Toughness evaluation of hard coatings and thin films

Enormous progress has been achieved over the past decade in evaluating the toughness of hard coatings and thin films. This paper reviews methodologies developed based on indentation, bending, and microtensile testing. In addition, we discuss a recent development in fracture toughness measurement which involves the application of macrotension to a substrate in order to induce microtension in a patterned thin film.     

Growth and characterization of electrosynthesised zinc oxide thin films

Zinc oxide (ZnO) films have been electrodeposited from an aqueous solution containing 0.1 M zinc nitrate as the electrolyte with pH around 5±0.1. The deposition was carried out by galvanostatic reduction with an applied cathodic current density in the range between 5 and 20 mA cm⁻². The influence of bath composition on the preparation of ZnO films is studied. The effects of zinc nitrate concentration and cathodic current density on the deposition rate of ZnO films were also studied. An optimum current density of 10 mA cm⁻² is identified for the growth of ZnO film with improved crystallinity and optical transmittance. The crystalline structure of the deposits studied by X-ray diffraction reveals the possibility of growing hexagonal ZnO films under suitable electrochemical conditions. The surface morphological studies by scanning electron micrographs revealed the presence of nodular appearance for films deposited at 800 °C bath temperatures.     

The influence of indenter bluntness on the apparent contact stiffness of thin coatings

In the present paper, the influence of punch tip sharpness on the interpretation of indentation measurements is considered.Firstly, in order to obtain analytical insight into the nature of the problem, closed form solutions are presented for the indentation of a homogeneous elastic half-space by an axisymmetric indenter of arbitrary shape, including Hertzian, conical, and conical indenter with a rounded tip.Next, a fast and efficient numerical implementation of a semi-analytical approach to the solution of problems about frictionless axisymmetric indentation of an elastic layer on a dissimilar substrate is described. The approach allows rapid determination of the load-displacement curves for an arbitrary punch shape.The aim of the study was to explore the implications of a finite indenter tip radius for the problem of property identification of thin films. The variation of the apparent substrate stiffness with indentation depth was established for several generic indenter shapes, namely for flat, conical and parabolic punches, and for a conical punch with a rounded tip. It is demonstrated that in each of these cases the depth variation can be described by a simple curve belonging to a family of two-parametric functions. On the basis of these findings we assess the efficiency of using different punch shapes for property determination. A procedure is proposed for this purpose which relies on the use of the depth variation profiles established here. Finally, the influence of imperfect punch shape on the accuracy of analysis is considered.     

Fabrication and characterization of Cu2ZnSnS4 thin films deposited by spray pyrolysis technique

We have investigated synthesis conditions and some properties of sprayed Cu₂ZnSnS₄ (CZTS) thin films in order to determine the best preparation conditions for the realization of CZTS based photovoltaic solar cells. The thin films are made by means of spraying of aqueous solutions containing copper chloride, zinc chloride, tin chloride and thiourea on heated glass substrates at various temperatures. In order to optimize the synthesis conditions of the CZTS films, two series of experiments are performed. In the first series the sprayed duration was fixed at 30 min and in the second it is fixed at 60 min. In each series, the substrate temperature was changed from 553°K to 633°K. The X-ray diffraction shows, on one hand, that the best crystallinity was obtained for 613°K as substrate temperature and 60 min as sprayed duration. On the other hand, these CZTS films exhibit the kesterite structure with preferential orientation along the [112] direction. Atomical Force Microscopy was used to determine the grain sizes and the roughness of these CZTS thin film. After the annealing treatment, we estimated the optical band-gap energy of the CZTS thin film exhibiting the best crystallinity as 1.5 eV which is quite close to the optimum value for a solar cell.     

Raman spectroscopy for quality control and process optimization of chalcopyrite thin films and devices

We will demonstrate in this paper that Raman scattering of visible light is a versatile tool both for research and industrial process monitoring of thin chalcopyrite films for solar cells. Thin films of Cu(In, Ga)(S,Se)₂ (CIGSSe) are produced by rapid thermal processing of stacked elemental Cu-In-Ga-Se layers. The Raman investigations are accompanied by grazing incidence X-ray diffraction (GI-XRD) and X-ray florescence (XRF) measurements. GI-XRD measurements confirm that the films show a two-fold elemental gradient: a sulfur gradient from the top and a Ga gradient from the CIGSSe/Mo interface. By Rietveld refinement of the GI-XRD spectra of the surface-near (∼ 100nm) ratio of sulfur to selenium can be obtained which corresponds well to the intensity ratio of the two Raman A1 modes of CuInS₂ and CuInSe₂. The asymmetric line shape of both XRD diffractograms and Raman spectra is attributed to the sulfur gradient. In addition we show that the intensity ratio of the satellite Raman B and E modes shows a correlation with the Cu to In + Ga ratio obtained by XRF.     

Preparation and characterization of new hybrid nanostructured thin films for biosensors design

The present paper reports on an innovative route for the preparation of new hybrid nanostructured thin films based on hydroxyapatite and functionalized polyurethane. Hybrid nanopowders based on hydroxyapatite and functionalized polyurethane have been synthesized by a hydrothermal method with high pressure and low temperature conditions and further used for spin coating deposition. Biocompatible thin films with a thickness of about 50 nm have been deposited onto Si/SiO₂/Ti/Au substrates and their properties recommend them suitable as possible electrodes for the fabrication of impedance biosensors. Hybrid materials with improved properties are obtained, combining the mechanical properties of polyurethane with biocompatible properties of hydroxyapatite (bioactivity and osteoconductivity). The presence of functional groups in polyurethane structure ensures the existence of strong interactions between components and an increased affinity of the thin films for further protein bonding in biosensor design. Hybrid nanostructured thin films based on hydrothermally synthesized hydroxyapatite-polyurethane nanopowders could enhance the amount of immobilized biomolecules in the construction of an impedance biosensor for diagnosis and therapy of bone diseases.     

Preparation and characterization of flash-evaporated CuInSe2 thin films

Thin films of CuInSe₂ have been evaporated onto glass substrates by flash evaporation. The as-deposited films are amorphous and annealing in selenium atmosphere produces polycrystalline films. The films were characterized bytem and x-ray diffraction techniques. The optical absorption of the films shows three energy gaps of 1·03, 1·07 and 1·22 eV. The crystal field and spin-orbit splitting are thus found to be 0·04 eV and 0·16 eV respectively. The percentaged-character of the valence band states is ∼35%. The Arrhenius plot of electrical conductivity of films showed impurity ionization ofE _A = 75 meV.     

Comparison of different dispersion models for single layer optical thin film index determination

We here determine the optical properties of different single-layer thin films containing Ta₂O₅, Si, Indium Tin Oxide and Au in the ultraviolet-visible and near infrared ranges. More specifically, we deduce the complex refractive index and thickness from the reflectance and transmittance measured using a spectrophotometer at normal incidence. One major difficulty is to find an appropriate selection of dispersion laws for various types of material (dielectric, semiconductors, and metals). For this purpose, a number of models have been investigated from a theoretical point of view in consideration of the Kramers-Kronig relation. These include the Forouhi-Bloomer model, combined with the modified Drude, Tauc-Lorentz and multiple-oscillator Tauc-Lorentz models. A global optimization procedure had to be employed because of the large number of parameters (from 3 to 15) required to describe the optical dispersion laws. The calculated reflectance and transmittance are in good agreement with experimental data and the complex refractive index is consistent with our knowledge and that already reported.     

Characterization of the porosity of thin zirconium oxide coatings prepared at low temperatures

In this work we investigated the possibilities to reduce the porosity of thin protective zirconium oxide films deposited with the sol-gel technique at low temperatures. Electrochemical investigations showed that the concentration of the stabilizing agent acetylacetone is a crucial parameter for the protection performance of the zirconium oxide films and that it is possible to run the deposition process at much lower temperatures with the optimum stabilizer concentration. This allows the application of the process to sensitive substrates that cannot be treated at high temperatures and reduces energy costs as well. Characterization of the film structure with secondary ion mass spectrometry revealed that the stabilizing agent is responsible for the formation of a mixed oxide layer at the interface of substrate and coating. The thickness of this layer can be tuned with the concentration of the stabilizing agent.     

Preparation and characterization of spray deposited n-type WO3 thin films for electrochromic devices

The n-type tungsten oxide (WO₃) polycrystalline thin films have been prepared at an optimized substrate temperature of 250 °C by spray pyrolysis technique. Precursor solution of ammonium tungstate ((NH₄)₂WO₄) was sprayed onto the well cleaned, pre-heated fluorine doped tin oxide coated (FTO) and glass substrates with a spray rate of 15 ml/min. The structural, surface morphological and optical properties of the as-deposited WO₃ thin films were studied. Mott-Schottky (M-S) studies of WO₃/FTO electrodes were conducted in Na₂SO₄ solution to identify their nature and extract semiconductor parameters. The electrochromic properties of the as-deposited and lithiated WO₃/FTO thin films were analyzed by employing them as working electrodes in three electrode electrochemical cell using an electrolyte containing LiClO₄ in propylene carbonate (PC) solution.     

NiTi thin film characterization by Rutherford backscattering spectrometry

Nickel and titanium can form alloys showing the shape memory effect when combined in the right stoichiometric proportion (1:1). Recently, such alloys have been produced as thin films by sputtering (RF or DC, with or without magnetron), with a view to making microelectromechanical actuators. Precise control of the characteristic transformation temperature is crucial for obtaining the shape memory effect. This requires analytical tools which can accurately determine the relative composition, and hence the transition temperature. In this paper, Rutherford backscattering spectrometry will be shown to meet the requirements of thin film processing of NiTi shape memory alloys, and to have advantages when compared with other techniques.     

Effect of substrate temperature on ac conduction properties of amorphous and polycrystalline GaSe thin films

X-ray diffraction analysis of GaSe thin films used in the present investigation showed that the as-deposited and the one deposited at higher substrate temperature are in amorphous and polycrystalline state, respectively. The alternating current (ac) conduction properties of thermally evaporated films of GaSe were studied ex situ employing symmetric aluminium ohmic electrodes in the frequency range of 120-10⁵ Hz at various temperature regimes. For the film deposited at elevated substrate temperature (573 K) the ac conductivity was found to increase with improvement of its crystalline structure. The ac conductivity (σ_ac) is found to be proportional to (ω^s) where s < 1. The temperature dependence of ac conductivity and the parameter, s, is reasonably well interpreted by the correlated barrier-hopping (CBH) model. The maximum barrier heights W_m calculated from ac conductivity measurements are compared with optical studies of our previous reported work for a-GaSe and poly-GaSe thin films. The distance between the localized centres (R), activation energy (ΔE_σ) and the number of sites per unit energy per unit volume N(E_F) at the Fermi level were evaluated for both a-GaSe and poly-GaSe thin films. Goswami and Goswami model has been invoked to explain the dependence of capacitance on frequency and temperature.     

Growth and characterization of electrosynthesized iron selenide thin films

Iron selenide (FeSe) thin films were electrodeposited onto indium doped tin oxide coated conducting glass (ITO) substrates at various bath temperatures from 30 °C to 90 °C in an aqueous electrolytic bath containing FeSO₄ and SeO₂. The deposition mechanism was investigated using cyclic voltammetry. The appropriate potential region where the formation of stoichiometric iron selenide thin films' occurs was found to be −1100 mV versus SCE. X-ray diffraction studies revealed that the deposited films are found to be hexagonal structure with a preferential orientation along (002) plane. The parameters such as crystallite size, strain, dislocation density are calculated from X-ray diffraction studies. Optical absorption measurements were used to estimate the band gap value of iron selenide thin films deposited at various bath temperatures. Scanning electron microscopy (SEM) was used to study the surface morphology. The composition of FeSe thin films was analyzed using an energy dispersive analysis by X-rays (EDX) set up attached with scanning electron microscopy. Preliminary studies for photoelectrochemical solar cells based on iron selenide thin films were carried out and the experimental observations are discussed.     

Glow discharge optical emission spectroscopy for accurate and well resolved analysis of coatings and thin films

In the last years, glow discharge optical emission spectrometry (GDOES) gained more and more acceptance in the analysis of functional coatings. GDOES thereby represents an interesting alternative to common depth profiling techniques like AES and SIMS, based on its unique combination of high erosion rates and erosion depths, sensitivity, analysis of nonconductive layers and easy quantification even for light elements such as C, N, O and H. Starting with the fundamentals of GDOES, a short overview on new developments in instrument design for accurate and well resolved thin film analyses is presented.The article focuses on the analytical capabilities of glow discharge optical emission spectrometry in the analysis of metallic coatings and thin films. Results illustrating the high depth resolution, confirmation of stoichiometry, the detection of light elements in coatings as well as contamination on the surface or interfaces will be demonstrated by measurements of: a multilayer system Cr/Ti on silicon, interface contamination on silicon during deposition of aluminum, Al₂O₃-nanoparticle containing conversion coatings on zinc for corrosion resistance, Ti₃SiC₂ MAX-phase coatings by pulsed laser deposition and hydrogen detection in a V/Fe multilayer system. The selected examples illustrate that GDOES can be successfully adopted as an analytical tool in the development of new materials and coatings. A discussion of the results as well as of the limitations of GDOES is presented.     

Characteristics of highly orientated BiFeO3 thin films on a LaNiO3-coated Si substrate by RF sputtering

BiFeO₃ (BFO) films were grown on LaNiO₃-coated Si substrate by a RF magnetron sputtering system at temperatures in the range of 300-700 °C. X-ray reflectivity and high-resolution diffraction measurements were employed to characterize the microstructure of these films. For a substrate temperature below 300 °C and at 700 °C only partially crystalline films and completely randomly polycrystalline films were grown, whereas highly (001)-orientated BFO film was obtained for a substrate temperature in the range of 400-600 °C. The crystalline quality of BFO thin films increase as the deposition temperature increase except for the film deposited at 700 °C. The fitted result from X-ray reflectivity curves show that the densities of the BFO films are slightly less than their bulk values. For the BFO films deposited at 300-600 °C, the higher the deposition temperature, the larger the remnant polarization and surface roughness of the films present.     

Electrophoretic deposition of siderite thin layers: Influence of electrode potential and deposition time

Siderite thin layers have been obtained by electrophoretic deposition on an inert substrate (gold). Scanning electron microscopy image exhibits a compact and homogeneous film composed of round grains which diameter is about 1-2 µm. The influence of two parameters, namely the electrode potential and the deposition time, on its thickness and its microstructure was investigated. The thickness was shown to be slightly dependent of the electrode potential (1.2 µm for − 0.70 V and 1.7 µm for − 0.95 V after 17 h). The crystallite size, estimated by X-ray diffraction patterns, was about 5 nm, depending on both electrode potential and deposition time. Despite its high sensitivity to oxygen, X-ray photoelectron spectroscopy spectra prove that the siderite surface has been kept out from oxidation. These siderite thin layers could be used as modified electrodes for further interaction studies.     

Growth and characterization of electrodeposited Cu(In,Al)Se2 thin films

Thin films of CuIn_1 − xAl_xSe₂ were grown using a cathodic electrodeposition technique. The CuIn_1 − xAl_xSe₂ films were electrodeposited on SnO₂ coated glass from aqueous baths containing different Al contents using deposition potentials ranging from − 650 mV to − 850 mV versus a saturated calomel electrode. The electrodeposited films were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive analysis of X-rays, atomic force microscopy, and UV-VIS-NIR spectroscopy. The results show that single phase CuIn_1 − xAl_xSe₂ films with Al content x around 0.27-0.33 having good stoichiometry can be produced in the above potential range. XRD and SEM studies show that films deposited at − 650 mV and − 750 mV have good crystallinity while those grown at − 850 mV have comparatively poorer crystallinity. SEM studies show that the particle size of the films grown at − 650 and − 750 mV is in the micron range but is around 100 nm when grown at − 850 mV. Optical studies show that the optical band gap shifts with Al content from 1.21 eV for x = 0.27 to about 1.42 eV for x = 0.33. The as-grown as well as vacuum annealed films were n-type in conductivity with resistivity in the range 3-5 × 10⁻³ Ω cm.     

Fabrication and characterization of vacuum deposited fluorescein thin films

Simple vacuum evaporation technique for deposition of dyes on various solid surfaces has been developed. The method is compatible with conventional solvent-free nanofabrication processing enabling fabrication of nanoscale optoelectronic devices. Thin films of fluorescein were deposited on glass, fluorine-tin-oxide (FTO) coated glass with and without atomically layer deposited (ALD) nanocrystalline 20 nm thick anatase TiO₂ coating. Surface topology, absorption and emission spectra of the films depend on their thickness and the material of supporting substrate. On a smooth glass surface the dye initially forms islands before merging into a uniform layer after 5 to 10 monolayers. On FTO covered glass the absorption spectra are similar to fluorescein solution in ethanol. Absorption spectra on ALD-TiO₂ is red shifted compared to the film deposited on bare FTO. The corresponding emission spectra at λ = 458 nm excitation show various thickness and substrate dependent features, while the emission of films deposited on TiO₂ is quenched due to the effective electron transfer to the semiconductor conduction band.     

Comparison of residual stress measurement in thin films using surface micromachining method

Conductive, dielectric, semiconducting, piezoelectric and ferroelectric thin films are extensively used for MEMS/NEMS applications. One of the important parameters of thin films is residual stress. The residual stress can seriously affect the properties, performance and long-term stability of the films. Excessive compressive or tensile stress results in buckling, cracking, splintering and sticking problems. Stress measurement techniques are therefore essential for both process development and process monitoring. Many suggestions for stress measurement in thin films have been made over the past several decades. This paper is concentrated on the in situ stress measurement using surface micromachining techniques to determine the residual stress. The authors review and compare several types of stress measurement methods including buckling technique, rotating technique, micro strain gauge and long-short beam strain sensor.     

Preparation and characterization of amorphous manganese sulfide thin films by SILAR method

Manganese sulfide thin films were deposited by a simple and inexpensive successive ionic layer adsorption and reaction (SILAR) method using manganese acetate as a manganese and sodium sulfide as sulfide ion sources, respectively. Manganese sulfide films were characterized for their structural, surface morphological and optical properties by means of X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis and optical absorption measurement techniques. The as-deposited film on glass substrate was amorphous. The optical band gap of the film was found to be thickness dependent. As thickness increases optical band gap was found to be increase. The water angle contact was found to be 34°, suggesting hydrophilic nature of manganese sulfide thin films. The presence of Mn and S in thin film was confirmed by energy dispersive X-ray analysis.