/Bi occupy the perovskite A-site and the Bi2O2 layer. Changes in unit cell volume are observed on substitution and are attributed to the ionic radii of the Ln3+ cations and also correlated to changes in the B-O bond distances in the BO6 octahedra, which are also observed in IR spectra. SEM images reveal anisotropic plate-like grains, which increase in size with the presence of Ln3+ ions. The ferroelectric transition temperature (Tc) decreases with decreasing degree of BO6 distortion as the influence of the 6s2 lone pair of Bi3+ is diminished. Relaxor ferroelectric behavior is observed with Ln3+ substitution, driven by the disorder of the A-site cations. The room temperature ferroelectric polarization increases with Ln3+ substitution, ascribed to the decreased dielectric loss.

Resonant Ultrasound Spectroscopy has been used to characterise strain coupling and relaxation behaviour associated with magnetic/magnetoelectric phase transitions in GdMnO3, TbMnO3 and TbMn0.98Fe0.02O3 through their influence on elastic/anelastic properties. Acoustic attenuation ahead of the paramagnetic ��� colinear-sinusoidal/incommensurate/antiferromagnetic transition at ~41 K correlates with anomalies in dielectric properties and is interpreted in terms of Debye-like freezing processes. A loss peak at ~150 K is related to a steep increase in electrical conductivity with a polaron mechanism. The activation energy, Ea, of ��� ~0.04 eV from a loss peak at ~80 K is consistent with the existence of a well-defined temperature interval in which the paramagnetic structure is stabilised by local, dynamic correlations of electric and magnetic polarisation that couple with strain and have relaxation times in the vicinity of ~10-6 s. Comparison with previously published data for Sm0.6Y0.4MnO3 confirms that this pattern may be typical for multiferroic orthorhombic RMnO3 perovskites (R = Gd, Tb, Dy). A frequency-dependent loss peak near 10 K observed for TbMnO3 and TbMn0.98Fe0.02O3, but not for GdMnO3, yielded Ea ��� ~0.002 eV and is interpreted as freezing of some magnetoelastic component of the cycloid structure. Small anomalies in elastic properties associated with the incommensurate and cycloidal magnetic transitions confirm results from thermal expansion data that the magnetic order parameters have weak but significant coupling with strain. Even at strain magnitudes of ~0.1-1 ���, polaron-like strain effects are clearly important in defining the development and evolution of magnetoelectric properties in these materials. Strains associated with the cubic - orthorhombic transition due to the combined Jahn-Teller/octahedral tilting transition in the vicinity of 1500 K are 2-3 orders of magnitude greater. It is inevitable that ferroelastic twin walls due to this transition would have significantly different magnetoelectric properties from homogeneous domains due to magnetoelastic coupling with steep strain gradients., This work was funded by EPSRC Grant No. EP/ P024904/1 (UK). RUS facilities were established through grants from the Natural Environment Research Council (Grants No. NE/B505738/1 and No. NE/F017081/1) and the Engineering and Physical Sciences Research Council (Grant No. EP/I036079/1) to MAC. The work at the University of Warwick was supported by EPSRC,UK through Grant EP/T005963/1.

We study the high-temperature phase diagram of the chiral magnetic insulator ${\mathrm{Cu}}_{2}\mathrm{O}\mathrm{Se}{\mathrm{O}}_{3}$ by measuring the spin-Hall magnetoresistance (SMR) in a thin Pt electrode. We find distinct changes in the phase and amplitude of the SMR signal at critical lines separating different magnetic phases of bulk ${\mathrm{Cu}}_{2}\mathrm{O}\mathrm{Se}{\mathrm{O}}_{3}$. The skyrmion lattice state appears as a strong dip in the SMR phase. A strong enhancement of the SMR amplitude is observed in the conical spiral state, which we explain by an additional symmetry-allowed contribution to the SMR present in noncollinear magnets. We demonstrate that the SMR can be used as an all-electrical probe of chiral surface twists and skyrmions in magnetic insulators.

Strain engineering as a method to control functional properties has seen in the last decades a surge of interest. Heterostructures comprising 2D-materials and containing van der Waals(-like) gaps were considered unsuitable for strain engineering. However, recent work on heterostructures based on Bi2Te3, Sb2Te3, and GeTe showed the potential of a different type of strain engineering due to long-range mutual straining. Still, a comprehensive understanding of the strain relaxation mechanism in these telluride heterostructures is lacking due to limitations of the earlier analyses performed. Here, we present a detailed study of strain in two-dimensional (2D/2D) and mixed dimensional (2D/3D) systems derived from mica/Bi2Te3, Sb2Te3/Bi2Te3, and Bi2Te3/GeTe heterostructures, respectively. We first clearly show the fast relaxation process in the mica/Bi2Te3 system where the strain was generally transferred and confined up to the second or third van der Waals block and then abruptly relaxed. Then we show, using three independent techniques, that the long-range exponentially decaying strain in GeTe and Sb2Te3 grown on the relaxed Bi2Te3 and Bi2Te3 on relaxed Sb2Te3 as directly observed at the growth surface is still present within these three different top layers a long time after growth. The observed behavior points at immediate strain relaxation by plastic deformation without any later relaxation and rules out an elastic (energy minimization) model as was proposed recently. Our work advances the understanding of strain tuning in textured heterostructures or superlattices governed by anisotropic bonding.

Optoelectronic devices based on layered perovskites containing fluorinated cations display a well-documented improved stability and enhanced performance over non-fluorinated cations. The effect of fluorination on the crystal structure and photophysics, however, has received limited attention up until now. Here, 3-fluorophenethylammonium lead iodide ((3-FPEA)(2)PbI4) single crystals are investigated and their properties to the non-fluorinated ((PEA)(2)PbI4) variant are compared. The bulkier 3-FPEA cation increases the distortion of the inorganic layers, resulting in a blue-shifted absorbance and photoluminescence. Temperature-dependent photoluminescence spectroscopy reveals an intricate exciton substructure in both cases. The fluorinated variant shows hot-exciton resonances separated by 12 to 15 meV, values that are much smaller than the 40 to 46 meV found for (PEA)(2)PbI4. In addition, high-resolution spectra show that the emission at lower energies consists of a substructure, previously thought to be a single line. With the analysis on the resolved photoluminescence, a vibronic progression is excluded as the origin of the emission at lower energies. Instead, part of the excitonic substructure is proposed to originate from bound excitons. This work furthers the understanding of the photophysics of layered perovskites that has been heavily debated lately.

Helium implantation in epitaxial thin films is a way to control the out-of-plane deformation independently from the in-plane strain controlled by epitaxy. In particular, implantation by means of a helium microscope allows for local implantation and patterning down to the nanometer resolution, which is of interest for device applications. We present here a study of bismuth ferrite (BiFeO3) films where strain was patterned locally by helium implantation. Our combined Raman, x-ray diffraction, and transmission electron microscopy (TEM) study shows that the implantation causes an elongation of the BiFeO3 unit cell and ultimately a transition towards the so-called supertetragonal polymorph via states with mixed phases. In addition, TEM reveals the onset of amorphization at a threshold dose that does not seem to impede the overall increase in tetragonality. The phase transition from the R-like to T-like BiFeO3 appears as first-order in character, with regions of phase coexistence and abrupt changes in lattice parameters.

We report on the magnetic properties of geometrically frustrated K3CrO4, in which Cr5+ cations are arranged on a distorted pyrochlore lattice. The crystal structure, static and dynamic magnetic properties of the compound are investigated in detail. A combination of DC and AC magnetic susceptibility measurements together with thermoremanent magnetization decay measurements reveal several magnetic transitions: the onset of glassy canted antiferromagnetic order occurs at 36 K, followed by the appearance of ferromagnetic/ferrimagnetic cluster glass behavior below the freezing temperature of 20 K. Further field-induced, temperature-dependent transitions are observed in the range 3-10 K. The frequency dependence of the freezing temperature for the cluster glass state is analyzed on the basis of dynamic scaling laws including the critical slowing down formula and the Vogel-Fulcher law., A high-resolution version with supplementary material can be found at https://www.sciencedirect.com/science/article/pii/S0304885321004893?via%3Dihub. arXiv admin note: text overlap with arXiv:1912.05997

In this thesis, I have investigated the structure and morphology of some typical thermoelectric materials and their effects on the performance of these materials. In our world, the energy crisis and environmental pollution are two major problems that people need to address. Thermoelectric materials have received a lot of attention in this respect due to their ability to convert directly between heat and electricity while doing so in a pollution-free, highly reliable and maintenance-free manner. The preparation methods in the thesis that involve quenching from high temperature are able not only to stabilize phases that appear at high-temperature in the phase diagram but also to obtain complex microstructures. The macroscopic properties of substances are expressed by microscopic atoms, and it is the laws of the microscopic physical world that are the essential laws of the macroscopic world. Elucidating the microstructure and morphology of materials is therefore of great importance to understand the macroscopic properties of materials.

We report a soft x-ray resonant magnetic scattering study of the spin configuration in multiferroic thin films of Co$_{0.975}$Ge$_{0.025}$Cr$_2$O$_4$ (Ge-CCO) and CoCr$_2$O$_4$ (CCO), under low- and high-magnetic fields, from 0.2 T up to 6.5 T. A characterization of Ge-CCO at a low magnetic field is performed and the results are compared to those of pure CCO. The ferrimagnetic phase transition temperature $T_C \approx 95$ K and the multiferroic transition temperature $T_S \approx 27$ K in Ge-CCO are comparable to those observed in CCO. In Ge-CCO, the ordering wave vector $\textit{(qq0)}$ observed below $T_S$ is slightly larger compared to that of CCO, and, unlike CCO, the diffraction intensity consists of two contributions that show a dissimilar x-ray polarization dependence. In Ge-CCO, the coercive field observed at low temperatures was larger than the one reported for CCO. In both compounds, an unexpected reversal of the spiral helicity and therefore the electric polarization was observed on simply magnetic field cooling. In addition, we find a change in the helicity as a function of momentum transfer in the magnetic diffraction peak of Ge-CCO, indicative of the presence of multiple magnetic spirals., Comment: 20 pages, 12 figures