X-ray photoelectron spectroscopy studies on the bonding properties of oxygenated amorphous carbon nitride thin films synthesized by pulsed laser deposition at different substrate temperatures

Oxygenated amorphous carbon nitride thin films (a-CN_xO_y) were deposited by pulsed laser deposition of camphoric carbon (CC) target at various substrate temperatures (ST). The influence of ST on the bonding properties of a-CN_xO_y films was investigated. The nitrogen to carbon (N/C) atomic ratio and oxygen to carbon (O/C) atomic ratio, bonding state and microstructure of the deposited a-CN_xO_y films were characterized by X-ray photoelectron spectroscopy (XPS) and been confirmed using standard measurement techniques. The bonding states between the C and N, and C and O in the deposited films are found significantly influenced by the ST during deposition process. The N/C and O/C atomic ratio of the a-CN_xO_y films reached the maximum value at 400 °C. The XPS C 1s shows the bonding state of a-CN_xO_y films changes from diamond-like tetrahedral (sp³) carbon and carbon (C–C) bonding to graphite-like trihedral (sp²) CC bonding with the increase of ST. While, the XPS N 1s shows the sp³ C–N bonds increases with higher rates compared with sp² CN bonds up to 400 °C, after which it decreases with higher ST. The C–N bonding of C–N, CN and CN were observed in the deposited a-CN_xO_y films.     

High diffusion length silicon germanium alloy thin films deposited by pulsed rf PECVD method

Hydrogenated amorphous silicon germanium (a-Si_1?xGe_x:H) alloy thin films were deposited in a rf (13.56 MHz) powered plasma CVD system from a mixture of silane, germane and hydrogen. The rf power was pulsed at a frequency of 1356 Hz with the duty cycle (Q) ranging from 50% to 100%. The Ge content in the films, found in the range 40–45%, was deduced from Raman spectra. The band gaps E_g of the films were in between 1.44 and 1.48 eV. We find a good correlation between the ambipolar diffusion length (L_d) and the microstructure factor ($R^1$) for different duty cycles. At Q = 75% the $R^1$ value is lowest (0.14) which correlates well with the maximum value of L_d (100 nm), the highest L_d value reported for a-Si_1?xGe_x:H films with E_g = 1.44 eV. It was also found to be very stable under light soaking. Powder incorporation within the films was also studied. Quality of the films is determined by two opposing effects viz. size of the powders incorporated into the films from the plasma and the bombardment of energetic ions and neutrals. Best transport properties were found at an optimum duty cycle of 75%.     

Amorphous and nanocrystalline silicon made by varying deposition pressure in PECVD process

Silicon thin films are deposited using plasma enhanced chemical vapor deposition (PECVD) of silane, argon, hydrogen mixture at various pressures in the range of 2–8 Torr. Raman scattering shows these to be amorphous in the pressure range 6–8 Torr, and nanocrystalline in the range 2–4 Torr. The volume fraction of nanocrystals is estimated by fitting the Raman data to three peaks and is found to be ～75% for the films deposited at low pressure, density of states of these films was measured. It is observed that the electrical conduction in these films depends on the crystalline volume fraction (ρ), estimated from the laser Raman Spectroscopy. Temperature dependence electrical conductivity shows that at lower temperatures thermionic emission dominates for the films with lower ρ, whereas, hopping is the main conduction mechanism for the films having high ρ. The density of states is estimated from the space charge limited currents (SCLC) observed at high fields. Photoconductivity at room temperature is also measured. The amorphous films are found to be more photosensitive than the nanocrystalline one. In the context of these findings, changes in the properties of silicon from amorphous to nanocrystalline are described.     

Surface enhanced Raman scattering in an amorphous matrix for Raman amplification

In order to improve the efficiency of Raman Amplifiers, the Surface Enhanced Raman Scattering (SERS) effect of an amorphous matrix of TiO₂ was studied. First, optimisation of the amorphous layer quality was performed by depositing thin films on glass substrates at different temperatures. Then, thin films of amorphous TiO₂ were deposited on silicon commercial gold SERS substrates (Klarite®) by a dip-coating process. The SERS effect was demonstrated by the great difference of Raman intensities of the amorphous TiO₂ matrix dip-coated on active and inactive parts of Klarite® substrate under 633 nm and 780 nm laser excitations in the tail of the Surface Plasmon Resonance band of gold nanoparticles.     

Crystallization of bismuth titanate and bismuth silicate grown as thin films by atomic layer deposition

Bismuth silicate and bismuth titanate thin films were deposited by atomic layer deposition (ALD). A novel approach with pulsing of two Bi-precursors was studied to control the Si/Bi atomic ratio in bismuth silicate thin films. The crystallization of compounds formed in the Bi₂O₃–SiO₂ and Bi₂O₃–TiO₂ systems was investigated. Control of the stoichiometry of Bi–Si–O thin films was studied when deposited on Si(1 0 0) and crystallization was studied for films on sapphire and MgO-, ZrO₂- and YSZ-buffered Si(1 0 0). The Bi–Ti–O thin films were deposited on Si(1 0 0) substrate. Both Bi–Si–O and Bi–Ti–O thin films were amorphous after deposition. Highly a-axis oriented Bi₂SiO₅ thin films were obtained when the Bi–Si–O thin films deposited on MgO-buffered Si(1 0 0) were annealed at 800 °C in nitrogen. The full-width half-maximum values for 200 peak were also studied. An excess of bismuth was found to improve the crystallization of Bi–Ti–O thin films and the best crystallinity was observed with Ti/Bi atomic ratio of 0.28 for films annealed at nitrogen at 1000 °C. Roughness of the thin films as well as the concentration depth distribution were also examined.     

Structure and properties of hydrogenated amorphous silicon carbide thin films deposited by PECVD

a-Si_1?xC_x:H films are deposited by RF plasma enhanced chemical vapor deposition (PECVD) at different RF powers with hydrogen-diluted silane and methane mixture as reactive gases. The structure and properties of the thin films are measured by infrared spectroscope (IR), Raman scattering spectroscope and ultra violet–visible transmission spectroscope (UV–vis), respectively. Results show that the optical band gap of the a-Si_1?xC_x:H thin films increases with increasing Si–C bond fraction. It can be easily controlled through controlling Si–C bond formed by modulating deposition power. At low deposition power, the bond configuration of the a-Si_1?xC_x:H thin film is more disordered owing to the distinct different bond lengths and bond strengths between Si and C atoms. At a too high deposition power, it becomes still high disordered due to dangling bonds appearing in the a-Si_1?xC_x:H thin film. The low disordered bond configuration appears in the thin film deposited with moderate deposition power density of about 2.5 W/cm².     

Device grade hydrogenated polymorphous silicon deposited at high rates

Hydrogenated polymorphous silicon (pm-Si:H) thin films have been deposited by plasma-enhanced chemical vapor deposition at high rate (8–10 Å/s), and a set of complementary techniques have been used to study transport, localized state distribution, and optical properties of these films, as well as the stability of these properties during light-soaking. We demonstrate that these high deposition rate pm-Si:H films have outstanding electronic properties, with, for example, ambipolar diffusion length (L_d) values up to 290 nm, and density of states at the Fermi level well below 10¹⁵ cm^?3 eV^?1. Consistent with these material studies, results on pm-Si:H PIN modules show no dependence of their initial efficiency on the increase of the deposition rate from 1 to 10 Å/s. Although there is some degradation after light-soaking, the electronic quality of the films is better than for degraded standard hydrogenated amorphous silicon (values of L_d up to 200 nm). This result is reflected in the light-soaked device characteristics.     

Effect of deposition pressure on microstructure and properties of hydrogenated carbon nitride films prepared by DC-RF-PECVD

Hydrogenated carbon nitride (a-CN:H films) were deposited on n-type (1 0 0) silicon substrates making use of dual direct current radio frequency plasma enhanced chemical vapor deposition (DC-RF-PECVD), at working pressure of 2–20 Pa, using a mixed gas of CH₄ and N₂ as the source gas. The growth rate, composition, bonding structure of the deposited films were characterized by means of XPS and FTIR, and the mechanical properties of the deposited films were investigated by nano-indentation test. It was found that the parameters for the DC-RF-PECVD process had significant effects on the growth rate, structure and properties of the deposited films. The growth rate of the deposited films increased at first with increasing deposition pressure, then saturated with further increase of the deposition pressure. The N/C ratio inside the deposited films increased with increasing working pressure except that it was as much as 0.50 at a working pressure of 5.0 Pa. The nano-hardness of the films decreased with increasing deposition pressure. CN radicals were remarkably formed in the deposited films at higher pressures, and their contents are related to the nitrogen concentrations in the deposited films.     

Smooth titania nanotubes: Self-organization and stabilization of anatase phase

We present transmission electron microscopy and Raman scattering measurements showing that niobium inhibits the processes of nucleation and growth of anatase crystallites in the initial amorphous titania nanotubes and thus shifts the temperature of the complete amorphous-to-anatase phase transition to higher values up to 550 °C. Niobium dopants stabilize the anatase phase in titania nanotubes up to 650 °C. The size of anatase crystallites can reach 30–50 nm. Excess niobium atoms which are pulled off from the volume of anatase crystallite form polymeric or monomeric Ti–O–NbO groups at the interface area. Slight shift and broadening of E_g (144 cm^?1), A_1g (515 cm^?1) and E_g (630 cm^?1) modes in Raman spectra can be explained by niobium insertion into the anatase structure.     

PECVD a-Sic:H Young’s modulus obtained by MEMS resonant frequency

In this paper we study the Young’s modulus of PECVD obtained silicon rich (x > 0.5) a-Si_xC_1?x:H thin films through the study of the resonance frequency of free standing cantilevers. These structures are fabricated based on front side bulk micromachining of Si substrate and actuated thermally. In this approach, an alternating electric current passes through a photolithography patterned metallic film deposited on the cantilever, heating the structure by Joule effect and inducing vibrations on the cantilever. This method of actuation is independent of the separation between the structure and substrate, which is its main advantage, because it allows the actuation of cantilevers that are bent upwards or downwards, which is an aspect of particular importance in the characterization of PECVD materials for MEMS applications. The work is focused on low stress silicon rich amorphous hydrogenated silicon carbide films obtained by PECVD at low temperatures (320 °C). The measurements were carried out in groups of cantilevers with different length (between 550 and 200 μm) and utilizing a-SiC:H films obtained with three different compositions. The results show that the films exhibit modulus of elasticity in the range of 20–35 GPa, low residual stress (～90 GPa) and maintain excellent chemical inertness in KOH and HF solutions.     

Microstructures of high-growth-rate (up to 8.3 nm/s) microcrystalline silicon photovoltaic layers and their influence on the photovoltaic performance of thin-film solar cells

Microstructures of microcrystalline silicon (μc-Si) deposited at a high-growth-rate have been investigated in order to apply to the photovoltaic i-layer. μc-Si films were prepared by very-high-frequency (100 MHz) plasma-enhanced chemical vapor deposition at 180 °C. High growth rates of 3.3–8.3 nm/s have been achieved utilizing high deposition pressures up to 24 Torr and large input powers. Applying μc-Si to n–i–p junction solar cells, as the optimum result in this experimental series, a conversion efficiency of 6.30% (J_SC: 22.1 mA/cm², V_OC: 0.470 V, and FF: 60.7%) has been achieved employing the i-layer deposited at 8.1 nm/s. Raman scattering and X-ray diffraction measurements revealed the crystalline volume fraction of around 50% with the (2 2 0) crystallographic preferential orientation, respectively. The cross-sectional transmission electron microscope image shows densely columnar structure grown directly on the underlying n-layer. These structural features are basically in good agreement those of low-growth-rate μc-Si used for a high efficiency solar cell as previously reported, implying advantages of the use of high pressures with regard to providing the photovoltaic i-layers. Finally, the implication is discussed from the photovoltaic performance as a function of the crystalline volume fraction of i-layer, and current problems in improving the photovoltaic performance are extracted.     

Optical properties and structure of amorphous films Agx(As0.33S0.67−ySey)100−x

As₃₃S_67−ySe_y, where y = 0, 16.75, 33.5, 50.25 and 67, amorphous thin films were prepared by a vacuum thermal evaporation technique. The films with known silver concentrations and good optical quality were prepared by thermal vacuum evaporation of a silver film on the top of As₃₃S_100−ySe_y films with sequential step-by-step optically- and thermally-induced diffusion and dissolution (OIDD) of silver. The range of silver content was x = 0–25 at.%. The kinetics of OIDD of silver were measured optically by monitoring the change of thickness of the undoped part of the chalcogenide during broadband illumination. Compositions of the reaction products have been determined by scanning electron microscope with energy-dispersive X-ray microanalyser EDS. Optical properties $(T\text{,}n\text{,}{E}_{\text{g}}^{\text{opt}})$ of thin films were measured and/or calculated by the Swanepoel method [R. Swanepoel, J. Phys. E: Sci. Instrum. 16 (1983) 1214]. The refractive index increase with increasing silver and selenium concentration has been shown. The difference of the refractive index (Δn) between undoped and silver doped films was ∼0.4 and between As₃₃S₆₇ and As₃₃Se₆₇ was films ∼0.42. Non-linear indices of refraction were estimated according to Tichy’s formula [H. Ticha, L. Tichy, J. Optoel, Adv. Mat. 4 (2002) 381]. The values of non-linear refractive index grew with increasing silver and selenium content. The difference of optical bandgap, $\mathrm{\Delta }{E}_{\text{g}}^{\text{opt}}$, between undoped As₃₃S₆₇ and fully doped films with Ag and Se was ∼1 eV. Raman spectroscopy showed a decrease in S–S or Se–Se bonds with increasing silver content.     

The characteristics of solid phase crystallized (SPC) polycrystalline silicon thin film transistors employing amorphous silicon process

We investigated the electrical properties of polycrystalline silicon (poly-Si) thin film transistors (TFTs) employing field-enhanced solid phase crystallization (FESPC). An n+ amorphous silicon (n+ a-Si) layer was deposited to improve the contact resistance between the active Si and source/drain (S/D) metal instead of ion doping. By using C–V measurement method, we could explain the diffused phosphorous ions (P+ ions) on the channel surface caused a negatively shifted threshold voltage (V_TH) of ?7.81 V at a drain bias of 0.1 V, and stretched out a subthreshold swing (S) of 1.698 V/dec. This process was almost compatible with the widely used hydrogenated amorphous silicon (a-Si:H) TFT fabrication process and also offers a better uniformity when compared to the conventional laser-crystallized poly-Si TFT process because of non-laser crystallization.     

Influence of the nitrogen flow rate on the order and structure of PECVD boron nitride thin films

Three sets of boron nitride (BN) thin films are deposited with different N₂/B₂H₆ flow ratios (r = 4, 10 and 25) by plasma enhanced chemical vapor deposition (PECVD). The variations of physical properties in different deposition sets are analyzed by optical (XPS, FTIR, UV–visible spectroscopies), mechanical and electrical measurements. The films are considered to be deposited in a turbostratic phase (t-BN). Evolution of bonding configurations with increasing r is discussed. Relatively higher nitrogen flow rate in the source gas mixture results in lower deposition rates, whereas more ordered films, which tend to reach a unique virtual crystal of band gap 5.93 eV, are formed. Anisotropy in the film structure and film inhomogeneity along the PECVD electrode radial direction are investigated.     

Effect of illumination on hydrogenated amorphous silicon thin films doped with chalcogens

Hydrogenated amorphous silicon thin films doped with chalcogens (Se or S) were prepared by the decomposition of silane (SiH₄) and H₂Se/H₂S gas mixtures in an RF plasma glow discharge on 7059 corning glass at a substrate temperature 230 °C. The illumination measurements were performed on these samples as a function of doping concentration, temperature and optical density. The activation energy varied with doping concentration and is higher in Se-doped than S-doped a-Si:H thin films due to a low defect density. From intensity versus photoconductivity data, it is observed that the addition of Se and S changes the recombination mechanism from monomolecular at low doping concentration films to bimolecular at higher doping levels. The photosensitivity (σ_ph/σ_d) of a-Si, Se:H thin films decreases as the gas ratio H₂Se/SiH₄ increased from 10^?4 to 10^?1, while the photosensitivity of a-Si, S:H thin films increases as the gas ratio H₂S/SiH₄ increased from 6.8 × 10^?7 to 1.0×10^?4.     

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.     

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).     

Hydrogenated amorphous and nanocrystalline silicon solar cells deposited by HWCVD and RF-PECVD on plastic substrates at 150 °C

In this work we present a study of the structural, optoelectronic and transport properties of a series of Si films deposited in a parameter region (namely hydrogen dilution) corresponding to a transition from amorphous-to-nanocrystalline silicon by hot-wire (HW) and radio-frequency plasma enhanced chemical vapor deposition (RF) on plastic substrates at 150 °C. To achieve a higher deposition rate of Si films by RF we used a relatively high power density (350 mW/cm²) and deposition pressure (1.5 Torr). For certain hydrogen dilution values, these deposition conditions can lead to the formation of Si crystals in the silane plasma and to a growth of polymorphous silicon film. This material has improved carrier transport properties (ambipolar diffusion length = 220 nm) and very high photosensitivity (>5 × 10⁶). The best HW amorphous silicon films exhibited lower photosensitivity (7 × 10⁴) and an ambipolar diffusion length of only 100 nm. For solar cell fabrication, we optimized the RF deposition conditions to produce very thin amorphous and nanocrystalline phosphorous and boron doped silicon layers. Our best n–i–p solar cell, with a polymorphous Si intrinsic layer deposited on plastic, has an efficiency of 5.5%, FF = 52.5%, V_OC = 920 mV, J_SC = 11.6 mA/cm². For solar cells with a nanocrystalline Si active layer deposited on glass the following results were achieved: efficiency = 3.4%, FF = 43.5%, V_OC = 460 mV, J_SC = 17.2 mA/cm²; and on plastic substrate: efficiency = 2.2%, FF = 32.7%, V_OC = 397 mV, J_SC = 17.2 mA/cm².     

Characteristics of sputtered amorphous carbon films prepared by a closed-field unbalanced magnetron sputtering method

We discuss the tribological performance of sputtered amorphous carbon (a-C) films deposited by closed-field unbalanced magnetron (CFUBM) sputtering with a graphite target using a mixture of helium (He) and argon (Ar) as sputtering gases. We investigated the effects of the graphite target power density on the micro-structural and physical properties. In the Raman spectra, the G-peak position moved to the higher wavenumbers. The I_D/I_G ratio increased with the increase of target power density in the fixed DC bias voltage. This was the result of the structural change in the a-C film that resulted with the increase in sp² bonding fraction. Also, the maximum hardness of the a-C film was 23 GPa, the friction coefficient was 0.1, and the critical load was 25.9 N on the Si wafer. In addition, the compressive residual stress of the film increased a little with increasing target power density. Consequently, the various properties of a-C films, with an increase of the target power density, were associated with the increase of cross-linked sp² bonding fraction and the cluster size. The tribological properties of a-C film showed clear dependence on the energy of ion bombardment with the increase of plasma density during film growth.     

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.