Two-dimensional melting of physisorbed submonolayers of argon and nitrogen

We have studied two-dimensional argon and nitrogen physisorbed on grafoil by conducting positron lifetime and Doppler broadening measurements as functions of adsorbate coverage and temperature. Positron lifetime and Doppler broadening parameters show turnarounds near one-half monolayer coverages at 77 K. The s parameter of the Doppler broadening spectra measured for one-half monolayer coverages of argon and nitrogen increases with temperature across the melting phase transition. We discuss the observed coverage and temperature effects following models based on Kosterlitz-Thouless-Nelson-Halperin-Young theory of two dimensional melting and positron localization in surface defects.     

Order-disorder transitions in a chemisorbed system: Hydrogen on Ni (111)

Atomic hydrogen chemisorbed on a Ni (111) surface forms at coverages between 0.3 and 0.6 an ordered 2 × 1-structure as observed by low energy electron diffraction (LEED). The intensity of the fractional-order LEED spots was measured at different coverages as a function of temperature. Continuous order-disorder transitions are found, the maximum transition temperature (270 K) being at θ = 0.5. The phase diagram, however, is asymmetric with respect to this coverage and can therefore presumably not be explained on the basis of (independent) pairwise interactions.     

Diffusion and compressibility of sodium on the (110) plane of tungsten

The surface diffusion parameters and the compressibility of sodium on the (110) plane of tungsten have been measured using the field emission fluctuation method for sodium coverages from 0.2 to 3 × 10¹⁴ atoms cm^?2 and for temperatures from 170 to 500 K. Two temperature regimes can be defined. In the high temperature regime (? 300 K) the diffusion is essentially normal with an activation energy ranging from 0.28 to 0.58 eV and a preexponential coefficient D₀ from 10^?8.1 to 10^?2.7 cm² s^?1. In this regime the compressibility increases with temperature indicating an effective repulsive adatoms interaction. In the low temperature regime (? 300 K) the diffusion coefficient decreases with temperature at high coverage and slowly increases with temperature at lower coverage. The transition between both regimes appears on the compressibility versus temperature curve as an inflection point. The comparison of the present results with slow electron diffraction results furnishes strong evidence that the observed transition corresponds to a continuous short-range order-disorder transition.     

Specific heats of the charge density wave compounds o-TaS and (TaSe ) I

Specific heats of the charge-density-wave compounds o-TaS₃ and (TaSe₄)₂I have been measured over the wide temperature interval 10 K-300 K. Both systems exhibit strong non-Debye behavior. Very weak and broad anomalies are observed at the Peierls transition temperatures. For o-TaS₃, the change in the curvature of the specific heat occurs at temperature of 40 K where glass transition has been deduced from dielectric measurements, and an extended scaling analysis suggests that the glass transition is associated with a dynamical cross over in length scales. We briefly discuss the characteristics and physical origins of the anomalies at both the Peierls and glass transitions. Received 5 April 2002 / Received in final form 28 June 2002 Published online 17 September 2002     

Growth and morphology of Cobalt thin films on Pd(1 1 1)

We report on the growth of thin Co films on Pd(1 1 1) at three different temperatures 180 K, 300 K, and 550 K. The structure and morphology was determined by scanning tunneling microscopy and low energy electron diffraction. The growth mode was found to vary with temperature. For 180 K and 300 K, we observed a tendency to double layer growth for the initial layers while at elevated temperatures, the initial film grows in single layer. For most conditions, non-ideal three-dimensional growth was observed. Two-dimensional growth was only found for growth temperature of 550 K and coverages above 5 ML. Depending on temperature, the Co islands at low coverages exhibit three principally different shapes: dendritic at 180 K, hexagonal at 300 K and triangular at 550 K. For growth at 550 K and coverages above 5 ML, the islands changed to an irregular shape. This transition is most likely responsible for the transition to 2D growth. Further, the large strain is relaxed by the creation of a dislocation network with mixed fcc and hcp stacking. Depending on the temperature and coverage, a hexagonal or a triangular network was observed. Finally, we have investigated the effect of annealing Co films prepared at 180 K and 300 K. Heating to 490 K leads to coarsening and intermixing.     

X-ray study of molecular oxygen adsorbed on graphite

We have performed a detailed X-ray diffraction study of O₂ adsorbed on UCAR-ZYX and Le Carbon Lorraine vermicular exfoliated graphite between 15 and 50 K. At least four phases of physisorbed oxygen are found. The monolayer δ phase consists of a centered parallelogram lattice, with the molecular axes parallel to the graphite surface. The data are consistent with a triple point at 26 K. The melting transition at a coverage of one monolayer appears to be first order. At higher coverages the molecules undergo a lying-down to standing-up transition; the higher coverage ζ phase froms an approximately triangular lattice with the molecular axes perpendicular to the graphite surface. Satellite peaks around the (1, 0) Bragg peak indicate, however, that this cannot be a simple triangular lattice; possible explanations include successively incommensurate layers or a sinusoidal density modulation. For coverages in the two-layer region the ζ phase modulation peaks disappear at 37 K, and at 40 K the adsorbed oxygen appears to undergo a first order melting transition into a fluid phase. With increasing coverage, the 2D X-ray diffraction profiles and phase boundaries do not connect smoothly onto those of the 3D α and β phases. At low temperatures (T < 30 K) the ζ phase always coexists with bulk crystallites; for temperatures near the 2D melting transition the 3D peaks are not observable. These data, taken together with the heat capacity results, suggest a wetting transition with only the bilayer lamellar phase or bulk O₂ being stable at low temperatures.     

Ultrasound attenuation in solid CD4

We have measured the attenuation of 4 and 12 MHz longitudinal and transverse sound in solid CD₄ between 4 and 77 K. Absolute values for absorption at 77 K were determined from the variation in output amplitude as the length of the solid was reduced. As temperature is varied, the excess attenuation over a constant background undergoes maxima in the vicinity of the phase transitions at 22.1 and 27.0 K. The peak around the upper transition, which involves orientational ordering but not structural change, does not obey all the criteria of a single-relaxation model, but that model produces useful information on the hindering of molecular reorientation near the transition temperature, consistent with inferences drawn from thermal expansion measurements. Neither a relaxation model nor a critical-exponent model fits the attenuation data for the lower transition, in which both orientational and structural changes are now known to occur.     

The thermoelectric power of MEM(TCNQ)2

MEM(TCNQ)₂ undergoes a first order semiconductor to metal transition at 340.8 K. We have measured the thermoelectric power (TEP) of MEM(TCNQ)₂ in the temperature range above 335 K. Above the transition the TEP is ?65 μV/°K, in the low temperature phase it is strongly temperature dependent and approaches zero near the transition. The indicated loss of spin entropy at the transition is discussed.     

Melting of the first monolayer of Ar adsorbed on the basal face of graphite

We have measured adsorption isotherms of Ar on graphite from 67 to 77 K in the range of coverages at which the monolayer freezes. The transition appears continuous and shows some similarity with a λ transition. The large increase of the isothermal compressibility at freezing seems to indicate that it cannot be accounted for by the Kosterlitz-Thouless-Halperin-Nelson-Young theory.     

N2 Monolayers on graphite: Specific heat and vapor pressure measurements — thermodynamics of size effects and steric factors

Calorimetric and vapor pressure measurements of N₂ monolayers on Grafoil have been made in the regions recently explored by neutron scattering. The phase transition at T = 48 K involves approximately symmetric specific heat anomalies of 2&#x0303; K FWHM, and the peak position shifts about 1 K from $\text{1}\text{3}$ to $\text{2}\text{3}$ of one monolayer. In spite of the peak width and temperature shift the transition is intrinsically first order, due to melting of the √3 registered structure into a disordered phase in the presence of 2D vapor. The shift and broadening are shown to be a consequence of size effects primarily due to large edge-to-area ratios of the ordered phase domains. A formula relating the domain size to the shift in transition temperature gives r = 50' A for the mean radius of the domains. At film densities above $\text{2}\text{3}$ monolayer the peak broadens and shifts to a higher temperature until a critical region is reached near T= 85 K. The combined heat capacity and vapor pressure data indicate that there is no two phase region at coverages near monolayer completion and that the transition near T = 85 K is higher than first order. Effects of molecular orientation and surface-normal vibration appear in certain regions of temperature and density. A phase diagram is constructed which is consistent with both calorimetric and neutron scattering results.     

Impurity cyclotron resonance in InGaAs/AlAs superlattice under ultra high magnetic fields

We have carried out cyclotron resonance (CR) measurements of (InGaAs)₈/(AlAs)₈ superlattice (SL) to investigate electronic properties of the SL under pulsed ultra-high magnetic fields. The magnetic fields up to 160 T were generated by using the single-turn-coil technique. Clear CR signals were obtained in the transmission of far-infrared laser through the SL at room temperature and lower temperature. We observed a shift of CR peak to lower magnetic field caused by transition from free-electron CR to impurity CR below 90 K. Compared with the previous works of GaAs/AlAs SL, the peak shift was small and the transition temperature was low. This result suggests that a binding energy of the impurity in the InGaAs/AlAs SL is smaller than the GaAs/AlAs SL.     

The surface structures growth’s features caused by Ge adsorption on the Au(111) surface

The initial stage of the adsorption of Ge on an Au(111) surface was investigated. The growth and stability of the structures formed at the surface were studied by ultrahigh-vacuum low-temperature scanning tunneling microscopy and analyzed using density functional theory. It was established that the adsorption of single Ge atoms at the Au(111) surface at room temperature leads to the substitution of Au atoms by Ge atoms in the first surface layer. An increasing of surface coverage up to 0.2–0.4 monolayers results in the growth of an amorphous binary layer composed of intermixed Au and Ge atoms. It was shown that the annealing of the binary layer at a temperature of T _s ? 500 K, as well as the adsorption of Ge on the Au(111) surface heated to T _s ? 500 K for coverages up to 1 monolayer lead to a structural transition and the formation of an Au–Ge alloy at least in the first two surface layers. Based on experimental and theoretical data, it was shown that the formation of single-layer germanene on the Au(111) surface for coverages ≤1 monolayer in the temperature range of T _s = 297–500 K is impossible.     

Absence of relaxor-like ferroelectric phase transition in (Pb,Sr)TiO3 thin films

We have performed dielectric and micro-Raman spectroscopy measurements in the 298–673 K temperature range in polycrystalline Pb_0.50Sr_0.50TiO₃ thin films prepared by a soft chemical method. The phase transition have been investigated by dielectric measurements at various frequencies during the heating cycle. It was found that the temperature corresponding to the peak value of the dielectric constant is frequency-independent, indicating a non-relaxor ferroelectric behavior. However, the dielectric constant versus temperature curves associated with the ferroelectric to paraelectric phase transition showed a broad maximum peak at around 433 K. The observed behavior is explained in terms of a diffuse phase transition. The obtained Raman spectra indicate the presence of a local symmetry disorder, due to a higher strontium concentration in the host lattice. The monitoring of some modes, conducted in the Pb_0.50Sr_0.50TiO₃ thin films, showed that the ferroelectric tetragonal phase undergoes a transition to the paraelectric cubic phase at around 423 K. However, the Raman activity did not disappear, as would be expected from a transition to the cubic paraelectric phase. The strong Raman spectrum observed for this cubic phase is indicative that a diffuse-type phase transition is taking place. This behavior is attributed to distortions of the perovskite structure, allowing the persistence of low-symmetry phase features in cubic phase high above the transition temperature. This result is in contrast to the forbidden first-order Raman spectrum, which would be expected from a cubic paraelectric phase, such as the one observed at high temperature in pure PbTiO₃ perovskite. PACS 78.30.-j; 77.80.Bh; 64.70.Kb; 68.55.-a; 77.22.-a; 77.55.+f     

Quasi two-dimensional electronic properties of the lithium molybdenum bronze,Li0.9Mo6O17

Four probe electrical resistivity measurements between 0.3K and 300K were made on single crystals of the violet-red bronze Li_0.9Mo₆O₁₇ grown by a temperature gradient flux technique. The temperature variation of the resistivity shows metallic conductivity and highly anisotropic behavior similar to K_0.9Mo₆O₁₇. The room temperature resistivity, measured in the direction parallel to the plate axis, is 9.5×10^-3Ωcm and 2.47Ωcm perpendicular to that axis. A phase transition observed at ～24K is possibly related to the onset of a charge density wave. A transition to the superconducting state is observed at Tc ～ 1.9K.     

Phase diagram of oxygen on Ni(100)

We have studied the coverage-temperature phase diagram of chemisorbed oxygen on Ni(100) with LEED and AES. We find that the oxygen p(2 × 2) structure undergoes a nearly reversible order- disorder phase transition for coverages between 0.15 and 0.30 monolayer (T_c ≈ 560 K for θ = 0.25). For these coverages, it is also found that the chemisorbed oxygen begins dissolving into the bulk nickel as the overlayer disorders. A reversible order-disorder transition is not seen for the oxygen c(2 × 2) structure, but there is evidence that bulk dissolution here also occurs coincident with the overlayer disordering.     

Quasi-elastic neutron scattering of benzene in Na-mordenite

The rotational and translational dynamics of benzene adsorbed in Na-mordenite have been studied by incoherent quasi-elastic neutron scattering. The measurements were performed at two benzene coverages at 300, 400 and 450 K. The observed quasi-elastic broadenings are described by a uniaxial rotational model about the six-fold axis of benzene. The mean time between successive jumps, at 300 K, is τ=1.45 × 10^?12 s at low coverage and 2.05×10^?12 s at high coverage. The correlation times follow an Arrhenius law with E_A=4.51 kJ mol^?1, at both coverages. The translational diffusion coefficient has been measured at 300 K and was found to be 0.67 × 10^?6 cm²s^?1.     

Direct experimental verification of the isomorphism hypothesis for critical phenomena

The heat capacity at constant volume of a mixture of methane and 0.0345 mole fractions of heptane is experimentally studied over a wide range of densities and temperatures. In the case when the transition from a three-phase state takes place in the presence of a noncritical liquid phase, it is found that the behavior of the heat capacity in the vicinity of the upper end critical point is fully isomorphic with the behavior of the heat capacity in the vicinity of the liquid-vapor critical point of one-component fluid. It is shown that the measured quantity in this experiment is the heat capacity at constant volume and constant chemical potential μ of the heavy impurity component C _{v, μ}. Thus, it has been confirmed by direct measurements that the anomaly of this heat capacity completely coincides in character with the anomaly of the heat capacity at constant volume in the vicinity of the liquid-vapor critical point of one-component fluids.     

Magnetic susceptibility of NbSe3 and TaSe3

The magnetic susceptibility of NbSe₃ shows a decrease beginning slightly above its upper charge density wave transition (CDW) of 144 K, but no change within our resolution near the 59 K transition. The change in the density of states at the Fermi level due to the upper transition is 0.14 states-eV/Nb. TaSe₃ on the other hand has a temperature independent susceptibility. In some cases the trichalcogenides are contaminated with their corresponding dichalcogenide. Such contamination can be observed by susceptibility measurements in the case of 2HTaSe₂ but not of 2HNbSe₂. We also report an anomaly in the susceptibility of 4HaNbSe₂, which suggests a CDW transition at 45 K.     

Phase transitions in adsorbed films of barium on W(011)

Phase transitions in barium submonolayers adsorbed on W(011) are studied in a wide range of temperatures and coverages by the LEED technique, including the temperature measurement of the diffraction intensity. The regions of ordered and disordered structures are determined, the result is presented in the form of phase diagram. The temperature dependence of the adfilm Bragg intensity in the low temperature limit (the lowest temperature is 5 K) shows an appreciable slope for all incoherent and almost all coherent structures, except for (3×2). The fact is discussed in terms of the adfilm long- and quasi-long-range order. The disordering of the (3 × 2) lattice near T_c=130 K is the second-order phase transition with the order parameter critical exponent β=0.16. the adfilm is two-phase in the range n=(3.2?3.8)×10¹⁴cm^?2 and singlehase for the rest of the coverages. The effect of the first-order phase transition on the character of the work function change in the two-phase region is discussed.     

Investigation of the thermal expansion and heat capacity of the CaCu3Ti4O12 ceramics

The thermal expansion of the CaCu₃Ti₄O₁₂ ceramics has been measured over a wide temperature range 120?C1200 K. The high quality of the samples under study has been confirmed by good agreement of the results of measurements of the heat capacity in the range 2?C300 K and in the vicinity of the phase transition of magnetic nature at 25 K with the data for the single crystal. No anomalies in the thermal expansion that can be associated with the phase transition at 726?C732 K assumed by other investigators have been found. The influence exerted on the thermal expansion by the heat treatment of the sample in a helium atmosphere and in air has been investigated.