Thin film composite optical waveguides for sensor applications: a review

We review the design and fabrication of thin-film composite optical waveguides (OWG) with high refractive index for sensor applications. A highly sensitive optical sensor device has been developed on the basis of thin-film, composite OWG. The thin-film OWG was deposited onto the surface of a potassium-ion-exchanged (K+) glass OWG by sputtering or spin coating (5-9 mm wide, and with tapers at both ends). By allowing an adiabatic transition of the guided light from the secondary OWG to the thin-film OWG, the electric field of the evanescent wave at the thin film was enhanced. The attenuation of the guided light in the thin film layer was small, and the guided light intensity changed sensitively with the refractive index of the cladding layer. Our experimental results demonstrate that thin-film, composite OWG gas sensors or immunosensors are much more sensitive than sensors based on other technologies. (c) 2004 Elsevier B.V. All rights reserved.

Two-dimensional images of dissolved sulfide and metals in anoxic sediments by a novel diffusive gradients in thin film probe and optical scanning techniques

A novel diffusive gradients in thin film probe developed comprises diffusive gel layer of silver iodide (AgI) and a back-up Microchelex resin gel layer. 2D high-resolution images of sulfide and trace metals were determined respectively on the AgI gel by densitometric analysis and on the Microchelex resin layer with laser-ablation-inductively-coupled plasma mass spectrometry (LA-ICP-MS).We investigated the validity of the analytical procedures used for the determination of sulfide and trace metals. We found low relative standard deviations on replicate measurements, linear trace-metal calibration curves between the LA-ICP-MS signal and the true trace-metal concentration in the resin gel, and a good agreement of the sulfide results obtained with the AgI resin gel and with other analytical methods. The method was applied on anoxic sediment pore waters in an estuarine and marine system. Simultaneous remobilization of sulfide and trace metals was observed in the marine sediment.

Growth and properties of gold and nickel nanorods in thin film alumina

Arrays of nickel and gold nanorods have been grown on glass and silicon substrates using porous alumina templates of less than 500 nm thickness. A method is demonstrated for varying the diameter of the nanorods whilst keeping the spacing constant. Optical extinction spectra for the gold nanorods show two distinct maxima associated with the transverse and longitudinal axes of the rods. Adding small quantities of oxygen to the aluminium before anodization is found to improve the sharpness of the extinction peaks. The spectral position of the longitudinal peak is shown to be sensitive to the nanorod diameter for constant length and spacing. For the nickel nanorods it is shown that the magnetic properties are governed by both interactions between the wires and shape anisotropy.

Characteristics of the interfacial capacitance in thin film Ba0.5Sr0.5TiO3 capacitors with SrRuO3 and (La, Sr)CoO3 bottom electrodes

Thin film Ba0.5Sr0.5TiO3 (BST) capacitors of thickness similar to75 nm to similar to1200 nm, with Au top electrodes and SrRuO 3 (SRO) or (La, Sr)CoO3 (LSCO) bottom electrodes were fabricated using Pulsed Laser Deposition. Implementing the "series capacitor model," bulk and interfacial capacitance properties were extracted as a function of temperature and frequency. 'Bulk' properties demonstrated typical ceramic behaviour, displaying little frequency dependence and a permittivity and loss peak at 250 K and 150 K respectively. The interfacial component was found to be relatively temperature and frequency independent for the LSCO/BST capacitors, but for the SRO/BST configuration the interfacial capacitance demonstrated moderate frequency and little temperature dependence below T similar to 300 K but a relatively strong frequency and temperature dependence above T similar to3 00 K. This was attributed to the thermal activation of a space charge component combined with a thermally independent background. The activation energy for the space charge was found to be E-A similar to 0.6 eV suggesting de-trapping of electrons from shallow level traps associated with a thin interfacial layer of oxygen vacancies, parallel to the electrodes.

Thin film capacitor cut from single crystals using focused ion beam milling

The focused ion beam microscope (FIB) has been used to fabricate thin parallel-sided ferroelectric capacitors from single crystals of BaTiO3 and SrTiO3. A series of nano-sized capacitors ranging in thickness from similar to660 nm to similar to300 nm were made. Cross-sectional high resolution transmission electron microscopy (HRTEM) revealed that during capacitor fabrication, the FIB rendered around 20 nm of dielectric at the electrode-dielectric interface amorphous, associated with local gallium impregnation. Such a region would act electrically in series with the single crystal and would presumably have a considerable negative influence on the dielectric properties. However, thermal annealing prior to gold electrodes deposition was found to fully recover the single crystal capacitors and homogenise the gallium profile. The dielectric testing of the STO ultra-thin single crystal capacitors was performed yielding a room temperature dielectric constant of similar to300, as is the case in bulk. Therefore, there was no evidence of a collapse in dielectric constant associated with thin film dimensions.

Progressive loss of ferroelectricity under bipolar pulsed fields and experimental determination of non-switchable polarization in Au/Ba0.5Sr0.5TiO3/SrRuO3 thin-film capacitors

175 nm-thick Ba0.5Sr0.5TiO3 (BST) thin film fabricated by pulsed laser deposition (PLD) technique is found to be a mixture of two distributions of material. We discuss whether these two components are nano-regions of paraelectric and ferroelectric phases, or a bimodal grain-size distribution, or an effect of oxygen vacancy gradient from the electrode interface. The fraction of switchable ferroelectric phase decreases under bipolar pulsed fields, but it recovers after removal of the external fields. The plot of capacitance in decreasing dc voltage (C(Vdown arrow) versus that in increasing dc 61 voltage C(Vup arrow) is a superposition of overlapping of two triangles, in contrast to one well-defined triangle for typical ferroelectric SrBi2Ta2O9 thin films.

Understanding thickness effects in thin film capacitors

Pulsed Laser Deposition (PLD) was used to make Au/(Ba0.5Sr0.5)TiO3/(La0.5Sr0.5) CoO3/MgO thin film capacitor structures. Functional properties were studied with changing BST thickness from similar to1265 nm to similar to63 nm. The dielectric constant was found to decrease, and migration of T-m (the temperature at which the dielectric constant is maximum) to lower temperatures occurred as thickness was reduced. Curie-Weiss plots of the as-obtained dielectric data, indicated that the Curie temperature was also systemmatically progressively depressed. Further, fitting to expressions previously used to describe diffuse phase transitions suggested increased diffuseness in transformation behaviour as film thickness decreased. This paper discusses the care needed in interpreting the observations given above. We make particular distinction between the apparent Curie-temperature derived from Curie-Weiss plots of as-measured data, and the inherent Curie temperature determined after correction for the interfacial capacitance. We demonstrate that while the apparent Curie temperature decreases as thickness decreases, the inherent Curie temperature is thickness independent. Thickness-invariant phase transition behaviour is confirmed from analysis of polarisation loops, and from examination of the temperature dependence of the loss-tangent. We particularly note that correction of data for interfacial capacitance does not alter the position of T-m. We must therefore conclude that the position of T-m is not related simply to phase transformation behaviour in BST thin films.

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.

Thin film sputtered silicon for silicon wafer bonding applications

The transfer of functional integrated circuit layers to other substrates is being investigated for smart-sensors, MEMS, 3-D ICs and mixed semiconductor circuits. There is a need for a planarisation and bondable layer which can be deposited at low temperature and which is IC compatible. This paper describes for the first time the successful use of sputtered silicon in this role for applications as outlined above where high temperature post bond anneals are not required. It also highlights the problems of using sputtered silicon as a bonding layer in applications where post bond temperatures greater than 400C are required.

Thickness-induced stabilization of ferroelectricity in SrRuO3/Ba0.5Sr0.5TiO3/Au thin film capacitors

Pulsed-laser deposition has been used to fabricate Au/Ba0.5Sr0.5TiO3/SrRuO3/MgO thin film capacitor structures. Crystallographic and microstructural investigations indicated that the Ba0.5Sr0.5TiO3 (BST) had grown epitaxially onto the SrRuO3 lower electrode, inducing in-plane compressive and out- of-plane tensile strain in the BST. The magnitude of strain developed increased systematically as film thickness decreased. At room temperature this composition of BST is paraelectric in bulk. However, polarization measurements suggested that strain had stabilized the ferroelectric state, and that the decrease in film thickness caused an increase in remanent polarization. An increase in the paraelectric-ferroelectric transition temperature upon a decrease in thickness was confirmed by dielectric measurements. Polarization loops were fitted to Landau-Ginzburg-Devonshire (LGD) polynomial expansion, from which a second order paraelectric-ferroelectric transition in the films was suggested at a thickness of similar to500 nm. Further, the LGD analysis showed that the observed changes in room temperature polarization were entirely consistent with strain coupling in the system. (C) 2002 American Institute of Physics.

Enhancement of dielectric constant and associated coupling of polarization behavior in thin film relaxor superlattices

Thin film capacitor structures in which the dielectric is composed of superlattices of the relaxors [0.2Pb(Zn1/3Nb2/3)O- 3-0.8BaTiO(3)] and Pb(Mg1/3Nb2/3)O-3 have been fabricated by pulsed laser deposition. Superlattice wavelength (Lambda) was varied between similar to3 and similar to 600 nm, and dielectric properties were investigated as a function of Lambda. Progressive enhancement of the dielectric constant was observed on decreasing Lambda, and, in contrast to previous work, this was not associated with the onset of Maxwell-Wagner behavior. Polarization measurements as a function of temperature suggested that the observed enhancement in dielectric constant was associated with the onset of a coupled response. The superlattice wavelength (Lambda =20 nm) at which coupled functional behavior became apparent is comparable to that found in literature for the onset of coupled structural behavior (between Lambda =5 nm and Lambda =10 nm). (C) 2001 American Institute of Physics.

Investigation of dead-layer thickness in SrRuO3/Ba0.5Sr0.5TiO3/Au thin-film capacitors

Thin-film capacitors, with barium strontium titanate (BST) dielectric layers between 7.5 and 950 nm in thickness, were fabricated by pulsed-laser deposition. Both crystallography and cation chemistry were consistent with successful growth of the BST perovskite. At room temperature, all capacitors displayed frequency dispersion such that epsilon (100 kHz)/epsilon (100 Hz) was greater than 0.75. The dielectric constant as a function of thickness was fitted, using the series capacitor model, for BST thicknesses greater than 70 nm. This yielded a large interfacial d(i)/epsilon (i) ratio of 0.40 +/-0.05 nm, implying a highly visible parasitic dead layer within the capacitor structure. Modeled consideration of the dielectric behavior for BST films, whose total thickness was below that of the dead layer, predicted anomalies in the plots of d/epsilon against d at the dead-layer thickness. In the capacitors studied here, no anomaly was observed. Hence, either (i) 7.5 nm is an upper limit for the total dead-layer thickness in the SRO/BST/Au system, or (ii) dielectric collapse is not associated with a distinct interfacial dead layer, and is instead due to a through-film effect. (C) 2001 American Institute of Physics.