Charge fluctuation,charge ordering,and zero-gap state in organic conductors

We have carried out a series of measurements of angular dependence of solid-state NMR spectrum using single crystal samples on various organic molecular conductors, in order to investigate the natures of the electronic states at low temperatures. We confirmed a charge ordered insulating state in α-(BEDT-TTF)₂I₃ and large charge disproportionation in the metallic state of this salt. In another charge ordered system, θ-(BEDT-TTF)₂RbZn(SCN)₄, we observed unusual NMR line broadening, proportional to resonance shift, in the metallic state above the transition. We found that this broadening is due to charge disproportionation, or more correctly, due to the inhomogeneity of local susceptibility at nuclear sites and analyzed its dynamics. We observed similar broadening in various organic molecular conductors as well, such as θ-(BEDT-TTF)₂CsZn(SCN)₄, an exotic Bechgaad salt, (TMTSF)₂FSO₃, and λ-type BETS salts, λ-(BETS)₂(Fe,Ga)Cl₄. We found the mechanism of CD in each system is different, respectively.     

On the stoichiometry of the organic metal bis(ethylenedioxy)-tetrathiafulvalene chloride

We report on Shubnikov-de Haas and de Haas-van Alphen measurements of an organic metal based on the molecular donor bis(ethylenedioxy)-tetrathiavulvalene (= BEDO-TTF) and the anion Cl^- with H₂O molecules. The observed single oscillation frequency perfectly follows the two-dimensional dependence with T. The Fermi-surface area of of the first Brillouin zone proves a quarter-filled band, i.e., a 2:1 stoichiometry of the BEDO-TTF donor with respect to the anion. The apparent discrepancy to X-ray data which give a 1:1 ratio between BEDO-TTF and Cl^- is understood by replacement of H₂O molecules with (H₃O)⁺ ions. The proposed stoichiometry therefore is (BEDO-TTF)₂ ⁺(H₅O₂)⁺(Cl^-)₂. The cyclotron effective mass is when deduced from the temperature dependence of the fundamental oscillation amplitude, but strongly reduced when extracted from higher harmonics. This and the strong harmonic content of the oscillations signals an influence of the two-dimensional electronic structure and can be qualitatively understood by applying the concept of magnetic interaction to the effect of the oscillatory chemical potential. Received: 16 April 1998 / Revised: 7 July 1998 / Accepted: 9 July 1998     

Electronic localization in an extreme 1-D conductor: the organic salt (TTDM-TTF) [Au(mnt) ]

This article reports the investigation of a new low-dimensional organic salt, (TTDM-TTF)₂ [Au(mnt)₂], by single crystal X-ray diffraction, static magnetic susceptibility, EPR, thermopower, electrical resistivity measurements under pressure up to 25 kbar and band structure calculations. The crystal structure consists in a dimerized head to tail stacking of TTDM-TTF molecules separated by layers of orthogonal Au(mnt)₂ anions. The absence of overlap between neighboring chains coming from this particular crystal structure leads to an extreme one-dimensionality (1-D) for which the carriers of the half-filled conduction band become strongly localized in a Mott-Hubbard insulating state. This material is the first 1-D conductor in which the Mott-Hubbard insulating character cannot be suppressed under pressure. Received 15 April 2002 / Received in final form 17 June 2002 Published online 17 September 2002     

Formation and crystal structure of metallic inclusions in a HPHT as-grown diamond single crystal

One of the most important characteristics associated with crystal growth technology is the entrapment of inclusions by the growing crystal. Diamond single crystals prepared under high temperature-high pressure (HPHT) usually contain metallic inclusions. In the present paper, metallic inclusions in a diamond grown from a Fe-Ni-C system using the HPHT method have been, for the first time, systematically examined by transmission electron microscopy (TEM). Energy dispersive X-ray spectrometry (EDS) , combined with selected area electron diffraction (SAD) patterns, has been used to identify the chemical composition and crystal structure of the metallic inclusions. The metallic inclusions were found to be composed mainly of cubic γ-(FeNi), face-centered cubic (FeNi)₂₃C₆, ortho-rhombic Fe₃C and hexagonal Ni₃C, which may have been formed through the entrapment of molten catalyst by the growth front or through reaction of the trapped melt with contaminants in the diamond. Received: 19 June 2000 / Accepted: 21 June 2000 / Published online: 16 August 2000     

Synthesis and Raman characterization of mono-sized single-wall carbon nanotubes in one-dimensional channels of AlPO4-5 crystals

Mono-sized single-wall carbon nanotubes were formed in one-dimensional channels of AlPO₄-5 single crystal (AFI) by pyrolysis of tripropylamine (TPA). Raman spectra have been measured for the TPA-AFI crystals thermally processed at different conditions. TPA molecules are carbonized at 400 °C, and carbon nanotubes were formed at 500 °C or above. The radial-breathing mode, which is special for carbon nanotube geometry, was observed. Three Raman-active modes with symmetry A _1g, E _1g, and E _2g were identified by detailed symmetrical analysis for the polarized-Raman spectra. Received: 29 October 1998 / Accepted: 29 March 1999 / Published online: 24 June 1999     

Staggered spin order of localized π-electrons in the insulating state of the organic conductor κ-(BETS)<Subscript>2</Subscript>Mn[N(CN)<Subscript>2</Subscript>]<Subscript>3</Subscript>

The magnetic properties of the conduction π-electron system of κ-(BETS)₂Mn[N(CN)₂]₃ have been probed using ¹³C NMR. At ambient pressure, the metal-insulator transition observed in the resistivity measurements below T ? 23 K is shown to be accompanied by ordering of the π-spins in a long-range staggered structure. As the metal-insulator transition is suppressed by applying a small pressure of ～0.5 kbar, the π-spin system maintains the properties of the metallic state down to 5 K.     

Hall effect plateaus and giant Shubnikov-de Haas oscillations in (BiSb)Telayered single crystals near the quantum limit

On bulk layered single crystals (Bi_0.25Sb_0.75)₂Te₃ with a hole concentration cm^-3 and a mobility cm²/Vs magnetoresistance and Hall effect investigations were performed in the temperature range T = 1.4 K ... 20 K in magnetic fields up to 18 T. For the magnetic field perpendicular to the layered structure giant Shubnikov-de Haas oscillations are measured; the positions of the maxima are triplets in the reciprocally scaled magnetic field. From the damping of the amplitudes with increasing temperature the cyclotron mass m _c = 0.12m ₀ is evaluated. Correlated with the SdH oscillations doublets of Hall effect plateaus (or kinks in low fields) are found. The weak well known Shubnikov-de Haas oscillations from the generally accepted multivallied highest valence band can be detected as a modulation on the giant oscillation. The high anisotropy of the SdH oscillations and their triplet structure in connection with the layered crystal structure lead us to suggest that the effects are caused by hole carrier pairing (mediated by the bipolaron mechanism) in quasi 2D sheets parallel to the crystal layer stacks. The measured Hall plateau resistances coincide with the quantum Hall effect values considering the number of layer stacks and the valley degeneracy of the 3D hole carrier reservoir. The ratio of spin splitting to Landau (cyclotron) splitting is observed to be . Received: 12 September 1997 / Revised: 8 January 1998 / Accepted: 22 January 1998     

ZrO2 films deposited by photo-CVD at low temperatures

Zirconium oxide layers have been successfully deposited by photo-CVD at low temperatures. ZrO₂ growth was observed at temperatures as low as 100 °C. When deposited at 250 °C and above, these films exhibited a polycrystalline structure with a mixture of different crystal phases. Deposition at 300 °C was found to form moisture-free ZrO₂ films with a high refractive index of 2.1, a very low effective density of trapped electrons of ∼8.8×10⁸ cm^-2 and an interface trap density of 6.6×10⁹ cm^-2 eV^-1 being readily obtained. Received: 17 December 2001 / Accepted: 6 January 2002 / Published online: 3 June 2002     

Room-temperature epitaxial growth of CeO2(001) films on YSZ buffered Si(001) substrates

2 (001) epitaxial thin films deposited on Si(001) with yttria-stabilized zirconia buffers have been obtained for the first time at room temperature by pulsed-laser deposition. The influence of oxygen pressure on the crystal quality of CeO₂ was studied for the films deposited at 100 °C. The rocking curve full width at half maximum of the CeO₂(002) peak for films deposited at room temperature and 100 °C was between 1° and 2°, for oxygen pressures below 3×10^-2 mbar. The best crystal quality was obtained at around 3×10^-3 mbar. Epitaxial growth at room temperature was confirmed by cross-sectional transmission electron microscopy. Scanning electron microscopy and atomic force microscopy revealed very smooth surfaces for oxygen pressure below 3×10^-2 mbar, with rms roughness values around 0.3 nm over 5 μm×5 μm. Received: 25 September 1997/Accepted: 22 April 1998     

Spectroscopic analysis and laser parameters of Nd3+ in Ca3Sc2Ge3O12 garnet crystals

3 Sc₂Ge₃O₁₂ (CaSGG) single crystals with the garnet structure have been grown by means of the flux growth technique. The doping with Nd³⁺ and Mg²⁺ (as charge compensator) yields samples suitable for optical spectroscopy experiments. The absorption and emission properties have been measured at temperatures ranging from 10 to 298 K. The emission spectra give evidence of the presence of non-equivalent Nd³⁺ sites. The decay time of the 1.06-μm emission band has been measured as a function of temperature and incident power. The intensities of the 298 K absorption transitions have been analyzed by means of the Judd–Ofelt theory. The radiative lifetimes, the branching ratios (β), and the spontaneous emission probabilities have been evaluated for the ⁴F_3/2 excited state using the calculated intensity parameters. The stimulated-emission cross sections and the branching ratios have been estimated from the experimental data for the most important laser transitions indicating that this crystal can be considered an interesting material for solid-state laser applications. Received: 2 June 1998 / Revised version: 28 October 1998 / Published online: 24 February 1999     

Frequency measurement of I2 lines in the NIR using Ca and CH4 optical frequency standards

2 lines have been carried out using difference-frequency mixing of the emission of CH₄ and Ca frequency standards at 88 THz (or 3.4 μm) and 456 THz (or 657 nm), respectively. A power of ≈10 pW for the mixing product at 815 nm was obtained using a critically phase-matched KTP crystal and input powers of the order of mW. The relative uncertainty of the measurement was a few times 10^-11, limited by the frequency instability of the laser source locked to I₂. Received: 3 December 1997/Revised version: 16 February 1998     

Fatigue-free Pb(Zr0.52Ti0.48)O3 thin films on indium tin oxide coated substrates by a sol-gel process

Fatigue-free Pb(Zr_0.52Ti_0.48)O₃ (PZT) ferroelectric thin films were successfully prepared on indium tin oxide (ITO) coated glass substrates using the sol-gel method combined with a rapid thermal annealing process (RTA). The films post-annealed at a temperature of 700 °C for 2 min by RTA process formed (110)-oriented Pb(Zr_0.52Ti_0.48)O₃ thin films with pure perovskite structure, and had a good morphology as well. The good ferroelectricity of the prepared PZT films was confirmed by P–E hysteresis loop measurements. Fatigue characteristics showed stable behavior. Degradation in polarization was not found while the repeating cycles were up to 10¹¹, and a low leakage current density of 10⁻⁸ A/cm² was also obtained from the highly fatigue-resisted PZT thin films on ITO/glass substrates. Received: 19 October 1998 / Accepted: 29 March 1999 / Published online: 26 May 1999     

Raman-scattering spectrum of GaN straight nanowires

The Raman spectrum of GaN straight nanowires deposited on a LaAlO₃ crystal substrate was studied. The E₂ (high) phonon frequency at 560 cm^-1 shows a 9 cm^-1 shift compared with the calculated value. The low-energy shift and band broadening of the Raman modes result from the nanosize effect. The unique property of the low intensity ratio of I_E2/I_A1(LO) on the Raman spectrum from the GaN straight nanowires was observed. Received: 5 June 2000 / Accepted: 7 June 2000 / Published online: 2 August 2000     

Slope efficiency of up to 73% for Yb:Ca4YO(BO3)3 crystal laser pumped by a laser diode

Yb:Ca₄YO(BO₃)₃ (Yb:YCOB) crystal with good quality and large size has been grown by the Czochralski method. The polarization absorption and fluorescence spectra have been measured. The laser action of the Yb:YCOB crystal has been demonstrated when it is pumped by a fiber-coupled laser diode (LD) at the wavelength of 976.4 nm. The pumping threshold is 55 mW, the light-light conversion efficiency is 58.7%, and a slope efficiency of up to 73% is thus calculated. Received: 16 December 1998 / Revised version: 4 February 1999 / Published online: 7 April 1999     

Vortex lattice accommodation on twin boundaries in studied by neutron diffraction

An extensive study of small angle neutron scattering was performed in twinned YBa₂Cu₃O₇ crystals in its superconducting state as a function of the angle between the c-axis of the crystal and the magnetic field. The half of the twin boundaries are oriented in the horizontal plane, which also contains the neutron beam and the magnetic field. Two different diffraction patterns are studied as a function of at 5 K and B = 0.5 T, one along the c-axis of the crystal, the other one along the applied field. These variations are interpreted in the model of accommodation of the vortices on the twin planes by zigzagging from these planes to the ab-planes of the crystal, in order to minimize their energy. Received: 9 March 1998 / Revised and Accepted: 12 June 1998     

Laser emission under flashlamp pumping of a new crystal: Nd-doped strontium-lanthanum-aluminate (Nd:ASL)

1-x Nd_yLa_x-yMg_xAl_12-xO₁₉) is a new material, tunable in the 1–1.1 μm band. We present the first results of pulsed laser emission of this crystal under flashlamp pumping. We obtain a slope efficiency of 3.3% with a maximum average power of 40 W at 40 Hz in free-lasing regime. Nd:Cr codoping of ASL is also tested, but with much lower efficiency. Received: 12 June 1998/Revised version: 30 September 1998     

Low temperature thermodynamical properties of the organic chain conductor (TMTSF)AsF

We report on specific heat measurements of the quasi-one-dimensional organic salt (TMTSF)₂AsF₆ in its spin density wave state between 75 mK and 7 K. Similarly to (TMTSF)₂PF₆, we find discontinuities in the lattice contribution at 1.9 K an d 3.5 K ascribed to sub-spin density wave phases. Time-dependent effects due to dynamics of low-energy excitations in metastable states occur only below 0.2 K which yields an activation energy for the equilibrium energy relaxation process of 0.34 K, 4-5 times smaller than found for (TMTSF)₂PF₆. Finally the reduction of the low-energy excitations contribution to the specific heat in comparison to PF₆ reveals an intermediate cubic-like regime between 0.25 and 0.5 K that we tentatively describe as the phason contribution of the incommensurate spin density wave modulation. Received: 17 March 1998 / Revised: 27 July 1998 / Accepted: 22 September 1998     

Electrical transport, magnetism, and magnetoresistance in La0.7Sr0.3(Mn1-xCox)O3

The crystal structure (rhombohedral) is not changed on the replacement of Mn by Co. The lattice parameters a and c decrease with the increasing Co concentration. In this paper we have systematically investigated the effect of Co doping on the Mn site in the La_0.7Sr_0.3MnO₃ and find that Co substitution leads to a drastic suppression of ferromagnetic long-range order and metallic state. However, we observed substantial enhancement of MR ratio over the entire temperature studied for x=0.1 and a large increase of one at the low temperature for the compositions of x=0.2 and 0.3. The largest MR ratio as high as ≈78% is observed at 15 K in x=0.2 and 0.3. As x is further increased toward 1, conduction and ferromagnetism strongly recover but the MR ratio decreases obviously. The end member with x=1.0 has metallic and cluster spin-glass ferromagnetic behavior (T<T_C) and a smaller value of MR (≈2–8%) in T<300 K with a maximum MR ratio of 8% at around T_C (=238 K). Received: 11 September 1998 / Accepted: 19 November 1998 / Published online: 17 March 1999     

Parametric study of Xe2 * dimer in high-pressure electrical discharges

Optical and electrical properties of a high-pressure discharge of pure xenon and xenon-helium and xenon-neon mixtures are studied experimentally. Uniform discharge at total gas pressure as high as 10 atm is achieved in xenon-lean mixtures. Vacuum ultraviolet emissions due to the first and second continua of Xe₂ ^* are examined spectroscopically. The vibrational relaxation rate constant k_He of Xe₂ ^* by helium is determined to be of the order of 10^-11 cm³ s^-1 from spectroscopic data. Laser oscillation for the 172-nm band was attempted without success. Discharge instability at high gas pressures is considered to the cause of the unsuccessful laser experiments. Some issues related to discharge instability in a high-pressure rare-gas discharge are discussed. Received: 1 October 2001 / Revised version: 11 June 2002 / Published online: 25 October 2002 RID="*" ID="*"Corresponding author. Fax: +852-2603/5204, E-mail: dlo@phy.mhk.edu.hk     

Large-scale synthesis of SnO2 nanobelts

Tin dioxide (SnO₂) nanobelts have been successfully synthesized in bulk quantity by a simple and low-cost process based on the thermal evaporation of tin powders at 800 °C. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations reveal that the nanobelts are uniform, with lengths from several-hundred micrometers to a few millimeters, widths of 60 to 250 nm and thicknesses of 10 to 30 nm. X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX) and selected-area electron diffraction analysis (SAED) indicate that the nanobelts are tetragonal rutile structure of SnO₂. The SnO₂ nanobelts grow via a vapor–solid (VS) process. Received: 3 June 2002 / Accepted: 10 June 2002 / Published online: 10 September 2002 RID="*" ID="*"Corresponding author. Fax: +86-551/559-1434, E-mail: gwmeng@mail.issp.ac.cn