Magnetic Order in Organic Superconductors

We have undertaken an electron spin resonance study at both low and high magnetic field on the superconducting phase of the ambient pressure superconductor (BEDT-TTF>₂I₃, (ET)₂I₃, over the temperature range 1-300 K and hydrostatic pressure range from 0 to 2 kbar. At ambient pressure the ESR results are consistent with the picture of (ET)₂I₃ as a metal. Superconductivity is observed at 1.6 K via low field ESR. Application of modest pressures strongly suppresses the superconducting transition temperature. At pressures above about 0.3 kbar the superconductivity is suppressed in favor of an as-yet-unidentified magnetic state whose onset is at 7K. Through an analysis of the microwave ESR lineshape we find that the microwave conductivity over the temperature range 5-50 K is in agreement with dc measurements.     

Problems on the mechanically induced polymorphic transformation

Some typical experimental results are presented and discussed phenomenologically on the topics; (i) the transformations which are readily carried out with the aid of mechanical stimulation but hardly by simple heating (PbO, ZnS); (ii) formation of metastable phases under the influence of mechanical stresses from the phase which is stable at room temperature under the atmospheric pressure (CdS, CdSe); (iii) pseudo-equilibrium between polymorphs during grinding (CaCO₃).     

Photoconductivity of ZnSe:Dy

Nature of dark current has been investigated as a function of different metallic electrodes and the ambient temperature. Photoconductivity rise and decay curves have been investigated as a function of different metallic electrodes, flux and impurity concentrations, ambient temperature and the cell thickness. A maximum increase of 59 times in I_pc has been reported. Possible explanations are given for the observed effects.     

Photoconductivity of (ZnS,CdSe): Dy

Photoconductivity rise and decay curves have been investigated for (ZnS, CdSe): Dy as a function of flux concentration, concentration of Dy, applied voltage, atmosphere during preparation and different excitation intensities. Substitution of Dy increases the photocurrent by five times. Maximum photocurrent is also observed at a particular concentration of flux. The decay is of hyperbolic nature and the trap depths are found at depths 0.49 eV and 0.54 eV which depend upon the concentration of Dy.     

The Process of Formation of Epitaxial Cadmium and Zinc Oxide Films by Interaction of Single-Crystal AIIBVI Layers with Oxygen

The results of electron microscopic and electron diffraction investigation of the surface during annealing of single-crystal A^IIB^VI (CdS, CdSe, ZnSe, ZnS) films in the presence of oxygen are reported. It is shown that the behaviour of islands of cadmium oxide formed by chemical interaction between O₂ and the CdS, CdSe substrate in the process of growth resembles that of the nuclei in film condensation. CdO films become “continuous” more quickly, if the size of blocks of substrate-epitaxial A^IIB^VI film is larger. Epitaxial ZnO films formed on the surface of epitaxial ZnS and ZnSe layers are of a wurtzite structure or a cubic structure with the parameter a = 4.5 Å.     

Structural,electrical and optical properties of Ge implanted GaSe single crystals grown by Bridgman technique

Structural, optical and electrical properties of Ge implanted GaSe single crystal have been studied by means of X‐Ray Diffraction (XRD), temperature dependent conductivity and photoconductivity (PC) measurements for different annealing temperatures. It was observed that upon implanting GaSe with Ge and applying annealing process, the resistivity is reduced from 2.1 × 10⁹ to 6.5 × 10⁵ Ω‐cm. From the temperature dependent conductivities, the activation energies have been found to be 4, 34, and 314 meV for as‐grown, 36 and 472 meV for as‐implanted and 39 and 647 meV for implanted and annealed GaSe single crystals at 500°C. Calculated activation energies from the conductivity measurements indicated that the transport mechanisms are dominated by thermal excitation at different temperature intervals in the implanted and unimplanted samples. By measuring photoconductivity (PC) measurement as a function of temperature and illumination intensity, the relation between photocurrent (I_PC) and illumination intensity (Φ) was studied and it was observed that the relation obeys the power law, I_PC αΦⁿ with n between 1 and 2, which is indication of behaving as a supralinear character and existing continuous distribution of localized states in the band gap. As a result of transmission measurements, it was observed that there is almost no considerable change in optical band gap of samples with increasing annealing temperatures for as‐grown GaSe; however, a slight shift of optical band gap toward higher energies for Ge‐implanted sample was observed with increasing annealing temperatures. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Cd‐Doping Effects on The Properties of Polycrystalline α‐In2Se3 Thin Films

The X‐ray diffraction has revealed that the polycrystalline hexagonal structured α‐In₂Se₃ thin films grown at substrate temperature of 200 °C with the unit cell parameters a = 4.03 Å and c = 19.23 Å becomes polycrystalline hexagonal structured InSe with a unit cell parameters of a = 4.00 Å and c = 16.63 Å by Cd‐doping. The analysis of the conductivity temperature dependence in the range 300‐40 K revealed that the thermionic emission of charged carriers and the variable range hopping are the predominant conduction mechanism above and below 100 K, respectively. Hall measurements revealed that the mobility is limited by the scattering of charged carriers through the grain boundaries above 200 K and 120 K for the undoped and Cd‐doped samples, respectively. The photocurrent (I_ph) increases with increasing illumination intensity (F) and decreasing temperature up to a maximum temperature of ∼100 K, below which I_ph is temperature invariant. It is found to have the monomolecular and bimolecular recombination characters at low and high illumination intensities, respectively. The Cd‐doping increases the density of trapping states that changes the position of the dark Fermi level leading to the deviation from linearity in the dependence of I_ph on F at low illumination intensities.     

Cr doping influence in ZnS single crystals on the complex disordered polytypical structure

The results of X-ray investigation of real structures of ZnS:Cr single crystals are presented. Doped ZnS single crystals were grown from the melt by Bridgman's high pressure method. Cr dopant converts the structure of ZnS crystals from 3C with individual stacking faults (for pure ZnS) to the complex polytypical structures disordered along one dimension and including specific orderings of cp layers that form polytype cells LH (L = 2l, l = 2, 3, 4 and 5). The structures are characterised by Farkas-Jahnkes statistical parameters π(m, p) and by parameters P_LH of the polytype unit cell formation probability (Kozielski, Tomaszewicz 1986; Palosz, Przedmojski).     

Plasma diagnostics in silane–methane–hydrogen plasmas under pm-Si1−xCx:H deposition conditions: Correlation with film properties

A systematic study has been done on the formation of nanoparticles in silane–methane–hydrogen plasmas and their effect on material properties. By increasing the total pressure we cover three phases of particle growth: nanocrystals nucleation and accumulation, agglomeration, and powder formation. The presence of particles in the plasma is detected from the evolution of the discharge electrical parameters such as the self-bias (V_DC) on the radio-frequency electrode and the peak-to-peak RF voltage (V_PP). Interestingly, optical emission spectroscopy measurements show that the presence of particles has a strong effect on the hydrogen emission bands. Indeed, while H_α emission is dominant at low pressure in a powder free discharge, the formation of particles leads to an intense H₂ Fulcher α band. Moreover the ratio I_Fulcher/I_Hα provides a clear signature of the transition from nucleation to agglomeration regimes, thus providing an easy way of characterizing the plasma regime. The changes in the deposition regime are also reflected on the film properties, in particular their photoluminescence characteristics.     

Fabrication and characteristics of CeO2 films on Si(1 0 0) substrates by pulsed laser deposition

A detailed investigation about the dependence of film orientation on deposition temperature and ambient oxygen pressure has been carried out for CeO₂ films on Si(1 0 0) substrates using pulsed laser deposition. It has been found that the CeO₂ film orientation varies with increasing oxygen pressure at 750°C deposition temperature. In addition, the recovery of preferential orientation of CeO₂ films grown at 20 Pa ambient oxygen pressure with increasing deposition temperature has also been found for the first time. X-ray photoelectron spectroscopy (XPS) measurements confirm that stoichiometric CeO₂ films can be grown at lower oxygen pressure (5×10⁻³ Pa). HRTEM result also indicates that the CeO₂ films grown at low oxygen pressure are of high crystallinity.     

Structural and optical property studies of CdSe crystalline nanorods synthesized by a solvothermal method

CdSe nanorods are synthesized via a simple solvothermal method at a moderate temperature of 180 °C. The influences of introducing hydrazine hydrate (N₂H₄·H₂O) as the reducing agent, and ammonia (NH₃·H₂O) as the complexing agent and also the reaction temperature, on the morphology and size of the obtained CdSe nanorods are investigated and reported. CdSe nanorods with a mean diameter and length of 25 and 82 nm, respectively, are synthesized and the problem of handling the stacking faults present in the long CdSe nanorods is analyzed. The use of increased quantity of hydrazine hydrate and also prolonged reaction time is found to reduce the stacking faults on the synthesized nanorods. The morphology, phase and the optical properties of CdSe nanoparticles are studied using powder X-ray diffraction, TEM and high-resolution transmission electron microscope (HRTEM), UV–visible absorption spectroscopy and photoluminescence (PL) spectroscopy. The low-resolution TEM images confirm the formation of CdSe nanorods, and also the agglomeration of nanoparticles and the presence of few spherical nanoparticles. The strong PL intensity from the CdSe nanorod at 702 nm confirms a blue shift of 14 nm, when compared with the bulk wurtzite CdSe.     

Spectroscopic Determination of Charge Formation Efficiency of Organic Photovoltaic Cells

The internal quantum efficiency (Φ_IQ) of an organic photovoltaic (OPV) cell is governed by plural processes, i.e., the carrier formation process at the D/A interface and the carrier transfer process toward the collector electrode. Then, Φ_IQ can be decomposed into the carrier formation (Φ_CF) and carrier transfer efficiencies (Φ_CT). By combination of femtosecond time-resolved and electrochemical spectroscopies, we determined absolute values of Φ_CF of F8T2/PC₇₁BM, P3HT/PCBM, and PTB7/PC₇₁BM solar cells. We found that Φ_CF at 400 nm of the F8T2/PC₇₁BM cell is higher than those of the P3HT/PCBM, and PTB7/PC₇₁BM cells, although Φ_IQ at 400 nm is the lowest.     

Crystal structure of the Lanthanum(III) complex [La(DMSO)6(H2O)PW12O40] · C2H5OH (DMSO is dimethyl sulfoxide)

The crystal structure of the [La(DMSO)₆(H₂O)PW₁₂O₄₀] · C₂H₅OH complex (I) (where DMSO is dimethyl sulfoxide) is determined by X-ray diffraction analysis. The coordination polyhedron of the La atom is a distorted tricapped trigonal prism in which two cap sites are occupied by oxygen atoms of the heteropolyanions. For these atoms, the La-O distances [2.760(9) and 2.801(9) Å] are considerably longer than the other distances [ranging from 2.441(10) to 2.569(10) Å] in the environment of the La atom. __________ Translated from Kristallografiya, Vol. 47, No. 6, 2002, pp. 1039–1041. Original Russian Text Copyright ? 2002 by Grigoriev, Shirokova, Fedoseev, Den Auwer.     

Cleavage Mechanoluminescence in Crystals

When a crystal is cleaved, initially the mechanoluminescence (ML) intensity increases linearly with time, attains an optimum-value I_m at a particular value of timet_m, and then decays exponentially with time. Cleavage ML provides a new tool to determine the velocity, v of cracks in crystals, and it may be given by v = H/t_m, where H is the thickness of the crystal. Both, the peak ML intensity I_m and total ML intensity I_T increase linearly with the area of newly created surfaces A as well as with the surface charge density γ. The ML intensity decreases with temperature primarily due to the decrease in the surface charge density. Beyond a particular temperature, the surface charge density may decrease to such a value where the breakdown of gases and solids may not be possible and thereby the ML may not appear. Depending on the prevailing conditions either the ML emission resembling gas discharge or other types of the luminescence of solids, or that having these two characters may be obtained. There exists a good correlation between the theoretical and experimental results obtained for cleavage ML in crystals.     

Antisolvent crystallization of aqueous ammonium dihydrogen phosphate solutions by addition of acetone at different rates

Results of an investigation of in situ measurements of laser‐beam intensity I_s and I_m transmitted through aqueous ammonium dihydrogen phosphate (ADP) solutions saturated at 30 °C and water, respectively, and temperature T_s of solution and T_m of water during feeding of antisolvent acetone at different rates R_A, using an indigenously designed experimental setup, are presented and discussed. It was found that: (1) for the measurement of MSZW, defined as the maximum volume fraction of acetone content Δx_max in the solution, obtained from temperature measurements are more reliable than transmitted laser‐beam intensity measurements for solutions, (2) two minima ΔT_min1 and ΔT_min2 associated with endothermic reactions, separated by a maximum ΔT_max due to exothermic reactions appear in the plots of temperature difference ΔT = T_s−T_m against acetone feeding time t, and (3) in the ΔT(t) plots there are time intervals Δt of constant rates R_T of increase in ΔT of aqueous ADP solutions, and these values of R_T increase linearly with acetone feeding time rate R_A. The experimental data on the observed dependence of MSZW on antisolvent feeding rate R_A, the appearance of minima ΔT_min1 and ΔT_min2 and maximum ΔT_max and their dependence on R_A, and the relationship between R_T and R_A are discussed from consideration of processes of nucleation and growth of crystallites.     

The structure of the scandium iodide complex with antipyrine (AP) and its comparison with the structure of nonisostructural analogues (Compounds [Ln(AP)6]I3 (Ln = La, Y, or Eu))

An X-ray diffraction study of the scandium iodide complex with antipyrine [Sc(AP)₆]I₃ (AP is antipyrine, i.e., 2,3-dimethyl-1-phenyl-3-pyrazolin-5-one) (I), which is not isostructural to the analogous compounds of Y, La, and Eu (II), is performed. Crystals I are trigonal; a = 24.911 ? and c = 10.140 ?; Z = 3, space group P $ \bar 3 $ \bar 3 . Crystal I is built of [Sc(AP)₆]³⁺ complex cations of two types and I⁻ anions. In both cations, the Sc atom is octahedrally coordinated by six O atoms of six AP ligands (Sc-O, 2.054–2.078 ?). Complexes I differ from II by the absence of π-π stacking interactions between AP molecules, resulting in a supramolecular cation. Complex cations I of both types form combined layers. All I⁻ anions are located in the interlayer space, being statistically disordered within a flat area limited by eight complex cations of Sc1 and Sc2.     

The growth of HgI2 crystals

The paper presents a system for αHgI₂ crystal growth by the temperature oscillation method. The system has a capability of crystal growing at an excess I₂ or Hg vapour pressure. Optimum conditions for producing crystals up to 2 cm³ by volume have been established. The crystals grown at an excess I₂ vapour pressure have higher resistivity and higher drift electron and hole mobilities — μ_e = 120 cm² V⁻¹ s⁻¹ and μ_h = 6 cm² V⁻¹ s⁻¹, respectively.     

The double phosphates MIMIIPO4 (MI – Na,K; MII – Mg,Mn, Co,Ni, Zn) – synthesis from chloride melts and characterization

The particularities of the chemical interaction in systems M^IPO₃‐M^IIO(or Mn₂O₃)‐M^ICl (M^I – Na, K; M^II – Mg, Co, Ni, Zn) have been investigated at the temperature 1073 K and molar ratios P/M^x = 1 or 2 and M^ICl/(M^IPO₃ + M^IIO(or Mn₂O₃)) = 30. The conditions of formation of complex phosphates M^ІM^IIPO₄ and Na₄Ni₃(PO₄)₂P₂O₇ have been found. Influences of the nature of alkali and bivalent metals on the products composition were discussed. The advantages of chloride melts using (synthesis time reduction and temperature reducing) for preparing of complex phosphates were shown. The synthesized compounds have been characterized using the powder X‐ray diffraction, Fourier transform infrared and diffuse reflectance spectroscopies.     

MOVPE Growth of Wide Band-Gap II—VI Compounds for Near-UV and Deep-Blue Light Emitting Devices

We report on the growth by metalorganic vapour phase epitaxy of high structural and optical quality ZnS, ZnSe and ZnS/ZnSe multiple quantum well (MQW) based heterostructures for applications to laser diodes operating in the 400 nm spectral region. High purity ^tBuSH, ^tBu₂Se and the adduct Me₂Zn:Et₃N were used as precursors of S, Se and Zn, respectively. The effect of the different MOVPE growth parameters on the growth rates and structural properties of the epilayers is reported, showing that the crystallinity of both ZnS and ZnSe is limited by the kinetics of the incorporation of Zn, S and Se species at the growing surface. Very good structural and optical quality ZnS and ZnSe epilayers are obtained under optimized growth conditions, for which also dominant (excitonic) band-edge emissions are reported. The excellent ZnS and ZnSe obtained by our MOVPE growth matches the stringent requirements needed to achieve high quality ZnS/ZnSe MQWs. Their structural properties under optimized MOVPE conditions are shown to be limited mostly by the formation of microtwins, a result of the intrinsic high lattice mismatch involved into the ZnS/ZnSe heterostructure. Despite the large amount of defects found, the optical quality of the MQWs turned out to be high, which made possible the full characterization of their electronic and lasing properties. In particular, photopumped lasing emission up to 50 K in the 3.0 eV energy region are reported for the present MQWs heterostructures under power excitation density above 100 kW/cm².     

Nanostructured crystals of Sr1?xRxF2+x fluorite phases and their ordering: 6. Microindentation analysis of crystals

Hardness, crack resistance, brittleness, and effective fracture energy have been studied for crystals of 24 fluorite phases Sr_{1 − x} R _x F_{2 + x} (R are 14 rare earth elements (REEs); 0 < x ≤ 0.5) and SrF2 grown by the Bridgman method from a melt. These characteristics change nonlinearly with an increase in the REE content for Sr_{1 − x} R _x F_{2 + x} (0 < x ≤ 0.5) with R = La, Nd, Sm, Gd, and Lu; it is maximum in the range x < 0.1 for all REEs. The changes in a number of REEs have been traced for an isoconcentration series of Sr_0.90 R _0.10F_2.10 crystals (R = La, Nd, Sm, Gd, Ho, Er-Lu, or Y) and crystals (similar in composition) with R = Tb and Dy. The hardness of Sr_{1 − x} R _x F_{2 + x} crystals is higher by a factor of ∼2–3 than that of SrF2. The effect of decrease in microstresses in SrF₂ crystals is confirmed by the isomorphic introduction of R ³⁺ ions into this crystalline matrix.