In this paper, we present results on magnetization properties of boron nitride-carbon (BN-C) and boron carbide-carbon (B4C-C) granular mixtures. The temperature-dependent magnetization for field-cooled during cooling and field-cooled during warming shows a kind of thermal hysteresis that is always seen around a metamagnetic phase transition from an antiferromagnetic martensite to a ferromagnetic austenite phase. The low-temperature magnetization has an upward turn that can be attributed to superparamagnetism, diamagnetic shielding, and trapped flux characteristic to high-temperature superconducting materials. After subtracting the diamagnetic background, the field-dependent magnetization loops M(B) are ferromagnetic-like, more significant for the BN-C than for the B4C-C mixture. In addition, the magnetization loops show the kink feature characteristic to granular superconductivity. The irreversibility temperature for a B4C-C mixture having 37.5 wt% B is Tc = 76 K. Combining our data with previous results on B-doped diamond and Q-carbon, we find that Tc increases linearly with the B concentration.
We examine the effect of boron doping in superconducting forms of amorphous carbon. By judiciously optimizing boron substitutional sites in simulated amorphous carbon we predict a superconducting transition temperature near 37 K at 14 % boron concentration. Our findings have direct implications for understanding the recently discovered high T_$c$ superconductivity in Q-carbon.
We study how attractive boron correlations in boron-doped diamond affect the superconducting critical temperature. The critical temperature is obtained from the McMillan formula for strong coupling superconductors with the density of states evaluated in the dynamical cluster approximation. Numerical results for the cluster of $2\times 2\times 2$ atoms show that attractive correlations lower the density of states at the Fermi level. We argue that this might explain experimentally observed differences in critical temperatures of 100 and 111 oriented films.
We study the concentration dependence of the superconducting critical temperature Tc in a boron-doped diamond. We evaluate the density of states at Fermi level within the dynamical cluster approximation obtaining higher values than from the coherent potential approximation. We discuss the Tc as a function of density of states within the BCS, the McMillan, and the Belitz theory. The simplified Belitz theory gives the best agreement with experimental data. Since the density of states follows a simple power-law for accessible doping concetrations, the present theory offers an analytical formula f…
We report the preparation method of, and boron isotope effect for MgB$_2$, a new binary intermetallic superconductor with a remarkably high superconducting transition temperature $T_c$($^{10}$B) = 40.2 K. Measurements of both temperature dependent magnetization and specific heat reveal a 1.0 K shift in $T_c$ between Mg$^{11}$B$_2$ and Mg$^{10}$B$_2$. Whereas such a high transition temperature might imply exotic coupling mechanisms, the boron isotope effect in MgB$_2$ is consistent with the material being a phonon-mediated BCS superconductor.
Carbon- and boron-2$p$ states of superconducting and non-superconducting boron-doped diamond samples are measured using soft X-ray emission and absorption spectroscopy. For the superconducting sample, a large density of hole states is observed in the valence band in addition to the states in the impurity band. The hole states in the valence band is located at about 1.3 eV below the valence band maximum regardless of the doping level, which cannot be interpreted within a simple rigid band model. Present experimental results, combined with the first principles calculations, suggest that supercon…
Anomalous resistive peaks below the superconducting transition temperature in heavily boron doped nanocrystalline diamond films could have potential application in switching devices, however the exact origin is still under study. We establish a temperature dependence of this resistive phase similar to what has been reported for in Josephson junction arrays and other granular superconductors where the charge duel of the Berezinskii-Kosterlitz-Thouless (BKT) transition has been observed. Non-linear magnetoresistance with a temperature dependent peak feature below the critical field are also pres…
We have investigated the low energy electronic state of a boron-doped diamond thin film by the ultrahigh resolution laser-excited photoemission spectroscopy. We observed a clear shift of the leading edge below 11 K indicative of a superconducting gap opening ($Δ\sim 0.78$ meV at 4.5 K). The gap feature is significantly broad and the well-defined quasiparticle peak is not recognizable even at the lowest temperature of measurement 4.5 K. We discuss our result in terms of possible disorder effect on superconductivity in this system.
In this work we probe the possibility of high-temperature conventional superconductivity in the boron-carbon system, using ab-initio screening. A database of 320 metastable structures with fixed composition (50$\%$/50$\%$) is generated with the Minima-Hopping method, and characterized with electronic and vibrational descriptors. Full electron-phonon calculations on sixteen representative structures allow to identify general trends in $T_{\textrm{c}}$ across and within the four families in the energy landscape, and to construct an approximate $T_{\textrm{c}}$ predictor, based on transparently i…
The discoveries of superconductivity in the heavily-boron doped semiconductors diamond (C:B) in 2004 and silicon (Si:B) in 2006 have renewed the interest in the physics of the superconducting state of doped semiconductors. Recently, we discovered superconductivity in the closely related ''mixed'' system heavily boron-doped silcon carbide (SiC:B). Interestingly, the latter compound is a type-I superconductor whereas the two aforementioned materials are type-II. In this paper we present an extensive analysis of our recent specific-heat study, as well as the band structure and expected Fermi surf…
By synthesizing MgB$_{2}$ using boron of different nominal purity we found values of the residual resistivity ratio ($RRR = R(300 K) / R(42 K)$) from 4 to 20, which covers almost all values found in literature. To obtain high values of $RRR$, high purity reagents are necessary. With the isotopically pure boron we obtained the highest $RRR \sim$ 20 for the stoichiometric compound. We also investigated Mg$_{x}$$^{11}$B$_{2}$ samples with 0.8 $< x <$ 1.2. For the range Mg$_{0.8}$$^{11}$B$_{2}$ up to Mg$_{1.2}$$^{11}$B$_{2}$ we found average values of $RRR$ between 14 and 24. For smaller variation…
NMR spectra and nuclear spin-lattice relaxation rate $T_1^{-1}$ of $^{11}$B have been measured in superconducting polycrystalline MgB$_{2}$ with $T_C^{ons}\cong 39.5K$. It is shown that $(T_{1}T)^{-1}$ and the Knight shift $K_{s}$ are independent of temperature and nearly isotropic above $T_C$. Both of these quantities are decreased gradually in going to superconducting state. According NMR data the density of states (DOS) near the Fermi level is flat at the scale $\approx$ 500K. Some conclusions on the orbital content of the DOS at the Fermi level was done and compared with the results of the…
Diamond, a wide band-gap semiconductor, can be engineered to exhibit superconductivity when doped heavily with boron. The phenomena has been demonstrated in samples grown by chemical vapour deposition where the boron concentration exceeds the critical concentration for the metal-to-insulator transition of $n_{MIT} \gtrsim 4\times10^{20}/\text{cm}^3$. While the threshold carrier concentration for superconductivity is generally well established in the literature, it is unclear how well correlated higher critical temperatures are with increased boron concentration. Previous studies have generally…
Among the many remarkable properties of diamond, the ability to superconduct when heavily doped with boron has attracted much interest in the carbon community. When considering the nanocrystalline boron doped system, the reduced dimensionality and confinement effects have led to several intriguing observations most notably, signatures of a mixed superconducting phase. Here we present ultra-high-resolution transmission electron microscopy imaging of the grain boundary and demonstrate how the complex microstructure leads to enhanced carrier correlations. We observe hallmark features of spin-orbi…
In 2004 the discovery of superconductivity in heavily boron-doped diamond (C:B) led to an increasing interest in the superconducting phases of wide-gap semiconductors. Subsequently superconductivity was found in heavily boron-doped cubic silicon (Si:B) and recently in the stochiometric ''mixture'' of heavily boron-doped silicon carbide (SiC:B). The latter system surprisingly exhibits type-I superconductivity in contrast to the type-II superconductors C:B and Si:B. Here we will focus on the specific heat of two different superconducting samples of boron-doped SiC. One of them contains cubic and…
A diamond anvil cell (DAC) which can generate extremely high pressure of multi-megabar is promising tool to develop a further physics such a high-transition temperature superconductivity. However, electrical transport measurements, which is one of the most important properties of such functional materials, using the DAC is quite difficult because the sample space is very small and a deformation of electrodes under extreme condition. In this study, we fabricated a boron-doped diamond micro-electrode and an undoped diamond insulation on a beveled culet surface of the diamond anvil. By using the …
We report on a detailed analysis of the superconducting properties of boron-doped silicon films grown along the 001 direction by Gas Immersion Laser Doping. The doping concentration cB has been varied up to approx. 10 at.% by increasing the number of laser shots to 500. No superconductivity could be observed down to 40mK for doping level below 2.5 at.%. The critical temperature Tc then increased steeply to reach 0.6K for cB = 8 at%. No hysteresis was found for the transitions in magnetic field, which is characteristic of a type II superconductor. The corresponding upper critical field Hc2(0) w…
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 analysi…
A superconducting boron doped nanocrystalline diamond (B-NCD) coplanar waveguide resonator (CPR) is presented for kinetic inductance ($L_k$) and penetration depth ($λ_{\rm{L}}$) measurements at microwave frequencies of 0.4 to 1.2 GHz and at temperatures below 3 K. Using a simplified effective medium CPR approach, this work demonstrates that thin granular B-NCD films ($t\approx $ 500 nm) on Si have a large penetration depth ($λ_{\rm{L}}\approx 4.3$ to 4.4 $μ$m), and therefore an associated high kinetic inductance ($L_{k,\square} \approx $ 670 to 690 pH/$\square$). These values are much larger t…
In this work we have demonstrated the growth of nanocrystalline diamond on boron nitride ceramic. We measured the zeta potential of the ceramics to select the diamond seeds. Diamond was then grown on the seeded ceramics using a microwave chemical vapour deposition system. A clear difference was found between the samples which were seeded with nanodiamond and the ones not seeded before growth. Raman spectroscopy confirmed the excellent quality of the diamond film. Dielectric measurements showed an increase in the dielectric constant of the material after diamond growth. The diamond was also dop…
Superconducting high entropy alloys (HEAs) are new members of disordered superconductors. We report the synthesis and investigation of a new superconducting high entropy alloy Mo$_{0.11}$W$_{0.11}$V$_{0.11}$Re$_{0.34}$B$_{0.33}$ (MWVRB). It crystallized in the tetragonal CuAl$_2$ crystal structure with space group (I4/$mcm$). Comprehensive transport, magnetization and heat capacity measurements confirmed bulk type-II superconductivity having transition temperature T$_{C}$ = 4.0 K. The low temperature electronic specific heat suggests a fully gapped superconducting state in weak coupling limit.
Scanning tunneling spectroscopies are performed below 100~mK on nano-crystalline boron-doped diamond films characterized by Transmission Electron Microscopy and transport measurements. We demonstrate a strong correlation between the local superconductivity strength and the granular structure of the films. The study of the spectral shape, amplitude and temperature dependence of the superconductivity gap enables us to differentiate intrinsically superconducting grains that follow the BCS model, from grains showing a different behavior involving the superconducting proximity effect.
Diamond is a material that offers potential in numerous device applications. In particular, highly boron doped diamond is attractive due to its superconductivity and high Young's Modulus. The fabrication of stable, low resistance, ohmic contacts is essential to ensure proper device function. Previous work has established the efficacy of several methods of forming suitable contacts to diamond at room temperature and above, including carbide forming and carbon soluble metallisation schemes. Herein, the stability of several contact schemes (Ti, Cr, Mo, Ta and Pd) to highly boron doped nanocrystal…
High-pressure techniques open exploration of functional materials in broad research fields. An established diamond anvil cell with a boron-doped diamond heater and transport measurement terminals has performed the high-pressure synthesis of a cubic Sn$_{3}$S$_{4}$ superconductor. X-ray diffraction and Raman spectroscopy reveal that the Sn$_{3}$S$_{4}$ phase is stable in the pressure range of P>5 GPa in a decompression process. Transport measurement terminals in the diamond anvil cell detect a metallic nature and superconductivity in the synthesized Sn$_{3}$S$_{4}$ with a maximum onset transiti…
Signatures of a high-temperature collective electronic phase with superconductivity-like characteristics and a giant pressure effect in networks of boron-doped ultrathin carbon nanotubes
The Hong Kong University of Science and Technology（香港科技大学）；Université Grenoble Alpes, Université Toulouse, INSA Toulouse, CNRS, LNCMI, EMFL（格勒诺布尔阿尔卑斯大学、图卢兹大学、图卢兹国立理工学院、法国国家科学研究中心、低温磁强研究所、欧洲磁场实验室）；Cambridge University（剑桥大学）
By using the five Angstrom diameter pores of calcined zeolite as the template, we have fabricated boron doped carbon nanotube networks via the chemical vapor deposition method. Raman data indicate the network to comprise segments of interconnected carbon nano tubes. Transport measurements showed a superconducting transition initiating at 40K, with a sharp downturn around 20K to a low resistance state at 2K, accompanied by a low resistance plateau in the current voltage characteristic, fluctuating around zero resistance. Magnetic measurements exhibited the Meissner effect characteristic of thin…
We report a high-throughput ab-initio study of the thermodynamic and superconducting proper- ties of the recently synthesized XB$_3$C$_3$ clathrates. These compounds, in which boron and carbon form a sponge-like network of interconnected cages each enclosing a central X atom, are attractive candidates to achieve high-Tc conventional superconductivity at ambient pressure, due to the simultaneous presence of a stiff B-C covalent network and a tunable charge reservoir, provided by the guest atom. Ternary compounds like CaB$_3$C$_3$, SrB$_3$C$_3$ and BaB$_3$C$_3$ are predicted to exhibit T$_c$ $\l…
We report on the transport properties of nanostructures made from boron-doped superconducting diamond. Starting from nanocrystalline superconducting boron-doped diamond thin films, grown by Chemical Vapor Deposition, we pattern by electron-beam lithography devices with dimensions in the nanometer range. We show that even for such small devices, the superconducting properties of the material are well preserved: for wires of width less than $100\, nm$, we measure critical temperatures in the Kelvin range and critical field in the Tesla range.
Superconducting transport properties of granular materials are greatly influenced by the microstructure. We show that in heavily boron-doped diamond films (HBDDF) films some sharp transport features can be manipulated by applying a magnetic field and controlled finite bias current. We demonstrate the conductivity cross-over from dirty metal to the superconducting state through an insulating peak arising at a very low current or magnetic field region and particularly pronounced negative magnetoresistance with periodic oscillatory features. The current-voltage characteristics show features of th…
Boron-doped diamond granular thin films are known to exhibit superconductivity with an optimal critical temperature of Tc = 7.2K. Here we report the measured complex surface impedance of Boron-doped diamond films in the microwave frequency range using a resonant technique. Experimentally measured inductance values are in good agreement with estimates obtained from the normal state sheet resistance of the material. The magnetic penetration depth temperature dependence is consistent with that of a fully-gapped s-wave superconductor. Boron-doped diamond films should find application where high ki…
We have studied the changes in the electronic structure and the superconducting transition temperature T_c of Mg(B_{1-x}C_{x})_{2} alloys as a function of x with 0\leq x\leq 0.3. Our density-functional-based approach uses coherent-potential approximation to describe the effects of disorder, Gaspari-Gyorffy formalism to estimate the electron-phonon matrix elements and Allen-Dynes equation to calculate T_c in these alloys. We find that the changes in the electronic structure of Mg(B_{1-x}C_{x})_{2} alloys, especially near the Fermi energy E_F, come mainly from the outward movement of E_F with in…
Diamond is an excellent band insulator. However, boron (B) doping is known to induce superconductivity. We present two interesting effects in superconducting B doped diamond (BDD) thin films: i) Wohlleben effect (paramagnetic Meissner effect, PME) and ii) a low field spin glass like susceptibility anomaly. We have performed electrical and magnetic measurements (under pressure in one sample) at dopings (1.4 , 2.6 and 3.6) X 1021 cm-3, in a temperature range 2 - 10 K. PME, a low field anomaly in inhomogeneous superconductors could arise from flux trapping, flux compression, or for non-trivial re…
Superconducting boron-doped silicon films prepared by gas immersion laser doping (GILD) technique are analyzed by atom probe tomography. The resulting three-dimensional chemical composition reveals that boron atoms are incorporated into crystalline silicon in the atomic percent concentration range, well above their solubility limit, without creating clusters or precipitates at the atomic scale. The boron spatial distribution is found to be compatible with local density of states measurements performed by scanning tunneling spectroscopy. These results, combined with the observations of very low…
We report synthesis, structural and magnetic (DC and AC) properties of Boron substituted MgCNi3 superconductor. A series of polycrystalline bulk samples Mg1.2C1.6-xBxNi3 (x = 0.0, 0.08 and 0.16) is synthesized through standard solid-state reaction route, which are found to crystallize in cubic perovskite structure with space group Pm3m. Rietveld analysis of observed XRD data show that lattice parameters expand from a = 3.8106 (4) Å for pure, to 3.8164 (2) Å and 3.8173 (5) Å for 5% and 10% Boron substituted samples respectively. DC magnetization exhibited superconducting transition (Tc) at arou…
We report a study of the relaxation time of the restoration of the resistive superconducting state in single crystalline boron-doped diamond using amplitude-modulated absorption of (sub-)THz radiation (AMAR). The films grown on an insulating diamond substrate have a low carrier density of about 2.5x10^{21} cm^{-3} and a critical temperature of about 2 K. By changing the modulation frequency we find a high-frequency rolloff which we associate with the characterstic time of energy relaxation between the electron and the phonon systems or the relaxation time for nonequilibrium superconductivity. …
We present the results of fully-relaxed, full-potential electronic structure calculations for the new superconductor MgB2, and BeB2, NaB2, and AlB2, using density-functional-based methods. Our results described in terms of (i) density of states (DOS), (ii) band-structure, and (iii) the DOS and the charge density around the Fermi energy EF, clearly show the importance of B p-band for superconductivity. In particular, we show that around EF, the charge density in MgB2, BeB2 and NaB2 is planar and is associated with the B plane. For BeB2 and NaB2, our results indicate qualitative similarities but…
