Nature of metal-nonmetal transition in metal-ammonia solutions. II. From uniform metallic state to inhomogeneous electronic microstructure

Applying semi-analytical models of nonideal plasma, we evaluate the behavior of the metallic phase in metal-ammonia solutions (MAS). This behavior is mainly controlled by the degenerate electron gas, which remains stable down to 5 MPM due to high solvent polarizability and strong dielectric screening of solvated ions. Comparing the behavior of the metallic state with those of localized solvated electrons, we have estimated the miscibility gap $\Delta n$ for various alkali metals and found $\Delta n$(Na)$> \Delta n($K$)$. It is rather narrow in Rb-NH$_3$ and does not occur in Cs-NH$_3$ solutions, which is in full agreement with the experiments. The case of Li is discussed separately. The difference calculated in the excess free energies of the metallic and nonmetallic phases is in the order of $k_BT$, yielding a thermally fluctuating mixed state at intermediate metal concentrations. It results in a continuous metal-nonmetal (MNM) transition above the consolute point $T_c$ and a phase separation below $T_c$. We propose a criterion for the MNM transition which may be attributed to the line of the maximum of compressibility above $T_c$. This line crosses the spinodal one at the critical temperature. Finally, we assert that a new electronic phase similar to microemulsion should also arise between the spinodal and the binodal lines.Comment: 22 pages, 10 figure

Nature of the metal-nonmetal transition in metal-ammonia solutions. I. Solvated electrons at low metal concentrations

Using a theory of polarizable fluids, we extend a variational treatment of an excess electron to the many-electron case corresponding to finite metal concentrations in metal-ammonia solutions (MAS). We evaluate dielectric, optical, and thermodynamical properties of MAS at low metal concentrations. Our semi-analytical calculations based on a mean-spherical approximation correlate well with the experimental data on the concentration and the temperature dependencies of the dielectric constant and the optical absorption spectrum. The properties are found to be mainly determined by the induced dipolar interactions between localized solvated electrons, which result in the two main effects: the dispersion attractions between the electrons and a sharp increase in the static dielectric constant of the solution. The first effect provides a classical phase separation for the light alkali metal solutes (Li, Na, K) below a critical temperature. The second effect leads to a dielectric instability, i.e., polarization catastrophe, which is the onset of metallization. The locus of the calculated critical concentrations is in a good agreement with the experimental phase diagram of Na-NH3 solutions. The proposed mechanism of the metal-nonmetal transition is quite general and may occur in systems involving self-trapped quantum quasiparticles.Comment: 13 figures, 42 page

The local phase transitions of the solvent in the neighborhood of a solvophobic polymer at high pressures

We investigate local phase transitions of the solvent in the neighborhood of a solvophobic polymer chain which is induced by a change of the polymer-solvent repulsion and the solvent pressure in the bulk solution. We describe the polymer in solution by the Edwards model, where the conditional partition function of the polymer chain at a fixed radius of gyration is described by a mean-field theory. The contributions of the polymer-solvent and the solvent-solvent interactions to the total free energy are described within the mean-field approximation. We obtain the total free energy of the solution as a function of the radius of gyration and the average solvent number density within the gyration volume. The resulting system of coupled equations is solved varying the polymer-solvent repulsion strength at high solvent pressure in the bulk. We show that the coil-globule (globule-coil) transition occurs accompanied by a local solvent evaporation (condensation) within the gyration volum

Structural and transport properties of GaAs/delta<Mn>/GaAs/InxGa1-xAs/GaAs quantum wells

We report results of investigations of structural and transport properties of GaAs/Ga(1-x)In(x)As/GaAs quantum wells (QWs) having a 0.5-1.8 ML thick Mn layer, separated from the QW by a 3 nm thick spacer. The structure has hole mobility of about 2000 cm2/(V*s) being by several orders of magnitude higher than in known ferromagnetic two-dimensional structures. The analysis of the electro-physical properties of these systems is based on detailed study of their structure by means of high-resolution X-ray diffractometry and glancing-incidence reflection, which allow us to restore the depth profiles of structural characteristics of the QWs and thin Mn containing layers. These investigations show absence of Mn atoms inside the QWs. The quality of the structures was also characterized by photoluminescence spectra from the QWs. Transport properties reveal features inherent to ferromagnetic systems: a specific maximum in the temperature dependence of the resistance and the anomalous Hall effect (AHE) observed in samples with both "metallic" and activated types of conductivity up to ~100 K. AHE is most pronounced in the temperature range where the resistance maximum is observed, and decreases with decreasing temperature. The results are discussed in terms of interaction of 2D-holes and magnetic Mn ions in presence of large-scale potential fluctuations related to random distribution of Mn atoms. The AHE values are compared with calculations taking into account its "intrinsic" mechanism in ferromagnetic systems.Comment: 15 pages, 9 figure

Herzfeld instability versus Mott transition in metal-ammonia solutions

Although most metal-insulator transitions in doped insulators are generally viewed as Mott transitions, some systems seem to deviate from this scenario. Alkali metal-ammonia solutions are a brilliant example of that. They reveal a phase separation in the range of metal concentrations where a metal-insulator transition occurs. Using a mean spherical approximation for quantum polarizable fluids, we argue that the origin of the metal-insulator transition in such a system is likely similar to that proposed by Herzfeld a long time ago, namely, due to fluctuations of solvated electrons. We also show how the phase separation may appear: the Herzfeld instability of the insulator occurs at a concentration for which the metallic phase is also unstable. As a consequence, the Mott transition cannot occur at low temperatures. The proposed scenario may provide a new insight into the metal-insulator transition in condensed-matter physics.Comment: 9 pages, 4 figure

Combined EUV reflectance and X-ray reflectivity data analysis of periodic multilayer structures

We present a way to analyze the chemical composition of periodical multilayer structures using the simultaneous analysis of grazing incidence hard X-Ray reflectivity (GIXR) and normal incidence extreme ultraviolet reflectance (EUVR). This allows to combine the high sensitivity of GIXR data to layer and interface thicknesses with the sensitivity of EUVR to the layer densities and atomic compositions. This method was applied to the reconstruction of the layered structure of a LaN/B multilayer mirror with 3.5 nm periodicity. We have compared profiles obtained by simultaneous EUVR and GIXR and GIXR-only data analysis, both reconstructed profiles result in a similar description of the layered structure. However, the simultaneous analysis of both EUVR and GIXR by a single algorithm lead to a ∼2x increased accuracy of the reconstructed layered model, or a more narrow range of solutions, as compared to the GIXR analysis only. It also explains the inherent difficulty of accurately predicting EUV reflectivity from a GIXR-only analysis

Pecularities of Hall effect in GaAs/{\delta}<Mn>/GaAs/In\timesGa1-\timesAs/GaAs (\times {\approx} 0.2) heterostructures with high Mn content

Transport properties of GaAs/{\delta}/GaAs/In\timesGa1-\timesAs/GaAs structures containing InxGa1-xAs (\times {\approx} 0.2) quantum well (QW) and Mn delta layer (DL) with relatively high, about one Mn monolayer (ML) content, are studied. In these structures DL is separated from QW by GaAs spacer with the thickness ds = 2-5 nm. All structures possess a dielectric character of conductivity and demonstrate a maximum in the resistance temperature dependence Rxx(T) at the temperature {\approx} 46K which is usually associated with the Curie temperature Tc of ferromagnetic (FM) transition in DL. However, it is found that the Hall effect concentration of holes pH in QW does not decrease below TC as one ordinary expects in similar systems. On the contrary, the dependence pH(T) experiences a minimum at T = 80-100 K depending on the spacer thickness, then increases at low temperatures more strongly than ds is smaller and reaches a giant value pH = (1-2)\cdot10^13 cm^(-2). Obtained results are interpreted in the terms of magnetic proximity effect of DL on QW, leading to induce spin polarization of the holes in QW. Strong structural and magnetic disorder in DL and QW, leading to the phase segregation in them is taken into consideration. The high pH value is explained as a result of compensation of the positive sign normal Hall effect component by the negative sign anomalous Hall effect component.Comment: 19 pages, 6 figure