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The hydrothermal synthesis of novel materials typically relies on both knowledge of the redox activities of all cations present in the reaction solution and a small toolset of so-called mineralizers to tune the solution's overall chemical potential. Upon the use of a less conventional mineralizer species, SiO$_2$, we show the stabilization of spiroffite-type Co$_2$Te$_3$O$_8$ under less forceful hydrothermal conditions than in previous reports. When synthesized in the presence of both SiO$_2$ and each respective alkali carbonate as a secondary mineralizer, silicon substitution in place of tellurium in the host structure becomes apparent, and the corresponding introduced disorder gives rise to enhanced low-temperature ferromagnetism. Our results highlight the complexities of underutilized and combined mineralizer species in the stabilization and tuning of complex magnetic ground states via hydrothermal synthesis techniques., Comment: Main text - 26 pages, 5 figures, 1 table. SI - 39 pages, 30 figures, 8 tables

Two-dimensional (2D) van der Waals (vdW) materials have been an exciting area of research ever since scientists first isolated a single layer of graphene. Single layer magnetic materials can provide a pathway for vdW heterostructures with magnetic properties. While most of the magnetic vdW materials exhibit ordering transitions in the bulk, here we report a successful exfoliation of a triangular lattice S=1 antiferromagnet NiGa$_2$S$_4$, which already demonstrates exotic magnetism in the bulk material. We establish the number of layers of the material by atomic force microscopy (AFM) and detail a careful characterization using Raman and optical spectroscopy to demonstrate how the optical, electronic, and structural properties of NiGa$_2$S$_4$ change as a function of sample thickness. Optical measurements and electronic structure calculations of bulk versus monolayer NiGa$_2$S$_4$ confirm the material to be a Mott insulator with an electronic gap of about 1.5 eV, which slightly increases for layers below 10 L. We conclude with a theoretical analysis of the possibility of doping monolayer NiGa$_2$S$_4$ by proximity to a metal., Comment: 11 pages, 8 figures

Magnetic metal-organic frameworks (MMOFs), where magnetic metal nodes are connected into a crystal structure by organic linkers, have a potential to host exotic magnetic states. We present a study of bulk magnetic properties of four metal-organic frameworks with boron imidazolate linkers, Zn-BIF, Cu-BIF, Co-BIF, and Ni-BIF, displaying a variety of lattice structures and nontrivial magnetic behaviors. While non-magnetic Zn-BIF provides an offset of magnetic response, magnetic susceptibility measurements of the other three magnetic materials demonstrate the presence of weak magnetic interactions in these MOFs, which differ between materials by sign and size. Cu-MOF, where magnetic nodes are connected into octahedral cages, shows simple paramagnetic behavior. Triangular lattice Co-MOF shows antiferromagnetic interactions on the order of 1 K, and a spin-crossover-like effect in magnetic susceptibility due to thermal depopulation of excited crystal electric field levels. Magnetic properties of Ni-BIF suggest sizable ferromagnetic interactions. Using DC/AC susceptibility and variable-field DC magnetization, we detect behavior that resembles that of superparamagnetic single-magnetic-domain nanoparticles, but with particle sizes on the scale of the unit cell, and discuss possible microscopic origins of this behavior. This work demonstrates the variety of magnetic properties that are possible with a single organic ligand, and establishes the low energy scale of magnetic interactions through superexchange in boron imidazolate frameworks.

Co-based materials have recently been explored due to potential to realise complex bond-dependent anisotropic magnetism. Prominent examples include Na$_2$Co$_2$TeO$_6$, BaCo$_2$(AsO$_4$)$_2$, Na$_2$BaCo(PO$_4$)$_2$, and CoX$_2$ (X = Cl, Br, I). In order to provide insight into the magnetic interactions in these compounds, we make a comparative analysis of their local crystal electric field excitations spectra via Raman scattering measurements. Combining these measurements with theoretical analysis confirms the validity of $j_{\rm eff} = 1/2$ single-ion ground states for all compounds, and provides accurate experimental estimates of the local crystal distortions, which play a prominent role in the magnetic couplings between spin-orbital coupled Co moments., Comment: 11 pages, 7 figures

A family of molecular Mott insulators on triangular lattice provided a few S=1/2 triangular quantum spin liquid candidates, with $\kappa$-(BEDT-TTF)$_2$Cu$_2$(CN)$_3$ being the most studied material of this group. The large number experimental works present a conflicting set of evidence, with some suggesting spin liquid behavior, while others point towards a valence bond solid with orphan spins. In this work we use Raman scattering spectroscopy to probe both local charge on molecular sites and lattice phonons as a function of temperature down to 6~K. Based on the analysis of the line shape of the BEDT-TTF charge sensitive vibration $\nu_2$ on cooling below 40 K, we suggest a development of disordered fluctuating charge disproportionation on (BEDT-TTF)$_2$ dimers of amplitude as small as 0.06$e$. The lattice phonons show strong anomalous broadening on cooling only in the (c,c) scattering channel, associated with the developing charge disproportionation. We suggest an interpretation, where the coupling of disordered charge dipoles on dimers to the lattice results in anisotropic modulation of charge transfer integrals between dimer lattice sites. Such fluctuations would result in modulation of magnetic coupling between spins which can produce fluctuating charge ordered spin-singlet pairs.

Using Raman scattering spectroscopy, we uncover a complex magnetic behavior of Nd$_2$Ir$_2$O$_7$, which stands out among magnetic pyrochlores by the lowest temperature of the all-in-all-out (AIAO) Ir moments ordering ($T^\mathrm{N}_{\small\rm{Ir}}=33$~K) and the highest temperature at which AIAO order of rare-earth Nd ions is detected ($T^\mathrm{*}_{\small\rm{Nd}}$=15~K). Our work suggests that in the temperature range between 15~K and 33~K, Nd magnetic moments exhibit characteristic spin ice fluctuations, which indicate a strong enhancement of magnetic interactions between Nd ions. This complex behavior emerges from the interplay of strong spin-orbit coupling, electronic correlations, and geometric frustration on two magnetic pyrochlore sublattices of Nd and Ir ions. The ordering of Ir magnetic moments is accompanied by an appearance of one-magnon Raman modes at 26.3 and 29.6 meV compatible with the AIAO order and of a broad mode at 14 meV, characteristic of the spinon continuum originated from Nd spin ice fluctuations. While two one-magnon excitations show minimal temperature evolution with decreasing temperature, the 14 meV mode shifts to higher frequencies as the temperature approaches a crossover to Nd AIAO order, broadens, and disappears below 15~K. An additional two-magnon excitation of the AIAO Nd order at around 33 meV appears in the spectra at low temperatures. These rather high energies of magnetic excitations of Nd moments make Nd$_2$Ir$_2$O$_7$ a particularly attractive playground to study the rare-earth magnetism on the pyrochlore lattice.

We present a Raman scattering spectroscopic study of boron imidazolate metal-organic frameworks (BIFs) with three different magnetic metal ions and one non-magnetic in a wide frequency range from 25 to 1700 cm$^{-1}$, which covers local vibrations of the linkers and well as collective lattice vibrations. We show that the spectral region above 800 cm$^{-1}$ belongs to the local vibrations of the linkers, which have the same frequencies for the studied BIFs without any dependence on the structure of the BIFs, and are easily interpreted based on the spectra of imidazolate linkers. In contrast, collective lattice vibrations, observed below 100 cm$^{-1}$, show a distinction between cage and two-dimensional BIFs structures, with a weak dependence on the metal node. We identify the range of vibrations around 200 cm$^{-1}$, which are distinct for each MOF, depending on a metal node. Our work demonstrates the energy hierarchy in the vibrational response of BIFs.

BaCo2(AsO4)2 (BCAO) has seen extensive study since its initial identification as a proximate Kitaev quantum spin liquid candidate. Thought to be described by the highly anisotropic XXZ-J_1-J_3 model, the ease with which magnetic order is suppressed in the system indicates proximity to a spin liquid phase. Upon chemical tuning via partial arsenic substitution with vanadium, we show an initial suppression of long-range incommensurate order in the BCAO system to T = 3.0 K, followed by increased spin freezing at higher substitution levels. Between these two regions, at around 10% substitution, the system is shown to pass through a critical point where the competing J_1/J_3 exchange interactions become more balanced, producing a more complex magnetic ground state, likely stabilized by quantum fluctuations. This state shows how slight compositional change in magnetically-frustrated systems may be leveraged to tune ground state degeneracies and potentially realize a quantum spin liquid state., Comment: Main text (43 pages, 9 figures, 1 table); Supplementary information (32 pages, 18 figures, 14 tables)

Corkite, PbFe3(PO4)(SO4)(OH)6, an understudied relative of the jarosite family of Heisenberg antiferromagnets, has been synthesized and its magnetic properties characterized for the first time. Relative to natural samples, synthetic corkite displays signatures in both infrared and Raman spectra of a more ordered arrangement of polyanion groups about the kagom\'e sublattice that retains inversion symmetry. Magnetic susceptibility measurements reveal that dried corkite undergoes a transition to a long-range, antiferromagnetically-ordered state below TN = 48 K, lower than that observed in the majority of jarosite phases, and indicative of further spin frustration. Curie-Weiss fitting of the measured magnetic susceptibility yields an effective magnetic moment of peff = 6.29(1) muB/Fe^3+ and theta_CW = -526.0(1.1) K, analogous to that observed in similar high-spin Fe^3+ systems, and indicative of strong antiferromagnetic coupling. Estimation of the change in magnetic entropy as a function of temperature from T = 0 K to T = 195 K, dS_mag = 14.86 J/mol_Fe^3+ K, is also in good agreement with the dS_mag = Rln(2S+1) = 14.9 J/mol K expected for a S = 5/2 system. In comparison to the pure jarosites, where both structure and magnetism remain largely invariant upon a variety of chemical substitutions, the replacement of one sulfate group per formula unit with a higher-valent phosphate group applies additional steric and electronic pressure on the kagom\'e lattice in corkite, further frustrating the magnetic ground state of the material. Corkite thus represents both an outlier in the known body of jarosite-type materials, and an illustration of how existing structures may be further strained in the development of highly frustrated magnetic systems., Comment: 27 pages, 5 figures, 4 tables

Pyrochlore iridates are thought to be a fertile ground for the realization of topologically non-trivial and strongly correlated states of matter. Here we provide a compelling evidence of interacting Weyl electrons in Nd$_2$Ir$_2$O$_7$ and quadratic band touching in Pr$_2$Ir$_2$O$_7$ by Raman scattering. We observe a magnetically-driven phase transition between the topological Weyl semimetal and a Luttinger semimetal with quadratic band touching in Nd$_2$Ir$_2$O$_7$. Our theoretical analysis of the Raman scattering from Weyl and Luttinger quasiparticles agrees with experimental observations, and enables a characterization of the material parameters while revealing interaction and disorder effects through a relatively short quasiparticle lifetime., Comment: 8 pages, 3 figures; improved fitting of theory to experiment

Mutual interactions in many-body systems bring about a variety of exotic phases, among which liquid-like states failing to order due to frustration are of keen interest. Recently, an organic system with an anisotropic triangular lattice of molecular dimers has been suggested to host a dipole liquid arising from intradimer charge-imbalance instability, possibly offering an unprecedented stage for the spin degrees of freedom. Here we show that an extraordinary unordered(unfrozen) spin state having soft-matter-like spatiotemporal characteristics is substantiated in this system. $^1$H NMR spectra and magnetization measurements indicate that gigantic, staggered moments are non-linearly and inhomogeneously induced by magnetic field whereas the moments vanish in the zero-field limit. The analysis of the NMR relaxation rate signifies that the moments fluctuate at a characteristic frequency slowing down to below MHz at low temperatures. The inhomogeneity, local correlation, and slow dynamics indicative of middle-scale dynamical correlation length suggest a novel frustration-driven spin clusterization., Comment: 13 pages, 11 figures, 1 table

Magnetic materials with pyrochlore crystal structure form exotic magnetic states due to the high lattice frustration. In this work we follow the effects of coupling of the lattice and electronic and magnetic degrees of freedom in two Praseodymium-based pyrochlores Pr$_2$Zr$_2$O$_7$ and Pr$_2$Ir$_2$O$_7$. In both materials the presence of magnetic interactions does not lead to magnetically ordered low temperature states, however their electronic properties are different. A comparison of Raman phonon spectra of Pr$_2$Zr$_2$O$_7$ and Pr$_2$Ir$_2$O$_7$ allows us to identify magneto-elastic coupling in Pr$_2$Zr$_2$O$_7$ that elucidates its magnetic properties at intermediate temperatures, and allows us to characterize phonon-electron coupling in the semimetallic Pr$_2$Ir$_2$O$_7$. We also show that the effects of random disorder on the Raman phonon spectra is small., Comment: 6 pages, 5 figures

Triangular lattice quasi-two-dimensional Mott insulators based on BEDT-TTF molecule and its analogies present a possibility to produce exotic phases by coupling charge and spin degrees of freedom. In this work we discuss magnetic properties of one of such materials, $\kappa$-(BEDT-TTF)$_2$Hg(SCN)$_2$Cl, which is found at the border of the phase transition between a Mott insulator into a charge ordered state. Our magnetic susceptibility and cantilever magnetisation measurements demonstrate how the charge degree of freedom defines magnetic properties for few different charge phases observed in this material as a function of temperature. Between $T_{CO}=30~K$ and $T_S=24~K$ we observe charge and spin separation due to one-dimensional charge stripes formed in this material below $T_{CO}=30~K$. Below $T_S=24~K$ charge and spin degrees of freedom demonstrate coupling. Spin singlet correlations develop below 24~K, however melting of charge order below 15~K prevents the spin singlet state formation, leaving the system in the inhomogeneous state with charge ordered spin singlet domains and charge and spin fluctuating ones.

Pr$_2$Zr$_2$O$_7$ is a pyrochlore quantum spin-ice candidate. Using Raman scattering spectroscopy we probe crystal electric field excitations of Pr$^{3+}$, and demonstrate the importance of their interactions with the lattice. We identify a vibronic interaction with a phonon that leads to a splitting of a doublet crystal field excitation at around 55~meV. We also probe a splitting of the non-Kramers ground state doublet of Pr$^{3+}$ by observing a double line of the excitations to the first excited singlet state $E^0_g \rightarrow A_{1g}$. We show that the splitting has a strong temperature dependence, with the doublet structure most prominent between 50~K and 100~K, and the weight of one of the components strongly decreases on cooling. We suggest a static or dynamic deviation of Pr$^{3+}$ from the position in the ideal crystal structure can be the origin of the effect, with the deviation strongly decreasing at low temperatures., Comment: 6 pages, 3 figures

We perform magnetic susceptibility and magnetic torque measurements on the organic $\kappa$-(BEDT-TTF)$_2$Hg(SCN)$_2$Br, which is recently suggested to host an exotic quantum dipole-liquid in its low-temperature insulating phase. Below the metal-insulator transition temperature, the magnetic susceptibility follows a Curie-Weiss law with a positive Curie-Weiss temperature, and a particular $M\propto \sqrt{H}$ curve is observed. The emergent ferromagnetically interacting spins amount to about 1/6 of the full spin moment of localized charges. Taking account of the possible inhomogeneous quasi-charge-order that forms a dipole-liquid, we construct a model of antiferromagnetically interacting spin chains in two adjacent charge-ordered domains, which are coupled via fluctuating charges on a Mott-dimer at the boundary. We find that the charge fluctuations can draw a weak ferromagnetic moment out of the spin singlet domains., Comment: 9 pages, 5 figures, Supplementary Material attached

NiGa$_2$S$_4$ is a triangular lattice S=1 system with strong two-dimensionality of the lattice, actively discussed as a candidate to host spin-nematic order brought about by strong quadrupole coupling. Using Raman scattering spectroscopy we identify a phonon of E$_g$ symmetry which can modulate magnetic exchange $J_1$ and produce quadrupole coupling. Additionally, our Raman scattering results demonstrate a loss of local inversion symmetry on cooling, which we associate with sulfur vacancies. This will lead to disordered Dzyaloshinskii-Moriya interactions, which can prevent long range magnetic order. Using magnetic Raman scattering response we identify 160~K as a temperature of an upturn of magnetic correlations. The temperature below 160~K, but above 50~K where antiferromagnetic magnetic start to increase, is a candidate for spin-nematic regime.

Strong electronic interactions can drive a system into a state with a symmetry breaking. Lattice frustration or competing interactions tend to prevent a symmetry breaking, leading to quantum disordered phases. In spin systems frustration can produce a spin liquid state. Frustration of a charge degree of freedom also can result in various exotic states, however, experimental data on these effects is scarce. In this work we demonstrate how a charge ordered ferroelectric looses the order on cooling to low temperatures using an example of a Mott insulator on a weakly anisotropic triangular lattice $\kappa$-(BEDT-TTF)$_2$Hg(SCN)$_2$Cl. Typically, a low temperature ordered state is a ground state of a system, and the demonstrated re-entrant behavior is unique. Raman scattering spectroscopy finds that this material enters an insulating ferroelectric `dipole solid' state at $T=30~K$, but below $T=15~K$ the order melts, while preserving the insulating energy gap. The resulting phase diagram is relevant to other quantum paraelectric materials.

Samarium hexaboride is an anomaly, having many exotic and seemingly mutually incompatible properties. It was proposed to be a mixed-valent semiconductor, and later - a topological Kondo insulator, and yet has a Fermi surface despite being an insulator. We propose a new and unified understanding of SmB$_6$ centered on the hitherto unrecognized dynamical bonding effect: the coexistence of two Sm-B bonding modes within SmB$_6$, corresponding to different oxidation states of the Sm. The mixed valency arises in SmB$_6$ from thermal population of these distinct minima enabled by motion of B. Our model simultaneously explains the thermal valence fluctuations, appearance of magnetic Fermi surface, excess entropy at low temperatures, pressure-induced phase transitions, and related features in Raman spectra and their unexpected dependence on temperature and boron isotope.

A necessary element for the predicted topological state in Kondo insulator SmB$_6$ is the hybridization gap which opens in this compound at low temperatures. In this work, we present a comparative study of the in-gap density of states due to Sm vacancies by Raman scattering spectroscopy and heat capacity for samples where the number of Sm vacancies is equal to or below 1 %. We demonstrate that hybridization gap is very sensitive to the presence of Sm vacancies. At the amount of vacancies above 1 % the gap fills in with impurity states and low temperature heat capacity is enhanced., Comment: SCES 2017 Proceedings

Mott insulators are commonly pictured with electrons localized on lattice sites. Their low-energy degrees of freedom involve spins only. Here we observe emerging charge degrees of freedom in a molecule-based Mott insulator $\kappa$-(BEDT-TTF)$_2$Hg(SCN)$_2$Br, resulting in a quantum dipole liquid state. Electrons localized on molecular dimer lattice sites form electric dipoles that do not order at low temperatures and fluctuate with frequency detected experimentally in our Raman spectroscopy experiments. The heat capacity and Raman scattering response are consistent with a scenario where the composite spin and electric dipole degrees of freedom remain fluctuating down to the lowest measured temperatures.

While topological superconductors are predicted to provide building blocks for fault-tolerant quantum computing, one of the remaining challenges is to find a convenient experimental platform that would allow patterning of circuits. We find that superconductivity can be patterned directly into Bi$_2$Se$_3$ nanostructures by selective doping with palladium (Pd). Superconducting regions are defined by depositing Pd on top of the nanostructures using electron beam lithography, followed by in-situ annealing. Electrical transport measurements at low temperatures show either partial or full superconducting transition, depending on the doping conditions. Structural characterization techniques indicate that Pd remains localized in the targeted areas, making it possible to pattern superconducting circuits of arbitrary shapes in this topological material., Comment: 5 pages, 4 figure

SmB6 is a proposed topological Kondo insulator where the presence of topological nontriviality can be tuned by variations in the Sm valence. Experimentally, Sm valence can be changed by tuning stoichiometry of SmB6. We show that Raman scattering can detect vacancies lower than 1% of Sm sites in SmB6 crystal by probing the intensity of defect-induced scattering of the acoustic phonon branch at 10~meV. In the electronic Raman spectra of SmB6 at temperatures below 130~K, we observe features developing in A$_{1g}$ and E$_g$ symmetries at 100 and 41~meV which we assign to excitations between hybridized bands, and depressed spectral weight below 20~meV associated with the hybridization gap. With the increased number of Sm vacancies up to 1% we observe an increase of spectral weight below 20~meV showing that the gap is filling in with electronic states. For the sample with the lowest number of vacancies the in-gap exciton excitations with long lifetimes protected by hybridization gap are observed at 16-18~meV in E$_g$ and T$_{2g}$ symmetries. These excitations broaden as a decrease in the lifetime with increasing number of vacancies and are quenched by the presence of in-gap states at concentration of Sm vacancies of about 1%. Based on this study we suggest that only the most stoichiometric SmB6 samples have a bulk gap necessary for topological Kondo insulators.

Using Raman scattering, the quasi-two dimensional organic superconductor k-(BEDT-TTF)2Cu[N(CN)2]Br (T_c=11.8 K) and the related antiferromagnet k-(BEDT-TTF)2Cu[N(CN)2]Cl are studied. Raman scattering provides unique spectroscopic information about magnetic degrees of freedom that has been otherwise unavailable on such organic conductors. Below T=200 K a broad band at about 500 cm-1 develops in both compounds. We identify this band with two-magnon excitation. The position and the temperature dependence of the spectral weight are similar in the antiferromagnet and in the metallic Fermi-liquid. We conclude that antiferromagnetic correlations are similarly present in the magnetic insulator and the Fermi-liquid state of the superconductor.