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.     

Films thickness effect on structural and optoelectronic properties of hydrogenated amorphous germanium (a-Ge:H)

Thin films of hydrogenated amorphous germanium (a-Ge:H) deposited at high growth rate by radiofrequency (RF) glow discharge with 1 sccm GeH₄ diluted in 40 sccm H₂ have been studied. The effect of the films thicknesses on the defect density and on the structural parameters was carefully investigated by means of infrared spectroscopy, optical transmission measurements, and the photothermal deflection spectroscopy (PDS) technique. The results of this investigation show that when the films thicknesses increase, the total hydrogen content (C_H) decreases and the hydrogen-bonding configuration changes. The results of these changes appear clearly on the defects density and on the microstructure parameter of the films, while the disorder parameter E_OV and the optical gap E_T remain practically constant (E_OV ≈ 45 ± 2 meV, E_T = 1.08 ± 0.02 eV). The improvement of these parameters is mainly due to the incorporation of the hydrogen in the bulk of the material as the monohydride groups (Ge-H) rather than the polyhydride groups (Ge-H₂ and Ge-H_2n) when the films thicknesses increase.     

Optical and structural properties of hydrogenated silicon films prepared by rf-magnetron sputtering at low growth temperatures: Study as function of argon gas dilution

Two series of hydrogenated silicon thin films were deposited by the rf-magnetron sputtering (RFMS) at relatively low growth temperatures (T_s = 100 °C), in order to use the new generation of substrates sensitive to elevated temperatures. The effect of the argon gas diluted in hydrogen, on the optical and on the structural properties was carefully investigated by means of optical transmission (OT) measurements, Fourier transform infrared spectroscopy and spectroscopic ellipsometry (SE) technique. The results of this investigation suggest the existence of a threshold dilution around a gas mixture of argon (40%) and hydrogen (60%) for which the crystallization occurs, even at low deposition temperatures. The difference between the amorphous and the crystallized structures is well revealed by the OT and the IR absorption results, and strongly confirmed by the SE ones. The production of Si crystallites in the plasma as means of producing nanocrystalline by RFMS is suggested.     

Growth of pure ZnO thin films prepared by chemical spray pyrolysis on silicon

Structural, morphological, optical and electrical properties of ZnO thin films prepared by chemical spray pyrolysis from zinc acetate (Zn(CH₃COO)₂ 2H₂O) aqueous solutions, on polished Si(1 0 0), and fused silica substrates for optical characterization, have been studied in terms of deposition time and substrate temperature. The growth of the films present three regimes depending on the substrate temperature, with increasing, constant and decreasing growth rates at lower, middle, and higher-temperature ranges, respectively. Growth rate higher than 15 nm min⁻¹ can be achieved at T_s=543 K. ZnO film morphological and electrical properties have been related to these growth regimes. The films have been characterized by X-ray diffraction, scanning electron microscopy and X-ray photoelectron spectroscopy.     

Effect of OH-content on thermal and chemical properties of SnOP2O5 glasses

Glasses with 55–60 mol% SnO and 40–45 mol% P₂O₅ have shown extremely large differences in the chemical and thermal properties depending on the temperature at which they were melted. Glasses prepared at low melting temperature, 450–550 °C, had low T_g, 150–200 °C, and low chemical stability. Glasses prepared at high melting temperature, 800–1200 °C, had much higher T_g, 250–300 °C, and much higher chemical stability. No significant differences were found by ¹¹⁹Sn Mössbauer and ³¹P Nuclear Magnetic Resonance spectroscopy. Large differences in the OH-content could be detected as the reason by infrared absorption spectroscopy, thermal analyses, and ¹H Nuclear Magnetic Resonance spectroscopy. In samples with low T_g, a broad OH – vibration band around 3000 nm with an absorption intensity >20 cm^?1, bands at 2140 nm with intensity ～5 cm^?1, at 2038 nm with intensity ～2.7 cm^?1, and at 1564 nm with intensity ～0.4 cm^?1 were measured. These samples have shown a mass loss of 3–4 wt% by thermal gravimetric analyses under argon in the temperature range 400–1000 °C. No mass loss and only one broad OH-band with a maximum at 3150 nm and low absorption intensity <4 cm^?1 could be detected in samples melted at high temperature, 1000–1200 °C, which have much higher T_g, ～300 °C, and much higher chemical stability.     

Effect of isothermal annealing and visible-light illumination on the AC-impedance behavior of undoped selenium thin films

The effect of post-deposition isothermal annealing (30 °C ? T_A ? 70 °C) and visible-light illumination on the complex AC-impedance of undoped selenium thin films deposited at the substrate temperatures T_S = 30, 50, 70 °C has been studied in the frequency range 0.2–12 kHz. The AC-impedance of amorphous selenium (a-Se) films (T_S, T_A < 50 °C) was mainly capacitive, with no loss peaks being observed in their Z″(ω)–ω curves, irrespective of illumination. This behavior was ascribed to a dominant charge-carrier trapping effect of bulk/surface charged defects usually present in a-Se. On the other hand, the measured Z″(ω)–Z′(ω) diagrams of illuminated polycrystalline Se samples (50 °C ? T_S, T_A ? 70 °C) exhibited almost full semicircles, whereas their Z″(ω)–ω curves revealed prominent loss peaks at well-defined frequencies. As the annealing temperature or light intensity is increased the loci of the points determined by intersections of these semicircles with the Z′-axis at the low-frequency side shift greatly towards the origin, while the loss-peak positions shift to higher frequencies. These experimental findings were explained in terms of a significant increase in electrical conductivity of selenium films due to thermally-induced crystallization at temperatures beyond glass-transformation region of undoped selenium and to creation of electron–hole pairs by visible-light illumination.     

Effect of vacuum annealing on charge transport and trapping in a-Si1 − xCx:H/c-Si heterostructures

The processes of charge transport and trapping in amorphous Si_1 ? xC_x:H films deposited on crystalline p-type Si wafers and annealed in vacuum in the temperature range 300–650 °C have been evaluated. Current–voltage (I–V), capacitance–voltage (C–V) and admittance–temperature (G–T) characteristics were measured in the temperature range 100–350 K. The spectrum of thermal effusion of hydrogen was measured from room temperature up to 1000 °C.C–V characteristics indicate a slight increase of the dielectric constant k and a large hysteresis after annealing at 450 °C. The hysteresis is believed to be associated with mobile hydrogen effusion from the a-SiC:H film, and it is not seen after a 650 °C anneal. From I–V data the maximum rectification ratio is observed after annealing at 450 °C. Variable-range hopping (VRH) conduction at the Fermi level is found to dominate the forward current of the as-deposited structure. After annealing at 450 °C the forward current can be described by space-charge limited (SCL) mechanisms with trapping at shallow levels with energy of about 0.12 eV. After annealing at 650 °C the process of VRH conduction appears again, but the density of hopping sites is much higher than in the as-grown sample. From admittance spectra, the energy position of respective traps in a-SiC:H is at (E_V + 0.45) eV for as-deposited material and it decreases slightly after vacuum annealing. On the basis of these results, an energy band diagram of the a-Si_1 ? xC_x:H/p-Si structure annealed at 450 °C is proposed.     

Enhancement of photoluminescence in SiCxNy nanoparticle films by addition of a Ni buffer layer

This work reports the effect of the presence of a Ni buffer layer on the photoluminescence (PL) of SiC_xN_y nanoparticle films prepared by RF plasma magnetron sputtering process in a reactive N₂ + Ar + H₂ gas mixture. An introduction of a Ni buffer of 80 nm or thicker remarkably improves the PL of the films. Annealing in a temperature range of 400–1100 °C is found to significantly affect the PL intensity. Optimal PL is achievable at 600 °C. X-ray photoelectron and Fourier-transform infrared spectroscopy suggest that the strong PL is directly related to the composition of the SiC_xN_y nanoparticle and the concentration of Si–O, and Si–N bonds. The results are relevant to the development of wide bandgap optoelectronic devices.     

Nanocrystalline silicon TFT process using silane diluted in argon–hydrogen mixtures

We have investigated the effect of Ar dilution on the deposition process of intrinsic nc-Si:H (hydrogenated nanocrystalline silicon) thin films used as active layers of top-gate TFTs, in order to improve the TFTs performances. The nc-Si:H films were deposited by plasma enhanced chemical vapor deposition (PECVD) at low temperature (165 °C) and the related TFTs were fabricated with a maximum process temperature of 200 °C. During the nc-Si:H films deposition, the SiH₄ fraction and the total flow of the diluting gases Ar + H₂ mixture was kept constant, H₂ being substituted by Ar. We have pointed out the active role played by the metastable states of excited Ar atoms in both the dissociation of SiH₄ and H₂ by quenching reactions in the plasma. The role of the atomic hydrogen during the film deposition seems to be promoted by the addition of argon into the discharge, leading to an increase of the deposition rate by a factor of about three and an enhancement of the crystalline quality of the nc-Si:H films. This effect is maximized when the Ar fraction in the Ar + H₂ gases mixture reaches 50%. The evolution with Ar addition of the carriers mobility of the related TFTs is closely connected to the evolution of the crystalline fraction of the intrinsic nc-Si:H film. Mobilities values as high as 8 cm² V^?1 s^?1 are obtained at the Ar fraction of 50%. For higher Ar fractions, the fall of the mobility comes with a degradation of the I_D–V_G transfer characteristics of the processed TFTs due to a degradation of the nc-Si:H films quality. OES measurements show that the evolution of the H_α intensity is closely connected to the evolution of the deposition rate, intrinsic films crystalline fraction and TFTs mobility, providing an interesting tool to monitor the TFTs performances.     

Stability and phase changes in thin layers of rare-earth metals/iron and other binary compounds

The structure, thermal stability and phase transformations in thin Gd–Fe films have been studied. The films were obtained by means of thermal evaporation in vacuum. At room temperature of substrates (T_s) amorphous films were formed, at T_s = 300–500 K – amorphous–crystal condensates, and at T_s > 500K – polycrystalline films. The crystal structure of condensates was determined at various temperatures and crystallization of amorphous films was found to have a heterogeneous character. During crystallization of Gd₂Fe₁₇ amorphous films, formation of two phases, viz. Gd₆Fe₂₃ and a-Fe was observed. In the films obtained at substrates temperature > 500K, the presence of three phases was established: a hexagonal phase Gd₂Fe₁₇ of the Th₂Ni₁₇-type structure, a rhombohedral phase Gd₂Fe₁₇ of the Th₂Zn₁₇-type structure and a hexagonal phase GdFe₅ of the CaCu₅-type structure. GdFe₂ films had a face-centered cubic structure, expected in bulk GdFe₂.     

Structure formation in Gd–Fe thin films

The structure, thermal stability and kinetics of phase transformations were explored for films of Gd₂Fe₁₇ compounds. The films were obtained by means of thermal evaporation in vacuum. Amorphous films were found to form at room temperature of substrates, amorphous-crystal condensates at T_s = 300–500 K, and polycrystalline films at T_s > 500 K. The crystal structure of condensates was determined at various temperatures and crystallization of amorphous films was found to be heterogeneous in character. Two phases, Gd₆Fe₂₃ and a-Fe, were observed in polycrystalline films, while three phases were found to exist in the films obtained at substrate temperatures >500 K: a hexagonal Gd₂Fe₁₇ phase of the Th₂Ni₁₇ structural type, a rhombohedral Gd₂Fe₁₇ phase of the Th₂Zn₁₇ structural type and a hexagonal GdFe₅ phase of the CaCu₅ structural type.     

GeO2 based high k dielectric material synthesized by sol–gel process

Recently, there has been lot of research on new high dielectric constant (high k) materials for use in future generations of ultra-large scale integrated circuits (ULSI). There are number of requirements for the new high k materials, such as high dielectric constant, thermal stability (400 °C or higher), high mechanical strength, and good adhesion to neighboring layers. Keeping in view the properties required for the replacement of existing SiO₂ dielectrics, new high k dielectric material based on GeO₂ has been synthesized. Polycrystalline GeO₂ thin films have been deposited by simple, and cost effective sol–gel spin coating process. The obtained xerogel films of germanium oxide have been annealed at 400 °C, 600 °C and 800 °C for 3 h in argon atmosphere. Elemental composition, morphology, and phase analysis have been measured by employing X-ray photoelectron spectroscopy, scanning electron microscopy, and X-ray diffraction techniques, respectively. The formation of the hexagonal GeO₂ phase at and above 400 °C has been reported. The composition of the annealed films have been measured and found to be 68 at.% of O, 32 at.% of Ge for GeO₂, which are close to the stoichiometry of the GeO₂.     

Electrical properties of annealed a-SiC:H thin films

In the present work the dependence of electrical properties of a-SiC:H thin films on annealing temperature, T_a, has been extensively studied. From the measurements of dark dc electrical conductivity, σ_D, in the high temperature range (from 283 up to 493 K), was found that the conductivity activation energy, E_a, is invariant for T_a ⩽ 673 K and equal to 0.64 eV, whereas for T_a from 673 up to 873 K, E_a increases at about 0.2 eV reaching to a maximum value 0.85 eV at T_a = 873 K, suggesting the optimum material quality. This behavior of E_a as a function of T_a is mainly attributed to relaxation of the strain in the amorphous network, which is possibly combined with weak hydrogen emission for temperatures up to 873 K. For further increase of T_a (>873 K) the phenomenon of hydrogen emission, causes rapid decrease of E_a down to 0.24 eV at T_a = 998 K, deteriorating the material quality. These results are also supported by the measurements of dark dc electrical conductivity in the low temperature range (from 133 up to 283 K), where the dependence of the density of gap states at the Fermi level, N(E_F), on annealing temperature presents the minimum value at T_a = 873 K. The Meyer–Nelder rule was found to hold for the a-SiC:H thin films for annealing temperatures up to 873 K. Finally, the dependence of dark dc electrical conductivity at room temperature, σ_DRT, on T_a showed to reflect directly the dependence of E_a on T_a.     

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.     

Low-temperature growth of nanocrystalline silicon films prepared by RF magnetron sputtering: Structural and optical studies

In order to contribute to the understanding of the optoelectronics properties of hydrogenated nanocrystalline silicon films, a detailed study has been conducted. Structural analysis (infrared absorption and Raman scattering spectroscopy), combined with optical measurements spectroscopy (optical transmission, photothermal deflection spectroscopy and photoconductivity) were used to characterize the films. The samples were elaborated by radio-frequency magnetron sputtering of crystalline silicon target, under a hydrogen (70%) and Argon (30%) gas mixture, at three different total pressures (2, 3 and 4 Pa) and varying substrate temperature (100, 150 and 200 °C). The results clearly indicate that the films deposited at 2 Pa are amorphous, while for 3 and 4 Pa nanocrystalline structures are observed. These results are discussed in the framework of the existing models.     

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.     

Nano-composite soda lime silicate glass prepared using silver ion exchange

Commercial soda lime silicate glasses have been subjected to ion exchange at different temperatures ranging from 320 to 500 °C in a molten mixture of AgNO₃ and NaNO₃ with molar ratio of 10:90, 02:98 and 50:50 for different time periods ranging from 40 to 180 min. Optical and structural properties of the ion exchanged glass are measured using UV–Vis–NIR absorption spectroscopy, Fourier transform infrared (FTIR) spectroscopy, fluorescence spectroscopy and transmission electron microscopy (TEM). Signature of silver nanoparticle formation is obtained from the UV–Vis–NIR spectra, which shows a peak at 425 nm due to surface plasmon resonance (SPR). Replacement of Na⁺ ions by Ag⁺ ions is inferred from FTIR spectra. Fluorescence spectra reveal the formation of Ag⁰ atoms from Ag⁺ ions at higher temperatures. TEM image shows the silver nanoparticles of average size 3.75 nm. At exchange temperature of 500 °C Ag nanoparticles are formed without post-exchange annealing treatment.     

Transition from amorphous semiconductor to amorphous insulator in hydrogenated carbon–germanium films investigated by IR spectroscopy

Thin a-Ge_XC_1?X:H plasma polymerized films, depending on deposition conditions, can be produced in two very different structures, namely amorphous semiconductor and amorphous insulator. The transition from amorphous insulator to amorphous semiconductor is related to the formation of germanium nanoclusters due to ions bombarding the surface of the growing material. This paper concentrates on investigations of the transition by means of IR spectroscopy. To this end a quantitative analysis of IR spectra obtained for thin films deposited on silicon substrate has been described and used for estimation of hydrogen atom concentration and bonding in the investigated material. It was found that the probability that a given H atom is bonded to a germanium or to a carbon atom is almost the same. This conclusion is true both for a-S and a-I films. The average concentration of hydrogen in the investigated material was found to be about 2.4–3.4 × 10²² cm^?2 which means that there are two times more atoms of the carbon family than hydrogen atoms in the film structure.     

Microstructure and properties of spark plasma sintered Fe–Cr–Mo–Y–B–C bulk metallic glass

Fabrication of Fe-based amorphous alloy using spark plasma sintering (SPS) process has been reported. Fully amorphous compacts with ～95% relative density were successfully sintered at temperature about 100 °C lower than glass transition temperature (T_g: 575 °C). Formation of crystalline Fe₂₃(C, B)₆ phases within near-fully dense (～99%) amorphous matrix is observed at sintering temperatures (>550 °C) close to glass transition temperature. Microstructure evolution in sintered compacts indicated that density, degree of crystallinity, and mechanical properties can be effectively controlled by optimizing SPS parameters.     

Crystal growth kinetics in cordierite and diopside glasses in wide temperature ranges

We measured and collected literature data for the crystal growth rate, u(T), of μ-cordierite (2MgO · 2Al₂O₃ · 5SiO₂) and diopside (CaO · MgO · 2SiO₂) in their isochemical glass forming melts. The data cover exceptionally wide temperature ranges, i.e. 800–1350 °C for cordierite and 750–1378 °C for diopside. The maximum of u(T) occurs at about 1250 °C for both systems. A smooth shoulder is observed around 970 °C for μ-cordierite. Based on measured and collected viscosity data, we fitted u(T) using standard crystal growth models. For diopside, the experimental u(T) fits well to the 2D surface nucleation model and also to the screw dislocation growth mechanism. However, the screw dislocation model yields parameters of more significant physical meaning. For cordierite, these two models also describe the experimental growth rates. However, the best fittings of u(T) including the observed shoulder, were attained for a combined mechanism, assuming that the melt/crystal interface growing from screw dislocations is additionally roughened by superimposed 2D surface nucleation at large undercoolings, starting at a temperature around the shoulder. The good fittings indicate that viscosity can be used to assess the transport mechanism that determines crystal growth in these two systems, from the melting point T_m down to about T_g, with no sign of a breakdown of the Stokes–Einstein/Eyring equation.