27Al NMR structural study on aluminum coordination state in bismuth doped silica glass

The aluminum coordination state in bismuth doped silica glass, which has new broad infrared emission at 1.3 μm regions, was investigated by using ²⁷Al NMR, and it is demonstrated that 6-fold coordinated aluminum ions with corundum structure are dominant in bismuth doped silica glass until Bi₂O₃ concentrations of 1.0 mol% with Al₂O₃. The aluminum ion efficiently affects the creation of a Bi luminescent center at an intensity of Bi₂O₃ (1.0 mol%)–Al₂O₃ (2.3 mol%)–SiO₂ (96.7 mol%); the sample is three orders of magnitude larger than the Bi₂O₃ (1.0 mol%)–SiO₂ (99.0 mol%) sample. Aluminum ions with corundum structure in silica glass have a very important role for the configuration of peculiar Bi luminescent centers.     

Electrical and optical properties of bismuth telluride/gallium nitride heterojunction diodes

Semiconducting bismuth telluride has a band gap energy of about 0.15 eV at room temperature and is a good material for middle wavelength IR (MWIR) detection [S.K. Mishra, S. Satpathy, O. Jepsen, J. Phys. Condens. Matter, p. 461]. We have grown bismuth telluride thin films on gallium nitride (on sapphire) by pulsed laser deposition at a substrate temperature of 300 °C. The structural characteristics and surface morphology of the films were studied by X-ray diffraction and scanning electron microscopy, respectively. The chemical composition of the as-deposited bismuth telluride thin films was determined by X-ray photoelectron spectroscopy and was found to be different from that of the bulk target, changing from stoichiometric Bi₂Te₃ to bismuth rich. A bismuth rich p-Bi₂Te₃/n-GaN/Al₂O₃ heterojunction was fabricated for photovoltaic detection of low energy photons. The wide band gap semiconducting n-GaN layer and the Al₂O₃ substrate act as a window for IR transmission. A sensitive IR photoresponse of the heterojunction is obtained by back-side illumination. The photocurrent measured is 0.18 μA according to the irradiation change in the current–voltage characteristics. The current–voltage characteristics allow us to evaluate the series resistance (R_s), zero-bias resistance (R₀) and ideality factors (n) of the junctions. Our results have suggested that bismuth telluride is a potential candidate for photovoltaic mid-infrared detection.     

Fabrication and ionic conductivity of amorphous Li–Al–Ti–P–O thin film

Li⁺ ion conducting Li–Al–Ti–P–O thin films were fabricated on ITO-glass substrates at various temperatures from 25 to 400 °C by RF magnetron sputtering method. When the substrate temperature is higher than 300 °C, severe destruction of ITO films were confirmed by XRD (X-ray diffraction) and the abrupt transformation of one semi-circle into two semi-circles on the impedance spectra. These as-deposited Li–Al–Ti–P–O solid state electrolyte thin films have an amorphous structure confirmed by XRD and a single semicircle on the impedance spectra. Good transmission higher than 80% in the visible light range of these electrolyte thin films can fulfill the demand of electro-chromic devices. Field emission scanning electron microscopy and atomic force microscopy showed the denser, smoother and more uniform film structure with the enhanced substrate temperature. Measurements of impedance spectra indicate that the gradual increased conductivity of these Li–Al–Ti–P–O thin films with the elevation of substrate temperature from room temperature to 300 °C is originated from the increase of the pre-exponential factor (σ₀). The largest Li-ion conductivity can come to 2.46 × 10^? 5 S cm^? 1. This inorganic solid lithium ion conductor film will have a potential application as an electrolyte layer in the field such as lithium batteries or all-solid-state EC devices.     

Structural study of undoped and (Mn, In)-doped SnO2 thin films grown by RF sputtering

Undoped and 5%(Mn, In)-doped SnO₂ thin films were deposited on Si(1 0 0) and Al₂O₃ (R-cut) by RF magnetron sputtering at different deposition power, sputtering gas mixture and substrate temperature. X-ray reflectivity was used to determine the films thickness (10–130 nm) and roughness (～1 nm). The combination of X-ray diffraction and Mössbauer techniques evidenced the presence of Sn⁴⁺ in an amorphous environment, for as-grown films obtained at low power and temperature, and the formation of crystalline SnO₂ for annealed films. As the deposition power, substrate temperature or O₂ proportion are increased, SnO₂ nanocrystals are formed. Epitaxial SnO₂ films are obtained on Al₂O₃ at 550 °C. The amorphous films are quite uniform but a more columnar growth is detected for increasing deposition power. No secondary phases or segregation of dopants were detected.     

Crystallization behavior of e-beam evaporated Ga5Ge15Te80 thin films

Ga₅Ge₁₅Te₈₀ thin films have been deposited by e-beam evaporation method. The chemical composition of the deposited films was identified using energy dispersive X-ray spectrometry. The electrical conductivity, σ of the deposited films during heating/cooling cycles was investigated in the temperatures 298–570 K. The conductivity curve showed two sudden upward trends during the first heating cycle. The first upward trend occurs in the temperature range 408–430 K and was attributed to the amorphous-to-crystalline phase transformation. While the second is in the temperature range 470–495 K, and can be attributed to the crystallization process. However, for second heating cycle the conductivity curve becomes reversible. The optical band gap of the as-deposited and annealed film at annealing temperature 423 K was determined from the recorded transmittance and reflectance spectra. The obtained results were confirmed throughout the X-ray and transmission electron microscope studies.     

Infrared spectroscopy of Li-diborate glassy thin films

This work presents a structural investigation of Li-borate thin film electrolytes prepared by rf-sputtering from targets having the nominal Li₂O–2B₂O₃ composition. Thin films of ca. 1 μm were deposited on Si wafers and gold-covered Si substrates under argon, and their infrared spectra were measured in the 30–5000 cm⁻¹ range. The measured spectra of thin films were compared with those calculated on the basis of the infrared properties of the bulk Li-diborate glass and by considering all optical effects in the film/substrate system. The results showed that the thin films have the key structural features of the bulk glass, but exhibit also differences in the short-range order structure and in the Li ion-site interactions. These findings were discussed in terms of cooling rate differences between melt-quenching for bulk glass and sputtering for thin films.     

Plasma enhanced chemical vapor deposition of ZnO thin films

Zinc oxide thin films were deposited on silicon and corning-7059 glass substrates by plasma enhanced chemical vapor deposition at different substrate temperatures ranging from 36 to 400 °C and with different gas flow rates. Diethylzinc as the source precursor, H₂O as oxidizer and argon as carrier gas were used for the preparation of ZnO films. Structural and optical properties of these films were investigated using X-ray diffraction, reflection high energy electron diffraction, atomic force microscopy and photoluminescence. Highly oriented films with (0 0 2) preferred planes were obtained on silicon kept at 300 °C with 50 ml/min flow rate of diethylzinc without any post annealing. Reflection high energy electron diffraction pattern also showed the crystalline nature of these films. A textured surface with rms roughness ∼28 nm was observed by atomic force microscopy for the films deposited at 300 °C. A sharp peak at 380 nm in the PL spectra indicated the UV band-edge emission.     

Optical and electrical properties of as-prepared and annealed (Se80Te20)100 − xAgx (0 ≤ x ≤ 4) ultra-thin films

Optical and electrical properties of the (Se₈₀Te₂₀)_100 ? xAg_x (0 ≤ x ≤ 4) ultra-thin films have been studied. The ultra-thin films were prepared by thermal evaporation of the bulk samples. Thin films were annealed below glass transition temperature (328 K) and in between glass transition temperature and crystallization temperature (343 K). Thin films annealed at 343 K showed crystallization peaks for Se–Te–Ag phases in the XRD spectra. The transmission and reflection of as-prepared and annealed ultra-thin films were obtained in the 300–1100 nm spectral region. The optical band gap has been calculated from the transmission and reflection data. The refractive index has been calculated by the measured reflection data. It has been found that the optical band gap increases, but the refractive index, extinction coefficient, real and imaginary dielectric constant decrease with increase in Ag content. The optical band gap and refractive index show the variation in their values with increase in the annealing temperature. The extinction coefficient increases with increasing annealing temperature. The surface morphology of ultra-thin films has been determined using a scanning electron microscope (SEM). The measured dc conductivity, under a vacuum of 10^? 5 mbar, showed thermally activated conduction with single activation energy in the measured temperature range (288–358 K) and it followed Meyer–Neldel rule. The dc activation energy decreases with increase in Ag content in pristine and annealed films. The results have been analyzed on the bases of thermal annealing effects in the chalcogenide thin films.     

Zr(IV) and Hf(IV) β-diketonate complexes as precursors for the photochemical deposition of ZrO2 and HfO2 thin films

In this paper amorphous ZrO₂ and HfO₂ thin films were obtained by direct UV irradiation of Zr(IV) and Hf(IV) β-diketonate precursor complexes on Si(1 0 0) and fused silica substrates. The precursors, Zr(CH₃COCHCOCH₃)₄ and Hf(C₆H₅COCHCOCH₃)₄ were deposited as amorphous thin films by spin coating. The photochemistry of these films was monitored by FT-IR spectroscopy. The photolysis with 254 nm light led to the loss of the ligands from the coordination complexes, and the production of metallic oxides. The thin films products were characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). These analyses revealed that as-deposited films are amorphous and that the presence of carbon is thought to arise from the ligands. However, post-annealing of the photodeposited films favors the stoichiometric and optical properties of ZrO₂ and HfO₂ thin films.     

Generating ordered Si nanocrystals via atomic force microscopy

We describe two successful routes for generating ordered arrays of Si nanocrystals by using atomic force microscopy (AFM) and amorphous silicon thin films (200–400 nm) on Ti/Ni coated glass substrates. First, we show that field-enhanced metal-induced solid phase crystallization at room temperature can be miniaturized to achieve highly spatially localized (below 100 nm) current-induced crystallization of the amorphous silicon films using a sharp tip in AFM. In the second route, resistive nano-pits are formed at controlled positions in the amorphous silicon thin films by adjusting (lowering and/or stabilizing) the exposure currents in the AFM process. Such templated substrates are further used to induce localized growth of Si nanocrystals in plasma-enhanced chemical vapor deposition process. In both cases the crystalline phase is identified in situ as features of enhanced current in current-sensing AFM maps.     

Effects of tantalum doping on microstructure and ferroelectric properties of Bi4Ti3O12 thin films prepared by a sol–gel method

Tantalum-substituted Bi₄Ti₃O₁₂ (Bi₄Ti_3-x/5Ta_x/5O₁₂, BTTO) thin films were fabricated on Pt(111)/Ti/SiO₂/Si(100) substrates by sol–gel technology. The effects of various processing parameters, including Ta content (x=0～0.08) and annealing temperature (500～800 °C), on the growth and properties of thin films were investigated. X-ray diffraction analysis shows that the BTTO thin films have a bismuth-layered perovskite structure with preferred (117) orientation. With the increase of Ta content, the grain size of film decreased slightly, and highly (117)-oriented BTTO films were obtained in the composition of x=0.06. Ta doping on the B-site of Bi₄Ti₃O₁₂ could induce the distortion of oxygen octahedral and decrease the oxygen vacancy concentration by a compensating effect. The highly (117)-oriented BTTO thin films with x=0.06 exhibits the maximum remanent polarization (2P_r) of 50 μC/cm² and a low coercive field (2E_c) of 104 kV/cm, fatigue free characteristics up to ≧ 10⁸ switching cycles.     

Electrodeposited and selenized CIGS thin films for solar cells

Cu(In,Ga)Se₂ polycrystalline thin films were deposited adopting the potentiostatic electrochemical method on Mo/soda lime glass substrate. All the as-deposited Cu(In,Ga)Se₂ thin films were annealed in a selenium atmosphere at 550 °C for 1 h to improve the film crystalline properties. The selenized CIGS thin films were characterized by energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) and scanning electron microscopy (SEM).The results indicate Cu(In,Ga)Se₂ thin films have single chalcopyrite structure and the grain size varies from 0.8 to 2.5 μm.     

Nanostructural and optical features of amorphous AlxSi0.45−xO0.55 (0 ⩽ x ⩽ 0.05) thin films prepared by RF-magnetron sputter techniques

The nanostructural, chemical, and optical features of Al_xSi_0.45−xO_0.55 (0 ⩽ x ⩽ 0.05) thin films were investigated in terms of Al concentration and post-deposition annealing conditions; the films were prepared by co-sputtering a Si main target and Al-chips, and the annealing was carried out at temperatures of 400–1100 °C. The a-Si_0.45O_0.55 films prepared without Al-chips and annealed at 800 °C contain ∼3.5 nm-sized Si nanocrystallites. The photoluminescence (PL) intensity as well as the volume fraction of Si nanocrystallites increased with increasing the concentration of Al to a certain level. In particular, the intensity of the PL spectra of the Al_0.025Si_0.425O_0.550 films which were annealed at 800 °C increased significantly at wavelengths of ∼580 nm. It is highly likely that the observed increase in the PL intensity is caused by the raise in the total volume of the ∼3.5 nm-sized nanocrystallites in the films. The addition of Al as well as the post-deposition annealing allow adjustment and control of the nanostructural and light-emission features of the a-SiO_x films.     

I–V Characteristics of tris(2,4-pentanedionato)manganese(III) thin films

Amorphous thin films of tris(acetylacetonate)manganese(III) were deposited on Si(P) substrates by thermal sublimation in vacuum. The deposited films were probed with X-ray fluorescence. Their electrical properties were studied as insulators for Al/Mn(acac)₃/Si(P) metal–insulator–semiconductor devices. Those devices were characterized by the measurement of the gate-voltage dependence of their capacitance, from which the relative permittivity (RP) and density of the charges in the insulator were determined. It was found that values of the RP of tris(acetylacetonate)manganese(III) films grown on Si(P) wafers were in the range of 30–40, which can be find applications in gate related technological uses. The dc-electrical conduction in the complex film was studied at room temperature and in temperature range of (293–325 K). It was found that the data of the as-deposited films follow the trap-charge-limited space-charge-limited conductivity (TCL-SCLC) mechanism, while the data of the annealed sample in vacuum of about 10⁻³ Pa at about 100 °C for 10 min obey the Richardson–Schottky (RS) mechanism. The parameters of both mechanisms were determined. It was concluded that the density of charged defects in the insulating film is critically determined the mechanism of the current-transfer.     

The effect of the underlying substrate on crystallization kinetics of TiNi thin films

The crystallization kinetics of amorphous thin TiNi films deposited on SiO₂ (or NaCl)/Al foils substrates were investigated. A dramatic acceleration of the crystallization rate was observed for amorphous attached-substrate films. The acceleration originated from the presence of the thin film/middle-wafer interface which served as a two-dimensional nucleus for the growth of the crystalline phase. In the process of non-isothermal annealing by DSC, apparent activation energies for two kinds of underlying thin TiNi films were determined to be 352.96 and 403.69 kJ/mol, respectively, which was lower than those free-standing films studied in previous works. For the process of isothermal annealing, the crystallization kinetics parameters had remarked drop, reflected from the lower Avrami exponent n (the range of 1.35–2.11) and shorter incubation time τ (the range of 0.1–0.4 min) between 758 and 775 K.     

Crystallization of amorphous Al2O3–SiO2 precursors doped with nickel

The crystallization of amorphous diphasic Al₂O₃–SiO₂ precursors doped with nickel has been studied by differential scanning calorimetry (DSC), XRD diffraction (XRD) and scanning and transmission electron microscopy (SEM, TEM) equipped with energy dispersive X-ray spectroscopy (EDS). Diphasic gels with constant atomic ratio (Al + Ni)/Si = 3:1, where 0, 1, 2 and 3 at.% of aluminum were replaced by nickel, have been prepared by hydrolyzing of TEOS in aqueous solution of aluminum nitrate. Crystallization of Ni-containing γ-Al₂O₃ preceded the crystallization of Al–Si spinel. Activation energy of 603 ± 16 kJ mol⁻¹ for crystallization of Ni-containing γ-Al₂O₃ was obtained in non-isothermal conditions. Ni-incorporated γ-Al₂O₃ transforms gradually with the temperature increase into Ni aluminate spinel, while Al–Si spinel reacts with amorphous silica forming mullite at about 1200 °C. Rietveld structure refinement of phases present in the samples annealed at 1600 °C and SEM-EDS and TEM-EDS analyses of related phases have shown that nickel predominantly crystallizes as NiAl₂O₄, but small amount of nickel is incorporated in mullite structure, as well as, dissolved in the glassy phase of the system.     

Structural heterogeneity in chalcogenide glass films prepared by thermal evaporation

GeSe₂ and Ge₂₈Sb₁₂Se₆₀ chalcogenide glass thin films have been deposited on single crystal silicon substrates by vacuum thermal evaporation. The surface morphology of these films has been investigated by field emission-scanning electron microscopy and atomic force microscopy, revealing heterogeneities in their microstructure consisting of granular regions ∼15–50 nm in size, which were coarser in the case of the GeSe₂ films. Typical RMS film surface roughness values were ∼0.9–1.3 nm.     

Fabrication and characterization of transparent conductive ZnO:Al thin films prepared by direct current magnetron sputtering with highly conductive ZnO(ZnAl2O4) ceramic target

Using a highly conductive ZnO(ZnAl₂O₄) ceramic target, c-axis-oriented transparent conductive ZnO:Al₂O₃ (ZAO) thin films were prepared on glass sheet substrates by direct current planar magnetron sputtering. The structural, electrical and optical properties of the films (deposited at different temperatures and annealed at 400°C in vacuum) were characterized with several techniques. The experimental results show that the electrical resistivity of films deposited at 320°C is 2.67×10⁻⁴ Ω cm and can be further reduced to as low as 1.5×10⁻⁴ Ω cm by annealing at 400°C for 2 h in a vacuum pressure of 10⁻⁵ Torr. ZAO thin films deposited at room temperature have flaky crystallites with an average grain size of ∼100 nm; however those deposited at 320°C have tetrahedron grains with an average grain size of ∼150 nm. By increasing the deposition temperature or the post-deposition vacuum annealing, the carrier concentration of ZAO thin films increases, and the absorption edge in the transmission spectra shifts toward the shorter wavelength side (blue shift).     

Crystallization of bismuth oxide nano-crystallites in a SiO2–PbO–Bi2O3 glass matrix

SiO₂–PbO–Bi₂O₃ glasses having the composition of 35SiO₂–xPbO–(65 ? x)Bi₂O₃ (where x = 5, 20 and 45; in mol%) have been prepared using the conventional melting and annealing method. Differential scanning calorimetry (DSC) was employed to characterize the thermal behavior of the prepared glasses in order to determine their crystallization temperatures (T_cr). It has been found that T_cr decreases with the decrease of Bi₂O₃ content. The amorphous nature of the prepared glasses as well as the crystallinity of the produced glass–ceramics were confirmed by X-ray powder diffraction (XRD) analysis. SiPbBi₂O₆ glass nano-composites, comprising bismuth oxides nano-crystallites, were obtained by controlled heat-treatment of the glasses at their (T_cr) for 10 h. Transmission electron microscopy (TEM) of the glass nano-crystal composites demonstrates the presence of cubic Bi₂O₃ nano-crystallites in the SiPbBi₂O₆ glass matrix. Nano-crystallites mean size has been determined from XRD line width analysis using Scherrer's equation as well as from TEM; and the sizes obtained from both analyses are in good agreement. These sizes varied from about 15 to 170 nm depending on the chemical compositions of parent glasses and, consequently, their structure. Interestingly, replacement of the Bi₂O₃ by PbO in the glass compositions has pronounced effect on the nature, morphology and size of the formed nano-crystallites. Decrease of the Bi₂O₃ content increases the size of the nano-crystallites, and at the lowest Bi₂O₃ extreme, namely 20 mol%, introduces minority of the monoclinic Bi₂O₄ in addition to the cubic Bi₂O₃. The crystallization mechanism is suggested to involve a diffusion controlled growth of the bismuth oxide nano-crystallites in the SiPbBi₂O₆ glass matrix with the zero nucleation rate.     

The (Bi,Pb)4Sr3Ca3Cu4Ox glass–ceramics: Disordered metal and superconductor

The (Bi_0.8Pb_0.2)₄Sr₃Ca₃Cu₄O_x glass, annealed under proper conditions, is transformed into a granular metal and superconductor. Oxide superconductors of the bismuth family crystallize as a result of annealing: (Bi,Pb)₂Sr₂CuO_x (2201, T_c = 10 K), (Bi,Pb)₂Sr₂CaCu₂O_x (2212, T_c = 85 K) and (Bi,Pb)₂Sr₂Ca₂Cu₃O_x (2223, T_c = 100 K). (Bi_0.8Pb_0.2)₄Sr₃Ca₃Cu₄O_x glass–ceramic samples were obtained by annealing an amorphous solid at temperatures between 650 °C and 870 °C. The temperature dependence of resistivity in annealed samples was measured with the conventional four-terminal method in the temperature range from 3 K to 300 K. The (Bi_0.8Pb_0.2)₄Sr₃Ca₃Cu₄O_x glass–ceramics may be considered as a disordered metal and superconductor. The material has high resistivity and a high, usually negative, temperature coefficient of resistivity (TCR). Its granular and disordered character is also reflected in its superconducting properties. The normal-state and superconducting properties are correlated.