Improved GaSb surfaces using a (NH4)2S/(NH4)2S04 solution

Bulk (1 0 0) n-GaSb surfaces have been treated with a sulphur based solution ((NH₄)₂S/(NH₄)₂SO₄) to which sulphur has been added, not previously reported for the passivation of GaSb surfaces. Au/n-GaSb Schottky barrier diodes (SBDs) fabricated on the treated material show significant improvement compared to that of the similar SBDs on the as-received material as evidenced by the lower ideality factor (n), higher barrier height (?_b) and lower contact resistance obtained. Additionally, the reverse leakage current, although not saturating, has been reduced by almost an order of magnitude at −0.2 V. The sample surfaces were studied by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The native oxide, Sb–O, present on the as-received material is effectively removed on treating with ([(NH₄)₂S/(NH₄)₂SO₄]+S) and (NH₄)₂S. Analysis of the as-received surface by XPS, prior to and after argon sputtering, suggests that the native oxide layer is ≤8.5 nm.     

Synthesis of high tap density Li3V2(PO4)3 cathode materials using mixed lithium precursors

High tap density Li₃V₂(PO₄)₃ cathode materials were synthesized using mixed LiF and LiNO₃ as lithium precursors, LiNO₃ was used as the sintering agent. Rietveld refinement results show that no impurities phases are detected in products. Particle size distribution and tap density measurement results show that particle size and tap density of products can be increased by the addition of LiNO₃. Electrochemical characterization results show that electrochemical performance of products is declined with the increase in contents of LiNO₃ in the lithium precursors. Only a small amount of LiNO₃ added in the lithium precursors (mole ratio of LiNO₃ to LiF is 1:9) can increase the tap density and also retain the good performance of products. Scanning electron microscopy (SEM) images indicate that the samples prepared by mixed lithium precursors present particles agglomerate, and the particle size increased with increase in contents of LiNO₃. Large amount of LiNO₃ added in the lithium precursors induces the particles to become spheric and smooth, which worsens the performance. The particles obtained with the mole ratio of LiNO₃ to LiF in 1:9 show a flake-like shape with a high specific surface area, which leads to good electrochemical performance.     

Nanostructuring Si surface and Si/SiO2 interface using porous-alumina-on-Si template technology. Electrical characterization of Si/SiO2 interface

In this work, anodic porous alumina thin films with pores in the nanometer range are grown on silicon by electrochemistry and are used as masking material for the nanopatterning of the silicon substrate. The pore diameter and density are controlled by the electrochemical process. Through the pores of the alumina film chemical oxidation of the silicon substrate is performed, leading to the formation of regular arrays of well-separated stoichiometric silicon dioxide nanodots on silicon, with a density following the alumina pores density and a diameter adjustable by adjusting the chemical oxidation time. The alumina film is dissolved chemically after the SiO₂ nanodots growth, revealing the arrays of silicon dioxide dots on silicon. In a next step, the nanodots are also removed, leaving a nanopatterned bare silicon surface with regular arrays of nanopits at the footprint of each nanodot. This silicon surface structuring finds interesting applications in nanoelectronics. One such application is in silicon nanocrystals memories, where the structuring of the oxidized silicon surface leads to the growth of discrete silicon nanocrystals of uniform size. In this work, we examine the electrical quality of the Si/SiO₂ interface of a nanostructured oxidized silicon surface fabricated as above and we find that it is appropriate for electronic applications (an interface trap density below 1–3×10¹⁰ eV⁻¹ cm⁻² is obtained, indicative of the high quality of the thermal silicon oxide).     

The effect of Si surface nitridation on the interfacial structure and electrical properties of (La2O3)0.5(SiO2)0.5 high-k gate dielectric films

Thermal stability, interfacial structures and electrical properties of amorphous (La₂O₃)_0.5(SiO₂)_0.5 (LSO) films deposited by using pulsed laser deposition (PLD) on Si (1 0 0) and NH₃ nitrided Si (1 0 0) substrates were comparatively investigated. The LSO films keep the amorphous state up to a high annealing temperature of 900 °C. HRTEM observations and XPS analyses showed that the surface nitridation of silicon wafer using NH₃ can result in the formation of the passivation layer, which effectively suppresses the excessive growth of the interfacial layer between LSO film and silicon wafer after high-temperature annealing process. The Pt/LSO/nitrided Si capacitors annealed at high temperature exhibit smaller CET and EOT, a less flatband voltage shift, a negligible hysteresis loop, a smaller equivalent dielectric charge density, and a much lower gate leakage current density as compared with that of the Pt/LSO/Si capacitors without Si surface nitridation.     

Spectroscopic studies of (AsSe)100−xAgx thin films

Thin (AsSe)_100−xAg_x films have been grown onto quartz substrates by vacuum thermal evaporation or pulsed laser deposition from the corresponding bulk materials. The amorphous character of the coatings was confirmed by X-ray diffraction investigations. Their transmission was measured within the wavelength range 400-2500 nm and the obtained spectra were analyzed by the Swanepoel method to derive the optical band gap E_g and the refractive index n. We found that both parameters are strongly influenced by the addition of silver to the glassy matrix: E_g decreases while n increases with Ag content. These variations are discussed in terms of the changes in the atomic and electronic structure of the materials as a result of silver incorporation.     

Structure and electrical properties of SrO-borovanadate (V2O5)0.5(SrO)0.5−y(B2O3)y glassses

SrO-borovanadate glasses with nominal composition (V₂O₅)_0.5(SrO)_0.5−y(B₂O₃)_y, 0.0≤y≤0.4 were prepared by a normal quench technique and investigated by direct current (DC) electrical conductivity, inductively coupled plasma (ICP) spectroscopy, infrared (IR) spectroscopy and X-ray powder diffraction (XRD) studies in an attempt to understand the nature of mechanism governing the DC electrical conductivity and the effect of addition of B₂O₃ on the structure and electrical properties of these glasses. XRD patterns confirm the amorphous nature of the present glasses and actual compositions of the glasses were determined by ICP spectroscopy. The temperature dependence of DC electrical conductivity of these glasses has been studied in terms of different hopping models. The IR results agree with previous investigations on similar glasses and it has been concluded that similar to SrO-vanadate glasses, metavandate chain-like structures of SrV₂O₆ and individual VO₄ units also occur in SrO-borovanadate glasses. The SrV₂O₆ and VO_n polyhedra predominate in the low B₂O₃-containing SrO-borovanadate glasses as B substitutes into the V sites of the various VO_n polyhedra and only when the concentration of B₂O₃ exceeds the SrO content do BO_n structures appear. This qualitative picture of three distinct structural groupings for Sr-vanadate and Sr-borovanadate glasses is consistent with the proposed glass structure on previous IR and extended X-ray absorption fine structure (EXAFS) studies on these types of glasses. The conductivity results were analyzed with reference to theoretical models existing in the literature and the analysis shows that the conductivity data are consistent with Mott's nearest neighbor hopping model. Analysis of the conductivity data shows that they are consistent with Mott's nearest neighbor hopping model. However, both Mott VRH and Greaves models are suitable to explain the data. Schnakenberg's generalized polaron hopping model is also consistent with temperature dependence of activation energy. However, various model parameters such as density of states, hopping energy, etc. obtained from the best fits were not found to be in accordance with the prediction of the Mott model.     

Effect of composition on the conductivity of CTAB-butanol-octane-nitrate salts (Al(NO3)3 + Zn(NO3)2) microemulsions and on the surface and textural properties of resulting spinels ZnAl2O4

The conductivity σ of a microemulsion series consisting of CTAB + butanol + octane, in which a solution of Al(NO₃)₃ 0.8 M + Zn(NO₃)₂ 0.4 M was gradually added, was studied at room temperature as a function of its composition φ. The addition of nitrate salts solution took place in four different ratios of (butanol + CTAB):octane = 0.2, 0.4, 0.6 and 0.8. Initially, all those four systems are (water in oil, w/o) microemulsions and the gradual addition of the solution of the nitrate salts transforms them to bicontinuous ones. The conductivity increases gradually, but with different rate in each case, and the corresponding critical exponents at the percolation threshold were determined from the curves σ = f(φ). Next at three different compositions of microemulsions, corresponding to ratios (butanol + CTAB):octane = 0.4, 0.6 and 0.8 and ratio of the nitrate salts solution x ≈ 0.25, spinels ZnAl₂O₄ were isolated/prepared. XRD, SEM and N₂ adsorption-desorption measurements were used to determine the structure and texture of those solids. From those measurements the surface area (S_p), the pore volume (V_p), the size of crystallites and the average pore connectivity (c) were found. Those properties showed considerable variation and dependence on the composition of the original microemulsions employed in the preparation, a fact indicating that the structure and texture of the obtained solids can be manipulated at will via the composition of microemulsion used.     

Dielectric and AC ionic conductivity investigations in K3H(SeO4)2 single crystal

Optical observation under the polarizing microscope and DSC measurements on K₃H(SeO₄)₂ single crystal have been carried out in the temperature range 25-200 °C. It reveals a high-temperature structural phase transition at around 110 °C. The crystal system transformed from monoclinic to trigonal. Electrical impedance measurements of K₃H(SeO₄)₂ were performed as a function of both temperature and frequency. The electrical conduction and dielectric relaxation have been studied. The temperature dependence of electrical conductivity indicates that the sample crystal became a fast ionic conductor in the high-temperature phase. The frequency dependence of conductivity follows the Jonscher's universal dynamic law with the relation σ(ω)=σ(0)+Aωⁿ, where ω is the frequency of the AC field, and n is the exponent. The obtained n values decrease from 1.2 to 0.1 from the room temperature phase to fast ionic phase. The high ionic conductivity in the high-temperature phase is explained by the dynamical disordering of protons between the neighboring SeO₄ groups, which provide more vacant sites in the crystal.     

Artifacts in the sputtering of inorganics by C60

In the present study, the basic issues in C₆₀ⁿ⁺ sputtering are studied using silicon, gold and platinum samples. Sputtering yields are measured for energies in the range of 5-30 keV, by sputtering micrometre sized craters on the surface of flat clean samples and measuring their volumes using atomic force microscopy (AFM). Net deposition of carbon occurs for all three materials at 5 keV, and is not specific to silicon which forms a carbide. The threshold energy for net sputtering is dependent on the sputtering yield and the stopping power of the substrate. Away from the threshold, the sputtering yields agree well with Sigmund and Claussen's thermal spike model after allowance for the sputtering of the deposited carbon atoms. AFM images show the formation of unusual surface topography around the transition region between sputtering and deposition. Analysis of the bottom of a crater using imaging SIMS shows a significant enhancement of carbon clusters as well as various silicon-carbon groups, indicating the importance of carbon deposition and implantation in a gradual mixed layer formed from sputtering. The thickness of this interface layer is shown to be approximately 5 nm.     

Synthesis and luminescence properties of red-emitting phosphors NaY0.87Eu0.13(WO4)1.2(MoO4)0.8

A series of NaY_1−yEu_y(WO₄)_2−x(MoO₄)_x (x=0−2 and y=0.06−0.15) phosphors have been prepared by a combustion route. X-ray powder diffraction, photoluminescence excitation and emission spectra were used to characterize the resulting samples. The excitation spectra of these phosphors show the strongest absorption at about 396 nm, which matches well with the commercially available n-UV-emitting GaN-based LED chip. Their emission spectra show an intense red emission at 616 nm due to the ⁵D₀→⁷F₂ electric dipole transition of Eu³⁺. As the Mo content increases, the intensity of the ⁵D₀→⁷F₂ emission of Eu³⁺ activated at wavelength of 396 nm increases and reaches a maximum when the relative ratio of Mo/W is 2:3. The intense red-emission of the tungstomolybdate phosphors at near-UV excitation suggests that the material is a potential candidate for white light emitting diode (WLEDs).     

Intercalation of [Fe8(μ3-O)2(μ2-OH)12(tacn)6] single molecule magnets in saponite clay

We have contacted Na-saponite with aqueous solutions containing a well-defined iron polycation with structuring ligands [Fe₈(μ₃-O)₂(μ₂-OH₂)₁₂(tacn)₆]⁸⁺, which is known as a promising candidate for molecular magnets. When the resulting suspensions were activated with either microwaves or ultrasound, macroscopic-level characterization of the solid phases obtained after centrifugation (elemental analysis, surface area, XRD) suggested the intercalation of stoichiometrically intact polycations in the interlayer space by cation exchange. Furthermore, ⁵⁷Fe Mössbauer spectroscopy and Fe K-edge EXAFS are compatible with a conservation of the structure of the polycations inorganic core: connectivity seems to be maintained, while the polycations must be somewhat flattened by strain due to intercalation. Magnetization curves also appear compatible with a conservation of the polycation nuclearity, although experiments with a magnetically clean clay sample are necessary to confirm this point.     

Linear-chain antiferromagnetism in Ni(N2H5)2(SO4)2

The compound dihydrazinium bis(sulfato) niccolate(II), Ni(N₂H₅)₂(SO₄)₂, containing sulfato-bridged chains of Ni(II) ions, can be described as an antiferromagnetic Heisenberg linear-chain system. A reasonable agreement of susceptibility measurements in the temperature region 2–80K, with a theory developed by Weng for antiferromagnetic Heisenberg linear chains with spin S=1, is obtained for a value of the intra-chain interaction $\text{J}\text{k}\text{=?3.35K}$. Preliminary results of specific heat measurements, on the other hand, do not fit quite well using this model. The origin of this discrepancy is suggested to be a zero-field splitting of the single ion.     

Crystal structure and ferromagnetism of (n-C3H7)4N[CoFe(dto)3] (dto=C2O2S2)

Recently, we have discovered a new type of first order phase transition around 120 K for (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] (dto=C₂O₂S₂), where the charge transfer transition between Fe^II and Fe^III occurs reversibly. In order to elucidate the origin of this peculiar first order phase transition. Detailed information about the crystal structure is indispensable. We have synthesized the single crystal of (n-C₃H₇)₄N[Co^IIFe^III(dto)₃] whose crystal structure is isomorphous to that of (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃], and determined its detailed crystal structure. Crystal data: space group P6₃, a=b=10.044(2) Å, c=15.960(6) Å, α=β=90°, γ=120°, Z=2 (C₁₈H₂₈NS₆O₆FeCo). In this complex, we found a ferromagnetic transition at T_c=3.5 K. Moreover, on the basis of the crystal data of (n-C₃H₇)₄N[Co^IIFe^III(dto)₃], we determined the crystal structure of (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] by simulation of powder X-ray diffraction results.     

Rotational spectra of gauche perfluoro-n-butane, C4F10; perfluoro-iso-butane, (CF3)3CF; and tris(trifluoromethyl)methane, (CF3)3CH

The microwave spectra of the gauche conformer of perfluoro-n-butane, n-C₄F₁₀, of perfluoro-iso-butane, (CF₃)₃CF, and of tris(trifluoromethyl)methane, (CF₃)₃CH, have been observed and assigned. The rotational and centrifugal distortion constants for gauche n-C₄F₁₀ are: A = 1058.11750(7) MHz, B = 617.6832(1) MHz, C = 552.18794(1) MHz, Δ_J = 0.0257(5) kHz, δ_J = 0.0052(3) kHz. A C-C-C-C dihedral angle, ω, of ∼55° has been determined. These values agree well with those obtained from a coupled cluster (CCSD/cc-PVTZ) calculation. The rotational and centrifugal distortion constants for iso-C₄F₁₀ and iso-C₄HF₉ are: B_o = 816.4519(4) MHz, D_J = 0.023(2) kHz, and B_o = 903.6985(25) MHz, D_J = 0.043(4) kHz, respectively. The dipole moment of iso-C₄F₁₀ and iso-C₄HF₉ have been measured and found to be 0.0338(8) and 1.69(9) D, respectively.     

Hydrogen bonds mediated magnetism in Cu(bmen)2Pd(CN)4

Results of synthesis, X-ray structure analysis, electron spin resonance, susceptibility, magnetization and specific heat measurements of powdered Cu(bmen)₂Pd(CN)₄ (,N^′-dimethyl-1,2-diaminoethane) are reported. Its structure is formed of quasi-linear chains of the [-Cu(bmen)₂-NC-Ni(CN)₂-CN-]_n composition; these are interlinked by hydrogen bonds (HBs) leading to two-dimensional patterns. Upon magnetic, spectral and thermodynamic measurements the compound was identified as an S=1/2 Heisenberg antiferromagnet on a square lattice with due to the dominant role of HBs in creating a square network. The long-range ordering observed at 0.24 K is proposed to be of a Néel type. The possibility of tuning the exchange interactions in various directions is considered.     

Surface texturing of Si, porous Si and TiO2 by laser ablation

Excimer laser ablation at 308 nm has been used to texture the surfaces of a variety of materials of interest for optoelectronic and biotechnological applications. Using a range of pre- and post-processing methods, we are able to produce nano-, micro- and meso-scale features over large areas rapidly in materials such as crystalline Si, porous silicon and TiO₂. Texturing of porous silicon leads to the growth of crystalline dendritic structures, which distinguishes them dramatically from the conical pillars formed from crystalline silicon. Regular arrays of Si microdots are formed by irradiating a Si surface pre-covered with a Cr thin film grating. Nano-crystalline porous TiO₂ films are easily ablated or compacted with laser irradiation. However, at low enough laser fluence, surface roughening without complete loss of porosity is possible.     

Third-order optical nonlinearities of lead-free (Na1−xKx)0.5Bi0.5TiO3 thin films

(Na_1−xK_x)_0.5Bi_0.5TiO₃ (NKBT) (x = 0.1, 0.2, and 0.3) thin films with good surface morphology and rhombohedral perovskite structure were fabricated on quartz substrates by a sol-gel process. The fundamental optical constants (the band gaps, linear refractive indices and absorption coefficients) of the films were obtained through optical transmittance measurements. The nonlinear optical properties were investigated by Z-scan technique performed at 532 nm with a picosecond laser. A two-photon absorption effect closely related with potassium-doping content was found in thin films, and the nonlinear refractive index n₂ increases evidently with potassium-doping. The real part of the third-order nonlinear susceptibility χ⁽³⁾ is much larger than its imaginary part, indicating that the third-order optical nonlinear response of the NKBT films is dominated by the optical nonlinear refractive behavior. These results show that NKBT thin films have potential applications in nonlinear optics.     

Properties of magnetocaloric La(Fe,Co,Si)13 produced by powder metallurgy

We present a comprehensive study of the magnetocaloric materials series La(Fe_1−xCo_x)_11.9Si_1.1 with 0.055<x<0.122. The ferromagnetic samples were manufactured using a novel powder metallurgy process by which industrial scale production is feasible. This new production method makes the materials more attractive as magnetic refrigerants for room temperature magnetic refrigeration. The Curie temperature of the compounds can be easily tuned by altering the Co content and all samples have little magnetic anisotropy and present a second-order magnetic transition so that thermal and magnetic hysteresis is absent. For all seven samples, we have calculated the magnetic entropy change, ΔS_M, from initial curve measurements and measured the adiabatic temperature change, ΔT_ad, directly. In addition, for two of the samples, we determined the heat capacity as a function of applied magnetic field and the thermal conductivity. Where relevant, the results are compared with those of Gd, the benchmark material for room temperature magnetic refrigeration.     

New phase transition in (CnH2n+1NH3)2MnCl4

(C_nH_2n+1NH₃)₂MnCl₄ consist of perovskite-type layers sandwiched between hydrocarbon radical layers. New phase transitions were found between liquid nitrogen and decomposition temperature in these compounds by differential thermal analysis and hot stage microscopy. A systematic research of the lattice dynamics, the transition mechanisms, their influence on physical properties and their dependence on the various possibilities of molecular engineering offered in these quasi two-dimensional perovskites was started.