Bulge testing and fracture properties of plasma-enhanced chemical vapor deposited silicon nitride thin films

The mechanical properties and fracture behavior of silicon nitride (SiN_x) thin film fabricated by plasma-enhanced chemical vapor deposition is reported. Plane-strain moduli, prestresses, and fracture strengths of silicon nitride thin films deposited both on a bare Si substrate and on a thermally oxidized Si substrate were extracted using bulge testing combined with a refined load-deflection model of long rectangular membranes. The plane-strain moduli and prestresses of SiN_x thin films have little dependence on the substrates, that is, for the bare Si substrate, they are 133 ± 19 GPa and 178 ± 22 MPa, respectively, while for the thermally oxidized substrate, they are 140 ± 26 GPa and 194 ± 34 MPa, respectively. However, the fracture strength values of SiN_x films grown on the two substrates are quite different, i.e., 1.53 ± 0.33 GPa and 3.08 ± 0.79 GPa for the bare Si substrate and the oxidized Si substrate, respectively. The reference stresses were computed by integrating the local stress of the membrane at the fracture over the edge, surface, and volume of the specimens and fitted with the Weibull distribution function. For SiN_x thin film produced on the bare Si substrate, the volume integration gave a significantly better agreement between data and model, implying that the volume flaws are the dominant fracture origin. For SiN_x thin film grown on the oxidized Si substrate, the fit quality of surface and edge integration was significantly better than the volume integration, and the dominant surface and edge flaws could be caused by buffered HF attacking the SiN_x layer during SiO₂ removal.     

Characterization of SiNx:H films deposited by rapid thermal chemical vapor deposition

Hydrogenated silicon nitride films were deposited with NH₃, SiH₄ and N₂ gas mixture at 700 °C by rapid thermal chemical vapor deposition (RTCVD) system. The NH₃/N₂ flow ratio and deposition pressure are found to influence the film properties. The stress of SiN_x:H films deposited by RTCVD is tensile, which can reach ~ 1.5 GPa in our study. The stress of SiN_x:H films is dependent on the deposition parameters, which can be associated with chemical configuration of the film. It is suggested that the presence of hydrogen atoms will relax the Si-N network, which results in the decrease of tensile stress of the SiN_x:H film.     

Size effect on fracture toughness of freestanding copper nano-films

We conducted fracture toughness experiments on freestanding copper films with thicknesses ranging from about 800 to 100 nm deposited by electron beam evaporation to elucidate the size effect on fracture toughness in the nano- or submicron-scale. It was found that initially, the crack propagated stably under loading, and then the crack propagation rate rapidly increased, resulting in unstable fracture. The fracture toughness K_C was estimated on the basis of the R-curve concept to be 7.81 ± 1.22 MPa m^1/2 for the 800-nm-thick film, 6.63 ± 1.05 MPa m^1/2 for the 500-nm-thick film and 2.34 ± 0.54 MPa m^1/2 for the 100-nm-thick film. Thus, a clear size effect was observed. The fracture surface suggested that the crack underwent large plastic deformation in the thicker 800-nm and 500-nm films, whereas it propagated with highly localized plastic deformation in the thinner 100-nm film. This size effect in fracture toughness might be related to a transition in deformation and fracture morphology near the crack tip.     

Transmission electron microscopy characterization of TiN/SiNx multilayered coatings plastically deformed by nanoindentation

Plastic deformation of TiN_5 nm/SiN_0.5 nm multilayers by nanoindentation was investigated by transmission electron microscopy in order to identify deformation mechanisms involved in film failure resulting from severe plastic deformation. The TiN layers exhibited a crystalline fcc structure with a [002] preferential orientation; further crystal growth was interrupted by the amorphous SiN_x layers. After severe plastic deformation collective vertical displacement of slabs of several TiN/SiN_x-bilayers, which resulted from shear sliding at TiN/TiN grain boundaries, was observed. They are, together with horizontal fractures along the SiN_x layers, vertical cracks under the indenter tip following the TiN grain boundaries and delamination from the substrate, the predominant failure mechanisms of these coatings. The deformation behaviour of these films provides an experimental support for the absence of dislocation activity in grains of 5 nm size.     

Effect of grain size on mechanical properties in CrAlN/SiNx multilayer coatings

Both CrAlN and SiN_x coatings were deposited sequentially by RF magnetron sputtering. During sputtering, thickness of SiN_x layer was set to be 1 nm, while that of CrAlN layer was controlled to be 4, 20, 40, 100, and 200 nm. According to XRD results, it was revealed that grain size of the CrAlN coatings increased from 3.6 nm to 24.2 nm with the increasing thickness. From HRTEM images, the variation on grain size was attributed to the amorphous SiN_x layer, which significantly retarded the continuous growth of CrAlN layer. Hardness of the CrAlN/SiN_x coatings with various bilayer thicknesses was measured by nanoindentation. The relationship between grain size and hardness could be interpreted by the Hall-Petch equation, and an improved hardness around 32 GPa was achieved.     

Tensile strain and water vapor transport testing of flexible, conductive and transparent indium-zinc-oxide/silver/indium-zinc-oxide thin films

Thin film laminates composed of sputtered indium zinc oxide and silver, optimized for conductance and transparency, were tested for water vapor permeation as well as mechanical durability in tension. The ~ 82 nm thick optimized indium-zinc-oxide/silver/indium-zinc-oxide (IZO/Ag/IZO) films were > 80% transparent in the visible range (400 nm-700 nm) with measured sheet resistances less than 5 Ω/sq. The water vapor permeation measurements using Ca test methods at several temperature/ humidity conditions indicated that the addition of the thin Ag layer provided little improvement relative to a single indium-zinc-oxide (IZO) layer of similar thickness. However, the critical strain in bending tests for IZO/Ag/IZO films was improved compared to IZO films. The modulus (E ~ 113 GPa), hardness (H ~ 7 GPa), fracture toughness (K_IC ~ 1.1 MPa⋅m^0.5), and interfacial shear (“adhesion”) (τ_c ~ 16 MPa) of/related to IZO, and measured by nanoindention are consistent with other brittle ceramic thin film materials.     

Effect of NH3 flow rate on growth, structure and luminescence of amorphous silicon nitride films by electron cyclotron resonance plasma

In this paper, hydrogenated amorphous silicon nitride (a-SiN_x:H) films have been deposited using an electron cyclotron resonance chemical vapor deposition system. The effect of NH₃ flow rate R on the deposition rate, structure and luminescence were studied using various techniques such as optical emission spectroscopy, Fourier Transform Infrared absorption (FTIR), X-ray photoelectron spectroscopy (XPS) and fluoro-spectroscopy, respectively. Optical emission behavior of SiH₄ + NH₃ plasma shows that atomic Si radical concentration determines the film deposition rate. Structural transition of a-SiN_x film from Si-rich one to near-stoichiometric/N-rich one with R was revealed by FTIR and the two phase separation of a-Si and a-Si₃N₄ was also convinced in Si-rich SiN_x films by XPS. Either photo- or electroluminescence for all the SiN_x films with R > 3 sccm shows a strong light emission in visible light wavelength range. As R < 6 sccm, recombination of electrons and holes in a-Si quantum dots is the main mechanism of photo/electroluminescence for Si-rich SiN_x films, however, for photoluminescence, gap states' luminescence is also in competition; as R > 6 sccm, light emission of the SiN_x film originates from defect states in its band gap.     

Magnetic properties and microstructure of TbCo/(SiNx/Co)n films

The Tb₃₂Co₆₈/(SiN_x/Co)_n films (n = 0 – 3) were prepared by magnetron sputtering. The magnetic anisotropy of all Tb₃₂Co₆₈/(SiN_x/Co)_n films are perpendicular to the film plane. It is found that the saturation magnetization (M_s) and perpendicular coercivity (H_c⊥) of the Tb₃₂Co₆₈/(SiN_x/Co)₃ film are 263 emu/cm³ and 3592 Oe, respectively. This film appears to be a promising material as a heat-assisted magnetic recording (HAMR) medium. The cross-sectional high resolution transmission electron microscope (HRTEM) images show that the interface roughness between the (SiN_x/Co)_n layers and TbCo layer increases as n is increased. The rough surface provides more obstacles and pinning sites that hinder the motion of the domain walls at interface between the (SiN_x/Co)_n layers and TbCo layer. Therefore, the H_c⊥ values are profoundly influenced by the interface roughness.     

Interfacial fracture for TiN/SiNx nano-multilayer coatings on Si(1 1 1) characterized by nanoindentation experiments

Fracture behavior for TiN/SiN_x nano-multilayer coatings on Si(1 1 1) substrates, deposited using magnetron sputtering Ti and Si, is characterized by nanoindentation experiments, and the morphologies of the indentations are revealed by scanning electron microscopy, along with in situ atomic force microscopy (AFM) in nanoindentation experiments. During nanoindentation experiments, under the condition that the displacement limit mode is used and a strain rate is kept at 0.05/s, an interfacial (between the coating and substrate) fracture is observed as the maximum indenter displacement into the coating reaches 2500 nm, and the corresponding unloading segment in the load–displacement curve shows an obvious discontinuity. This discontinuity is attributed to the rebound of the detached film during unloading. The interfacial fracture toughness for TiN/SiN_x nano-multilayer coating on Si(1 1 1), which is strongly dependent on the preferred orientation for the TiN layer as well as the interfaces between TiN and SiN_x layer in the multilayer stack, is calculated.     

Microstructure and mechanical properties of CrAlN/SiNx nanostructure multilayered coatings

Multilayered CrAlN and SiN_x films were deposited periodically by radio frequency reactive magnetron sputtering. In the CrAlN/SiN_x multilayered coatings, the thickness of CrAlN layer was fixed at 4 nm, while that of SiN_x layer was adjusted from 4 nm to 0.3 nm. The dependence of the SiN_x layer thickness on the preferred orientation, crystalline behavior and mechanical properties of multilayered coatings were discussed with the aid of XRD patterns and HRTEM. It was demonstrated that amorphous SiN_x layer transformed to a crystallized one when the thickness decreased from 4 nm to 0.3 nm. The crystalline SiN_x layer grew epitaxially, formed the coherent interface with the CrAlN layer, and the columnar structure was exhibited. The critical layer thickness for the transition from amorphous SiN_x to a crystallized one was found to be around 0.4 nm, and maximum hardness of 33 GPa was revealed.     

Annealing optimization of silicon nitride film for solar cell application

Hydrogenated films of silicon nitride (SiNx:H) is commonly used as an antireflection coating as well as passivation layer in crystalline silicon solar cell. SiNx:H films deposited at different conditions in Plasma Enhanced Chemical Vapor Deposition (PECVD) reactor were investigated by varying annealing condition in infrared (IR) heated belt furnace to find the optimized condition for the application in silicon solar cells. By varying the gases ratio (R = NH₃/SiH₄ + NH₃) during deposition, the SiNx:H films of refractive indices 1.85-2.45 were obtained. Despite the poor deposition rate, the silicon wafer with SiNx:H film deposited at 450 °C showed the best effective minority carrier lifetime. The film deposited with the gases ratio of 0.57 shows the best peak of carrier lifetime at the annealing temperature of 800 °C. The single crystalline silicon solar cells fabricated in conventional industrial production line applying the optimized film deposition and annealing conditions on large area substrates (125 mm × 125 mm) were found to have the conversion efficiencies as high as 17.05 %. Low cost and high efficiency single crystalline silicon solar cells fabrication sequence employed in this study has also been reported in this paper.     

Fracture behavior and mechanism of 2D C/SiC-BCx composite at room temperature

2D C/SiC composite was modified with partial BC_x matrix by low pressure chemical vapor infiltration technique (LPCVI), which was named as 2D C/SiC-BC_x composite. The flexural fracture behavior, mechanism, and strength distribution of 2D C/SiC-BC_x composite are investigated. The results indicate that the flexural strength, fracture toughness, and fracture work are 442.1 MPa, 22.84 MPa m^1/2, and 19.2 kJ m⁻², respectively. The flexural strength of C/SiC-BC_x composite decrease about 20% than that of C/SiC composite. However, the fracture toughness and fracture work increase about 19% and 18.5%, respectively. The properties varieties between C/SiC-BC_x composite and C/SiC composite can be attributed to the weak-bonding interface between BC_x/SiC matrices according to the results of detailed microstructure analysis. The strength distribution of 2D C/SiC-BC_x composite follows as Normal distribution or Weibull distribution with σ_u = 0, and m = 8.1393. The mean value of flexural strength for 2D C/SiC-BC_x composite is 443 MPa obtained by theory calculation, which is consistent with experiment result (442.1 MPa) very well.     

Influence of N2 flow rate on the mechanical properties of SiNx films deposited by microwave electron cyclotron resonance magnetron sputtering

Hydrogen-free amorphous silicon nitride (SiN_x) films were deposited at room temperature by microwave electron cyclotron resonance plasma-enhanced unbalance magnetron sputtering. Varying the N₂ flow rate, SiN_x films with different properties were obtained. Characterization by Fourier-transform infrared spectrometry revealed the presence of Si-N and Si-O bonds in the films. Growth rates from 1.0 to 4.8 nm/min were determined by surface profiler. Optical emission spectroscopy showed the N element in plasma mainly existed as N⁺ species and N₂⁺ species with 2 and 20 sccm N₂ flow rate, respectively. With these results, the chemical composition and the mechanical properties of SiN_x films strongly depended on the state of N element in plasma, which in turn was controlled by N₂ flow rate. Finally, the film deposited with 2 sccm N₂ flow rate showed no visible marks after immersed in etchant [6.7% Ce(NH₄)₂(NO₃)₆ and 93.3% H₂O by weight] for 22 h and wear test for 20 min, respectively.     

Structures and mechanical properties of TiN/SiNx multilayer films deposited by magnetron sputtering at different N2/Ar gas flow ratios

Polycrystalline TiN/SiN_x multilayer films are deposited using reactive magnetron sputtering Ti and Si, respectively, discharging a mixture of N₂ and Ar gas with different N₂/Ar gas flow ratios, and their structures and mechanical properties are characterized by X-ray reflectivity (XRR), X-ray diffraction (XRD) and nanoindentation. It is found that when the N₂/Ar gas flow ratio is low, the interface between TiN and SiN_x layer for the obtained TiN/SiN_x film is sharp and the preferred orientation for TiN layer is TiN (200). In contrast, when the N₂/Ar gas flow ratio is high, the interface becomes rough and the preferred orientation for TiN layer changes to TiN (111). Nanoindentation experiments exhibit that the TiN/SiN_x film with a TiN (111) preferred orientation is harder than that with a TiN (200) preferred orientation, and all films have nano-scale fracture characteristics.     

Deposition and characterization of ultra-high barrier coatings for flexible electronic applications

A barrier structure consisting of SiO_x and SiN_x films was deposited on the polymer substrate at 80 °C via plasma-enhanced chemical vapor deposition (PECVD). However, the low radius of curvature (R_c) of the barrier-coated substrate may cause the inconvenience of the following fabrication processes. By depositing a 150 nm-SiN_x film, the R_c of the barrier-coated polycarbonate (PC) substrate can increase from 80 to 115 mm without inducing any cracks in the barrier structure. Furthermore, the thermal stress of the barrier structure can be adjusted via extending the PECVD process duration in the chamber and replacing PC by the polyethersulone (PES) substrate. The R_c can increase to ∼356 mm by depositing the 150 nm-SiN_x film on the other side of the PES substrate. Finally, the calcium test result of the barrier films/PES/SiN_x sample was calculated to be around 3.05 × 10⁻⁶ g/m²/day, representing that the barrier structure did not fail after modification.     

Fracture toughness of grade D ship steel

Results from fracture mechanics tests on 15 mm thick grade D ship steel and weld are organised into a toughness distribution indexed to the Charpy 27 joule temperature, T_27J. The tests are carried out at 300 MPa√m/s to simulate the strain rate appropriate to a long (≈1 m) through thickness crack in the deck of a ship under storm conditions. Most of the data are in the brittle to ductile transition region and end in cleavage fracture. A best fit to the data is found using the exponential curve fit (ECF) method. Lack of censoring of invalid results means that the trend line is not a true ‘plane strain’ fit. It is argued that inclusion of ‘plane stress’ data makes the resultant toughness distribution more relevant to ship fracture predictions. Equations are presented which allow the toughness to be plotted at any chosen probability level as a function of temperature relative to T_27J. A safe lower bound to the data is given by the 0.1% probability trend assuming that T_27J for grade D plate and weld is no higher than −20 °C. The data are also used to propose that it is impossible to generate an elastic ductile tearing instability in ship steel with Charpy upper shelf values of 100 J or more.     

Protection of organic light-emitting diodes over 50 000 hours by Cat-CVD SiNx/SiOxNy stacked thin films

Silicon oxynitride (SiO_xN_y) films have been formed by adding proper amount of oxygen gas to usual forming condition of silicon nitride (SiN_x) films in catalytic chemical vapor deposition (Cat-CVD) method. The composition and refractive index of the film can be systematically controlled by changing oxygen flow rate. Organic light-emitting diodes (OLEDs) covered with SiN_x/SiO_xN_y stacked films have been completely protected from damage due to oxygen and moisture and their initial emission intensity is maintained over 1000 hours under 60 °C and 90% RH, which is equivalent to 50 000 hours in normal temperature and humidity conditions.     

Mechanical and environmental properties of Ge1−xCx thin film

Ge_1−xC_x thin film was prepared by plasma-enhanced chemical vapor deposition (PECVD) using GeH₄ and CH₄ as precursors and its mechanical and environmental properties were investigated. The samples were measured by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectrum, FT-IR spectrometer, WS-92 testing apparatus of adhesion and FY-03E testing apparatus of salt and fog. The results show that the infrared refractive index of Ge_1−xC_x thin film varies from 2 to 4 with different x values. The adhesion increases with increasing gas flow ratio of GeH₄/CH₄ and decreases with increasing film thickness. The nanoindentation hardness number decreases with increasing germanium content. Three series films exhibit the best anti-corrosion property when the RF power is about 80 W, or substrate temperature is about 150 °C, or DC bias is about −100 V. Furthermore, increasing the gas flow ratio of GeH₄/CH₄ improves the anti-corrosion property of these films.     

Inclusion-controlled high cycle fatigue behavior of a high V alloyed powder metallurgy cold-working tool steel

Axial loading fatigue tests were carried out to study the influence of inclusion on high cycle fatigue behavior of a high V alloyed powder metallurgy cold-working tool steel (AISI 11). The fatigue strength of 1538 MPa with endurance life of 10⁷ cycles were obtained by stair-case method. The fatigue specimens were also subjected to a constant maximum stress of 1650 MPa to investigate the relationship among inclusion origin size (10-30 μm), fish-eye size (70-130 μm) and fatigue life (10⁵-10⁷ cycles). The fatigue life was found to be dependent on the inclusion size and the crack propagating length. A compressive residual stress of 300-450 MPa turned out to be present at the specimen surface, and finally induced the interior failure mode. Further investigation into the correlation between stress intensity factors of inclusion origin and corresponding stages of fatigue crack growth and fatigue life revealed that the high cycle fatigue behavior was controlled by crack propagation. According to the fractographic investigation, two distinct zones were observed in fish-eye, representing Paris-Law and fast fatigue crack growth stage, respectively. Threshold stress intensity for crack propagation of 3.9 MPa√m was obtained from the well correlated line on the ΔK_I-log N_? graph. The fracture toughness can also be estimated by the mean value of stress intensity factor ranges for fish-eye.     

Excellent passivation effect of Cat-CVD SiNx/i-a-Si stack films on Si substrates

We have demonstrated that the surface recombination velocity can be lowered to as low as 1.3 cm/s for n-type c-Si wafers and to 9.0 cm/s for p-type wafers by using amorphous Si (a-Si) and Si nitride (SiN_x) stacked films prepared by catalytic chemical vapor deposition (Cat-CVD). These values are much lower than those of c-Si wafers passivated by same stacked structures formed by low-damage remote plasma-enhanced CVD (PECVD). It is revealed that Cat-CVD a-Si insertion layers play an important role to improve interface quality, and also SiN_x films are also essential for reducing the surface recombination velocity down to such low levels.