Evidence for two-phase regions in BST thin films from capacitance-voltage data

The Curie-Weiss plots of reciprocal dielectric constant versus temperature, in Ba0.5Sr0.5TiO3 films grown onto SrRuO3 lower electrodes by pulsed-laser deposition, show two minima below film thicknesses of 280 nm. This double minima implies possible mixed phases in the thin films. A graphical plot of capacitance for decreasing dc voltage versus that of increasing dc voltage shows a well-defined triangular shape for both Pb(Zr0.4Ti0.6)O-3 and SrBi2Ta2O9 thin films. However, for a 175-nm-thick Ba0.5Sr0.5TiO3 thin film, the plot shows an overlapping of two triangles, suggesting mixed phases. This graphical method appears to be effective in detecting structural subtleties in ferroelectric capacitors.

Electrode field penetration: A new interpretation of tunneling currents in barium strontium titanate (BST) thin films

This paper shows that penetration of the applied electric field into the electrodes of a ferroelectric thin film capacitor produces both an interfacial capacitance and an effective mechanism for electron tunneling. The model predictions are compared with experimental results on Au-BST-SrRuO3 capacitors of varying thicknesses, and the agreement is excellent.

The effect of tungsten trioxide thin films at ferroelectric-electrode boundaries on fatigue behaviour

A conventional thin film capacitor heterostructure, consisting of sol-gel deposited lead zirconium titanate (PZT) layers with sputtered platinum top and bottom electrodes, was subjected to fatiguing pulses at a variety of frequencies. The fatigue characteristics were compared to those of a similarly processed capacitor in which a ~20nm tungsten trioxide layer had been deposited, using pulsed laser deposition, between the ferroelectric and upper electrode. The expectation was that, because of its ability to accommodate considerable oxygen non-stoichiometry, tungsten trioxide (WO3) might act as an efficient sink for any oxygen vacancies flushed to the electrode-ferroelectric boundary layer during repetitive switching, and hence would improve the fatigue characteristics of the thin film capacitor. However, it was found that, in general, the addition of tungsten trioxide actually increases the rate of fatigue. It appears that any potential benefit from the WO3, in terms of absorbing oxygen vacancies, is far outweighed by it causing dramatically increased charge injection in the system.

Light emission from gold and silver thin films in a scanning tunneling microscope: role of contamination and interpretation of grain structure in photon maps

Scanning tunnelling microscope (STM) tip-induced light emission from Au and Ag has been studied. Thin film samples similar to100nm thick were prepared by thermal evaporation at 0.5nm/s onto a room-temperature glass substrate to produce grains of 20-50nm in lateral dimension at the surface. Light emission from the samples in the STM was quasi-simultaneously recorded with the topography, at 1.8V tip bias and 3-40nA current, alternating pixel by pixel at the same bias. Typically, a surface scan range of 150 nm x 150 nm was surveyed. Au, W and PtIr tips were used.

Photodecomposition of ozone sensitised by a film of titanium dioxide on glass

High levels of ozone (typically 850 ppm) are readily decomposed by semiconductor photocatalysis, using a thin film of the semiconductor titanium dioxide (Degussa P25 TiO2) cast on a glass tube, and UVA light, i.e. light of energy greater than that of the bandgap of the semiconductor (ultra-bandgap light); in the absence of this light the thermal decomposition of ozone is relatively slow. The semiconductor films show no evidence of chemical or photochemical wear with repeated use. At high levels of ozone, i.e. 100 ppm less than or equal to [O-3] less than or equal to 1400 ppm, the initial rate of ozone decomposition by semiconductor photocatalysis is independent of [O-3], whereas, at lower ozone concentrations, i.e. 5 ppm less than or equal to [O-3] less than or equal to 100 ppm, the initial rate of ozone photodestruction decreases in a smooth, but non-linear, manner with decreasing [O-3]. The kinetics of ozone photodecomposition fit a Langmuir-Hinshelwood type kinetic equation and the possible mechanistic implications of these results are briefly discussed. (C) 2002 Elsevier Science B.V. All rights reserved.

Effect of plasticizer-polymer compatibility on the response characteristics of optical thin CO2 and O-2 sensing films

A homologous family of dialkyl phthalates has been used to investigate the effect of plasticizer/polymer compatibility on the response characteristics of transparent, plastic, thin optical gas sensing films for CO2 and oxygen. Plasticizer/polymer compatibilities were determined through the value of the difference in solubility parameter, i.e. Delta delta, for the plasticizer and polymer with a Delta delta value of zero indicating high compatibility. A strong correlation was found between plasticizer/polymer compatibility and sensitivity in phenol red/ethyl cellulose CO2-sensitive films and this relationship extended to CO2-sensitive films based on other polymers such as polystyrene and poly(methyl methacrylate). It extended also to optical O-2-sensitive films implying that the relationship is general for thin-film optical sensors. Other results from the CO2-sensitive films in different polymers indicated that the film sensitivity is largely independent of the polymer matrix regardless of its inherent gas permeability, when a sufficient quantity of compatible plasticizer is present. (C) 1998 Elsevier Science B.V.

Plastic colorimetric film sensors for gaseous ammonia

The preparation and characterization of three different plastic thin-film colorimetric sensors for gaseous ammonia is described. In the film sensors, the neutral form of a pH-sensitive dye (Bromophenol Blue, Bromocresol Green or Chlorophenol Red) was encapsulated in a plastic medium, either poly(vinyl butyral) or ethylcellulose plasticized with tributyl phosphate. Each of these film optodes gave a reproducible and reversible response towards gaseous ammonia. The sensitivity of the film sensors towards ammonia was found to be strongly dependent upon the pK(a) of the encapsulated dye. Thus, the film with Chlorophenol Red (pK(a) = 6.25), proved to be very insensitive (operating range: 0.29%

Labile ferroelastic nanodomains in bilayered ferroelectric thin films

Bilayered Pb(Zr((1-x)),Ti(x))O(3) ferroelectric thin film heterostructures show complex ferroelastic nanodomain patterns. These ferroelastic nanodomains exist only in the upper layer, and hence are able to move under the application of an external electric field. Quantitative analysis reveals an enhanced piezoelectric coefficient of similar to 220 pm V(-1), rendering them attractive for a variety of electromechanical devices.

Contrasting damage characteristics in direct incidence and surface plasmon mediated single-shot laser ablation of aluminium films

Thin, oxidised Al films grown an one face of fused silica prisms are exposed. tinder ambient conditions, to single shots from an excimer laser operating at wavelength 248 nm. Preliminary characterisation of the films using attenuated total reflection yields optical and thickness data for the Al and Al oxide layers; this step facilitates the subsequent, accurate tuning of the excimer laser pulse to the: surface plasmon resonance at the Al/(oxide)/air interface and the calculation of the fluence actually absorbed by the thin film system. Ablation damage is characterised using scanning electron, and atomic force microscopy. When the laser pulse is incident, through the prism on the sample at less than critical angle, the damage features are molten in nature with small islands of sub-micrometer dimension much in evidence, a mechanism of film melt-through and subsegment blow-off due to the build up of vapour pressure at the substrate/film interface is appropriate. By contrast, when the optical input is surface plasmon mediated, predominately mechanical damage results with the film fragmenting into large flakes of dimensions on the order of 10 mu m. It is suggested that the ability of surface plasmons to transport energy leads to enhanced, preferential absorption of energy at defect sites causing stress throughout the film which exceeds the ultimate tensile stress for the film: this in turn leads to film break-up before melting can onset. (C) 1998 Elsevier Science B.V.

Chalcogenide thin films for solar cells: growth and properties

Thin film solar cells have in recent years gained market quota against traditional silicon photovoltaic panels. These developments were in a large part due to CdTe solar panels on whose development started earlier than their competitors. Panels based on Cu(In,Ga)Se2 (CIGS), despite being more efficient in a laboratory and industrial scale than the CdTe ones, still need a growth technology cheaper and easier to apply in industry. Although usually presented as a good candidate to make cheap panels, CIGS uses rare and expensive materials as In and Ga. The price evolution of these materials might jeopardize CIGS future. This thesis presents three different studies. The first is the study of different processes for the incorporation of Ga in a hybrid CIGS growth system. This system is based on sputtering and thermal evaporation. This technology is, in principle, easier to be applied in the industry and solar cells with efficiencies around to 7% were fully made in Aveiro. In the second part of this thesis, a new material to replace CIGS in thin film solar cells is studied. The growth conditions and fundamental properties of Cu2ZnSnSe4 (CZTSe) were studied in depth. Suitable conditions of temperature and pressure for the growth of this material are reported. Its band gap energy was estimated at 1.05 eV and the Raman scattering peaks were identified. Solar cells made with this material showed efficiencies lower than 0.1%. Finally, preliminary work regarding the incorporation of selenium in Cu2ZnSnS4 (CZTS) thin films was carried out. The structural and morphological properties of thin films of Cu2ZnSn(S,Se)4 have been studied and the results show that the incorporation of selenium is higher in films with precursors rather with already formed Cu2SnS3 or Cu2ZnSnS4 thin films. A solar cell with 0.9 % of efficiency was prepared.

Electrical characterization of organic based transistors: stability issues

An investigation into the stability of metal insulator semiconductor (MIS) transistors based on alpha-sexithiophene is reported. In particular the kinetics of the threshold voltage shift upon application of a gate bias has been determined. The kinetics follow a stretched-hyperbola type behavior, in agreement with the formalism developed to explain metastability in amorphous-silicon thin film transistors. Using this model, quantification of device stability is possible. Temperature-dependent measurements show that there are two processes involved in the threshold voltage shift, one occurring at T approximate to 220 K and the other at T approximate to 300 K. The latter process is found to be sample dependent. This suggests a relation between device stability and alpha-sexithiophene deposition parameters. Copyright (c) 2005 John Wiley A Sons, Ltd.

Effects of sulphurization time on Cu2ZnSnS4 absorbers and thin films solar cells obtained from metallic precursors

We report the results of a study of the sulphurization time effects on Cu2ZnSnS4 absorbers and thin film solar cells prepared from dc-sputtered tackedmetallic precursors. Three different time intervals, 10 min, 30min and 60 min, at maximum sulphurization temperature were considered. The effects of this parameter' change were studied both on the absorber layer properties and on the final solar cell performance. The composition, structure, morphology and thicknesses of the CZTS layers were analyzed. The electrical characterization of the absorber layer was carried out by measuring the transversal electrical resistance of the samples as a function of temperature. This study shows an increase of the conductivity activation energy from 10 meV to 54meV for increasing sulphurization time from 10min to 60min. The solar cells were built with the following structure: SLG/Mo/CZTS/CdS/i-ZnO/ZnO:Al/Ni:Al grid. Several ac response equivalent circuit models were tested to fit impedance measurements. The best results were used to extract the device series and shunt resistances and capacitances. Absorber layer's electronic properties were also determined using the Mott–Schottky method. The results show a decrease of the average acceptor doping density and built-in voltage, from 2.0 1017 cm−3 to 6.5 1015 cm−3 and from 0.71 V to 0.51 V, respectively, with increasing sulphurization time. These results also show an increase of the depletion region width from approximately 90 nm–250 nm.

Hopping conduction and persistent photoconductivity in Cu2ZnSnS4 thin films

The temperature dependence of electrical conductivity and the photoconductivity of polycrystalline Cu2ZnSnS4 were investigated. It was found that at high temperatures the electrical conductivity was dominated by band conduction and nearest-neighbour hopping. However, at lower temperatures, both Mott variable-range hopping (VRH) and Efros–Shklovskii VRH were observed. The analysis of electrical transport showed high doping levels and a large compensation ratio, demonstrating large degree of disorder in Cu2ZnSnS4. Photoconductivity studies showed the presence of a persistent photoconductivity effect with decay time increasing with temperature, due to the presence of random local potential fluctuations in the Cu2ZnSnS4 thin film. These random local potential fluctuations cannot be attributed to grain boundaries but to the large disorder in Cu2ZnSnS4.

Detection of ZnS phases in CZTS thin-films by EXAFS

Copper zinc tin sulfide (CZTS) is a promising Earthabundant thin-film solar cell material; it has an appropriate band gap of ~1.45 eV and a high absorption coefficient. The most efficient CZTS cells tend to be slightly Zn-rich and Cu-poor. However, growing Zn-rich CZTS films can sometimes result in phase decomposition of CZTS into ZnS and Cu2SnS3, which is generally deleterious to solar cell performance. Cubic ZnS is difficult to detect by XRD, due to a similar diffraction pattern. We hypothesize that synchrotron-based extended X-ray absorption fine structure (EXAFS), which is sensitive to local chemical environment, may be able to determine the quantity of ZnS phase in CZTS films by detecting differences in the second-nearest neighbor shell of the Zn atoms. Films of varying stoichiometries, from Zn-rich to Cu-rich (Zn-poor) were examined using the EXAFS technique. Differences in the spectra as a function of Cu/Zn ratio are detected. Linear combination analysis suggests increasing ZnS signal as the CZTS films become more Zn-rich. We demonstrate that the sensitive technique of EXAFS could be used to quantify the amount of ZnS present and provide a guide to crystal growth of highly phase pure films.

Growth and characterization of Cu2ZnSn(S,Se)4 thin films for solar cells

Cu2ZnSnS4 (CZTS) and Cu2ZnSnSe4 (CZTSe) with their band gap energies around 1.45 eV and 1.0 eV, respectively, can be used as the absorber layer in thin film solar cells. By using a mixture of both compounds, Cu2ZnSn(S,Se)4 (CZTSSe), a band gap tuning may be possible. The latter material has already shown promising results such as solar cell efficiencies up to 10.1%. In this work, CZTSSe thin films were grown in order to study its structure and to establish the best growth precursors. SEM micrographs reveal an open columnar structure for most samples and EDS composition profiling of the cross sections show different selenium gradients. X-ray diffractograms show different shifts of the kesterite/stannite (1 1 2) peak, which indicate the presence of CZTSSe. From Raman scattering analysis, it was concluded that all samples had traces of CZTS and CZTSSe. The composition of the CZTSSe layer was estimated using X-ray diffraction and Raman scattering and both results were compared. It was concluded that Se diffused more easily in precursors with ternary Cu–Sn–S phases and metallic Zn than in precursors with ZnS and/or CZTS already formed. It was also showed that a combination of X-ray diffraction and Raman scattering can be used to estimate the ratio of S per Se in CZTSSe samples.