Interfacial processing and adhesion of diamond,diamond-like,and TiN films on metallic and polymeric substrates

Diamond, diamond-like, and titanium nitride (TiN) films have extremely desirable chemical, electrical, and mechanical properties for a variety of applications ranging from corrosion- and erosion-resistant coatings to electronics packaging of microelectronic devices. However, many of these applications are limited by the poor adhesion of these films to metal and polymer substrates. The adhesion of a film is determined primarily by internal stresses in the film, thermal and lattice mismatch, and most importantly by interfacial bonding. We have developed methods based on mechanical interlocking, chemical bonding, grading of interatomic potentials, and the multilayer discontinuous thin films approach to control stresses and strains in thin films. A substantial improvement in adhesion and wear properties is obtained by using these methods selectively. We review issues related to the adhesion of diamond, diamond-like carbon, and TiN films on metal and polymeric substrates.     

Effects of heat treatment on the mechanical properties at elevated temperatures of plain-woven SiC/SiC composites

The effects of heat treatment on the mechanical properties of plain-woven SiC/SiC composites at 927 °C and 1200 °C in argon were evaluated through tensile tests at room temperature and at elevated temperature on the as-received and heat-treated plain-woven SiC/SiC composites, respectively. Heat treatment can improve the mechanical properties of composites at room temperature due to the release of thermal residual stress. Although heat treatment can damage the fiber, the effect of this damage on the mechanical properties of composites is generally less than the effect of thermal residual stress. Heat treatment will graphitize the pyrolytic carbon interface and reduce its shear strength. Testing temperature will affect the expansion or contraction of the components in the composites, thereby changing the stress state of the components. This study can provide guidance for the optimization of processing of ceramic matrix composites and the structural design in high-temperature environments.     

Temperature field and residual stress analysis of multilayer pyroelectric thin film

The two-dimensional finite element model was built for the multilayer pyroelectric thin film. The temperature field and residual stress were simulated. The results show that porous silica film as a thermal-insulation layer and a reasonable model structure are effective for decreasing the heat loss. The silicon substrate and pyroelectric thin film that influence the temperature variation rate in pyroelectric thin film are also discussed. The annealing temperature and model structure have significant influence on residual stresses of pyroelectric thin film. The residual stresses increase rapidly with the increase of annealing temperature. The scanning electron microscopy (SEM) is employed to investigate the morphology of the pyroelectric thin film. The results show that the pyroelectric thin film annealed at 750 °C has a crack structure.     

A study of the initial stages of diamond deposition on ferrous substrates coated by a nitrided chromium interlayer and on nitrided polycrystalline chromium substrates

The use of a nitrided chromium interlayer has been found to improve the interfacial properties of diamond films deposited on ferrous substrates. This is achieved by hindering diffusion process of carbon and iron, good adhesion of the interlayer to the steel substrate, and very stable mechanical and chemical bonding between the interlayer and the diamond film. In the present study the initial stages of diamond deposition on steel substrates coated by a nitrided chromium interlayer and on nitrided polycrystalline chromium substrates are reported. Nitridation of chromium films deposited by electrochemical methods and polycrystalline chromium substrates resulted in the formation of two chromium nitrides phases, CrN and Cr₂N, and a rough surface morphology. The initial stages of diamond deposition were found to be accompanied by carburization of the substrates surface resulting in chromium carbide formation. The incubation time, diamond particle density and growth rate at the very initial stages of the deposition process were found to differ for these two substrates. It is suggested that these differences originate from different carburization rates of the two substrates. Phase transformation, recrystallization and diffusion processes in the near surface regions of both substrates resulted in very stable chemical bonding and good adhesion of the diamond film to the substrates. Raman spectra of the deposited films, on both substrates, show shift of the diamond peak position to higher wave numbers and split of the peak. These effects are associated with compressive stresses in the diamond film. Residual stresses in the deposited films were calculated from the shift of the diamond Raman peak. The residual stresses, as calculated from the Raman spectra, were found to increase with deposition time reaching values of 8.4 and 6.9 GPa for continuous diamond films on steel substrate coated with the nitrided chromium film and on nitrided chromium substrates, respectively. Based on a simple model it was estimated that thermal stress, arising from mismatch between the thermal expansion coefficient of diamond and the underlying substrates, is the major component of the compressive stress in the diamond films.     

Effects of thermal annealing and Si incorporation on bonding structure and fracture properties of diamond-like carbon films

The effects of thermal annealing and Si incorporation on the structure and properties of diamond-like carbon (DLC) films were investigated. As-deposited DLC film (DLC) and Si incorporated DLC film (Si-DLC), both with and without thermal annealing, were analyzed for bonding structure, residual stress, film thickness, elastic modulus and fracture properties using Raman spectroscopy, wafer curvature, nanoindentation, four-point bend fracture testing, and X-ray photoelectron spectroscopy (XPS). Raman spectroscopy clearly showed that thermal annealing of DLC films promotes more sp² bonding character, whereas Si incorporation into the films promotes more sp³ bonding character. Interfacial fracture energies, film hardness and elastic modulus, and residual film stress were all found to vary strongly with the degree of sp³ bonding in the DLC film. These changes in mechanical properties are rationalized in terms of the degree of three dimensional inter-links within the atomic bond network.     

Thermal annealing behaviour of alloyed DLC films on steel: Determination and modelling of mechanical properties

A shortcoming of diamond-like carbon (DLC) films is the poor stability of their microstructure and properties at elevated temperatures. In this study, the effect of annealing on the stability of DLC films alloyed with silicon and deposited on steel is investigated. A comprehensive study of the mechanical properties is carried out by a novel method combining normal indentations with micro- and macroindentors assisted by finite element calculations of the indentation. The mechanical properties of the layers are correlated to structural changes in the film and to interface reactions.While it has become a common practice to determine hardness and the Young's modulus of thin films by nanoindentation and to calculate residual stresses from the bending of the film/substrate system, evaluation of the interface toughness, which is a measure of adhesion, and of the film rupture strength is less straightforward. Here, Hertzian-type ring cracks are generated in the film by nanoindentation of the film/substrate system with spherical diamond tips. From the critical load for crack generation the film rupture strength is deduced using finite element calculations. Similarly, Rockwell C hardness tests in combination with calculations are performed to measure the interface toughness.Applying these methods to DLC films on steel, it has been found that the Young's modulus decreases with increasing silicon content and the residual stress drops below 1 GPa. The rupture strength approaches its theoretical limit of E/10. Annealing at 500 °C reduces the adhesion energy significantly. The variation of mechanical properties can be attributed to structural changes in the film as investigated by Raman spectroscopy.     

Characterization of the mechanical properties of diamond-like carbon films

A recently suggested method to measure the elastic modulus of diamond-like carbon (DLC) films was reviewed. This method used a DLC bridge or free overhang which is free from the mechanical constraint of the substrate. Because of the high residual compressive stress of the DLC film, the bridge or the overhang exhibited a sinusoidal displacement on removing the mechanical constraint. Measuring the amplitude and wavelength of the sinusoidal displacement made it possible to measure the strain of the film which occurred by stress relaxation. Combined with independent stress measurement using the laser reflection method, this method allowed the calculation of the biaxial elastic modulus of the DLC film. This method was successfully applied to obtain the elastic properties of various DLC films from polymeric hydrogenated amorphous carbon (a-C:H) to hard tetrahedral amorphous carbon (ta-C) films. Since the substrate is completely removed from the measurement system, this method is insensitive to the mechanical properties of substrate. The mechanical properties of very thin DLC films could be thus measured and then can reveal the structural evolution of a-C:H films during the initial stages of deposition.     

Thermal,optical, and electrical characterization of thin film coated RTV 655 bilayer system

Adhesion of thin films to hydrophobic elastomeric substrates is of particular interest in the area of flexible electronics and nano‐sensor technology. Here, nanometer‐thick Au films were deposited directly onto hydrophobic RTV 655 substrates by means of sputtering, thermal evaporation, and electroless techniques without an adhesion‐promoting layer. The bilayer system was exposed to repeat thermal cycling and changes to the surface morphology of the thin film were monitored electrically and optically. Buckle formation in the as‐deposited film was attributed to stress in the film and substrate stiffness rather than thermal coefficient mismatch between films. The Au‐RTV 655 interface was water tight and maintained a strong adhesion despite repeated thermal cycles. Sputtered and thermally evaporated carbon‐coated RTV 655 substrates were also studied in parallel for comparison. Periodic arrays of buckles formed in pre‐strained RTV 655 samples showed reproducibility in their optical properties demonstrating good adhesion between the two layers without an interfacial layer. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41396.     

Influence of Residual Stresses, Interface Roughness, and Fiber Coatings on Interfacial Properties in Ceramic Composites

Fiber pushout tests are performed on zircon-matrix composites especially fabricated with a variety of silicon carbide reinforcing fibers and fiber coatings in order to create samples with different interfacial properties, surface roughness, and possibly in different states of residual stress to demonstrate their role on the interfacial and mechanical properties of fiber-reinforced composites. The data obtained from fiber pushout tests are analyzed using linear, shear-lag, and progressive debonding models to extract important interfacial properties, residual stresses, and surface roughness. The nature and magnitude of residual stresses in composites are independently characterized by measuring the coefficient of thermal expansion of the fiber, the matrix, and the composite for comparison with similar values measured using the fiber pushout tests. These results are then compared for self-consistency among different ways of analyzing data and with independently measured and calculated values. The results have shown that independent and complementary methods of data acquisition and analysis are required to fully understand interfacial properties in ceramic composites. In particular, independent measures of the coefficient of thermal expansion, residual stresses, and surface roughness are required to confidently interpret interfacial properties obtained by different analytical approaches and then relate them to the overall mechanical response of composites. It is also shown that composites with optimum mechanical response can be created by suitably engineering the interface using multiple fiber coatings.     

Relationship Between Interphase Composition,Material Properties,and Residual Thermal Stresses in Composite Materials

A methodology for predicting the formation and influence of interphase regions in composite materials is illustrated through an investigation of the relationship of sizing-induced interphase regions to the development of residual thermal stresses in a carbon fiber epoxy-amine composite. Fiber surface and sizing induced concentration gradients in the epoxy-amine system were predicted. Material property data was measured for bulk epoxy-amine systems corresponding to the predicted interphase concentrations and the properties mapped into property profiles in the vicinity of the fiber surface. Micromechanical models were used to predict residual thermal stresses for carbon fiber epoxy-amine composites with these interphase properties. The analyses predict that the thermal stress state is significantly affected by modulus variations in the interphase region. The variations in the properties of the interphase material can be affected through processing conditions and/or material selections.     

Relationship Between Interphase Composition, Material Properties, and Residual Thermal Stresses in Composite Materials

A methodology for predicting the formation and influence of interphase regions in composite materials is illustrated through an investigation of the relationship of sizing-induced interphase regions to the development of residual thermal stresses in a carbon fiber epoxy-amine composite. Fiber surface and sizing induced concentration gradients in the epoxy-amine system were predicted. Material property data was measured for bulk epoxy-amine systems corresponding to the predicted interphase concentrations and the properties mapped into property profiles in the vicinity of the fiber surface. Micromechanical models were used to predict residual thermal stresses for carbon fiber epoxy-amine composites with these interphase properties. The analyses predict that the thermal stress state is significantly affected by modulus variations in the interphase region. The variations in the properties of the interphase material can be affected through processing conditions and/or material selections.     

Residual stress and mechanical properties of polyimide thin films

Four different structure polyimide thin films based on 1,4‐phenylene diamine (PDA) and 4,4′‐oxydianiline (ODA) were synthesized by using two different dianhydrides, pyromellitic dianhydride (PMDA) and 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), and their residual stress behavior and mechanical properties were investigated by using a thin film stress analyzer and nanoindentation method. The residual stress behavior and mechanical properties were correlated to the morphological structure in polyimide films. The morphological structure of polyimide thin films was characterized by X‐ray diffraction patterns and refractive indices. The residual stress was in the range of ?5 to 38 MPa and increased in the following order: PMDA‐PDA < BPDA‐PDA < PMDA‐ODA < BPDA‐ODA. The hardness of the polyimide films increased in the following order: PMDA‐ODA < BPDA‐ODA < PMDA‐PDA < BPDA‐PDA. The PDA‐based polyimide films showed relatively lower residual stress and higher hardness than the corresponding ODA‐based polyimide films. The in‐plane orientation and molecularly ordered phase were enhanced with the increasing order as follows: PMDA‐ODA < BPDA‐ODA < BPDA‐PDA ～ PMDA‐PDA. The PDA‐based polyimides, having a rigid structure, showed relatively better‐developed morphological structure than the corresponding ODA‐based polyimides. The residual stress behavior and mechanical properties were correlated to the morphological structure in polyimide films. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Residual stress and electrical properties of Pb(Zr0.52,Ti0.48)O3 thin films RF sputtered directly on Cu foils

Polycrystalline Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films between 250 and 1000 nm thick were deposited on Cu foils via RF magnetron sputtering. Samples were crystallized ex situ between 550°C and 750°C in a low oxygen partial pressure atmosphere, pO₂, in order to avoid oxidation of the substrate. These were compared to films made on more common Pt/TiO_x/SiO₂/Si substrates also crystallized under low pO₂ conditions. The mismatch of the coefficients of thermal expansion for Cu and PZT caused large compressive residual stresses to develop in the films, whereas films on Pt‐Si experienced more moderate tensile stresses. Stress was measured using the sin²ψ method. In addition to mechanical implications, i.e., film cracking and delamination, the effect of residual stress on electrical properties is discussed. Dielectric constants of PZT were lower on Cu than on Pt/TiO_x/SiO₂/Si. This could be due either to a dead layer effect or to the residual stress imposed by the substrate. The remanent polarizations for films on Cu were between 18 and 41 μC/cm², while coercive fields were between 37 and 54kV/cm. Rayleigh analysis was used to describe the role of defects affecting domain wall mobility, as they act as pinning centers and decrease the extrinsic polarization response.     

Effect of carbonitriding temperature process on the adhesion properties of diamond like-carbon coatings deposited by PECVD on austenitic stainless steel

The deposition of adherent coatings such as diamond-like carbon (DLC) on substrates of iron-based materials is difficult to obtain for two reasons: high residual compressive stress occurs in the inner film formation, and the mismatch of thermal expansion coefficient between steel and DLC film generates delamination effects. In order to determine the carbonitriding temperature prior to film deposition, the steel substrate and the DLC films were analyzed for their microstructure and mechanical properties of adhesion as a function of temperature. The technique used to deposit the coating was DC-pulsed plasma enhanced chemical vapor deposition. The delamination distances and the critical load of the film were obtained by scratch testing. The surface analysis by X-ray diffraction indicated the formation of nitride phases on the steel. Raman spectroscopy showed the fraction of sp³ carbon bonds in DLC films. Hardness profiling was used to verify the extent of the interface modified by carbonitriding along the cross section. For this, the steel sample with the appropriate surface modification to have high adhesion of the DLC film was used.     

Mechanical performance of ITO/Ag/ITO multilayer films deposited on glass substrate by RF and DC magnetron sputtering

ITO/Ag/ITO multilayer thin films have been a potential substitute of the conventional single-layer transparent conducting film. Nevertheless, the mechanical stability under preparation and in-service conditions still limits their applications and developments. In this paper, the influences of different structural properties as well as layer structure on both surface morphological properties and mechanical properties of the ITO/Ag/ITO multilayer thin films in comparison with commercial single-layer ITO thin film were systematically investigated. The results demonstrate that, i) the tri-layer composite has large impacts on the preferential orientation, and exhibits the decreased values of surface roughness, net lattice distortion and residual stress; ii) the increased hardness (H) and decreased Young's modulus (E) for full annealed ITO/Ag/ITO multilayer films indicate that it is possible to tailor mechanical properties of the materials by manufacturing multilayer composite; iii) the ITO/Ag/ITO multilayer thin film exhibits remarkable improvements in wear resistance with the increase of annealing temperature, which is mainly attributed to the increased ratios of H/E and H³/E².     

Synthesis and characterization of new functional poly(urethane‐imide) crosslinked networks

To synthesize new functional poly(urethane‐imide) crosslinked networks, soluble polyimide from 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride, 4,4′‐oxydianiline, and maleic anhydride and polyurethane prepolymer from polycaprolactone diol, tolylene 2,4‐diisocyanate and hydroxyl ethyl acrylate were prepared. Poly(urethane‐imide) thin films were finally prepared by the reaction between maleimide end‐capped soluble polyimide (PI) and acrylate end‐capped polyurethane (PU). The effect of polyurethane content on dielectric constant, residual stress, morphology, thermal property, and mechanical property was studied by FTIR, prism coupler, Thin Film Stress Analyzer (TFSA), XRD, TGA, DMTA, and Nano‐indentation. Dielectric constant of poly(urethane‐imide) thin films (2.39–2.45) was lower than that of pure polyimide (2.46). Especially, poly(urethane‐imide) thin films with 50% of PU showed lower dielectric constant than other poly(urethane‐imide) thin films did. Lower residual stress and slope in cooling curve were achieved in higher PU content. Compared to typical polyurethane, poly(urethane‐imide) thin films exhibited better thermal stability due to the presence of the imide groups. The glass transition temperature, modulus, and hardness decreased with increase in the flexible PU content even though elongation and thermal expansion coefficient increased. Finally, poly(urethane‐imide) thin films with low residual stress and dielectric constant, which are strongly affected by the morphological structure, chain mobility, and modulus, can be suggested to apply for electronic devices by variation of PU. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 113–123, 2006     

Size effects of electrocaloric cooling in ferroelectric nanowires

Considering finite size effect, ferroelectric nanowires may show novel phenomena compared to ferroelectric thin film and bulk. Here we investigated the effect of width and surface compressive stress on electrocaloric cooling in ferroelectric nanowire by using thermodynamic calculations and phase‐field simulations. It was found that the isothermal entropy change and adiabatic temperature change in nanowire are 50% larger than that in thin film due to different mechanical boundary conditions of nanowire and thin film. The largest electrocaloric temperature changes were shown to increase significantly either with the decrease in nanowire width or the increase with the surface compressive stress. It was also revealed that the largest intrinsic entropy changes are almost the same for different nanowires with different widths and various stresses. The present study therefore contributes to the understanding of size effects of electrocaloric cooling and provides guidance for experiments to design high‐efficiency cooling devices using ferroelectric nanosystems.     

Investigation of the coefficient of thermal expansion in nanocrystalline diamond films

Nanocrystalline diamond films are a promising class of nanomaterials with tunable properties. An especially appealing field of application for NCD are nitrogen doped semiconducting films.The residual stress in the films is an important film property directly influencing the adhesion of the film on the substrate and thus the film performance. The residual stress consists of two components: a thermal part due to the different coefficients of thermal expansion of film and substrate and an intrinsic part. The residual stress in most films that are deposited at high temperatures is dominated by an effect arising from the difference in coefficients of thermal expansion in film and substrate. By measuring the residual stress in the film at different temperatures it is possible to calculate the coefficient of thermal expansion of the films. For this purpose an ex-situ optical device was used to measure the residual stress of the film.Nanocrystalline diamond films were deposited by microwave-plasma CVD at a pressure of 200 mbar from an Ar/H₂/CH₄ plasma while the hydrogen fraction in the process gas and the substrate temperature were varied between 3 to 6% to 600 to 800 °C respectively.To investigate the influence of the nitrogen admixture in the plasma on the thermal expansion coefficient more films were deposited at a pressure of 200 mbar with admixtures of nitrogen of 2.5% and 7.5%.It is shown that by controlling the process parameters the coefficient of thermal expansion in the NCD films can be matched with the silicon substrate for insulating as well as for conductive films and therefore the thermal stress component be minimized. The results are important for the development of MEMS where silicon as a substrate is widely used.     

Uniaxial tensile and structural properties of poly(vinyl alcohol) films: The influence of heating and film thickness

Poly(vinyl alcohol) as pure or composite materials is widely used in the food and textile industries, andbiomedical applications due to some important properties such as uniaxial tensile, biocompatibility, and noncarcinogenicity. Investigation of the influence of the film thickness and heating on the uniaxial tensile, spectroscopic, and surface properties of PVA films investigated in this study is quite important for improving the properties of such materials and their applicability in different conditions. In this study, with the influence of heating, a necking behavior was observed at around 2% for thin films and 4–9% strain for thicker PVA films for which a kind of transition point at around 1–2% strain was observed. The mechanical strength of PVA films, strain at break, and Young's modulus were enhanced greatly as the temperature increased from 80 to around 110 °C, and then most of them decreased. The degree of crystallinity increased linearly with the heat temperature from around 36–40%. Although PVA thin films obtained a very smooth surface structure after being heated at 80 °C, with increasing heat temperature, the surface roughness of both thin and thick PVA films increased and the PVA thin films obtained more degraded film surface. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44915.     

Effects of the lamination temperature on the properties of poly(ethylene terephthalate-co-isophthalate) in polyester-laminated tin-free steel can — I. Characterization of poly(ethylene terephthalate-co-isophthalate)

The effects of lamination temperature on the properties of poly(ethylene terephthalate-coisophthalate) (co-PET), such as thermal, mechanical, and barrier properties, have been investigated in co-PET laminated steel. The variation of the degree of crystallinity and the orientation of the co-PET film during the lamination process was examined using DSC, X-ray diffraction, and birefringence, and water vapor permeability was also measured with varying lamination temperature. Both the degree of crystallinity and the orientation of the co-PET film decreased and water vapor permeability increased with increasing lamination temperature. The stress-strain curves of the co-PET films were different, depending on the lamination temperature. The stress in the co-PET film laminated at higher temperature was lower at a given strain, due to the increase of the amorphous region. The effects of annealing temperature and the extent of drawing on the residual stress in co-PET/tin-free steel (TFS) joints were investigated by examining the stress relaxation behavior of co-PET. It was necessary to heat co-PET/TFS joints at more than 150°C in order to eliminate the residual stress.