Scanning probe microscopy of single Au ion implants in Si

We have studied 5 MeV Au²⁺ ion implantation with fluences between 7 × 10⁷ and 2 × 10⁸ cm^− 2 in Si by deep level transient spectroscopy (DLTS) and scanning capacitance microscopy (SCM). The DLTS measurements show formation of electrically active defects such as the two negative charge states of the divacancy (V₂(/–) and V₂(–/0)) and the vacancy–oxygen (VO) center. It is observed that the intensity of the V₂(/–) peak is lower compared to that of V₂(–/0) by a factor of 5. This has been attributed to a highly localized distribution of the defects along the ion tracks, which results in trapping of the carriers at V₂(–/0) and incomplete occupancy of V₂(/–). The SCM measurements obtained in a plan view show a random pattern of regions with a reduced SCM signal for the samples implanted with fluence above 2 × 10⁸ cm^− 2. The reduced SCM signal is attributed to extra charges associated with acceptor states, such as V₂(–/0), formed along the ion tracks in the bulk Si. Indeed, the electron emission rate from the V₂(–/0) state is in the range of 10 kHz at room temperature, which is well below the probing frequency of the SCM measurements, resulting in “freezing” of electrons at V₂(–/0).     

Deposition and DC electrical characterisation of rf magnetron sputtered silicon nitride thin films

Silicon nitride (Si₃N₄) is an important insulator, frequently used in VLSI technology and for encapsulation. Conventionally it is prepared by low pressure and plasma-enhanced chemical vapour deposition, but may also be successfully deposited by RF sputtering. In the present work the sputtering process was characterised, together with some measurements on the high-field DC electrical properties in sandwich samples with Au electrodes. Films were Ar-sputtered using a Si₃N₄ sputtering target at gas pressures up to 2.12 Pa and RF discharge powers of 60–200 W. The deposition rate R was in the range 0.03–0.19 nm s^− 1 and was directly proportional to the discharge power and varied linearly with the pressure. Au electrodes formed sandwich structures with thicknesses of 50 nm–1 μm. Conductivity was essentially ohmic below 300 nm, while for the thicker films space-charge limited conductivity, dominated by an exponential distribution of traps, was observed. A mobility value of μ = 2.89 × 10^− 6 m² V^− 1 s^− 1 was derived from temperature measurements, and further analysis of the J–V data indicated a thermally generated electron concentration of 3.23 × 10¹⁹ m^− 3 and a trap concentration of 1.57 × 10²⁴ m^− 3. It was concluded that this method is suitable for the deposition of thin films, which have similar electrical properties to those prepared by chemical vapour deposition methods.     

Stoichiometric and non-stoichiometric films in the Si–O–N system: mechanical,electrical, and dielectric properties

A novel low-temperature (600–850 °C), chemical vapor deposition method, involving a simple reaction between disiloxane (H₃Si–O–SiH₃) and ammonia (NH₃), is described to deposit stoichiometric, Si₂N₂O, and non-stoichiometric, SiO_xN_y, silicon oxynitride films (5–500 nm) on Si substrates. Note, the gaseous reactants are free from carbon and other undesirable contaminants. The deposition of Si₂N₂O on Si (with (1 0 0) orientation and a native oxide layer of 1 nm) was conducted at a pressure of 2 Torr and at extremely high rates of 20–30 nm min⁻¹ with complete hydrogen elimination. The deposition rate of SiO_xN_y on highly-doped Si (with (1 1 1) orientation but without native oxide) at 10⁻⁶ Torr was ∼1.5 nm min⁻¹, and achieved via the reaction of disiloxane with N atoms, generated by an RF source in an MBE chamber. The phase, composition and structure of the oxynitride films were characterized by a variety of analytical techniques. The hardness of Si₂N₂O, and the capacitance–voltage (C–V) as a function of frequency and leakage current density–voltage (J_L–V) characteristics were determined on MOS (Al/Si₂N₂O/SiO/p-Si) structures. The hardness, frequency-dispersionless dielectric permittivity (K), and J_L at 6 V for a 20 nm Si₂N₂O film were determined to be 18 GPa, 6 and 0.05–0.1 nA cm⁻², respectively.     

Effect of solvent ratio on the properties of highly oriented sprayed fluorine-doped tin oxide thin films

Transparent conducting thin films of F:SnO₂ have been deposited onto preheated glass substrates by a spray pyrolysis technique using pentahydrate stannic chloride (SnCl₄·5H₂O) and ammonium fluoride (NH₄F) as precursors and mixture of water and propane-2-ol as solvent. The concentration of SnCl₄·5H₂O and NH₄F is kept fixed and the ratio of water and propane-2-ol solvent in the spraying solution is varied. A fine spray of the source solution using air as a carrier gas has grown films of thickness up to 995 nm. Optical absorption, X-ray diffraction, Van der Pauw technique for measurement of a sheet resistance and Hall effect measurements at room temperature for determination of carrier density and conductivity have been used. The as-deposited films are of polycrystalline SnO₂ with a tetragonal crystal structure and are preferentially having orientation along the (200) direction with texture coefficient as high as 6.16. The average grain size for the as-deposited sample is found to be of the order of 44 nm. The films have moderate optical transmission (up to 70–85% at 550 nm). The figure of merit (ϕ) values vary from 1.95 · 10^− 3 to 35.68 · 10^− 3 Ω^− 1. The films are heavily doped, degenerate and exhibit n-type electrical conductivity. The lowest sheet resistance (R_s) for the optimized sample is 5.1 Ω. The films have a resistivity of 5.43 · 10^− 4 Ω cm and mobility around 7.38 cm² V^− 1 s^− 1.     

Space charge limited conduction in bulk Se100 − xSbx chalcogenide glasses

The present paper reports the measurements on space charge limited conduction in bulk glassy Se_100 − xSb_x (x = 2, 4, 6, 8). I–V characteristics have been measured at various fixed temperatures. These characteristics show that, at low electric fields, an ohmic behaviour is observed. However, at high electric fields (E ∼10⁴ V/cm), the current becomes superohmic.At high fields (10⁴ V/cm), current could be fitted to the theory of space charge limited conduction in case of uniform distribution of localized states in the mobility gap of these materials. Using the theory of SCLC for the uniform distribution of the traps, the density of localized states near Fermi level is also calculated. Density of localized states initially increases with Sb concentration till 6 at.% of Sb and then decreases with further increase of Sb. This decrease is explained in terms of average coordination number.     

Compression behaviour and micro-structure evaluation of Zr57Nb5Cu15.4Ni12.6Al10 bulk metallic glass under high pressure

Compression behaviour and micro-structure evaluation of Zr₅₇Nb₅Cu_15.4Ni_12.6Al₁₀ bulk metallic glass is investigated at room temperature up to 32.8 GPa using in-situ high pressure energy dispersive X-ray diffraction with a synchrotron radiation source. The equation of state of the bulk metallic glass is − ΔV / V = 0.012P − 2.49 × 10^− 4P² − 9.5 × 10^− 7P³ + 5.02 × 10^− 8P⁴. The result shows that the nearest atom pair of the as-quenched bulk metallic glass corresponds to Zr–Zr correlations. And with pressure increasing, the nearest atom pair changes to a new one at 32.8 GPa.     

Negative thermal expansion in silicalite-1 and zirconium silicalite-1 having MFI structure

In situ high temperature X-ray diffraction (HTXRD) studies on monoclinic silicalite-1 (S-1, silica polymorph of ZSM-5) and an orthorhombic metallosilicate molecular sieve, zirconium silicalite-1 (ZrS-1) with MFI structure (Si/Zr = 50) have been carried out using a laboratory X-ray diffractometer with an Anton Parr HTK 1600 attachment. While the structure of the S-1 collapsed at 1123 K forming α-cristobalite. S-1 and ZrS-1 showed a complex thermal expansion behavior in the temperature range 298–1023 K, ZrS-1 was stable. Powder X-ray diffraction (PXRD) data taken in this region have shown strong negative lattice thermal expansion coefficient, α_V = −6.75 × 10⁻⁶ and −17.92 × 10⁻⁶ K⁻¹ in the temperature range 298–1023 K⁻¹ for S-1 and ZrS-1 samples, respectively. The thermal expansion behavior of S-1 and ZrS-1 is anisotropic, with the relative strength of contraction along a axis is more than that along b and c axes. Three different thermal expansion regions could be identified in the overall temperature range (298–1023 K) studied, corroborating with the three steps of weight loss in the TG curve of ZrS-1 sample. While the region between 298 and 423 K, displays positive thermal expansion coefficient with α_V = 2.647 × 10⁻⁶ and 4.24 × 10⁻⁶ K⁻¹, the second region between 423 and 873 K shows strong negative thermal expansion (NTE) coefficient α_V = −7.602 × 10⁻⁶ and −15.04 × 10⁻⁶ K⁻¹, respectively, for S-1 and ZrS-1 samples. The region between 873 and 1023 K, shows a very strong NTE coefficient with α_V = −12.08 × 10⁻⁶ and −45.622 × 10⁻⁶ K⁻¹ for S-1 and ZrS-1, respectively, which is the highest in the whole temperature range studied. NTE seen over a temperature range 298–1023 K could be associated with transverse vibrations of bridging oxygen atoms in the structure which results in an apparent shortening of the Si–O distances.     

Nanocrystalline diamond/amorphous carbon composite films for applications in tribology,optics and biomedicine

Nanocrystalline diamond/amorphous carbon (NCD/a-C) composite thin films have been deposited by microwave plasma chemical vapour deposition from methane-rich CH₄/N₂ mixtures. The films have been thoroughly characterized with respect to basic properties such as growth rates, morphology and structure, composition, crystallinity, and bonding environment. They consist of diamond nanocrystals with diameters of 3–5 nm, which are embedded in an amorphous carbon matrix. Further studies are aimed at application relevant properties. I/V and Hall measurements showed that the films are p-type conductive with a resistitivity of 0.14 Ω cm, a carrier concentration of 1.9 × 10¹⁷ cm^− 3, and a carrier mobility of 250 cm²/Vs. Reflection, scattering and ellipsometric measurements revealed a refractive index of 1.95–2.1 in the visible region and an rather high extinction coefficient of about 0.14 at 400 nm. The films possess a hardness of ca. 40 GPa and a Young's modulus of ca. 390 GPa. Nano tribo test and nano scratch tests proved a low friction coefficient, and a strong protective effect and good adhesion on silicon substrates. First biomedical tests showed that the films are not cytotoxic but bioinert. Finally, the deposition of multilayers nano/polycrystalline diamond with improved properties is demonstrated.     

Spectroscopic properties of Tm3+/Al3+ co-doped sol–gel silica glass

Tm³⁺/Al³⁺ co-doped silica glass was prepared by sol–gel method combined with high temperature sintering. Glasses with compositions of xTm₂O₃–15xAl₂O₃–(100 − 16x) SiO₂ (in mol%, x = 0.1, 0.3, 0.5, 0.8 and 1.0) were prepared. The high thulium doped silica glass was realized. Their spectroscopic parameters were calculated and analyzed by Judd–Ofelt theory. Large absorption cross section (4.65 × 10⁻²¹ cm² at 1668 nm) and stimulated emission cross section (6.00 × 10⁻²¹ cm² at 1812 nm), as well as low hydroxyl content (0.180 cm⁻¹), long fluorescence lifetime (834 μs at 1800 nm), large σ_em × τ_rad (30.05 × 10⁻²¹ cm² ms) and large relative intensity ratio of the 1.8 μm (³F₄ → ³H₆) to 1.46 (³H₄ → ³F₄) emissions (90.33) are achieved in this Tm³⁺/Al³⁺ co-doped silica glasses. According to emission characteristics, the optimum thulium doping concentration is around 0.8 mol%. The cross relaxation (CR) between ground and excited states of Tm³⁺ ions was used to explain the optimum thulium doping concentration. These results suggest that the sol–gel method is an effective way to prepare Tm³⁺ doped silica glass with high Tm³⁺ doping and prospective spectroscopic properties.     

Low temperature synthesis,crystal structure and thermal stability studies of nanocrystalline VN particles

The simultaneous thermal decomposition and nitridation of [VO(NH₂O)₂Gly]·H₂O complex in NH₃ atmosphere at 723–973 K gives the nanocrystalline vanadium nitride (VN) having crystallite size of 8–32 nm. It shows cubic NaCl structure with lattice parameter of a = 4.137 nm. XRD pattern Rietveld analysis program for crystal structure of VN shows the space group-Fm3m. The particle sizes measured by BET and SEM techniques are in the range of 26–100 nm. The particles are spherical and distributed homogeneously and found larger than XRD crystallite size because of agglomeration of crystallites. The fundamental IR absorption of VN material is found at 995 cm⁻¹ which gives the force constant of 634.3 Nm⁻¹. The electrical resistivity and magnetic studies show the superconducting to normal transition (T_c) at 9.2 K. Thermal decomposition of VN is carried out in O₂ atmosphere which goes through the formation of an oxynitride (V–N_p–O_q) intermediate phase up to 913 K. Finally, nanocrystalline V₂O₅ is formed at 973 K. The V₂O₅ has orthorhombic structure with lattice parameters of a = 11.537, b = 3.568 and c = 4.380 Å and the XRD crystallite size of 10 nm.     

The polyaniline–V2O5 system:: improvement as insertion electrode in lithium batteries

The application of a hybrid PAni–V₂O₅ cathode material in reversible lithium electrochemical cells is reported. We have studied the influence of synthesis conditions and subsequent treatments of the hybrid under oxygen in order to optimize its performance as a lithium-insertion cathode. The temperature and length of this treatment is a key parameter in determining the final specific charge of the cathode. The optimal material yielded a specific charge as high as 302 A h kg^–1 measured at low discharge rate (C/48) corresponding to the insertion of 2.72 lithium ions per formula unit (C₆H₄N)_0.6V₂O₅–0.3H₂O). Higher scan rates of C/12 lead to specific capacities of 200 A h kg⁻¹. The thermal and electrochemical stability of the hybrid, especially in relation to the decomposition of the organic polymer and their effect on battery performance and cyclability are also discussed.     

Electric isolation of porous silicon by electro generated polyethyleneimine film,comparison to thermal oxide

Electrochemical oxidation of diethylenetriamine (DETA) charged with 0.1 M LiSO₃CF₃, leads to a polymeric coating (polyethyleneimine film: PEI) on the porous silicon (PS) surface. The obtained passivated electrode is characterized through IRTF spectrometry and through C(V) curves on PS/PEI structures showing good insulating properties of the PEI film. The passivated electrode presents a linear pH sensitivity close to 62 mV per pH unit. Such sensitivity is higher compared to flat PEI passivated silicon electrode. The results were fitted with the generalized site-binding theory and the following parameters were found: the surface site density N_s was found to be equal to 3.6 × 10¹⁶ cm^− 2 and pK_H (K_H acido-basic constant of the amino group) is − 5.54.     

Crystal growth and spectral properties of pure and Co2+-doped Mg3B2O6 crystal

Novel pure and cobalt-doped magnesium borate crystals (Mg₃B₂O₆) have been grown successfully by the Czochralski technique for the first time. Crystal growth, X-ray powder diffraction (XRD) analysis, absorption spectrum, fluorescence spectrum as well as fluorescence decay curve of Co²⁺:Mg₃B₂O₆ (MBO) were described. From the absorption peaks for the octahedral Co²⁺ ions, the crystal-field parameter Dq and the Racah parameter B were estimated to be 943.3 cm⁻¹ and 821.6 cm⁻¹, respectively. The fluorescence lifetime of the transition ⁴T₁(⁴P) → ⁴T₂ centered at 717 nm was measured to be 9.68 ms.     

Temperature influence on the voltage-controlled diffractive property of Mn-doped potassium sodium tantalate niobate crystal

We report the temperature influence on the voltage-controlled diffractive property of Mn-doped potassium sodium tantalate niobate crystal. The crystal was grown by the top seeded solution growth method. Its quadratic electro-optic coefficients achieved as high as R₁₁ = 3.50 × 10⁻¹⁵ m²/V² and R₁₂ = −0.44 × 10⁻¹⁵ m²/V² near the Curie temperature, while they declined with the increasing temperature. The external electric field which correspond to the maximum diffraction efficiency of photorefractive grating moved from 166 V/mm to 512 V/mm as the temperature increased from 25 °C to 32.5 °C. The maximum diffraction efficiencies all reached the maximum value of 60% at different temperatures. The results were discussed and compared with the theoretical equations.     

Luminescence quantum efficiency at 1.5 μm of Er3+-doped tellurite glass determined by thermal lens spectroscopy

Erbium doped tellurite glasses (TeO₂ + Li₂O + TiO₂) were prepared by conventional melt-quenching method to study the influence of the Er³⁺ concentration on the luminescence quantum efficiency (η) at 1.5 μm. Absorption and luminescence data were used to characterize the samples, and the η parameter was measured using the well-known thermal lens spectroscopy. For low Er³⁺ concentration, the measured values are around 76%, and the concentration behavior of η shows Er–Er and Er–OH⁻ interactions, which agreed with the measured lifetime values.     

Influence of W5+ ions on the optical properties of doped Bi12TiO20

There have been studied single crystals of undoped and doped Bi₁₂TiO₂₀ with two concentrations of W⁵⁺ (2.62 × 10¹⁷ cm⁻³ and 2.62 × 10¹⁸ cm⁻³). There have been obtained absorption spectra in the energy range of 10,482–15,408 cm⁻¹ by classical measurements. There have been determined the cross-section (σ_a) of the impurity absorption and the oscillator strength of d–d transitions. There have been calculated the refractive index of doped crystals and the concentration of Ti³⁺ ions in an undoped sample through an experiment.     

Influence of Ar/O2 ratio on the properties of transparent conductive ZnO:Ga films prepared by DC reactive magnetron sputtering

Ga-doped zinc oxide (ZnO:Ga) transparent conductive films with highly (002)-preferred orientation were deposited on glass substrates by DC reactive magnetron sputtering method in Ar + O₂ ambience with different Ar/O₂ ratios. The structural, electrical, and optical properties were investigated by X-ray diffraction, Hall measurement, and optical transmission spectroscopy. The resistivity and optical transmittance of the ZnO:Ga thin films are of the order of 10^− 4 Ω cm and over 85%, respectively. The lowest electrical resistivity of the film is found to be about 3.58 × 10^− 4 Ω cm. The influences of Ar/O₂ gas ratios on the resistivity, Hall mobility, and carrier concentration were analyzed.     

(C2N2H10)[FexV1−x(HPO3)F3] (x = 0.44, 0.72): Two new organically templated phosphites: Solvothermal synthesis and structural,thermal, spectroscopic and magnetic studies

(C₂N₂H₁₀)[Fe_xV_1−x(HPO₃)F₃] (x = 0.44, 0.72) have been synthesized using mild solvothermal conditions under autogenous pressure and the ethylenediamine molecule as templating agent. The crystal structures have been determined from X-ray single-crystal diffraction data. The compounds crystallize in the orthorhombic P2₁2₁2₁ space group with Z = 4 and unit-cell parameters a = 12.8494(9), b = 9.5430(6), c = 6.4372(5) Å, and a = 12.8578(1), b = 9.5342(1), c = 6.4370(7) Å for (C₂N₂H₁₀)[Fe_0.44V_0.56(HPO₃)F₃] and (C₂N₂H₁₀)[Fe_0.72V_0.28(HPO₃)F₃], (1) and (2), respectively. These isostructural compounds exhibit a monodimensional crystal structure formed by pillared double anionic chains with the formula [M(HPO₃)F₃]²⁻, extended along the [0 0 1] direction. These doubled ionic chains are the result of the linking of two simple chains in which there are alternating octahedral [MO₃F₃] and tetrahedral groups [HPO₃]. The ethylendiammonium cations are placed in the space delimited by three different chains. The metallic ions are interconnected by the pseudo-pyramidal (HPO₃)²⁻ phosphite oxoanions, adopting a slightly distorted octahedral geometry. The IR spectra show bands corresponding to the phosphite oxoanion and the ethylendiamonium cation at 2400 and 1600 cm⁻¹, respectively. The thermogravimetric analyses show that these phases are stable up to ca. 280 °C, at higher temperatures, the decomposition of the crystal structure begins by calcination of the organic cation and the elimination of the fluoride anions. The diffuse reflectance spectra show bands of the V³⁺ ion (d²) in octahedral symmetry. The values of the Dq (1540, 1540 cm⁻¹), and Racah parameters, B (560, 535 cm⁻¹) and C (3055, 3140 cm⁻¹) for (1) and (2), respectively, correspond with those usually found for octahedrically coordinated V(III) compounds. Magnetic measurements, performed on a powered sample from 5.0 to 300 K at 1000 G, in the ZFC and FC modes, indicate the existence of antiferromagnetic interactions.     

Temperature dependent transport properties in molybdenum oxide doped α-NPD

The temperature dependent transport properties of molybdenum oxide (MoO₃) doped N,N′-di(1-naphthyl)-N,N′-diphenylbenzidin (α-NPD) were studied over a frequency range of 100 Hz to 1 MHz. The value of trap density and mobility calculated by detailed analysis of current–voltage (I–V) characteristics are 9.43 × 10²⁶ m^?3 and 1.23 × 10^?6 cm² V^?1 s^?1, respectively. The relaxation time for the carriers in the bulk and in the interface region decreases with temperature. The Cole–Cole plot indicates the device can be modeled as the combination of two parallel resistor–capacitor (R–C) circuits with a series resistance of around 70 Ω. The dc conductivity shows two different regions in the studied temperature range with activation energy of E_a ～ 0.107 eV (region I) and E_a ～ 52 meV (region II), respectively. The ac conductivity follows the universal power law and the onset frequency increases with increase of temperature. The temperature dependent conduction mechanism can be explained by correlated hopping barrier (CBH) model.     

Effect of growth rate on microstructure and tensile properties of Ti–45Al–2Cr–2Nb prepared by electromagnetic cold crucible directional solidification

Ti–45Al–2Cr–2Nb alloy was directionally solidified at different growth rates varying from 0.2 to 1.2 mm/min by applying an electromagnetic cold crucible directional solidification technique. It was determined that well-aligned α₂ (Ti₃Al)/γ(TiAl) lamellar structures, B₂ phase and blocky γ phase were generated in columnar grains. The interlamellar spacing (λ) decreases with the increasing growth rate (V) according to the relationship λ ∝ V^− 0.48, but the volume fraction of B₂ is increased as growth rate is increasing. Results of uniaxial tensile tests show that the B₂ phase and the blocky γ phase have significant influence on tensile failure when they are presented in the matrix of α₂/γ lamellar structures, because they are usually employed to act as cracking sources during the tension process.