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The monoclinic (m-LBO) and tetragonal (t-LBO) polymorphs of LiBO2 have significant potential for applications such as solid electrolytes and electrode coatings of lithium-ion batteries. While comparative experimental studies of electron and lithium transport in these polymorphs exist, the role of lattice vacancies on lithium transport remains unclear. In this study, we employed density functional theory (DFT) to investigate the impact of boron and oxygen vacancies on the lattice structure, electronic properties, and lithium migration energy barrier (Em) in m-LBO and t-LBO. Our DFT results reveal that boron and oxygen vacancies affect lithium transport in both the polymorphs, but in different ways. While oxygen vacancies lower Em in m-LBO, they increases Em in t-LBO. In contrast, boron vacancies significantly reduce Em in both m-LBO and t-LBO, leading to enhanced diffusivity and ionic conductivity in both polymorphs. This improvement suggests a potential strategy for improving ionic conductivity in LiBO2 through boron vacancy generation., Comment: 34 pages, 9 figures, 6 tables, submitted for publication in Journal of Materials Chemistry A

The layered ATMPn$_2$ (A = alkali earth or rare earth atom, TM = transition metal, Pn = Sb, Bi) compounds are widely studied for their rich magnetism and electronic structure topology. Here, we characterize the physical properties of LaMn$_x$Sb$_2$, an understudied member of the ATMPn$_2$ family. LaMn$_x$Sb$_2$ forms with intrinsic Mn vacancies, and we demonstrate synthetic control of the Mn occupancy to produce single crystals with x = 0.74-0.97. Magnetization and transport measurements indicate LaMn$_x$Sb$_2$ has a rich temperature-composition (T-x) magnetic phase diagram with physical properties strongly influenced by the Mn occupancy. LaMn$_x$Sb$_2$ orders antiferromagnetically at T$_{1}$ = 130--180 K, where T$_{1}$ increases with x. Below T$_{1}$, the T-x phase diagram is complicated. At high x, there is a second transition T$_2$ that decreases in temperature as x is lowered, vanishing below x $\leq$ 0.85. A third, first-order, transition T$_3$ is detected at x $\approx$ 0.92, and the transition temperature increases as x is lowered, crossing above T$_2$ near x $\approx$ 0.9. On moving below x $<$ 0.79, we find the crystal structure changes from the P4/nmm arrangement to a I$\bar{4}$2m structure with partially ordered Mn vacancies. The change in crystal structure results in the appearance of two new low temperature phases and a crossover between regimes of negative and positive magnetoresistance. Finally, we provide neutron diffraction for x = 0.93, and find that the high x compositions first adopt a G-type AFM structure with the Mn moments aligned within the ab-plane which is followed on cooling by a second transition to a different, non-collinear structure where the moments are rotated within the basal plane. Our results demonstrate that LaMn$_x$Sb$_2$ is a highly tunable material with six unique magnetically ordered phases, depending on T and x.

The magnetic and electronic properties of the layered Zintl-phase compound EuAl$_2$Ge$_2$ crystallizing in the trigonal CaAl$_2$Si$_2$-type structure are reported. Our neutron-diffraction measurements show that EuAl$_2$Ge$_2$ undergoes A-type antiferromagnetic (AFM) ordering below $T_{\rm N} = 27.5(5)$~K, with the Eu moments (Eu$^{2+}$, $S = 7/2$) aligned ferromagnetically in the $ab$ plane. The $H = 0$ magnetic structure consists of trigonal AFM domains associated with $ab$-plane magnetic anisotropy and a field-induced reorientation of the Eu spins in the domains is evident at $T = 2$~K below the critical field $H_{c1} = 2.5(1)$ kOe. Electrical resistivity and ARPES measurements show that EuAl$_2$Ge$_2$ is metallic both above and below $T_{\rm N}$. In the AFM phase, we directly observe folded bands in ARPES due to the doubling of the magnetic unit cell along the $c$ axis with an enhancement of quasiparticle weight due to the complex change in the coupling between the magnetic moments and itinerant electrons on cooling below $T_{\rm N}$. The observed electronic structure is well reproduced by first-principle calculations, which also predict the presence of nontrivial electronic states near the Fermi level in the AFM phase with $Z_2$ topological numbers 1;(000)., Comment: 16 pages, 13 captioned figures, 53 references Updated several affiliations

We report neutron-diffraction results on single-crystal CaMn$_2$P$_2$ containing corrugated Mn honeycomb layers and determine its ground-state magnetic structure. The diffraction patterns consist of prominent (1/6, 1/6, $L$) reciprocal lattice unit (r.l.u.; $L$ = integer) magnetic Bragg reflections, whose temperature-dependent intensities are consistent with a first-order antiferromagnetic phase transition at the N\'eel temperature $T_{\rm N} = 70(1)$ K. Our analysis of the diffraction patterns reveals an in-plane $6\times6$ magnetic unit cell with ordered spins that in the principal-axis directions rotate by 60-degree steps between nearest neighbors on each sublattice that forms the honeycomb structure, consistent with the $P_Ac$ magnetic space group. We find that a few other magnetic subgroup symmetries ($P_A2/c$, $P_C2/m$, $P_S\bar{1}, P_C2, P_Cm, P_S1$) of the paramagnetic $P\bar{3}m11^\prime$ crystal symmetry are consistent with the observed diffraction pattern. We relate our findings to frustrated $J_1$-$J_2$-$J_3$ Heisenberg honeycomb antiferromagnets with single-ion anisotropy and the emergence of Potts nematicity

Eu-based Zintl-phase materials EuA$_2$Pn$_2$ (A = Mg, In, Cd, Zn; Pn = Bi, Sb, As, P) have generated significant recent interest owing to the complex interplay of magnetism and band topology. Here, we investigated the electronic, magnetic, and electronic properties of the layered Zintl-phase single crystals of EuMg$_2$Sb$_2$ with the trigonal CaAl$_2$Si$_2$ crystal structure (space group $P\bar{3}m1$). Electrical resistivity measurements complemented with angle-resolved photoemission spectroscopy (ARPES) studies find an activated behavior with the intrinsic conductivity at high temperatures indicating a semiconducting electronic ground state with a narrow energy gap of 370 meV. Magnetic susceptibility and zero-field heat-capacity measurements indicate that the compound undergoes antiferromagnetic (AFM) ordering at the Neel temperature $T_{\rm N}$ = 8.0(2) K. Zero-field neutron-diffraction measurements reveal that the AFM ordering is A-type where the Eu ordered moments (Eu$^{2+}$, S= 7/2) arranged in ab-plane layers are aligned ferromagnetically in the ab plane with the Eu moments in adjacent layers aligned antiferromagnetically. We also find that Eu-moment reorientation in the trigonal AFM domains within the ab planes occurs below $T_{\rm N}$ at low fields < 0.05 T due to very small in-plane anisotropy. Although isostructural semimetallic EuMg$_2$Bi$_2$ is reported to host Dirac surface states, the observation of narrow-gap semiconducting behavior in EuMg$_2$Sb$_2$ implies a strong role of spin-orbit coupling in tuning the electronic states of these materials., Comment: 15 pages, 15 captioned figures, 33 references

CaCo2As2 is a unique itinerant system having strong magnetic frustration. Here we report the effect of electron doping on the physical properties resulting from Ni substitutions for Co. The A-type antiferromagnetic transition temperature TN = 52 K for x = 0 decreases to 22 K with only 3 percent Ni substitution and is completely suppressed for x > 0.11. For 0.11 < x < 0.52 strong ferromagnetic (FM) fluctuations develop as revealed by magnetic susceptibility chi(T) measurements. Heat-capacity Cp(T) measurements reveal the presence of FM quantum spin fluctuations for 0.11 < x < 0.52. Our density-functional theory (DFT) calculations confirm that FM fluctuations are enhanced by Ni substitutions for Co. The Sommerfeld electronic heat-capacity coefficient is enhanced for x = 0, 0.21, and 0.42 by about a factor of two compared to DFT calculations of the bare density of states at the Fermi energy. The crystals with x > 0.52 do not exhibit FM spin fluctuations or magnetic order, which was found from the DFT calculations to arise from a Stoner transition. Neutron-diffraction studies of crystals with x = 0.11 and 0.16 found no evidence of A-type ordering as observed in CaCo2As2 or of other common magnetic structures., Comment: 19 pages, 18 captioned figures, 7 tables, 79 references

The trigonal compound EuSn2As2 was recently discovered to host Dirac surface states within the bulk band gap and orders antiferromagnetically below the Neel temperature TN = 24 K. Here the magnetic ground state of single-crystal EuSn2As2 and the evolution of its properties versus temperature T and applied magnetic field H are reported. Included are zero-field single-crystal neutron-diffraction measurements versus T, magnetization M(H,T), magnetic susceptibility chi(H,T) = M(T)/H, heat capacity Cp(H,T), and electrical resistivity rho(H,T) measurements. The neutron-diffraction and chi(T) measurements both indicate a collinear A-type antiferromagnetic (AFM) structure below TN =23.5(2) K, where the Eu{2+} spins S = 7/2 in a triangular ab-plane layer (hexagonal unit cell) are aligned ferromagnetically in the ab plane whereas the spins in adjacent Eu planes along the c axis are aligned antiferromagnetically. The chi(H{ab},T) and chi(H{c},T) data together indicate a smooth crossover between the collinear AFM alignment and an unknown magnetic structure at H ~ 0.15 T. Dynamic spin fluctuations up to 60 K are evident in the chi(T), Cp(T) and rho(H,T) measurements, a temperature that is more than twice TN. The rho(H,T) of the compound does not reflect a contribution of the topological state, but rather is consistent with a low-carrier-density metal with strong magnetic scattering. The magnetic phase diagrams for both H||c and H||ab in the H-T plane are constructed from the TN(H), chi(H,T), Cp(H,T), and rho(H,T) data., Comment: 15 pages, 19 captioned figures, 2 tables, 66 references

Disorder can have a dominating influence on correlated and quantum materials leading to novel behaviors which have no clean limit counterparts. In magnetic systems, spin and exchange disorder can provide access to quantum criticality, frustration, and spin dynamics, but broad tunability of these responses and a deeper understanding of strong limit disorder is lacking. In this work, we demonstrate that high entropy oxides present an unexplored route to designing quantum materials in which the presence of strong local compositional disorder hosted on a positionally ordered lattice can be used to generate highly tunable emergent magnetic behavior--from macroscopically ordered states to frustration-driven dynamic spin interactions. Single crystal La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3 films are used as a structurally uniform model system hosting a magnetic sublattice with massive microstate disorder in the form of site-to-site spin and exchange type inhomogeneity. A classical Heisenberg model is found to be sufficient to describe how compositionally disordered systems can paradoxically host long-range magnetic uniformity and demonstrates that balancing the populating elements based on their discrete quantum parameters can be used to give continuous control over ordering types and critical temperatures. Theory-guided experiments show that composite exchange values derived from the complex mix of microstate interactions can be used to design the required compositional parameters for a desired response. These predicted materials are synthesized and found to possess an incipient quantum critical point when magnetic ordering types are designed to be in direct competition; this leads to highly controllable exchange bias sensitivity in the monolithic single crystal films previously accessible only in intentionally designed bilayer heterojunctions.

Layered trigonal EuMg$_2$Bi$_2$ is reported to be a topological semimetal that hosts multiple Dirac points that may be gapped or split by the onset of magnetic order. Here, we report zero-field single-crystal neutron-diffraction and bulk magnetic susceptibility measurements versus temperature $\chi(T)$ of EuMg$_2$Bi$_2$ that show the intraplane ordering is ferromagnetic (Eu$^{2+},\, S= 7/2$) with the moments aligned in the $ab$-plane while adjacent layers are aligned antiferromagnetically (i.e., A-type antiferromagnetism) below the N\'eel temperature.

Neutron diffraction and magnetic susceptibility studies show that orthorhombic single-crystals of topological semimetals ${\rm Sr(Mn_{0.9}Cu_{0.1})Sb_2}$ and ${\rm Sr(Mn_{0.9}Zn_{0.1})Sb_2}$ undergo three dimensional C-type antiferromagnetic (AFM) ordering of the Mn$^{2+}$ moments at $T_N = 200\pm10$ and $210\pm12$ K, respectively, significantly lower than that of the parent SrMnSb$_2$ with $T_N=297 \pm 3$ K. Magnetization versus applied magnetic field (perpendicular to MnSb planes) below $T_N$ exhibits slightly modified de Haas van Alphen oscillations for the Zn-doped crystal as compared to that of the parent compound. By contrast, the Cu-doped system does not show de Haas van Alphen magnetic oscillations, suggesting that either Cu substitution for Mn changes the electronic structure of the parent compound substantially, or that the Cu sites are strong scatterers of carriers that significantly shorten their mean free path thus diminishing the oscillations. Density functional theory (DFT) calculations including spin-orbit coupling predict the C-type AFM state for the parent, Cu-, and Zn-doped systems and identify the $a$-axis (i.e., perpendicular to the Mn layer) as the easy magnetization direction in the parent and 12.5% of Cu or Zn substitutions. In contrast, 25% of Cu content changes the easy magnetization to the $b$-axis (i.e., within the Mn layer). We find that the incorporation of Cu and Zn in SrMnSb$_2$ tunes electronic bands near the Fermi level resulting in different band topology and semi-metallicity. The parent and Zn-doped systems have coexistence of electron and hole pockets with opened Dirac cone around the Y-point whereas the Cu-doped system has dominant hole pockets around the Fermi level with a distorted Dirac cone. The tunable electronic structure may point out possibilities of rationalizing the experimentally observed de Haas van Alphen magnetic oscillations.

Magnetic neutron scattering measures spin-spin correlations giving information about the long-range spin order as well as the shape of the spin density in magnetic materials. Similarly, detailed first principles calculations directly compute the spin density in materials. In this work, the authors carefully compare experimentally measured magnetic neutron intensities to three levels of theory: density functional theory in two approximations, and fixed-node diffusion Monte Carlo. While each theory performs similarly for the simple antiferromagnet MnO, there are significant differences between density functional theory and diffusion Monte Carlo in NiO. For both materials, fixed-node diffusion Monte Carlo shows the lowest RMS error with respect to experiment for the form factor and the intensity. Through connection of the intensities and form factors to the real-space spin densities, it is shown that diffusion Monte Carlo spin density becomes more diffuse by spreading spin away from the bond directions. This benchmark is of importance when considering the efficacy of an ab initio calculation in capturing both the long-range magnetic correlations and the microscopic spin details of magnetic systems.

Local configurational disorder can have a dominating role in the formation of macroscopic functional responses in strongly correlated materials. Here, we use entropy-stabilization synthesis to create single crystal epitaxial ABO3 perovskite thin films with equal atomic concentration of 3d transition metal cations on the B-site sublattice. X-ray diffraction, atomic force microscopy, and scanning transmission electron microscopy of La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3 (L5BO) films demonstrate excellent crystallinity, smooth film surfaces, and uniform mixing of the 3d transition metal cations throughout the B-site sublattice. The magnetic properties are strongly dependent on substrate-induced lattice anisotropy and suggest the presence of long-range magnetic order in these exceptionally disordered materials. The ability to populate multiple elements onto a single sublattice in complex crystal structures opens new possibilities to design functionality in correlated systems and enable novel fundamental studies seeking to understand how diverse local bonding environments can work to generate macroscopic responses, such as those driven by electron-phonon channels and complex exchange interaction pathways.

We report on the crystal and magnetic structures, magnetic, and transport properties of SrMnSb$_2$ single crystals grown by the self-flux method. Magnetic susceptibility measurements reveal an antiferromagnetic (AFM) transition at $T_{\rm N} = 295(3)$ K. Above $T_{\rm N}$, the susceptibility slightly increases and forms a broad peak at $T \sim 420$ K, which is a typical feature of two-dimensional magnetic systems. Neutron diffraction measurements on single crystals confirm the previously reported C-type AFM structure below $T_{\rm N}$. Both de Haas-van Alphen (dHvA) and Shubnikov-de Haas (SdH) effects are observed in SrMnSb$_2$ single crystals. Analysis of the oscillatory component by a Fourier transform shows that the prominent frequencies obtained by the two different techniques are practically the same within error regardless of sample size or saturated magnetic moment. Transmission electron microscopy (TEM) reveals the existence of stacking faults in the crystals, which result from a horizontal shift of Sb atomic layers suggesting possible ordering of Sb vacancies in the crystals. Increase of temperature in susceptibility measurements leads to the formation of a strong peak at $T \sim {570}$ K that upon cooling under magnetic field the susceptibility shows a ferromagnetic transition at $T_{\rm C} \sim 580$ K. Neutron powder diffraction on crushed single-crystals does not support an FM phase above $T_{\rm N}$. Furthermore, X-ray magnetic circular dichroism (XMCD) measurements of a single crystal at the $L_{2,3}$ edge of Mn shows a signal due to induced canting of AFM moments by the applied magnetic field. All evidence strongly suggests that a chemical transformation at the surface of single crystals occurs above 500 K concurrently producing a minute amount of ferromagnetic impurity phase., Comment: 17 figures

We present neutron scattering results on the magnetic excitations in the spinel compounds Li$_x$[Mn$_{1.96}$Li$_{0.04}$]O$_4$ (x= 0.2, 0.6, 0.8, 1.0). We show that the dominant excitations below T ~ 70 K are determined by clusters of Mn^4+ ions, and that these excitations mimic the E/T-scaling found in quantum critical systems that also harbor magnetic clusters, such as CeRu$_{0.5}$Fe$_{1.5}$Ge$_2$. We argue that our results for this classical spinel compound show that the unusual response at low temperatures as observed in quantum critical systems is (at least) partially the result of the fragmentation of the magnetic lattice into smaller units. This fragmentation in quantum critical systems is the direct and unavoidable result of intrinsic disorder., Comment: 8 pages, 8 figures; to be submitted to PRB