Boron-doped nanocrystalline silicon thin films for solar cells

This article reports on the structural, electronic, and optical properties of boron-doped hydrogenated nanocrystalline silicon (nc-Si:H) thin films. The films were deposited by plasma-enhanced chemical vapour deposition (PECVD) at a substrate temperature of 150 °C. Crystalline volume fraction and dark conductivity of the films were determined as a function of trimethylboron-to-silane flow ratio. Optical constants of doped and undoped nc-Si:H were obtained from transmission and reflection spectra. By employing p⁺ nc-Si:H as a window layer combined with a p′ a-SiC buffer layer, a-Si:H-based p-p′-i-n solar cells on ZnO:Al-coated glass substrates were fabricated. Device characteristics were obtained from current-voltage and spectral-response measurements.     

Investigation on preparation and physical properties of nanocrystalline Si/SiO2 superlattices for Si-based light-emitting devices

Structures containing silicon nanocrystals (nc-Si) are very promising for Si-based light-emitting devices. Using a technology compatible with that of silicon, a broader wavelength range of the emitted photoluminescence (PL) was obtained with nc-Si/SiO₂ multilayer structures. The main characteristic of these structures is that both layers are light emitters. In this study we report results on a series of nc-Si/SiO₂ multilayer periods deposited on 200 nm thermal oxide SiO₂/Si substrate. Each period contains around 10 nm silicon thin films obtained by low-pressure chemical vapour deposition at T=625°C and 100 nmSiO₂ obtained by atmospheric pressure chemical vapour deposition T=400°C. Optical and microstructural properties of the multilayer structures have been studied by spectroscopic ellipsometry (using the Bruggemann effective medium approximation model for multilayer and multicomponent films), FTIR and UV–visible reflectance spectroscopy. IR spectroscopy revealed the presence of SiO_x structural entities in each nc-Si/SiO₂ interface. Investigation of the PL spectra (using continuous wave-CW 325 nm and pulsed 266 nm laser excitation) has shown several peaks at 1.7, 2, 2.3, 2.7, 3.2 and 3.7 eV, associated with the PL centres in SiO₂, nc-Si and Si–SiO₂ interface. Their contribution to the PL spectra depends on the number of layers in the stack.     

Modulating microstructure and optical properties of hydrogenated nanocrystalline silicon photovoltaic materials prepared under hydrogen diluted silane PECVD by various DC bias

Hydrogenated nanocrystalline silicon (nc-Si:H) thin films were fabricated by plasma enhanced chemical vapor deposition under the various negative substrate bias voltages with hydrogen as a diluent of silane. The microstructure and optical properties of nc-Si:H thin films were studied by Raman scattering spectroscopy, X-ray diffraction (XRD), transmission electron microscopy, and optical transmission spectroscopy. Raman spectra and XRD pattern reveal that applying negative bias voltages at the moderate level favors the enhancement of crystalline volume fraction, increase of crystallite sizes and decrease of residual stress. We also demonstrated that the negative direct current bias can be used to modulate the volume fraction of voids, refractive index, absorption coefficient, compactness and ordered degree of nc-Si:H films. It is found that the film deposited at −80 V shows not only high crystallinity, size of crystallite, and static index n₀ but also low residual stress and volume fraction of voids. Furthermore, the microstructural evolution mechanism of nc-Si:H thin films prepared at different bias voltages is tentatively explored.     

An influence of deposition temperature on structural,optical and electrical properties of sprayed ZnO thin films of identical thickness

Nanocrystalline ZnO thin films were deposited at different temperatures (T_s = 325 °C–500 °C) by intermittent spray pyrolysis technique. The thickness (300 ± 10 nm) independent effect of T_s on physical properties was explored. X-Ray diffraction analysis revealed the growth of wurtzite type polycrystalline ZnO films with dominant c-axis orientation along [002] direction. The crystallite size increased (31 nm–60 nm) and optical band-gap energy decreased (3.272 eV–3.242 eV) due to rise in T_s. Scanning electron microscopic analysis of films deposited at 450 °C confirmed uniform growth of vertically aligned ZnO nanorods. The films deposited at higher T_s demonstrated increased hydrophobic behavior. These films exhibited high transmittance (>91%), low dark resistivity (～10^?2 Ω-cm), superior figure of merit (～10^?3 Ω^?1) and low sheet resistance (～10² Ω/□). The charge carrier concentration (η -/cm³) and mobility (μ – cm²V^?1s^?1) are primarily governed by crystallinity, grain boundary passivation and oxygen desorption effects.     

Influence of deposition pressure on structural, optical and electrical properties of nc-Si:H films deposited by HW-CVD

Hydrogenated nanocrystalline silicon (nc-Si:H) thin films were deposited using HW-CVD technique at various deposition pressures. Characterisation of these films from Raman spectroscopy revealed that nc-Si:H thin films consist of a mixture of two phases, crystalline phase and amorphous phase containing small Si crystals embedded therein. We observed increase in crystallinity in the films with increase in deposition pressure whereas the size of Si nanocrystals was found ∼2 nm over the entire range of deposition pressure studied. The FTIR spectroscopic analysis showed that with increasing deposition pressure the predominant hydrogen bonding in the films shifts from, Si-H to Si-H₂ and (Si-H₂)_n complexes and the hydrogen content in the films was found in the range 6.2-9.3 at% over the entire range of deposition pressure studied. The photo and dark conductivities results also indicate that the films deposited with increasing deposition pressure get structurally modified. It has been found that the optical energy gap range was between 1.72 and 2.1 eV with static refractive index between 2.85 and 3.24. From the present study it has been concluded that the deposition pressure is a key process parameter to induce the crystallinity in the Si:H thin films using HW-CVD.     

Microstructural properties of plasma-enhanced chemical vapor deposited WNx films using WF6–H2–N2 precursor system

A WF₆–H₂–N₂ precursor system was used for plasma-enhanced chemical vapor deposition (PECVD) of WN_x films. We examined the microstructural changes of the WN_x films depending on N₂/H₂ flow-rate ratio and post-annealing (600–800 °C for 1 h). As the N₂/H₂ flow rate was increased from 0 to 1.5, as-deposited WN_x films exhibited various different crystalline states, such as nanocrystalline and/or amorphous structure comprising W, WN, and W₂N phases, a fine W₂N granular structure embedded in an amorphous matrix, and a crystalline structure of β-W₂N phase. After post-annealing above 600 °C, crystalline recovery with phase separation to β-W₂N and α-W was observed from the WN_x films deposited at an optimized deposition condition (flow-rate ratio = 0.25). From this PECVD method, an excellent step coverage of ∼90% was obtained from the WN_x films at a contact diameter of 0.4 μm and an aspect ratio of 3.5.     

Cerium (III) doping effects on optical and thermal properties of PVA films

Cerium chloride (CeCl₃) doped polyvinyl alcohol (PVA) films were prepared by casting technique. The effect of CeCl₃ concentrations on the structural, optical and thermal properties of the PVA films was studied by X-ray diffraction (XRD), FT-IR, UV-visible, transmittance (T), reflectance (R), differential scanning calorimetry (DSC) and thermogravimetry (TG). Both of the XRD and the DSC results affirm the increase in amorphousity. Absorption spectra of the doped films have shown an absorption band at 260 nm assigned to the trivalent state of cerium ions. Absorption, transmittance and reflectance spectra were used for the determination of the optical constants. The results indicate that the optical band gap (E_g) was derived from Tauc's extrapolation and decreases with the cerium content. The refractive index increases with monotonic behavior as the cerium content increases. The dispersion of the refractive index is discussed in terms of the single-oscillator Wemple–DiDomernico model for obtaining the dispersion parameters. The obtained optical parameters were found to be strongly affected by CeCl₃ dopant. Thermal analysis showed that the thermal parameters of PVA are enhanced by CeCl₃. The dependence of the activation energy of the decomposition temperature on doping level was estimated.     

Morphological and optical properties changes in nanocrystalline Si (nc-Si) deposited on porous aluminum nanostructures by plasma enhanced chemical vapor deposition for Solar energy applications

Photoluminescence (PL) spectroscopy was used to determine the electrical band gap of nanocrystalline silicon (nc-Si) deposited by plasma enhancement chemical vapor deposition (PECVD) on porous alumina structure by fitting the experimental spectra using a model based on the quantum confinement of electrons in Si nanocrystallites having spherical and cylindrical forms. This model permits to correlate the PL spectra to the microstructure of the porous aluminum silicon layer (PASL) structure. The microstructure of aluminum surface layer and nc-Si films was systematically studied by atomic force microscopy (AFM), transmission electron microscopy (TEM), Raman spectroscopy and X-ray diffraction (XRD). It was found that the structure of the nanocrystalline silicon layer (NSL) is dependent of the porosity (void) of the porous alumina layer (PAL) substrate. This structure was performed in two steps, namely the PAL substrate was prepared using sulfuric acid solution attack on an Al foil and then the silicon was deposited by plasma enhanced chemical vapor deposition (PECVD) on it. The optical constants (n and k as a function of wavelength) of the deposited films were obtained using variable angle spectroscopic ellipsometry (SE) in the UV-vis-NIR regions. The SE spectrum of the porous aluminum silicon layer (PASL) was modeled as a mixture of void, crystalline silicon and aluminum using the Cauchy model approximation. The specific surface area (SSA) was estimated and was found to decrease linearly when porosity increases. Based on this full characterization, it is demonstrated that the optical characteristics of the films are directly correlated to their micro-structural properties.     

Structural and magnetic properties of thin epitaxial Fe films on (1 1 0) GaAs prepared by metalorganic chemical vapor deposition

Iron films have been grown on (1 1 0) GaAs substrates by atmospheric pressure metalorganic chemical vapor deposition at substrate temperatures (T_s) between 135°C and 400°C. X-ray diffraction (XRD) analysis showed that the Fe films grown at T_s between 200°C and 330°C were single crystals. Amorphous films were observed at T_s below 200°C and it was not possible to deposit films at T_s above 330°C. The full-width at half-maximum of the rocking curves showed that crystalline qualities were improved at T_s above 270°C. Single crystalline Fe films grown at different substrate temperature showed different structural behaviors in XRD measurements. Iron films grown at T_s between 200°C and 300°C showed bulk α-Fe like behavior regardless of film thickness (100–6400 Å). Meanwhile, Fe films grown at 330°C (144 and 300 Å) showed a biaxially compressed strain between substrate and epilayer, resulting in an expanded inter-planar spacing along the growth direction. Magnetization measurements showed that Fe films (>200 Å) grown at 280°C and 330°C were ferromagnetic with the in-plane easy axis along the [1 1 0] direction. For the thinner Fe films (⩽200 Å) regardless of growth temperature, square loops along the [1 0 0] easy axis were very weak and broad.     

Effect of calcination atmosphere on photoluminescence properties of nanocrystalline ZrO2 thin films prepared by sol–gel dip coating method

Highly transparent and homogeneous nanocrystalline ZrO₂ thin films were prepared by the sol–gel dip coating method. The X-ray diffraction (XRD) pattern of ZrO₂ thin films calcined in air, O₂ or N₂ shows the formation of tetragonal phase with varying crystallite size. X-ray photoelectron spectroscopy (XPS) gives Zr 3d and O 1s spectra of thin film annealed in air, which reveal zirconium suboxide component (ZrO_x, 0<x<2), Zr–O bond and surface defects. An average transmittance greater than 85% (in UV–vis region) is observed in all calcined samples. Photoluminescence (PL) reveals an intense emission peak at 379 nm and weak peaks at 294, 586 and 754 nm for ZrO₂ film calcined in air. An enhancement of PL intensity and red-shift is observed in films calcined in O₂ and N₂ atmosphere. This is due to the reconstruction of zirconium nanocrystal interfaces and vacancies, which help passivate the non-radiative defects. The oxygen deficient defect, which is due to the distorted Zr–O bond, is suggested to be responsible for photoluminescence. The defect states in the nanocrystalline zirconia thin films play an important role in the energy transfer process. The luminescence defects in the film make it suitable for gas sensors development and tunable lasers.     

Optical properties of nanostructured InSe thin films

Thin films of InSe were prepared by thermal evaporation technique. The as-deposited films have nano-scale crystalline nature and the annealing enhanced the degree of crystallinity. The optical properties of nanocrystalline thin films of InSe were studied using spectrophotometric measurements of transmittance, T, and reflectance, R, at normal incidence of light in the wavelength range 200–2500 nm. The optical constants (refractive index, n, and absorption index, k) were calculated using a computer program based on Murmann's exact equations. The calculated optical constants are independent of the film thickness. The optical dispersion parameters have been analysed by single oscillator model. The type of transition in InSe films is indirect allowed with a value of energy gap equals to 1.10 eV, which increased to 1.23 eV upon annealing.     

椭偏透射法测量氢化非晶硅薄膜厚度和光学参数

针对多角度椭偏测量透明基片上薄膜厚度和光学参数时基片背面非相干反射光的影响问题,报道了利用椭偏透射谱测量等离子增强化学气相沉积法(PECVD)制备的a-Si:H薄膜厚度和光学参数的方法,分析了基片温度T_s和辉光放电前气体温度T_g的影响.研究表明,用椭偏透射法测量的a-Si:H薄膜厚度值与扫描电镜(SEM)测得的值相当,推导得到的光学参数与其他研究者得到的结果一致.该方法可用于生长在透明基片上的其他非晶或多晶薄膜. 关键词： 椭偏测量 透射法 光学参数 氢化非晶硅薄膜     

Microwave synthesis of nitrogen doped Ti4O7 for photocatalytic applications

The nitrogen (N) doped Ti₄O₇ photocatalyst was prepared from urea as a nitrogen source by a microwave method. The resulting photocatalyst was characterized by X-ray diffraction (XRD), Field Emission Scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), UV–visible diffuse reflectance spectroscopy (UV–Vis DRS) and UV–vis spectroscopy (UV–Vis). 0.1 M N doped Ti₄O₇ photocatalyst exhibited methylene blue decomposition efficiency of 100% which was prepared by microwave treatment for above 30 min. Rate constant was found to be 0.028910 min⁻¹ in the first order kinetic.     

Characterization of CBD-CdSe1-ySy deposited at low-temperature for photovoltaic applications

We present the structural and optical characterization of cadmium selenide sulphur (CdSe_1-yS_y) deposited by chemical bath deposition (CBD) technique at low-temperature (20 ± 2 °C). The sulphur molar fraction is varied from 0 to 42.13%. The chemical stoichiometry is estimated by energy-dispersive X-ray spectroscopy (EDS). The CdSe_1-yS_y shows hexagonal wurtzite crystalline phase, which was found by X-ray diffraction (XRD) analysis and it was confirmed by Raman spectroscopy. The average grain size of the CdSe_1-yS_y films was ranged from 1.20 to 1.68 nm that was determined by Debye-Scherrer equation from W(002) direction and it was confirmed by high resolution transmission electron microscopy (HRTEM). This average grain size indicates a high quantum confinement because of it is smaller than the Bohr radii of CdS (2.8 nm) and CdSe (4.9 nm). Raman spectra show two dominant vibrational bands about 208 and 415 cm⁻¹ associated at CdSe-1LO-like and CdSe-2LO-like. By transmittance measurements at room temperature are found that the optical band gap energies vary from 1.86 to 2.16 eV in the range of investigated sulphur molar fraction. Room temperature photoluminescence shows radiative bands in the visible range and a dominant band in the UV range, approximately 3.0 eV, which can be associated with a radiative transition, bound exciton to donor impurity.     

Growth and characterization of polycrystalline Ge1−xCx by reactive pulsed laser deposition

Polycrystalline thin films of Ge-C were grown on Si (1 1 1) substrates by means of reactive pulsed laser deposition with methane pressure of 100 mTorr. Effect substrate temperature, T_s, on C incorporation to substitutional sites (x) in Ge_1−xC_x was investigated systematically by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyzes. The substrate temperatures were ranging from 250 to 400 °C. The substitutional C composition x in the films by XRD were estimated using the Vegard's linear law. The maximum value of x calculated by XRD was 0.032 for T_s of 350 °C. The position of the C 1s peak at 283.4 eV in the XPS spectrum confirmed the germanium-carbon alloys. XRD measurements indicated that x increased with T_s from 250 °C to 350 °C. At T_s = 400 °C, the estimation of x was lowered. However, the C content calculated by XPS analyzes increased with T_s being more these values than substitutional C composition x. XPS and XRD analyzes demonstrate that the remaining C atoms are incorporated to interstitial sites. The use of the T_s plays important roles in the incorporation of substitutional C and in restraining C-cluster formation in the reactive pulsed laser deposition growth of Ge-C/Si.     

Growth, microstructure and electrical properties of sputter-deposited hafnium oxide (HfO2) thin films grown using a HfO2 ceramic target

Hafnium oxide (HfO₂) thin films have been made by radio-frequency (rf) magnetron-sputtering onto Si(1 0 0) substrates under varying growth temperature (T_s). HfO₂ ceramic target has been employed for sputtering while varying the T_s from room temperature to 500 °C during deposition. The effect of T_s on the growth and microstructure of deposited HfO₂ films has been studied using grazing incidence X-ray diffraction (GIXRD), and high-resolution scanning electron microscopy (HR-SEM) coupled with energy dispersive X-ray spectrometry (EDS). The results indicate that the effect of T_s is significant on the growth, surface and interface structure, morphology and chemical composition of the HfO₂ films. Structural characterization indicates that the HfO₂ films grown at T_s < 200 °C are amorphous while films grown at T_s > 200 °C are nanocrystalline. An amorphous-to-crystalline transition occurs at T_s = 200 °C. Nanocrystalline HfO₂ films crystallized in a monoclinic structure with a (−1 1 1) orientation. An interface layer (IL) formation occurs due to reaction at the HfO₂-Si interface for HfO₂ films deposited at T_s > 200 °C. The thickness of IL increases with increasing T_s. EDS at the HfO₂-Si cross-section indicate that the IL is a (Hf, Si)-O compound. The electrical characterization using capacitance-voltage measurements indicate that the dielectric constant decreases from 25 to 16 with increasing T_s. The current-voltage characteristics indicate that the leakage current increases significantly with increasing T_s due to increased ILs.     

Spectroscopic study of nanocrystalline V2O5·nH2O films doped with Li ions

Optical properties of nanocrystalline, Li_xV₂O₅·nH₂O films (0<x<22 mol%), are explored in the present work. These films have been produced by the sol–gel technique (colloidal route), which was used for the preparation of high purity and homogeneity films. Optical measurements were carried out using a double-beam spectrophotometer. The optical constants such as refractive index n, the extinction coefficient k, absorption coefficient α, and optical band gap of the films material have been evaluated. The optical absorption coefficient was calculated from the measured normal reflectance, R, and transmittance, T, spectra. The optical spectra of all samples exhibited two distinct regions: at high energy, which suggests a direct forbidden transition with optical gap ranging from 1.75 to 2.0 eV and increases with increase in Li-content. On the other hand a second low-energy band suggests a direct allowed transition with optical gap ranging from 0.40 to 0.42 eV. The width of the localized states (band tail) E_e was also estimated for all samples. Additional calculations applying the real part of the optical dielectric function led to the evaluation of the charge carrier concentration and their effective mass.     

Characterization of doped hydrogenated nanocrystalline silicon films prepared by plasma enhanced chemical vapour deposition

The B- and P-doped hydrogenated nanocrystalline silicon films (nc-Si\jz{0.2ex}{:}H) are prepared by plasma-enhanced chemical vapour deposition (PECVD). The microstructures of doped nc-Si\jz{0.2ex}{:}H films are carefully and systematically characterized by using high resolution electron microscopy (HREM), Raman scattering, x-ray diffraction (XRD), Auger electron spectroscopy (AES), and resonant nucleus reaction (RNR). The results show that as the doping concentration of PH₃ increases, the average grain size (d) tends to decrease and the crystalline volume percentage (X_c) increases simultaneously. For the B-doped samples, as the doping concentration of B₂H\xj{6} increases, no obvious change in the value of d is observed, but the value of X_c is found to decrease. This is especially apparent in the case of heavy B₂H₂ doped samples, where the films change from nanocrystalline to amorphous.     

Structural, chemical and optical features of nanocrystalline Si films prepared by PECVD techniques

The nanostructural and chemical features of nanocrystalline Si (nc-Si) films, which were prepared by plasma-enhanced chemical vapor deposition (PECVD), were investigated in terms of various deposition conditions such as reaction gas fractions and substrate temperature. Such features were related with the photoluminescence (PL) phenomena of the nc-Si films. The phase of the nc-Si films prepared at room temperature is somewhere between amorphous and crystalline states, containing about 2 nm size nanocrystallites, which are well passivated by hydrogen. These films exhibit significant PL intensities near blue light region; the PL peaks shift to lower wavelength with decreasing nanocrystallite size.     

Structure sensitivity of propene oxidation over Co-Mn spinels

Single-phase cobalt–manganese spinel oxides (Co_3?nMn_nO₄, CMO) were studied for the catalytic oxidation of propene in a systematic optimization strategy. CMO films were synthesized by pulsed-spray evaporation chemical vapor deposition (PSE–CVD) and characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR), Raman and Ultraviolet–Visible (UV–Vis) spectroscopy. The effect of Co/Mn ratio in the mixed oxide systems on their catalytic activity was investigated in a fixed-bed reactor at T = 100–800 °C, with a space velocity of 90,000 mL/g_cat h and a feed of 2% C₃H₆/20% O₂/78% Ar. XRD patterns, FTIR and Raman spectroscopy reveal that a cubic single-phase spinel structure is obtained for n ? 1.23, while a tetragonal spinel structure is observed for n > 1.23. With increasing of the manganese content, the temperature–programmed analysis demonstrates a lower reducibility, a general decrease of the temperature required for the reduced samples to be re-oxidized and increasing thermal stability. The catalytic tests show that the involvement of cobalt–manganese oxides in propene oxidation suppresses the formation of reaction intermediates, favoring the selectivity toward CO₂ at low temperatures. Co_2.35Mn_0.65O₄ exhibits the best catalytic performance, which follows in line with its better reducibility compared with the other compositions in the series of CMO oxides. These results show the great potential of CMO for future industrial application as a low-temperature catalytic system which does not rely on precious metals.