Thermal dissolution of Ag(Cu) in amorphous Ge(Sx Se1 − x)2 system

Thermally induced solid state reaction of Ag(Cu) into thin Ge(S_x Se_1 − x)₂ films with x = 0, 0.1, 0.4 and 1.0 was investigated using a step by step technique in order to design films with exact Ag(Cu) concentrations for applications in integrated IR optical devices. A thin film of Ag(Cu) was deposited on top of the host Ge(S_x Se_1 − x)₂ films followed by annealing in vacuum at constant temperature, which resulted in homogeneous films of good optical quality. The variation in Ag(Cu) concentration in the films ranged between 5 and 35 at.%. The kinetics of the diffusion and dissolution of metal in the host films was measured by optically monitoring the change in thickness of doped chalcogenide during consecutive thermal annealing steps. The kinetics studies revealed that the thermal dissolution rate of the Cu is greater than that of Ag. Optical UV-VIS transmission spectra of chalcogenide glass layers, undoped and thermal doped by Ag(Cu), were measured to establish the optical properties of the films. The spectra were analyzed using the technique proposed by Swanepoel and the results show that the addition of metal increases the absorption coefficient in the power-law regime and consequently the optical gap decreases and the refractive index increases. The amorphous character of the films was checked by X-ray diffraction which confirmed the amorphous structure of all Ag(Cu)GeSSe thin films.     

Growth and structure properties of La1−xSrxMnO3−σ (x=0.2, 0.3, 0.45) thin film grown on SrTiO3 (0 0 1) single-crystal substrate by laser molecular beam epitaxy

La_1−xSr_xMnO_3−σ (LSMO) thin films have been grown on SrTiO₃ (0 0 1) single-crystal substrates using the laser molecular beam epitaxy (MBE) technique. The two-dimensional layer-by-layer growth was in-situ monitored by reflection high-energy electron diffraction (RHEED). Kinetic growth with surface relaxation was also observed, and crystallinity of the thin films was investigated by high-resolution X-ray diffraction. Results of 2θ−ω scans revealed a strong correlation between out-of-plane lattice constant and oxygen content as well as strontium doping concentration. However, further analysis of rocking curve measurements around (0 0 2) plane of thin films grown under different oxygen pressure (P_O2) shown the effects of oxygen content on the crystal structure. An exceptionally low full-width at half-maximum (FWHM) of 0.02° was measured from the sample grown at P_O2 of 5.0 Pa, indicating the almost perfect epitaxial growth of LSMO thin films.     

Effect of hot-wire passivation on the properties of hydrogenated microcrystalline silicon films to reduce post-deposition oxidation

Hydrogenated microcrystalline silicon (μc-Si:H) films have a large number of grain boundaries that oxidize after deposition, leading to deterioration of device performance. In this study, post-treatment of μc-Si:H thin films was carried out with methane-related radicals generated by a hot wire. The effect of the hot-wire passivation on the properties of the μc-Si:H thin films was investigated using Fourier-transform infrared (FT-IR) transmission spectroscopy. Through post-treatment, hydrogen on the silicon-crystallite surface was substituted with hydrocarbon. Further, an increase in filament temperature (T_ft) was found to enhance passivation. For films treated at T_ft above 1700 °C, post-oxidation and nitridation hardly occurred, whereas films treated at T_ft below 1400 °C were oxidized and nitrided even after post-treatment.     

Calculation of phase diagrams in AlxIn1−xAs/InP,AsxSb1−xAl/InP and AlxIn1−xSb/InSb nano-film systems

The models for calculation of phase diagrams of semiconductor thin films with different substrates were proposed by considering the contributions of strain energy, the self-energy of misfit dislocations and surface energy to Gibbs free energy. The phase diagrams of the Al_xIn_1−xAs and As_xSb_1−xAl thin films grown on the InP (1 0 0) substrate, and the Al_xIn_1−xSb thin films grown on the InSb (1 0 0) substrate at various thicknesses were calculated. The calculated results indicate that when the thickness of film is less than 1 μm, the strain-induced zinc-blende phase appears, the region of this phase extends with decreasing of the layer thickness, and there is small effect of surface energies of liquid and solid phases on the phase diagrams.     

Influence of annealing on the physical properties of filtered vacuum arc deposited tin oxide thin films

Tin oxide (SnO₂) thin films were deposited on UV fused silica (UVFS) substrates using filtered vacuum arc deposition (FVAD). During deposition, the substrates were at room temperature (RT). As-deposited films were annealed at 400 and 600 °C in Ar for 30 min. The film structure, composition, and surface morphology were determined as function of the annealing temperature using X-ray diffraction (XRD), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The XRD patterns of the SnO₂ thin films deposited on substrates at RT indicated that the films were amorphous, however, after the annealing the film structure became polycrystalline. The grain size of the annealed films, obtained from the XRD analysis, increased with the annealing temperature, and it was in the range 8-34 nm. The AFM analysis of the surface revealed an increase in the film surface average grain size from 15 nm to 46 nm, and the surface roughness from 0.2 to 1.8 nm, as function of the annealing temperature. The average optical transmission of the films in the visible spectrum was >80%, and increased by the annealing ∼10%. The films’ optical constants in the 250-989 nm wavelength range were determined by variable angle spectroscopic ellipsometry (VASE). The refractive indexes of as-deposited and annealed films were in the range 1.83-2.23 and 1.85-2.3, respectively. The extinction coefficients, k(λ), of as-deposited and annealed films were in the range same range ∼0-0.5. The optical energy band gap (E_g), as determined by the dependence of the absorption coefficient on the photon energy at short wavelengths, increased with the annealing temperature from 3.90 to 4.35 eV. The lowest electrical resistivity of the as-deposited tin oxide films was 7.8 × 10⁻³ Ω cm, however, film annealing resulted in highly resistive films.     

Influence of hydrogen on structural and optical properties of low temperature polycrystalline Ge films deposited by RF magnetron sputtering

To improve the properties of polycrystalline Ge thin films, which are a candidate material for the bottom cells of low cost monolithic tandem solar cells, ∼300 nm in situ hydrogenated Ge (Ge:H) thin films were deposited on silicon nitride coated glass by radio-frequency magnetron sputtering. The films were sputtered in a mixture of 15 sccm argon and 10 sccm hydrogen at a variety of low substrate temperatures (T_s)≤450 °C. Structural and optical properties of the Ge:H thin films were measured and compared to those of non-hydrogenated Ge thin films deduced in our previous work. Raman and X-ray diffraction spectra revealed a structural evolution from amorphous to crystalline phase with increase in T_s. It is found that the introduction of hydrogen gas benefits the structural properties of the polycrystalline Ge film, sputtered at 450 °C, although the onset crystallization temperature is ∼90 °C higher than in those sputtered without hydrogen. Compared with non-hydrogenated Ge thin films, hydrogen incorporated in the films leads to broadened band gaps of the films sputtered at different T_s.     

Effect of Mn concentration and growth temperature on nanostructures and magnetic properties of Ge1−xMnx grown on Si

The nanostructures and magnetic properties of Ge_1−xMn_x thin films grown on Si substrates by molecular beam epitaxy, with different nominal Mn concentrations (1−4%) and different growth temperatures, have been systematically investigated by transmission electron microscopy and superconducting quantum interference device. It was discovered that when Ge_1−xMn_x thin films were grown at 70 °C, with increase in Mn concentration, Mn-rich tadpole shaped clusters started to nucleate at 1% Mn and become dominate in the entire film at 4% Mn. While for the thin films grown at 150 °C, tadpoles was firstly seen in the film with 1% Mn and subsequently Mn-rich secondary precipitates became dominant. The magnetic properties show specific features, which are mainly related to the nature and amount of Mn-rich clusters/precipitates within these thin films.     

Thin chalcogenide films prepared by pulsed laser deposition – new amorphous materials applicable in optoelectronics and chemical sensors

Principles, advantages, applications and drawbacks of pulsed laser deposition (PLD) technique for thin films preparation are reviewed. The PLD method is promising for preparation of thin films of complex composition, including rare-earth and Ag-doped chalcogenide films; all components of the target can be evaporated at once. Low volatility and refractory materials can be also deposited. The deposition in vacuum, inert or reactive atmosphere is possible. Results obtained in a study of chalcogenide films are discussed and the current state-of-the-art is reviewed. The composition and structure of PLD films can be different from thermally evaporated films and new materials or materials with new properties applicable in optics and optoelectronics can be prepared. The method can be used for fabrication of different chalcogenide-based sensors and memory materials of complex composition. Photoinduced changes of structure and properties of PLD films and chalcogenides exposed to intense laser pulses are also discussed. The intense laser pulses can change the properties of the materials prepared and can be used for fabrication of chalcogenide-based waveguides, diffractive elements and high-density optical data storage media.     

An analytical model to represent crystallization kinetics in materials with metastable phase formation

The aim of this article is to propose a simple analytical model that can describe the isothermal crystallization process in materials when the formation of a stable crystalline phase is preceded by the formation of a metastable phase. This model explains deviations from the well-known Johnson-Mehl-Avrami-Kolmogorov kinetics theory and predicts the three slopes in Avrami’s plot. The model predictions were compared with experimental results obtained from X-ray measurements in the chalcogenide glasses with composition of Ge₂Sb₂Te₅ (thin films) and in aqueous solutions of methylhydrazine monohydrate during isothermal phase transformations. In order to validate the proposed model to represent experimental results, a computer program was developed. This program uses experimental data from measurements of the total volume fraction at different times during isothermal transformations and fits the model parameters that best represent the kinetic behavior of the system.     

Surface morphology,structural and optical properties of polar and non-polar ZnO thin films: A comparative study

The polar and non-polar ZnO thin films were fabricated on cubic MgO (1 1 1) and (0 0 1) substrates by plasma-assisted molecular beam epitaxy. Based on X-ray diffraction analysis, the ZnO thin films grown on MgO (1 1 1) and (1 0 0) substrates exhibit the polar c-plane and non-polar m-plane orientation, respectively. Comparing with the c-plane ZnO film, the non-polar m-plane ZnO film shows cross-hatched stripes-like morphology, lower surface roughness and slower growth rate. However, low-temperature photoluminescence measurement indicates the m-plane ZnO film has a stronger 3.31 eV emission, which is considered to be related to stacking faults. Meanwhile, stronger band tails absorbance of the m-plane ZnO film is observed in optical absorption spectrum.     

Effect of high electronic energy loss of 100 MeV gold heavy ions in copper chalcogenides (CuX,X = S,Se) at nanoscale: Opto-electronic properties study

The copper chalcogenide (CuX, X = S, Se) thin films have been irradiated with 100 MeV gold swift heavy ions (SHI) at 10¹¹ and 10¹² ions/cm² fluences. The irradiation effects were probed by characterizing physical properties such as XRD, AFM, optical band gap and electrical resistivity of copper chalcogenide thin films. The increase in irradiation fluence increases the particle size, electrical conductivity and PL intensity of the materials, and the optical band edges were red shifted. The results are explained by quantifying electronic energy loss of ions in both the materials.     

Surface morphology of spin-coated As–S–Se chalcogenide thin films

Surface morphology and roughness of amorphous spin-coated As–S–Se chalcogenide thin films were determined using atomic force microscopy. Prepared films were coated from butylamine solutions with thicknesses d ∼ 100 nm and then annealed in a vacuum furnace at 45 °C and 90 °C for 1 h for their stabilization. The root mean square surface roughness analysis of surfaces of as-deposited spin-coated As–S–Se films indicated a very smooth film surface (with R_q values 0.42–0.45 ± 0.2 nm depending on composition). The nanoscale images of as-deposited films confirmed that surface of the films is created by domains with dimensions 20–40 nm, which corresponds to diameters of clusters found in solutions. The domain character of film surfaces gradually disappeared with increasing annealing temperature while the solvent was removed from the films. Middle-infrared transmission spectra recorded a decrease of intensities of vibration bands connected to N–H (at 3367 and 3292 cm⁻¹) and C–H (at 2965, 2935 and 2880 cm⁻¹) stretching vibrations. Temperature regions of solvent evaporation T = 60–90 °C and glass transformation temperatures T_g = 135–150 °C of spin-coated As–S–Se thin films were determined using a modulated differential scanning calorimetry.     

Influence of silver concentration in Agx(Sb0.33S0.67)100−x thin amorphous films on photoinduced crystallization

One of the recent applications of thin chalcogenide films is in rewritable optical data recording. This technology is based on reversible phase transition between crystalline and amorphous state. Currently, the primary materials for rewritable optical are Ge–Sb–Te and Ag–In–Sb–Te alloys, but materials research still continues due to the need for increased storage capacity and data recording rates. (Ag)–Sb–S thin films were prepared by thermal evaporation of Sb₃₃S₆₇ bulk and optically induced diffusion and dissolution of thermally evaporated Ag films. Prepared samples were characterized by electron microprobe (SEM-EDX), differential scanning calorimetry (DSC) and by UV–Vis–NIR and Raman spectroscopy. The phase-change recording processes in (Ag)–Sb–S films were carried out by photocrystallization experiments done by Ar⁺ ion laser. The laser exposed dots were studied by scanning electron microscopy (SEM) and transmission optical microscopy. Micro X-ray diffraction (μ-XRD) was used for the exposed dots crystallinity study. Photocrystallization kinetic curves (showing the dependence of optical transmission on laser exposure time) were also established. Crystallization mechanism of Ag_x(Sb_0.33S_0.67)_100−x samples was discussed.     

Electron microscopy studies of epitaxial MgB2 superconducting thin films grown by in situ reactive evaporation

The morphology and chemistry of epitaxial MgB₂ thin films grown using reactive Mg evaporation on different substrates have been characterized by transmission electron microscopy methods. For polycrystalline alumina and sapphire substrates with different surface planes, an MgO transition layer was found at the interface region. No such layer was present for films grown on MgO and 4-H SiC substrates, and none of the MgB₂ films had any detectable oxygen incorporation nor MgO inclusions. High-resolution electron microscopy revealed that the growth orientation of the MgB₂ thin films was closely related to the substrate orientation and the nature of the intermediary layer. Electrical measurements showed that very low resistivities (several μΩ cm at 300 K) and high superconducting transition temperatures (38 to 40 K) could be achieved. The correlation of electrical properties with film microstructure is briefly discussed.     

Optical characterization of As2Se3-Ag4SSe-SnTe amorphous thin films

Amorphous thin films from the system As₂Se₃-Ag₄SSe-SnTe were prepared by thermal vacuum evaporation from the corresponding bulk glassy samples. The film structure and surface morphology were investigated by scanning electron microscopy and atomic force microscopy; the results revealed uniform, smooth and homogeneous coatings. The amorphous chalcogenide films are transparent in a wide spectral range as shown by transmission and reflection measurements in the VIS and NIR regions. The optical band gap was determined and its compositional dependence is discussed in terms of structural considerations and the formation of charged defect centers.     

Optical band gap and refractive index dispersion parameters of In-Se-Te amorphous films

Different compositions of In_x(Se_0.75Te_0.25)_100 − x (where 0 ≤ x ≤ 10 at.%) chalcogenide glasses were prepared by the usual melt quench technique. Chalcogenide thin films of these glasses were prepared by using thermal evaporation method. The film transmittance (T(λ)) at normal incidence for these films was measured in the wavelength range 400-2500 nm using a double beam spectrophotometer. Successfully applying Swanepoel's method helps us to determine the film thickness and the real (n) and imaginary (k) parts of the complex index of refraction with high accuracy. Optical absorption measurements show that, the fundamental absorption is due to the allowed non-direct transitions. It was found that, the addition of In content leads to the increase of the refractive index increases while the optical band gap decreases. The obtained results are well discussed in terms of the chemical bond approach and the cohesive energy.     

Influence of pulsed laser deposition rate on the microstructure and thermoelectric properties of Ca3Co4O9 thin films

The effects of deposition rate on the microstructure and thermoelectric (TE) properties of Ca₃Co₄O₉ thin films fabricated by pulsed laser deposition (PLD) technique were investigated. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HR-TEM) revealed that a fast deposition rate resulted in not only low crystallinity but also the existence of the Ca_xCoO₂ secondary phase. Formation of Ca_xCoO₂ was inevitable during the thin film growth, and this was discussed from both structural and compositional point of view. With longer deposition interval or with sufficient oxygen at a lower deposition rate, the Ca_xCoO₂ phase was able to transit into the desired Ca₃Co₄O₉ phase during the coalescence process. The quality of the thin films was further analyzed by electrical properties measurements. The Ca₃Co₄O₉ thin film fabricated at a slower deposition rate was found to exhibit a low electrical resistivity of 9.4 mΩ cm and high Seebeck coefficient of 240 μV/K at about 700 °C, indicating a good quality film.     

Investigation of optical parameters of Ag-In-Se thin films deposited by e-beam technique

The optical properties of the Ag-In-Se (AIS) thin films deposited by e-beam technique were investigated by means of the optical transmittance measurements. The optical absorption coefficients of the films were found to vary from 10³ to 10⁵ cm⁻¹ over the wavelength range of 300-1100 nm. The real and imaginary parts of the refractive index and dielectric constant for the as-grown and annealed films in between 100 and 400 °C were evaluated by means of both envelope method (EM) and continuous wavelet transform (CWT) method and the results were in quite good agreement with each other. The refractive index, n, dispersion over the measured wavelength range was explained by applying single-oscillator model (SOM) and the related parameters were calculated. The optical absorption process for the AIS thin films was characterized by three direct transitions from three closely spaced valence bands to a single conduction band due to the splitting of the valence band under the influence of the tetragonal crystalline field and spin-orbit interaction. The direct optical band gap energy decreases as the annealing temperature increases because of the increase in the width of band tail states near valence-band edge caused by the Se segregation. The two distinct parameters of the quasicubic model; crystal-field splitting, Δ_CF, and spin-orbit splitting, Δ_SO, were calculated for as-grown and annealed AIS thin films.     

High-quality ZnO thin films prepared by two-step thermal oxidation of the metallic Zn

In this paper, we report the preparation of nanocrystalline ZnO thin films on Si (1 0 0) substrates using a simple method, in which a resistive thermal evaporation of Zn and a two-step annealing process were employed. The aim of the first annealing step in an oxygen ambient at 300°C for 2 h is to form ZnO layers on the surface of the Zn films to prevent the diffusion of the metallic Zn from the films during the high-temperature annealing process. To obtain high-quality ZnO films, a high-temperature annealing step was performed at temperature in the range of 600–900°C. The effects of the annealing temperature on the photoluminescence (PL) and orientation of ZnO nanocrystalline thin films were studied. A very strong near-band-edge emission around 375 nm with a full-width at half-maximum of 105 meV and a relatively weak emission around 510 nm related to deep-level defects were observed, which indicated that high-quality ZnO films have been obtained.