Laser and electrical current induced phase transformation of In<Subscript>2</Subscript>Se<Subscript>3</Subscript> semiconductor thin film on Si(111)

Phase transformation of thin film (∼30 nm)In₂Se₃/Si(111) (amorphous→crystalline) was performed by resistive annealing and the reverse transformation (crystalline→amorphous) was performed by nanosecond laser annealing. As an intrinsic-vacancy, binary chalcogenide semiconductor, In₂Se₃ is of interest for non-volatile phase-change memory. Amorphous In _x Se _y was deposited at room temperature on Si(111) after pre-deposition of a crystalline In₂Se₃ buffer layer (0.64 nm). Upon resistive annealing to 380°C, the film was transformed into a γ-In₂Se₃ single crystal with its {0001} planes parallel to the Si(111) substrate and parallel to Si , as evidenced by scanning tunneling microscopy, low energy electron diffraction, and X-ray diffraction. Laser annealing with 20-ns pulses (0.1 millijoules/pulse, fluence≤50 mJ/cm²) re-amorphized the region exposed to the laser beam, as observed with photoemission electron microscopy (PEEM). The amorphous phase in PEEM appears dark, likely due to abundant defect levels inhibiting electron emission from the amorphous In _x Se _y film.     

Correlation between raman spectra and structural properties of Zn<Subscript>2 − 2<Emphasis Type="Italic">x</Emphasis></Subscript>Cu<Subscript>x</Subscript>In<Subscript>x</Subscript>Se<Subscript>2</Subscript> films

The Raman spectra of Zn_{2 ? 2x} Cu_xIn_xSe₂ (ZCIS) semiconductor films designed for use as optically active layers in thin-film solar cells have been investigated. The Raman spectra of ZCIS films are characterized by the presence of the dominant mode A ₁, which is observed in A^IB^IIIC ₂ ^VI compounds with chalcopyrite structure. The spectra of CuInSe₂ films (x = 1) obtained at low temperatures (T ≤ 400°C) contain and additional mode at 258 cm^?1, which is due to the presence of the impurity Cu_xSe phase. All modes observed in the spectra of ZCIS films with a Zn concentration ≤20 at % obtained under optimal conditions (520–540°C) correspond to the symmetry of vibrations in the chalcopyrite structure. The broadening and blue shift of the A ₁ mode occurring with an increase in the Zn concentration are indicative of degradation of the chalcopyrite crystal structure and the chalcopyrite → sphalerite phase transition at Zn concentrations exceeding 20 at %.     

12.95 mW sixth harmonic generation with KBe<Subscript>2</Subscript>BO<Subscript>3</Subscript>F<Subscript>2</Subscript> crystal

We obtained the second harmonic of a frequency-tripled Nd:YVO₄ laser at wavelength of 177.3 nm with 12.95 mW output by using an optically contacted KBe₂BO₃F₂-CaF₂ prism-coupled device with a 2.1 mm thick KBe₂BO₃F₂ crystal, which is to our knowledge the best result at this wavelength. PACS 42.65.Ky; 42.70.Mp; 42.55.Xi     

Calculation of refractive indices for the (NH<Subscript>2</Subscript>CH<Subscript>2</Subscript>COOH)<Subscript>2</Subscript> · HNO<Subscript>3</Subscript> crystal

The refraction R of the diglycine nitrate (DGN) crystal, (NH₂CH₂COOH)₂ · HNO₃, in the para-and ferroelectric phases has been calculated in the model of noninteracting diatomic chemical bonds of the elementary unit cell of the crystal on the basis of the longitudinal and transversal polarizabilities of these bonds. The calculated magnitudes of the principal refractive indices n _p , n _m , and n _g and the orientations of the optical indicatrix of the crystal agree satisfactorily with experimentally observed values. Introducing the coefficient of Lorenz-Lorentz interaction x into the corresponding formula permits better agreement of the calculated and experimental refractive indices of DGN crystal to be obtained. The temperature changes of these x coefficients upon the ferroelectric phase transition in the DGN crystal have been analyzed.     

Optical activity of γ<Subscript>1</Subscript>-(Ga<Subscript>x</Subscript>In<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>2</Subscript>Se<Subscript>3</Subscript> crystals

The optical activity of uniaxial γ₁-(Ga_xIn_1?x )₂Se₃ crystals (x=0.1, 0.2, 0.3, 0.4) is studied at T=295 and 77 K in the spectral range 0.5–0.8 πm. It is found that the cationic substitution In → Ga leads to a nonlinear increase in the specific rotation of the plane of polarization ρ and the component g ₃₃ of the gyration tensor. It is shown that the gyrotropy of the crystals studied is determined by high-energy transitions whose energy exceeds the energy of the edge transitions and that the gyrotropy observed has a molecular origin.     

Proton NMR study of the organic metal κ-(BETS)<Subscript>2</Subscript>Mn[N(CN)<Subscript>2</Subscript>]<Subscript>3</Subscript>

Magnetic properties of the organic conductor κ-(BETS)₂Mn[N(CN)₂]₃ above and below the temperature of the metal-insulator transition that occurs at T _MI ≈ 25 K are studied by ¹H NMR. The proton spectrum is shown to be determined by the static dipolar fields from Mn²⁺ localized moments, while the ¹H spin-lattice relaxation is dominated by fluctuating fields from Mn²⁺ electrons. The NMR data, both static (the spectra) and dynamic (the spin-lattice relaxation), indicate the freezing of Mn²⁺ moments into a short-range or an incommensurate long-range antiferromagnetic order below T _MI.     

TiO<Subscript>2</Subscript> microstructures by inversion of macroporous silicon using atomic layer deposition

An approach is presented which is capable of fabricating arbitrarily shaped three-dimensional microstructures. Two methods—namely, macroporous silicon and atomic layer deposition—are combined to realize structures in the micrometer and submicrometer range. Using TiO₂ as an example, the fabrication of single hollow objects as well as complex network structures is shown. The scalability and the wide range of applicable materials are the key points of this method for future applications.     

Dielectric properties of modified As<Subscript>2</Subscript>Se<Subscript>3</Subscript>〈Bi〉<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> layers

The dielectric parameters (permittivity ? and dielectric loss tangent tanδ) for As₂Se₃〈Bi〉 _x layers are calculated using the polarization current relaxation curves measured at different strengths of the applied electric field. It is revealed that the bismuth dopant has a considerable effect on the frequency dependences of ? and tanδ, which is probably associated with the existence of microinhomogeneous regions with an increased dopant concentration.     

In Situ Charge Characterization of TiO<Subscript>2</Subscript> and Cu–TiO<Subscript>2</Subscript> Nanoparticles in a Flame Aerosol Reactor

Charge distribution characteristics were investigated for nanoparticles synthesized in a diffusion flame aerosol reactor. The nanoparticles considered were pristine TiO₂ and Cu–TiO₂, with Cu dopant concentrations ranging from 1 to 5 wt% with particle size from 25 to 60 nm. In situ measurements were conducted by integrating a tandem differential mobility analyzer (TDMA) experimental setup with the flame aerosol reactor. A charging model was used to identify the important parameters that govern the two charging mechanisms (diffusion and thermo-ionization) in the flame and their relative importance at different operating parameters. The results indicate that TiO₂ and Cu–TiO₂ nanoparticles carry single as well as double unit charges. The charged fraction depends on particle size as well as on dopant concentration. The charged fraction increased with increasing particle size and decreased with copper dopant concentration. Measured charged fractions were similar for both the polarities at different mobility diameters. Based on the flame operating parameters, the calculations indicate that diffusion charging is dominant in the flame, which is consistent with the experimental results.     

Magnetic structure of molecular magnet Fe[Fe(CN)<Subscript>6</Subscript>]·4H<Subscript>2</Subscript>O

We have studied the magnetic structure of Fe[Fe(CN)₆]·4H₂O, prepared by precipitation method, using neutron diffraction technique. Temperature dependent DC magnetization study down to 4.2 K shows that the compound undergoes from a high temperature disordered (paramagnetic) to an ordered magnetic phase transition at 22.6 K. Rietveld analysis of neutron diffraction pattern at 60 K (in its paramagnetic phase) revealed a face centred cubic structure with space group Fm3m. The structure contains three-dimensional network of straight Fe³⁺-C≡N-Fe³⁺ chains along the edges of the unit cell cube. Fe³⁺ ions occupy 4a (0, 0, 0) and 4b (1/2, 1/2, 1/2) positions. Fe³⁺(0, 0, 0) is surrounded octahedrally by six nitrogen atoms and Fe³⁺ (1/2, 1/2, 1/2) is surrounded octahedrally by six carbon atoms. Magnetic Rietveld refinement of neutron diffraction data at 11 K shows a ferromagnetic coupling between the two inequivalent Fe³⁺ sites. Refinement yielded an ordered moment of 4.4(6) and 0.8(6) μ_B per Fe ion located at (0, 0, 0) and (1/2, 1/2, 1/2), respectively. Ordered moments are found to align along the face diagonal. The observed net moment from low temperature neutron diffraction study is consistent with DC magnetization results.     

Critical evolution of the local order parameters related to the nanopolar domains in Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> ceramics

In the present paper, Pb(Mg_1/3Nb_2/3)O₃ (PMN) ceramics prepared by the columbite method were investigated. The dielectric study indicates typical relaxor properties, with a frequency dispersion in the range of 200–350 K. The relaxor-to-paraelectric phase transition was evidenced by the continuous decrease of the local order parameter derived from the permittivity-temperature data. As a result of the critical behavior, the main Raman modes show anomalies at: (i) ∼150 K; (ii) ∼220 K (i.e. close to the critical temperature reported for the field-induced ferroelectric state in PMN single crystal); (iii) ∼260 K (i.e. the temperature of the permittivity maximum); (iv) ∼350 K (the temperature for initiation of the cluster freezing process T ^*); (v) ∼620 K (Burns temperature). The frequency split of the doublet at ∼605 and ∼500 cm⁻¹ presents a critical behavior related to the local symmetry lowering and to the structure ordering due to a phase transformation which takes place below T ^*. The tunability in the paraelectric state was interpreted in terms of reorientation of the non-interacting nanopolar clusters in a double-well potential. The temperature dependence of the nanopolar domain size also shows anomalies in the range of T ^*. The size and dynamics of the polar nanodomains is essential in determining the functional properties of the Pb(Mg_1/3Nb_2/3)O₃ relaxor.     

Temperature dependence of the quenching of N<Subscript>2</Subscript> (C <Superscript>3</Superscript>Π<Subscript>u</Subscript>) by N<Subscript>2</Subscript> (X) and O<Subscript>2</Subscript> (X)

The temperature dependences of the quenching rate constants of the states N₂ (${\rm C} \ {^{3}{ \rm \Pi }_{u}}${\rm C} \ {^{3}{ \rm \Pi }_{u}} v^′=0,1) by N₂ (X) and of the state N₂ (${\rm C} \ {^{3}{ \rm \Pi }_{u}} \ v^{\prime}=0${\rm C} \ {^{3}{ \rm \Pi }_{u}} \ v^{\prime}=0) by O₂ (X) are studied. Time-resolved light emission from the gas was analyzed in the temperature range from 300 K to 210 K keeping the gas at constant density. In case of quenching by N₂ (X), the quenching rate constant for the vibrational level v^′= 0 increases by (13 ±3)% with gas cooling whereas the quenching rate constant for v^′= 1 decreases by (5.0 ±2.5)% in this temperature range. For quenching by O₂ (X), the quenching rate constant decreases by (3 ±2)% with gas cooling. The temperature variation of the N₂ (C ³Π_u v^′=0) emission intensity for pure nitrogen and dry air are calculated using the obtained quenching rate constants and is compared with the experimental data available in the literature.     

Ab initio simulation of the electronic structure of δ-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> with oxygen vacancy and comparison with experiment

The electronic structure of a Ta₂O₅ insulator with oxygen vacancies is studied theoretically and experimentally. The ab initio calculations of δ-Ta₂O₅ are performed in terms of density functional theory using the generalized gradient (GGA) and GGA + U approximations. The electronic structure of Ta₂O₅ is experimentally studied by X-ray photoelectron spectroscopy (XPS). To study oxygen vacancies, an amorphous Ta₂O₅ film is irradiated by argon ions. The calculated XPS spectra of the valence band of δ-Ta₂O₅ agree satisfactorily with the corresponding experimental spectra of the amorphous films. The oxygen vacancy in δ-Ta₂O₅ is found to be a trap for holes and electrons. The minimum and maximum effective masses of electrons and holes in δ-Ta₂O₅ are calculated.     

Superconductivity at normal pressure in κ-(BEDT-TTF)<Subscript>2</Subscript>Cu[N(CN)<Subscript>2</Subscript>]Cl crystals

Single crystals of the κ-(BEDT-TTF)₂Cu[N(CN)₂]Cl cation-radical salt are obtained. These crystals exhibit metallic properties and pass to a superconducting state with T_c = 11.5 K at ambient pressure.     

High-Temperature Heat Capacity of Zn<Subscript>2</Subscript>V<Subscript>2</Subscript>O<Subscript>7</Subscript>–Cu<Subscript>2</Subscript>V<Subscript>2</Subscript>O<Subscript>7</Subscript> Solid Solutions

Differential scanning calorimetry has been used to study the influence of temperature on the heat capacity of synthesized vanadates Zn₂V₂O₇, (Cu_0.56Zn_1.44)V₂O₇, and (Cu_1.0Zn_1.0)V₂O₇. It is found that dependences C_p = f(T) have extremes. The thermodynamic properties of Zn₂V₂O₇ have been determined.     

Interface interaction and wetting of Sc<Subscript>2</Subscript>O<Subscript>3</Subscript> exposed to Cu–Al and Cu–Ti melts

Scandia is a thermodynamically stable oxide and could be used as a structural material for a crucible in order to avoid a melt contamination. In the present study wetting experiments of Cu–Al and Cu–Ti melts on Scandia substrate were preformed at 1423 K by a sessile drop method. It was established that Al and Ti additions lead to the improved wetting and that the final contact angle decreases with increasing the additives concentration. For Al containing melts, the contact angle changes gradually with time, and a relatively thick interaction layer, which consists of Al₂O₃, Sc₂O₃, and metallic channels, was formed at the Sc₂O₃/Cu–Al interface. For Ti containing melts, the final contact angle is achieved already during heating, and an extremely thin layer based on a Ti–Sc–O compound was detected by AES at the Sc₂O₃/Cu–Ti interface. The results of a thermodynamic analysis, which takes into account the formation free energy of the oxides, involved in the systems, and the thermodynamic properties of the liquid solutions are in a good agreement with the experimental observations.     

Long-range magnetic order in copper nitrate monohydrate Cu(NO<Subscript>3</Subscript>)<Subscript>2</Subscript> · H<Subscript>2</Subscript>O

The magnetic phase diagram of copper nitrate monohydrate Cu(NO₃)₂ · H₂O and the basic parameters of its magnetic subsystem have been determined by measuring the thermodynamic properties of this compound. This compound becomes antiferromagnetically ordered at T _N = 3.6 K, undergoes the spin-flop and spin-flip transitions at H _C1 ～ 0.06 T and H _C2 ～ 1.1 T, respectively, at low temperatures. The magnetization of Cu(NO₃)₂ · H₂O at T _SR = 2.7 K exhibits an additional anomaly, which is likely attributed to the spin-reorientation transition.     

Effect of process parameters and post-deposition annealing on the microwave dielectric and optical properties of pulsed laser deposited Bi<Subscript>1.5</Subscript>Zn<Subscript>1.0</Subscript>Nb<Subscript>1.5</Subscript>O<Subscript>7</Subscript> thin films

Bismuth Zinc niobate (Bi_1.5Zn_1.0Nb_1.5O₇) thin films were deposited by pulsed laser deposition (PLD) method on fused silica substrates at different oxygen pressures. The structural, microwave dielectric and optical properties of these thin films were systematically studied for both the as-deposited and the annealed films at 600°C. The as-deposited films were all amorphous in nature but crystallized on annealing at 600°C in air. The surface morphology as studied by atomic force microscopy (AFM) reveals ultra-fine grains in the case of as-deposited thin films and cluster grain morphology on annealing. The as-deposited films exhibit refractive index in the range of 2.36–2.53 (at a wavelength of 750 nm) with an optical absorption edge value of 3.30–3.52 eV and a maximum dielectric constant of 11 at 12.15 GHz. On annealing the films at 600°C they crystallize to the cubic pyrochlore structure accompanied by an increase in band gap, refractive index and microwave dielectric constant.     

Effect of γ irradiation on the thermochromic phase transition in [(C<Subscript>2</Subscript>H<Subscript>5</Subscript>)<Subscript>2</Subscript>NH<Subscript>2</Subscript>]<Subscript>2</Subscript>CuCl<Subscript>4</Subscript> crystals (as derived from heat capacity measurements)

The heat capacity of [(C₂H₅)₂NH₂]₂CuCl₄ crystals, both nonirradiated and γ-irradiated to a dose of 10⁷R, was studied in the temperature interval 90–330 K by adiabatic calorimetry. The temperature dependence of C_p(T) was found to have a peak-shaped anomaly in the region of the thermochromic phase transition (PT) at T = 322.7 K. Smoothened experimental heat capacity data were used to calculate the changes in the thermodynamic functions. The changes in the entropy and enthalpy of the thermochromic PT were determined to be ΔS = 42 J K^?1 mol^?1 and ΔH = 13653 J mol^?1 for the nonirradiated crystals and ΔS = 39 J K^?1 mol^?1 and ΔH = 12120 J mol^?1 for the irradiated crystals, respectively. Irradiation of a [(C₂H₅)₂NH₂]₂CuCl₄ crystal by γ rays to a dose of 10⁷ R was shown to shift the PT point toward lower temperatures by ΔT ≈ 1.7 K.