The influence of stoichiometry on the structural stability and on the optical emission of erbium silicate thin films

We report the effects of thermal annealing performed in N2 or O2 ambient at 1200 °C on the structural and optical properties of Er silicate films having different compositions (Er2Si O 5,Er2 Si2 O7, and their mixture). We demonstrate that the chemical composition of the stoichiometric films is preserved after the thermal treatments. All different crystalline structures formed after the thermal annealing are identified. Thermal treatments in O 2 lead to a strong enhancement of the photoluminescence intensity, owing to the efficient reduction of defect density. In particular the highest optical efficiency is associated to Er ions in the α phase of Er 2 Si2 O7. © 2008 American Institute of Physics.

Synthesis and luminescence properties of erbium silicate thin films

We have studied the structure and the room temperature luminescence of erbium silicate thin films deposited by rf magnetron sputtering. Films deposited on silicon oxide layers are characterized by good structural properties and excellent stability. The optical properties of these films are strongly improved by rapid thermal annealing processes performed in the range of temperature 800-1250 °C. In fact through the reduction of the defect density of the material, a very efficient room temperature photoluminescence at 1535 nm is obtained. We have also investigated the influence of the annealing ambient, by finding that treatments in O2 atmosphere are significantly more efficient in improving the optical properties of the material with respect to processes in N2. Upconversion effects become effective only when erbium silicate is excited with high pump powers. The evidence that all Er atoms (about 1022 cm-3) in erbium silicate films are optically active suggests interesting perspectives for optoelectronic applications of this material. © 2007 Elsevier B.V. All rights reserved.

Anisotropic behaviour in the magnetic field dependence of the low temperature electrical resistance of calcium-doped lanthanum manganate thin films grown by RF magnetron sputtering

We report about the magnetoresistive properties of calcium-doped lanthanum manganate thin films grown by RF magnetron sputtering on single crystalline LaAlO3 and MgO substrates. Two orientations of the magnetic field with respect to the electrical current have been studied: (i) magnetic field in the plane of the film and parallel to the electrical current, and (ii) magnetic field perpendicular to the plane of the film. The film grown on LaAlO 3 is characterised by an unusual magnetoresistive behaviour when the magnetic field is applied perpendicular to the film plane: the appearance of two bumps in the field dependence of the resistance is shown to be related to the occurrence of anisotropic magnetoresistive effects in manganate films. © 2004 Elsevier B.V. All rights reserved.

Water, salt water, and alkaline solution uptake in epoxy thin films

As a means of characterizing the diffusion parameters of fiber reinforced polymer (FRP) composites within a relatively short time frame, the potential use of short term tests on epoxy films to predict the long-term behavior is investigated. Reference is made to the literature to assess the effectiveness of Fickian and anomalous diffusion models to describe solution uptake in epoxies. The influence of differing exposure conditions on the diffusion in epoxies, in particular the effect of solution type and temperature, are explored. Experimental results, where the solution uptake in desiccated (D) or undesiccated (U) thin films of a commercially available epoxy matrix subjected to water (W), salt water (SW), or alkali concrete pore solution (CPS) at either 20 or 60°C, are also presented. It was found that the type of solution did not significantly influence the diffusion behavior at 20°C and that the mass uptake profile was anomalous. Exposure to 60°C accelerated the initial diffusion behavior and appeared to raise the level of saturation. In spite of the accelerated approach, conclusive values of uptake at saturation remained elusive even at an exposure period of 5 years. This finding questions the viability of using short-term thin film results to predict the long-term mechanical performance of FRP materials. © 2013 Wiley Periodicals, Inc.

Polarization switching induced decrease of bulk resistivity in ferroelectric Pb(Zr0.45Ti0.55)O3 thin films and a method to improve their fatigue endurance

Significant reduction of the bulk resistivity in a ferroelectric Pb(Zr 0.45Ti0.55)O3 thin film is observed before the remnant polarization started to decrease noticeably at the onset of its fatigue switching process. It is associated with the increase of charge carriers within the central bulk region of the film. The decrease of bulk resistivity would result in the increase of Joule heating effect, improving the temperature of the thin film, which is evaluated by the heat conduction analysis. The Joule heating effect in turn accelerates the polarization reduction, i.e. fatigue. Enhancing the heat dissipation of a ferroelectric capacitor is shown to be able to improve the device's fatigue endurance effectively. © 2013 Chinese Physical Society and IOP Publishing Ltd.

Measurement of residual stresses in ferroelectric Pb(Zr 0.3Ti0.7)O3 thin films by X-ray diffraction

The residual stresses in Pb(Zr0.3Ti0.7)O3 thin films were measured by the sin2 Ψ method using the normal X-ray incidence. The spacing of different planes (hkl) parallel to the film surface were converted to the spacing of a set of inclined planes (100). The angles between (100) and (hkl) were equivalent to the tilting angles of (100) from the normal of film surface. The residual stresses were extracted from the linear slope of the strain difference between the equivalent inclined direction and normal direction with respect to the sin2 Ψ. The results were in consistency with that derived from the conventional sin2 Ψ method. © 2013 The Japan Society of Applied Physics.

Controllable nanodomain defects in ferroelectric/ferroelastic biferroic thin films

Ferroelectric thin films have been intensively studied at the nanometre scale due to the application in many fields, such as non-volatile memories. Enhanced piezo-response force microscopy (E-PFM) was used to investigate the evolution of ferroelectric and ferroelastic nanodomains in a polycrystalline thin film of the simple multi-ferroic PbZr0.3Ti0.7O 3 (PZT). By applying a d.c. voltage between the atomic force microscopy (AFM) tip and the bottom substrate of the sample, we created an electric field to switch the domain orientation. Reversible switching of both ferroelectric and ferroelastic domains towards particular directions with predominantly (111) domain orientations are observed. We also showed that along with the ferroelectric/ferroelastic domain switch, there are defects that also switch. Finally, we proposed the possible explanation of this controllable defect in terms of flexoelectricity and defect pinning. © 2013 IEEE.

Effect of process parameters on the morphology and nanostructure of roll-to-roll printed P3HT:PCBM thin films for organic photovoltaics

Roll-to-roll (R2R) gravure exhibits significant advantages such as high precision and throughput for the printing of photoactive and conductive materials and the fabrication of flexible organic electronics such as organic photovoltaics (OPVs). Since the photoactive layer is the core of the OPV, it is important to investigate and finally control the process parameters and mechanisms that define the film morphology in a R2R process. The scope of this work is to study the effect of the R2R gravure printing and drying process on the nanomorphology and nanostructure of the photoactive P3HT:PCBM thin films printed on PEDOT:PSS electrodes towards the fabrication of indium tin oxide (ITO)-free flexible OPVs. In order to achieve this, P3HT:PCBM blends of different concentration were R2R printed under various speeds on the PEDOT:PSS layers. Due to the limited drying time during the rolling, an amount of solvent remains in the P3HT:PCBM films and the slow-drying process takes place which leads to the vertical and lateral phase separation, according to the Spectroscopic Ellipsometry and Atomic Force Microscopy analysis. The enhanced slow-drying leads to stronger phase separation, larger P3HT crystallites according to the Grazing Incidence X-Ray Diffraction data and to weaker mechanical response as it was shown by the nanoindentation creep. However, in the surface of the films the P3HT crystallization is controlled by the impinged hot air during the drying, where the more the drying time the larger the surface P3HT crystallites. The integration of the printed P3HT:PCBM and PEDOT:PSS layers in an OPV device underlined the feasibility of fabricating ITO-free flexible OPVs by R2R gravure processes. © 2013 Elsevier B.V.

Substrate treatment and drying conditions effect on the properties of roll-to-roll gravure printed PEDOT:PSS thin films

The optical, structural and electrical properties of poly(3,4- ethylenedioxythiophene):poly(4-styrenesulfonic acid) (PEDOT:PSS) thin films printed by roll-to-roll gravure have been investigated. Corona treatment has been applied to enhance the adhesion of PEDOT:PSS on PolyEthylene Terephthalate (PET) web. It has been found that there was a stronger in-depth surface modification of PET with the increase of corona efficiency; however, the adhesion of PEDOT:PSS was not actually affected. Also, Spectroscopic Ellipsometry and Atomic Force Microscopy have been used to extract information on the mechanisms that define PEDOT:PSS properties. The increase of the drying temperature of the PEDOT:PSS films has been found to reduce the remaining water inside the films and lead to the decrease of the PEDOT:PSS particles size. © 2011 Elsevier B.V. All rights reserved.

Evolution of vertical phase separation in P3HT:PCBM thin films induced by thermal annealing

The achievement of the desirable morphology at the nanometer scale of bulk heterojunctions consisting of a conjugated polymer with fullerene derivatives is a prerequisite in order to optimize the power conversion efficiency of organic solar cells. The various experimental conditions such as the choice of solvent, drying rates and annealing have been found to significantly affect the blend morphology and the final performance of the photovoltaic device. In this work, we focus on the effects of post deposition thermal annealing at 140 °C on the blend morphology, the optical and structural properties of bulk heterojunctions that consist of poly(3-hexylthiophene) (P3HT) and a methanofullerene derivative (PCBM). The post thermal annealing modifies the distribution of the P3HT and the PCBM inside the blend films, as it has been found by Spectroscopic Ellipsometry studies in the visible to far-ultraviolet spectral range. Phase separation was identified by AFM and GIXRD as a result of a slow drying process which took place after the spin coating process. The increase of the annealing time resulted to a significant increase of the P3HT crystallinity at the top regions of the blend films. © 2011 Elsevier B.V. All rights reserved.

Thermal annealing effect on the nanomechanical properties and structure of P3HT:PCBM thin films

Nanostructured polymer-fullerene thin films are among the most prominent materials for application in high efficient polymer solar cells. Specifically, poly(3-hexylthiophene) (P3HT) and fullerene derivatives (PCBM) blends are used as the donor/acceptor materials forming a bulk heterojunction. Although P3HT:PCBM properties have been extensively studied, less light has been set on its nanomechanical properties, which affect the device service life. In this work Atomic Force Acoustic Microscopy (AFAM), Atomic Force Spectroscopy and Nanoindentation were used to study the effect of the fullerene presence and the annealing on the P3HT:PCBM nanomechanical behavior. The P3HT:PCBM thin films were prepared by spin coating on glass substrates and then annealed at 100 °C and 145 °C for 30 min. Large phase separation was identified by optical and Atomic Force Microscopy (AFM) for the annealed samples. Needle-like PCBM crystals were formed and an increase of the polymer crystallinity degree with the increase of the annealing temperature was confirmed by X-ray diffraction. AFAM characterization revealed the presence of aggregates close to stiff PCBM crystals, possibly consisting of amorphous P3HT material. AFM force-distance curves showed a continuous change in stiffness in the vicinity of the PCBM crystals, due to the PCBM depletion near its crystals, and the AFM indentation provided qualitative results about the changes in P3HT nanomechanical response after annealing. © 2011 Elsevier B.V. All rights reserved.

Picosecond laser patterning of PEDOT:PSS thin films

Picosecond pulsed laser (10.4 ps, 1064 nm, 5 and 50 kHz) patterning studies were performed, of PEDOT:PSS thin films of varying thickness deposited by spin coating on glass substrates, by ablating the films or by changing locally by laser irradiation the optical and electrical properties of the polymer. From a detailed observation of the morphology of single pulse ablated holes on the surfaces of the films, in combination with simple calculations, it is concluded that photomechanical ablation is the likely ablation mechanism of the films. The single pulse ablation thresholds were measured equal to 0.13-0.18 J/cm 2 for films with thicknesses in the region of ∼100-600 nm. The implications on ablation line patterning of the films using different fluences, scanning speeds and pulse repetition rates, were investigated systematically. Laser irradiation of the films before ablation induces a metal-insulator transition of the polymer because of the formation of charge localization due to a possible creation of molecular disorder in the polymer and shortening of its conjugation length. © 2010 Elsevier B.V. All rights reserved.

In situ intercalation dynamics in inorganic-organic layered perovskite thin films.

The properties of layered inorganic semiconductors can be manipulated by the insertion of foreign molecular species via a process known as intercalation. In the present study, we investigate the phenomenon of organic moiety (R-NH3I) intercalation in layered metal-halide (PbI2)-based inorganic semiconductors, leading to the formation of inorganic-organic (IO) perovskites [(R-NH3)2PbI4]. During this intercalation strong resonant exciton optical transitions are created, enabling study of the dynamics of this process. Simultaneous in situ photoluminescence (PL) and transmission measurements are used to track the structural and exciton evolution. On the basis of the experimental observations, a model is proposed which explains the process of IO perovskite formation during intercalation of the organic moiety through the inorganic semiconductor layers. The interplay between precursor film thickness and organic solution concentration/solvent highlights the role of van der Waals interactions between the layers, as well as the need for maintaining stoichiometry during intercalation. Nucleation and growth occurring during intercalation matches a Johnson-Mehl-Avrami-Kolmogorov model, with results fitting both ideal and nonideal cases.