We report the structural, magnetic, transport and electronic properties of Nb substituted LaCo$_{1-x}$Nb$_x$O$_3$ ($x =$ 0--0.2). The Rietveld analysis of x-ray diffraction data demonstrate structural phase transitions from rhombohedral to orthorhombic and further to monoclinic with increasing the Nb concentration up to $x \ge$ 0.2. Interestingly, we observed dramatic changes in the magnetization (M) with increasing the Nb concentration, as the M sharply increases below 10~K even at 2.5\% substitution. Furthermore, ac susceptibility data show the spin-glass behavior in $x=$ 0.1 sample. We find that the density of states near the Fermi level decreases and the activation energy increases, which results in the decreasing conductivity with higher Nb concentration. A significant shift in the peak position of A$_{2g}$ phonon mode has been observed using Raman spectroscopy, which indicates the change in the coupling due to the structural distortion with Nb substitution. The core-level photoemission study confirms that the Nb is present in 5+ valence state. Our study reveals that the nonmagnetic Nb$^{5+}$ ($d^0$) substitution converts Co$^{3+}$ ions to Co$^{2+}$ and stabilize both in the high-spin state. Our results suggest that structural and spin-state transitions as well as the difference in the ionic radii between Nb$^{5+}$ and Co$^{3+}$ are playing an important role in tuning the physical properties.
Neutron diffraction for a polycrystalline sample of LaCo$_{0.8}$Rh$_{0.2}$O$_{3}$ and synchrotron x-ray diffraction for polycrystalline samples of LaCo$_{0.9}$Rh$_{0.1}$O$_{3}$ and LaCo$_{0.8}$Rh$_{0.2}$O$_{3}$ have been carried out in order to investigate the structural properties related with the spin state of Co$^{3+}$ ions. We have found that the values of the Co(Rh)-O bond lengths in the Co(Rh)O$_{6}$ octahedron of LaCo$_{0.8}$Rh$_{0.2}$O$_{3}$ are nearly identical at 10 K. The lattice volume for the Rh$^{3+}$ substituted samples decreases with the thermal expansion coefficient similar to…
Magnetization and x-ray diffraction have been measured on polycrystalline samples of LaCo$_{0.8-y}$Rh$_{0.2}$Ga$_{y}$O$_{3}$ for $0 \leq y \leq 0.15$ in order to understand the spin state of Co$^{3+}$ through the Ga$^{3+}$ substitution effect. The ferromagnetic order in LaCo$_{0.8}$Rh$_{0.2}$O$_{3}$ below 15 K is dramatically suppressed by the Ga$^{3+}$ substitution, where the ferromagnetic volume fraction is linearly decreased. The normal state susceptibility also systematically decreases with the Ga content, from which we find that one Ga$^{3+}$ ion reduces 4.6 $μ_{\rm B}$ per formula unit. …
We show that Pr${_{0.5}}$Ca$_{0.5}$MnO${_3}$ with 2.5% Al substitution and La${_{0.5}}$Ca$_{0.5}$MnO${_3}$ (LCMO) exhibit qualitatively similar and visibly anomalous M-H curves at low temperature. Magnetic field causes a broad first-order but irreversible antiferromagnetic (AF)-insulating (I) to ferromagnetic (FM)-metallic (M) transition in both and gives rise to soft FM state. However, the low temperature equilibrium state of Pr$_{0.5}$Ca$_{0.5}$Mn$_{0.975}$Al$_{0.025}$O$_3$ (PCMAO) is FM-M whereas that of LCMO is AF-I. In both the systems the respective equilibrium phase coexists with the ot…
Non magnetic insulators/semiconductors with induced magnetism introduced via transition metal substitution are one of the promising materials in the field of spintronic, magnetoelectronics and magneto optical devices. In this context, here, we focus on magnetism induced in a non magnetic insulator CaHfO3, by the substitution of 4d element Ru, at Hf site. Structural investigations indicate that substitution of Ru4+ (up to 50%) does not affect the original crystal structure of the parent compound. Magnetic studies divulge a crossover from a diamagnetic to paramagnetic state with 20% Ru substitut…
The magnetic and magnetotransport properties of the oxygen deficient perovskites, SrCo1-xMxO3-d with M = Nb and Ru, were investigated. Both Nb- and Ru-substituted cobaltites are weak ferromagnets, with transition temperatures Tm of 130-150 K and 130-180 K, respectively, and both exhibit a spin glass behavior at temperatures below Tf = 80-90 K. It is demonstrated that there exists a strong competition between ferromagnetism and spin glass state, where Co4+ induces ferromagnetism, whereas Nb or Ru substitution at the cobalt sites induces magnetic disorder, and this particular magnetic behavior i…
We report the results of de-Haas-van-Alphen (dHvA) measurements in Cd doped CeCoIn$_5$ and LaCoIn$_5$. Cd doping is known to induce an antiferromagnetic order in the heavy fermion superconductor CeCoIn$_5$, whose effect can be reversed with applied pressure. We find a slight but systematic change of the dHvA frequencies with Cd doping in both compounds, reflecting the chemical potential shift due to the addition of holes. The frequencies and effective masses are close to those found in the nominally pure compounds with similar changes apparent in the Ce and La compounds with Cd substitution. W…
We have investigated magnetic, electrical and thermal transport properties (Seebeck effect and thermal conductivity) of LaSr$_{2}$Mn$_{2-y}$Cr$_{y}$O$_{7}$ polycrystalline samples ($y$=0.1, 0.2, 0.4 and 0.6). The Cr$^{3+}$ substitution for Mn$^{3+}$ sites causes a removal of $d_{x^2-y^2}$ orbital of $e_g$-electron resulting in a volume shrinkage of lattice. Magnetic measurements reveal the appearance of a glassy behavior for Cr-doped samples, accompanied by both a collapse of the A-type antiferromagnetic structure and the growth of ferromagnetic clusters. Cr-doping effect on electrical transpo…
A detailed investigation of first order ferrimagnetic (FRI) to antiferromagnetic (AFM) transition in Co (15%) doped $Mn_2Sb$ is carried out. These measurements demonstrate anomalous thermomagnetic irreversibility and glass-like frozen FRI phase at low temperatures. The irreversibility arising between the supercooling and superheating spinodals is distinguised in an ingenious way from the irreversibility arising due to kinetic arrest. Field annealing measurements shows reentrant FRI-AFM-FRI transition with increasing temperature. These measurements also show that kinetic arrest band and superco…
We combine the results of magnetic and transport measurements with Mossbauer spectroscopy and room-temperature diffraction data to construct the magnetic phase diagram of the new family of cubic perovskite manganites SrMn_1-xFe_xO_3. We have found antiferromagnetic ordering for lightly and heavily Fe-substituted material, while intermediate substitution leads to spin-glass behavior. Near the SrMn_0.5Fe_0.5O_3 composition these two types of ordering are found to coexist and affect one another. The spin glass behavior may be caused by competing ferro- and antiferromagnetic interactions among Mn^…
The inversion and volume effects on magnetism in a spinel-type magnetically frustrated compound, CoAl2O4, and its gallium-substituted system, CoAl2-xGaxO4, were investigated. Magnetically frustrated Co2+ with spin S = 3/2 on the tetrahedral site formed a diamond lattice in CoAl2O4 located in the vicinity of the magnetic phase boundary between Neel and spin-spiral states. In the Ga-substituted system, the number of Co ions, the so-called inversion h dominating the octahedral site, increased with increasing x. From comprehensive crystallographic, magnetic, and thermal measurements, increments of…
Magneto-dielectric spectra of La0.95Ca0.05CoO3 covering the crossover of spin states reveals strong coupling of its spin and dipolar degrees of freedom. Signature of spin-state transition at 30K clearly manifests in magnetization, supported by Co L_3,2-edge XAS data on the doped-specimen as consistent with its suppressed T_SST vs. ~150K for pure LaCoO3. Dispersive activation-step Δε'(T_ω)~O(10^2) and relaxation-peak ε"(T_ω) reflect the allied influence of coexistent spin-states on the dielectric character. Dipolar relaxation in the LS regime below T_SST is partly segmental (VFT kinetics) featu…
Chemical substitution is commonly used to explore new ground states in materials, yet the role of disorder is often overlooked. In Mn-substituted BaFe$_{2}$As$_{2}$ (MnBFA), superconductivity (SC) is absent, despite being observed for nominal hole-doped phases. Instead, a glassy magnetic phase emerges, associated with the $S=5/2$ Mn local spins. In this work, we present a comprehensive investigation of the electronic structure of MnBFA using angle-resolved photoemission spectroscopy (ARPES). We find that Mn causes a small and orbital-specific reduction of the electron pockets, only partially d…
We report the structure, magnetic, and thermal property measurements on single crystalline and polycrystalline samples of Ru substituted honeycomb lattice iridate Na$_2$Ir$_x$Ru$_{1-x}$O$_3$ (x = 0, 0.05, 0.1, 0.15, 0.2, 0.3, 0.5). The evolution of magnetism in Na$_2$Ir$_x$Ru$_{1-x}$O$_3$ has been studied using dc and ac magnetic susceptibility, and heat capacity measurements. The parent compound Na$_2$IrO$_3$ is a spin-orbit driven Mott insulator with magnetic order of reduced moments below $T_N = 15$~K\@. In the Ru substituted samples the antiferromagnetic long range state is replaced by a s…
Physical properties of partially Ca substituted hole-doped Dy2Ti2O7 have been investigated by ac magnetic susceptibility χ_ac(T), dc magnetic susceptibility χ(T), isothermal magnetization M(H) and heat capacity C_p(T) measurements on Dy1.8Ca0.2Ti2O7. The spin-ice system Dy2Ti2O7 exhibits a spin-glass type freezing behavior near 16 K. Our frequency dependent χ_ac(T) data of Dy1.8Ca0.2Ti2O7 show that the spin-freezing behavior is significantly influenced by Ca substitution. The effect of partial nonmagnetic Ca2+ substitution for magnetic Dy3+ is similar to the previous study on nonmagnetic isova…
We report a quantum phase transition from a spin-liquid state to a spin-glass state in the quasi-one dimensional (1D) spin-1 system Sr1-xCaxNi2V2O8, induced by a small amount of Ca-substitution at Sr site. The ground state of the parent compound (x = 0) is found to be a spin-liquid type with a finite energy gap of 26.6 K between singlet ground state and triplet excited state. Both dc-magnetization and ac-susceptibility studies on the highest Ca-substituted compound (x = 0.05) indicate a spin-glass type magnetic ground state. With increasing Ca-concentration, the spin-glass ordering temperature…
We combine the results of magnetic and transport measurements with neutron diffraction data to construct the structural and magnetic phase diagram of the entire family of SrMn$_{1-x}$Ru$_{x}$O$_3$ ($0 \leqslant x \leqslant 1$) perovskites. We have found antiferromagnetic ordering of the C type for lightly Ru-substituted materials ($0.06 \leqslant x \leqslant 0.5$) in a similar manner to $R_{y}$Sr$_{1-y}$MnO$_3$ ($R$=La, Pr), due to the generation of Mn$^{3+}$ in both families of manganite perovskites by either $B$-site substitution of Ru$^{5+}$ for Mn$^{4+}$ or $A$-site substitution of $R^{3+}…
Polycrystalline members of the GaV$_4$S$_{8-y}$Se$_y$ family of materials with small levels of substitution between $0 \leq y \leq 0.5$ and $7.5 \leq y\leq 8$ have been synthesized in order to investigate their magnetic and structural properties. Substitutions to the skyrmion hosting parent compounds GaV$_4$S$_8$ and GaV$_4$Se$_8$, are found to suppress the temperature of the cubic to rhombohedral structural phase transition that occurs in both end compounds and to create a temperature region around the transition where there is a coexistence of these two phases. Similarly, the magnitude of th…
We have probed the low temperature magnetic behavior of the ordered spin ice material Tb2Sn2O7 through ac magnetic susceptibility measurements of both the pure material and samples with small percentages of Ti substituted on the Sn sublattice. We observe a clear signature for the previously reported ordering transition at TC = 850 mK, as well as evidence for dynamic freezing at temperatures well below TC, confirming the persistence of significant magnetic fluctuations deep in the spin-ordered regime. The long range ordering transition was completely suppressed with as little as 5% Ti for Sn su…
Recently, the bi-layer Kagome lattice material Ca$_{10}$Cr$_7$O$_{28}$ has been shown to be a quasi-two-dimensional quantum spin liquid (QSL) where the frustration arises from a balance between competing ferromagnetic and antiferromagnetic exchange within a bi-layer. In an attempt to understand what happens when this balance is disturbed, we present a magnetic dilution study. Specifically, we have synthesized Ca$_{10}$(Cr$_{1-x}$V$_x$)$_7$O$_{28}$ (0 $\leq$ x $\leq$ 0.5) where magnetic Cr$^{5+}$ ($S = 1/2$) is partially replaced by non-magnetic V$^{5+}$ ($S = 0$). We also synthesized the fully…
The magnetic and electronic properties of Sr1-xLaxRuO3 were studied by means of dc-magnetization, ac-susceptibility, specific heat, and electrical resistivity measurements. The dc-magnetization and ac-susceptibility measurements have revealed that the transition temperature and the ordered moment of the ferromagnetic order are strongly suppressed as La is substituted for Sr. The ac-susceptibility exhibits a peak at T* due to the occurrence of spontaneous spin polarization. Furthermore, we observed that T* shows clear frequency variations for x>= 0.3. The magnitude of the frequency shifts of T*…
We have grown a series of nickel substituted single crystals of the layered ferromagnet (FM) Fe$_3$GeTe$_2$. The large single crystalline samples of (Fe$_{1-x}$Ni$_x$)$_3$GeTe$_2$ with $x = 0-0.84$ were characterized with single crystal X-ray diffraction, magnetic susceptibility, electrical resistance and muon spin spectroscopy. We find Fe can be continuously substituted with Ni with only minor structural variation. In addition, FM order is suppressed from $T_\mathrm{C}=212$~K for $x=0$ down to $T_\mathrm{C}=50$~K for $x=0.3$, which is accompanied with a strong suppression of saturated and eff…
Ba$_2$Cu$_3$O$_4$Cl$_2$ has two inter-penetrating square Cu sublattices, one with square root 2 times the in-plane spacing of the other. Isotropic magnetic interactions between the two sublattices are completely frustrated. Quantum fluctuations resolve the intrinsic degeneracy in the ordering direction of the more weakly coupled sublattice in favor of collinear ordering. We present neutron scattering and magnetization studies of the magnetic structure when the Cu ions are substituted with Co. The Co spins create new magnetic interactions between the two sublattices. The ordering behavior of bo…
Spin-state transitions are the hallmark of rare-earth cobaltates. In order to understand them, it is essential to identify all relevant parameters which shift the energy balance between spin states, and determine their trends. We find that Δ, the eg-t2g crystal-field splitting, increases by ~250 meV when increasing pressure to 8 GPa and by about 150 meV when cooling from 1000K to 5K. It changes, however, by less than 100 meV when La is substituted with another rare earth. Also the Hund's rule coupling J_avg is about the same in systems with very different spin-state transition temperature, lik…
Single crystals of Ca[Co_(2-x)Ir_(x)]_(2-y)As2 with 0 <= x <= 0.35 and 0.10 <= y <= 0.14 have been grown using the self-flux technique and characterized by single-crystal x-ray diffraction (XRD), energy-dispersive x-ray spectroscopy, magnetization M and magnetic susceptibility chi measurements versus temperature T, magnetic field H, and time t, and heat capacity Cp(H,T) measurements. The XRD refinements reveal that all the Ir-substituted crystals crystallize in a collapsed-tetragonal structure as does the parent CaCo_(2-y)As2 compound. A small 3.3% Ir substitution for Co in CaCo_(1.86)As2 dras…
Emergent magnetism, heavy electrons and pressure-induced reentrant superconductivity in the iron substituted 4d transition-metal sulfides
Zhejiang University of Technology（浙江工业大学）；Fudan University（复旦大学）；Qufu Normal University（曲阜师范大学）；Nanjing University of Posts and Telecommunications（南京邮电大学）；Suzhou University of Technology（苏州科技大学）；Hangzhou Dianzi University（杭州电子科技大学）；National Taiwan Normal University（台湾师范大学）；Academia Sinica（中央研究院）；Zhejiang University（浙江大学）；Ningbo University（宁波大学）；Hangzhou Normal University（杭州师范大学）；Shanghai Jiao Tong University（上海交通大学）
Ba$_3$Mn$_2$O$_8$ is a geometrically frustrated spin dimer compound. We investigate the effect of site disorder on the zero field phase diagram of this material by considering the solid solution Ba$_{3}$(Mn$_{1-x}$V$_{x}$)$_{2}$O$_{8}$, where nonmagnetic V$^{5+}$ ions partially substitute magnetic Mn$^{5+}$ ions. This substitution results in unpaired $S=1$ moments for half-substituted dimers, which are ungapped and therefore susceptible to types of magnetic order not present in the parent compound. AC susceptibility measurements of compositions between $x=0.046$ and $x=0.84$ show a sharp frequ…
Thermally quenched metastability in metal-insulator transitions via elemental substitution
The University of Tokyo（东京大学）；National Institute of Advanced Industrial Science and Technology（产业技术综合研究所）；Graduate School of Engineering and Science, Shibaura Institute of Technology（芝浦工业大学研究生院理工学研究科）；RIKEN Center for Emergent Matter Science（理化学研究所新兴物质科学研究中心）；University of Tsukuba（筑波大学）；Institute of Science Tokyo（东京科学大学）；National Institute for Materials Science（国立材料研究所）
We study the structural, magnetic, transport and electronic properties of LaCoO$_3$ with Sr/Nb co-substitution, i.e., La$_{(1-2x)}$Sr$_{2x}$Co$_{(1-x)}$Nb$_{x}$O$_3$ using x-ray and neutron diffraction, dc and ac-magnetization, neutron depolarization, dc-resistivity and photoemission measurements. The powder x-ray and neutron diffraction data were fitted well with the rhombohedral crystal symmetry (space group \textit{R$\bar{3}$c}) in Rietveld refinement analysis. The calculated effective magnetic moment ($\approx$3.85~$μ_B$) and average spin ($\approx$1.5) of Co ions from the analysis of magn…
We report on the effects of introducing magnetic and non-magnetic disorder in the hyperkagome iridate quantum spin liquid (QSL) candidate Na$_4$Ir$_3$O$_8$ by partially replacing Ir$^{4+}$ ($S = 1/2$) with Ru$^{4+}$ ($S = 1$) or Ti$^{4+}$ ($S = 0$). Specifically, we synthesized Na$_4$(Ir$_{1-x}$Ru$_x$)$_3$O$_8 (x = 0.05, 0.10, 0.2, 0.3)$ and Na$_4$Ir$_{2.7}$Ti$_{0.3}$O$_8$ samples and measured electrical transport, AC and DC magnetization, and heat capacity down to $T = 1.8$ K. Na$_4$Ir$_3$O$_8$ is associated with a large Weiss temperature $θ= -650$ K, a broad anomaly in magnetic heat capacity…
We studied Zn-substitution effect on the high-T_c superconductors, underdoped La_{2-x}Sr_xCu_{1-y}Zn_yO_4 (x=0.10; y=0, 0.01, 0.02), optimally doped (x=0.15; y=0, 0.02), and overdoped (x=0.20; y=0, 0.03, 0.06) in a temperature range of T=4.2-300 K, using Cu nuclear quadrupole resonance (NQR) spin-echo technique. We found full disappearance of the Cu NQR signals for the Zn-substituted, Sr-underdoped x=0.10 samples below about 40 K, partial disappearance for the Sr-optimally doped ones below about 50 K, but not for the overdoped x=0.20 ones. From the Zn-doping, the Sr-doping and the temperature …
We report the magnetic susceptibility and NMR studies of a spin-gapped layered compound Na2Cu2TeO6 (the spin gap $Δ\sim$ 250 K), the hole doping effect on the Cu2TeO6 plane via a topochemical Na deficiency by soft chemical treatment, and the static spin vacancy effect by nonmagnetic impurity Zn substitution for Cu. A finite Knight shift at the $^{125}$Te site was observed for pure Na2Cu2TeO6. The negative hyperfine coupling constant $^{125}A_{tr}$ is an evidence for the existence of a superexchange pathway of the Cu-O-Te-O-Cu bond. It turned out that both the Na deficiency and Zn impurities in…
A systematic study using neutron diffraction and magnetic susceptibility are reported on Mn substituted ferrimagnetic inverse spinel Ti$_{1-x}$Mn$_{x}$Co$_2$O$_4$ in the temperature interval 1.6 K $\leq$ $T$ $\leq$ 300 K. Our neutron diffraction study reveals cooperative distortions of the $T$O$_6$ octahedral for all the Jahn-Teller active ions $T$ = Mn$^{3+}$, Ti$^{3+}$ and Co$^{3+}$, which are confirmed by the X-ray photoelectron spectroscopy. Two specific compositions ($x$ = 0.2 and 0.4) have been chosen because of their unique features: noncollinear Yafet-Kittel type ordering, and weak tet…
Zero-field and longitudinal-field muon-spin-relaxation measurements have been performed in partially Fe-substituted La2-xSrxCu1-yFeyO4 in a wide range of hole concentration, to investigate the magnetic state induced by the Fe substitution recently suggested from the neutron-scattering measurements [Phys. Rev. Lett. 107, 127002 (2011)]. It has been found that the magnetic transition temperature is notably enhanced through the 1% Fe substitution in a wide range of hole concentration where superconductivity appears in Fe-free La2-xSrxCuO4. In the underdoped regime, the Fe-induced magnetic order c…
We have performed extensive zero field muSR experiments on pure YBa2Cu3O6+y and diluted Y-rare-earth substituted Y0.92Eu0.08Ba2Cu3O6+y and Y0.925Nd0.075Ba2Cu3O6+y at light hole-doping. A common magnetic behavior is detected for all the three families, demonstrating negligible effects of the isovalent Y-substituent disorder. Two distinct regimes are identified, separated by a crossover, whose origin is attributed to the concurrent thermal activation of spin and charge degrees of freedom: a thermally activated and a re-entrant quenched-hole antiferromagnetic regime. The peculiar temperature and …
We have systematically investigated the influence of gradual replacement of Ca by Gd on the magnetic and complex dielectric properties of the well-known geometrically frustrated spin-chain system, Ca3Co2O6 (T_N= 24 K with additional magnetic transitions below 12K), by studying the series, Ca3-xGdxCo2O6 (x less than 0.7), down to 1.8K. Heat capacity measurements establish that the reduction of T_N with Gd substitution is much less as compared to that by Y substitution. The magnetic moment data reveal that there are changes in the oxidation state of Co as well, unlike for Y-substitution, beyond …
