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Transition metal dichalcogenides (TMDs) are an emergent class of low-dimensional materials with growing applications in the field of nanoelectronics. However, efficient methods for synthesizing large monocrystals of these systems are still lacking. Here, we describe an efficient synthetic route for a large number of TMDs that were obtained in quartz glass ampoules by sulfuric vapor transport and liquid sulfur. Unlike the sublimation technique, the metal enters the gas phase in the form of molecules, hence containing a greater amount of sulfur than the growing crystal. We have investigated the physical properties for a selection of these crystals and compared them to state-of-the-art findings reported in the literature. The acquired electronic properties features demonstrate the overall high quality of single crystals grown in this work as exemplified by CoS2, ReS2, NbS2, and TaS2. This new approach to synthesize high-quality TMD single crystals can alleviate many material quality concerns and is suitable for emerging electronic devices. Correction in: Cryst. Growth Des. 2023, 23, 6, 4720DOI: 10.1021/acs.cgd.3c00436

Organic semiconducting polymers exhibited promising photocatalytic behavior for hydrogen (H2) evolution, especially when prepared in the form of polymer dots (Pdots). However, the Pdot structures were formed using common nonconjugated amphiphilic polymers, which have a negative effect on charge transfer between photocatalysts and reactants and are unable to participate in the photocatalytic reaction. This study presents a new strategy for constructing binary Pdot photocatalysts by replacing the nonconjugated amphiphilic polymer typically employed in the preparation of polymer nanoparticles (Pdots) with a low-molecular-weight conjugated polyelectrolyte. The as-prepared polyelectrolyte/hydrophobic polymer-based binary Pdots truly enhance the electron transfer between the Pt cocatalyst and the polymer photocatalyst with good water dispersibility. Moreover, unlike the nonconjugated amphiphilic polymer, the photophysics and mechanism of this photocatalytic system through time-correlated single-photon counting (TCSPC) and transient absorption (TA) measurements confirmed the Forster resonance energy transfer (FRET) between the polyelectrolyte as a donor and the hydrophobic polymer as an acceptor. As a result, the designated binary Pdot photocatalysts significantly enhanced the hydrogen evolution rate (HER) of 43 900 μmol g-1 h-1 (63.5 μmol h-1, at 420 nm) for PTTPA/PFTBTA Pdots under visible-light irradiation.

We present measurements of the magnetic torque, specific heat and thermal expansion of the bulk transition metal dichalcogenide (TMD) superconductor NbS2 in high magnetic fields, with its layer structure aligned strictly parallel to the field using a piezo rotary positioner. The upper critical field of superconducting TMDs in the 2D form is known to be dramatically enhanced by a special form of Ising spin orbit coupling. This Ising superconductivity is very robust to the Pauli paramagnetic effect and can therefore exist beyond the Pauli limit for superconductivity. We find that superconductivity beyond the Pauli limit still exists in bulk single crystals of NbS2 for a precisely parallel field alignment. However, the comparison of our upper critical field transition line with numerical simulations rather points to the development of a Fulde-Ferrell-Larkin-Ovchinnikov state above the Pauli limit as a cause. This is also consistent with the observation of a magnetic field driven phase transition in the thermodynamic quantities within the superconducting state near the Pauli limit. © 2021, The Author(s). We thank U. Lampe for technical support. This work was supported by grants from the Research Grants Council of the Hong Kong Special Administrative Region, China (GRF-16302018, GRF-16303820, C6025-19G-A, SBI17SC14). M.A.-H. acknowledges the financial support from the Swedish Research Council (VR) under the project no. 2018-05393 and by the Arab-German Young Academy of Sciences and Humanities (AGYA). M.A.-H and D.C. acknowledge the financial support by the Megagrant 2020-220-08-6358 of the Government Council on Grants of the Russian Federation.

Zn1-xRxO (R = Li, Mg, Cr, Mn, Fe and Cd) were obtained by using co-precipitation synthesis technique with constant weight percent of 3% from R ions. The phase composition, crystal structure, morphology, density functional theory (DFT), and magnetic properties were examined to comprehend the influence of Zn2+ partial substitution with R ions. X-ray diffraction shows that the ZnO lattice parameters were slightly affected by R doping and the doped sample crystallinity is enhanced. Our results show that introducing Cr, Mn and Fe along with Mg into ZnO induces a clear magnetic moment without any apparent distortion in the structural morphology. The spatial configuration of dopant atoms is determined from first-principles calculations, giving a better understanding of the position of the dopant atom responsible for the magnetism. The magnetic moments obtained from our calculations are 3.67, 5.0, and 4.33 μB per dopant atom for Cr, Mn, and Fe, respectively, which agree with the experimental values. While Cr and Fe tend to form clusters, Mn has more propensity to remain evenly distributed within the system, avoiding cluster-derived magnetism.

Due to their physical properties and potential applications in energy conversion and storage, transition-metal dichalcogenides (TMDs) have garnered substantial interest in recent years. Among this class of materials, TMDs based on molybdenum, tungsten, sulfur, and selenium are particularly attractive due to their semiconducting properties and the availability of bottom-up synthesis techniques. Here we report a method which yields high-quality crystals of transition-metal diselenide and ditelluride compounds (PtTe2, PdTe2, NiTe2, TaTe2, TiTe2, RuTe2, PtSe2, PdSe2, NbSe2, TiSe2, VSe2, ReSe2) from their solid solutions, via vapor deposition from a metal-saturated chalcogen melt. Additionally, we show the synthesis of rare-earth-metal polychalcogenides and NbS2 crystals using the aforementioned process. Most of the crystals obtained have a layered CdI2 structure. We have investigated the physical properties of selected crystals and compared them to state of the art findings reported in the literature. Remarkably, the charge density wave transition in 1T-TiSe2 and 2H-NbSe2 crystals is well-defined at TCDW ≈ 200 and 33 K, respectively. Angle-resolved photoelectron spectroscopy and electron diffraction are used to directly access the electronic and crystal structures of PtTe2 single crystals and yield state of the art measurements. © 2020 American Chemical Society. M.A.-H. acknowledges support from the VR starting grant 2018-05339 and KL1824/6. The crystal growth experiments were supported by the Russian Science Foundation, Project 19-12-00414. The work has been supported by the program 211 of the Russian Federation Government agreements 02.A03.21.0006 and 02.A03.21.0011, by the Russian Government Program of Competitive Growth of Kazan Federal University. We acknowledge MAX IV Laboratory for time on Beamline Bloch under Proposal 20190335. Research conducted at MAX IV, a Swedish national user facility, is supported by the Swedish Research council under contract 2018-07152 the Swedish Governmental Agency for Innovation Systems under contract 2018-04969, and Formas under contract 2019-02496. We acknowledge ARPES experiment support from Craig Polley (MAX IV), Maciej Dendzik (KTH) Antonija Grubisic-Cabo (KTH) and Oscar Tjernberg (KTH). H.R., D.P. and G.J.M. acknowledge the Swedish Research Council (2018-06465, 2018-04330) and the Swedish Energy Agency (P43549-1) for financial support.

Through advanced experimental techniques on CrI$_{3}$ single crystals, we derive a previously not discussed pressure-temperature phase diagram. We find that $T_{c}$ increases to $\sim$ 66\,K with pressure up to $\sim$ 3\,GPa followed by a decrease to $\sim$ 10\,K at 21.2\,GPa. The experimental results are reproduced by theoretical calculations based on density functional theory where electron-electron interactions are treated by a static on-site Hubbard U on Cr 3$d$ orbitals. The origin of the pressure induced reduction of the ordering temperature is associated with a decrease of the calculated bond angle, from 95$^{\circ}$ at ambient pressure to $\sim$ 85$^{\circ}$ at 25\,GPa. Above 22\,GPa, the magnetically ordered state is essentially quenched, possibly driving the system to a Kitaev spin-liquid state at low temperature, thereby opening up the possibility of further exploration of long-range quantum entanglement between spins. The pressure-induced semiconductor-to-metal phase transition was revealed by high-pressure resistivity that is accompanied by a transition from a robust ferromagnetic state to gradually more dominating anti-ferromagnetic interactions and was consistent with theoretical modeling.

We report on the magnetocaloric effect and critical phenomenon on La0.8K0.2MnO3 nanoparticle through a systematic magnetic and electrical measurement. The magnetic entropy change (ΔSM) presents close values obtained from resistivity and magnetic measurements, however, with a discrepancy in the magnetic entropy maximum values. This discrepancy is due to the presence of an extrinsic effect associated with the nanometric grain size affecting the electrical behavior. Interestingly, our results show a good agreement with the calculation of the critical exponents and the temperature coefficient of resistance shows positive and negative values. The obtained critical exponents are close to that of the mean-field theory (with β = 0.5, γ = 1, and δ = 3). This indicates a long-range interaction between spins a consequence of the presence the presence of dipole- dipole interaction in this system.

High-quality single crystals of ${\mathrm{CoTiO}}_{3}$ are grown and used to elucidate in detail structural and magnetostructural effects by means of high-resolution capacitance dilatometry studies in fields up to 15 T which are complemented by specific heat and magnetization measurements. In addition, we refine the single-crystal structure of the ilmenite ($R\overline{3}$) phase. At the antiferromagnetic ordering temperature ${T}_{\mathrm{N}}$ pronounced $\ensuremath{\lambda}$-shaped anomaly in the thermal expansion coefficients signals shrinking of both the $c$ and $b$ axes, indicating strong magnetoelastic coupling with uniaxial pressure along $c$ yielding six times larger effect on ${T}_{\mathrm{N}}$ than pressure applied in-plane. The hydrostatic pressure dependency derived by means of Gr\"uneisen analysis amounts to $\ensuremath{\partial}{T}_{\mathrm{N}}/\ensuremath{\partial}p\ensuremath{\approx}2.7(4)\phantom{\rule{4pt}{0ex}}\mathrm{K}/\mathrm{GPa}$. The high-field magnetization studies in static and pulsed magnetic fields up to 60 T along with high-field thermal expansion measurements facilitate in constructing the complete anisotropic magnetic phase diagram of ${\mathrm{CoTiO}}_{3}$. While the results confirm the presence of significant magnetodielectric coupling, our data show that magnetism drives the observed structural, dielectric, and magnetic changes both in the short-range ordered regime well above ${T}_{\mathrm{N}}$ as well as in the long-range magnetically ordered phase.

Mossbauer spectra of single crystals of sulfur-doped iron selenide FeSe0.91S0.09 are studied in a wide temperature range, including the vicinity of structural and superconducting transitions. It is found that iron atoms exhibit a nonmagnetic state even in the range of helium temperatures, which can be attributed to the low-spin state of Fe2+ (3d6, S = 0) ions. It is shown that this state remains nearly unchanged at temperatures close to the superconducting transition temperature. This means that the low-spin state of iron ions most probably results from some structural features and is not directly related to superconductivity. The temperature dependence of the parameters characterizing the hyperfine interaction exhibits several anomalies in the ranges of structural and electronic transitions. The Debye temperature ΘM = 478 K determined for the iron sublattice turns out to be much higher than the value ΘM = 285 K for the undoped FeSe1 - δ compound.

The presence of both strong interchain and intrachain interactions of an antiferromagnetic as well as an ferromagnetic nature may lead to the appearance of a gap in the magnetic excitation spectrum of LiCu2(VO4)(OH)2 as evidenced by the hump in magnetic susceptibility χ at T* ≈ 30 K. The temperature range of short-range magnetic order is terminated by the onset of long-range magnetic order at TN = 10 K, which is triggered by substantial interchain exchange interactions. This observation is corroborated by the specific heat, Cp, singularity, electron spin resonance, and nuclear magnetic resonance measurements. The latter reveals a broad distribution of the resonance fields ascribed to the formation of a helix magnetic structure. First-principles calculations allow estimations of both intrachain and interchain exchange interaction parameters, suggesting the implementation of a strongly coupled scenario with competing inter- and intrachain interactions.

Rhenium(I)-carbonyl-diimine complexes are promising photocatalysts for CO2 reduction. Covalent organic frameworks (COFs) can be perfect sensitizers to enhance the reduction activities. Here we investigated the excited state dynamics of COF (TpBpy) with 2,2'-bipyridine incorporating Re(CO)5Cl (Re-TpBpy) to rationalize the underlying mechanism. The time-dependent DFT calculation first clarified excited state structure of the hybrid catalyst. The studies from transient visible and infrared spectroscopies revealed the excitation energy-dependent photo-induced charge transfer pathways in Re-TpBpy. Under low energy excitation, the electrons at the LUMO level are quickly injected from Bpy into ReI center (1–2 ps) followed by backward recombination (13 ps). Under high energy excitation, the hot-electrons are first injected into the higher unoccupied level of ReI center (1–2 ps) and then slowly relax back to the HOMO in COF (24 ps). There also remains long-lived free electrons in the COF moiety. This explained the excitation energy-dependent CO2 reduction performance in our system.

In the last decade, nanosized metal organic frameworks (NMOFs) have gained an increasing applicability as multifunctional nanocarriers for drug delivery in cancer therapy. However, only a limited number of platforms have been reported that can serve as an effective targeted drug delivery system (DDSs). Herein, we report rational design and construction of doxorubicin (DOX)-loaded nanoscale Zr (IV)-based NMOF (NH2-UiO-66) decorated with active tumor targeting moieties; folic acid (FA), lactobionic acid (LA), glycyrrhetinic acid (GA), and dual ligands of LA and GA, as efficient multifunctional DDSs for hepatocellular carcinoma (HCC) therapy. The success of modification was exhaustively validated by various structural, thermal and microscopic techniques. Biocompatibility studies indicated the safety of pristine NH2-UiO-66 against HSF cells whereas DOX-loaded dual-ligated NMOF was found to possess superior cytotoxicity against HepG2 cells which was further confirmed by flow cytometry. Moreover, fluorescence microscopy was used for monitoring cellular uptake in comparison to the non-ligated and mono-ligated NMOF. Additionally, the newly developed dual-ligated NMOF depicted a pH-responsiveness towards the DOX release. These findings open new avenues in designing various NMOF-based DDSs that actively target hepatic cancer to achieve precise therapy.

We present magnetic torque, specific heat and thermal expansion measurements combined with a piezo rotary positioner of the bulk transition metal dichalcogenide (TMD) superconductor NbS2 in high magnetic fields applied strictly parallel to its layer structure. The upper critical field of superconducting TMDs in the 2D form is known to be dramatically enhanced by a special form of Ising spin orbit coupling. This Ising superconductivity is very robust against the Pauli limit for superconductivity. We find that superconductivity beyond the Pauli limit still exists in bulk single crystals of NbS2. However, the comparison of our upper critical field transition line with numerical simulations rather points to the development of a Fulde-Ferrell-Larkin-Ovchinnikov state above the Pauli limit as a cause. This is also consistent with the observation of a magnetic field driven phase transition in the thermodynamic quantities within the superconducting state near the Pauli limit.

We present measurements of the magnetic torque, specific heat and thermal expansion of the bulk transition metal dichalcogenide (TMD) superconductor NbS2 in high magnetic fields, with its layer structure aligned strictly parallel to the field using a piezo rotary positioner. The upper critical field of superconducting TMDs in the 2D form is known to be dramatically enhanced by a special form of Ising spin orbit coupling. This Ising superconductivity is very robust to the Pauli paramagnetic effect and can therefore exist beyond the Pauli limit for superconductivity. We find that superconductivity beyond the Pauli limit still exists in bulk single crystals of NbS2 for a precisely parallel field alignment. However, the comparison of our upper critical field transition line with numerical simulations rather points to the development of a Fulde-Ferrell-Larkin-Ovchinnikov state above the Pauli limit as a cause. This is also consistent with the observation of a magnetic field driven phase transition in the thermodynamic quantities within the superconducting state near the Pauli limit., Superconductivity is often destroyed under magnetic field larger than a critical value called Pauli limit. Here, the authors report superconductivity beyond the Pauli limit in bulk single crystals of NbS2, suggesting the development of a Fulde-Ferrell-Larkin-Ovchinnikov state.

The coexistence of charge density wave (CDW) and superconductivity in tantalum disulfide (2H-TaS$_2$) at ambient pressure, is boosted by applying hydrostatic pressures up to 30GPa, thereby inducing a typical dome-shaped superconducting phase. The ambient pressure CDW ground state which begins at TCDW = 76 K, with critically small Fermi surfaces, was found to be fully suppressed at Pc = 8.7GPa. Around Pc, we observe a superconducting dome with a maximum superconducting transition temperature Tc = 9.1 K. First-principles calculations of the electronic structure predict that, under ambient conditions, the undistorted structure is characterized by a phonon instability at finite momentum close to the experimental CDW wave vector. Upon compression, this instability is found to disappear, indicating the suppression of CDW order. The calculations reveal an electronic topological transition (ETT), which occurs before the suppression of the phonon instability, suggesting that the ETT alone is not directly causing the structural change in the system. The temperature dependence of the first vortex penetration field has been experimentally obtained by two independent methods and the corresponding lower critical field H$_{c1}$ was deduced. While a d wave and single-gap BCS prediction cannot describe our H$_{c1}$ experiments, the temperature dependence of the H$_{c1}$ can be well described by a single-gap anisotropic s-wave order parameter., 6 Pages, 4 figures

We report on the structural phase transitions in the S doped FeSe superconductor by powder synchrotron X ray diffraction at high pressures up to 18.5 GPa under compression and decompression modes. In order to create high quasi hydrostatic pressures, diamond anvil cells filled with helium as a pressure transmitting medium were used. It was found that at ambient pressure and room temperature, S doped FeSe has a tetragonal structure. Under compression, in the region of 10 GPa, a phase transition from the tetragonal into the orthorhombic structure is observed, which persists up to 18.5 GPa. Our results strongly suggest that, at decompression, as the applied pressure decreases to 6 GPa and then is completely removed, most of the sample recrystallizes into the hexagonal phase of the structural type NiAs. However, the other part of the sample remains in the high pressure orthorhombic phase, while the tetragonal phase is not restored. These observations illustrate a strong hysteresis of the structural properties of S doped FeSe during a phase transition under pressure., 13 pages, 10 figures

Despite intense efforts on all known quasi-two-dimensional superconductors, the origin and exact boundary of the electronic orderings, particularly charge density waves and superconductivity, are still attractive problems with several open questions. Here, in order to reveal how the superconducting gap evolves, we report on high quality complementary measurements of magneto-optical imaging, specific heat, magnetic susceptibility, resistivity measurements, Andreev spectroscopy, and London penetration depth ${\ensuremath{\lambda}}_{ab}(T)$ measurements supplemented with theoretical calculations for $2\mathrm{H}\text{\ensuremath{-}}\mathrm{Nb}{\mathrm{Se}}_{2}$ and $2\mathrm{H}\text{\ensuremath{-}}\mathrm{Nb}{\mathrm{S}}_{2}$ single crystals. The temperature dependence of ${\ensuremath{\lambda}}_{ab}(T)$ calculated from the lower critical field and Andreev spectroscopy can be well described by using a two-band model with $s$-wave-like gaps. The effect of pressure on the superconducting gap of both systems illustrates that both bands are practically affected. Upon compression, the Fermi surfaces do not change significantly, and the nesting remains almost unaffected compared to that at ambient condition. However, a strong bending in the upper critical fields (${H}_{\mathrm{c}2}$) curves is obtained under pressure and support the presence of a strong Pauli paramagnetic effect. In $\mathrm{Nb}{\mathrm{Se}}_{2}$, using a two-band model with $s$-wave-like gaps, the temperature dependence ${H}_{\mathrm{c}2}(T)$ can be properly described. In contrast to that, the behavior of ${H}_{\mathrm{c}2}$ for $\mathrm{Nb}{\mathrm{S}}_{2}$ is ruled by the spin paramagnetic effect. The estimated values of the penetration depth at $T=0\phantom{\rule{0.16em}{0ex}}\mathrm{K}$ confirm that $\mathrm{Nb}{\mathrm{Se}}_{2}$ and $\mathrm{Nb}{\mathrm{S}}_{2}$ superconductors depart from a Uemura-style relationship between ${T}_{\mathrm{c}}$ with ${\mathbit{\ensuremath{\lambda}}}_{ab}^{\ensuremath{-}2}(T)$, the in-plane superconducting penetration depth.

The importance of type-II superconductors with strong pinning comes from their ability to carry large electrical currents in the presence of a magnetic field. We report on the results of the bulk m ...

We report high-resolution dilatometry on high-quality single crystals of ${\mathrm{NiTiO}}_{3}$ grown by means of the optical floating-zone technique. The anisotropic magnetic phase diagram is constructed from thermal expansion and magnetostriction studies up to $B=15\phantom{\rule{0.16em}{0ex}}\mathrm{T}$ and magnetization studies in static (15-T) and pulsed (60-T) magnetic fields. Our data allow us to quantitatively study magnetoelastic coupling and to determine uniaxial pressure dependencies. While the entropy changes are found to be of magnetic nature, Gr\"uneisen analysis implies only one relevant energy scale in the whole low-temperature regime. Thereby, our data suggest that the observed structural changes due to magnetoelastic coupling and previously reported magnetodielectric coupling [L. Balhorn, J. Hazi, M. C. Kemei, and R. Seshadri, Phys. Rev. B 93, 104404 (2016)] are driven by the same $magnetic$ degrees of freedom that lead to long-range magnetic order in ${\mathrm{NiTiO}}_{3}$.

The importance of type-II superconductors with strong pinning comes from their ability to carry large transport currents in the presence of a magnetic field. We report on the results of the bulk magnetization measurements in the superconducting state in clean single crystals of NdFeAsO0.9F0.1 at various temperatures. The zero-temperature superconducting critical current density, Jc, where the superconducting transition temperature Tc reaches a maximum of 45(1) kelvin, displays a remarkable high value. The field dependence of the critical current density was analyzed within the collective pinning model. A remarkably good agreement between the experimental results and theoretical δ1 pinning curve is obtained. This indicates that pinning in NdFeAsO0.9F0.1 crystal originates from spatial variation of the mean free path. Additionally, the normalized pinning force density, Fp, curves verses H/Hirr (Hirr is the irreversibility field) were scaled using the Dew-Hughes model. Our analysis suggests that point pinning alone cannot explain the observed field variation of Fp.

The solvo-thermal syntheses of [(CoSalphen)2Co (SCN)2]n (1), CoSalphen(NH3)(N3)(2), Na[CoIIIsalphen(N3)2](3), Na[CoIIIsalen(N3)2](4) and CoIIIsalen(NH3)(N3) (5) {salphen = N,N’-o-phenylene-bis(salicylideneimine)} are reported. The structural studies using X-ray diffraction measurements revealed that 1 crystalizes in a monoclinic C2/c space group. Two cobalt (II) metal centers in penta-coordinated and octahedral local coordination environments are bridged via alternating O and μ1,3 SCN bridges resulting in a novel 2D layered coordination polymer. Compound 2 is a trivalent mononuclear cobalt azido complex with an octahedral coordination environment. The magnetic investigations of 1 revealed ferromagnetic coupling (J = +49.1 cm−1) and meta-magnetic ordering. Time resolved photoluminescence studies of the complexes showed excited state lifetimes of (τ1 = 0.4675 ns, τ2 = 5.23 ns) for 1 and (τ1 = 0.5078 ns, τ2 = 6.79 ns) for 2.

We report the evolution of charge density wave states under pressure for two NbS3 phases: triclinic (phase I) and monoclinic (phase II) at room temperature. Raman and x-ray diffraction (XRD) techni ...

Cr-doped ZnO was synthesized by using a low-temperature co-precipitation technique producing Zn1−x Cr x O nanoparticles. The effects of the Cr concentration (0, 0.03, 0.05, and 0.07) on the structural, optical, and magnetic properties of ZnO were investigated by first-principles calculations, X-ray diffraction, scanning electron microscope, the optical spectroscopy (UV–Vis), and magnetization measurements. The results show that Cr atoms are substituted for Zn ions successfully. The Cr ions exhibited + 3 valence state other than + 2 valence state, which is supported by the fact of high-spin configurations of Cr ions in the first-principle calculations. X-ray diffraction confirms that the samples have a single-phase wurtzite structure with the main crystal size decreases with increasing dopant concentration. This decrease occurs due to the small ionic radius of Cr ions in compared to Zn ions. The morphology on the surface shows further that the samples had a spherical shape with an average particle size of 75 nm. The optical band gap of ZnO nanoparticles varies with Cr doping, which is attributed to the s-d and p interaction. Introducing Cr into ZnO induces a strong magnetic moment. The estimated that the effective magnetic moment is very close to the magnetic moment obtained from total energy calculations.

We report on superconducting properties of high-quality single crystals of F-substituted NdOBiS2 using low-temperature magnetization and transport measurements. Using the mixture of CsCl and KCl as the flux, we have synthesized our single crystals. This compound exhibits bulk superconductivity with a transition temperature of about T c∼4.6 K. The critical current density J c as a function of temperature has been derived and decreases with the increasing temperature. We construct the phase diagram H c2(T). The zero-temperature value for $H_{\mathrm {c2}}^{B\parallel c}$ for value for $T_{c}^{90~\%}$ and $T_{c}^{0~\%}$ is estimated to be approximately 2.17 and 1.72 T respectively by using Werthamer-Helfand-Hohenberg model.

High-quality single crystals of the unconventional superconductor NdFeAsO1 &minus, xFx were grown. We developed a new optimized flux technique to overcome the difficulties in single-crystal growth and the sample quality limitations of NdFeAsO1 &minus, xFx. The normal state of the F-doped samples exhibits simple metallic behavior upon cooling down from room temperature, followed by a sharp superconducting transition. The values of residual resistivity ratio (RRR) is 3.2, 6.4, and 10.3 for x = 0.1, 0.15, and 0.2, respectively. Both the large RRR and the narrow superconducting transition signpost the high quality of the crystals. We have examined the in- and out-of-plane lower critical fields, and the field at which vortices penetrate the sample of NdFeAsO1 &minus, xFx (x = 0.1). The anisotropy ratio [&gamma, Hc1 (0)] increased slightly with increasing temperature from 0.8 Tc to Tc. The temperature dependence of the first vortex penetration field was obtained under the static magnetic field, H, parallel to the c- and ab- axis, and pronounced changes in the Hc1(T) curvature were observed, which are attributed to the multi-band superconductivity.

We investigated transport and magnetic properties of single crystal ${\mathrm{NdFeAsO}}_{0.9}{\mathrm{F}}_{0.1}$ under hydrostatic pressures up to 50 GPa. The ambient pressure superconductivity at ${T}_{c}\ensuremath{\sim}$ 45.4 K was fully suppressed at ${P}_{c}\ensuremath{\sim}21$ GPa. Upon a further increase of pressure, ferromagnetism associated with the order of the rare-earth subsystem was induced at the border of superconductivity. Our finding is supported by the hysteresis in the magnetization $M(H$) loops and the strong increase in the field cooled data $M(T$) toward low temperatures. We also show that the temperature evolution of the electrical resistivity as a function of pressure is consistent with a crossover from a Fermi liquid to non-Fermi liquid to Fermi liquid. The Hall measurements suggest that the multiband electronic structures have changed with pressure, which should also affect the resistivity behavior. These results give access to the high-pressure side of the superconducting phase diagram in the 1111 type of materials.

We report on the Andreev spectroscopy and specific heat of high-quality single crystals of ${\mathrm{BaFe}}_{1.9}{\mathrm{Ni}}_{0.1}{\mathrm{As}}_{2}$. The intrinsic multiple Andreev reflection spectroscopy reveals two anisotropic superconducting gaps ${\mathrm{\ensuremath{\Delta}}}_{L}\ensuremath{\approx}3.2\ensuremath{-}4.5\phantom{\rule{4pt}{0ex}}\mathrm{meV}$, ${\mathrm{\ensuremath{\Delta}}}_{S}\ensuremath{\approx}1.2\ensuremath{-}1.6\phantom{\rule{4pt}{0ex}}\mathrm{meV}$ (the ranges correspond to the minimum and maximum value of the coupling energy in the ${k}_{x}{k}_{y}$ plane). The $25%\ensuremath{-}30%$ anisotropy shows the absence of nodes in the superconducting gaps. Using a two-band model with $s$-wave-like gaps ${\mathrm{\ensuremath{\Delta}}}_{L}\ensuremath{\approx}3.2\phantom{\rule{4pt}{0ex}}\mathrm{meV}$ and ${\mathrm{\ensuremath{\Delta}}}_{S}\ensuremath{\approx}1.6\phantom{\rule{4pt}{0ex}}\mathrm{meV}$, the temperature dependence of the electronic specific heat can be well described. A linear magnetic field dependence of the low-temperature specific heat offers further support of $s$-wave type of the order parameter. We find that a $d$-wave or single-gap BCS theory under the weak-coupling approach cannot describe our experiments.

We report on magneto-optical imaging and the temperature dependency of the upper critical fields ${H}_{c2}^{c}(T)$ parallel to the $c$ axis and ${H}_{c2}^{ab}(T)$ parallel to the $ab$ plane in ${\mathrm{Ba}}_{2}{\mathrm{Ti}}_{2}{\mathrm{Fe}}_{2}{\mathrm{As}}_{4}\mathrm{O}$ single crystals. These data were inferred from the measurements of the temperature-dependent resistance in static magnetic fields up to 14 T and magnetoresistance in pulsed fields up to 60 T. ${H}_{c2}$ values are found to be 52 and 50 T for $H\ensuremath{\parallel}ab$ and $H\ensuremath{\parallel}c$, respectively. These values are 1.2--1.35 times larger than the weak-coupling Pauli paramagnetic limit $({H}_{p}\ensuremath{\sim}1.84{T}_{c})$, indicating that enhanced paramagnetic limiting is essential and this superconductor is unconventional. Our observations of strong bending in the ${H}_{c2}^{ab}(T)$ curves and a nearly isotropic maximum upper critical field ${H}_{c2}^{ab}(0)\phantom{\rule{0.16em}{0ex}}\ensuremath{\approx}\phantom{\rule{0.16em}{0ex}}{H}_{c2}^{c}(0)$ support the presence of a strong Pauli paramagnetic effect. We show that the Werthamer-Helfand-Hohenberg (WHH) formula that includes the spin-orbit scattering can effectively describe the ${H}_{c2}^{ab}(T)$ curve, whereas ${H}_{c2}$ deviates from the conventional WHH theoretical model without considering the spin paramagnetic effect for the $H\ensuremath{\parallel}c$ and $H\ensuremath{\parallel}ab$ directions. For $H\ensuremath{\parallel}c$, a two-band model is required to fully reproduce the behavior of ${H}_{c2}$, while for $H\ensuremath{\parallel}ab$ the spin paramagnetic effect is responsible for the behavior of ${H}_{c2}$. The anisotropy of ${H}_{c2}$ is close to 3 near ${T}_{c}$ and decreases rapidly at lower temperatures.

Single crystals of sulfur-substituted iron selenide, FeSe1-xSx, were grown within eutectics of molten halides, AlCl3/KCl, AlCl3/KCl/NaCl or AlCl3/KBr, under permanent temperature gradient. The innovative "ampoule in ampoule" design of a crystallization vessel allows obtaining mm-sized plate-like single crystals with a sulfur content up to x ∼ 0.19. The sharp anomalies in the physical properties indicate the superconducting and nematic phase transitions in FeSe0.96 at TC = 8.4 K and TN = 90 K, respectively. Scanning tunneling microscopy reveals the presence of dumbbell defects associated with Fe vacancies and dark defects at the chalcogen site associated with S within the FeSe1-xSx series of compounds. Scanning tunneling spectroscopy shows the presence of two different superconducting gaps at both hole and electron pockets of the Fermi surface for low S content levels. As a function of sulfur content, TC follows the conventional dome-shaped curve while TN decreases with x. The overall appearance of the T-x phase diagram of FeSe1-xSx suggests the importance of nematic fluctuations for the formation of the superconducting state in these compounds. © 2018 The Royal Society of Chemistry.

We investigate the temperature dependence of the lower critical field $H_{c1}(T)$, the field at which vortices penetrate into the sample, of a high-quality fluorine-doped NdFeAsO single crystal under static magnetic fields $H$ parallel to the $c$-axis. The temperature dependence of the first vortex penetration field has been experimentally obtained and pronounced changes of the $H_{c1}$(T) curvature are observed, which is attributed to the multiband superconductivity. Using a two-band model with $s$-wave-like gaps, the temperature-dependence of the lower critical field $H_{c1}(T)$ can be well described. These observations clearly show that the superconducting energy gap in fluorine-doped NdFeAsO is nodeless. The values of the penetration depth at $T$ = 0\,K have been determined and confirm that the pnictide superconductors obey an Uemura-style relationship between $T_{c}$ and $\lambda_{ab}(0)^{-2}$, Comment: 7 pages, 4 figures

This work investigates the high-pressure structure of freestanding superconducting ($T_{c}$ = 4.3\,K) boron doped diamond (BDD) and how it affects the electronic and vibrational properties using Raman spectroscopy and x-ray diffraction in the 0-30\,GPa range. High-pressure Raman scattering experiments revealed an abrupt change in the linear pressure coefficients and the grain boundary components undergo an irreversible phase change at 14\,GPa. We show that the blue shift in the pressure-dependent vibrational modes correlates with the negative pressure coefficient of $T_{c}$ in BDD. The analysis of x-ray diffraction data determines the equation of state of the BDD film, revealing a high bulk modulus of $B_{0}$=510$\pm$28\,GPa. The comparative analysis of high-pressure data clarified that the sp$^{2}$ carbons in the grain boundaries transform into hexagonal diamond., Comment: 7 pages, 4 figures

Single crystals of Na1−δ (Fe1−x T x )As with T = Pd, Ni, Cr, and Mn were investigated by magnetic susceptibility, specific heat, and electronic transport measurements. The structural and spin density wave phase transitions are completely suppressed when Fe in NaFeAs is substituted by those different heterovalent dopings. While superconductivity is only observed for formal electron doping (viz. by substituting Fe with either Pd or Ni), a non-superconducting phase down to 1.8 K is achieved by formal hole doping when Fe is substituted by Cr or Mn in NaFeAs along with the formation of a magnetic phase. This magnetic phase has also strong impact on the material properties.

A commercially available calorimeter has been used to investigate the specific heat of a high-quality \kn\ single crystal. The addenda heat capacity of the calorimeter is determined in the temperature range $0.02 \, \mathrm{K} \leq T \leq 0.54 \, \mathrm{K}$. The data of the \kn\ crystal imply the presence of a large $T^2$ contribution to the specific heat which gives evidence of $d$-wave order parameter symmetry in the superconducting state. To improve the measurements, a novel design for a calorimeter with a paramagnetic temperature sensor is presented. It promises a temperature resolution of $\Delta T \approx 0.1 \, \mathrm{\mu K}$ and an addenda heat capacity less than $200 \, \mathrm{pJ/K}$ at $ T < 100 \, \mathrm{mK}$.