Structural, electrical and optical properties of ZnS films deposited by close-spaced evaporation

ZnS films have been deposited on glass substrates by close-spaced evaporation (CSE) technique. The films were grown at different temperatures in the range, 200-350 °C. The layers have been characterized with X-ray diffractometer (XRD), atomic force microscope (AFM), energy dispersive analysis of X-rays (EDAX) and optical spectrophotometer to evaluate the quality of the layers for photovoltaic applications. The studies showed that the optimum substrate temperature for the growth of ZnS layers was 300 °C. The films grown at these temperatures exhibited cubic structure with nearly stoichiometric composition. The AFM data revealed that the films had nano-sized grains with a grain size of ∼40 nm. The optical studies exhibited direct allowed transition with an energy band gap of 3.61 eV. The other structural and optical parameters such as lattice stress, dislocation density, refractive index and extinction coefficient were also evaluated. The temperature-dependent conductivity measured in the range, 303-523 K showed a change in the conduction mechanism at 120 °C. The activation energy values evaluated using the temperature dependence of electrical conductivity are 7 and 29 meV at low and high temperature regions, respectively.     

Synthesis and characterization of electro-crystallized Cd-Sn-Se semiconductor films for application in non-aqueous photoelectrochemical solar cells

In the present investigation, thin films of CdSnSe have been developed on transparent conducting oxide (TCO) coated glasses by electrolytic deposition. The controlled incorporation of Sn in the semiconducting layer have been achieved by varying the concentration of Sn²⁺ from 5 to 22 g/l of SnCl₂ in the deposition bath. The semiconductor film grown on the glass substrate consisted of n-type CdSnSe semiconductor compounds (alloyed and/or mixed type) in the form of highly dispersed, spherically shaped polycrystallites as detected from X-ray diffraction (XRD) studies, atomic force microscopy (AFM) and scanning electron microscopy (SEM). Their optoelectronic properties were determined by spectroscopic analysis and electrochemical measurements. The performance characteristics of a photoelectrochemical (PEC) cell fabricated with the prepared photo-electrode and ferrocene-ferricenium redox couple in dimethyl formamide were observed under dark and illuminated conditions. The prepared semiconductor films were electrochemically characterized through capacitance-voltage measurements. The film that was obtained from 10 g/l of Sn²⁺ in the bath, showed an optimum spectral sensitivity and corresponded to a film thickness of 0.65 μm and stoichiometry of Cd:Sn:Se as 1:1:1. The pronounced PEC activity of this film compared to the others was attributed to the combined effect of space charge properties, electron-hole recombination processes and transfer of charges through the Helmholtz layer at the semiconductor-solution interface.     

Monocrystalline Si waffles for thin solar cells fabricated by the novel perforated-silicon process

2 for this waffle-shaped film when it is attached to glass substrates. Received: 15 May 1998/Accepted: 28 May 1998     

Comparison and semiconductor properties of nitrogen doped carbon thin films grown by different techniques

Amorphous carbon nitride (a-CN_x) thin films have been synthesised by three different deposition techniques in an Ar/N₂ gas mixture and have been deposited by varying the percentage of nitrogen gas in the mixture (i.e. the N₂/Ar + N₂ ratio) from 0 to 10%. The variation of the electrical conductivity and the gap values of the deposited films versus the N₂/Ar + N₂ ratio were investigated in relation with their local microstructure. Film composition was analysed using Raman spectroscopy and optical transmission experiments. The observed variation of electrical conductivity and optical properties are attributed to the changes in the atomic bonding structures, which were induced by N incorporation, increasing both the sp² carbon content and their relative disorder. The low N content samples seem to be an interesting material to produce films with interesting properties for optoelectronic applications considering the facility to control the gas composition as a key parameter.     

Properties of NiO thin films deposited by chemical spray pyrolysis using different precursor solutions

NiO thin films have been deposited by chemical spray pyrolysis using a perfume atomizer to grow the aerosol. The influence of the precursor, nickel chloride hexahydrate (NiCl₂·6H₂O), nickel nitrate hexahydrate (Ni(NO₃)₂·6H₂O), nickel hydroxide hexahydrate (Ni(OH)₂·6H₂O), nickel sulfate tetrahydrate (NiSO₄·4H₂O), on the thin films properties has been studied. In the experimental conditions used (substrate temperature 350 °C, precursor concentration 0.2-0.3 M, etc.), pure NiO thin films crystallized in the cubic phase can be achieved only with NiCl₂ and Ni(NO₃)₂ precursors. These films have been post-annealed at 425 °C for 3 h either in room atmosphere or under vacuum. If all the films are p-type, it is shown that the NiO films conductivity and optical transmittance depend on annealing process. The properties of the NiO thin films annealed under room atmosphere are not significantly modified, which is attributed to the fact that the temperature and the environment of this annealing is not very different from the experimental conditions during spray deposition. The annealing under vacuum is more efficient. This annealing being proceeded in a vacuum no better than 10⁻² Pa, it is supposed that the modifications of the NiO thin film properties, mainly the conductivity and optical transmission, are related to some interaction between residual oxygen and the films.     

Effects of experimental parameters on composition of boron carbon nitride thin films deposited by magnetron sputtering

We have synthesized boron carbon nitride thin films by radio frequency magnetron sputtering. The films structure and composition were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The results indicate that the three elements of B, C, N are chemically bonded with each other and atomic-level hybrids have been formed in the films. The boron carbon nitride films prepared in the present experiment possess a disordered structure. The influence of PN₂/PN₂+Ar, total pressure and substrate bias voltage on the composition of boron carbon nitride films is investigated. The atomic fraction of C atoms increases and the fractions of B, N decrease with the decrease of PN₂/PN₂+Ar from 75% to 0%. There is an optimum total pressure. That is to say, the atomic fractions of B, N reach a maximum and the fraction of C atoms reaches a minimum at the total pressure of 1.3 Pa. The boron carbon nitride films exhibit lower C content and higher B, N contents at lower bias voltages. And the boron carbon nitride films show higher C content and lower B, N contents at higher bias voltages.     

Flexible a‐Si:H/nc‐Si:H tandem thin film silicon solar cells on plastic substrates with i ‐layers made by hot‐wire CVD

In this letter we report the result of an a‐Si:H/nc‐Si:H tandem thin film silicon solar mini‐module fabricated on plastic foil containing intrinsic silicon layers made by hot‐wire CVD (efficiency 7.4%, monolithically series‐connected, aperture area 25 cm²). We used the Helianthos cell transfer process. The cells were first deposited on a temporary aluminum foil carrier, which allows the use of the optimal processing temperatures, and then transferred to a plastic foil. This letter reports the characteristics of the flexible solar cells obtained in this manner, and compares the results with those obtained on reference glass substrates. The research focus for implementation of the hot‐wire CVD technique for the roll‐to‐roll process is also discussed. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Preparation of chemically deposited thin films of CdS/PbS solar cell

The present paper reports the preparation of a solar cell which has a cross-sectional scheme: ITO/CdS/PbS, containing a commercially transparent conductive ITO; chemically deposited n-type CdS (340 nm) and absorbed layer of p-type PbS (1400 nm). The structural and optical properties of the constituent films are presented. X-ray diffraction showed that all of the thin films are polycrystalline. Using scanning electron microscopy, the present study revealed that the films have uniform surface morphology over the substrate. The solar cell was characterized by determining the open circuit voltage, short-circuit current density, and J–V under 40 mW/cm² solar radiation. The efficiency of the solar cells was 1.35%, which is much higher (0.041, 0.5 and 0.1–0.4%) and slightly smaller (1.65%) than some solar cells reported in the literature.     

A comparative study on Zn0.8Cd0.2O films deposited on different substrates

Highly (0 0 2)-oriented Zn_0.8Cd_0.2O crystal films were prepared on different substrates, namely, glass, Si(1 1 1) and α-Al₂O₃(0 0 1) wafers by the dc reactive magnetron sputtering technique. The Zn_0.8Cd_0.2O/α-Al₂O₃ film has the best crystal quality with a FWHM of (0 0 2) peak of 0.3700°, an average grain size of about 200 nm and a root-mean-square surface roughness of about 70 nm; yet the Zn_0.8Cd_0.2O/glass holds the worst crystal quality with a much larger FWHM of 0.6281°. SIMS depth profile shows that the Zn and O compositions change little along the film depth direction; the Cd incorporation also almost holds the line towards the top surface other than an accumulation at the interface between the film and the substrate. The Cd content in the film is nearly consistent with that in target.     

High-temperature processing of crystalline silicon thin-film solar cells

The crystalline silicon thin-film solar cell combines, in principle, the advantages of crystalline silicon wafer-based solar cells and of thin-film solar cell technologies. Its efficiency potential is the highest of all thin-film cells. In the “high-temperature approach” thin silicon layers are deposited on substrates that withstand processing temperatures higher than 1000 °C. The basic features of the high-temperature crystalline silicon thin-film cell technology are described and some important results are discussed. Received: 1 March 1999 / Accepted: 28 March 1999 / Published online: 24 June 1999     

Properties of conductive polymer films deposited by infrared laser ablation

Thin films of the conducting polymer poly(3,4-ethylenedioxy-thiophene):poly(styrenesulfonate) (PEDOT:PSS) were deposited by resonant infrared laser vapor deposition (RIR-LVD). The PEDOT:PSS was frozen in various matrix solutions and deposited using a tunable, mid-infrared free-electron laser (FEL). The films so produced exhibited morphologies and conductivities that were highly dependent on the solvent matrix and laser irradiation wavelength used. When deposited from a native solution (1.3% by weight in water), as in matrix-assisted pulsed laser evaporation (MAPLE), films were rough and electrically insulating. When the matrix included other organic “co-matrices” that were doped into the solution prior to freezing, however, the resulting films were smooth and exhibited good electrical conductivity (0.2 S/cm), but only when irradiated at certain wavelengths. These results highlight the importance of the matrix/solute and matrix/laser interactions in the ablation process.     

Preparation and characterization of ZnS/CdS bi-layer for CdTe solar cell application

In this work, bilayer ZnS/CdS film was prepared as an improved window layer of CdTe solar cell. TEM was used to observe the cross section of the bilayer structure. The total thickness of ZnS/CdS film was about 60 nm, which could allow more photons to pass through it and contribute to the photocurrent. Optical properties of the bilayers were investigated using UV–vis spectroscopy. Compared with poor transmission of standard CdS film in the short wavelength range of 350–550 nm, the transmission of ZnS/CdS was improved and reached above 50%. The ZnS/CdS was annealed with CdCl₂. X-ray photoelectron spectroscopy (XPS) was used to investigate its chemical properties. A possible diffusion between CdS and ZnS was observed after annealing. The efficiency of standard CdS/CdTe solar cell was 9.53%. The device based on ZnS/CdS window layer had a poor 6% efficiency. With annealing treatment on ZnS/CdS layer, the performance was improved and reached 10.3%. In addition, the homogeneity of solar cell performance was improved using ZnS/CdS window layer. A thin ZnS layer was quite effective to reduce the possible shunt paths and short parts of window layer and consequently contributed to fabrication of a homogeneous CdTe solar cell.     

Decoupling crystalline volume fraction and VOC in microcrystalline silicon pin solar cells by using a µc‐Si:F:H intrinsic layer

Microcrystalline silicon thin film pin solar cells with a highly crystallized intrinsic μc‐Si:F:H absorber were prepared by RF‐plasma enhanced chemical vapour deposition using SiF₄ as the gas precursor. The cells were produced with a vacuum break between the doped layer and intrinsic layer depositions, and the effect of different subsequent interface treatment processes was studied. The use of an intrinsic μc‐Si:H p/i buffer layer before the first air break increased the short circuit current density from 22.3 mA/cm² to 24.7 mA/cm². However, the use of a hydrogen‐plasma treatment after both air breaks without an interface buffer layer improved both the open circuit voltage and the fill factor. Although the material used for the absorber layer showed a very high crystalline fraction and thus an increased spectral response at long wavelengths, an open‐circuit voltage (V_OC) of 0.523 V was nevertheless observed. Such a value of V_OC is higher than is typically obtained in devices that employ a highly crystallized absorber as reported in the literature (see abstract figure). Using a hydrogen‐plasma treatment, a single junction μc‐Si:F:H pin solar cell with an efficiency of 8.3% was achieved.

     

Chromium carbide thin films deposited by ultra-short pulse laser deposition

Pulsed laser deposition performed by a laser with a pulse duration of 250 fs has been used to deposit films from a Cr₃C₂ target. Due to the different processes involved in the laser ablation when it is performed by an ultra-short pulse source instead of a conventional short pulse one, it has been possible to obtain in vacuum films containing only one type of carbide, Cr₃C₂, as shown by X-ray photoelectron spectroscopy. On the other hand, Cr₃C₂ is not the only component of the films, since a large amount of amorphous carbon is also present. The films, deposited at room temperature, are amorphous and seem to be formed by the coalescence of a large number of particles with nanometric size. The film composition can be explained in terms of thermal evaporation from particles ejected from the target.     

Investigation of the effect of CdCl2 processing on vacuum deposited CdS/CdTe thin film solar cells by DLTS

Thin film CdS/CdTe solar cells have been prepared by conventional vacuum deposition technique. Deep level transient spectroscopy (DLTS), temperature and frequency dependent capacitance-voltage (C-V) measurements were utilised to investigate the performance limiting defect states in the CdTe layer subjected to the post deposition treatments such as CdCl₂-dipping and/or annealing in air. Five hole traps, all of which have been previously reported in the literature, were identified in as-grown CdTe at 0.19, 0.20, 0.22, 0.30 and 0.40 eV above the valence band. A single hole trap level has been evidenced at 0.45 eV after both post deposition heat and CdCl₂ treatments.     

Effects of processing on the electrical and structural properties of spray deposited CdS:In thin films

Polycrystalline CdS:In thin films were prepared by the Spray pyrolysis technique (SP) at a substrate temperature T_s=490 °C. The effects of annealing in nitrogen atmosphere at 400 °C and HCl-etching on the electrical and structural properties of the films were investigated. The electrical properties were studied through the analysis of the I-V curves, while the structural properties were studied through the analysis of the X-ray diffraction (XRD) patterns and the scanning electron microscope (SEM) images. An increase in the films’ resistivity was occurred after annealing and/or HCl-etching, which was accompanied by changes in the XRD patterns and SEM images. These changes were related to a phase change from the mixed (cubic and hexagonal) phase to the hexagonal phase which was expected to occur during the aforementioned processes. The X-ray diffraction (XRD) patterns and the scanning electron microscope images confirm this expectation.     

Electrical conductivity of nitride carbon films with different nitrogen content

The electrical conductivity of nitride carbon (DLC: N) films has been studied. It is found that the electrical conductivity of the deposited films increases slowly with increasing nitrogen content, however, it decreases after the nitrogen content in the film reaches a certain value of 12.8 at%. Thermal treatment results show that the electrical conductivity of the lowly nitrogen doped DLC film increases rapidly, while that of the heavily doped film decreases after annealing at 300 °C for 30 min. Raman and XPS spectra results show that when the nitrogen content in the films reaches a certain value, there appears nonconductive phases. Therefore the electrical conductivity of the heavily doped films decreases. FTIR spectra analysis results show that the nitrogen atom as an impurity center undergoes an ‘activation’ process during the thermal treatment, which leads to the increase of the electrical conductivity. Therefore, the nitrogen in these two kinds of films has different effects on the electrical conductivity.     

Electroluminescence and its excitation mechanism of SiOx films deposited by electron-beam evaporation

Blue electroluminescence from SiO_x films deposited by electron beam evaporation was observed. This blue emission blueshifted from 450 to 410 nm with increasing applied voltage. The dependences of blue emission on applied voltage, frequency and conduction current were studied. Our experimental data support that blue emission from SiO_x films is the result of both recombination of charge carriers injected from opposite electrodes and impact excitation of hot electrons, the recombination of carriers injected is dominant in low and medium electric fields but hot electron impact excitation is dominant under high electric fields.     

Selective ablation of thin films with short and ultrashort laser pulses

Micromachining of CuInSe₂ (CIS)-based photovoltaic devices with short and ultrashort laser pulses has been investigated. Therefore, ablation thresholds and ablation rates of ZnO, Mo and CuInSe₂ thin films have been measured for irradiation with nanosecond laser pulses of ultraviolet and visible light and subpicosecond laser pulses of a Ti:sapphire laser. The experimental results were compared to the theoretical evaluation of the samples heat regime. In addition, the cells photo-electrical properties were measured before and after laser machining. Scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) analyses were employed to characterise the laser-induced ablation channels. Using nanosecond laser pulses, two phenomena were found to limit the laser-machining process. Residues of Mo that were projected onto the walls of the ablation channel and the metallization of the CuInSe₂ semiconductor close to the channel lead to a shunt. The latter causes the decrease of the photovoltaic efficiency. As a consequence of these limiting effects, only subpicosecond laser pulses allowed the selective or complete ablation of the thin layers without a relevant change of the photo-electrical properties.     

Microstructural investigations of Y2O3 thin films deposited by laser ablation on MgO

The epitaxial relationships and the microstructure of thin Y₂O₃ film, in situ grown by laser ablation at 700 °C under 0.5 mbar oxygen pressure on MgO substrate, are studied by X-ray and HRTEM investigations. X-ray φ-scanexperiments show that Y₂O₃ exhibits two different crystallographic growing directions <111> and <100> on (100) single-crystalline MgO substrate. The <111> growing direction appears with four different epitaxial relationships where the <110> Y₂O₃ in-plane direction is parallel to the <110> in-plane direction of MgO. The <100> growing direction appears with one epitaxial relationship, cube Y₂O₃ on cube MgO. The HRTEM experiments show the columnar aspect of the Y₂O₃ thin film. Both (111) and (100) Y₂O₃-oriented grains are observed in good agreement with the X-ray experiments. Received: 16 May 2000 / Accepted: 22 May 2000 / Published online: 13 September 2000